CN1196881A - High concentration stable chlorine dioxide solid sterilizing tablets and its prepn. - Google Patents
High concentration stable chlorine dioxide solid sterilizing tablets and its prepn. Download PDFInfo
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- CN1196881A CN1196881A CN 97106395 CN97106395A CN1196881A CN 1196881 A CN1196881 A CN 1196881A CN 97106395 CN97106395 CN 97106395 CN 97106395 A CN97106395 A CN 97106395A CN 1196881 A CN1196881 A CN 1196881A
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 235000019398 chlorine dioxide Nutrition 0.000 title claims abstract description 56
- 239000004155 Chlorine dioxide Substances 0.000 title claims description 54
- 239000007787 solid Substances 0.000 title claims description 25
- 230000001954 sterilising effect Effects 0.000 title description 2
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 230000008025 crystallization Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 54
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 239000003826 tablet Substances 0.000 claims description 22
- 238000010521 absorption reaction Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 14
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 14
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- BHDAXLOEFWJKTL-UHFFFAOYSA-L dipotassium;carboxylatooxy carbonate Chemical compound [K+].[K+].[O-]C(=O)OOC([O-])=O BHDAXLOEFWJKTL-UHFFFAOYSA-L 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 8
- 229940045872 sodium percarbonate Drugs 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 7
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- ISAOUZVKYLHALD-UHFFFAOYSA-N 1-chloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)NC(=O)NC1=O ISAOUZVKYLHALD-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229960005069 calcium Drugs 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229960001922 sodium perborate Drugs 0.000 claims description 5
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 claims description 5
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 5
- 239000007938 effervescent tablet Substances 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000007738 vacuum evaporation Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 abstract 2
- 230000000249 desinfective effect Effects 0.000 abstract 1
- 239000012263 liquid product Substances 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 239000011780 sodium chloride Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000004659 sterilization and disinfection Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000000645 desinfectant Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 239000007832 Na2SO4 Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WBZRSFDJNJXREC-UHFFFAOYSA-N Cl[Cl]Cl Chemical compound Cl[Cl]Cl WBZRSFDJNJXREC-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 238000009621 Solvay process Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000009920 food preservation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
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Abstract
A high-concentration stable disinfecting tablet of ClO2 is prepared through preparing gas of ClO2, suction, concentration, crystallization and tabletting, and features high active component content up to more than 50%, high concentration increased by at least 25 times compared with liquid product, and stable storage period (longer than 2 years).
Description
The invention relates to a broad-spectrum and high-efficiency disinfectant and a preparation method thereof, in particular to a high-concentration stable chlorine dioxide solid disinfection tablet and a preparation method thereof.
Chlorine dioxide is an ideal disinfectant with broad spectrum and high efficiency, can be widely used in the fields of water treatment, sterilization, bleaching, food preservation, air purification and the like, and is classified as A1 grade safe disinfectant by the world health organization. However, the substance is a yellow-green or orange gaseous substance, has a strong pungent smell similar to chlorine gas, is explosive, has high solubility in water but is unstable, and is a dangerous substance which is difficult to store and transport. The characteristics make it only be prepared and used on site for a long time, and the popularization and application of the product are severely restricted. In order to solve this conflict, experts in various countries have conducted intensive research and have developed technologies for preparing stable aqueous solutions of chlorine dioxide and solid chlorine dioxide. However, although there are many reports on the articles and patent documents in this field, the content of the prepared product is not high. (environmental protection 1995 3 rd stage P34 ~ 36.)
Currently, there are several methods for producing chlorine dioxide, the main raw material being sodium chlorate. The earliest production method was the Mathieson method, which uses SO2As reducing agent, also using H2SO4The disadvantage of this process is the low yield. Rapson in CanadaR for teaching invention1Method adopts NaClO3、SO2And H2Production of ClO from O2R of the invention2Method adopts NaClO3NaCl and H2SO4As a starting material, R2Simple operation, high yield, more sulfuric acid and by-product Na2SO4Recovery is difficult. The Solvey method is a process developed by Allied, USA, and uses NaClO3H2SO4And CH3OH as starting material, process for preparing ClO2The yield is improved to 85-90%. Subsequently, on the basis of the above-mentioned various processes, the Allied company has successively developed a series of new processes of R series, named R respectively3Method, R3H method, R4Method, R5Method, R6Method, R7Methods and R developed in the early 1980 s8The method is a method widely adopted in the process. R3Reaction principle of the process and R2The method mainly changes the used equipment and the circulation of the solution, and improves the concentration of the chlorine dioxide aqueous solution. R3H method and R3The method is characterized in that sodium chloride is partially or completely replaced by aqueous hypochlorous acid or anhydrous hydrochloric acid, and acid is added to reduce the amount of sulfuric acid and byproduct Na2SO4The amount of (c). R4The process aims to convert the screen sodium chloride by metathesis and recycle the acid to the generator, but is not economically valuable. R5Also known as hydrochloric acid method, namely NaClO3Reaction with HCl to form ClO2The process equipment and process conditions are similar to those of R3The method generates chlorine dioxide under vacuum and reaction temperature, and is characterized by recovering pure sodium chloride crystal, but it uses anhydrous hydrochloric acid as raw material, and its cost is high. R6By the process of R5The method process is combined with a sodium chlorate electrolysis production device. The reactor feed is sodium chlorate bath from the electrolyzer, which contains sodium dichromate, sodium chloride and sodium chlorate. R6The method comprises a sodium chloride electrolysis device, so the investment cost is high. R in the early 1980 s7The method is first industrialized in North America, and it uses SO2As a reducing agent, the total reaction is as follows:
wherein the by-product Na2SO4Is greatly reduced.
The R8 method has been put into operation in the United states in 1985, and is currently being expanded because of its easy control of the process operation and high production efficiency, which is well appreciated by operators.
The raw materials for the R8 process are the same as in the Solvay process described above, and the main reactions are as follows:
the method adopts a high-acidity reaction medium, the main reaction can be continuously carried out, the conversion rate reaches 99-100%, and a small amount of chlorine byproducts can be generated in the side reaction. The R8 process uses a reaction-evaporation-crystallization unit reactor. The reaction is carried out under the pressure of 100-400 mmHg and the boiling temperature of the reactant, and then the product ClO is obtained2The gas is absorbed by cold water in an absorption tower to become a solution, wherein ClO2The concentration of (b) is 10-12 g/L. The method can be operated smoothly and continuously. For the purpose of efficient mixing of the acid with the reactants, the acid-containing gas stream should have a relatively high injection velocity into the recycle stream. The acid should be as highly atomized as possible before entering the recycle stream and a large flow circulation pump is required to circulate the reaction liquid between the reactor and reboiler. The R8 method has the disadvantages of reaction under higher negative pressure and boiling state, complicated equipment and the likeAnd the obtained ClO2The concentration of the solution is low.
U.S. Pat. No. 5,416,88, Japanese patent application laid-open No. 4, 231304, Japanese patent application laid-open No. 60, 161307, European patent application laid-open No. EP 581,550 and JP58,161904 disclose solid chlorine dioxide products, which are generally produced by adsorbing and solidifying the chlorine dioxide products by an adsorbent based on liquid phase absorption. Common adsorbents comprise calcium silicate, granular silicon dioxide, talc, diatomite, volcanic ash and the like, and the pH value of the absorption liquid is generally controlled to be 8.5-9; and if an acidic absorbent is used, the pH value of the absorption liquid is usually lower than 3, and when the absorbent is used, an alkaline solution is added, the pH value of the solution is adjusted to be 8.5-9, and the chlorine dioxide is slowly released to form liquid for application. In addition, a binary solid composite reaction type powder chlorine dioxide product formed by binary vacuum packaging is also provided, the product is P11-12 in No. 1 of 1995 in Henan preventive medicine journal, and a chlorine dioxide tablet which is prepared by preparing microcapsules by related components and pressing the microcapsules into a tablet can be used for personal drinking water disinfection (Chinese invention patent CN 1094698). However, the content of the components of the solid chlorine dioxide product is not high.
The invention aims to provide a high-concentration steady-state chlorine dioxide solid disinfection tablet and a preparation method thereof.
The above object of the present invention is achieved by:
a stable chlorine dioxide tablet comprising:
60-80 parts by weight of steady chlorine dioxide powder with effective components of at least 50%,
2 parts by weight of sodium carboxymethylcellulose,
15 to 32 parts by weight of sodium bicarbonate,
3-7 parts by weight of citric acid to form the effervescent tablet.
Characterized in that it further comprises
1-10 parts of a material A consisting of potassium percarbonate and 3-10 parts of chloroisocyanuric acid by weight of citric acid 50-90 parts by weight; and uniformly mixing the material B consisting of 8-30 parts by weight of sodium bicarbonate and 2 parts by weight of sodium carboxymethyl cellulose, and tabletting to form the composite functional tablet.
A preparation method of a stable chlorine dioxide tablet comprises the steps of preparing a 4-6% stable chlorine dioxide solution by taking sodium chlorate, sulfuric acid and methanol as raw materials and sodium percarbonate as a stabilizer, and is characterized in that the stable chlorine dioxide solution with low concentration is further taken as an absorption liquid, the generated chlorine dioxide is introduced into the absorption liquid by adopting negative pressure, and 8-20% of compound stabilizing liquid in weight is added into the absorption liquid in batches according to the following proportion:
sodium perborate, sodium percarbonate, calcium percarbonate, potassium percarbonate and sodium hydroxide in a ratio of 1: 3-20: 0.1-5: 1-20: 5-40
Simultaneously, adjusting the pH value of the absorption liquid to 7.5-9 by using sodium carbonate, controlling the reaction to 0-2 ℃ to prepare 15-20% of stable chlorine dioxide solution, filtering to remove inorganic salt, performing vacuum evaporation concentration to obtain chlorine dioxide with the concentration of at least 25%, performing cooling crystallization, and uniformly mixing 60-80 parts by weight of the crushed solid, 2 parts by weight of sodium carboxymethylcellulose, 15-32 parts by weight of sodium bicarbonate and 3-7 parts by weight of citric acid at the cooling temperature of-1 ℃ -10 ℃ to obtain solid with the effective component of the chlorine dioxide of at least 50%, and performing dry tabletting to obtain the effervescent tablet.
The method is characterized by further comprising the steps of adding 1-10 parts by weight of potassium percarbonate into a material A before mixing and tabletting, and uniformly mixing the material A with a material B consisting of 50-90 parts by weight of citric acid, 3-10 parts by weight of chloroisocyanuric acid, 8-30 parts by weight of sodium bicarbonate and 2 parts by weight of sodium carboxymethylcellulose, and tabletting to prepare the composite functional tablet.
The advantages of the invention are obvious: the effective concentration of the chlorine dioxide solid product with the effective components of more than 50 percent is at least 25 times higher than that of the existing solution product, the transportation and the use are convenient, the stable period can reach more than two years, the process of the product is simple, the cost is lower, the sale price is only one third of that of the solution, the social demand of the chlorine dioxide disinfectant is extremely large, the successful development of the stabilized solid chlorine dioxide tablet is a great contribution to the disinfection science, and the economic benefit is also considerable. In addition, the action product of the chlorine dioxide as the disinfectant is harmless substances such as sodium chloride, water, carbon oxides and the like, carcinogens are not formed, and the chlorine dioxide can oxidize carcinogens without polluting the environment, so that the environmental benefit is also influenced profoundly.
Hereinafter, the present invention will be described in further detail by way of specific examples. Example 1:
the R8 method is adopted, andthe main reaction is as follows:
h is put into the reactor according to the ratio of 20: 30: 72SO4、NaClO3And CH3Adding some water into the OH, uniformly mixing, heating to 75-80 ℃ to generate yellow ClO2The gas, which is withdrawn from the upper outlet of the reactor, passes through an absorption column containing a sodium percarbonate solution having a pH of around 9, which is connected to an evacuation system which maintains the pressure at the upper outlet of the reactor at around 700 mmHg. Analyzing the obtained ClO2Solutions containing free radicalsClO26.5%, discharging the precipitate from the lower part of the reactor, evaporating by an evaporator to obtain byproduct Na3H(SO4)2。
Then using the above-mentioned ClO26.5% solution as absorption liquid, ClO will be generated2While introducing the mixture into the absorption liquid for negative pressure absorption, adding 8-20% of stable aqueous solution of the following formula in batches:
sodium perborate, sodium percarbonate, calcium percarbonate, potassium percarbonate, sodium hydroxide in a ratio of 1: 5: 1: 10: 5,
adjusting the pH value to be 7.5-9 by using sodium carbonate until the concentration of chlorine dioxide is at least 18%, filtering after the reaction is finished, removing inorganic salt, carrying out vacuum evaporation and concentration until the concentration of chlorine dioxide is at least 25%, cooling and crystallizing in a crystallizer, and controlling the temperature to be below-8 to-10 ℃ to obtain a steady solid containing 52% of chlorine dioxide. Example 2
The procedure of example 1 was repeated as described aboveClO26.5% of the solution as an absorption solution, ClO to be generated2While this solution was pumped in for negative pressure absorption, a 15% stable aqueous solution of the formulation was fed in batch:
sodium perborate, sodium percarbonate, calcium percarbonate, potassium percarbonate and sodium hydroxide are aqueous solutions of 1: 10: 3: 20: 10, the pH value is adjusted to be 7.5-9 by using sodium carbonate until the concentration of chlorine dioxide is 20%, inorganic salts are removed by filtration after the reaction is finished, the inorganic salts are concentrated in vacuum until the concentration of the chlorine dioxide reaches 25%, and then the mixture is cooled and crystallized in a crystallizer, and the temperature is controlled to be below-5 ℃ to-8 ℃, so that stable solid containing 55% of chlorine dioxide is obtained. Example 3
The procedure of example 1 was repeated with ClO as described above2ClO generated by using 6.5% solution as absorption liquid2While this solution was passed through for negative pressure absorption, a 20% stable aqueous solution of the following formulation was added in portions.
Sodium perborate, sodium percarbonate, calcium percarbonate, potassium percarbonate and sodium hydroxide are aqueous solutions of 1: 20: 5: 15: 40, the pH value is adjusted to be 7.5-9 by using sodium carbonate until the concentration of chlorine dioxide is 15%, inorganic salts are removed by filtration after the reaction is finished, the inorganic salts are concentrated in vacuum until the concentration of the chlorine dioxide reaches 26%, and then the mixture is cooled and crystallized in a crystallizer, and the temperature is controlled to be below-1 to-8 ℃, so that stable solid containing 50% of chlorine dioxide is obtained. Example 4
The procedure of example 1 was repeated using the R7 method to obtain a steady state solid containing 52% chlorine dioxide, the main reaction of which was as follows:
wherein the by-product Na2SO4Is greatly reduced.Example 5
The procedure of example 2 was repeated using the R7 method to obtain a steady state solid containing 55% chlorine dioxide. Example 6
The procedure of example 3 was repeated using the R7 method to obtain a steady-state solid containing 50% chlorine dichloride. Example 7
ClO was prepared using the following starting materials2The main reaction is as follows:
the procedure of example 1 was repeated to obtain a steady solid containing 52% chlorine dioxide. Example 8
ClO was prepared by performing the reaction using the starting materials of example 72The procedure of example 2 was repeated to obtain a steady solid containing 55% chlorine dioxide. Example 9
ClO was prepared by performing the reaction using the starting materials of example 72The procedure of example2 was repeated to obtain a steady-state solid containing 50% chlorine dichloride. Examples 10 to 12
An effervescent instant tablet (example 10) was obtained by mixing 70 parts by weight of the steady state solid containing 52% chlorine dioxide obtained in example 1 or example 4 or example 7, 2 parts by weight of sodium carboxymethylcellulose, 25 parts by weight of sodium bicarbonate, and 5 parts by weight of citric acid, and then compressing the mixture into a tablet by a dry method.
Tablets were dry-compressed using 60 parts by weight of the steady state solid containing 55% of chlorine dichloride obtained in example 2 or example 5 or example 8, 2 parts by weight of sodium carboxymethylcellulose, 32 parts by weight of sodium bicarbonate and 7 parts by weight of lemon (example 11).
Tablets were dry-compressed using 80 parts by weight of 20 steady-state solids containing 50% of chlorous dichloride prepared in example 3 or example 6 or example 9, 2 parts by weight of sodium carboxymethylcellulose, 15 parts by weight of sodium bicarbonate and 3 parts by weight of citric acid (example 12). Examples 13 to 15
Using the uniformly mixed powder obtained in example 10, 1 part by weight of potassium percarbonate was added to prepare a material A, and after uniformly mixing with a material B comprising 70 parts by weight of citric acid, 15 parts by weight of sodium bicarbonate, 2 parts by weight of sodium carboxymethylcellulose and 7 parts by weight of chloroisocyanuric acid, an AB material double-layer composite tablet was prepared by dry tableting (example 13).
Using the uniformly mixed powder obtained in example 11, 20 parts by weight of potassium percarbonate was added to prepare a material A, and after uniformly mixing with 50 parts by weight of citric acid, 30 parts by weight of sodium bicarbonate, 2 parts by weight of sodium carboxymethylcellulose and 10 parts by weight of chloroisocyanuric acid, an AB material bilayer complex function tablet was prepared by dry tableting (example 13).
The uniformly mixed powder obtained in example 12 was added with 10 parts by weight of potassium percarbonate to prepare a material a, and the uniformly mixed material a was dry-compressed with 90 parts by weight of citric acid, 8 parts by weight of sodium bicarbonate and 2 parts by weight of sodium carboxymethylcellulose to prepare an AB material double-layer composite functional tablet.
The above-described embodiments are for illustrative purposes only, and the scope of the present invention will be indicated in the claims.
Claims (4)
1. A stable chlorine dioxide tablet comprising:
60-80 parts by weight of steady chlorine dioxide powder with effective components of at least 50%,
2 parts by weight of sodium carboxymethylcellulose,
15 to 32 parts by weight of sodium bicarbonate,
3-7 parts by weight of citric acid to form the effervescent tablet.
2. A stable chlorine dioxide tablet as claimed in claim 1, further comprising a material a consisting of 1-10 parts by weight of potassium percarbonate and 3-10 parts by weight of chloroisochlorouric acid with 50-90 parts by weight of citric acid; and uniformly mixing the material B consisting of 8-30 parts by weight of sodium bicarbonate and 2 parts by weight of sodium carboxymethyl cellulose, and performing double-layer tabletting by adopting the material AB to form the composite functional tablet.
3. A preparation method of a stable chlorine dioxide tablet comprises the steps of preparing a 4-6% stable chlorine dioxide solution by taking sodium chlorate, sulfuric acid and methanol as raw materials and sodium percarbonate as a stabilizer, and is characterized in that the stable chlorine dioxide solution with low concentration is further taken as an absorption liquid, the generated chlorine dioxide is introduced into the absorption liquid by adopting negative pressure, and 8-20% of compound stabilizing liquid in weight is added into the absorption liquid in batches according to the following proportion:
sodium perborate, sodium percarbonate, calcium percarbonate, potassium percarbonate and sodium hydroxide in a ratio of 1: 3-20: 0.1-5: 1-20: 5-40
Simultaneously, adjusting the pH value of the absorption liquid to 7.5-9 by using sodium carbonate, controlling the reaction to 0-2 ℃ to prepare 15-20% of stable chlorine dioxide solution, filtering to remove inorganic salt, performing vacuum evaporation concentration to obtain chlorine dioxide with the concentration of at least 25%, performing cooling crystallization, and uniformly mixing 60-80 parts by weight of the crushed solid, 2 parts by weight of sodium carboxymethylcellulose, 15-32 parts by weight of sodium bicarbonate and 3-7 parts by weight of citric acid at the cooling temperature of-1 ℃ -8 ℃ to obtain solid with the effective component of the chlorine dioxide of at least 50%, and performing dry tabletting to obtain the effervescent tablet.
4. The method of claim 3, further comprising adding potassium percarbonate 1-10 parts by weight to form a material A before mixing and tabletting, and uniformly mixing with a material B consisting of 50-90 parts by weight of citric acid, 3-10 parts by weight of chloroisocyanuric acid, 8-30 parts by weight of sodium bicarbonate and 2 parts by weight of sodium carboxymethylcellulose, and tabletting to form A, B double-layer composite functional tablets.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 97106395 CN1196881A (en) | 1997-04-21 | 1997-04-21 | High concentration stable chlorine dioxide solid sterilizing tablets and its prepn. |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 97106395 CN1196881A (en) | 1997-04-21 | 1997-04-21 | High concentration stable chlorine dioxide solid sterilizing tablets and its prepn. |
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| CN1196881A true CN1196881A (en) | 1998-10-28 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436308C (en) * | 2004-12-08 | 2008-11-26 | 龙膺厚 | Long-effective instant aqueous chlorine solution |
| CN101300993B (en) * | 2008-06-06 | 2010-07-14 | 浙江省农业科学院 | A kind of fresh-keeping method of seafood |
| WO2021242225A1 (en) * | 2020-05-26 | 2021-12-02 | Spectrum Doxyicide Llc | Devices, systems and methods of making and using chlorine dioxide based formulation with improved stability |
-
1997
- 1997-04-21 CN CN 97106395 patent/CN1196881A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436308C (en) * | 2004-12-08 | 2008-11-26 | 龙膺厚 | Long-effective instant aqueous chlorine solution |
| CN101300993B (en) * | 2008-06-06 | 2010-07-14 | 浙江省农业科学院 | A kind of fresh-keeping method of seafood |
| WO2021242225A1 (en) * | 2020-05-26 | 2021-12-02 | Spectrum Doxyicide Llc | Devices, systems and methods of making and using chlorine dioxide based formulation with improved stability |
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