CN114318371B - Weakly alkaline sodium hypochlorite aqueous solution and preparation method and application thereof - Google Patents
Weakly alkaline sodium hypochlorite aqueous solution and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a weak alkaline sodium hypochlorite aqueous solution, a preparation method and application thereof, and belongs to the technical field of electrolytic water treatment. The invention prepares weak alkaline sodium hypochlorite aqueous solution by adopting a corresponding diaphragm-free electrolysis device to electrolyze and mix dilute brine, and the solution contains low-concentration effective chlorine, has a pH value close to neutral and has relatively low irritation and corrosiveness. Experiments prove that the weak alkaline sodium hypochlorite aqueous solution prepared by the method has strong sterilization capability, and has the advantages of rapidness, high efficiency, safety and the like. In actual production, the method can be used for preventing and controlling agricultural diseases, treating seeds, storing and preserving fresh and the like, and can also be used for killing harmful bacteria and fungi in livestock and poultry breeding environments; meanwhile, the cleaning agent has good removal effect on peculiar smell, odor and the like generated in daily life, and can be used for daily environmental purification treatment, so that the cleaning agent has good practical application value.
Description
Technical Field
The invention belongs to the technical field of electrolytic water treatment, and particularly relates to a weak alkaline sodium hypochlorite aqueous solution, a preparation method and application thereof.
Background
The information disclosed in the background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an admission or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
The electrolyzed water is also called electrolyzed ion water or electrolyzed oxidizing water (EPW), and can be made into strong acid electrolyzed water, strong alkaline electrolyzed water, weak acid electrolyzed water or weak alkaline electrolyzed water according to the difference of an electrolysis device, electrolysis conditions and the like. At present, the water electrolysis technology is widely applied to the agriculture field and is widely accepted at home and abroad. In particular, the acidic electrolyzed water is used as a common novel bactericide, has been confirmed to have a good disinfection effect on a plurality of pathogenic bacteria and fungi, has been widely reported in the food industry of agriculture, fruits and vegetables and the like, has a wide application prospect, but has slow popularization and application progress, and has the main problems of great corrosiveness on metals and unstable available chlorine. The strong alkaline electrolyzed water has a higher pH value, can be used for washing and decontaminating, and can also remove pesticide residues on plant leaves, and the alkaline electrolyzed water (pH 13.5) is known to have a sterilization effect on agricultural pathogens, but can cause harm to agricultural products and soil and generate safety problems such as chlorine gas when in use. The weakly alkaline electrolyzed water has higher safety because the weakly neutral pH value and the lower effective chlorine concentration do not cause the problems. So far, weak alkaline electrolyzed water has few researches on domestic agricultural sterilization and disinfection, and the researches on safety of weak alkaline electrolyzed water are also rarely reported. Therefore, there is a need to perfect the sterilization effect and safety research of agriculture.
Meanwhile, formaldehyde, sweat smell, smoke smell and kitchen and toilet odor and the like generated indoors also plague the daily life of people. At present, the technology of deodorization and peculiar smell removal mainly comprises the following steps: chemical absorption oxidation method, ozone oxidation method, biological filtration method, active material adsorption deodorization and peculiar smell removal method, etc. However, the use of weakly alkaline electrolyzed water for the above-mentioned off-flavor and odor has been reported to be still less, and thus it is also necessary to study it.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a weak alkaline sodium hypochlorite aqueous solution, a preparation method and application thereof. Experiments prove that the weak alkaline sodium hypochlorite aqueous solution prepared by the method has strong sterilization capability, and has the advantages of rapidness, high efficiency, safety and the like. In actual production, the method can be used for preventing and controlling agricultural diseases, treating seeds, storing and preserving fresh and the like, and can also be used for killing harmful bacteria and fungi in livestock and poultry breeding environments; meanwhile, the cleaning agent has good removal effect on peculiar smell, odor and the like generated in daily life, and can be used for daily environmental purification treatment, so that the cleaning agent has good practical application value.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a weakly alkaline aqueous sodium hypochlorite solution having an initial effective chlorine concentration of 100 to 250mg/L and an initial conductivity of 410 to 500us/cm (25 ℃).
Preferably, the aqueous solution of weakly alkaline sodium hypochlorite has a pH of less than 9, more preferably a pH of 7.5 to 8.5.
The initial effective chlorine concentration in the weak alkaline sodium hypochlorite aqueous solution is 100-200 mg/L.
In a second aspect of the present invention, there is provided a method for preparing the above-mentioned weakly basic aqueous sodium hypochlorite solution, the method comprising:
mixing water with an electrolyte, and then electrolyzing.
The water may be tap water after softening treatment.
The electrolyte may be sodium chloride.
Further, the addition amount of the electrolyte sodium chloride is controlled to be 1-5 per mill (w/v), preferably 3 per mill, and experiments prove that the weak alkaline sodium hypochlorite aqueous solution prepared by adding 3 per mill sodium chloride has good sterilization effect and excellent stability, and the decrease rate is less than 10% after the solution is placed for 3 months at the normal temperature of 37 ℃, and the solution can be effectively stored for 2 years according to the 2002 edition of disinfection technical Specification.
The electrolysis may be performed using an electrolysis device.
In a third aspect of the invention there is provided the use of the above-described weakly basic aqueous sodium hypochlorite solution in agricultural production.
Specifically, the application in agricultural production at least comprises:
a) Killing plant pathogenic bacteria;
b) Sterilizing seeds and seedlings;
c) Preventing and controlling plant diseases in the field;
d) Storing and preserving fruits and vegetables after harvesting;
e) Killing pathogenic microorganisms of livestock and poultry.
In a fourth aspect of the invention there is provided the use of a weakly basic aqueous sodium hypochlorite solution as described above in environmental purification.
In particular, the environmental cleaning includes daily deodorization and/or deodorization;
more specifically, the daily deodorizing and/or deodorizing comprises at least:
a) Removing formaldehyde;
b) Removing sweat smell;
c) Removing smoke smell;
d) Removing peculiar smell of kitchen and toilet.
The beneficial technical effects of one or more of the technical schemes are as follows:
the weak alkaline sodium hypochlorite aqueous solution prepared by the invention has strong sterilization capability, and has the advantages of rapidness, high efficiency, safety and the like. In actual production, the method can be used for preventing and controlling agricultural diseases, treating seeds, storing and preserving fresh and the like, and can also be used for killing harmful bacteria and fungi in livestock and poultry breeding environments; the invention can effectively remove formaldehyde, sweat smell, smoke smell and kitchen and toilet peculiar smell generated in daily life, and meanwhile, the safety test proves that the weak alkaline sodium hypochlorite aqueous solution is safe and effective and has no irritation, so that the weak alkaline sodium hypochlorite aqueous solution has good and wide practical application value.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a schematic view of an electrolytic device according to an embodiment of the present invention;
wherein, 1-power supply controller, 2-power supply driver, 3-solenoid valve, 4-lift pump, 5-peristaltic pump, 6-former feed bucket, 7-first electrolysis trough, 8-second electrolysis trough.
FIG. 2 is a schematic view of an electrolytic cell in an embodiment of the invention;
wherein 7-1 is a liquid inlet, and 7-2 is a first anode; 7-3 is a first carbon plate, 7-4 is a first cathode, 7-5 is a second anode, 7-6 is a second carbon plate, 7-7 is a second cathode, and 7-8 is a liquid outlet.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The invention will now be further illustrated with reference to specific examples, which are given for the purpose of illustration only and are not intended to be limiting in any way. If experimental details are not specified in the examples, it is usually the case that the conditions are conventional or recommended by the reagent company; reagents, consumables, etc. used in the examples described below are commercially available unless otherwise specified.
As described above, weakly alkaline electrolyzed water has been studied less in domestic agricultural sterilization and disinfection, and studies on safety thereof have been reported. Therefore, there is a need to perfect the sterilization effect and safety research of agriculture.
In view of the above, in one exemplary embodiment of the present invention, a weakly alkaline aqueous sodium hypochlorite solution is provided, wherein the weakly alkaline aqueous sodium hypochlorite solution has an initial effective chlorine concentration of 100 to 250mg/L and an initial conductivity of 410 to 500us/cm (25 ℃).
In yet another embodiment of the present invention, the aqueous solution of weakly basic sodium hypochlorite has a pH of less than 9, more preferably a pH of 7.5 to 8.5.
In yet another embodiment of the present invention, the initial available chlorine concentration in the weakly basic aqueous sodium hypochlorite solution is 100 to 200mg/L.
In still another embodiment of the present invention, there is provided a method for preparing the above-mentioned weakly basic aqueous sodium hypochlorite solution, the method comprising:
mixing water with an electrolyte, and then electrolyzing.
The water may be tap water after softening treatment.
The electrolyte may be sodium chloride.
In a further specific embodiment of the invention, the addition amount of the electrolyte sodium chloride is controlled to be 1-5 per mill (w/v), preferably 3 per mill, and experiments prove that the weak alkaline sodium hypochlorite aqueous solution prepared by adding 3 per mill sodium chloride has good sterilization effect and excellent stability, and the decrease rate is less than 10% after the solution is placed for 3 months at the normal temperature of 37 ℃, and can be effectively stored for 2 years according to the 2002 edition of disinfection technical Specification.
The electrolysis may be performed using an electrolysis device, which in one embodiment of the invention comprises:
the power supply controller controls a power supply driver which is respectively and electrically connected with the electromagnetic valve, the lift pump, the peristaltic pump and the electrolytic tank so as to drive the components to work;
the electrolysis device further comprises a water inlet pipeline and a feeding pipeline, wherein one end of the water inlet pipeline is provided with a water inlet, an electromagnetic valve and a lift pump are sequentially arranged on the water inlet pipeline, one end of the feeding pipeline is connected with the peristaltic pump, and the peristaltic pump inputs an electrolyte in the raw material barrel into the feeding pipeline when working; the other end of the feeding pipeline is converged with the other end of the water inlet pipeline and connected with the electrolytic tank;
it should be noted that, for convenience of mixing and transmission, the electrolyte in the raw material barrel may be a high-concentration sodium chloride solution (e.g. 20% -30% (w/v) sodium chloride), and the concentration of sodium chloride in the solution finally flowing into the electrolytic tank is 1-5%o (w/v) by controlling the dosage ratio of the high-concentration sodium chloride solution to water.
In still another specific embodiment of the present invention, when the number of the electrolytic tanks is one or more, the plurality of electrolytic tanks are connected in series through a pipeline, the electrolytic tanks are diaphragm-free electrolytic tanks, inert anodes, carbon plates and inert cathodes are alternately arranged in the diaphragm-free electrolytic tank in the order of anode-carbon plate-cathode-anode-carbon plate-cathode, and two ends of the diaphragm-free electrolytic tank are respectively communicated with the liquid inlet and the liquid outlet. Unlike conventional electrolyzer, the present invention has carbon plate between the anode and the cathode, and the carbon plate is electrically conducting plate to raise electrolysis efficiency, raise salt water converting rate, reduce temperature rise and power consumption. Meanwhile, the electrolyzed water generated in the invention is alkalescent, thereby reducing the corrosion to equipment; the weak alkaline sodium hypochlorite disinfectant fluid prepared by the invention can achieve the effect of strong acid and strong alkaline disinfectant fluid which is conventionally used, but is safer, low in corrosiveness, stable in quality and capable of achieving the quality guarantee period of more than 2 years.
In yet another embodiment of the present invention, the method for preparing the weakly basic aqueous sodium hypochlorite solution comprises: the water and the electrolyte are electrolyzed by the above-mentioned electrolyzer, the voltage of the electrolyzer is controlled to be 6-12V, and the current is controlled to be 5-10A.
In a further specific embodiment of the invention, the power supply controller is turned on, the power supply driver drives the electromagnetic valve, the lift pump, the peristaltic pump and the electrolytic tank to be turned on, tap water flowing out of the electromagnetic valve and the lift pump and high-concentration sodium chloride solution flowing out of the raw material barrel and the peristaltic pump are mixed into dilute brine (the concentration of sodium chloride is 1-5 per mill), and the dilute brine is fed into the electrolytic tank for electrolysis to prepare weak alkaline sodium hypochlorite aqueous solution.
It should be noted that the above-mentioned electrolytic device of the present invention may also be used for the production and preparation of sterile water, specifically, when the feeding pipeline and the matching equipment (such as peristaltic pump) are closed, i.e. only water is introduced into the electrolytic tank, the electrolytic tank is opened to perform electrolytic sterilization on the water, so that the sterile water can be obtained. The electrolysis conditions of the electrolytic cell, such as voltage and current, can be determined and adjusted based on the microbial load in water, and in one specific embodiment of the invention, the voltage of the electrolytic cell is 36V 6 direct current), and the current is 30-50A, so that the microbes in water are effectively killed, and the sterile water is obtained.
In yet another embodiment of the present invention, there is provided the use of the above-described weakly basic aqueous sodium hypochlorite solution in agricultural production.
Specifically, the application in agricultural production at least comprises:
a) Killing plant pathogenic bacteria;
b) Sterilizing seeds and seedlings;
c) Preventing and controlling plant diseases in the field;
d) Storing and preserving fruits and vegetables after harvesting;
e) Killing pathogenic microorganisms of livestock and poultry.
Wherein,,
in the a), the plant pathogenic bacteria include plant pathogenic bacteria and plant pathogenic fungi such as fusarium oxysporum (Fusarium oxysporum), botrytis cinerea (Botrytis cinerea) and ralstonia solanacearum (Ralstonia solanacearum).
Tests prove that the weak alkaline sodium hypochlorite aqueous solution has the effective chlorine concentration within the range of 30-200mg/L, can effectively kill the plant pathogenic bacteria within a short time (within 5 min), and under the condition of the same effective chlorine concentration, the result shows that the weak alkaline sodium hypochlorite aqueous solution with the effective chlorine concentration of 30mg/L and 50mg/L has better sterilization effect than the conventional sodium hypochlorite by using sodium hypochlorite as a comparison test and the weak alkaline electrolytic water has stronger sterilization capability than the sodium hypochlorite even better sterilization effect than the conventional sodium hypochlorite disinfectant under the condition of low concentration.
The disinfection and sterilization of seeds and seedlings in b) also comprises the promotion of seed germination, and experiments prove that the weak alkaline sodium hypochlorite aqueous solution has the effective chlorine concentration of 30-100mg/L and has the promotion effect on seed germination. While weak alkaline aqueous sodium hypochlorite solutions inhibit seed germination when the available chlorine concentration is increased to 200mg/L.
In the c), the prevention and control of the plant diseases in the field are specifically expressed as follows: the weak alkaline sodium hypochlorite aqueous solution has the effective chlorine concentration in the range of 30-200mg/L, has good control effect on plant diseases, is extremely obviously higher than 500 times of 50% carbendazim wettable powder, and has the highest control effect on the diseases by using electrolyzed water with the effective chlorine concentration of 200mg/L, which reaches 96.5%.
In the d), the storage and preservation of the picked fruits and vegetables is specifically shown as follows: prolonging the fresh-keeping period of fruits and vegetables and improving the quality and quality of fruits and vegetables.
In said e), said pathogenic microorganisms of livestock and poultry include but are not limited to E.coli, candida albicans and Staphylococcus aureus. Experiments prove that the weak alkaline sodium hypochlorite aqueous solution has the effective chlorine concentration within the range of 30-100mg/L and has good bactericidal effect on common escherichia coli, staphylococcus aureus and candida albicans in pathogenic microorganisms of livestock and poultry. Meanwhile, the weak alkaline sodium hypochlorite aqueous solution with 100mg/L of available chlorine shows a good sterilization effect within 1min, the sterilization rate reaches 99.99999%, and the sterilization logarithmic value is more than 5, so that the application value is good.
In yet another embodiment of the present invention, there is provided the use of the above-described weakly basic aqueous sodium hypochlorite solution in environmental purification.
In particular, the environmental cleaning includes daily deodorization and/or deodorization;
more specifically, the daily deodorizing and/or deodorizing comprises at least:
a) Removing formaldehyde;
b) Removing sweat smell;
c) Removing smoke smell;
d) Removing peculiar smell of kitchen and toilet.
Experiments prove that the removal rate of the weak alkaline sodium hypochlorite aqueous solution prepared by the method to formaldehyde, smoke smell, sweat smell and kitchen and toilet peculiar smell can reach more than 90%.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
EXAMPLE 1 preparation of slightly alkaline aqueous sodium hypochlorite solution (slightly alkaline electrolyzed Water)
The concentration of the mixed diluted sodium chloride aqueous solution is 1-5 per mill (w/v) by adjusting a water flow pump adjusting switch and a peristaltic pump adjusting switch in the electrolysis device, so that the weak alkaline sodium hypochlorite aqueous solution with the pH value of 7.5-8.5 and the effective chlorine content of 100-200mg/L is generated. The cell voltage was controlled to 6V and the current to 8A.
(1) Component analysis of weakly alkaline aqueous sodium hypochlorite solution (weakly alkaline electrolyzed water)
The following table shows the analysis of the components for preparing a weakly alkaline aqueous sodium hypochlorite solution (weakly alkaline electrolyzed water)
TABLE 1
The following are explained: the weak alkaline sodium hypochlorite aqueous solution prepared in example 1 is subjected to performance test, the specific implementation process refers to 2.1.1.7.4 in the 2002 edition of disinfection technical Specification for quantitative sterilization test of suspension, and the stability test refers to 2.2.3 in the 2002 edition of disinfection technical Specification for product stability determination. Firstly, placing the disinfectant prepared in the example 1 in a 37 ℃ incubator for 3 months, and testing the reduction rate of available chlorine; then, according to the reduction level of available chlorine, the optimal NaCl addition with good stability is optimized, and the sterilization test of the model strain is carried out according to the suspension quantification method. The specific contents are as follows:
(2) Relation between NaCl addition amount and weak alkaline electrolyzed water stability of each group design
As can be seen from the data in Table 2, the weakly alkaline electrolyzed water prepared in example 1 of the present invention with different NaCl addition amounts has a decrease rate of less than 10% when left for 3 months at 37℃under normal temperature conditions, and has better treatment stability than other treatments. According to the requirements of the 'disinfection technical Specification' issued by the ministry of health, the reduction rate is less than 10 percent, and the product can be stored for at least 2 years under the normal temperature condition.
TABLE 2 influence of weakly alkaline electrolyzed water with different NaCl addition amounts on stability
(3) Initial test of killing effect of weakly alkaline electrolyzed water of 3 permillage NaCl on mode bacterial strain
Based on the above data, the weakly alkaline electrolyzed water prepared in the embodiment 1 of the present invention preferably produces 3% of NaCl for quantitative sterilization of suspension, and the data in table 3 shows that the weakly alkaline electrolyzed water can achieve the effect of killing escherichia coli, staphylococcus aureus and candida albicans within 1min, and the sterilization effect is unchanged after the weakly alkaline electrolyzed water is left for 3 months, so that the 3% of weakly alkaline electrolyzed water prepared in the embodiment 1 of the present invention has the characteristics of broad spectrum, high efficiency and rapid sterilization.
Table 33% NaCl addition amount of weakly alkaline electrolyzed water with killing effect (viable count) on model bacteria
In the above production examples, weakly alkaline electrolyzed water of 3% NaCl aqueous solution was preferable, and the following studies of sterilization techniques and safety-related techniques of pathogenic microorganisms in agriculture and livestock and poultry cultivation were conducted.
Example 2 3 per mill study and application of weakly alkaline electrolyzed Water in agriculture
1. Test method and content
1) Test strain
Fusarium wilt germ: fusarium oxysporum (Fusarium oxysporum); gray mold fungus: botrytis cinerea; bacterial wilt germ: ralstonia solanacearum (Ralstonia solanacearum)
2) Preparation of bacterial liquid
The test bacteria are cultured by potato liquid culture medium and shaking table at 25 ℃ for about 72-96 hours for test. Before the test, the bacterial liquid is roughly counted by a blood cell counting plate under a microscope, and the concentration of the bacterial liquid is adjusted to be 5 multiplied by 10 by using sterilized physiological saline 8 ～6×10 8 cfu/ml; putting the test bacteria into a liquid culture medium, and carrying out shake culture at 37 ℃ for about 24 hours. Before the test, the colony number was observed with a microscope (100 times), and the bacterial solution was adjusted with sterilized pure waterAt a concentration of 1X 10 8 ～5×10 8 cfu/ml。
3) Test method
(1) Comparison of the sterilizing effect of weakly alkaline electrolyzed water and sodium hypochlorite under the same concentration
The weakly alkaline electrolyzed water and sodium hypochlorite used in the research contain active chlorine components with the same concentration, and the selection principle of low concentration and high effect is adopted: the weak alkaline electrolyzed water and the sodium hypochlorite disinfectant are diluted to 200mg/L, 100mg/L, 50mg/L and 30mg/L respectively, and sterilized pure water is used as a positive control. Taking ralstonia solanacearum as an example, the concentration of the bacterial solution of the test bacteria is adjusted by 10-fold dilution with sterilized pure water. 1ml of the bacterial liquid was collected and inoculated into test tubes of various concentrations, followed by mixing. After 10 minutes, 0.5ml of the mixed solution was taken out of each test tube sample and added to a 4.5ml neutralizing agent test tube, followed by neutralization for 10 minutes. 1ml was taken out for viable count. After 1 day of incubation at 37 ℃, colonies appearing on the plates were counted. Evaluation criteria: for each sample treated at different concentrations, the number of viable bacteria was counted for a certain period of time, and then the killing rate was calculated according to the following formula, thereby evaluating the sterilizing effect.
The killing rate (%) = [1-10≡6-killing logarithmic value) ]%100%
Wherein: the killing log is the log of microbial reduction before and after disinfection.
(2) Comparison of the sterilizing effect of weakly alkaline electrolyzed water with sodium hypochlorite at the lowest effective concentration and different action time
At the lowest available chlorine concentration, the optimal available time is determined. Taking Ralstonia solanacearum as an example, placing a disinfectant and an experimental strain in a water bath at the temperature of (20+/-1) ℃ for 10min. Adding 4.0ml of disinfectant (the electrolyzed water, the sodium hypochlorite disinfectant and the positive control group are diluted solutions) and 1.0ml of bacterial suspension into a sterile test tube, uniformly mixing, then taking out 0.5ml of mixed solution at 4 time points of 1min, 3min, 5min and 8min respectively, adding into a 4.5ml neutralizing agent test tube, taking out 1ml of the mixed solution after neutralization for 10min, counting viable bacteria, culturing at 37 ℃ for 24h, and calculating a killing logarithmic value. All experiments were repeated 3 times.
Evaluation criteria: at the lowest available chlorine concentration, the number of viable bacteria was examined for each sample at different time treatments and the bactericidal effect was evaluated.
(3) Influence of electrolyzed water on germination rate of tomato seeds
The electrolyzed water can be used for disinfection and sterilization of seeds and seedlings. The invention researches that the electrolyzed water counts the germination rate, bud length and seed rot condition of plant seeds under different effective chlorine concentrations, and selects the optimal concentration range.
An in-house dish bioassay was used. The experimental setup 5 treatments were: tap water (CK), electrolyzed water 30mg/L, 50mg/L, 100mg/L, 200mg/L. The test seeds are sterilized with 70% alcohol for 30s, washed 3 times with sterile water, added into a test tube filled with 10mL of different treatment liquids for seed soaking for 24h, the dilution liquid is discarded, the seeds are placed in a sterilization culture dish paved with filter paper, 10 seeds are placed in each dish, and the culture is carried out at room temperature, and each treatment is repeated 3 times. The germination rate and germination length of the seeds were measured at 10d and 14d, respectively. Germination rate 6%) =number of germinated seeds/total number of seeds x100
(4) Test of effect of electrolyzed water on prevention and control of plant diseases in field
And selecting a tomato planting area with serious damage caused by soil-borne diseases. The field test set 6 treatments were: 30mg/L, 50mg/L, 100mg/L and 200mg/L of electrolyzed water, and 50% carbendazim wettable powder and clear water are used as controls. Root irrigation treatment was performed 1 time per week for 5 consecutive weeks, with a dose of about 300ml per plant. Investigation of the control effect was performed 20 days after the last 1 root irrigation treatment. And 5-point sampling method is used to survey and count the number of disease plants and calculate the disease index and the prevention and treatment effect. Disease severity grading criteria were as follows: grade 0-whole plant is disease-free and externally asymptomatic; 1 grade-less than 1/4 of the total number of leaves of the whole plant, or less than 1/4 of the intrastem vascular bundle turns brown; 2-stage, 1/4-1/2 of the total number of leaves of the whole plant, or 1/4-1/2 of the intrastem vascular bundle turns brown; 3-stage, wherein more than 1/2 of the total number of leaves of the whole plant are diseased, or more than 3/4 of the intrastem vascular bundle is browned, and part of leaves are withered; grade 4-whole plant died from disease.
Disease index = Σ (number of disease plants at each stage×number of disease stages)/(total number of investigation×highest stage) ×100
Disease refers to the rate of increase = (post-dose index-pre-dose index)/pre-dose index x 100%
Control effect= (control disease refers to increasing rate-treatment disease refers to increasing rate) ×100%
(5) Application of electrolyzed water in storage and preservation of fruits and vegetables after harvesting
At present, most agricultural products such as fruits and vegetables can remain organic pesticides when being harvested, which endangers the health of people. After fruits and vegetables are picked, proper fresh-keeping treatment measures are not adopted, and decay and deterioration are easily caused by physiological aging, germ invasion, mechanical damage and the like. Tomatoes should be picked in the early morning or after picking, the tomatoes are subjected to field heat dissipation and then treatment, the tomatoes are treated by using electrolytic water with the effective chlorine concentration of 30mg/L, 50mg/L, 100mg/L and 200mg/L (after soaking for 5-8 min), tap water is used as a control, and sensory evaluation is carried out when the tomatoes are stored for 10d and 15 d.
2. Test results
1. Comparison of the sterilizing effect of weakly alkaline electrolyzed Water at different concentrations with sodium hypochlorite
The weakly alkaline electrolyzed water has good sterilization effect on plant pathogenic bacteria and fungi. As shown in Table 4 below, the results of the comparative test with sodium hypochlorite and weakly alkaline electrolyzed water under the same effective chlorine concentration showed that the weakly alkaline electrolyzed water having the effective chlorine concentrations of 30mg/L and 50mg/L used in the test was more excellent in sterilization effect than sodium hypochlorite, and it was found that the weakly alkaline electrolyzed water was more excellent in sterilization ability than sodium hypochlorite at low concentrations.
TABLE 4 comparison of the sterilizing effect of weakly alkaline electrolyzed water at various concentrations with sodium hypochlorite on plant diseases
2. Comparison of the sterilizing effect of electrolyzed Water and sodium hypochlorite at the lowest effective concentration and different action time
In summary, the lowest effective concentration range of the indoor weakly alkaline electrolyzed water and the sodium hypochlorite is determined, and the sterilizing effect of the weakly alkaline electrolyzed water with the effective chlorine concentration of 30mg/L and the sodium hypochlorite with the effective chlorine concentration of 200mg/L in 1, 3, 5 and 8min is selected. In 3 plant pathogenic bacteria of the test, 30mg/L of weakly alkaline electrolytic water can kill all bacteria within 5 minutes compared with sodium hypochlorite treatment. Therefore, the weak alkaline electrolyzed water is further described to have better killing effect on plant pathogenic bacteria.
TABLE 5 comparison of the sterilizing effect of weakly alkaline electrolyzed water and sodium hypochlorite on plant diseases under different time treatments
3. Influence of electrolyzed water on germination rate of tomato seeds
The influence of weak alkaline electrolytic water soaking on tomato seeds is studied, and the influence of different available chlorine concentrations on seed germination is as follows: the germination rate of the seeds 15d is 100%, 100% and 86.67% respectively when the concentration of the electrolyzed water is 30mg/L, 50mg/L and 100mg/L, and is larger than that of the control group, and the germination rate of the seeds is 73.33% when the concentration is increased to 200mg/L, and is lower than that of the control group. It was found that the electrolytic water at concentrations of 30mg/L, 50mg/L, 100mg/L had an effect of promoting seed germination, whereas the electrolytic water inhibited seed germination when the concentration was increased to 200mg/L.
TABLE 6 influence of weakly basic electrolyzed water on tomato seed germination
4. Test of field plant disease prevention and control effect of electrolyzed water
The test results show that the electrolytic water has good control effects on plant diseases by 30mg/L, 50mg/L, 100mg/L and 200mg/L, and the control effect is extremely higher than that of 500 times of 50% carbendazim wettable powder. The highest disease control effect of 200mg/L of electrolyzed water reaches 96.4 percent. Therefore, the electrolyzed water has better control effect under the field condition. 200mg/L weakly alkaline electrolyzed water is recommended for large-area control of plant diseases.
TABLE 7 control effect of weakly alkaline electrolyzed water on plant diseases
5. Application of electrolyzed water in storage and preservation of fruits and vegetables after harvesting
After soaking for 5-8min by using weak alkaline electrolyzed water with concentration of 30mg/L, 50mg/L, 100mg/L, 200mg/L and tap water (ck), the collected tomatoes are stored for 10d and 15d, and then the color, smell and weightlessness are observed. As shown in Table 8, the use of weakly alkaline electrolyzed water can effectively improve the fresh-keeping period of fruits and vegetables by 15d or more, and effectively improve the quality and quality of fruits and vegetables as compared with tap water (ck).
TABLE 8 sensory evaluation of slightly alkaline electrolyzed water on post-harvest tomatoes
Example 3 test of sterilizing Effect of weakly alkaline electrolyzed Water on microorganisms in livestock and poultry raising Environment
A large number of microorganisms including bacteria and fungi exist in the livestock and poultry breeding environment, and various diseases of livestock and poultry are easy to cause. At present, chemical preparations are mainly used for disinfecting the breeding environment to prevent or reduce the occurrence of livestock and poultry diseases, but most chemical preparations not only pollute the breeding environment and the surrounding environment, but also have the risks of aggravating the livestock and poultry diseases due to improper use and accumulating residues in animal bodies. The weakly alkaline electrolyzed water can be used as a novel efficient, safe and environment-friendly bactericide.
Weak alkaline electrolyzed water was diluted to 4 different effective chlorine concentrations of 200, 100, 50, 30mg/L, respectively, as test samples. Comparing the sterilizing effect of 3 pathogenic bacteria under different concentrations and different action times, counting the number of surviving bacteria by using a suspension quantitative method, and determining the optimal effective chlorine concentration and time.
Results: as is clear from Table 9, the bactericidal effect of Escherichia coli, staphylococcus aureus and Candida albicans, which are common in pathogenic microorganisms of livestock and poultry, was measured using 30mg/L, 50mg/L, 100mg/L and 200mg/L of weakly alkaline electrolyzed water. The sterilizing effect of 100mg/L and 200mg/L of electrolyzed water is better, and the sterilizing rate reaches 100 percent.
TABLE 9 sterilizing effect of weakly alkaline electrolyzed water on pathogenic microorganisms of livestock and poultry at different concentrations
Results: the alkalescent electrolyzed water with 100mg/L available chlorine is selected to sterilize common escherichia coli, staphylococcus aureus and candida albicans in pathogenic microorganisms of livestock and poultry under different action time, and as can be seen from the table 10, the alkalescent electrolyzed water shows good sterilization effect within 1min of the action time, the sterilization rate reaches 99.99999%, and the sterilization logarithmic value is more than 5.
TABLE 10 sterilizing effect of weakly alkaline electrolyzed water on pathogenic microorganisms of livestock and poultry under different action time
EXAMPLE 4 safety determination of weakly alkaline electrolyzed Water
(1) The safety performance of weakly alkaline electrolyzed water was evaluated by an acute oral test.
Test animals: mice, 20, male and female halves; test sample preparation: 5.00g of electrolyzed water (the effective chlorine concentration is 200 mg/L) is weighed, the volume is fixed to 200ml, and the mixture is uniformly mixed for standby. Animals are firstly raised for 4 days, mice with the weight of 18-22g are taken, fasted for 5 hours before the test, the test adopts a limiting method, the weight of 5000mg/kg, the oral gastric lavage is carried out once, and the administration volume is 20mL/kg.
Observations index the animals were observed for toxic manifestations and death immediately after dosing, followed by at least 1 day for 14 days. During the observation period, the weight and death of the animal are recorded, and the dead animal is subjected to autopsy, so as to observe whether the tissue viscera are abnormal.
Results: as shown in tables 11 and 12, the mice did not see any poisoning symptoms and death during the 14-day observation period after the contamination (administration of electrolytic water), and the animals of each sex had a growing tendency. After the observation period, the animals were examined by dissection, and no abnormal symptoms were found in organs and tissues.
TABLE 11 analysis of body weight in animals 14d with weakly basic electrolyzed water
Table 12 summary data of clinical symptoms and death status of mice
(2) Skin irritation test, the safety performance of weakly alkaline electrolyzed water was evaluated.
Test animals: 3 white rabbits are raised for 7 days, the hairs on the two sides of the spine of the back of the 3 rabbits are removed 24 hours before the test, the epidermis is not damaged, the hair removal range is about 3cm multiplied by 3cm, 0.5ml of electrolyzed water (the effective chlorine concentration is 200 mg/L) is taken for the test, the rabbits are directly smeared on the skin on one side of the hair removal, gauze is covered and fixed by a non-irritating binding belt, the skin on the other side is applied for 4 hours, and the skin on the other side is not treated as a control. After the test, the residual test substance was removed with warm water, and skin reactions at the application site were observed 1h, 24h, and 48h after the test substance was removed, respectively, and a stimulus response score was made.
And (3) observing the indexes: the skin on the application site was observed for erythema and edema formation, and scored according to skin irritation scoring criteria based on the extent of response. The total integral and the integral mean of the skin stimulus response scores at each time point of all the tested animals are calculated.
Test results: at the time point of observation, the skin of 3 animals tested did not develop erythema and edema, and the results are shown in Table 13 below
TABLE 13 results of one-time complete skin irritation test
Conclusion: a complete skin irritation test shows that the sample stimulates the skin of rabbits, the integral average value of each animal is 0, and the skin irritation intensity grading standard is 2.3.3 according to the disinfection technical specification, thus the sample belongs to nonirritating skin irritation.
Example 5 application of weakly alkaline electrolyzed Water in deodorizing, etc
In the embodiment, the formaldehyde, the smoke smell, the sweat smell and the kitchen and toilet peculiar smell are detected by using weak alkaline electrolyzed water with the available chlorine of 200mg/L according to a GB27948-2011 laboratory sterilization simulation field test. The results are shown in Table 14.
TABLE 14 experimental results of weakly alkaline electrolyzed water for deodorizing and deodorizing
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. A method for preparing a weakly alkaline aqueous sodium hypochlorite solution, comprising:
mixing water with an electrolyte, and then electrolyzing to obtain the water-based electrolyte;
the electrolyte is sodium chloride;
the addition amount of the electrolyte sodium chloride is controlled to be 3 per mill w/v;
the electrolysis of the weakly alkaline aqueous sodium hypochlorite solution is performed by an electrolysis device; the electrolysis apparatus includes:
the power supply controller controls a power supply driver which is respectively and electrically connected with the electromagnetic valve, the lift pump, the peristaltic pump and the electrolytic tank so as to drive the components to work;
the electrolysis device further comprises a water inlet pipeline and a feeding pipeline, wherein one end of the water inlet pipeline is provided with a water inlet, an electromagnetic valve and a lift pump are sequentially arranged on the water inlet pipeline, one end of the feeding pipeline is connected with the peristaltic pump, and the peristaltic pump inputs an electrolyte in the raw material barrel into the feeding pipeline when working; the other end of the feeding pipeline is converged with the other end of the water inlet pipeline and connected with the electrolytic tank;
the electrolytic tank is a diaphragm-free electrolytic tank, and inert anodes, carbon plates and inert cathodes are longitudinally and alternately arranged in the diaphragm-free electrolytic tank according to the sequence of anode-carbon plate-cathode-anode-carbon plate-cathode;
the concentration of the mixed and diluted sodium chloride aqueous solution is 3 per mill w/v by adjusting a water flow pump adjusting switch and a peristaltic pump adjusting switch in the electrolysis device, so that a weak alkaline sodium hypochlorite aqueous solution with the pH value of 7.5-8.5 and the effective chlorine content of 100-200mg/L is generated; the cell voltage was controlled to 6V and the current to 8A.
2. The method for preparing a weakly alkaline aqueous sodium hypochlorite solution according to claim 1, wherein the electrolyte in the raw material barrel is a high concentration sodium chloride solution; the number of the electrolytic tanks is one or more, and when the number of the electrolytic tanks is multiple, the plurality of electrolytic tanks are connected in series through pipelines; and two ends of the diaphragm-free electrolytic tank are respectively communicated with the liquid inlet and the liquid outlet.
3. A weakly basic aqueous sodium hypochlorite solution obtained by the process according to any one of claims 1-2.
4. Use of the weakly basic aqueous sodium hypochlorite solution of claim 3 in agricultural production; the application in the agricultural production at least comprises:
a) Killing plant pathogenic bacteria;
b) Sterilizing seeds and seedlings;
c) Preventing and controlling plant diseases in the field;
d) Storing and preserving fruits and vegetables after harvesting;
e) Killing pathogenic microorganisms of livestock and poultry.
5. The use according to claim 4, wherein in said a), said plant pathogenic bacteria comprise fusarium oxysporum, botrytis cinerea and ralstonia solanacearum;
the disinfection and sterilization of seeds and seedlings in b) also comprises the promotion of seed germination;
in the c), the prevention and control of the plant diseases in the field are specifically expressed as follows: controlling the effective chlorine concentration of the weak alkaline sodium hypochlorite aqueous solution to be in the range of 30-200 mg/L;
in the d), the storage and preservation of the picked fruits and vegetables is specifically shown as follows: prolonging the fresh-keeping period of fruits and vegetables and improving the quality and quality of the fruits and vegetables;
in the e), the pathogenic microorganisms of livestock and poultry comprise escherichia coli, candida albicans and staphylococcus aureus.
6. Use of the weakly basic aqueous sodium hypochlorite solution of claim 3 in environmental purification; the environmental cleaning includes daily deodorization and/or removal of off-flavors.
7. Use according to claim 6, wherein said daily deodorizing and/or deodorizing comprises at least:
a) Removing formaldehyde;
b) Removing sweat smell;
c) Removing smoke smell;
d) Removing peculiar smell of kitchen and toilet.
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