CN112495341B - Medical stone adsorbent and preparation method thereof, chlorine dioxide preparation and preparation method and application thereof - Google Patents
Medical stone adsorbent and preparation method thereof, chlorine dioxide preparation and preparation method and application thereof Download PDFInfo
- Publication number
- CN112495341B CN112495341B CN201911171740.0A CN201911171740A CN112495341B CN 112495341 B CN112495341 B CN 112495341B CN 201911171740 A CN201911171740 A CN 201911171740A CN 112495341 B CN112495341 B CN 112495341B
- Authority
- CN
- China
- Prior art keywords
- chlorine dioxide
- preparation
- medical stone
- adsorbent
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Abstract
The invention provides a medical stone adsorbent and a preparation method thereof, a chlorine dioxide preparation and a preparation method and application thereof, and belongs to the technical field of chlorine dioxide preparation. The preparation method of the medical stone adsorbent provided by the invention comprises the following steps: mixing diammonium phosphate solution and medical stone, and carrying out modification reaction to obtain modified medical stone; roasting the modified medical stone to obtain the medical stone adsorbent. The invention utilizes diammonium hydrogen phosphate solution to modify medical stone, the active center of the microporous structure of the modified medical stone is mainly weak acid, so that the medical stone adsorbent has the advantages of high adsorption and slow release on chlorine dioxide in a liquid-phase weak acid environment required by the slow release of chlorine dioxide gas. After the medical stone adsorbent is used for adsorbing stable chlorine dioxide solution, the obtained chlorine dioxide preparation can slowly release high-purity chlorine dioxide gas, and can be applied to multiple fields.
Description
Technical Field
The invention relates to the technical field of chlorine dioxide preparation, and particularly relates to a medical stone adsorbent and a preparation method thereof, a chlorine dioxide preparation and a preparation method and application thereof.
Background
Chlorine dioxide is a fourth generation disinfectant, is the only high-efficiency disinfectant in the chlorine-containing disinfectants recognized internationally, and proved by a large number of experiments and field sterilization tests at home and abroad, the chlorine dioxide can almost kill all microorganisms including viruses, fungi, mycobacteria, bacterial propagules, bacterial spores and the like, and has the advantages of broad spectrum, high efficiency, rapidness, no residue, no drug resistance and the like. Since the beginning of the 19 th century, it has become one of the most widely used disinfecting articles in the world. The action mechanism of the chlorine dioxide determines that only microorganisms are killed, the safety of the chlorine dioxide is evaluated by a food additive expert committee (JECFA) which is formed by the World Health Organization (WHO) and the Food and Agriculture Organization (FAO) of the United nations, the safety level ADI (human body intake allowance standard) is A1 level, and the chlorine dioxide is understood as the only authenticator in the disinfectant, and the safety is guaranteed.
Since the beginning of the disinfection of drinking water by chlorine dioxide in the united states in 1944, the drinking water in the united states and european countries is almost disinfected by chlorine dioxide at present, and is widely applied to the fields of sewage treatment, air disinfection, medicine and health, food preservation and preservation, deodorization, preservation, algae removal, bleaching and the like in agriculture and animal husbandry.
The research and application of chlorine dioxide in China are started late, and remarkable effects are achieved from the 80 s of the last century to the present. The chlorine dioxide disinfectant plays an important role when SARS and 2004 highly pathogenic avian influenza epidemic situation occur. With the development of the innovation, the development of the information-based society and the continuous improvement of the quality of life of people, the requirements on the environmental quality and the health care are higher and higher, so that the stable chlorine dioxide serving as a novel sterilizing disinfectant has a very wide market prospect in China. Compared with the foreign countries, the preparation and mechanism research of chlorine dioxide in China is relatively lagged, and the current market application is not wide and mature due to the reasons of cost, standard establishment delay and the like.
The chlorine dioxide is divided into a preparation and a generator according to the production mode, the commodity state is liquid or solid, the generation mechanism is binary or unitary reaction, the application state is liquid or gaseous, and the chemical property is very active and is very easy to decompose and disproportionate, and the problems of low purity, poor stability, inconvenience, unsafety, high cost and the like exist in the chlorine dioxide products and stable chlorine dioxide products applied in the current market to different degrees, so that the use of the high-efficiency safe disinfectant is greatly limited, and the high-efficiency safe disinfectant is particularly obvious to the influence of commercial and civil scattered households. Compared with liquid chlorine dioxide, the gaseous chlorine dioxide has the advantages of good penetrability, strong diffusivity and no residue, and is particularly suitable for disinfection treatment of pipe cavities, gaps and large-area space environments. Therefore, the research and development of a preparation which has long-acting stability, safety, convenience and low cost and can generate high-purity chlorine dioxide gas must have wide application prospect and great social value.
Disclosure of Invention
The invention aims to provide a medical stone adsorbent and a preparation method thereof, a chlorine dioxide preparation and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a medical stone adsorbent, which comprises the following steps:
mixing diammonium phosphate solution and medical stone, and carrying out modification reaction to obtain modified medical stone;
roasting the modified medical stone to obtain the medical stone adsorbent.
Preferably, the mass concentration of the diammonium hydrogen phosphate solution is 5-10%.
Preferably, the dosage ratio of the medical stone to the diammonium phosphate solution is preferably 100g (100-300) mL.
Preferably, the time of the modification reaction is 15-90 min, and the modification reaction is carried out under the condition of stirring.
Preferably, the roasting temperature is 70-120 ℃, and the roasting time is 60-120 min.
Preferably, after the modification reaction, washing and drying the solid obtained by the modification reaction are also included.
The invention provides a medical stone adsorbent prepared by the preparation method in the scheme.
The invention provides a preparation method of a chlorine dioxide preparation, which comprises the following steps:
the medical stone adsorbent is soaked into stable chlorine dioxide solution and dried to obtain the chlorine dioxide preparation.
The invention provides a chlorine dioxide preparation prepared by the preparation method in the scheme, which comprises the medical stone adsorbent in the scheme and stable chlorine dioxide positioned in pore passages and/or surfaces of the medical stone adsorbent.
The invention provides application of the chlorine dioxide preparation in the scheme in the fields of disinfection, food preservation and fresh keeping or air purification.
The invention provides a preparation method of a medical stone adsorbent, which comprises the following steps: mixing diammonium phosphate solution and medical stone, and carrying out modification reaction to obtain modified medical stone; roasting the modified medical stone to obtain the medical stone adsorbent. The medical stone has high adsorbability, and after the medical stone is modified by diammonium hydrogen phosphate solution, the medical stone has the characteristic of solid acid, the acidic characteristic is rich in B acid capable of providing protons, the active center of the microporous structure of the modified medical stone is mainly weak acid, so that the medical stone has a liquid-phase weak acid environment required by the slow release of chlorine dioxide gas, and the medical stone adsorbent obtained after roasting and activation has the advantages of high adsorbability and slow release of chlorine dioxide.
The chlorine dioxide preparation obtained by adsorbing the stable chlorine dioxide solution by using the medical stone adsorbent prepared by the invention as a carrier can slowly release high-purity chlorine dioxide gas, can be applied to the fields of disinfection, food preservation and preservation or air purification, and specifically can create huge social and economic benefits in various environments such as a filter, air disinfection and purification equipment, medical instrument disinfection equipment, indoor air purification equipment, small-space formaldehyde-removing mildew prevention, food preservation and the like.
In addition, the invention can also control the release flux of the chlorine dioxide gas by controlling the preparation conditions of the medical stone adsorbent (such as the mass concentration of the diammonium hydrogen phosphate solution), the composition of the stable chlorine dioxide solution and the application conditions of the chlorine dioxide preparation, thereby meeting the actual requirements of different application scenes and really realizing the artificial control, safety, convenience, long-term and stable release of the chlorine dioxide gas.
Besides the release of chlorine dioxide gas can be manually controlled, the chlorine dioxide preparation prepared by the invention can automatically adjust the release amount of chlorine dioxide according to the concentration of environmental pollutants, overcomes the defects of low purity, instability, inconvenience, insecurity and uncontrollable of the existing chlorine dioxide, and ensures that the green disinfectant which has three effects (broad spectrum, high efficiency and rapidness) and no three causes (carcinogenesis, teratogenesis and mutagenicity) and has the characteristics of good penetrability, strong dispersivity and easiness and uniformity has higher application value.
Drawings
FIG. 1 is a graph showing the release of chlorine dioxide in 24 hours from the chlorine dioxide preparations of examples 1 to 4;
FIG. 2 is a graph showing the generation of hydroxyl radicals in the absence of formaldehyde stimulation;
FIG. 3 is a graph showing the generation of hydroxyl radicals by formaldehyde stimulation.
Detailed Description
The invention provides a preparation method of a medical stone adsorbent, which comprises the following steps:
mixing diammonium phosphate solution and medical stone, and carrying out modification reaction to obtain modified medical stone;
roasting the modified medical stone to obtain the medical stone adsorbent.
The invention mixes diammonium hydrogen phosphate solution and medical stone for modification reaction to obtain modified medical stone. In the invention, the mass concentration of the diammonium hydrogen phosphate solution is preferably 5-10%, and more preferably 5%. The particle size of the medical stone is preferably 100-200 meshes, and the specific surface area of the medical stone is preferably more than 150m 2 A pore volume of more than 0.5m 3 The static water absorption is preferably greater than 30%. In the invention, the dosage ratio of the medical stone to the diammonium phosphate solution is preferably 100g (100-300) mL, more preferably 100g: 300 mL. The invention has no special requirement on the mixing mode of the diammonium phosphate solution and the medical stone, and the mixing mode can be any one known in the field. In the present invention, the modification isThe temperature is preferably normal temperature, i.e. no additional heating or cooling is needed; the time of the modification reaction is preferably 15 to 90min, more preferably 30 to 60min, and most preferably 30 min. In the present invention, the modification reaction is preferably carried out under stirring conditions, and the present invention has no particular requirement on the stirring rate and does not cause liquid splashing. After the modification reaction, the invention preferably also comprises washing and drying the solid obtained by the modification reaction to obtain the modified medical stone. The invention preferably employs water for the washing, followed by filtration and then washing until the wash liquor is neutral. In the present invention, the drying is preferably vacuum drying, the temperature of the vacuum drying is preferably 80 ℃, and the time of the vacuum drying is preferably 2 h.
The invention utilizes diammonium hydrogen phosphate solution to modify medical stone, so that the medical stone has solid acid characteristic, the acidic characteristic is rich in B acid capable of providing protons, and the active center of the microporous structure of the modified medical stone is mainly weak acid, so that the medical stone can have a liquid-phase weak acid environment required by the slow release of chlorine dioxide gas.
After the modified medical stone is obtained, the modified medical stone is roasted to obtain the medical stone adsorbent. In the invention, the roasting temperature is preferably 70-120 ℃, more preferably 100 ℃, and the roasting time is preferably 60-120 min, more preferably 90 min; the atmosphere for the calcination is preferably an air atmosphere. In the roasting process, the modified medical stone is activated, and has the characteristics of high adsorption and slow release on chlorine dioxide.
The invention provides a preparation method of a chlorine dioxide preparation, which comprises the following steps: the medical stone adsorbent is soaked into stable chlorine dioxide solution and dried to obtain the chlorine dioxide preparation.
The composition of the stable chlorine dioxide solution is not particularly required in the present invention, and stable chlorine dioxide solutions well known in the art can be used. In the present invention, the stable chlorine dioxide solution is preferably obtained by mixing a stabilizer, a chlorite salt and water. The stabilizer preferably comprises "sodium hydroxide, sodium chloride, sodium carbonate, sodium bicarbonate, sodium borate, sodium percarbonate, sodium perborate, sodium silicate, 8-hydroxyquinoline or diethylenetriamine pentamethylenephosphonic acid" + hydrogen peroxide; more preferably "sodium percarbonate + hydrogen peroxide" or "8-hydroxyquinoline + hydrogen peroxide"; the chlorite preferably comprises one or more of sodium chlorite, potassium chlorite, magnesium chlorite, lithium chlorite, and barium chlorite, and more preferably is sodium chlorite. In the invention, the content of the chlorite in the stable chlorine dioxide solution is preferably 5 to 20%, more preferably 8 to 10%, and most preferably 8%. In the invention, the pH value of the stable chlorine dioxide solution is preferably 9.5-10.5. The pH value of the stable chlorine dioxide solution is not required to be adjusted by additionally adding acid or alkali, and the dosage of the stabilizer and the chlorite in the stable chlorine dioxide solution can be adjusted. The invention controls the pH value of the stable chlorine dioxide solution in the range, and is beneficial to ensuring the stable slow release of chlorine dioxide gas. In the examples of the present invention, the stable chlorine dioxide solution comprises, in mass percent, 10% sodium chlorite, 2% sodium percarbonate, 2% hydrogen peroxide and the balance water, or comprises 10% sodium chlorite, 2% 8-hydroxyquinoline, 2% hydrogen peroxide and the balance water. The mass percentage of the hydrogen peroxide refers to the mass percentage of water, and the mass concentration of the hydrogen peroxide is preferably 20%.
In the present invention, the solid-to-liquid ratio of the adsorbent to the stable chlorine dioxide solution is preferably 100g: (100-250) mL, more preferably 100g: 100 mL. In the invention, the time for the impregnation is preferably 0.5-1.5 h, more preferably 1h, and the impregnation is preferably carried out under stirring. The rate of agitation is not particularly critical to the present invention and may be any rate known in the art. The invention soaks the medical stone adsorbent into the stable chlorine dioxide solution, and the stable chlorine dioxide solution is adsorbed to the pore canal and/or the surface of the medical stone adsorbent.
In the present invention, the drying preferably includes airing and vacuum drying which are performed in sequence; the air drying is preferably dried by a fan, and the air drying time is preferably 0.5-1.5 h; the temperature of the vacuum drying is preferably 75-85 ℃, and more preferably 80 ℃; the time of vacuum drying is preferably 3.5-4.5 h, and more preferably 4 h.
The invention provides a chlorine dioxide preparation prepared by the preparation method in the scheme, which comprises the medical stone adsorbent in the scheme and stable chlorine dioxide positioned in pore passages and/or surfaces of the medical stone adsorbent. The chlorine dioxide preparation can slowly release high-purity chlorine dioxide gas, has the advantages of long acting and stability, is nontoxic and tasteless, is convenient to store and transport, does not need to be activated in use, and has the advantages of safety and convenience.
The invention provides application of the chlorine dioxide preparation in the scheme in the fields of disinfection, food preservation and fresh keeping or air purification. The invention has no special requirements for the mode of application, and can be applied by the mode of application well known in the field. In the invention, the application of the chlorine dioxide preparation in the disinfection field can be particularly but not limited to the preparation of air disinfection and purification equipment, medical equipment disinfection equipment and the like; the application of the chlorine dioxide preparation in the field of air purification can be, but is not limited to, formaldehyde removal and mildew prevention, preparation of indoor air purification equipment and the like.
When pollutants such as microorganisms, formaldehyde or ozone exist, the pollutants can promote a chlorine dioxide preparation to release chlorine dioxide gas, the chlorine dioxide preparation has strong adsorption effect on the pollutants, the pollutants are combined with acid active centers on the chlorine dioxide preparation in an activated complex form, a large amount of chlorine dioxide with strong oxidation effect and the pollutants are simultaneously gathered on the surface of the chlorine dioxide preparation, and the activation energy of the chlorine dioxide reaction is reduced 2 、·ClO 2 And ClO, O, H and the like, so that a plurality of factors form a cascade chain reaction, the oxidation reaction is promoted together, and the pollutant removal efficiency is greatly improved. In addition, the chlorine dioxide and the pollutants are not on the surface of the medical stone adsorbentThe dynamic process of broken adsorption, consumption and desorption is favorable for recycling the adsorbent, the service life of the medical stone adsorbent is greatly prolonged, the material is durable, the stability and the use convenience of derivative products are improved, the application cost is greatly reduced while the environment is protected, and the medical stone adsorbent can be applied to various environments.
The medical stone adsorbent and the preparation method thereof, the chlorine dioxide preparation and the preparation method and application thereof provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1. Preparing a medical stone adsorbent:
1) weighing a certain amount of medical stone (100-200 meshes), and placing the medical stone in a triangular flask; 2) preparing a diammonium hydrogen phosphate solution with the concentration of 5 wt.%; 3) according to the following steps of 1: 3 (100g medical stone: 300mL diammonium hydrogen phosphate solution), putting the crushed medical stone into diammonium hydrogen phosphate solution, mechanically stirring for 30min, filtering, adding water for cleaning, and filtering again until the pH value of the filtrate is neutral; 4) drying in a vacuum drying oven at 80 deg.C for 2 hr to obtain modified Maifanitum; 5) activating the modified Maifanitum in muffle furnace at 100 deg.C for 90min to obtain Maifanitum adsorbent.
2. Preparation of chlorine dioxide preparation:
1) preparing a stable chlorine dioxide solution: preparing a stable chlorine dioxide solution (with the pH value of 9.5) which comprises 10% of sodium chlorite, 2% of sodium percarbonate and 2% of hydrogen peroxide in percentage by mass;
2) according to the proportion of 1:1 (100g medical stone adsorbent: 100mL of stable chlorine dioxide solution), then pouring the impregnation solution into a reaction kettle, stirring and adsorbing for 1h, airing for 1h, and then carrying out vacuum drying for 4h at 80 ℃ to prepare the chlorine dioxide preparation.
Example 2
1. Preparing a medical stone adsorbent:
1) weighing a certain amount of medical stone (100-200 meshes), and placing the medical stone in a triangular flask; 2) preparing 10 wt.% diammonium hydrogen phosphate solution; 3) according to the following steps of 1: 3 (100g medical stone: 300mL diammonium hydrogen phosphate solution), putting the crushed medical stone into the diammonium hydrogen phosphate solution, mechanically stirring for 30min, filtering, adding water for cleaning, and filtering again until the pH value of the filtrate is neutral; 4) drying in a vacuum drying oven at 80 deg.C for 2 hr to obtain modified Maifanitum; 5) activating the modified Maifanitum in muffle furnace at 100 deg.C for 90min to obtain Maifanitum adsorbent.
2. Preparation of chlorine dioxide preparation:
1) preparing a stable chlorine dioxide solution: preparing a stable chlorine dioxide solution (with the pH value of 9.5) which comprises 10% of sodium chlorite, 2% of sodium percarbonate and 2% of hydrogen peroxide in percentage by mass;
2) according to the proportion of 1:1 (100g medical stone adsorbent: 100mL of stable chlorine dioxide solution), then pouring the impregnation solution into a reaction kettle, stirring and adsorbing for 1h, airing for 1h, and then carrying out vacuum drying for 4h at 80 ℃ to prepare the chlorine dioxide preparation.
Example 3
1. Preparing a medical stone adsorbent:
the same as in example 1.
2. Preparation of chlorine dioxide preparation:
1) preparing a stable chlorine dioxide solution: preparing a stable chlorine dioxide solution (with the pH value of 9.5) which comprises 5% of sodium chlorite, 2% of 8-hydroxyquinoline and 2% of hydrogen peroxide in percentage by mass;
2) according to the proportion of 1:1 (100g medical stone adsorbent: 100mL of stable chlorine dioxide solution), then pouring the impregnation solution into a reaction kettle, stirring and adsorbing for 1h, airing for 1h, and then carrying out vacuum drying for 4h at 80 ℃ to prepare the chlorine dioxide preparation.
Example 4
1. Preparing a medical stone adsorbent:
the same as in example 2.
2. Preparation of chlorine dioxide preparation:
1) preparing a stable chlorine dioxide solution: preparing a stable chlorine dioxide solution with the mixture ratio of 10% of sodium chlorite, 2% of 8-hydroxyquinoline and 2% of hydrogen peroxide and the pH value of 9.5 in percentage by mass;
2) according to the proportion of 1:1 (100g medical stone adsorbent: 100mL of stable chlorine dioxide solution), then pouring the impregnation solution into a reaction kettle, stirring and adsorbing for 1h, airing for 1h, and then carrying out vacuum drying for 4h at 80 ℃ to prepare the chlorine dioxide preparation.
Performance testing
1. Chlorine dioxide gas release within 24 hours
Four groups of samples (chlorine dioxide preparations of examples 1 to 4) were prepared, with the preparation date of 2018, 7 and 02 months, and were stored in dark and sealed.
And detecting the release of chlorine dioxide gas in 2018, 7 and 03 days.
An electrochemical detector is used for detecting chlorine dioxide gas (chlorine dioxide sensor module SK-600-CL21000PPM, produced by Shenzhen Dongyi Ying energy science and technology Limited).
100g of each sample was taken and left open at 0.03m 3 In the detection box, the natural light is placed in a closed manner for 24 hours for dynamic detection, the data reading interval time is 10 seconds, the number is read in each hour, the average value is obtained, and the concentration unit is mg/m 3 . The release profile is shown in figure 1.
As can be seen from fig. 1, the sample has a large release amplitude within 16 hours, and gradually levels after 16 hours, which shows that the chlorine dioxide preparation of the present invention can slowly release chlorine dioxide gas. In addition, fig. 1 also shows that when the stable chlorine dioxide solution has the following mixture ratio: the sample is well released when the sodium chlorite with the concentration of 10 percent, the 8-hydroxyquinoline with the concentration of 2 percent and the hydrogen peroxide with the concentration of 2 percent are used, and the effect of the modified diammonium phosphate solution on the release is not obvious.
2. Stability testing of chlorine dioxide formulations
Four groups of samples (chlorine dioxide formulations of examples 1-4) were prepared on two days, with preparation dates of 2018, 7/month, 05 days (table 1) and 2018, 7/month, 09 days (table 2).
And selecting the time periods of 24 hours, 1 month, 2 months, 3 months, 6 months and 12 months after preparation for detection, and keeping the sample in dark and sealed conditions during detection.
An electrochemical detector is used for detecting chlorine dioxide gas (chlorine dioxide sensor module SK-600-CL21000PPM, produced by Shenzhen Dongyi Ying energy science and technology Limited).
100g of each sample was taken and left open at 0.03m 3 In the detection box, after the detection box is placed in a sealed mode under natural light for 10 hours, the detection is carried out for 30 minutes, the data reading interval time is 5 seconds, the number is read, the average value is obtained, and the concentration unit is mg/m 3 . The results are shown in tables 1 and 2, respectively.
TABLE 1 chlorine dioxide gas release (preparation date 2018, 7 month, 05 day, unit: mg/g)
TABLE 2 chlorine dioxide gas release (preparation date 2018, 7, 9, month, unit: mg/g)
As can be seen from tables 1 and 2, after one year, the release attenuation rates of four groups of samples are less than 24%, which shows that the chlorine dioxide preparation of the present invention has the advantage of long-term stability, wherein the release attenuation rates of two groups of samples modified by a 5% diammonium phosphate solution are less than 10%, the release attenuation rates of two groups of samples modified by a 10% diammonium phosphate solution are greater, and are respectively 23.6% (example 2 sample) and 19% (example 4 sample), and it is analyzed that the high concentration diammonium phosphate solution significantly increases the acid strength of the active center after the catalyst is modified, accelerates the solid-liquid catalytic reaction, and causes the catalyst to be stably weakened.
3. Chlorine dioxide gas release purity detection (purity greater than 95% after absorption into solution)
Four groups of samples (chlorine dioxide formulations of examples 1-4) were prepared on two days, with preparation dates of 7 months and 5 days in 2018 (table 3) and 7 months and 9 days in 2018 (table 4).
100g of each group of samples are taken and placed in self-developed generating equipment (Chinese patent with application number of 201910857945.8 and invention name of 'adsorption type chlorine dioxide solid preparation generating device and detection method'), 200ml of deionized water is taken as absorption liquid, and after 24 hours of absorption, a five-step iodometry method is applied to detect the content of each substance in the solution. The detection dates were 11 days in 2018, 7 months and 13 days.
TABLE 3 chlorine dioxide purity test (preparation date 2018, 7 and 5 days, test date 2018, 7 and 11 days)
TABLE 4 chlorine dioxide purity test (preparation date 2018, 7 and 9 months, test date 2018, 7 and 13 months)
The results show that the purity of the absorption liquid of the four groups of samples is greater than 95%, and no obvious difference exists, which indicates that the chlorine dioxide preparation prepared by the invention can release high-purity chlorine dioxide gas.
4. Chlorine dioxide release after substrate stimulation (automatically adjusting the amount of chlorine dioxide release with the concentration of contaminants)
The chlorine dioxide preparation of example 3 (the sample stable chlorine dioxide solution is 10% sodium chlorite, 2% 8-hydroxyquinoline and 2% hydrogen peroxide, and the modified concentration is 5% diammonium hydrogen phosphate solution) is selected for detection, the preparation date is 7 months and 9 days in 2018, and the preparation is carried out in a dark and sealed way.
The detection dates were 7 and 15 days in 2018, 16 days in 7 and 16 months in 2018 and 17 days in 7 and 17 months in 2018, respectively.
250 g of samples are taken and divided into 5 groups, each group is 50 g, chlorine dioxide concentration detection is respectively carried out under the conditions of no substrate, ultraviolet irradiation of different wave bands and formaldehyde stimulation of different concentrations, and the substrate stimulation conditions are shown in Table 5.
Each group of samples are simultaneously and respectively placed in 5 detection boxes with the same specification, and the size of each detection box is 0.02m 3 An ultraviolet lamp tube is arranged inside the lamp. The 5 detection boxes are simultaneously connected with an electrochemical detector (chlorine dioxide sensor die)Set SK-600-CL21000PPM, produced by shenzhen Dongying energy science and technology ltd).
Each group of samples is placed in a detection box in an open way, after being placed in a closed way for 10 hours under natural light, the detection is carried out for 30 minutes, the data reading interval time is 5 seconds, the number is read, the average value is obtained, and the concentration unit is mg/m 3 The results are shown in Table 5.
TABLE 5 chlorine dioxide gas release flux under stimulation with different substrates
As can be seen from Table 5, the release flux of chlorine dioxide gas is significantly increased under the stimulation of ultraviolet rays and formaldehyde, and the stimulation of high-concentration formaldehyde is more significantly increased than the stimulation of low-concentration formaldehyde. The existence of substrates (such as formaldehyde and ultraviolet light) is proved, the chlorine dioxide preparation can be promoted to release chlorine dioxide gas, the activation energy of the chlorine dioxide reaction is reduced, and meanwhile, the chlorine dioxide preparation can automatically adjust the release amount of chlorine dioxide according to the concentration of pollutants.
5. Hydroxyl radical detection
The chlorine dioxide preparation of example 3 (the sample stable chlorine dioxide solution is 10% sodium chlorite, 2% 8-hydroxyquinoline and 2% hydrogen peroxide, and the modified concentration is 5% diammonium hydrogen phosphate solution) is selected for detection, the preparation date is 2019, 9, 18 days, and the preparation is carried out in a dark and sealed way.
The detection dates were respectively 2019, 9 and 23 days (without formaldehyde stimulation) and 2019, 9 and 25 days (with formaldehyde stimulation).
A20 mg sample is not treated, hydroxyl free radicals of the sample are detected by using DMPO as a free radical trapping agent under the condition of normal-temperature illumination, the test result is shown in figure 2 (the abscissa represents the magnetic field intensity, and the ordinate represents the signal intensity), a random noise signal is obtained within the range of the tested field intensity, and no hydroxyl free radical signal is detected, namely under the condition, almost no hydroxyl free radicals are generated.
20mg of sample is placed in a culture dish and placed in an instrument, formaldehyde gas is continuously introduced, the introduction amount is 120-150ppm, hydroxyl free radicals of the sample are detected when the time is 3 minutes, the test result is shown in figure 3 (the abscissa represents the magnetic field intensity, and the ordinate represents the signal intensity), absorption peak signals are detected within the range of the detected field intensity, the peak area is 1:2:2:1, and the signals are signals of the hydroxyl free radicals by combining literature analysis. That is, under this condition, hydroxyl radicals are generated on the surface of the sample.
6. Medical stone adsorbent recycling experiment
The chlorine dioxide preparation of example 3 (the sample stable chlorine dioxide solution is 10% sodium chlorite, 2% 8-hydroxyquinoline and 2% hydrogen peroxide, and the modification concentration is 5% diammonium hydrogen phosphate solution) is selected for detection, the first modification preparation date is 4 months and 10 days in 2019, the second modification preparation date is 5 months and 20 days in 2019, and the preparation is sealed in the dark after preparation.
The first detection date is 12-18 days in 5-2019, and the second detection date is 23 days in 5-2019.
An electrochemical detector is used for detecting formaldehyde and chlorine dioxide gas (formaldehyde sensor module SK-500-HCHO 10PPM, chlorine dioxide sensor module SK-600-CL21000PPM, produced by Shenzhen Dongying Engineers Limited).
All data reading time is 30 minutes, each time interval is 5 seconds, the reading number is averaged, the first and the recycling detection are carried out after being placed in a sealed manner for 10 hours, and the concentration unit is mg/m 3 。
200 g of samples were taken and divided into two groups, 100g of samples in each group were placed at 0.03m in an open state 3 In the detection box, the detection box is placed in a fume hood, and the formaldehyde concentration is kept between 0.8 and 1.2mg/m by intermittently feeding formaldehyde for 10 hours every day 3 And stopping formaldehyde feeding at night, and continuously placing the sample in the closed box.
The release of chlorine dioxide gas is accelerated under the stimulation of high-concentration formaldehyde, and a sensor shows that almost no chlorine dioxide is released in the chlorine dioxide preparation in the afternoon (5 and 18 months in 2019) of the seventh day, and the stable chlorine dioxide in the chlorine dioxide preparation is considered to be completely consumed, and only the medical stone adsorbent is remained.
The test was carried out after re-impregnation of the stabilized chlorine dioxide solution according to example 3, step 2.
The secondary detection results are shown in Table 6.
TABLE 6 medical stone adsorbent recycling test results
As can be seen from table 6, the recycling effect of the remaining maifanite adsorbent after the chlorine dioxide of the chlorine dioxide preparation is completely desorbed and consumed is good, the release attenuation of the two groups of samples is within 15%, the attenuation can be compensated by increasing the concentration of the adsorption solution, and the subsequent tests prove that the attenuation is compensated.
7. Detection of Sterilization and Formaldehyde removal Effect
The chlorine dioxide preparation of example 3 (the sample stable chlorine dioxide solution is 10% sodium chlorite, 2% 8-hydroxyquinoline and 2% hydrogen peroxide, and the modified concentration is 5% diammonium hydrogen phosphate solution) is selected for detection, the preparation date is 2019, 04 and 10 days, and the preparation is carried out in a dark and sealed manner.
The detection dates were 2019, 4 and 17 days-4 and 30 days (microorganisms), and the detection date was 2019, 5 and 8 days (formaldehyde).
30 g of killed microorganism detection sample, and the size of test chamber test box is 0.02m 3 The test time was 18 hours, and the analysis results are shown in Table 7.
20 g of sample for formaldehyde removal detection, and the size of the test chamber is 1.5m 3 The test time was 24 hours, and the analysis results are shown in Table 8.
TABLE 7 kill of microorganisms test
TABLE 8 Formaldehyde removal test
As can be seen from tables 7 and 8, the chlorine dioxide preparation of the present invention has excellent sterilizing and formaldehyde removing effects, and can be used in the field of sterilization, food preservation, or air purification.
Comparative test
The chlorine dioxide preparation of example 3 (the sample stable chlorine dioxide solution is 10% sodium chlorite, 2% 8-hydroxyquinoline and 2% hydrogen peroxide, and the modified concentration is 5% diammonium hydrogen phosphate solution) is selected for detection, the preparation date is 2019, 4 months and 10 days, and the preparation is carried out in a dark and sealed manner.
A500-air-volume air purification device is selected, the formaldehyde removal rate is detected by comparing with the famous brand Bruyuer, and the analysis result is shown in Table 8.
TABLE 8 comparative test for formaldehyde removal
| Brand | Test chamber (m) 3 ) | Time (min) | Formaldehyde removal rate (%) |
| Chlorine dioxide preparation model machine | 30 | 42 | 96.3 |
| Bruyaer | 30 | 60 | 92.6 |
As can be seen from the data in table 8, the chlorine dioxide preparation of the present invention has better formaldehyde removal effect than the existing air cleaning apparatus.
The embodiment of the invention shows that after the medical stone adsorbent prepared by the invention adsorbs stable chlorine dioxide solution, the obtained chlorine dioxide preparation can slowly release high-purity chlorine dioxide gas and has the advantages of long-term stability, no toxicity, no odor, convenience in storage and transportation, no need of activation in use, safety and convenience, and can be applied to the field of disinfection, food preservation and preservation or air purification.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. The preparation method of the medical stone adsorbent is characterized by comprising the following steps:
mixing diammonium phosphate solution and medical stone, and carrying out modification reaction to obtain modified medical stone; the mass concentration of the diammonium hydrogen phosphate solution is 5-10%; the dosage ratio of the medical stone to the diammonium phosphate solution is 100g (100-300) mL; the time of the modification reaction is 15-90 min, and the modification reaction is carried out under the stirring condition;
roasting the modified medical stone to obtain a medical stone adsorbent; the roasting temperature is 70-120 ℃, and the roasting time is 60-120 min; and after the modification reaction, washing and drying the solid obtained by the modification reaction.
2. The medical stone adsorbent prepared by the preparation method of claim 1.
3. The preparation method of the chlorine dioxide preparation is characterized by comprising the following steps:
the chlorine dioxide preparation is obtained by immersing the medical stone adsorbent of claim 2 in a stable chlorine dioxide solution and drying.
4. The chlorine dioxide preparation prepared by the preparation method of claim 3, which comprises the medical stone adsorbent of claim 2 and stable chlorine dioxide located in the pores and/or surfaces of the medical stone adsorbent.
5. Use of the chlorine dioxide preparation according to claim 4 in the field of disinfection, food preservation and preservation or air purification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911171740.0A CN112495341B (en) | 2019-11-26 | 2019-11-26 | Medical stone adsorbent and preparation method thereof, chlorine dioxide preparation and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911171740.0A CN112495341B (en) | 2019-11-26 | 2019-11-26 | Medical stone adsorbent and preparation method thereof, chlorine dioxide preparation and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112495341A CN112495341A (en) | 2021-03-16 |
| CN112495341B true CN112495341B (en) | 2022-09-16 |
Family
ID=74924017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911171740.0A Active CN112495341B (en) | 2019-11-26 | 2019-11-26 | Medical stone adsorbent and preparation method thereof, chlorine dioxide preparation and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112495341B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115738996A (en) * | 2022-11-16 | 2023-03-07 | 贵州电网有限责任公司 | Be applied to SF 6 Method for preparing equipment adsorbent and product thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0543263A2 (en) * | 1991-11-16 | 1993-05-26 | Dr. Karl Thomae GmbH | Benziimidazoles, pharmaceuticals containing them and process for their preparation |
| JP2016124765A (en) * | 2015-01-06 | 2016-07-11 | サンマテリアル株式会社 | Chlorine dioxide agent, chlorine dioxide agent enclosed product, and chlorine dioxide agent kit |
| CN106106532A (en) * | 2016-06-27 | 2016-11-16 | 郭迎庆 | A kind of method utilizing Maifanitum to prepare fruit and vegerable slow-release bactericide |
| CN108464302A (en) * | 2018-04-28 | 2018-08-31 | 张志� | A kind of slow-release chlorine dioxide of solid carrier Zeolite support and preparation method thereof |
| CN110292050A (en) * | 2019-04-30 | 2019-10-01 | 广州超威生物科技有限公司 | It is a kind of to adjust the method and chlorine dioxide slow-release gel that chlorine dioxide steadily discharges |
-
2019
- 2019-11-26 CN CN201911171740.0A patent/CN112495341B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0543263A2 (en) * | 1991-11-16 | 1993-05-26 | Dr. Karl Thomae GmbH | Benziimidazoles, pharmaceuticals containing them and process for their preparation |
| JP2016124765A (en) * | 2015-01-06 | 2016-07-11 | サンマテリアル株式会社 | Chlorine dioxide agent, chlorine dioxide agent enclosed product, and chlorine dioxide agent kit |
| CN106106532A (en) * | 2016-06-27 | 2016-11-16 | 郭迎庆 | A kind of method utilizing Maifanitum to prepare fruit and vegerable slow-release bactericide |
| CN108464302A (en) * | 2018-04-28 | 2018-08-31 | 张志� | A kind of slow-release chlorine dioxide of solid carrier Zeolite support and preparation method thereof |
| CN110292050A (en) * | 2019-04-30 | 2019-10-01 | 广州超威生物科技有限公司 | It is a kind of to adjust the method and chlorine dioxide slow-release gel that chlorine dioxide steadily discharges |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112495341A (en) | 2021-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106512941A (en) | Composite nanometer titanium dioxide and active carbon adsorbent | |
| CN111713490B (en) | Chlorine dioxide disinfection gel and preparation method thereof | |
| CN102153162B (en) | Application of KOH activated active carbon in removing antibiotics in water body through adsorption | |
| CN104209000A (en) | Method for treating indoor air pollution | |
| US20160213003A1 (en) | Application of polyoxometalate in preparation of disinfectant for sterilizing and removing formaldehyde | |
| CN108786432A (en) | A kind of biological enzyme air purifying preparation and the preparation method and application thereof | |
| CN111298178A (en) | Chlorine dioxide refrigerator bacteriostatic deodorant and preparation method thereof | |
| CN112495341B (en) | Medical stone adsorbent and preparation method thereof, chlorine dioxide preparation and preparation method and application thereof | |
| CN112205420A (en) | Negative oxygen ion disinfectant, and preparation method and application thereof | |
| CN112495338B (en) | Adsorbent and preparation method thereof, chlorine dioxide preparation and preparation method and application thereof | |
| CN104307017A (en) | Air purifying agent with good purification effect | |
| CN104225656A (en) | Indoor air purifying agent | |
| CN106344948A (en) | Composite material with sterilization and odor-removal functions as well as preparation method and use method thereof | |
| CN101143225B (en) | Air purifying agent and its preparing process | |
| CN102318644B (en) | Method for preparing material slowly releasing chlorine dioxide and application thereof | |
| CN108479346B (en) | Green odorless formaldehyde scavenger | |
| CN106890563A (en) | A kind of efficient ozone remover | |
| CN104874004A (en) | Refrigerator deodorant | |
| CN113662004A (en) | Slow-release chlorine dioxide disinfection card using zeolite as carrier | |
| CN112495163A (en) | Chlorine dioxide preparation capable of generating free radicals and preparation method and application thereof | |
| CN114011377A (en) | Air sterilizing and purifying material and preparation method thereof | |
| CN111841599A (en) | Carbon quantum dot doped carbon nitride composite nano material with photocatalytic antibacterial performance and preparation method and application thereof | |
| CN110624408A (en) | Air purifying agent and preparation method thereof | |
| CN110508128A (en) | A kind of preparation and application of solid air scavenging material | |
| CN102388919A (en) | Soil composite disinfectant and using method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |