CN1781846A - Process for preparing potassium hydrogen persulfate composite salts - Google Patents
Process for preparing potassium hydrogen persulfate composite salts Download PDFInfo
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- CN1781846A CN1781846A CN 200410084727 CN200410084727A CN1781846A CN 1781846 A CN1781846 A CN 1781846A CN 200410084727 CN200410084727 CN 200410084727 CN 200410084727 A CN200410084727 A CN 200410084727A CN 1781846 A CN1781846 A CN 1781846A
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Abstract
The present invention discloses the preparation process of potassium monopersulfate composite salt. The preparation process includes the following steps: the oxidation reaction between hydrogen peroxide and fuming sulfuric acid; the neutralization between the potassium hydroxide aqua and the product of the preceding step to obtain the water solution of the destination product potassium monopersulfate; concentration; adding stabilizer, cooling to crystallize, collecting solid potassium monopersulfate, and drying to obtain the product. The reaction may be performed in a conventional reactor, and the process of the present invention has simple operation, no need of special equipment and high product stability, and is suitable for industrial production.
Description
Technical Field
The invention relates to a preparation method of potassium peroxymonosulfate composite salt.
Background
The potassium monopersulfate complex salt is also called potassium monopersulfate complex salt, potassium monopersulfate complex salt or potassium monopersulfate complex salt, is a free flowing white granular powder, is easily soluble in water, and has a molecular formula of KHSO5。
The potassium hydrogen peroxymonosulfate composite salt is an effective oxidant and disinfectant, is stable and convenient, has wide application, and relates to the application fields of oral cavity cleaning, swimming pool and hot spring water body disinfection, circuit board etching agent, paper pulp bleaching, wool fabric shrink-proof treatment, precious metal extraction and the like; the potassium hydrogen peroxymonosulfate composite salt is also an important auxiliary agent in organic synthesis, can epoxidize double bonds in organic molecules, and is a free radical initiator for a plurality of polymerization reactions; the potassium monopersulfate composite salt can also be used as an oxidant for sulfur-containing substances such as hydrogen sulfide and the like in wastewater treatment, a low-temperature oxygen bleaching agent in a detergent, an oxygen supply agent in the breeding industry and the like.
The current method for industrially preparing the potassium peroxymonosulfate composite salt is an anodic oxidation method, namely, a platinum electrolytic cell is used for electrolyzing sulfuric acid to generate peroxydisulfuric acid, then the peroxydisulfuric acid is hydrolyzed into peroxymonosulfate at room temperature, and potassium carbonate is added to obtain the potassium peroxymonosulfate composite salt.
In order to solve the problem of high energy consumption and large investment in preparing potassium peroxymonosulfate composite salt by an anodic oxidation method, a U.S. granted patent No. US 5,139,763 discloses a chemical preparation method of potassium peroxymonosulfate composite salt, which comprises the steps of preparing Caro's acid by reacting hydrogen peroxide and fuming sulfuric acid, and preparing KHSO by reacting common potassium compound with Caro's acid5、KHSO4And K2A mixture of SO, adding themixture to a KHSO-rich atmosphere5Adjusting KHSO in the solution5/(KHSO4+K2SO) in such a proportion that the final mixture isMedium KHSO5/(KHSO4+K2SO) is between 1.4 and 6.1, the mixture is separated to form a slurry sample, crystallized and dried by a vacuum tube to ensure that the final weight concentration is between 14 and 60 percent. Although the method overcomes the problem of high energy consumption of an electrochemical method, the reaction steps are relatively complicated, and the following problems still exist: 1) further preparation of KHSO-rich5To increase KHSO5/(KHSO4+K2SO) ratio; 2) adding MgCO3To prevent caking of the mixture, etc.; 3) when Caro's acid is prepared, hydrogen peroxide and fuming sulfuric acid are subjected to oxidation reaction, the reaction temperature is high, heat release is severe, boiling is easy to occur, a reaction device is opened, danger is easy to cause, and environmental sanitation is influenced; 4) the prepared potassium hydrogen peroxymonosulfate composite salt has high humidity and low active oxygen content, and is difficult to meet the quality requirement of products. Therefore, the key point of the industrial preparation of the potassium monopersulfate composite salt is to find a simple, efficient and environment-friendly preparation method.
Chinese patent application publication CN 1528660The preparation method comprises the steps of firstly adding hydrogen peroxide containing a stabilizer into a four-neck flask, then dropwise adding oleum to react, dropwise adding a potassium hydroxide solution, simultaneously adding a crystal form modifier, performing vacuum concentration, cooling crystallization and drying to obtain a potassium monopersulfate composite salt dry product, wherein the concentration of the hydrogen peroxide is 45-80%, and the concentration of the oleum is 35-65%. Themethod does not need to prepare KHSO-rich product in advance5The mother liquor is added with the stabilizer and the crystal form modifier, so that the average active oxygen loss rate per month is effectively reduced, and 20-200-mesh particles account for more than 90 percent. But still has the problems of high impurity content of the product, low vacuum concentration efficiency, high water content after concentration, serious pollution in the open preparation process, adverse influence on human bodies and environment and certain problems in large-scale industrial application caused by adding the stabilizer and the crystal form modifier. Therefore, the key of the current problem is to find a safe, environment-friendly and efficient method for preparing the potassium monopersulfate composite salt.
Disclosure of Invention
The invention aims to solve the technical problem of disclosing a novel preparation method of potassium peroxymonosulfate composite salt so as to overcome the defects in the prior art.
The preparation method comprises the following steps:
(1) firstly, carrying out oxidation reaction on hydrogen peroxide and fuming sulfuric acid to obtain strong acid, also called Caro's acid, wherein the reaction formula is as follows:
the reaction temperature is 35-40 ℃, the optimal temperature is 37 ℃, and the reaction time is 1-4 hours;
the molar ratio of the hydrogen peroxide to the fuming sulfuric acid is as follows:
hydrogen peroxide and fuming sulfuric acid are 1: 0.6-1.3;
preferably, 35-70% of hydrogen peroxide, especially 50% ofhydrogen peroxide is adopted;
the sulfuric acid can adopt fuming sulfuric acid with the concentration of 60-70%;
(2) performing neutralization reaction on the potassium hydroxide aqueous solution and the product obtained in the step (1) to obtain the aqueous solution of the target product potassium monopersulfate;
the reaction formula is as follows:
the reaction temperature is 10-50 ℃, and the reaction time is 1-120 minutes;
the reaction is carried out in vacuum, and the vacuum degree is 0.085-0.1 MPa;
the inventor finds that the neutralization reaction is carried out in vacuum, which is beneficial to the smooth progress of the reaction, because the reaction is exothermic and generates a large amount of heat to vaporize water in the reaction system, which is not beneficial to the reaction, and therefore, the reaction is carried out more completely by removing the water vapor generated in the reaction system through a vacuumizing method; meanwhile, the excessive concentration of local potassium ions during charging can cause HSO5 -Fast decomposition, boiling state formed on the surface of the reaction mixture when feeding under vacuum state, and more effective decomposition than stirringThe problem of rapid dispersion of potassium ions is solved. Therefore, the neutralization reaction carried out under the conditions of the inventor effectively avoids the occurrence of side reaction and ensures KHSO5The formation of this principal component.
The weight concentration of the potassium hydroxide aqueous solution is 35-45%;
(3) concentrating the aqueous solution of potassium monopersulfate under the conditions of a vacuum degree of 0.085-0.10 MPa and a temperature of 10-50 ℃ until the weight concentration of the potassium monopersulfate is 50-70%;
(4) cooling to 0-minus 10 ℃ for crystallization and dehydration, and then collecting solid potassium monopersulfate by a conventional method; adding a stabilizer and drying to obtain a product;
the stabilizer is selected from carbonate, and the carbonate is preferably magnesium carbonate or calcium carbonate, and the addition amount of the stabilizer is 0.5-9% of the weight of potassium monopersulfate.
According to a preferred embodiment of the invention, oleum is addedAdding hydrogen peroxide, stirring for 30-60 minutes, adding water to dilute the mixture into the reaction mixture H2SO5The mass percentage content of the organic silicon compound is 20-40%;
according to the preferred technical scheme of the invention, the crystallization dehydration mother liquor is added into the solution after the oxidation reaction to dilute H2SO5Concentration, low cost and no pollution caused by mother liquid discharge.
The method of the invention can be carried out in a conventional reaction kettle without special equipment.
According to the technical scheme disclosed by the invention, the method is simple to operate, has no special requirements on equipment, and is convenient for industrial production. The product stability is greatly improved, the monthly average active oxygen loss rate is 0.1 percent, and the quality index reaches or exceeds the related specification.
Detailed Description
Example 1
(1) Carrying out oxidation reaction on 100 kg of50% hydrogen peroxide and 140 kg of 65% fuming sulfuric acid at the reaction temperature of 37 ℃ for 120 minutes;
(2) reacting 170 kg of 40% potassium hydroxide solution with the product obtained in the step (1) to obtain a target product, namely an aqueous solution of potassium monopersulfate, wherein the reaction temperature is 50 ℃ and the reaction time is 90 minutes; the reaction was carried out under vacuum at a vacuum of 0.1 MPa;
(3) concentrating the aqueous solution of potassium monopersulfate at 55 deg.C under 0.1 MPa of vacuum degree until the weight concentration of potassium monopersulfate is 50%;
(4) cooling to-4 ℃ for crystallization, then filtering, adding stabilizer magnesium carbonate accounting for 1 percent of the weight of the potassium monopersulfate, and drying to obtain 180 kg of product.
The purity of the product is as follows: active oxygen is more than or equal to 4.8 percent.
The monthly average active oxygen loss rate was 0.1%.
The method for detecting active oxygen can be as follows:
method for measuring active oxygen: 0.3g of potassium hydrogen peroxymonosulfate composite salt is put into an iodometric flask, dissolved by a small amount of deionized water, 10ml of 25% potassium iodide solution is added, a bottle stopper is covered, the mixture is placed in the shade for 10 minutes, 10ml of 1+1 sulfuric acid is added, and the titration is carried out to the end point by using 0.1mol/l sodium thiosulfate solution.
The method for measuring the monthly average active oxygen loss rate comprises the following steps: the ratio of the decrease in active oxygen to the initial active oxygen after one month.
Example 2
The same procedure was followed as in example 1, except that:
the neutralization reaction temperature is 20 ℃, the reaction time is 60 minutes, the reaction is carried out under vacuum, and the vacuum degree is 0.085 MPa;
concentrating the aqueous solution of potassium monopersulfate at 10 deg.C under 0.085 MPa of vacuum degree until the weight concentration of potassium monopersulfate is 70%;
the stabilizer is calcium carbonate and water (1: 1, weight), the adding amount is 3% of the weight of the potassium monopersulfate, and the detection result is as follows:
the purity of the product is as follows: active oxygen is more than or equal to 4.6 percent.
The monthly average active oxygen loss rate was 0.1%.
Claims (8)
1. A preparation method of potassium hydrogen peroxymonosulfate composite salt is characterized by comprising the following steps:
(1) firstly, carrying out oxidation reaction on hydrogen peroxide and fuming sulfuric acid, wherein the reaction formula is as follows:
the reaction temperature is 35-40 ℃, and the reaction time is 1-4 hours;
the weight concentration of the hydrogen peroxide is 35-70%;
(2) performing neutralization reaction on the potassium hydroxide aqueous solution and the product obtained in the step (1) to obtain the aqueous solution of the target product potassium monopersulfate;
the reaction formula is as follows:
the reaction temperature is 10-50 ℃, and the reaction time is 1-120 minutes;
the reaction is carried out in vacuum, and the vacuum degree is 0.085-0.1 MPa;
(3) concentrating the aqueous solution of potassium monopersulfate until the weight concentration of the potassium monopersulfate is 50-70%;
(4) cooling to 0-minus 10 ℃ for crystallization and dehydration, then collecting solid potassium monopersulfate by a conventional method, adding a stabilizer, and drying to obtain a product;
the stabilizer is selected from carbonate, and the carbonate is preferably magnesium carbonate or calcium carbonate, and the addition amount of the stabilizer is 0.5-9% of the weight of potassium monopersulfate.
2. The method of claim 1, wherein the oxidation reaction temperature is 37 ℃.
3. The method according to claim 1, wherein the molar ratio of hydrogen peroxide to oleum is 1: 0.6-1.3.
4. The method as claimed in claim 1, wherein the oleum is added into the hydrogen peroxide, and then after stirring for 30-60 minutes, the oleum is added into water to dilute the oleum into the reaction mixture H2SO5In percentage by mass ofThe content is 20-40%.
5. The process according to claim 1 or 4, wherein the mother liquor for dehydration of crystals is added to the solution after the oxidation reaction.
6. The process according to claim 1, wherein the concentration by weight of oleum is 60-70%.
7. The method according to claim 1, wherein the aqueous solution of potassium hydroxide has a concentration of 35 to 45% by weight.
8. The method of claim 1, wherein the aqueous solution of potassium monopersulfate is concentrated under a vacuum of 0.085 to 0.1 MPa at a temperature of 20 to 60 ℃ to a concentration of 50 to 70% by weight of potassium monopersulfate.
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| CN 200410084727 CN1781846A (en) | 2004-12-01 | 2004-12-01 | Process for preparing potassium hydrogen persulfate composite salts |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864578A (en) * | 2010-04-12 | 2010-10-20 | 西安建筑科技大学 | Method for preparing peroxysulfuric acid by sonoelectrochemical method |
| CN102311100A (en) * | 2011-05-11 | 2012-01-11 | 宋海鹏 | Method for preparing potassium hydrogen peroxymonosulfate composite salt |
| CN101503383B (en) * | 2009-03-16 | 2013-04-24 | 嘉兴学院 | Preparation of o-nitro p-methylsulfonylbenzoic acid |
| CN104844446A (en) * | 2015-04-24 | 2015-08-19 | 巨化集团技术中心 | Preparation method for perfluorohexyl acetate |
| CN108821242A (en) * | 2018-07-12 | 2018-11-16 | 绍兴上虞洁华化工有限公司 | The preparation method of potassium hydrogen persulfate composite salts |
| CN108849977A (en) * | 2018-06-11 | 2018-11-23 | 河北纳泰化工有限公司 | Potassium persulfate is in the preparation method for preparing application and potassium peroxymonosulfate in potassium peroxymonosulfate |
| CN113767900A (en) * | 2021-09-27 | 2021-12-10 | 惠州市栢诗新材料有限公司 | Anti-caking high-stability potassium hydrogen persulfate active salt disinfectant and preparation method thereof |
| CN113845093A (en) * | 2021-10-23 | 2021-12-28 | 浙江金科日化原料有限公司 | Method for continuously preparing peroxysulfuric acid by using microchannel reactor |
| CN114455548A (en) * | 2022-01-21 | 2022-05-10 | 绍兴上虞洁华化工有限公司 | Method for continuously producing peroxysulfuric acid |
-
2004
- 2004-12-01 CN CN 200410084727 patent/CN1781846A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503383B (en) * | 2009-03-16 | 2013-04-24 | 嘉兴学院 | Preparation of o-nitro p-methylsulfonylbenzoic acid |
| CN101864578A (en) * | 2010-04-12 | 2010-10-20 | 西安建筑科技大学 | Method for preparing peroxysulfuric acid by sonoelectrochemical method |
| CN101864578B (en) * | 2010-04-12 | 2012-02-01 | 西安建筑科技大学 | Method for preparing peroxysulfuric acid by sonoelectrochemical method |
| CN102311100A (en) * | 2011-05-11 | 2012-01-11 | 宋海鹏 | Method for preparing potassium hydrogen peroxymonosulfate composite salt |
| CN102311100B (en) * | 2011-05-11 | 2014-02-05 | 宋海鹏 | Method for preparing potassium hydrogen peroxymonosulfate composite salt |
| CN104844446A (en) * | 2015-04-24 | 2015-08-19 | 巨化集团技术中心 | Preparation method for perfluorohexyl acetate |
| CN108849977A (en) * | 2018-06-11 | 2018-11-23 | 河北纳泰化工有限公司 | Potassium persulfate is in the preparation method for preparing application and potassium peroxymonosulfate in potassium peroxymonosulfate |
| CN108849977B (en) * | 2018-06-11 | 2020-10-30 | 河北纳泰化工有限公司 | Application of potassium peroxydisulfate in preparation of potassium monopersulfate composite salt and preparation method of potassium monopersulfate composite salt |
| CN108821242A (en) * | 2018-07-12 | 2018-11-16 | 绍兴上虞洁华化工有限公司 | The preparation method of potassium hydrogen persulfate composite salts |
| CN113767900A (en) * | 2021-09-27 | 2021-12-10 | 惠州市栢诗新材料有限公司 | Anti-caking high-stability potassium hydrogen persulfate active salt disinfectant and preparation method thereof |
| CN113845093A (en) * | 2021-10-23 | 2021-12-28 | 浙江金科日化原料有限公司 | Method for continuously preparing peroxysulfuric acid by using microchannel reactor |
| CN114455548A (en) * | 2022-01-21 | 2022-05-10 | 绍兴上虞洁华化工有限公司 | Method for continuously producing peroxysulfuric acid |
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