CN106719811B - Self-thickening high-content iodophor solution for aquatic products and preparation method thereof - Google Patents

Abstract

The invention discloses a self-thickening high-content iodophor solution for aquatic products, which is prepared from the following raw materials in percentage by weight: 40-50% of polyalcohol ether nonionic surfactant; 10 to 25 percent of amide surfactant; 10 to 13 percent of iodine; 1.0 to 4.0 percent of potassium iodide; 0.1 to 0.3 percent of potassium iodate; 0.5 to 1.0 percent of auxiliary agent; the balance being water. The invention also discloses a preparation method of the iodophor solution, which comprises the following steps: adding an alcohol ether nonionic surfactant, an amide surfactant and iodine into a reaction kettle, wherein the reaction temperature is 50-60 ℃, and stirring; adding the dissolved potassium iodide and potassium iodate, and reacting for 1-2 h; and adding the dissolved auxiliary agent, closing the heating device, and reacting for 30-60 min. The obtained self-thickening high-content iodophor solution for aquatic products can improve the effective iodine content, and the product has self-thickening performance after being diluted and has good sterilization and disinfection effects.

Description

Self-thickening high-content iodophor solution for aquatic products and preparation method thereof

Technical Field

The invention belongs to the technical field of aquatic product sterilization and disinfection, and particularly relates to a self-thickening high-content iodophor solution for aquatic products and a preparation method thereof.

Background

Aquaculture is one of the large-scale industries in the animal husbandry of China. With the continuous improvement of aquaculture scale and intensification degree, the stocking density of aquaculture animals is continuously increased, the morbidity of the aquaculture animals is higher and higher, the disease condition is more and more complicated, some even the aquaculture animals reach the place which is difficult to control, and the healthy development of the aquaculture industry is seriously hindered. The safe and efficient disinfectant is used for killing pathogens in the water body and on the surfaces of cultured animals, so that the cutoff of the transmission of the pathogens is an effective measure for improving the water body environment and controlling aquatic animal diseases.

The iodophor solution has the advantages of safety, broad spectrum, high efficiency, quick action and the like, can quickly kill various bacteria and pathogenic microorganisms such as propagules, spores, viruses, fungi and the like of the bacteria, has unique effect on preventing and treating viruses and bacterial diseases of fish, shrimps, crabs, shellfish and the like, has quick and thorough effects on water disinfection and preventing and treating diseases such as bleeding, gill rot, ulcer and the like of aquatic animals, gradually becomes a preferred disinfectant in aquaculture, and is widely applied to multiple links such as water disinfection, tool disinfection, organism disinfection and the like in aquaculture.

Iodophors generally consist of iodine, a carrier, a stabilizer and other adjuvants. At present, the domestic iodophors mainly comprise two types of povidone iodine and polyether iodine, the effective iodine content of povidone iodine raw material products can reach 10-20% by mass, the povidone iodine raw material products are generally solid powder, polyvinylpyrrolidone is used as a complexing carrier, the povidone iodine raw material products are relatively high in cost, and the povidone iodine raw material products are inconvenient to dilute, dissolve and use and are not suitable for large-scale aquaculture. The conventional alcohol ether nonionic surfactant is used as a complexing carrier, so that the price is low, the cost is low, the alcohol ether iodine is a liquid preparation, the dissolution and dilution are convenient, but the complexing capacity of the alcohol ether is limited, the effective iodine content of the product is only about 6 percent at most, and the further popularization and application of the product are limited to a great extent.

On the other hand, the water quality in the aquatic environment depends to a large extent on the quality of the bottom mud of the pool, and when the interference factors such as stocking density, bait throwing and the like exceed the ecological capacity of the pool, the deterioration of the bottom mud and water quality of the pool is formed. The conventional povidone iodine and the conventional polyether-alcohol-ether iodine are dissolved and diluted to about 0.5-1% of effective iodine when being used, but the diluted and dissolved solution has low consistency, is rapidly dispersed in water when being sprayed on the water and is difficult to settle at the bottom of the water, so that the temporary water quality problem can be effectively solved, but the temporary water quality problem has no disinfection effect on the bottom mud of the pool, the problem of water quality deterioration is not fundamentally solved, and the problem is also the main reason for the repeated disease occurrence of aquaculture animals.

Chinese patent CN 104013573B discloses a preparation method of high-content liquid povidone iodine, the liquid povidone iodine effectively solves the problem that the conventional powder povidone iodine is difficult to dissolve, but the diluted solution has low consistency, can only disinfect water, and cannot fundamentally solve the problem of disinfection of bottom mud of a pool. Meanwhile, polyvinyl pyrrolidone is used as a complexing agent, so that the cost is high.

Chinese patent CN 103503863A discloses a special hanging bag colloid iodine disinfection medicine for aquatic products, high-consistency povidone iodine solution is prepared by gel and thickener, the problem of low solution consistency is effectively solved, slow effect is achieved, but iodine content is low, and great problems exist in storage and transportation, meanwhile, the gel and the thickener are high molecular weight compounds, the problems of difficult dissolution and easy agglomeration exist, special equipment is required to be added for dissolving the high molecular weight compounds, the complexity and the complexity of the process are greatly improved, the production and preparation cost is increased, and the expansion and application of the iodine preparation in the field of aquatic products are not facilitated.

In the literature, "preparation of high-concentration iodophors and stability research thereof" (journal of disinfection science, guo rui wang xiao dong, 2009, 4 th page 368-370), a preparation method of a polyether-ether-iodine disinfectant with an effective iodine content of 10% -20% is mentioned, but the method only prepares high-content iodophors, but does not pay attention to turbidity instability when a diluent of the polyether-ether-iodine disinfectant is used, and has no practical application value at all.

In conclusion, the existing iodophor products still have the problems of low effective iodine content, low consistency after dilution and incomplete disinfection in the fields of aquatic products and the like. Therefore, it is necessary to develop a low-cost alcohol ether iodine which can maintain high consistency and high iodine content after being diluted so as to solve the defects of the conventional iodophor disinfection products.

Disclosure of Invention

According to the invention, through deep research on the reaction process principle, the polyalcohol ether nonionic surfactant, the amide surfactant, the iodine, the stabilizer, the auxiliary agent and the like are compounded for use, and scientific optimization experiments are carried out on the use proportion and the addition mode of the related components, and as a result, the iodophor solution obtained by the method disclosed by the invention can effectively improve the effective iodine content to more than 10%, reaches the specification of powder povidone iodine, obviously improves the application range of the polyalcohol ether iodophor, has good solution consistency, has a good disinfection effect on bottom mud and water quality of an aquatic tank, radically solves the problem of repeated aquatic morbidity, and effectively improves the survival rate of aquaculture.

Therefore, the invention aims to provide a self-thickening high-content iodophor solution for aquatic products, so as to solve the problems of low effective iodine content, low consistency after dilution and incomplete disinfection in the fields of aquatic products and the like of the existing iodophor products.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention aims to provide a self-thickening high-content iodophor solution for aquatic products, which is prepared from the following raw materials in percentage by weight:

according to the invention, the polyalcohol ether nonionic surfactant is one or more of alkyl alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and the like.

Furthermore, the number of the ethoxy groups of the alkyl alcohol polyoxyethylene ether and the alkylphenol polyoxyethylene ether is 7-12, and the number of alkyl carbon chains is 8-14.

Preferably, the polyalcohol ether nonionic surfactant is one or more of AEO-7, AEO-9 or NP-10, NP-12 and the like.

According to the present invention, the amide-type surfactant is a surfactant containing an amide group.

Preferably, the amide surfactant is one or more of lauryl fatty acid diethanolamide, coconut fatty acid diethanolamide, lauramidopropyl betaine, cocamidopropyl hydroxysultaine, and the like.

According to the invention, the auxiliary agent is one or more of sodium citrate, sodium polyphosphate or sodium dihydrogen phosphate and the like, and is used for assisting in dissolving iodine and adjusting pH.

The second purpose of the invention is to provide a preparation method of the aquatic self-thickening high-content iodophor solution, which comprises the following steps:

1) preparing the raw materials according to the formula for later use;

2) adding an alcohol ether nonionic surfactant, an amide surfactant and iodine into a reaction kettle, controlling the reaction temperature to be 50-60 ℃, stirring for 2-3 hours, and controlling the stirring speed to be 50-100 r/min (excessive stirring speed is easy to generate bubbles, and is not beneficial to the complex reaction);

3) adding a small amount of water into potassium iodide and potassium iodate, completely dissolving, adding into a reaction kettle, and reacting for 1-2 hours;

4) and adding the auxiliary agent into the balance of water, dissolving, adding into the reaction kettle, closing the heating device, and continuing to react for 30-60 min to obtain the self-thickening high-content iodophor solution for the aquatic products.

The third purpose of the invention is to provide the application of the self-thickening high-content iodophor solution for aquatic products in aquatic product disinfection.

The self-thickening high-content iodophor solution for the aquatic products has the beneficial effects that: the effective iodine content is improved, the product has self-thickening performance after being diluted, the sterilization and disinfection effect is good, and the method is specifically embodied as follows:

1. according to the invention, through the compound use of the alcohol ether surfactant and the amide surfactant, the amide group has strong polarity and large dipole moment, can generate strong hydrogen bonding action with water, and generates a stable complexing effect with iodine, so that the effective iodine content of the poly (alcohol ether iodine) solution is effectively increased to more than 10%, the specification of powder povidone iodine type iodophor is reached, and the application range of the product is remarkably improved. Meanwhile, the stability of the stable complexing effect of the amide group is far stronger than that of the micelle solubilization mode of the polyether-ether-iodine, the stability of the polyether-ether-iodine is effectively improved, and the method has very important significance for long-term storage and application of the polyether-ether-iodine.

2. After the polyalcohol ether iodine solution is diluted, the consistency of the diluent is greatly improved by the strong polar dipole moment action of amido bonds and the micelle hydration action of the surfactant, so that the diluent still has good solution consistency under the dilution condition of the polyalcohol ether iodine solution. Compared with the prior art, the thickening effect of the gel or the thickening agent is greatly improved in process and cost, the complex and complicated production procedures are avoided, and the thickening efficiency is obviously superior to the thickening component.

3. When the polyalcohol ether iodine solution is used for disinfecting aquatic products, the diluent ensures good solution consistency, and when the solution is sprayed into a pond, the solution can be settled at the bottom of the water and slowly dispersed, so that the solution has good disinfection effect on sludge at the bottom of the pond and water quality, the problem of repeated attack of the aquatic products is fundamentally solved, and the survival rate of aquaculture is effectively improved.

4. The potassium iodide and the potassium iodate are used for further improving the stability of the polyether-ether-iodine solution.

5. The production equipment and the method of the environment-friendly aquaculture disinfectant provided by the invention are simple, the production cost is low, no toxic substance is released in the preparation process, and the popularization of large-scale production is facilitated.

Detailed Description

The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.

AEO is fatty alcohol-polyoxyethylene ether, wherein AEO-7 and AEO-9 respectively represent fatty alcohol-polyoxyethylene ether with 7 Ethoxy (EO) numbers and fatty alcohol-polyoxyethylene ether with 9 Ethoxy (EO) numbers;

NP is nonylphenol polyoxyethylene ether, wherein NP-10 and NP-12 respectively represent nonylphenol polyoxyethylene ether having an Ethoxy (EO) number of 10 and nonylphenol polyoxyethylene ether having an Ethoxy (EO) number of 12.

The invention relates to a self-thickening high-content iodophor solution for aquatic products, which is prepared from the following raw materials in percentage by weight:

the preparation method of the self-thickening high-content iodophor solution for the aquatic products comprises the following steps of:

preparing raw materials according to the formula for later use;

adding an alcohol ether nonionic surfactant, an amide surfactant and iodine into a reaction kettle, controlling the reaction temperature to be 50-60 ℃, stirring for 2-3 hours, controlling the stirring speed to be 50-100 r/min, easily generating bubbles at an excessively high stirring speed, and not facilitating the complex reaction;

adding a small amount of water into potassium iodide and potassium iodate, completely dissolving, adding into a reaction kettle, and reacting for 1-2 hours;

adding the auxiliary agent into the balance of water, dissolving, adding into the reaction kettle, closing the heating device, and continuing to react for 30-60 min to obtain the self-thickening high-content iodophor solution for the aquatic products;

and step five, after the reaction is finished, sampling and detecting, and after the reaction is qualified, discharging, canning, packaging and warehousing.

The present invention lists 9 sets of examples, and the raw material components and parts by weight of the iodophor solutions of examples 1-9 are shown in table 1. The process conditions for examples 1-9 are shown in Table 2. The results of testing the iodophor solutions of examples 1-9 are shown in Table 3.

Wherein, in the embodiments 1-4, the polyalcohol ether nonionic surfactant and the amide surfactant are used in a compound way with iodine, a stabilizer, an auxiliary agent and the like; examples 5 to 9 were carried out by compounding a polyol ether nonionic surfactant alone with iodine, a stabilizer, an auxiliary agent, etc.

TABLE 1 formulation of iodophor solutions of examples 1-9

Table 2 process conditions for iodophor solutions of examples 1-9

TABLE 3 results of measurement of iodophor solutions of examples 1 to 9

And (4) conclusion: it can be seen from comparative examples 5-9 that the effective iodine in the solution increases somewhat with the increase of the effective iodine, but the increase of the effective iodine is not obvious when the iodine dosage is more than 8%. Further improve the iodine dosage, along with the polyalcohol ether use amount is compressed, effective iodine is reduced on the contrary. The complexing ability of the polyether to iodine is poor, and the effective iodine is difficult to further improve. The effective iodine content of the embodiments 1-4 of the invention is more than 10%, which reaches the specification of povidone iodine type iodophor powder, the effective iodine content is obviously improved, and the application scope of the polyether glycol iodine product is obviously improved.

EXAMPLE 10 stability test of polyol Ether iodine Diluent

The high-content iodophor solution cannot be directly used for disinfection, and needs to be diluted in actual use until the effective iodine is 0.5-1.0%, so that whether the properties of the diluted solution meet the requirements or not is the standard for inspecting the highest complexing ability. In this example, the above-mentioned examples 1 to 9 were diluted and the solution state was examined. The results are shown in Table 4.

TABLE 4 solution state of polyol ether iodine dilutions of examples 1-9

As can be seen from table 4, the iodophor solutions of examples 1-4 have good stability after dilution and maintain good stability after freezing experiments. The iodophor solutions of examples 5 to 9 have unstable properties of the diluent with the increase of the content of available iodine, and the examples with the available iodine of more than 6 percent have certain problems in stability, and even the iodophor solutions are turbid soil gray liquid after being diluted at normal temperature, and have no practical use value at all. This is why the highest available iodine content of the polyether ether iodine is only 6%.

And (4) conclusion: the dilution solutions of examples 1-4 have good stability, and the actual complexing ability of the iodophor solutions to iodine is significantly improved compared to the actual complexing ability of traditional polyether iodides (employing polyether nonionic surfactants).

Example 11 consistency Change experiments of Iodophor solution dilutions

1. Consistency change experiments for iodophor solution dilutions of examples 1-6

The existing iodophor preparation has the problems that the consistency of the diluted solution is low, great inconvenience is brought in the fields of aquatic products, dairy cow disinfection and the like which have requirements on the consistency of the solution, a thickening component needs to be additionally added for thickening, and the process is complicated and troublesome; meanwhile, special thickener dissolving equipment is additionally required for the thickener, and the cost investment of manufacturers is greatly increased, so that the iodophor product capable of thickening automatically after being diluted has great significance for disinfection application in related fields. This example was conducted by diluting the above-mentioned examples 1 to 6, and the change in consistency of the stock solution of iodophor solution and the diluted solution thereof was examined. The results are shown in Table 5.

TABLE 5 consistency changes of stock iodophor solutions of examples 1-6 and their dilutions

As can be seen from Table 5, the iodophor solutions of examples 1-4 maintain a high consistency effect after dilution by a factor of 10-20. In particular at 10-fold dilution, the consistency is even higher than that of the stock solution. This is because the undiluted solution has a low water content, the hydrogen bonding and micelle action of the amide group and the surfactant are not significant, and the action of the amide group and the surfactant becomes stronger after dilution, and the consistency of the solution is rather increased. The single amide group does not obviously improve the consistency, the effect of obviously improving the consistency of the solution can be achieved only by the synergy of the single amide group and the micelle hydration of the polyalcohol ether, and simultaneously, experiments prove that the better selection is controlled in the mass ratio m (amide type surfactant): m (polyalcohol ether nonionic surfactant) is 0.2-0.625: 1.

Whereas the iodophor solutions of examples 5-6 were diluted 10-20 times, the consistency of the iodophor solution gradually decreased and after 20 times dilution, they had almost no thickening effect.

And (4) conclusion: the iodophor solutions of examples 1-4 have a self-thickening function and are less affected by the dilution factor of the solution.

2. Consistency change test of dilution of iodophor solution of example 1 and dilution of iodophor solution of example 5 thickened with xanthan gum

The 0.5% available iodine diluent of example 1, the 0.5% available iodine diluent of example 5, was further diluted by adding 0.5% by mass of a xanthan gum-thickened diluent, and the consistency of the comparative solution was changed, and the results are shown in table 6.

Table 6 consistency change after thickening with xanthan gum in examples 1 and 5

As can be seen from table 6, the consistency of the dilution thickened by the conventional thickener in example 5 has a nearly linear relationship with the addition amount of the thickener, while the self-thickening iodophor solution in example 1 still maintains good consistency effect under high dilution, and is obviously superior to the conventional thickener in thickening efficiency.

And (4) conclusion: the consistency of the iodophor solution of example 1 is less affected by the dilution factor of the solution, and example 1 has a significant increase in thickening efficiency and is not significantly affected by the dilution factor compared to example 5, in which thickening is performed using a thickener. Therefore, compared with the conventional iodophor solution prepared by compounding the polyalcohol ether nonionic surfactant, the amide surfactant, iodine, the stabilizer, the auxiliary agent and the like, the iodophor solution prepared by the method has the advantages that the process and the cost are greatly improved, the complicated production procedures are avoided, and the thickening efficiency is obviously superior to that of a thickening component.

EXAMPLE 12 aquatic Pond Disinfection test

In 2016, 4 months, fish farming experiments were conducted on fish ponds in somewhere in Jiangsu using the self-thickening, high iodophor-containing solution described in example 1. 10 days before the fish is put into the fry and put into the culture, disinfectant liquid with the concentration of 0.5 percent is prepared to comprehensively disinfect the pond. And then putting fish fries according to normal steps for culturing. And (4) preparing a disinfectant according to the concentration of 0.5ppm every 15 days after the fry placement to carry out conventional disinfection on the fishpond. The experiment is carried out for 150 days, the fish school grows normally in the experiment process, and no viral diseases or sudden death phenomenon of the fish school is found in the whole process.

And (4) conclusion: the iodophor solution of the invention has very effective effect on improving fish culture success rate and reducing disease occurrence. Meanwhile, the complexation of iodine by the iodophor is obviously improved, the toxicity to fish schools and water bodies is obviously reduced, the survival rate of the fish schools is favorably improved, and the iodophor has strong popularization and application significance in related fields.

Claims (6)

1. The self-thickening high-content iodophor solution for the aquatic products is characterized by being prepared from the following raw materials in percentage by weight:

the polyalcohol ether nonionic surfactant is one or more of alkyl alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether;

the auxiliary agent is one or more of sodium citrate, sodium polyphosphate and sodium dihydrogen phosphate;

the polyalcohol ether nonionic surfactant is one or more of AEO-7, AEO-9 and NP-12.

2. The iodophor solution of claim 1, wherein the alkyl alcohol polyoxyethylene ether and the alkylphenol polyoxyethylene ether have 7 to 12 ethoxy groups and 8 to 14 alkyl carbon chains.

3. The iodophor solution of claim 1, wherein the amide-type surfactant is a surfactant containing an amide group.

4. The iodophor solution of claim 3, wherein the amide-type surfactant is one or more of lauric fatty acid diethanolamide, coconut fatty acid diethanolamide, lauramidopropyl betaine, cocamidopropyl hydroxysultaine.

5. The method for preparing a self-thickening high-iodine solution according to any one of claims 1 to 4, comprising the steps of:

1) preparing raw materials according to the formulation of claim 1 for use;

2) adding an alcohol ether nonionic surfactant, an amide surfactant and iodine into a reaction kettle, controlling the reaction temperature to be 50-60 ℃, stirring for 2-3 hours, and controlling the stirring speed to be 50-100 r/min;

3) adding a small amount of water into potassium iodide and potassium iodate, completely dissolving, adding into a reaction kettle, and reacting for 1-2 hours;

4) and adding the auxiliary agent into the balance of water, dissolving, adding into the reaction kettle, closing the heating device, and continuing to react for 30-60 min to obtain the self-thickening high-content iodophor solution for the aquatic products.

6. Use of the self-thickening high content iodophor solution of any of claims 1-4 for aquadisinfection.