CN1060138C - Method for preparing high-purity high-concentration and stable chlorine dioxide - Google Patents
Method for preparing high-purity high-concentration and stable chlorine dioxide Download PDFInfo
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- CN1060138C CN1060138C CN97100560A CN97100560A CN1060138C CN 1060138 C CN1060138 C CN 1060138C CN 97100560 A CN97100560 A CN 97100560A CN 97100560 A CN97100560 A CN 97100560A CN 1060138 C CN1060138 C CN 1060138C
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Abstract
The present invention relates to a method for preparing stable chlorine dioxide with high purity and high concentration. Sodium bisulfite or sodium sulfite are used for reducing sodium chlorate to generate chlorine dioxide gas under a certain technological parameter and a technological flow in acidic medium water solution containing sulphuric acid, the chlorine dioxide gas is absorbed by overoxidation sodium carbonate water solution after the chlorine dioxide gas is purified by sodium chlorite, stable chlorine dioxide water solution with high purity and high concentration is formed, and the content of the chlorine dioxide is from 20, 000 to 60, 000 ppm. Compared with other methods at home and abroad, the method has the advantages of easily obtained raw materials, innocuity, simple technology, energy saving, high product purity and concentration and stable performance.
Description
The invention relates to a method for preparing high-purity high-concentration stable chlorine dioxide, belonging to the technical field of inorganic chemical industry.
Chlorine dioxide has high-efficiency broad-spectrum bactericidal power, comprises almost all common pathogenic microorganisms, fungi and viruses, has strong oxidizing power, has wide application fields, such as being used for disinfecting drinking water, has superior chlorine dioxide to chlorine, does not generate organic chloride which can make animals carcinogenic with organic substances in water, and can oxidize carcinogen 3.4-benzopyrene into non-carcinogenic quinoid structurizationA compound (I) is provided. The device and the pipeline device used in the beverage industry have the functions of disinfection, and are used for disinfection of the devices and the environment in the food industry, and the like. It is used for sterilizing clothes, quilt and environment in hotel and hospital, and sterilizing sewage. Is used for sterilizing livestock pens and drinking water in feedlots. The method is used for industrial wastewater treatment, sterilization and algae removal of circulating cooling water, bleaching of paper pulp and fabrics and the like; in addition, the method can also be used for keeping aquatic products, vegetables and fruits fresh. However, chlorine dioxide has poor stability and is easily decomposed by light and heat. Meet H2、NH3The sulfide and the organic matter capable of promoting oxidation are easy to explode, the explosion can occur when the partial pressure in the air is 40KPa, and the aqueous solution is safe when the concentration is below 10 g/L.
CLO manufactured by comprehensive domestic and overseas current industrial chemical method2The process comprises reducing chlorate (such as NaCLO) in an acidic medium3) The common reducing agents include sodium chloride, hydrochloric acid, sulfur dioxide and methanol, and the method for preparing chlorine dioxide by electrolyzing sodium chloride aqueous solution (see Chinese patent CN2069863U), CLO of the method2The yield and concentration are low.
The method for preparing chlorine dioxide by using sodium chloriteas a raw material (see Chinese patent CN1048682A) has higher cost and smaller output scale.
Method for reducing chlorate by using sodium chloride as reducing agent (professor Rapson Canada, called R)2Method) has the disadvantages of more waste acid and CL byproduct2Much, R, which is no longer adopted at present but developed in the next eighties8Faw (by Albright USA)&Wilson American corporation) is widely adopted by some countries, using methanol as a reducing agent.
The method using hydrochloric acid as a reducing agent (see British patent GB2155459) has smaller scale; on an industrial scale, the Kestin process (Kesting) is a process which is long and complicated (six reactors, electrolysis cells, absorption columns, etc.).
The method using sulfur dioxide as a reducing agent is developed and industrialized by Mathieson alkali company in America, called as a Marteson method (Mathieson), the process of the method is also complex, the method comprises two reactors, a stripping tower and an absorption tower, and the reducing agent is gaseous sulfur dioxide, so the control difficulty is relatively large, and a gas washing device is also required.
The method for reducing sodium chlorate by methanol in China has two patents, CN1058193A (applicant: Tennecaceae Canada division, inventor: M.C.J. Ferrey, etc.) and CN2169622Y (designer: university of continental engineering, Korea, Liberjie) wherein the raw materials, reaction principle and preparation process conditions are all selected from R8The method, which uses a circulating pump in the apparatus, needs special structure and material because the circulating pump is used for conveying the liquid which is close to boiling state and contains strong acid, chlorate and chlorine dioxide with strong oxidizing property under vacuum state, and the method produces chlorine dioxide aqueous solution containing 1O% of free chlorine, which is not ideal, and also contains formic acid (the content of which is 20% of the yield of chlorine dioxide in the main reaction), because of CLO2Explosive, low product concentration, CLO2The vacuum system in the patent (CN2169622Y) adopts a mechanical vacuum pump, and in order to prolong the service life of the mechanical vacuum pump, equipment such as activated carbon adsorption, alkali absorption, scrap iron reduction and the like needs to be installed in front of the pump.
The invention aims to develop chlorine dioxide which has easily obtained raw materials, no toxicity, simple process, energy conservation, high product purity, high concentration and stable performance and is suitable for the national conditions.
The process of the invention is illustrated as follows:
1. the raw materials used
(1) Sodium chlorate (NaClO)3) And the content of industrial products (GB1609-79) is more than or equal to 98 percent (products of Dalian methyl chlorate factory).
(2) Sulfuric acid (H)2SO4) And the content of industrial products (GB534-65) is more than or equal to 98 percent (products of Dalian chemical industry company).
(3) Sodium bisulfite (NaHSO)3) Industrial product (Enterprise Standard) NaHSO3The content is more than or equal to 99.5 percent (Tianjin chemical plant products).
(4) Sodium sulfite (Na)2SO3) The content of industrial products (HG1-209-65) is more than or equal to 96 percent (products of Jinzhou chemical plants).
(5) Sodium chlorite (NaClo)2) Industrial products (ZBG12015-89), sodium chlorite content is more than or equal to 82.0%, sodium chlorate content is less than or equal to 3.5%, sodium chloride content is less than or equal to 13.5%, and water content is less than or equal to 1.0% (Shanghai county pond Bay chemical plant products).
(6) Sodium peroxycarbonate (2 Na)2CO3．2H2O2) And the quality index of industrial products is as follows: active oxygen is more than or equal to 13 percent, and iron ions are less than 20ppm (reagent factory of blue company).
(7) Deionized water
2. Main process parameters
Temperature of the reaction medium: 65-75 deg.C
Reaction zone pressure: 18-21kPa
Acidity of reaction medium: 3-4 mol
3. Chemical reaction and operation process (description of the Process)
Preparing a 38% aqueous solution from sodium chlorate serving as a raw material, preparing a 50% solution from sulfuric acid, preparing a 17% aqueous solution from sodium bisulfite (preparing a 20% aqueous solution from sodium sulfite), respectively filling the aqueous solutions into raw material storage tanks 1, 1' and 1 ″, filling a saturated aqueous solution of sodium chlorite into a converter 6, filling an aqueous solution of sodium peroxycarbonate (with a concentration of 12-13%) into an absorption tower 7, turning on a jet vacuum pump system, mixing the aqueous solutions of sulfuric acid and sodium chlorate at the same volume flow rate, adding the aqueous solution of sodium bisulfite into the reactor from an inlet at the lower part of the reactor (positioned at a height from the bottom 1/4), and adding the aqueous solution of sodium bisulfite into the storage tank through a Venturi feeder (positioned at the top 1/5 of the reactor).
Under the conditions of pressure of 18-21KPa and temperature of 65-75 deg.C, the following oxidation-reduction reaction can be made to occur
Or (a) )
Reaction ofThe reaction liquid carried by the generated chlorine dioxide gas when passing through the separator 4 is separated and then enters the converter 6, and if the reaction conditions are not well controlled, a small amount of CL is generated2Conversion to CLO in a converter2The gas is purified and the following chemical reactions take place in the converter:
the purified gas is absorbed by sodium percarbonate (also known as a stabilizer) in an aqueous solution to form a stable aqueous solution of chlorine dioxide (sodium percarbonate forms a complex with dissolved chlorine dioxide to form a stable solution, see us patent 3591515).
The device used in the invention is the prior art, and is described as follows:
the apparatus of the present invention is sized to produce chlorine dioxide.
1. The reactor has a tubular shell with a diameter-height ratio of 1: 10, the material is titanium steel GB3621-830, and the outer wall is wound by KD type insulating heating belt.
2. The separator is made of titanium steel (GB3621-83) and is internally provided with a wire mesh defoaming layer.
3. A cooler and a tube type fixed tube plate heat exchanger (JB 1145-73).
4. The device comprises a converter and an absorption tower, wherein the converter and the absorption tower are both packing absorption towers with the same structure. The tower is filled with absorption liquid and filler.
The material of the converter is titanium steel (GB3621-83), the material of the absorption tower is divided into two types, the yield is less than 50 kg/h of stable chlorine dioxide aqueous solution, the tower body is made of chemical hard polyvinyl chloride pipe materials (GB4219-84), and the tower body of the device larger than the scale is made of titanium steel (GB 3612-83).
5. The jet pump is a PSB series jet vacuum pump (product of Shanghai Hujiang jet pump factory).
6. The concentration monitor is a pHS-511 intelligent acidimeter.
7. The temperature automatic control system adopts an XMT-102 regulator (widely connected with products of a fourth instrument factory and provided with an overtemperature alarm).
8. The pressure monitoring system adopts a Hall pressure transmitter (YSH-3 type) matched with an XMT-103 display adjusting instrument (Shanghai automatic instrument factory product) and is matched with an overpressure alarm.
The invention has the following advantages:
1. the product prepared by the method is a stable chlorine dioxide water solution, the concentration of the stable chlorine dioxide water solution is 20000-60000 ppm (2% -6%), the product is non-toxic, tasteless and not easy to decompose, the storage life is longer than 1 year, the product purity is high, and the product does not contain formic acid and chlorine and is more suitable for drinking water and the application in the field of food processing.
2. The reaction material sodium bisulfite (or sodium sulfite) is wide in source, low in cost and easy to obtain, is a byproduct of tail gas recovery of a sulfuric acid plant, and is used for treating SO in flue gas of petroleum refineries, industrial boilers and kilns2When the pollution is caused, the by-product obtained by absorbing the alkali liquor, namely the raw material, for example, a coal-fired industrial boiler at 20 t/h is adopted to treat the discharged flue gas, and if the desulfurization efficiency is more than 60 percent, the SO can be recovered every year2151 tons (see the broad project of the national environmental protection agency B in 1992, 92-B-G-048) can produce NaHSO3245 ton.
3. CLO is currently produced domestically2(see patent CN1058193A, CN2169622Y) the used raw material methanol belongs to dangerous goods, is toxic (causing blindness), is volatile, inflammable, and explosive when exposed to heat and open fire(flash point 15.6 ℃, explosion limit 6-36.5%), and NaHSO is used in the patent3(or Na)2SO3) These disadvantages are not present.
4. NaHSO for use in the invention4(or Na)2SO3) Does not affect CLO2The quality of the product, the impurities contained in it only affect the recovered by-product NaHSO4(or Na)2SO4) The purity of (2).
5. Preparation of CLO according to the invention2The production process has no three wastes discharge.
Description of the drawings:
FIG. 1 is a schematic process flow diagram of the present invention.
The equipment comprises a sodium chlorate storage tank 1, a sulfuric acid storage tank 1 ', a sodium sulfite storage tank 1', a feeder 2, a reactor 3, a separator 4, a cooler 5, a converter 6, an absorption tower 7, a jet vacuum pump 8, a concentration monitor 9, a pressure monitor 10, a reaction liquid storage tank 11 and a temperature controller 12. The above devices are known in the art, and the devices are connected by using pipes and flanges.
Example (b):
example 1: according to the operation process in the process specification, the reaction process conditions are as follows:
the reactor temperature: 67 deg.C (fluctuation range + -2 deg.C)
Reaction system pressure: 20kPa (fluctuation range. + -. 1.5 kPa)
Acidity of reaction medium: 4 mol of
Sodium chlorate excess, sodium bisulfite (NaHSO)3) (17%) 0.61, reaction time 90min, and concentration of the produced 5kg stable chlorine dioxide aqueous solution 3% (30093ppm)
NaHSO3The conversion was 96.6%.
Example 2: according to the operation process in the process specification, the reaction process conditions are as follows:
the reactor temperature: 67 deg.C (fluctuation range + -2 deg.C)
Reaction system pressure: 20kPa (fluctuation range. + -. 1.5 kPa)
Acidity of reaction medium: 4 mol of
Sodium chlorate excess, sodium bisulfite (NaHSO)3) (17%) 1.21 was added, the reaction time was 2 hours, and after completion the concentration of the resulting 5kg of stable aqueous chlorine dioxide solution was 6% (59688ppm)
NaHSO3The conversion was 95.8%.
Example 3: according to the operation process in the process specification, the reaction process conditions are as follows:
the reactor temperature: 75 ℃ (fluctuationrange +/-2 ℃)
Reaction system pressure: 20kPa (fluctuation range. + -. 1.5 kPa)
Acidity of reaction medium: 4 mol of
Sodium chlorate excess, sodium bisulfite (NaHSO)3) (17%) 0.61 was added, the reaction time was 50min, and after completion, the concentration of the produced 5kg of stable aqueous chlorine dioxide solution was 3% (29679ppm)
NaHSO3The conversion was 95.3%.
Example 4: according to the operation process in the process specification, the reaction process conditions are as follows:
the reactor temperature: 67 deg.C (fluctuation range + -2 deg.C)
Reaction system pressure: 20kPa (fluctuation range. + -. 1.5 kPa)
Acidity of reaction medium: 4 mol of
Sodium chlorate excess, sodium bisulfite (NaHSO)3) (17%) 0.61, 90min reaction time, and 3% (29502ppm) of 5kg stable chlorine dioxide aqueous solution
NaHSO3The conversion was 94.7%.
When the product obtained in the four embodiments is prepared into a 2% aqueous solution, the properties are as follows:
the pH value is 8.5, and the liquid is colorless, tasteless, nontoxic, non-corrosive, transparent, nonflammable, nonvolatile, and non-decomposable, and the effective components of the liquid are reduced by less than or equal to 3 percent (measured after the liquid is stored at the constant temperature of 56 ℃ for 14 days) after being stored for 1 year.
The above examples show that:
1. under the reaction process conditions (temperature, pressure and acidity) defined by the invention, when the amount of the absorption liquid is not changed, the product solution is added with NaHSO3The amount of the compound (see examples 1 and 2) is increased, and the product with the concentration of 2 percent is prepared (the concentration of the American commercial product is 2 percent)
2. Increasing the reaction temperature without changing other reaction process conditions leads to an increase in the reaction rate (less fluctuation in conversion) (see examples 3, 1).
3. Under the reaction process conditions (temperature, pressure, acidity) specified in the invention, NaHSO3Has higher conversion rate (94% -96%).
4. Under the same reaction process conditions, Na2SO3Has a conversion rate lower than that of NaHSO3Transformation of (2)The ratio (see example 4 in comparison with examples 1, 2 and 3).
Claims (2)
1. A method for preparing high-purity high-concentration stable chlorine dioxide is characterized in that sodium bisulfite is used in an acid medium aqueous solution containing sulfuric acid, sodium chlorate is reduced under certain process parameters and process flows to generate chlorine dioxide gas, and the chlorine dioxide gas is absorbed by a sodium peroxycarbonate aqueous solution to form a high-purity high-concentration stable chlorine dioxide aqueous solution after being purified by sodium chlorite; the technological parameters and the reduction reaction process are as follows:
respectively filling 38% sodium chlorate aqueous solution, 50% sulfuric acid aqueous solution and 17% sodium bisulfite aqueous solution into storage tanks (1), (1 ') (1'), filling a saturated sodium chlorite aqueous solution into a converter (6), filling 12-13% sodium peroxide aqueous solution into an absorptiontower (7), maintaining the negative pressure of the system by using a jet vacuum pump (8), adding the sodium chlorate and the sulfuric acid in the storage tanks (1) and (1 ') into a reactor, adding the sodium bisulfite aqueous solution in the storage tank (1') into the reactor through a Venturi feeder (2), carrying out reduction reaction under the conditions that the temperature of a reaction medium is 65-75 ℃, the pressure of the reaction zone is 18-21KPa, the acidity of the reaction medium is 3-4 mol, and adding excessive sodium chlorate during the reaction; chlorine dioxide gas generated in the reaction is separated from entrained reaction liquid by a separator (4) and then enters a converter (6), for example, a small amount of CL generated when the reaction conditions are poor2Converted to CLO in a converter (6)2Purification of the gas, purified CLO2The gas enters an absorption tower (7) and is absorbed by sodium percarbonate in the tower to generate stable chlorine dioxide water solution, and when the chlorine dioxide content of the solution is 2-6 ten thousand ppm, the stable chlorine dioxide water solution can be discharged to be a finished product.
2. The method of claim 1, wherein said process further comprises cooling and separating NaHSO from the raffinate exiting the reactor4And Na2SO4And the residual acid liquor is returned for use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97100560A CN1060138C (en) | 1997-01-31 | 1997-01-31 | Method for preparing high-purity high-concentration and stable chlorine dioxide |
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| CN97100560A CN1060138C (en) | 1997-01-31 | 1997-01-31 | Method for preparing high-purity high-concentration and stable chlorine dioxide |
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| CN1189449A CN1189449A (en) | 1998-08-05 |
| CN1060138C true CN1060138C (en) | 2001-01-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102090417A (en) * | 2010-12-22 | 2011-06-15 | 韶关蓝威消毒药业有限公司 | Preparation method of living disinfectant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063154C (en) * | 1998-08-06 | 2001-03-14 | 李全喜 | Method for producing aqueous chlorine dioxide solution |
| CN101891288A (en) * | 2010-07-07 | 2010-11-24 | 王永仪 | Method for preparing chlorine dioxide disinfectant and ferric salt coagulant in co-production way |
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| CN102327631B (en) * | 2011-03-14 | 2013-11-06 | 青岛市明珠制药有限公司 | Air purifying preparation and use thereof, air purifying preparation hanging bag and use thereof and production method of hanging bag |
| CN103145154B (en) * | 2013-04-11 | 2015-01-21 | 常州和方环保科技有限公司 | Method for recovering sodium chlorite liquid waste |
| CN105280284A (en) * | 2015-12-01 | 2016-01-27 | 江苏戴普科技有限公司 | Corrosion-resistant cable manufacturing technique |
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| DE102018205009A1 (en) * | 2018-04-04 | 2019-10-10 | Krones Ag | Container treatment plant |
| CN108477208A (en) * | 2018-05-22 | 2018-09-04 | 广东至诚化学工业有限公司 | A kind of long-acting neutral aqueous solution of chlorine dioxide and preparation method thereof |
| CN117401649B (en) * | 2023-12-15 | 2024-03-08 | 山东华实药业有限公司 | Pure activation-free stable chlorine dioxide solution |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4780304A (en) * | 1987-01-30 | 1988-10-25 | Tenneco Canada Inc. | Acid introduction in chlorine dioxide production |
| EP0473560A1 (en) * | 1990-08-31 | 1992-03-04 | Eka Nobel Ab | Process for the production of chlorine dioxide |
| CN1075298A (en) * | 1992-02-13 | 1993-08-18 | 青岛海洋大学 | A kind of method of producing chlorine dioxide of high concentration and stable state |
-
1997
- 1997-01-31 CN CN97100560A patent/CN1060138C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4780304A (en) * | 1987-01-30 | 1988-10-25 | Tenneco Canada Inc. | Acid introduction in chlorine dioxide production |
| EP0473560A1 (en) * | 1990-08-31 | 1992-03-04 | Eka Nobel Ab | Process for the production of chlorine dioxide |
| CN1075298A (en) * | 1992-02-13 | 1993-08-18 | 青岛海洋大学 | A kind of method of producing chlorine dioxide of high concentration and stable state |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102090417A (en) * | 2010-12-22 | 2011-06-15 | 韶关蓝威消毒药业有限公司 | Preparation method of living disinfectant |
| CN102090417B (en) * | 2010-12-22 | 2013-07-03 | 韶关蓝威消毒药业有限公司 | Preparation method of living disinfectant |
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| CN1189449A (en) | 1998-08-05 |
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