CN106937646B - Preparation method of iodic acid mixed solution and iodic acid mixed solution prepared by same - Google Patents

Preparation method of iodic acid mixed solution and iodic acid mixed solution prepared by same Download PDF

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CN106937646B
CN106937646B CN201710200963.XA CN201710200963A CN106937646B CN 106937646 B CN106937646 B CN 106937646B CN 201710200963 A CN201710200963 A CN 201710200963A CN 106937646 B CN106937646 B CN 106937646B
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iodide
sulfuric acid
mixed solution
acid
stirring
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CN106937646A (en
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徐奇清
李成应
周淑贞
张庆
聂姣
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Foshan Nanhai Eastern Along Pharmaceutical Co ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/12Iodine, e.g. iodophors; Compounds thereof

Abstract

The invention provides a preparation method of an iodic acid mixed solution and the iodic acid mixed solution prepared by the method. In the method, the stabilizer is added in the preparation reaction process, so that the stability of the prepared iodic acid mixed solution can be effectively improved. Meanwhile, the iodic acid mixed solution has the advantages of high effective iodine content of the solution, good stability and the like.

Description

Preparation method of iodic acid mixed solution and iodic acid mixed solution prepared by same
Technical Field
The invention relates to the field of disinfectant preparations, in particular to a preparation method of an iodic acid mixed solution and the iodic acid mixed solution prepared by the method.
Background
The iodic acid mixed solution is a common livestock and poultry disinfectant, and the action mechanism of the iodic acid mixed solution is mainly as follows: iodine combines with protein in microbial cell wall and cytoplasm, thereby having rapid killing effect on virus, bacteria and spores thereof, mold and yeast; meanwhile, a large amount of iodine molecules are released when the disinfectant is diluted by water through the high-efficiency activation of acid, so that the disinfectant is a high-efficiency microbicidal disinfectant. However, the high activity of iodine also affects the stability of the mixed solution of iodic acid, which also adversely affects the disinfection effect of iodic acid.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a method for preparing an iodic acid mixed solution, wherein a stabilizer is added in the preparation reaction process, so that the stability of the prepared iodic acid mixed solution can be effectively improved; meanwhile, the method has the advantages of simple process, easy control, no need of large-scale equipment and easy large-scale industrial production.
The second purpose of the invention is to provide an iodic acid mixed solution, which is prepared by the method of the invention, and thus has the advantages of good solution stability and the like.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a method for preparing an iodic acid mixed solution, comprising the following steps:
a) dissolving iodide to obtain an iodide solution;
b) adding sulfuric acid into the stabilizer, and stirring; then, adding hydrogen peroxide and stirring; then, adding an emulsifier, and uniformly stirring; then, sequentially adding elemental iodine and an iodide solution;
c) adding phosphoric acid, continuing stirring, then adding sulfuric acid and water, and uniformly stirring to obtain an iodic acid mixed solution;
wherein the stabilizer is one or a mixture of several nitrogen heterocyclic ring compounds or tertiary amine compounds containing cyclic groups.
Optionally, in the present invention, the stabilizer is one or a mixture of several of pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, pyrazine, quinoline, coco dimethylamine, N-dimethylaniline, N-dimethylbenzylamine, N-diethylbenzylamine, N-methylpiperidine, N-ethylpiperidine, N-methylpiperazine, N' -dimethylpiperazine, triethylenediamine, N-methylmorpholine, N-ethylmorpholine, N-methylpyrrole, or N, N-dimethylcyclohexylamine.
Optionally, in the present invention, the iodide is hydrogen iodide or a water-soluble iodide salt;
preferably, the iodide is a water-soluble iodide salt.
Optionally, in the present invention, the water-soluble iodine salt is one or a mixture of more of sodium iodide, potassium iodide, and calcium iodide.
Optionally, in the present invention, the emulsifier is a nonionic surfactant.
Optionally, in the invention, the nonionic surfactant is one or a mixture of more of octanol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether, or lauryl alcohol polyoxyethylene ether.
Optionally, in the invention, the mass ratio of the phosphoric acid, the total sulfuric acid, the iodine simple substance and the iodide is (15-25): (5-15): (0.2-5): (0.1-5);
preferably, the mass ratio of the phosphoric acid to the total sulfuric acid to the iodine elementary substance to the iodide is (20-25): (5-10): (2-4): (2-3);
wherein the total sulfuric acid is the total amount of sulfuric acid in step b) and step c).
Optionally, in the invention, the mass ratio of the sulfuric acid in the step b) to the sulfuric acid in the step c) is (1-5): (95-99).
Optionally, in the invention, the mass ratio of the phosphoric acid to the total sulfuric acid to the stabilizer is (15-25): (5-15): (0.1-5);
preferably, the mass ratio of the phosphoric acid to the total sulfuric acid to the stabilizer is (20-25): (5-10): (0.1-5);
wherein the total sulfuric acid is the total amount of sulfuric acid in step b) and step c).
Further, the invention also provides the iodic acid mixed solution prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method has the advantages of simple preparation process, convenient operation and capability of simply and efficiently preparing the iodic acid mixed solution with excellent stability; meanwhile, the method can be further applied to the preparation of other iodine preparations such as povidone iodine and the like;
(2) the method has the advantages that the cost of raw materials and equipment is low, and the cost for preparing the iodic acid mixed solution can be effectively controlled;
(3) the iodic acid mixed solution has high effective iodine content and good stability.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The iodic acid mixed solution is prepared from the following raw materials: phosphoric acid, sulfuric acid, a stabilizer, elemental iodine, iodide, an emulsifier and hydrogen peroxide;
the preparation method mainly comprises the following steps:
a) dissolving iodide to obtain an iodide solution;
preferably, the solvent used for dissolution is water;
preferably, the iodide is hydrogen iodide or a water-soluble iodide salt; more preferably, the iodide is a water-soluble iodide salt, such as but not limited to sodium iodide, potassium iodide, or calcium iodide; further preferably, the iodide is potassium iodide;
b) adding sulfuric acid into the stabilizer, and stirring; then, adding hydrogen peroxide and stirring; then, adding an emulsifier, and uniformly stirring; then, sequentially adding elemental iodine and an iodide solution;
preferably, the stabilizer is one or a mixture of several of nitrogen heterocyclic ring compounds or tertiary amine compounds containing cyclic groups, and the addition of the stabilizer can also effectively improve the stability of the product iodic acid, and the reduction of the content of available iodine cannot be caused even if the product is stored for a long time;
in a preferred embodiment of the present invention, the nitrogen-containing aromatic ring compound contains at least one nitrogen heteroatom and does not contain a tertiary amine structure, and at least one of the nitrogen heteroatoms is an unsaturated nitrogen atom; that is, at least one R is present in the nitrogen heterocyclic ring structure of the nitrogen heterocyclic aromatic ring compound1-N=R2A structural fragment of (1), wherein R1And R2Each independently is C or N, preferably, R1And R2Are all carbon; more preferably, the aromatic heterocycle of the nitrogen heterocyclic ring compound has only one or two nitrogen atoms, and the nitrogen atoms are unsaturated nitrogen atoms, and the nitrogen heterocyclic ring compound does not contain a tertiary amine structure; further preferably, the nitrogen heterocyclic aromatic ring compound is one or more of pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, pyrazine and quinoline;
in a preferred embodiment of the present invention, the tertiary amine compound having a cyclic group is a tertiary amine compound having a cyclic substituent structure; for example, the formula of the compound may be as follows: NR (nitrogen to noise ratio)3R4R5(ii) a Wherein R is3、R4、R5Are respectively and independently alkyl, substituted alkyl, aryl or substituted aryl with the same or different structures; wherein R is3、R4、R5In which at least one R group is a substituent bearing at least one cycloalkyl group, e.g. R3、R4、R5Wherein at least one R group is a cyclic hydrocarbon group, a heteroatom-based cyclic hydrocarbon group, a linear or branched alkyl cyclic hydrocarbon group, a linear or branched substituted alkyl cyclic hydrocarbon group, a linear or branched alkenyl cyclic hydrocarbon group, a linear or branched substituted alkenyl or cycloalkenyl group, a linear or branched alkynyl cyclic hydrocarbon group, or a linear or branched substituted alkynyl cyclic hydrocarbon group, wherein the cyclic hydrocarbon group is a cycloalkyl group, a cyclic aryl group, a substituted cycloalkyl group, or a substituted aryl group with or without heteroatoms;
in a preferred embodiment of the present invention, the tertiary amine compound having a cyclic group is a nitrogen-heterocyclic tertiary amine compound, and the nitrogen heteroatom is a tertiary amine nitrogen; for example, the formula of the compound may be as follows: NR'3R'4R'5(ii) a Wherein R'3、R'4、R'5In (2), two R groups form a ring structure;
still more preferably, the tertiary amine compound with cyclic hydrocarbon group is one or a mixture of several of coco dimethyl amine, N-dimethyl aniline, N-dimethyl benzylamine, N-diethyl benzylamine, N-methyl piperidine, N-ethyl piperidine, N-methyl piperazine, N' -dimethyl piperazine, triethylene diamine, N-methyl morpholine, N-ethyl morpholine, N-methyl pyrrole, and N, N-dimethyl cyclohexylamine.
Preferably, the sulfuric acid is concentrated sulfuric acid, the concentrated sulfuric acid is added into the stabilizer and then needs to be further stirred and mixed, and the stirring time is preferably 5-30 min;
after adding sulfuric acid and stirring, it is necessary to further add hydrogen peroxide and mix them. In a preferred scheme of the invention, the hydrogen peroxide is hydrogen peroxide with a concentration of 30%, preferably, after the hydrogen peroxide is added, the temperature of the system needs to be controlled at 50-80 ℃, and the mixture is stirred for 10-60 min under the temperature condition;
wherein the hydrogen peroxide is preferably 20-30% of hydrogen peroxide; more preferably, the hydrogen peroxide is 25-30% of hydrogen peroxide;
adding hydrogen peroxide, mixing and stirring, further adding an emulsifier into the system, and uniformly stirring; in a preferred embodiment of the present invention, the emulsifier is a nonionic surfactant; more preferably, the nonionic surfactant is one or a mixture of more of octanol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether or lauryl alcohol polyoxyethylene ether; for example, the nonionic surfactant can be, but is not limited to, n-octyl alcohol polyoxyethylene ether JFC, isooctyl alcohol polyoxyethylene ether JFC-2, fatty acid methyl ester polyoxyethylene ether, lauryl alcohol polyoxyethylene ether AEO (e.g., AEO-9), and the like.
After the emulsifier is added, continuously stirring uniformly, and then sequentially adding the elemental iodine and the iodide solution respectively; preferably, in this step, the added elementary iodine is refined iodine; further, after the elemental iodine and the iodide are added, preferably stirring for 5-30 min at 50-80 ℃;
c) adding phosphoric acid, continuing stirring, then adding sulfuric acid and water, and uniformly stirring to obtain an iodic acid mixed solution;
in the stirring process of the step, the temperature of the system is still kept between 50 and 80 ℃;
in the step, the phosphoric acid is concentrated phosphoric acid with the concentration of more than or equal to 99 percent, and is preferably stirred for 5-30 min after the phosphoric acid is added;
in the step, the sulfuric acid is concentrated sulfuric acid, stirring is continuously carried out for 10-60 min after the sulfuric acid and water are added, and after stirring is finished, the system is naturally cooled to room temperature, so that an iodic acid mixed solution is obtained.
The method can also comprise a step of sampling detection, namely canning the obtained iodic acid mixed solution after the sampling detection is qualified, and the iodic acid mixed solution can be sold and used as a commodity.
Further, in the above preparation method, the mass ratio of phosphoric acid, total sulfuric acid, iodine simple substance and iodide is (15-25): (5-15): (0.2-5): (0.1-5); preferably, the mass ratio of the phosphoric acid to the total sulfuric acid to the iodine elementary substance to the iodide is (20-25): (5-10): (2-4): (2-3); more preferably, the mass ratio of the sum of the mass of phosphoric acid and total sulfuric acid to the mass of iodine simple substance and iodide is (20-40): (2-4): (2-3);
further preferably, the mass ratio of the phosphoric acid to the total sulfuric acid is (3-5): 1, more preferably the mass ratio of phosphoric acid to total sulfuric acid is 4: 1;
wherein, the total sulfuric acid is the total amount of concentrated sulfuric acid used in the steps b) and c); further preferably, the mass ratio of the sulfuric acid in the step b) to the sulfuric acid in the step c) is (1-5): (95-99);
in a preferred embodiment of the invention, the mass ratio of the phosphoric acid to the total sulfuric acid to the stabilizer is (15-25): (5-15): (0.1-5); more preferably, the mass ratio of the phosphoric acid to the total sulfuric acid to the stabilizer is (20-25): (5-10): (0.1-5);
in a preferred embodiment of the present invention, the mass ratio of phosphoric acid, total sulfuric acid, emulsifier and hydrogen peroxide is (15-25): (5-15): (5-20): (0.1-6); more preferably, the mass ratio of the phosphoric acid to the total sulfuric acid to the emulsifier to the hydrogen peroxide is (20-25): (5-10): (5-15): (3-5).
The method of the invention specifically comprises the following steps:
a) dissolving iodide to obtain an iodide solution;
b) adding sulfuric acid into the stabilizer, and stirring for 5-30 min; then adding 30% hydrogen peroxide, and stirring for 10-60 min at the temperature of 50-80 ℃; then, adding an emulsifier, and uniformly stirring; then, adding refined iodine and iodide solution in turn;
c) adding phosphoric acid, and stirring for 5-30 min; and then, sequentially adding sulfuric acid and water, continuing stirring for 10-60 min, stopping stirring, and cooling to obtain an iodic acid mixed solution.
And further, sampling and detecting the prepared iodic acid mixed solution, and canning for sale or directly using after the detection is qualified.
The iodic acid provided by the invention has good stability, can be stored in the production period, does not deteriorate or reduce the content of effective iodine, and can effectively reduce the preparation and use costs of the iodic acid.
Example 1
a) Dissolving 2g of potassium iodide in water to obtain an iodide solution;
b) adding 0.3g of concentrated sulfuric acid into 3g of pyridine, and stirring for 15 min; then adding 5g of 30% hydrogen peroxide, and stirring for 30min at the temperature of 60 ℃; then, adding 10g of n-octanol polyoxyethylene ether JFC, and uniformly stirring; then, 3g of refined iodine and iodide solution are added in sequence;
c) adding 24g of concentrated phosphoric acid, and stirring for 15 min; then, 5.7g of concentrated sulfuric acid and water were sequentially added, and stirring was continued for 45min, and the stirring was stopped, followed by cooling to obtain the iodic acid mixed solution of example 1.
Example 2
a) Dissolving 3g of sodium iodide in water to obtain an iodide solution;
b) adding 0.1g of concentrated sulfuric acid into 5g of coco dimethyl amine, and stirring for 20 min; then adding 4g of 30% hydrogen peroxide, and stirring for 45min at the temperature of 60 ℃; then, 13g of fatty acid methyl ester polyoxyethylene ether is added and stirred uniformly; then, 3.5g of refined iodine and iodide solution are added in sequence;
c) adding 24g of concentrated phosphoric acid, and stirring for 20 min; then, 5.9g of concentrated sulfuric acid and water were sequentially added, and stirring was continued for 45min, and the stirring was stopped, followed by cooling to obtain the iodic acid mixed solution of example 2.
Example 3
a) Dissolving 3g of potassium iodide in water to obtain an iodide solution;
b) adding 0.4g of concentrated sulfuric acid into 4g of quinoline, and stirring for 5-30 min; then 6g of 30% hydrogen peroxide is added, and the mixture is stirred for 50min under the condition of heat preservation, wherein the heat preservation temperature is 70 ℃; then adding 7g of isooctanol polyoxyethylene ether JFC-2, and uniformly stirring; then, 2.5g of refined iodine and iodide solution are added in sequence;
c) adding 30g of concentrated phosphoric acid, and stirring for 20 min; then, 9.6g of concentrated sulfuric acid and water were sequentially added, and stirring was continued for 45min, and the stirring was stopped, followed by cooling to obtain the iodic acid mixed solution of example 3.
Example 4
a) Dissolving 4g of sodium iodide in water to obtain an iodide solution;
b) 0.2g of concentrated sulfuric acid was added to 4.5g N, N-diethylbenzylamine and stirred for 25 min; then adding 3g of 30% hydrogen peroxide, and stirring for 60min at the temperature of 80 ℃; then, 12g of lauryl alcohol polyoxyethylene ether AEO-9 is added and stirred uniformly; then, 3g of refined iodine and iodide solution are added in sequence;
c) adding 25g of concentrated phosphoric acid, and stirring for 25 min; then, 4.9g of concentrated sulfuric acid and water were sequentially added, the stirring was continued for 15min, and the stirring was stopped, followed by cooling to obtain the iodic acid mixed solution of example 4.
Experimental example 1
First, test sample, i.e. iodic acid mixed solution prepared by the method of example 1 and qualified by spot inspection
II, a test scheme: an appropriate amount of iodic acid mixed solution which is prepared by the method in example 1 and qualified by sampling inspection is taken, and the influence factor test, the accelerated test and the long-term test are sequentially carried out according to appendix 246 of 2010 edition of pharmacopoeia of the people's republic of China-veterinary pharmacopoeia-veterinary drug stability test guiding principle and veterinary chemical drug stability research technical guiding principle. The specific test scheme is as follows:
1. influence factor test scheme includes that a batch of iodic acid mixed solution which is prepared by the method in example 1 and is qualified by spot inspection is packaged according to market, the mixed solution is respectively placed under two conditions of high temperature (60 ℃) and strong light (4500+500Lx) to carry out high temperature and strong light influence factor tests, the mixed solution is placed for 10 days, and detection of iodine content, acid content, relative density and ph is carried out respectively in 0 day, 5 days and 10 days, so that stability of test samples is inspected by taking the test solutions as indexes.
2. Accelerated test protocol: three batches of iodic acid mixed solution which is prepared by the method of example 1 and qualified by sampling inspection are packaged according to the market and placed for 6 months under the conditions of 40 ℃ plus or minus 2 ℃ and relative humidity of 75 percent plus or minus 5 percent. Sampling is carried out once at the end of 0 month, 1 month, 2 months, 3 months and 6 months during the test period, and the detection of iodine content, acid content, relative density and ph is carried out, so as to examine the stability of the test sample by taking the detection as an index.
3. Long-term test protocol: three batches of iodic acid mixed solution which is prepared by the method of example 1 and qualified by sampling inspection are placed for 12 months at the temperature of 25 +/-2 ℃ and the relative humidity of 60 +/-10%. Sampling every 3 months, sampling at 0 month, 3 months, 6 months, 9 months, 12 months, 18 months, 24 months and 36 months respectively, detecting the iodine content, the acid content, the relative density and the ph, and taking the detection as an index to investigate the stability of the test sample.
Thirdly, test results: the test results are shown in tables 1, 2 and 3 below:
table 1 example 1 influence factor experiment results of iodic acid mixed solution
Figure BDA0001258080360000101
Table 2 example 1 results of accelerated test of mixed iodic acid solution
Figure BDA0001258080360000111
Table 3 example 1 long-term experimental results
Figure BDA0001258080360000112
Figure BDA0001258080360000113
Figure BDA0001258080360000121
As can be seen from the test results in tables 1, 2 and 3, the iodic acid mixed solution prepared in example 1 does not have significant decrease in available iodine content and acid content under the conditions of influence factor test (high temperature, strong light), accelerated test and long-term test, and the pH of the solution can be kept stable. Therefore, the iodic acid mixed solution has good stability.
Further, similar tests were carried out using the mixed iodic acid solutions prepared in examples 2 to 4 as raw materials, and the test results showed that the mixed iodic acid solutions of examples 2 to 4 also maintained good stability under the conditions of influencing factor tests (high temperature and strong light), accelerated tests and long-term tests, and the available iodine content of the solutions decreased by less than 0.5% when stored at normal temperature for a long time.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (8)

1. A method for preparing an iodic acid mixed solution is characterized by comprising the following steps:
a) dissolving iodide to obtain an iodide solution;
b) adding sulfuric acid into the stabilizer, and stirring for 5-30 min; then adding 30% hydrogen peroxide, and stirring for 10-60 min at the temperature of 50-80 ℃; then, adding an emulsifier, and uniformly stirring; then, sequentially adding elemental iodine and an iodide solution;
c) adding phosphoric acid, continuing stirring, then adding sulfuric acid and water, and uniformly stirring to obtain an iodic acid mixed solution;
wherein the stabilizer is one or a mixture of more of pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, pyrazine, quinoline, N-dimethylaniline, N-dimethylbenzylamine, N-diethylbenzylamine, N-methylpiperidine, N-ethylpiperidine, N-methylpiperazine, N' -dimethylpiperazine, triethylenediamine, N-methylmorpholine, N-ethylmorpholine, N-methylpyrrole, or N, N-dimethylcyclohexylamine;
the mass ratio of the phosphoric acid to the total sulfuric acid to the iodine elementary substance to the iodide is (15-25): (5-15): (0.2-5): (0.1-5); wherein the total sulfuric acid is the total amount of sulfuric acid in step b) and step c);
the mass ratio of the phosphoric acid to the total sulfuric acid to the stabilizer is (15-25): (5-15): (0.1-5), wherein the total sulfuric acid is the total amount of sulfuric acid in the step b) and the step c); the mass ratio of the sulfuric acid in the step b) to the sulfuric acid in the step c) is (1-5): (95-99).
2. The method according to claim 1, wherein the iodide is hydrogen iodide or a water-soluble iodide salt.
3. The method according to claim 2, wherein the water-soluble iodine salt is one of sodium iodide, potassium iodide, and calcium iodide.
4. The method according to claim 1, wherein the emulsifier is a nonionic surfactant.
5. The preparation method according to claim 4, wherein the nonionic surfactant is one or more of octyl alcohol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether, or lauryl alcohol polyoxyethylene ether.
6. The preparation method according to claim 1, wherein the mass ratio of phosphoric acid, total sulfuric acid, iodine and iodide is (20-25): (5-10): (2-4): (2-3).
7. The preparation method according to claim 1, wherein the mass ratio of the phosphoric acid to the total sulfuric acid to the stabilizer is (20-25): (5-10): (0.1-5).
8. An iodic acid mixed solution prepared according to the method of any one of claims 1 to 7.
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