CN102318644B - Method for preparing material slowly releasing chlorine dioxide and application thereof - Google Patents
Method for preparing material slowly releasing chlorine dioxide and application thereof Download PDFInfo
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- CN102318644B CN102318644B CN 201110153780 CN201110153780A CN102318644B CN 102318644 B CN102318644 B CN 102318644B CN 201110153780 CN201110153780 CN 201110153780 CN 201110153780 A CN201110153780 A CN 201110153780A CN 102318644 B CN102318644 B CN 102318644B
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Abstract
The invention discloses a method for preparing a material slowly releasing chlorine dioxide and application thereof. The material releasing chlorine dioxide, provided by the invention, a comprise A and a component B which are respectively packed individually, wherein the component A is a compound material obtained after adsorbed substances are loaded on an absorbing medium; the adsorbed substances are one or two components in a disinfectant; the disinfectant comprises a component a, a component b and a component c; the component a is soluble chlorate; the component b is oxalic acid or solubleoxalate; the component c is citric acid; the component B is an activating agent; and the activating agent comprises other components in the disinfectant except the adsorbed substances. The material slowly releasing chlorine dioxide, with a nano composite structure, provided by the invention, can be used for slowly releasing chlorine dioxide gas in long action, prolonging the effective service life of an antistaling agent and effectively inhibiting and killing bacteria, and has good anticorrosive, mildewproof and freshness-preserving effects on fruits and vegetables.
Description
Technical field
The present invention relates to chlorine dioxide slow-release preparation methods and application thereof.
Background technology
China is a fruits and vegetables big producing country, and the fruit and vegetable varieties of production is various, and is best in quality, and unique flavor has the market competitiveness, still, owing to lack efficient storage technique, causes fruit-vegetable quality to descend, and waste is serious.Along with the progressively raising of people's living standard, people are also strengthening gradually to the demand of fresh fruit of vegetables.Preserving fruit and vegetable utilizing from pluck, transport, be sold to edible process has become a very major issue.In fruit vegetables storing, the process of circulation, pathogenic microorganisms such as a large amount of bacteriums that grow are to influence the fruits and vegetables taste, accelerate the corrupt moldy metamorphism of fruits and vegetables, shorten the major reason in fruit vegetables storing life-span.Therefore, efficient, with low cost, the safe and harmless nontoxic preserving fruit and vegetable utilizing agent material of sterilization has boundless application prospect.
At present, the fruits and vegetables sterilization and anticorrosion method used always of people has: photocatalytic oxidation, sulfur dioxide treatment etc.But, above method or cost height and efficient is low, or can fruits and vegetables be polluted, be difficult to large-scale application.
Summary of the invention
An object of the present invention is to provide a kind of material that discharges chlorine dioxide.
The material of release chlorine dioxide provided by the present invention is made up of A and B, and described A and described B independent packaging respectively;
Described A be on the adsorbing medium load composite that obtains behind the adsorbed material; Described adsorbed material is one or both components in the disinfectant; Described disinfectant is made up of component a, components b and amount of component b; Described component a is the soluble chlorine hydrochlorate; Described components b is oxalic acid or solubility oxalate; Described amount of component b is citric acid;
Described B is activator; Described activator is all the other components except described adsorbed material in the described disinfectant.
In the material of described release chlorine dioxide, the mass ratio of described component a, described components b and described amount of component b is (1-5): (5-1): (0.1-2) or 7.4: 10: 10 or 2: 2: 1 or 9: 5: 10 or 30: 7: 6 or 2: 1: 1 or 4: 1: 1.7.
Described activator exists with the solution form, and wherein, solvent is water or ethanol;
Described adsorbing medium is silica gel, molecular sieve, active carbon, diatomite or mesoporous silicon.
The material of described release chlorine dioxide is to prepare according to following method.
Another object of the present invention provides a kind of method for preparing the material of described release chlorine dioxide.
The method of the material of the described release chlorine dioxide of preparation provided by the present invention may further comprise the steps:
Described adsorbed material is carried on the described adsorbing medium, obtains composite; With described composite and the independent packaging respectively of described activator, namely obtain discharging the material of chlorine dioxide.
Described composite is to prepare by the method that may further comprise the steps:
Described adsorbing medium be impregnated in the solution that contains described adsorbed material the composite of adsorbed material that namely obtained load after the placement; In the described solution that contains described adsorbed material, solute is described adsorbed material, and solvent is water or ethanol.
Described method also comprises filtration, collects the also step of dry described composite after placement.
The time of described placement is 10 minutes-60 minutes or 10 minutes or 60 minutes or 30 minutes or 40 minutes;
The temperature of described drying is 20 ℃-80 ℃ or 40 ℃ or 80 ℃ or 20 ℃ or 60 ℃, and the time of described drying is 24 hours-60 hours or 24 hours or 60 hours or 50 hours.
The application of the material of described release chlorine dioxide in antibacterial and/or sterilization also belongs to protection scope of the present invention.
The application of the material of described release chlorine dioxide in preserving fruit and vegetable utilizing also belongs to protection scope of the present invention.
Nano composite structure chlorine dioxide slow-release material provided by the invention can long-acting sustained-release chlorine dioxide gas, prolongs the antistaling agent Acceptable life; Restraining and sterilizing bacteria has good fruit and vegetables corrosion protection anti-mildew fresh-keeping effect efficiently.Active substance chlorine dioxide (the ClO that this material discharges
2) gas, as a kind of Broadspectrum environment-protective type disinfection sanitizer, sterilizing ability is strong, safety non-toxic, there is not " three cause " effect (carcinogenic, teratogenesis, mutagenesis), environment is not caused secondary pollution, be known as safe, nontoxic green disinfectant in the world, classified as A I level disinfectant by the United Nations's health organization (WHO).This chlorine dioxide slow-release material preparation is simple, raw material is cheap and easy to get, be fit to large-scale production, is the very potential fruit and vegetable preserving antistaling agent of a class.
Embodiment
Employed experimental technique is conventional method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
The preparation method of embodiment 1, chlorine dioxide slow-release agent material and application thereof
Method I
One, preparation chlorine dioxide slow-release material
At first dispose the 500mL mass percent concentration and be 20% sodium chlorate aqueous solution, then with the 1Kg active carbon (available from Chemical Reagent Co., Ltd., Sinopharm Group, catalog number is 10006792) be immersed among this sodium chlorate aqueous solution, place after 10 minutes, filter and collect active carbon, in 40 ℃ of dryings 24 hours, naturally cooling, can be with the sodium chlorate uniform load on the inwall of active carbon duct, formed the sodium chlorate-absorbent charcoal composite material of load sodium chlorate, the load capacity of sodium chlorate is 7.4% (mass percent) in the composite.
Oxalic acid and citric acid is soluble in water, be mixed with the mixed aqueous solution that contains oxalic acid and citric acid, the mass percent concentration of its mesoxalic acid is 10%, the mass percent concentration of citric acid is 10%, namely obtains oxalic acid-citric acid activator solution.
Two, the restraining and sterilizing bacteria of chlorine dioxide slow-release agent material experiment
Get the closed container of two 4L, place the above-mentioned chlorine dioxide slow-release agent material for preparing in a closed container therein, as the medicament group, concrete grammar is: place 1g sodium chlorate-active carbon sandwich (containing sodium chlorate 0.074g) in closed container, oxalic acid-citric acid the activator solution that adds 1ml simultaneously (contains oxalic acid 0.1g, citric acid 0.1g), the mass ratio of sodium chlorate, oxalic acid and citric acid is 7.4: 10: 10.
Another closed container is not then placed the above-mentioned chlorine dioxide slow-release agent material for preparing, in contrast group.
Contain identical colony diameter Escherichia coli (E.coli Competent Cells DH5 α with two parts again, available from precious biotechnology Co., Ltd, Takara code:D9057) agar medium is put into above-mentioned two closed containers respectively, then with two closed containers 37 ℃ of temperature, placed 15 days under the condition of relative moisture 50%, carry out bacteriostatic experiment, observe the situation of change of colony diameter, and calculate inhibiting rate.Three repetitions are established in experiment, results averaged, and each repeats to establish 3 processing.
The computing formula of inhibiting rate is as follows:
The result: after adding the chlorine dioxide slow-release agent material, inhibiting rate maintains 90%-100% (the 1st day to the 13rd day inhibiting rate be 100%, the 14 day be 97%, the 15 day be 90%) within 15 days.
Above experimental result illustrates that this chlorine dioxide slow-release agent material has good restraining and kills the effect of removing the Escherichia coli in the environment.
Three, the chlorine dioxide slow-release agent material is used for antiseptic preservation of fruits and vegetables
Get the apple (1000g) that two parts of quality equate, it is placed two volumes separately is the closed container of 4L, place the above-mentioned chlorine dioxide slow-release agent material for preparing in a closed container therein, as processed group, concrete grammar is: place 1g sodium chlorate-active carbon sandwich (containing sodium chlorate 0.074g) in closed container, oxalic acid-citric acid the activator solution (containing oxalic acid 0.1g, citric acid 0.1g) that adds 1ml simultaneously; The mass ratio of sodium chlorate, oxalic acid and citric acid is 7.4: 10: 10.Another closed container is not then placed the above-mentioned chlorine dioxide slow-release agent material for preparing, in contrast group.With the airtight preservation separately of two closed containers, 37 ℃ of temperature, placed 30 days under relative moisture 50% condition then, in put procedure, the situation that rots of observed and recorded processed group and control group fruits and vegetables.
Three repetitions are established in experiment, and each establishes 3 processing in repeating.
The result: the apple in the processed group closed container is placed continuously and was not changed in 30 days, and the surface is still glossy, not crumple, and not deliquescing, without putrefaction is mouldy.And the deliquescing after having placed 10 days of the apple in the control group closed container, mouldy rotten.
The adding of above experimental result explanation chlorine dioxide slow-release agent material can prevent rotting of apple effectively, prolongs the freshness date of apple.
Method II
One, preparation chlorine dioxide slow-release agent material
At first dispose 1000mL sodium chlorate-citric acid mixed aqueous solution, wherein, the mass percent concentration of sodium chlorate be 30% and the mass percent concentration of citric acid be 10%; Then with the mesoporous silicon of 500g (available from Chemical Reagent Co., Ltd., Sinopharm Group, catalog number is 30212492) be immersed in this sodium chlorate-citric acid mixed aqueous solution, place after 1 hour, filter and collect mesoporous silicon, in 80 ℃ of dryings 60 hours, naturally cooling, sodium chlorate and citric acid can be carried on the duct inwall of mesoporous silicon uniformly, formed the sodium chlorate-citric acid-mesoporous silicon composite of load sodium chlorate and citric acid, the load capacity of sodium chlorate is 20% (mass percent) in the composite, the load capacity of citric acid is 10% (mass percent).
Oxalic acid is soluble in water, be mixed with oxalic acid aqueous solution, the mass percent concentration of its mesoxalic acid is 20%, namely obtains the oxalic acid activator solution.
Two, the restraining and sterilizing bacteria of chlorine dioxide slow-release agent material experiment
Get the closed container of two 4L, place the above-mentioned chlorine dioxide slow-release agent material for preparing in a closed container therein, as the medicament group, concrete grammar is: place 2g sodium chlorate-citric acid-mesoporous silicon composite structure material (containing sodium chlorate 0.4g and citric acid 0.2g) in closed container, add the oxalic acid activator solution (containing oxalic acid 0.4g) of 2ml simultaneously, the mass ratio of sodium chlorate, oxalic acid and citric acid is 2: 2: 1.
Another closed container is not then placed the above-mentioned chlorine dioxide slow-release agent material for preparing, in contrast group.
Again with two parts of aspergillus niger (Aspergillus niger) (CGMCC3.6479 that contain identical colony diameter, available from Chinese common micro-organisms culture presevation administrative center) suspension put into two closed containers, then with two closed containers 37 ℃ of temperature, placed 10 days under relative moisture 50% condition, carry out bacteriostatic experiment, observe the situation of change of colony diameter, and calculate inhibiting rate.
Three repetitions are established in experiment, results averaged, and each repeats to establish 3 processing.
The computing formula of inhibiting rate is identical with method I.
The result: after adding the chlorine dioxide slow-release agent material, inhibiting rate maintains 90%-100% (the 1st day to the 8th day inhibiting rate be 100%, the 9 day be 95%, the 10 day be 90%) within 10 days.
Above experimental result illustrates that this sodium chlorate-absorbent charcoal composite material has good restraining and kills the effect of removing the aspergillus niger in the environment.
Three, the chlorine dioxide slow-release agent material is used for antiseptic preservation of fruits and vegetables
Get the banana (1000g) that two parts of quality equate, it is placed two volumes separately is the closed container of 4L, place the above-mentioned chlorine dioxide slow-release agent material for preparing in a closed container therein, as processed group, concrete grammar is: place 5g sodium chlorate-citric acid-mesoporous silicon composite structure material (containing sodium chlorate 1g and citric acid 0.5g) in closed container, add the oxalic acid activator solution (containing oxalic acid 1g) of 5ml simultaneously; The mass ratio of sodium chlorate, oxalic acid and citric acid is 2: 2: 1.Another closed container is not then placed the above-mentioned chlorine dioxide slow-release agent material for preparing, in contrast group.With the airtight preservation separately of two closed containers, 37 ℃ of temperature, placed 15 days under relative moisture 50% condition then, in put procedure, the situation that rots of observed and recorded processed group and control group fruits and vegetables.
Three repetitions are established in experiment, and each establishes 3 processing in repeating.
The result: the banana in the processed group closed container is placed continuously and was not changed in 15 days, and the surface is still glossy, not blackening, not deliquescing.And the deliquescing after having placed 5 days of the banana in the control group closed container, blackening, mouldy rotting.
The adding of above experimental result explanation chlorine dioxide slow-release agent material can suppress the rotting of banana, mouldy, the freshness date that prolongs banana effectively.
Method III
One, preparation chlorine dioxide slow-release agent material
At first dispose 800mL sodium chlorate-oxalic acid mixed aqueous solution, wherein, the mass percent concentration of sodium chlorate be 40% and the mass percent concentration of oxalic acid be 20%; Then 1Kg diatomite (is rolled into a ball chemical reagent Co., Ltd available from traditional Chinese medicines, catalog number is 20020693) be immersed in this sodium chlorate-oxalic acid mixed aqueous solution, place after 30 minutes, filter and collect diatomite, in 20 ℃ of dryings 50 hours, naturally cooling can be carried on sodium chlorate and oxalic acid on the diatomite uniformly, has formed the sodium chlorate-oxalic acid-diatomite composite material of load sodium chlorate and oxalic acid.The load capacity of sodium chlorate is that the load capacity of 18% (mass percent), oxalic acid is 10% (mass percent) in the composite.
Citric acid is soluble in water, be mixed with aqueous citric acid solution, wherein, the mass percent concentration of citric acid is 20%, namely obtains the citric acid activator solution.
Two, the restraining and sterilizing bacteria of chlorine dioxide slow-release agent material experiment
Get the closed container of two 4L, place the above-mentioned chlorine dioxide slow-release agent material for preparing in a closed container therein, as the medicament group, concrete grammar is: place 3g sodium chlorate-oxalic acid-compound structural material of diatomite (containing sodium chlorate 0.54g and oxalic acid 0.3g) in closed container, add the citric acid activator solution (containing citric acid 0.6g) of 3ml simultaneously, the mass ratio of sodium chlorate, oxalic acid and citric acid is 9: 5: 10.
Another closed container is not then placed the above-mentioned chlorine dioxide slow-release agent material for preparing, in contrast group.
Contain the colibacillary agar medium of identical colony diameter with two parts again and put into above-mentioned two closed containers respectively, then with two closed containers 37 ℃ of temperature, placed under relative moisture 50% condition 20 days, carry out bacteriostatic experiment, observe the situation of change of colony diameter, and calculate inhibiting rate.
Three repetitions are established in experiment, results averaged, and each repeats to establish 3 processing.
The computing formula of inhibiting rate is identical with method I.
The result: after adding the chlorine dioxide slow-release material, inhibiting rate maintains 90%-100% (the 1st day to the 17th day inhibiting rate be 100%, the 18 day and be 99%, the 19 day be 94%, the 20 day be 90%) within 20 days.
Above experimental result illustrates that this chlorine dioxide slow-release material has fine inhibition and kills the effect of removing the Escherichia coli in the environment.
Three, the chlorine dioxide slow-release material is used for antiseptic preservation of fruits and vegetables
Get the strawberry (500g) that two parts of quality equate, it is placed two volumes separately is the closed container of 4L, place the above-mentioned chlorine dioxide slow-release material for preparing in a closed container therein, as processed group, concrete grammar is: place 5g sodium chlorate-oxalic acid-compound structural material of diatomite (containing sodium chlorate 0.9g and oxalic acid 0.5g) in closed container, add the citric acid activator solution (containing citric acid 1g) of 5ml simultaneously; The mass ratio of sodium chlorate, oxalic acid and citric acid is 9: 5: 10.Another closed container is not then placed the above-mentioned chlorine dioxide slow-release material for preparing, in contrast group.With the airtight preservation separately of two closed containers, 37 ℃ of temperature, placed 12 days under relative moisture 50% condition then, in put procedure, the situation that rots of observed and recorded processed group and control group fruits and vegetables.
Three repetitions are established in experiment, and each establishes 3 processing in repeating.
The result: the strawberry in the processed group closed container is placed continuously and was not changed in 12 days, and the surface is still glossy, not deliquescing, without putrefaction.And the deliquescing after having placed 4 days of the strawberry in the control group closed container, rotten.
The adding of above experimental result explanation chlorine dioxide slow-release material can suppress the rotten mouldy of strawberry effectively, prolongs the freshness date of strawberry.
Method IV
One, preparation chlorine dioxide slow-release material
At first dispose 500mL citric acid-oxalic acid mixed aqueous solution, wherein, the mass percent concentration of citric acid be 10% and the mass percent concentration of oxalic acid be 20%; Then with 500g silica gel (available from Chemical Reagent Co., Ltd., Sinopharm Group, catalog number is 20034393) be immersed in this citric acid-oxalic acid mixed aqueous solution, place after 40 minutes, filter and collect silica gel, in 80 ℃ of dryings 24 hours, naturally cooling can be carried on citric acid and oxalic acid on the silica gel uniformly, has formed the citric acid-oxalic acid-material silica gel composite of load citric acid and oxalic acid.The load capacity of citric acid is that the load capacity of 6% (mass percent), oxalic acid is 7% (mass percent) in the composite.
Sodium chlorate is soluble in water, be mixed with the sodium chlorate aqueous solution, wherein, the mass percent concentration of sodium chlorate is 30%, namely obtains the sodium chlorate activator solution.
Two, the restraining and sterilizing bacteria of chlorine dioxide slow-release material experiment
Get the closed container of two 4L, place the above-mentioned chlorine dioxide slow-release material for preparing in a closed container therein, as the medicament group, concrete grammar is: place 4g citric acid-oxalic acid-silica gel sandwich (containing citric acid 0.24g and oxalic acid 0.28g) in closed container, add the sodium chlorate activator solution (containing sodium chlorate 1.2g) of 4ml simultaneously, the mass ratio of sodium chlorate, oxalic acid and citric acid is 30: 7: 6.
Another closed container is not then placed the above-mentioned chlorine dioxide slow-release material for preparing, in contrast group.
Contain the colibacillary agar medium of identical colony diameter with two parts again and put into above-mentioned two closed containers respectively, then with two closed containers 37 ℃ of temperature, placed under relative moisture 50% condition 18 days, carry out bacteriostatic experiment, observe the situation of change of colony diameter, and calculate inhibiting rate.
Three repetitions are established in experiment, results averaged, and each repeats to establish 3 processing.
The computing formula of inhibiting rate is identical with method I.
The result: after adding the chlorine dioxide slow-release material, inhibiting rate maintains 90%-100% (the 1st day to the 16th day inhibiting rate be 100%, the 17 day be 95%, the 18 day be 90%) within 18 days.
Above experimental result illustrates that this chlorine dioxide slow-release material has fine inhibition and kills the effect of removing the Escherichia coli in the environment.
Three, the chlorine dioxide slow-release material is used for antiseptic preservation of fruits and vegetables
Get the pears (1000g) that two parts of quality equate, it is placed two volumes separately is the closed container of 4L, place the above-mentioned chlorine dioxide slow-release material for preparing in a closed container therein, as processed group, concrete grammar is: place 3g citric acid-oxalic acid-silica gel sandwich (containing citric acid 0.18g and oxalic acid 0.21g) in closed container, add the sodium chlorate activator solution (containing sodium chlorate 0.9g) of 3ml simultaneously; The mass ratio of sodium chlorate, oxalic acid and citric acid is 30: 7: 6.Another closed container is not then placed the above-mentioned chlorine dioxide slow-release material for preparing, in contrast group.With the airtight preservation separately of two closed containers, 37 ℃ of temperature, placed 30 days under relative moisture 50% condition then, in put procedure, the situation that rots of observed and recorded processed group and control group fruits and vegetables.
Three repetitions are established in experiment, and each establishes 3 processing in repeating.
The result: the pears in the processed group closed container are placed continuously and were not changed not deliquescing, without putrefaction in 30 days.And the deliquescing after having placed 10 days of the pears in the control group closed container, rotten mouldy.
The adding of above experimental result explanation chlorine dioxide slow-release material can prevent the rotten moldy metamorphism of pears, the freshness date that prolongs pears effectively.
Method V
One, preparation chlorine dioxide slow-release material
At first dispose the 500mL oxalic acid aqueous solution, the mass percent concentration of its mesoxalic acid is 40%; Then the 500g molecular sieve (please be illustrated the model of molecular sieve, available from Chemical Reagent Co., Ltd., Sinopharm Group, catalog number is 20027892) be immersed in this oxalic acid aqueous solution, place after 30 minutes, filter and also to collect molecular sieve, in 60 ℃ of dryings 60 hours, cool off naturally, can with the oxalic acid uniform load on molecular sieve, form the oxalic acid-molecular sieves compound material of load oxalic acid.The load capacity of composite mesoxalic acid is 20% (mass percent).
Sodium chlorate and citric acid is soluble in water, be mixed with sodium chlorate-citric acid mixed aqueous solution, wherein, the mass percent concentration of sodium chlorate be 40% and the mass percent concentration of citric acid be 20%, namely obtain sodium chlorate-citric acid activator solution.
Two, the restraining and sterilizing bacteria of chlorine dioxide slow-release material experiment
Get the closed container of two 4L, place the above-mentioned chlorine dioxide slow-release material for preparing in a closed container therein, as the medicament group, concrete grammar is: place 2g oxalic acid-molecular sieves compound material (containing oxalic acid 0.4g) in closed container, add sodium chlorate-citric acid activator solution (containing sodium chlorate 0.8g and citric acid 0.4g) of 2ml simultaneously, the mass ratio of sodium chlorate, oxalic acid and citric acid is 2: 1: 1.
Another closed container is not then placed the above-mentioned chlorine dioxide slow-release material for preparing, in contrast group.
Contain the colibacillary agar medium of identical colony diameter with two parts again and put into above-mentioned two closed containers respectively, then with two closed containers 37 ℃ of temperature, placed under relative moisture 50% condition 20 days, carry out bacteriostatic experiment, observe the situation of change of colony diameter, and calculate inhibiting rate.
Three repetitions are established in experiment, results averaged, and each repeats to establish 3 processing.
The computing formula of inhibiting rate is identical with method I.
The result: after adding the chlorine dioxide slow-release material, inhibiting rate maintains 90%-100% (it is 90% that the 1st day to the 19th day inhibiting rate is 100%, the 20 day) within 20 days.
Above experimental result illustrates that above-mentioned nano composite structure material has fine inhibition and kills the effect of removing the Escherichia coli in the environment.
Three, the chlorine dioxide slow-release material is used for antiseptic preservation of fruits and vegetables
Get the granulated sugar tangerine (600g) that two parts of quality equate, it is placed two volumes separately is the closed container of 4L, place the above-mentioned chlorine dioxide slow-release material for preparing in a closed container therein, as processed group, concrete grammar is: place 2g oxalic acid-molecular sieves compound material (containing oxalic acid 0.4g) in closed container, add sodium chlorate-citric acid activator solution (containing sodium chlorate 0.8g and citric acid 0.4g) of 2ml simultaneously; The mass ratio of sodium chlorate, oxalic acid and citric acid is 2: 1: 1.Another closed container is not then placed the above-mentioned chlorine dioxide slow-release material for preparing, in contrast group.With the airtight preservation separately of two closed containers, 37 ℃ of temperature, placed 15 days under relative moisture 50% condition then, in put procedure, the situation that rots of observed and recorded processed group and control group fruits and vegetables.
Three repetitions are established in experiment, and each establishes 3 processing in repeating.
The result: the granulated sugar tangerine in the processed group closed container is placed continuously and was not changed in 15 days, and the surface is still glossy, not deliquescing, without putrefaction.And the deliquescing after having placed 5 days of the granulated sugar tangerine in the control group closed container, rotten mouldy.
The adding of above experimental result explanation chlorine dioxide slow-release material can suppress the rotten mouldy of granulated sugar tangerine effectively, prolongs the freshness date of granulated sugar tangerine.
Method VI
One, preparation chlorine dioxide slow-release material
At first dispose the 1000mL aqueous citric acid solution, wherein the mass percent concentration of citric acid is 30%; Then the 500g active carbon is immersed in this aqueous citric acid solution, places after 30 minutes, filter and collect active carbon, in 60 ℃ of dryings 24 hours, naturally cooling can form the citric acid-absorbent charcoal composite material of load citric acid with the citric acid uniform load on active carbon.The load capacity of citric acid is 17% (mass percent) in the composite.
Sodium chlorate and oxalic acid is soluble in water, be mixed with sodium chlorate-oxalic acid mixed aqueous solution, wherein, the mass percent concentration of sodium chlorate be 40% and the mass percent concentration of oxalic acid be 10%, namely obtain sodium chlorate-oxalic acid activator solution.
Two, the restraining and sterilizing bacteria of chlorine dioxide slow-release material experiment
Get the closed container of two 4L, place the above-mentioned chlorine dioxide slow-release material for preparing in a closed container therein, as the medicament group, concrete grammar is: place 5g citric acid-absorbent charcoal composite material (containing citric acid 0.85g) in closed container, add sodium chlorate-oxalic acid activator solution (containing sodium chlorate 2g and oxalic acid 0.5g) of 5ml simultaneously, the mass ratio of sodium chlorate, oxalic acid and citric acid is 4: 1: 1.7.
Another closed container is not then placed the above-mentioned chlorine dioxide slow-release material for preparing, in contrast group.
Again two parts of suspensions that contain identical colony diameter aspergillus niger are put into two closed containers, then with two closed containers 37 ℃ of temperature, placed under relative moisture 50% condition 25 days, carry out bacteriostatic experiment, observe the situation of change of colony diameter, and calculate inhibiting rate.
Three repetitions are established in experiment, results averaged, and each repeats to establish 3 processing.
The computing formula of inhibiting rate is identical with method I.
The result: after adding the chlorine dioxide slow-release material, inhibiting rate maintains 90%-100% (the 1st day to the 23rd day inhibiting rate be 100%, the 24 day be 94%, the 25 day be 90%) within 25 days.
Above experimental result illustrates that above-mentioned nano composite structure material has fine inhibition and kills the effect of removing the aspergillus niger in the environment.
Three, the chlorine dioxide slow-release material is used for antiseptic preservation of fruits and vegetables
Get the naked oats dish (1000g) that two parts of quality equate, it is placed two volumes separately is the closed container of 8L, place the above-mentioned chlorine dioxide slow-release material for preparing in a closed container therein, as processed group, concrete grammar is: place 10g citric acid-absorbent charcoal composite material (containing citric acid 1.7g) in closed container, add sodium chlorate-oxalic acid activator solution (containing sodium chlorate 4g and oxalic acid 1g) of 10ml simultaneously; The mass ratio of sodium chlorate, oxalic acid and citric acid is 4: 1: 1.7.Another closed container is not then placed the above-mentioned chlorine dioxide slow-release material for preparing, in contrast group.With the airtight preservation separately of two closed containers, 37 ℃ of temperature, placed 14 days under relative moisture 50% condition then, in put procedure, the situation that rots of observed and recorded processed group and control group fruits and vegetables.
Three repetitions are established in experiment, and each establishes 3 processing in repeating.
The result: the naked oats dish in the processed group closed container is placed continuously and was not changed in 14 days, and the surface is still glossy, not mouldy rotting.And the naked oats dish in the control group closed container is rotten mouldy after having placed 4 days.
It is mouldy that the adding of above experimental result explanation chlorine dioxide slow-release material can suppress rotting of naked oats dish effectively, the freshness date that prolongs the naked oats dish.
Claims (8)
1. a material that discharges chlorine dioxide is made up of A and B, and described A and described B independent packaging respectively;
Described A be on the adsorbing medium load composite that obtains behind the adsorbed material; Described adsorbed material is one or both components in the disinfectant; Described disinfectant is made up of component a, components b and amount of component b; Described component a is the soluble chlorine hydrochlorate; Described components b is oxalic acid or solubility oxalate; Described amount of component b is citric acid;
Described B is activator; Described activator is all the other components except described adsorbed material in the described disinfectant
In the material of described release chlorine dioxide, the mass ratio of described component a, described components b and described amount of component b is (1-5): (5-1): (0.1-2).
2. the material of release chlorine dioxide according to claim 1, it is characterized in that: described adsorbing medium is silica gel, molecular sieve, active carbon, diatomite or mesoporous silicon.
3. method for preparing the material of claim 1 or 2 described release chlorine dioxide may further comprise the steps:
Claim 1 or 2 described adsorbed materials are carried on claim 1 or the 2 described adsorbing mediums, obtain composite; With described composite and claim 1 or 2 described activator independent packagings respectively, namely obtain discharging the material of chlorine dioxide.
4. method according to claim 3 is characterized in that:
Described composite is to prepare by the method that may further comprise the steps:
Described adsorbing medium be impregnated in the solution that contains described adsorbed material the composite of adsorbed material that namely obtained load after the placement; In the described solution that contains described adsorbed material, solute is described adsorbed material, and solvent is water or ethanol.
5. method according to claim 4 is characterized in that:
Described method also comprises filtration, collects the also step of dry described composite after placement.
6. method according to claim 5 is characterized in that:
The time of described placement is 10 minutes-60 minutes;
The temperature of described drying is 20 ℃-80 ℃; The time of described drying is 24 hours-60 hours.
7. the application of material in antibacterial and/or sterilization of claim 1 or 2 described release chlorine dioxide.
8. the application of material in preserving fruit and vegetable utilizing of claim 1 or 2 described release chlorine dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110153780 CN102318644B (en) | 2011-06-09 | 2011-06-09 | Method for preparing material slowly releasing chlorine dioxide and application thereof |
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| CN107136206A (en) * | 2017-03-22 | 2017-09-08 | 京博农化科技股份有限公司 | A kind of anti-corrosive fresh-keeping composition containing chlorine dioxide and preparation method thereof |
| CN108786410A (en) * | 2018-06-12 | 2018-11-13 | 御林军生物科技（深圳）有限公司 | A kind of preparation method and applications of slow released ClO 2 |
| CN110250199B (en) * | 2019-05-20 | 2021-07-02 | 天津大学 | Chlorine dioxide disinfectant containing supported solid acid and preparation method and application thereof |
| CN112136827A (en) * | 2020-09-29 | 2020-12-29 | 黄俊雄 | Slow-release chlorine dioxide solid gel and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1505934A (en) * | 2002-12-08 | 2004-06-23 | 新疆大学 | Grape preservative of chlorine dioxide |
| CN101861890A (en) * | 2009-04-20 | 2010-10-20 | 新疆大学 | Slow-release solid chlorine dioxide preservative |
| CN101946798A (en) * | 2010-10-11 | 2011-01-19 | 河北科技大学 | Binary natural chlorine dioxide disinfectant and preparation method thereof |
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| CN1505934A (en) * | 2002-12-08 | 2004-06-23 | 新疆大学 | Grape preservative of chlorine dioxide |
| CN101861890A (en) * | 2009-04-20 | 2010-10-20 | 新疆大学 | Slow-release solid chlorine dioxide preservative |
| CN101946798A (en) * | 2010-10-11 | 2011-01-19 | 河北科技大学 | Binary natural chlorine dioxide disinfectant and preparation method thereof |
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| 新型消毒剂-ClO2的制备方法及应用现状;郑建华,韩舞鹰;《水处理技术》;20010630;第27卷(第3期);第133-137页 * |
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| 郑建华,韩舞鹰.新型消毒剂-ClO2的制备方法及应用现状.《水处理技术》.2001,第27卷(第3期),第133-137页. |
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