CN115872940B - Sodium dichloroisocyanurate particles and preparation method thereof - Google Patents
Sodium dichloroisocyanurate particles and preparation method thereof Download PDFInfo
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Abstract
The invention provides sodium dichloroisocyanurate particles and a preparation method thereof, and belongs to the field of sodium dichloroisocyanurate. The preparation method of the sodium dichloroisocyanurate particles comprises the following steps: chloridizing, neutralizing and granulating. According to the preparation method of the sodium dichloroisocyanurate particles, in the preparation process of sodium dichloroisocyanurate, the reaction process is stable, and side reactions are effectively inhibited; the production of a large amount of heat in the granulating process is effectively avoided, the heat accumulation of granulating materials is avoided, the decomposition of sodium dichloroisocyanurate by heating is avoided, and the fire safety hidden trouble is eliminated; effectively improves the stability of the sodium dichloroisocyanurate particles, improves the long-term storage performance and improves the solubility of the sodium dichloroisocyanurate particles after long-term storage.
Description
Technical Field
The invention relates to the field of sodium dichloroisocyanurate, in particular to sodium dichloroisocyanurate particles and a preparation method thereof.
Background
Sodium Dichloroisocyanurate (DCCNA) with molecular formula of C 3 Cl 2 N 3 NaO 3 The pure product is white powdery crystal or granule under normal temperature, and has chlorine smell.
Sodium dichloroisocyanurate is a high-efficiency disinfectant, has high solubility in water, lasting sterilization capability and low toxicity, and is widely used as a drinking water disinfectant and a household disinfectant. Meanwhile, sodium dichloroisocyanurate can hydrolyze hypochlorous acid in water, and can replace hypochlorous acid in some occasions, so that the sodium dichloroisocyanurate can also be used as a bleaching agent. In the prior art, the sodium dichloroisocyanurate has realized large-scale industrial production and lower price, so the sodium dichloroisocyanurate is widely applied to a plurality of industries. Sodium dichloroisonitrile urate has the following uses: wool shrink-proof treating agent, textile industry bleaching, disinfection and disinfectant of the breeding industry, civil disinfectant, industrial circulating water treating agent, food industry disinfectant, cleaning and disinfection of public places, etc.
In the prior art, the sodium dichloroisocyanurate product has the following characteristics: (1) The sterilizing and disinfecting capability is strong, the effective chlorine content in the sodium dichloroisocyanurate pure product is 64.5%, the effective chlorine content of the high-quality product is 60%, and the sterilizing and disinfecting effect is strong, and the sterilizing rate can reach 99% when the concentration reaches 20 ppm. Has strong killing effect on various bacteria, algae, fungi, germs and the like. (2) Has low toxicity and half-lethal dose (LD 50) of 1.67g/kg, and can be used for disinfecting food and drinking water. (3) The application range is wide, and the water-based sterilizing agent not only can be used for sterilizing food and beverage processing industries and drinking water, but also has good application effects in the aspects of industrial circulating water treatment, household sanitary sterilization, disinfection of the breeding industry and the like. (4) The effective chlorine utilization rate is high, the solubility of the sodium dichloroisocyanurate in water is very high, and 30g of the sodium dichloroisocyanurate can be dissolved in every 100mL of water at 25 ℃, so that the disinfection and sterilization effects of the sodium dichloroisocyanurate are fully exerted.
At present, the existing preparation method of sodium dichloroisocyanurate particles comprises the steps of dissolving cyanuric acid in an alkali solution, carrying out chlorination reaction with chlorine to generate sodium dichloroisocyanurate, and preparing sodium dichloroisocyanurate after the reaction of the sodium dichloroisocyanurate and sodium metal salt; and granulating the sodium dichloroisocyanurate to obtain sodium dichloroisocyanurate particles.
However, in the preparation process of sodium dichloroisocyanurate, particularly in the chlorination reaction process, the reaction process is unstable and side reaction is easy to occur, and byproducts are generated, so that the quality of the prepared sodium dichloroisocyanurate is influenced, and the disinfection and sterilization effects of sodium dichloroisocyanurate products are finally influenced; meanwhile, in the granulating process of sodium dichloroisocyanurate, the sodium dichloroisocyanurate is easy to thermally decompose due to the thermosensitive property of the sodium dichloroisocyanurate, and has the problem of fire when serious, so that potential safety hazards exist; furthermore, the stability of the sodium dichloroisocyanurate particles prepared by granulation needs to be further improved, and the sodium dichloroisocyanurate particles have the problem of higher loss of available chlorine after long-term storage under high-temperature and high-humidity conditions; moreover, after long-term storage, the sodium dichloroisocyanurate particles have the problem of reduced solubility, and the disinfection and sterilization effects are affected.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides the sodium dichloroisocyanurate particles and the preparation method thereof, which can inhibit side reactions in the preparation process of sodium dichloroisocyanurate, and the reaction process is stable; meanwhile, in the granulating process of the sodium dichloroisocyanurate, a large amount of heat is effectively avoided, the sodium dichloroisocyanurate is prevented from being decomposed by heating, and potential safety hazards are eliminated; further, the stability of the sodium dichloroisocyanurate particles is effectively improved, and the problems of effective chlorine loss and solubility reduction after long-term storage under high-temperature and high-humidity conditions are solved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation method of the sodium dichloroisocyanurate particles comprises the following steps: chloridizing, neutralizing and granulating.
The chloridization is carried out, deionized water, cyanuric acid and modified calcium carbonate are mixed, and stirred for a certain time; introducing chlorine to carry out chlorination reaction under stirring; in the chlorination reaction process, the chlorination reaction temperature is controlled to be 35-40 ℃; stopping introducing chlorine when the pH value of the material in the chlorination kettle is 1.5-2, keeping the temperature and continuing stirring for a certain time, filtering out solid matters, and leaching and filtering to obtain dichloro isocyanuric acid;
in the chlorination, the weight ratio of deionized water to cyanuric acid to modified calcium carbonate is 100-120:15-20:1.2-1.5.
The modified calcium carbonate is prepared by the following steps: preparing emulsion and modifying.
The emulsion is prepared, sodium carbonate and polyvinylpyrrolidone are put into deionized water and stirred uniformly to prepare a first liquid; adding sodium dodecyl benzene sulfonate into deionized water, and stirring until the sodium dodecyl benzene sulfonate is completely dissolved to prepare a second liquid; mixing the first liquid and the second liquid, and performing ultrasonic dispersion for a certain time to obtain emulsion;
in the emulsion preparation, the weight ratio of sodium carbonate to polyvinylpyrrolidone to deionized water in the first liquid is 11-13:2.5-3.5:100;
in the second liquid, the weight ratio of the sodium dodecyl benzene sulfonate to the deionized water is 0.4-0.5:100;
the volume ratio of the first liquid to the second liquid is 2-2.2:1.
Adding calcium chloride and polyvinylpyrrolidone into deionized water, stirring uniformly to prepare a third liquid, heating to 55-65 ℃, adding the emulsion into the third liquid under stirring, keeping the temperature and stirring for a certain time, standing for 10-16h, and filtering out solid matters; washing the solid by deionized water, soaking the solid in fourth liquid with the volume of 2-4 times, filtering out the solid after soaking for a certain time, and placing the solid at the temperature of 70-80 ℃, and carrying out heat preservation and drying until the weight is constant to obtain modified calcium carbonate;
in the modification, the fourth liquid is tetraethylammonium bromide aqueous solution with the concentration of 7-8wt%;
in the third liquid, the weight ratio of the calcium chloride to the polyvinylpyrrolidone to the deionized water is 2-2.5:0.5-0.8:100;
the volume ratio of the emulsion to the third liquid is 1.5-1.6:1.
The neutralization is carried out by mixing dichloro isocyanuric acid prepared in the chlorination step with sodium carbonate, and carrying out neutralization reaction to obtain dichloro isocyanuric acid sodium;
in the neutralization, the weight ratio of the dichloro isocyanuric acid to the sodium carbonate is 4.5-5:1.
The granulation is carried out by putting dichlor isonitrile sodium urea, modified stabilizer, polyethylene glycol 4000, hydroxy ethylidene diphosphonate tetrasodium and sodium sulfate into rotary drum granulator, spraying polyvinylpyrrolidone water solution under rotary drum rotation condition, granulating; after the granulation is completed, the granules obtained by the granulation are dried to obtain sodium dichloroisocyanurate granules;
in the granulation, the weight ratio of the dichloroisonitrile sodium urea to the modified stabilizer to the polyethylene glycol 4000 to the hydroxy ethylidene disodium bisphosphonate to the sodium sulfate to the polyvinylpyrrolidone aqueous solution is 100-110:7-8:2-2.5:1-1.6:1-2:10-14;
in the polyvinylpyrrolidone aqueous solution, the polyvinylpyrrolidone concentration is 20-25wt%;
the rotating speed of the rotary drum granulator is 10-14rpm.
The preparation method of the modified stabilizer comprises the steps of uniformly ball-milling talcum powder, sodium silicate, alpha-alkenyl sodium sulfonate and deionized water, mixing with sodium citrate and carboxymethyl starch sodium, and continuing ball milling for a certain time to obtain a ball-milled product; drying the ball-milled material to prepare a modified stabilizer;
in the preparation of the modified stabilizer, the weight ratio of talcum powder, sodium silicate, alpha-alkenyl sodium sulfonate, deionized water, sodium citrate and carboxymethyl starch sodium is 10-12:1-2:8-10:8-10:3-4:1-2.
Sodium dichloroisocyanurate particles are prepared by adopting the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the sodium dichloroisocyanurate particles, the modified calcium carbonate prepared by a specific method is arranged in the chlorination process of the sodium dichloroisocyanurate particles, sodium dodecyl benzene sulfonate and tetraethylammonium bromide can be slowly released by the modified calcium carbonate in the chlorination reaction process, the whole chlorination reaction process is stable, the occurrence of side reactions is effectively inhibited, and the effective chlorine content of the prepared sodium dichloroisocyanurate can reach 63.83-64.24%.
(2) According to the preparation method of the sodium dichloroisocyanurate particles, a granulating raw material with specific composition and proportion is arranged in the granulating process of the sodium dichloroisocyanurate particles, a modified stabilizer is arranged in the granulating raw material, and a polyvinylpyrrolidone aqueous solution is sprayed in the granulating process of a rotary drum granulator. On one hand, a large amount of heat is effectively avoided in the granulating process, the heat accumulation of granulating materials is avoided, the sodium dichloroisocyanurate is prevented from being decomposed by heating, and the fire safety hidden trouble is eliminated; on the other hand, the stability of the sodium dichloroisocyanurate particles is effectively improved, the long-term storage performance in high-temperature and high-humidity environments is improved, the effective chlorine loss after long-term storage is reduced, and the solubility of the sodium dichloroisocyanurate particles after long-term storage is improved.
(3) The sodium dichloroisocyanurate particles disclosed by the invention have the advantages that after being stored for 60 days under the environment that the temperature is 54 ℃ and the relative humidity is 60%, the effective chlorine loss is 2.6-3.1%, the solubility is almost the same as that of the sodium dichloroisocyanurate particles which are prepared newly, and the sodium dichloroisocyanurate particles are loose, free of adhesion and free of caking.
(4) The sodium dichloroisocyanurate particles disclosed by the invention have the advantages that after being stored for 60 days under the environment that the temperature is 45 ℃ and the relative humidity is 75%, the effective chlorine loss is 2.2-2.6%, the solubility is almost the same as that of the sodium dichloroisocyanurate particles which are prepared newly, and the sodium dichloroisocyanurate particles are loose, free of adhesion and free of caking.
(5) The sodium dichloroisocyanurate particles disclosed by the invention have the advantages that after being stored for 180 days under the environment that the temperature is 30 ℃ and the relative humidity is 40%, the effective chlorine loss is 0.8-1.1%, the solubility is almost the same as that of the sodium dichloroisocyanurate particles which are prepared newly, and the sodium dichloroisocyanurate particles are loose, free of adhesion and free of caking.
(6) The preparation method of the sodium dichloroisocyanurate particles has the advantages of simple and efficient production process and high safety, and is suitable for large-scale industrial production.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
A method for preparing sodium dichloroisocyanurate particles, which comprises the following steps: chloridizing, neutralizing and granulating.
1. Chlorination
Sequentially adding a preset amount of deionized water, cyanuric acid and modified calcium carbonate into a chlorination kettle, and stirring at 100rpm for 20min; then under the stirring condition of 30rpm, introducing chlorine into a chlorination kettle at an introducing rate of 5kg/min for chlorination reaction; in the chlorination reaction process, controlling the chlorination reaction temperature to be 35 ℃; stopping introducing chlorine when the pH value of the material in the chlorination kettle is 1.5, keeping the temperature and continuing stirring for 1h, filtering out solid matters, leaching the solid matters by using deionized water with the volume of 2 times, and carrying out suction filtration to obtain the dichloro isocyanuric acid.
Wherein the weight ratio of deionized water to cyanuric acid to modified calcium carbonate is 100:15:1.2.
The water content of the dichloro isocyanuric acid obtained in the chlorination step is 15wt%.
The modified calcium carbonate is prepared by the following method:
1) Preparation of an emulsion
Adding sodium carbonate and polyvinylpyrrolidone into deionized water, and uniformly stirring to obtain a first liquid; adding sodium dodecyl benzene sulfonate into deionized water, and stirring until the sodium dodecyl benzene sulfonate is completely dissolved to prepare a second liquid; mixing the first liquid and the second liquid, and performing ultrasonic dispersion for 20min to obtain emulsion.
In the first liquid, the weight ratio of the sodium carbonate to the polyvinylpyrrolidone to the deionized water is 11:2.5:100.
In the second liquid, the weight ratio of the sodium dodecyl benzene sulfonate to the deionized water is 0.4:100.
The volume ratio of the first liquid to the second liquid is 2:1.
In the ultrasonic dispersion process, the ultrasonic frequency is 35kHz, and the ultrasonic power is 600W.
2) Modification
Adding calcium chloride and polyvinylpyrrolidone into deionized water, stirring uniformly to obtain a third liquid, heating to 55 ℃, adding the emulsion into the third liquid under the stirring condition of 500rpm, keeping the temperature and stirring for 2 hours, standing for 10 hours, and filtering out solid matters; washing the solid by 3 times of deionized water, immersing the solid into 2 times of fourth liquid, immersing for 2 hours, filtering out, placing at 70 ℃, and drying at a constant temperature until the weight is constant, thus obtaining the modified calcium carbonate.
Wherein the fourth liquid is tetraethylammonium bromide aqueous solution with concentration of 7 wt%.
In the third liquid, the weight ratio of the calcium chloride to the polyvinylpyrrolidone to the deionized water is 2:0.5:100.
The volume ratio of the emulsion to the third liquid was 1.5:1.
2. Neutralization
Transferring the dichloro isocyanuric acid prepared in the chlorination step into a neutralization kettle, and then adding sodium carbonate for neutralization reaction to prepare the dichloro isocyanuric acid sodium.
Wherein the weight ratio of the dichloro isocyanuric acid to the sodium carbonate is 4.5:1.
The available chlorine content of the prepared sodium dichloroisocyanurate is 64.01%.
3. Granulating
Adding sodium dichloroisonitrile urea, a modified stabilizer, polyethylene glycol 4000, tetra sodium hydroxyethylidene diphosphonate and sodium sulfate into a rotary drum granulator, and keeping the rotating speed of the rotary drum at 10rpm; spraying polyvinylpyrrolidone aqueous solution under the rotation condition of the rotary drum, and granulating; after the granulation is completed, transferring the granules obtained by the granulation into a fluidized bed dryer, controlling the drying temperature to be 50 ℃, and drying to obtain the sodium dichloroisocyanurate granules.
Wherein, the weight ratio of the dichloroisonitrile sodium urea to the modified stabilizer to the polyethylene glycol 4000 to the hydroxy ethylidene diphosphonic acid tetrasodium, the sodium sulfate to the polyvinylpyrrolidone aqueous solution is 100:7:2:1:1:10.
In the aqueous solution of polyvinylpyrrolidone, the concentration of polyvinylpyrrolidone was 20wt%.
The modified stabilizer is prepared by the following steps of putting talcum powder, sodium silicate, alpha-sodium alkenyl sulfonate and deionized water into a ball mill, controlling the ball-material ratio to be 4:1, and performing ball milling treatment for 5min at the speed of 300 rpm; continuously adding sodium citrate and sodium carboxymethyl starch, and continuously ball-milling for 10min to obtain ball-milled materials; and drying the ball-milled material by a rotary drum dryer to obtain the modified stabilizer.
Wherein, the weight ratio of talcum powder, sodium silicate, alpha-alkenyl sodium sulfonate, deionized water, sodium citrate and carboxymethyl starch sodium is 10:1:8:8:3:1.
Example 2
A method for preparing sodium dichloroisocyanurate particles, which comprises the following steps: chloridizing, neutralizing and granulating.
1. Chlorination
Sequentially adding a preset amount of deionized water, cyanuric acid and modified calcium carbonate into a chlorination kettle, and stirring at 150rpm for 30min; then under the stirring condition of 40rpm, introducing chlorine into a chlorination kettle at an introducing rate of 5.5kg/min for chlorination reaction; in the chlorination reaction process, the chlorination reaction temperature is controlled to be 38 ℃; stopping introducing chlorine when the pH value of the material in the chlorination kettle is 1.8, keeping the temperature and continuing stirring for 1.2 hours, filtering out solid matters, leaching the solid matters by using deionized water with the volume of 3 times, and carrying out suction filtration to obtain the dichloro isocyanuric acid.
Wherein the weight ratio of deionized water to cyanuric acid to modified calcium carbonate is 110:18:1.3.
The water content of the dichloro isocyanuric acid obtained in the chlorination step is 12wt%.
The modified calcium carbonate is prepared by the following method:
1) Preparation of an emulsion
Adding sodium carbonate and polyvinylpyrrolidone into deionized water, and uniformly stirring to obtain a first liquid; adding sodium dodecyl benzene sulfonate into deionized water, and stirring until the sodium dodecyl benzene sulfonate is completely dissolved to prepare a second liquid; mixing the first liquid and the second liquid, and performing ultrasonic dispersion for 25min to obtain emulsion.
In the first liquid, the weight ratio of the sodium carbonate to the polyvinylpyrrolidone to the deionized water is 12:3:100.
In the second liquid, the weight ratio of the sodium dodecyl benzene sulfonate to the deionized water is 0.45:100.
The volume ratio of the first liquid to the second liquid is 2.1:1.
In the ultrasonic dispersion process, the ultrasonic frequency is 38kHz, and the ultrasonic power is 700W.
2) Modification
Adding calcium chloride and polyvinylpyrrolidone into deionized water, stirring uniformly to obtain a third liquid, heating to 60 ℃, adding the emulsion into the third liquid under the stirring condition of 600rpm, keeping the temperature and stirring for 2.5 hours, standing for 12 hours, and filtering out solid matters; washing the solid by 5 times of deionized water, immersing the solid into 3 times of fourth liquid, immersing for 2.5 hours, filtering out, placing at 75 ℃, and drying at a constant temperature until the weight is constant, thus obtaining the modified calcium carbonate.
Wherein the fourth liquid is tetraethylammonium bromide aqueous solution with concentration of 7.5 wt%.
In the third liquid, the weight ratio of the calcium chloride to the polyvinylpyrrolidone to the deionized water is 2.3:0.6:100.
The volume ratio of the emulsion to the third liquid was 1.55:1.
2. Neutralization
Transferring the dichloro isocyanuric acid prepared in the chlorination step into a neutralization kettle, and then adding sodium carbonate for neutralization reaction to prepare the dichloro isocyanuric acid sodium.
Wherein the weight ratio of the dichloro isocyanuric acid to the sodium carbonate is 4.8:1.
The available chlorine content of the prepared sodium dichloroisocyanurate is 64.24%.
3. Granulating
Adding sodium dichloroisonitrile urea, a modified stabilizer, polyethylene glycol 4000, tetra sodium hydroxyethylidene bisphosphonate and sodium sulfate into a rotary drum granulator, and keeping the rotating speed of the rotary drum at 12rpm; spraying polyvinylpyrrolidone aqueous solution under the rotation condition of the rotary drum, and granulating; after the granulation is completed, transferring the granules obtained by the granulation into a fluidized bed dryer, controlling the drying temperature to be 55 ℃, and drying to obtain the sodium dichloroisocyanurate granules.
Wherein, the weight ratio of the dichloroisonitrile sodium urea to the modified stabilizer to the polyethylene glycol 4000 to the hydroxy ethylidene tetra sodium diphosphonate to the sodium sulfate to the polyvinylpyrrolidone aqueous solution is 105:7.5:2.3:1.4:1.5:12.
In the aqueous polyvinylpyrrolidone solution, the concentration of polyvinylpyrrolidone was 22wt%.
The modified stabilizer is prepared by the following steps of putting talcum powder, sodium silicate, alpha-sodium alkenyl sulfonate and deionized water into a ball mill, controlling the ball-material ratio to be 5:1, and performing ball milling treatment for 8min at the speed of 350 rpm; continuously adding sodium citrate and sodium carboxymethyl starch, and continuously ball-milling for 15min to obtain ball-milled materials; and drying the ball-milled material by a rotary drum dryer to obtain the modified stabilizer.
Wherein, the weight ratio of talcum powder, sodium silicate, alpha-alkenyl sodium sulfonate, deionized water, sodium citrate and carboxymethyl starch sodium is 11:1.5:9:89:3.6:1.5.
Example 3
A method for preparing sodium dichloroisocyanurate particles, which comprises the following steps: chloridizing, neutralizing and granulating.
1. Chlorination
Sequentially adding a preset amount of deionized water, cyanuric acid and modified calcium carbonate into a chlorination kettle, and stirring at 200rpm for 50min; then under the stirring condition of 50rpm, introducing chlorine into a chlorination kettle at an introduction rate of 6kg/min for chlorination reaction; in the chlorination reaction process, the temperature of the chlorination reaction is controlled to be 40 ℃; stopping introducing chlorine when the pH value of the material in the chlorination kettle is 2, keeping the temperature and continuously stirring for 1.5 hours, filtering out solid matters, leaching the solid matters by adopting deionized water with the volume of 4 times, and carrying out suction filtration to obtain the dichloro isocyanuric acid.
Wherein the weight ratio of deionized water to cyanuric acid to modified calcium carbonate is 120:20:1.5.
The water content of the dichloro isocyanuric acid obtained in the chlorination step is 13wt%.
The modified calcium carbonate is prepared by the following method:
1) Preparation of an emulsion
Adding sodium carbonate and polyvinylpyrrolidone into deionized water, and uniformly stirring to obtain a first liquid; adding sodium dodecyl benzene sulfonate into deionized water, and stirring until the sodium dodecyl benzene sulfonate is completely dissolved to prepare a second liquid; mixing the first liquid and the second liquid, and performing ultrasonic dispersion for 30min to obtain emulsion.
In the first liquid, the weight ratio of the sodium carbonate to the polyvinylpyrrolidone to the deionized water is 13:3.5:100.
In the second liquid, the weight ratio of the sodium dodecyl benzene sulfonate to the deionized water is 0.5:100.
The volume ratio of the first liquid to the second liquid is 2.2:1.
In the ultrasonic dispersion process, the ultrasonic frequency is 40kHz, and the ultrasonic power is 800W.
2) Modification
Adding calcium chloride and polyvinylpyrrolidone into deionized water, stirring uniformly to obtain a third liquid, heating to 65 ℃, adding the emulsion into the third liquid under the stirring condition of 700rpm, keeping the temperature, stirring for 3 hours, standing for 16 hours, and filtering out solid matters; washing the solid by using deionized water with the volume of 6 times, immersing the solid into fourth liquid with the volume of 4 times, immersing for 3 hours, filtering out, placing the solid at the temperature of 80 ℃, and drying the solid at the temperature of constant temperature to obtain the modified calcium carbonate.
Wherein the fourth liquid is tetraethylammonium bromide aqueous solution with concentration of 8 wt%.
In the third liquid, the weight ratio of the calcium chloride to the polyvinylpyrrolidone to the deionized water is 2.5:0.8:100.
The volume ratio of the emulsion to the third liquid was 1.6:1.
2. Neutralization
Transferring the dichloro isocyanuric acid prepared in the chlorination step into a neutralization kettle, and then adding sodium carbonate for neutralization reaction to prepare the dichloro isocyanuric acid sodium.
Wherein the weight ratio of the dichloro isocyanuric acid to the sodium carbonate is 5:1.
The available chlorine content of the prepared sodium dichloroisocyanurate was 63.83%.
3. Granulating
Adding sodium dichloroisonitrile urea, a modified stabilizer, polyethylene glycol 4000, tetra sodium hydroxyethylidene bisphosphonate and sodium sulfate into a rotary drum granulator, and keeping the rotating speed of the rotary drum at 14rpm; spraying polyvinylpyrrolidone aqueous solution under the rotation condition of the rotary drum, and granulating; after the granulation is completed, transferring the granules obtained by the granulation into a fluidized bed dryer, controlling the drying temperature to be 60 ℃, and drying to obtain the sodium dichloroisocyanurate granules.
Wherein, the weight ratio of the dichloroisonitrile sodium urea to the modified stabilizer to the polyethylene glycol 4000 to the hydroxy ethylidene tetra sodium diphosphonate to the sodium sulfate to the polyvinylpyrrolidone aqueous solution is 110:8:2.5:1.6:2:14.
In the aqueous polyvinylpyrrolidone solution, the concentration of polyvinylpyrrolidone was 25wt%.
The modified stabilizer is prepared by the following steps of putting talcum powder, sodium silicate, alpha-sodium alkenyl sulfonate and deionized water into a ball mill, controlling the ball-material ratio to be 6:1, and performing ball milling treatment for 10min at the speed of 400 rpm; continuously adding sodium citrate and sodium carboxymethyl starch, and continuously ball-milling for 20min to obtain a ball-milled product; and drying the ball-milled material by a rotary drum dryer to obtain the modified stabilizer.
Wherein, the weight ratio of talcum powder, sodium silicate, alpha-sodium alkenyl sulfonate, deionized water, sodium citrate and sodium carboxymethyl starch is 12:2:10:10:4:2.
Comparative example 1
The technical scheme of the embodiment 2 is adopted, and the difference is that: in the chlorination step, modified calcium carbonate is omitted, and calcium carbonate, sodium dodecyl benzene sulfonate and tetraethylammonium bromide are added instead. The ratio of the parts by weight of cyanuric acid, calcium carbonate, sodium dodecyl benzene sulfonate and tetraethyl ammonium bromide is 18:1.3:0.5:0.3.
Wherein the effective chlorine content of the sodium dichloroisocyanurate prepared in the neutralization step is 59.83 percent.
Comparative example 2
The technical scheme of the embodiment 2 is adopted, and the difference is that: 1) In the granulating step, talcum powder, sodium silicate and sodium citrate are adopted to replace the original weight parts of modified stabilizer; the weight ratio of talcum powder to sodium silicate to sodium citrate is 11:1.5:3.5. 2) The polyvinylpyrrolidone aqueous solution is directly added into the rotary drum granulator, and the mode of spraying and adding in the rotation of the rotary drum is not adopted any more.
The sodium dichloroisocyanurate particles prepared in examples 1-3 and comparative examples 1-2 were placed in an environment with a temperature of 54 ℃ and a relative humidity of 60%, and after being stored for 60 days, the sodium dichloroisocyanurate particles were tested for effective chlorine loss, dissolution performance and anti-caking performance, and specific test results are as follows:
the sodium dichloroisocyanurate particles prepared in examples 1-3 and comparative examples 1-2 were placed in an environment with a temperature of 45 ℃ and a relative humidity of 75%, and after 60 days of storage, the sodium dichloroisocyanurate particles were tested for effective chlorine loss, dissolution performance and anti-caking performance, and specific test results are as follows:
the sodium dichloroisocyanurate particles prepared in examples 1-3 and comparative examples 1-2 were placed in an environment with a temperature of 30 ℃ and a relative humidity of 40%, and after being stored for 180 days, the sodium dichloroisocyanurate particles were tested for effective chlorine loss, dissolution performance and anti-caking performance, and specific test results are as follows:
according to the invention, in the chlorination process of preparing the sodium dichloroisocyanurate particles, the modified calcium carbonate prepared by a specific method is arranged, the modified calcium carbonate can slowly release sodium dodecyl benzene sulfonate and tetraethylammonium bromide in the chlorination reaction process, the whole chlorination reaction process is stable, the occurrence of side reaction is inhibited, and the effective chlorine content of the prepared sodium dichloroisocyanurate can reach 63.83-64.24%.
Meanwhile, a granulating raw material with specific composition and proportion is arranged in the granulating process of the sodium dichloroisocyanurate particles, a modified stabilizer is arranged in the granulating raw material, and a polyvinylpyrrolidone aqueous solution is sprayed in the granulating process of a rotary drum granulator. On one hand, a large amount of heat is effectively avoided in the granulating process, the heat accumulation of granulating materials is avoided, the sodium dichloroisocyanurate is prevented from being decomposed by heating, and the fire safety hidden trouble is eliminated; on the other hand, the stability of the sodium dichloroisocyanurate particles is effectively improved, the long-term storage performance in high-temperature and high-humidity environments is improved, the effective chlorine loss after long-term storage is reduced, and the problem of the reduction of the solubility of the sodium dichloroisocyanurate particles after long-term storage is solved.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the sodium dichloroisocyanurate particles is characterized by comprising the following steps of: chloridizing, neutralizing and granulating;
the chloridization is carried out, deionized water, cyanuric acid and modified calcium carbonate are mixed, and stirred for a certain time; introducing chlorine to carry out chlorination reaction under stirring; in the chlorination reaction process, the chlorination reaction temperature is controlled to be 35-40 ℃; stopping introducing chlorine when the pH value of the material in the chlorination kettle is 1.5-2, keeping the temperature and continuing stirring for a certain time, filtering out solid matters, and leaching and filtering to obtain dichloro isocyanuric acid;
in the chlorination, the weight ratio of deionized water to cyanuric acid to modified calcium carbonate is 100-120:15-20:1.2-1.5;
the modified calcium carbonate is prepared by the following steps: preparing emulsion and modifying;
the emulsion is prepared, sodium carbonate and polyvinylpyrrolidone are put into deionized water and stirred uniformly to prepare a first liquid; adding sodium dodecyl benzene sulfonate into deionized water, and stirring until the sodium dodecyl benzene sulfonate is completely dissolved to prepare a second liquid; mixing the first liquid and the second liquid, and performing ultrasonic dispersion for a certain time to obtain emulsion;
adding calcium chloride and polyvinylpyrrolidone into deionized water, stirring uniformly to prepare a third liquid, heating to 55-65 ℃, adding the emulsion into the third liquid under stirring, keeping the temperature and stirring for a certain time, standing for 10-16h, and filtering out solid matters; washing the solid by deionized water, soaking the solid in fourth liquid with the volume of 2-4 times, filtering out the solid after soaking for a certain time, and placing the solid at the temperature of 70-80 ℃, and carrying out heat preservation and drying until the weight is constant to obtain modified calcium carbonate;
in the modification, the fourth liquid is tetraethylammonium bromide aqueous solution with the concentration of 7-8wt%;
the neutralization is carried out by mixing dichloro isocyanuric acid prepared in the chlorination step with sodium carbonate, and carrying out neutralization reaction to obtain dichloro isocyanuric acid sodium;
in the neutralization, the weight ratio of the dichloro isocyanuric acid to the sodium carbonate is 4.5-5:1;
the granulation is carried out by putting dichlor isonitrile sodium urea, modified stabilizer, polyethylene glycol 4000, hydroxy ethylidene diphosphonate tetrasodium and sodium sulfate into rotary drum granulator, spraying polyvinylpyrrolidone water solution under rotary drum rotation condition, granulating; after the granulation is completed, the granules obtained by the granulation are dried to obtain sodium dichloroisocyanurate granules;
in the granulation, the weight ratio of the dichloroisonitrile sodium urea to the modified stabilizer to the polyethylene glycol 4000 to the hydroxy ethylidene disodium bisphosphonate to the sodium sulfate to the polyvinylpyrrolidone aqueous solution is 100-110:7-8:2-2.5:1-1.6:1-2:10-14;
in the polyvinylpyrrolidone aqueous solution, the polyvinylpyrrolidone concentration is 20-25wt%;
the preparation method of the modified stabilizer comprises the steps of uniformly ball-milling talcum powder, sodium silicate, alpha-alkenyl sodium sulfonate and deionized water, mixing with sodium citrate and carboxymethyl starch sodium, and continuing ball milling for a certain time to obtain a ball-milled product; drying the ball-milled material to prepare a modified stabilizer;
in the preparation of the modified stabilizer, the weight ratio of talcum powder, sodium silicate, alpha-alkenyl sodium sulfonate, deionized water, sodium citrate and carboxymethyl starch sodium is 10-12:1-2:8-10:8-10:3-4:1-2.
2. The method for preparing sodium dichloroisocyanurate particles according to claim 1, wherein in the emulsion, the weight ratio of sodium carbonate, polyvinylpyrrolidone and deionized water in the first liquid is 11-13:2.5-3.5:100;
in the second liquid, the weight ratio of the sodium dodecyl benzene sulfonate to the deionized water is 0.4-0.5:100.
3. The method for preparing sodium dichloroisocyanurate particles according to claim 1, wherein the volume ratio of the first liquid to the second liquid in the prepared emulsion is 2-2.2:1.
4. The method for preparing sodium dichloroisocyanurate particles according to claim 1, wherein in the modification, the ratio of the parts by weight of calcium chloride, polyvinylpyrrolidone and deionized water in the third liquid is 2-2.5:0.5-0.8:100;
the volume ratio of the emulsion to the third liquid is 1.5-1.6:1.
5. The method for producing sodium dichloroisocyanurate particles according to claim 1, wherein in the granulating, a rotating speed of a drum granulator is 10 to 14rpm.
6. Sodium dichloroisocyanurate particles prepared by the preparation method according to any one of claims 1 to 5.
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| CN1073346C (en) * | 1998-06-05 | 2001-10-24 | 李雪松 | Disinfecting detergent tablet |
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| CN110437169B (en) * | 2019-07-31 | 2022-06-24 | 青岛职业技术学院 | Preparation method of sodium dichloroisocyanurate |
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