CN1234597C - Method for preparing chlorine dioxide using chlorate method - Google Patents
Method for preparing chlorine dioxide using chlorate method Download PDFInfo
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- CN1234597C CN1234597C CN200410013828.7A CN200410013828A CN1234597C CN 1234597 C CN1234597 C CN 1234597C CN 200410013828 A CN200410013828 A CN 200410013828A CN 1234597 C CN1234597 C CN 1234597C
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- Prior art keywords
- reaction
- raffinate
- negative pressure
- reactor
- temperature
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- 238000000034 method Methods 0.000 title claims abstract description 31
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 title claims abstract description 26
- 239000004155 Chlorine dioxide Substances 0.000 title claims abstract description 15
- 235000019398 chlorine dioxide Nutrition 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 150000002978 peroxides Chemical class 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract 5
- 230000000630 rising effect Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001919 chlorite Inorganic materials 0.000 description 2
- 229910052619 chlorite group Inorganic materials 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000003206 sterilizing agent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- Saccharide Compounds (AREA)
Abstract
The present invention discloses a method for preparing chlorine dioxide by a chlorate method. The present invention comprises the processing steps: A. mixed solution containing chlorine is prepared; B. the mixed solution containing chlorine, sulfuric acid and industrial hydrogen peroxide are proportionally added in a first order reactor at the uniform speed so as to carry out a first order reaction; generated chlorine dioxide is collected; the residual liquid of the reaction is sent to a second order reactor; C. in the second order reactor, a second order reaction is carried out to the residual liquid, and the generated chlorine dioxide is collected; the residual liquid is discharged; the reaction is ended, or the residual liquid is sent to a next order reactor to carry out a next order reaction to the residual liquid. Because the reactions are carried out under the conditions of temperature rising step by step, independent cascade and negative pressure in the method, the method has the advantages of high conversion rate, high purity of the chlorine dioxide, low production cost and safe production process.
Description
One, technical field
The present invention relates to a kind of preparation method of dioxide peroxide, especially a kind of method of preparing chlorine dioxide by chlorate method.
Two, background technology
Dioxide peroxide is the sterilizing agent of efficient, wide spectrum, safety; when being used for water sterilization, can prevent effectively that (traditional sterilizing agent is a liquid chlorine to organic halogen, when liquid chlorine is used for water sterilization; can produce organic halogen with " three cause " effect) generation, the protection people's is healthy.But because dioxide peroxide can not store and transport, so must on-the-spotly use, the scene takes place.The preparation technology of existing dioxide peroxide mainly contains electrolytic process and chemical method, and electrolytic process is owing to technical elements, and the content of dioxide peroxide contains dioxide peroxide very less or not in the gas that is produced.Chemical method mainly contains chlorate process and chlorite method, the chlorite method is because cost is higher, be not suitable for the national conditions of China, chlorate process mainly is to be oxygenant with the sodium chlorate, in certain temperature, utilize reductive agent (as methyl alcohol in certain acidic medium, sulfurous gas, chlorine, sodium-chlor etc.) the sodium chlorate reduction is generated dioxide peroxide, but because what generally adopt on the present stage market is single variety reductive agent and fixation response time, low and the transformation efficiency problem on the low side of purity that has dioxide peroxide, how improving the purity and the transformation efficiency of preparing chlorine dioxide by chlorate method, is the focus of studying now.
Three, summary of the invention
The objective of the invention is to, overcome the defective that prior art exists, the novel method of the preparation dioxide peroxide of a kind of high purity, high conversion is provided.
The method of preparing chlorine dioxide by chlorate method of the present invention, its processing step is:
A, prepare chloride mixing solutions: with water solvent, wherein, the mass percent 3～40% of sodium chlorate, the mass percent 1～10% of sucrose;
B, with chloride mixed solution, sulfuric acid, industrial hydrogen peroxide by 1: (0.1～10): the volume ratio of (0.1～10) at the uniform velocity adds first step reactor, is 10～30 ℃, reaction chamber negative pressure value for (reacting under the condition of 10KPa～20KPa) in temperature of reaction; Collect the dioxide peroxide that produces, the raffinate of reaction is sent into second stage reactor;
C, in the reactor of the second stage, temperature of reaction be 30～90 ℃ and be higher than upper level temperature of reaction more than 10 ℃ or 10 ℃, the reaction chamber negative pressure value is (20KPa～30KPa) react under the condition; The dioxide peroxide that collect to produce is discharged raffinate, termination reaction, or raffinate sent into the next stage reactor, raffinate is carried out the next stage reaction;
D, in temperature of reaction for≤90 ℃ and be higher than upper level temperature of reaction more than 10 ℃ or 10 ℃, reaction chamber negative pressure value≤70Kpa and be higher than and react under the upper level negative pressure value 10KPa condition; Collect the dioxide peroxide that produces, raffinate is discharged, termination reaction, or still can satisfy temperature of reaction for≤90 ℃ and be higher than upper level temperature of reaction more than 10 ℃ or 10 ℃, reaction chamber negative pressure value≤70Kpa and be higher than under the situation of upper level negative pressure value 10KPa condition, raffinate is sent into the next stage reactor, raffinate is carried out the next stage reaction.
The method of preparing chlorine dioxide by chlorate method of the present invention, owing to adopt cascade raising temperature, independent, the condition of negative pressure reaction down of tandem, transformation efficiency height, purity of chlorine dioxide height, production cost is low, production process is safer.
Four, embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
The preparation method of embodiment 1, preparing chlorine dioxide by chlorate method, its processing step is:
A, prepare chloride mixing solutions: with water solvent, wherein, the mass percent 30% of sodium chlorate, the mass percent 5% of sucrose;
B, chloride mixed solution, commercial sulphuric acid, industrial hydrogen peroxide at the uniform velocity being added first step reactor by 1: 1.5: 0.5 volume ratio, is 25 ℃, negative pressure for (reacting under the condition of 10KPa～20KPa) in temperature of reaction; Collect the dioxide peroxide that produces, the raffinate of reaction is sent into second stage reactor;
C, in the reactor of the second stage, be 45 ℃, reaction chamber negative pressure value for (reacting under the condition of 20KPa～30KPa) in temperature of reaction; Collect the dioxide peroxide that produces, raffinate is sent into third stage reactor, carry out third stage reaction;
D, in third stage reactor, under temperature of reaction is 60 ℃, reaction chamber negative pressure value≤70KPa condition, react; Collect the dioxide peroxide that produces, raffinate is discharged termination reaction.
After reaction residue is discharged, can also be with in the alkali and reconcentration, reclaim(ed) sulfuric acid sodium, but the necessary step of this not to be the present invention realize goal of the invention.
The method of embodiment 2, preparing chlorine dioxide by chlorate method, its processing step is:
A, prepare chloride mixing solutions: be solvent with water, wherein, sodium chlorate content is mass percent 10%, and sucrose content is a mass percent 1%;
B, chloride mixed solution, commercial sulphuric acid, industrial hydrogen peroxide at the uniform velocity being added first step reactor by 1: 10: 10 volume ratio, is 10 ℃ in temperature of reaction, and the reaction chamber negative pressure value is (10KPa～20KPa) react under the condition; Collect the dioxide peroxide that produces, the raffinate of reaction is sent into second stage reactor;
C, in the reactor of the second stage, be that 30 ℃, reaction chamber negative pressure value are (20KPa～30KPa) react under the condition in temperature of reaction; Collect the dioxide peroxide that produces, raffinate is sent into third stage reactor, raffinate is carried out third stage reaction;
D, in third stage reactor, under temperature of reaction is 90 ℃, reaction chamber negative pressure value≤70KPa condition, react; Collect the dioxide peroxide that produces, raffinate is discharged termination reaction.
The preparation method of embodiment 3, preparing chlorine dioxide by chlorate method, its processing step is:
A, prepare chloride mixing solutions: be solvent with water, wherein, sodium chlorate content is mass percent 40%, and sucrose content is a mass percent 10%;
B, chloride mixed solution, commercial sulphuric acid, industrial hydrogen peroxide at the uniform velocity being added first step reactor by 1: 1: 0.1 volume ratio, is 30 ℃, negative pressure for (reacting under the condition of 10KPa～20KPa) in temperature of reaction; Collect the dioxide peroxide that produces, the raffinate of reaction is sent into second stage reactor;
C, in the reactor of the second stage, be 90 ℃, reaction chamber negative pressure value for (reacting under the condition of 20KPa～30KPa) in temperature of reaction; Collect the dioxide peroxide that produces, raffinate is discharged termination reaction.
Embodiment 4, substantially the same manner as Example 1, different is: sodium chlorate content is mass percent 3%.
Embodiment 5, substantially the same manner as Example 1, different is: chloride mixed solution, commercial sulphuric acid, industrial hydrogen peroxide react by 1: 0.1: 5 volume ratio.
ClO 2 solution to above embodiment preparation is analyzed, and its transformation efficiency all is not less than 83.2%, and purity all is not less than 95.4%
The negative pressure that adopts in the reaction can successfully migrate out reactor with the dioxide peroxide that produces in the reaction, improves reaction safety, can reduce the generation of side reaction simultaneously effectively, improves the transformation efficiency and the purity of dioxide peroxide.
In suitability for industrialized production, pressure can fluctuate in this scope during the range of negative pressure in each order reaction of mentioning in the method was represented to allow to produce, and did not influence reaction effect.
Claims (1)
1, the method for preparing chlorine dioxide by chlorate method, its processing step is:
A, prepare chloride mixing solutions: with water solvent, wherein, the mass percent 3～40% of sodium chlorate, the mass percent 1～10% of sucrose;
B, with chloride mixed solution, sulfuric acid, industrial hydrogen peroxide by 1: (0.1～10): the volume ratio of (0.1～10) at the uniform velocity adds first step reactor, is that 10～30 ℃, reaction chamber negative pressure value are to react under the condition of 10KPa～20KPa in temperature of reaction; Collect the dioxide peroxide that produces, the raffinate of reaction is sent into second stage reactor;
C, in the reactor of the second stage, temperature of reaction be 30～90 ℃ and be higher than upper level temperature of reaction more than 10 ℃ or 10 ℃, the reaction chamber negative pressure value is to react under 20KPa～30KPa condition; The dioxide peroxide that collect to produce is discharged raffinate, termination reaction, or raffinate sent into the next stage reactor, raffinate is carried out the next stage reaction;
D, in temperature of reaction for≤90 ℃ and be higher than upper level temperature of reaction more than 10 ℃ or 10 ℃, reaction chamber negative pressure value≤70Kpa and be higher than and react under the upper level negative pressure value 10KPa condition; Collect the dioxide peroxide that produces, raffinate is discharged, termination reaction, or still can satisfy temperature of reaction for≤90 ℃ and be higher than upper level temperature of reaction more than 10 ℃ or 10 ℃, reaction chamber negative pressure value≤70Kpa and be higher than under the situation of upper level negative pressure value 10KPa condition, raffinate is sent into the next stage reactor, raffinate is carried out the next stage reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410013828.7A CN1234597C (en) | 2004-01-07 | 2004-01-07 | Method for preparing chlorine dioxide using chlorate method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410013828.7A CN1234597C (en) | 2004-01-07 | 2004-01-07 | Method for preparing chlorine dioxide using chlorate method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1556029A CN1556029A (en) | 2004-12-22 |
| CN1234597C true CN1234597C (en) | 2006-01-04 |
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| CN200410013828.7A Expired - Fee Related CN1234597C (en) | 2004-01-07 | 2004-01-07 | Method for preparing chlorine dioxide using chlorate method |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538017B (en) * | 2008-03-21 | 2011-05-25 | 东莞市中加消毒科技有限公司 | Process for producing high-purity chlorine dioxide |
| CN106645576B (en) * | 2016-12-16 | 2019-07-05 | 山东省计量科学研究院 | The preparation method of chlorine dioxide standard substance in a kind of nitrogen |
| CN109205563A (en) * | 2017-07-05 | 2019-01-15 | 冠亚腾达（北京）科技有限公司 | A kind of chlorine dioxide generator with reaction of high order and raffinate separator |
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- 2004-01-07 CN CN200410013828.7A patent/CN1234597C/en not_active Expired - Fee Related
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