阅读说明：本技术 一种抗结块高稳定性过硫酸氢钾活性盐消毒剂及制备方法 (Anti-caking high-stability potassium hydrogen persulfate active salt disinfectant and preparation method thereof ) 是由 李�泳 于 2021-09-27 设计创作，主要内容包括：本发明属于消毒杀菌剂技术领域,公开了一种抗结块高稳定性过硫酸氢钾活性盐消毒剂及制备方法。所述制备方法包括将双氧水在稳定剂及低温条件下与发烟硫酸反应,得到过氧化反应液,然后加入碳酸钾或氢氧化钾溶液进行中和反应,得到中和液,再加入液态硅酸钠搅拌溶解均匀,真空浓缩,降温结晶,离心烘干,得到单过硫酸氢钾复合盐,最后与表面活性剂、有机酸、无机缓冲盐搅拌混合均匀,得到过硫酸氢钾活性盐消毒剂产品。本发明通过在单过硫酸氢钾复合盐浓缩结晶的过程中加入一定量的液态硅酸钠,可显著提高产品收率、抗结块性和稳定性。本发明方法具有成本低,产物性能好的优点。(The invention belongs to the technical field of disinfectants and discloses an anti-caking high-stability potassium hydrogen persulfate active salt disinfectant and a preparation method thereof. The preparation method comprises the steps of reacting hydrogen peroxide with fuming sulfuric acid under the conditions of a stabilizer and low temperature to obtain peroxide reaction liquid, then adding potassium carbonate or potassium hydroxide solution to carry out neutralization reaction to obtain neutralization liquid, then adding liquid sodium silicate, stirring and dissolving uniformly, carrying out vacuum concentration, cooling and crystallizing, carrying out centrifugal drying to obtain potassium monopersulfate composite salt, and finally stirring and mixing uniformly with a surfactant, organic acid and inorganic buffer salt to obtain the potassium monopersulfate active salt disinfectant product. According to the invention, a certain amount of liquid sodium silicate is added in the process of concentrating and crystallizing the potassium monopersulfate composite salt, so that the product yield, caking resistance and stability can be obviously improved. The method has the advantages of low cost and good product performance.)

1. The preparation method of the anti-caking high-stability potassium hydrogen persulfate active salt disinfectant is characterized by comprising the following preparation steps of:

(1) adding hydrogen peroxide and a stabilizer into a reactor, controlling the temperature to be 0-5 ℃, dropwise adding fuming sulfuric acid under the stirring condition, and controlling the temperature to be below 15 ℃ for heat preservation reaction to obtain peroxidation reaction liquid;

(2) dropwise adding a potassium carbonate or potassium hydroxide solution into the peroxidation reaction liquid in the step (1) to carry out neutralization reaction to obtain a neutralization liquid;

(3) adding liquid sodium silicate into the neutralized solution obtained in the step (2), stirring and dissolving uniformly, concentrating in vacuum, cooling and crystallizing, and centrifugally drying to obtain potassium monopersulfate composite salt;

(4) and (4) uniformly stirring and mixing the potassium monopersulfate composite salt obtained in the step (3) with a surfactant, an organic acid and an inorganic buffer salt to obtain the anti-caking high-stability potassium monopersulfate active salt disinfectant.

2. The method for preparing anti-caking high-stability oxone active salt disinfectant according to claim 1, wherein the stabilizer in step (1) is trisodium phosphate or sodium polyphosphate; the addition amount of the stabilizer is 0.5 to 2 percent of the mass of the hydrogen peroxide.

3. The method for preparing the anti-caking high-stability oxonium persulfate active salt disinfectant according to claim 1, wherein the hydrogen peroxide and oleum in step (1) are both diluted to a mass concentration of 20-50% before reaction.

4. The preparation method of the anti-caking high-stability potassium hydrogen persulfate active salt disinfectant as claimed in claim 1, wherein the molar ratio of hydrogen peroxide to oleum in step (1) is (1-3): 1.

5. The preparation method of the anti-caking high-stability potassium hydrogen persulfate active salt disinfectant as claimed in claim 1, wherein the molar ratio of the addition amount of the potassium carbonate or the potassium hydroxide in the step (2) to the fuming sulfuric acid is (4.8-5.2): 4 in terms of the molar amount of potassium.

6. The method for preparing the anti-caking high-stability oxone active salt disinfectant according to claim 1, wherein the addition amount of the liquid sodium silicate in the step (3) is 0.2-4% of the mass of the neutralization solution.

7. The method for preparing the anti-caking high-stability oxone active salt disinfectant according to claim 1, wherein the vacuum concentration in step (3) is vacuum concentration at 45-55 ℃ to saturation; the cooling crystallization refers to standing crystallization after cooling to-4 ℃.

8. The method for preparing anti-caking high-stability oxone active salt disinfectant according to claim 1, wherein the surfactant in step (4) is at least one of sodium alkyl benzene sulfonate and sodium alkyl sulfonate; the organic acid is at least one of malic acid, citric acid and tartaric acid; the inorganic buffer salt is sodium polyphosphate.

9. The preparation method of the anti-caking high-stability potassium monopersulfate active salt disinfectant as claimed in claim 8, wherein the mass parts of the potassium monopersulfate composite salt, the surfactant, the organic acid and the inorganic buffer salt are as follows: 55-75 parts of potassium monopersulfate composite salt, 3-15 parts of surfactant, 5-20 parts of organic acid and 2-10 parts of inorganic buffer salt.

10. An anti-caking high-stability potassium hydrogen persulfate active salt disinfectant, which is prepared by the method of any one of claims 1 to 9.

Technical Field

The invention belongs to the technical field of disinfectants, and particularly relates to an anti-caking high-stability potassium hydrogen persulfate active salt disinfectant and a preparation method thereof.

Background

The potassium peroxymonosulfate active salt mainly comprises potassium peroxymonosulfate complex salt, also called potassium peroxymonosulfate complex salt, and potassium peroxymonosulfate complex salt, which is prepared from potassium peroxymonosulfate KHSO₅KHSO, potassium hydrogen sulfate₄Potassium sulfate K₂SO₄A compound salt composed of three components. Is an effective oxidant and disinfectant. Can be widely applied to aquaculture disinfection, livestock breeding disinfection, common environment disinfection and the like.

The existing methods for preparing the potassium monopersulfate composite salt comprise a chlorosulfonic acid method, an anodic oxidation method and a fuming sulfuric acid method, wherein the main method is the fuming sulfuric acid method.

Patent CN108849977A discloses a preparation method of potassium monopersulfate composite salt, which reasonably improves the process of producing potassium monopersulfate composite salt by the existing sulfuric acid method, and potassium peroxodisulfate is added in the reaction process, so that the reaction process can be carried out under normal pressure, thereby not only simplifying the production process, accelerating the reaction, shortening the reaction time, but also stabilizing the reaction intermediate, and the potassium peroxodisulfate can be converted into potassium monopersulfate in the reaction process without influencing the purity of the final product; the crystallization dehydration mother liquor is also added in the reaction process, so that seed crystals can be provided for subsequent crystallization, and the utilization rate of raw materials and the product yield are improved; the alkaline potassium compound solid is added in the reaction process, so that the preparation process of the solution is reduced, the production safety is improved, and the production process is simplified; and finally adding an anti-caking agent to stabilize the product.

Patent CN108821242A discloses a preparation method of potassium peroxymonosulfate composite salt, potassium peroxydisulfate is used for replacing high-concentration hydrogen peroxide to react with fuming sulfuric acid, and potassium peroxymonosulfate are hydrolyzed under the action of a catalyst, the reaction is mild, the reaction heat is small, and the risk degree of the reaction is effectively reduced. However, the method still needs to adopt conventional evaporation concentration and cooling crystallization to separate the product, and because the solubility of the potassium monopersulfate composite salt in water is higher, the raw material utilization rate and the product yield are not high by adopting the concentration crystallization method only, which can only reach about 70 percent, and the production cost is increased. In addition, the method adopts potassium peroxodisulfate produced by electrolyzing sulfuric acid as a reaction raw material, which is substantially equivalent to an anodic oxidation method, thereby further improving the industrial production cost.

In addition, because the potassium hydrogen persulfate active salt product is white powder which can flow freely under the conventional conditions and has strong hygroscopicity, no matter the potassium hydrogen persulfate active salt product is bagged or bulked, the composite salt can continuously absorb moisture from the air in the storage process, thereby causing caking. In addition, in the process of stacking, due to certain pressure, the loose crystalline structures of the materials are changed and are adhered to each other, and finally, the materials are combined into a large hard block, so that great inconvenience is caused to storage and use.

Patent CN 101372318A discloses an anti-caking treatment method for potassium monopersulfate composite salt, which is characterized in that a surfactant is added into wet potassium monopersulfate composite salt in a spraying manner to serve as an anti-caking agent, and a magnesium compound is added after drying to serve as a separant, so that the non-caking storage time of the potassium monopersulfate composite salt can be remarkably prolonged. However, the method increases the difficulty of process treatment to a certain extent, and a solution is not provided for improving the product yield.

Disclosure of Invention

Aiming at the defects and shortcomings of the prior art, the invention aims to provide a preparation method of an anti-caking high-stability oxone active salt disinfectant. The method adopts a fuming sulfuric acid method with low cost to prepare the potassium monopersulfate composite salt, and a certain amount of liquid sodium silicate is added in the concentration and crystallization process of the potassium monopersulfate composite salt, so that the crystallization and precipitation of the potassium monopersulfate composite salt in a solution are facilitated, and the utilization rate of raw materials and the yield of products are improved. And further discovers that the addition of the sodium silicate can obviously improve the anti-caking performance and stability of the potassium monopersulfate composite salt. The method has the advantages of low cost and good product performance.

The invention also aims to provide the anti-caking high-stability oxone active salt disinfectant prepared by the method.

The purpose of the invention is realized by the following technical scheme:

the preparation method of the anti-caking high-stability potassium hydrogen persulfate active salt disinfectant comprises the following preparation steps:

(1) adding hydrogen peroxide and a stabilizer into a reactor, controlling the temperature to be 0-5 ℃, dropwise adding fuming sulfuric acid under the stirring condition, and controlling the temperature to be below 15 ℃ for heat preservation reaction to obtain peroxidation reaction liquid;

(2) dropwise adding a potassium carbonate or potassium hydroxide solution into the peroxidation reaction liquid in the step (1) to carry out neutralization reaction to obtain a neutralization liquid;

(3) adding liquid sodium silicate into the neutralized solution obtained in the step (2), stirring and dissolving uniformly, concentrating in vacuum, cooling and crystallizing, and centrifugally drying to obtain potassium monopersulfate composite salt;

(4) and (4) uniformly stirring and mixing the potassium monopersulfate composite salt obtained in the step (3) with a surfactant, an organic acid and an inorganic buffer salt to obtain the anti-caking high-stability potassium monopersulfate active salt disinfectant.

Further, the stabilizer in the step (1) is trisodium phosphate or sodium polyphosphate; the addition amount of the stabilizer is 0.5 to 2 percent of the mass of the hydrogen peroxide.

Further, the hydrogen peroxide and the oleum in the step (1) are diluted to the mass concentration of 20-50% before reaction.

Further, the molar ratio of the hydrogen peroxide to the fuming sulfuric acid in the step (1) is (1-3) to 1.

Furthermore, in the step (2), the molar ratio of the addition amount of the potassium carbonate or the potassium hydroxide to the oleum (calculated as sulfate radical) in terms of the molar amount of potassium is (4.8-5.2): 4.

Further, the adding amount of the liquid sodium silicate in the step (3) is 0.2-4% of the mass of the neutralizing liquid.

Further, the vacuum concentration in the step (3) is to perform vacuum concentration to saturation at the temperature of 45-55 ℃; the cooling crystallization refers to standing crystallization after cooling to-4 ℃.

Further, in the step (4), the surfactant is at least one of sodium alkyl benzene sulfonate and sodium alkyl sulfonate.

Further, in the step (4), the organic acid is at least one of malic acid, citric acid and tartaric acid.

Further, in the step (4), the inorganic buffer salt is sodium polyphosphate.

Further, in the step (4), the mass parts of the potassium monopersulfate composite salt, the surfactant, the organic acid and the inorganic buffer salt are as follows: 55-75 parts of potassium monopersulfate composite salt, 3-15 parts of surfactant, 5-20 parts of organic acid and 2-10 parts of inorganic buffer salt.

An anti-caking high-stability potassium hydrogen persulfate active salt disinfectant is prepared by the method.

Compared with the prior art, the invention has the beneficial effects that:

(1) according to the invention, a certain amount of liquid sodium silicate is added in the process of concentrating and crystallizing the potassium monopersulfate composite salt, so that the crystallization of the potassium monopersulfate composite salt in the solution is promoted to be separated out, and the utilization rate of raw materials and the yield of products are improved. And further discovers that the addition of the sodium silicate can obviously improve the anti-caking performance and stability of the potassium monopersulfate composite salt.

(2) The preparation method has the advantages of simple and convenient operation and low cost.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1

The preparation method of the anti-caking high-stability potassium hydrogen persulfate active salt disinfectant provided by the embodiment comprises the following specific preparation steps:

(1) adding 30% of hydrogen peroxide and 1% of stabilizer sodium tripolyphosphate by mass of the hydrogen peroxide into a reactor, controlling the temperature to be about 0 ℃, dropwise adding 30% of fuming sulfuric acid under the stirring condition, controlling the molar ratio of hydrogen peroxide to fuming sulfuric acid to be 2:1, and controlling the temperature to be below 15 ℃ for heat preservation reaction to obtain peroxidation reaction liquid.

(2) And (2) dropwise adding a potassium carbonate solution into the peroxidation reaction liquid in the step (1) to perform neutralization reaction, wherein the molar ratio of the potassium carbonate to fuming sulfuric acid (calculated as sulfate radical) is 5:4 based on the molar amount of potassium, so as to obtain a neutralized liquid.

(3) Respectively adding liquid sodium silicate with the mass concentration of 0, 0.1%, 0.2%, 0.4%, 0.8%, 1.5%, 3.0%, 4.0% and 5.0% into the neutralized solution obtained in the step (2), stirring and dissolving uniformly, carrying out vacuum concentration at about 50 ℃ until saturation, cooling to 0 ℃ for crystallization, and carrying out centrifugal drying to obtain the potassium monopersulfate composite salt.

(4) And (3) uniformly stirring and mixing 65 parts by mass of the potassium monopersulfate composite salt obtained in the step (3) with 10 parts by mass of sodium dodecyl benzene sulfonate, 20 parts by mass of citric acid and 5 parts by mass of sodium tripolyphosphate to obtain the anti-caking high-stability potassium monopersulfate active salt disinfectant. The active oxygen content of the obtained oxone active salt disinfectant and the ratio of particles passing through a 10-mesh screen were measured.

The product yield of the potassium monopersulfate composite salt obtained in the step (3) in the case of different liquid sodium silicate addition amount in this example (the mass of the obtained potassium monopersulfate composite salt minus the percentage of the sodium silicate addition amount to the raw material addition amount), and the anti-caking performance (the ratio of the weight of particles passing through a 10-mesh sieve after being packaged and stored in a sealed bag at normal temperature environment for 6 months to the weight of particles passing through a 10-mesh sieve before storage) and the stability (the retention rate of active oxygen after 7 days of 1% solution in 300ppm hard water at 20 ℃) of the finally obtained potassium monopersulfate active salt disinfectant were tested. The test results are shown in table 1 below.

TABLE 1

Sodium silicate addition	Product yield	Anti-caking Properties	Stability of
				0	72.3％	0.47	83.8％
0.1％	73.6％	0.69	88.7％
				0.2％	81.4％	0.74	90.5％
0.4％	86.6％	0.79	91.2％
				0.8％	89.7％	0.83	91.9％
1.5％	90.4％	0.87	92.8％
				3.0％	88.7％	0.90	94.0％
4.0％	83.6％	0.91	95.1％
				5.0％	75.2％	0.91	96.0％

It can be seen from the results in table 1 that, as the addition amount of sodium silicate increases, the product yield tends to increase first and then decrease, and when the addition amount of sodium silicate is in the range of 0.1% to 5.0%, the product yield is improved compared with the product yield obtained without adding sodium silicate, and it is presumed that the strong hydration of sodium silicate can promote the crystallization of the oxone compound salt, and the excessive addition amount of sodium silicate can increase the solution viscosity, affect the centrifugal separation process, and decrease the product yield. The product yield can reach more than 80 percent when the adding amount of the sodium silicate is 0.2 to 4.0 percent. With the increase of the addition of the sodium silicate, the anti-caking performance and the stability of the finally obtained product are increased, which shows that the introduction of the sodium silicate can obviously improve the anti-caking performance and the stability of the potassium monopersulfate composite salt. It is speculated that the silica generated in situ during the hydrolytic condensation and subsequent crystallization and drying processes of part of sodium silicate is beneficial to improving the anti-caking performance and stability of the potassium monopersulfate composite salt.

Example 2

The preparation method of the anti-caking high-stability potassium hydrogen persulfate active salt disinfectant provided by the embodiment comprises the following specific preparation steps:

(1) adding 30% of hydrogen peroxide and 1% of stabilizer sodium tripolyphosphate by mass of the hydrogen peroxide into a reactor, controlling the temperature to be about 0 ℃, dropwise adding 30% of fuming sulfuric acid under the stirring condition, controlling the molar ratio of hydrogen peroxide to fuming sulfuric acid to be 2:1, and controlling the temperature to be below 15 ℃ for heat preservation reaction to obtain peroxidation reaction liquid.

(2) And (2) dropwise adding a potassium carbonate solution into the peroxidation reaction liquid in the step (1) to perform neutralization reaction, wherein the molar ratio of the potassium carbonate to fuming sulfuric acid (calculated as sulfate radical) is 5:4 based on the molar amount of potassium, so as to obtain a neutralized liquid.

(3) Respectively adding liquid sodium silicate, sodium chloride, sodium sulfate, nano calcium silicate powder and nano silicon dioxide powder with the mass concentration of 1.0% into the neutralized liquid obtained in the step (2), stirring, dissolving or dispersing uniformly, taking no coprecipitator as a blank control, concentrating under vacuum at about 50 ℃ until the solution is saturated, cooling to 0 ℃ for crystallization, and centrifugally drying to obtain the potassium monopersulfate composite salt.

(4) And (3) uniformly stirring and mixing 65 parts by mass of the potassium monopersulfate composite salt obtained in the step (3) with 10 parts by mass of sodium dodecyl benzene sulfonate, 20 parts by mass of citric acid and 5 parts by mass of sodium tripolyphosphate to obtain the anti-caking high-stability potassium monopersulfate active salt disinfectant.

The product yield, anti-caking properties and stability were tested according to the method of example 1 with different crystalline co-precipitants added. The test results are shown in table 2 below.

TABLE 2

Different crystal coprecipitates	Product yield	Anti-caking Properties	Stability of
				Blank control	72.3％	0.47	83.8％
Liquid sodium silicate	91.1％	0.86	92.3％
				Sodium chloride	77.7％	0.52	83.4％
Sodium sulfate	78.2％	0.36	84.1％
				Nano calcium silicate powder	72.1％	0.89	86.7％
Nano silicon dioxide powder	72.5％	0.87	88.0％

As can be seen from the results in table 2, the product yield can be improved to some extent by adding soluble sodium salt as co-precipitation, but the improvement effect is significantly different from that of liquid sodium silicate, and the anti-caking property and stability are not significantly improved. Good anti-caking properties can be achieved by adding common inorganic anti-caking additives, but the product yield is not significantly improved. And the liquid sodium silicate adopted by the invention has more remarkable effect of improving the stability of the product.

Example 3

The preparation method of the anti-caking high-stability potassium hydrogen persulfate active salt disinfectant provided by the embodiment comprises the following specific preparation steps:

(1) adding 20% of hydrogen peroxide and 0.5% of stabilizer trisodium phosphate by mass of hydrogen peroxide into a reactor, controlling the temperature to be about 0 ℃, dropwise adding 50% fuming sulfuric acid under the stirring condition, controlling the molar ratio of hydrogen peroxide to fuming sulfuric acid to be 1:1, and controlling the temperature to be below 15 ℃ for heat preservation reaction to obtain peroxidation reaction liquid.

(2) And (2) dropwise adding a potassium hydroxide solution into the peroxidation reaction liquid in the step (1) to carry out neutralization reaction, wherein the molar ratio of the added potassium hydroxide to fuming sulfuric acid (calculated as sulfate radical) is 4.8:4 based on the molar amount of potassium, so as to obtain a neutralized liquid.

(3) And (3) adding liquid sodium silicate with the mass concentration of 1.0% into the neutralized liquid obtained in the step (2), stirring and dissolving uniformly, concentrating in vacuum at about 50 ℃ until the solution is saturated, cooling to 0 ℃ for crystallization, and centrifugally drying to obtain the potassium monopersulfate composite salt.

(4) And (3) uniformly stirring and mixing 55 parts by mass of the potassium monopersulfate composite salt obtained in the step (3) with 15 parts by mass of sodium dodecyl sulfate, 20 parts by mass of malic acid and 10 parts by mass of sodium tripolyphosphate to obtain the anti-caking high-stability potassium monopersulfate active salt disinfectant.

The product yield obtained in this example was 88.5%, the anti-caking performance test result was 0.82, and the stability test result was 91.5%.

Example 4

The preparation method of the anti-caking high-stability potassium hydrogen persulfate active salt disinfectant provided by the embodiment comprises the following specific preparation steps:

(1) adding 50% of hydrogen peroxide and 2% of stabilizer trisodium phosphate by mass of hydrogen peroxide into a reactor, controlling the temperature to be about 0 ℃, dropwise adding 20% fuming sulfuric acid under the stirring condition, controlling the molar ratio of hydrogen peroxide to fuming sulfuric acid to be 3:1, and controlling the temperature to be below 15 ℃ for heat preservation reaction to obtain peroxidation reaction liquid.

(2) And (2) dropwise adding a potassium hydroxide solution into the peroxidation reaction liquid in the step (1) to carry out neutralization reaction, wherein the molar ratio of the added potassium hydroxide to fuming sulfuric acid (calculated as sulfate radical) is 5.2:4 based on the molar amount of potassium, so as to obtain a neutralized liquid.

(3) And (3) adding liquid sodium silicate with the mass concentration of 1.0% into the neutralized liquid obtained in the step (2), stirring and dissolving uniformly, concentrating in vacuum at about 50 ℃ until the solution is saturated, cooling to 0 ℃ for crystallization, and centrifugally drying to obtain the potassium monopersulfate composite salt.

(4) And (3) uniformly stirring and mixing 75 parts by mass of the potassium monopersulfate composite salt obtained in the step (3) with 10 parts by mass of sodium dodecyl sulfate, 10 parts by mass of malic acid and 5 parts by mass of sodium tripolyphosphate to obtain the anti-caking high-stability potassium monopersulfate active salt disinfectant.

The product yield of this example was 91.7%, the anti-caking performance test result was 0.84, and the stability test result was 90.7%.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.