CN101746731B - Method for producing chlorine dioxide with high purity by adopting combined reducing agent - Google Patents
Method for producing chlorine dioxide with high purity by adopting combined reducing agent Download PDFInfo
- Publication number
- CN101746731B CN101746731B CN2009101146387A CN200910114638A CN101746731B CN 101746731 B CN101746731 B CN 101746731B CN 2009101146387 A CN2009101146387 A CN 2009101146387A CN 200910114638 A CN200910114638 A CN 200910114638A CN 101746731 B CN101746731 B CN 101746731B
- Authority
- CN
- China
- Prior art keywords
- chlorine dioxide
- reducing agent
- sodium
- hydrogen peroxide
- combined reducing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000004155 Chlorine dioxide Substances 0.000 title claims abstract description 30
- 235000019398 chlorine dioxide Nutrition 0.000 title claims abstract description 30
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 72
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 29
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000006227 byproduct Substances 0.000 claims abstract description 15
- 230000002829 reductive effect Effects 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000012452 mother liquor Substances 0.000 claims description 24
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 20
- 239000000460 chlorine Substances 0.000 abstract description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010413 mother solution Substances 0.000 abstract 2
- 239000010446 mirabilite Substances 0.000 abstract 1
- 150000002978 peroxides Chemical class 0.000 description 33
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 15
- 238000003860 storage Methods 0.000 description 10
- 241000370738 Chlorion Species 0.000 description 9
- 230000008569 process Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000004061 bleaching Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000009795 derivation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004076 pulp bleaching Methods 0.000 description 3
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229940005991 chloric acid Drugs 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 229940077239 chlorous acid Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- -1 chlorate anions Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical group [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treating Waste Gases (AREA)
Abstract
The present invention relates to a method for producing chlorine dioxide with high purity by adopting a combined reducing agent. The method comprises the following steps of: injecting concentrated sulfuric acid and a sodium chlorate solution into a generator to form a reacting mother solution; maintaining the reacting mother solution to a certain acidity, temperature and the content of sodium chlorate; then adding a combined reducing agent comprising methanol, hydrogen peroxide, hydrochloric acid or sodium chlorate to react for generating chlorine dioxide gas and a byproduct namely acid mirabilite; cooling and then absorbing the chlorine dioxide gas by using low temperature frozen water to obtain a water solution of chlorine dioxide; and simultaneously recovering the byproduct. The conversion rate of the chlorine dioxide produced by the method is improved by 3-6 percent as comparison with that of the chlorine dioxide produced by a single reducing agent, the stability of chemical reaction is improved, the production cost is reduced, and the chlorine amount in the chlorine dioxide solution and tail gas exhausted from a chlorine dioxide absorbing tower is remarkably reduced.
Description
Technical field
The present invention relates to the production method of dioxide peroxide, relate in particular to the method that a kind of sodium chlorate method is produced dioxide peroxide.
Background technology
Dioxide peroxide is a kind of strong oxidizer, and stabilized chlorine dioxide is known as respond well sterilant, sterilizing agent by the World Health Organization, also is good papermaking SYNTHETIC OPTICAL WHITNER.From 1830s beginning suitability for industrialized production, 1000 chlorine dioxide production factories at present have an appointment in North America and Europe.Current China has realized the production domesticization of small-sized sterilization with chlorine dioxide production equipment, but, for on-site preparation and the on-the-spot large-scale chlorine dioxide preparation system that uses digestion, the domestic development that also is in, the large-scale chlorine dioxide production system that existing papermaking enterprise adopts is the suite of equipment technology of import.
The main application of dioxide peroxide is association with pulp bleaching and drinking water disinfection, dioxide peroxide be used for association with pulp bleaching have high whiteness, whiteness stable, keep intensity and the low hypotoxic characteristics of color of draining, its unique superiority is that any other chemical is incomparable so far.In view of the toxicity of ClO 2 bleaching superiority and chlorine bleaching effluent, it is one of chemical of association with pulp bleaching that dioxide peroxide has been recommended by National Development and Reform Committee, and progressively eliminates the chlorine bleaching process.
The production technology of dioxide peroxide generally can be divided three classes according to different preparation technologies: electrolytic process, sodium chlorate method and Textone method.Electrolytic process is progressively replaced by chemical method at present because productive rate is low, product is impure, power consumption is big.Textone method ratio is easier to discharge dioxide peroxide and productive rate height, but the Textone price exceeds about twice than sodium chlorate price, and the industrial production of therefore extensive dioxide peroxide is used the sodium chlorate method usually.The sodium chlorate method mainly uses sulfurous gas, sodium-chlor or hydrochloric acid as reductive agent, and raw material obtains extensively, and is cheap, but these methods all exist shortcomings such as transformation efficiency is not high, the chlorine ratio is big.Hydrogen peroxide is produced the method that dioxide peroxide is new research and development as reductive agent, and its process is efficient, speed of response is fast, but the hydrogen peroxide price is more expensive, and hydrogen peroxide is a kind of relative unstable compounds, easily decomposes, and causes the meaningless increase of cost.The methyl alcohol method is present leading production method, its transformation efficiency only time and hydrogen peroxide method, but contain a certain amount of chlorine in the product, increase the bleaching effluent processing cost on the one hand, also cause reaction system chlorion disappearance and cause the chemical reaction instability.
Summary of the invention
Technical problem to be solved by this invention provides a kind of production method of utilizing combined reducing agent to prepare dioxide peroxide, to improve the transformation efficiency from the sodium chlorate to the dioxide peroxide, improves the stability of chemical reaction, and reduces the production cost of dioxide peroxide.
The present invention solves the problems of the technologies described above with following technical scheme:
The inventive method is at first injected producer with the vitriol oil, sodium chlorate solution and is formed reaction mother liquor, and make reaction mother liquor keep certain acidity, temperature and sodium chlorate content, add the reductive agent reaction then and produce chlorine dioxide and the acid saltcake of byproduct, chlorine dioxide absorbs with cryogenic freezing water after cooling off, obtain aqueous solution of chlorine dioxide, simultaneously byproduct is reclaimed.
The combined reducing agent that described reductive agent is made up of methyl alcohol, hydrogen peroxide, hydrochloric acid or sodium-chlor, the add-on of this combined reducing agent is the 9-10% that adds sodium chlorate weight, and the methyl alcohol in this combined reducing agent, hydrogen peroxide, hydrochloric acid or sodium-chlor proportioning by mass percentage is: methyl alcohol 70-90% ︰ hydrogen peroxide 7-25% ︰ hydrochloric acid or sodium-chlor 3-5%.
The addition sequence of combined reducing agent optimization of the present invention is hydrochloric acid or sodium-chlor, methyl alcohol and hydrogen peroxide, sees accompanying drawing 1 for details.
Methyl alcohol in the described combined reducing agent, hydrogen peroxide, hydrochloric acid or sodium-chlor optimum ratio by mass percentage is: methyl alcohol 86% ︰ hydrogen peroxide, 10% ︰ hydrochloric acid or sodium-chlor 4%.
Reaction mother liquor is kept acidity 8.0～8.2N and sodium chlorate content 158～266g/l, keeps 68～78 ℃ of temperature.
Described chlorine dioxide absorbs with cryogenic freezing water after cooling off, and is with 4～10 ℃ of refrigerated waters.
The inventive method produces the reaction principle of dioxide peroxide:
HClO
3+CH
3OH→HClO
2+CH
3OOH (1)
H
2O
2+HClO
3→HClO
2+H
2O+O
2 (2)
HClO
2+CH
3OH→HOCl+CH
3O0H (3)
HOCl+CH
3OH→HCl+CH
3O0H (4)
HClO
3+HCl→HClO
2+HOCl (5)
HClO
3+HClO
2→ClO
2+H
2O (6)
HOCl+HCl→Cl
2+H
2O (7)
5HClO
2→3HClO
3+Cl
2+H
2O (8）
H
2O
2+Cl
2→H
++2Cl
－+O
2 (9)
Chloric acid progressively is reduced to chlorion by reaction (1)-(4).Chlorion and chlorate anions reaction (5) generate chlorous acid, and chlorous acid generates dioxide peroxide with chloric acid reaction (6) again.In this group reaction, the hypochlorous acid that reaction (3) and reaction (5) generate is reduced into chlorion in reaction (4), and reaction (4) is continued therefrom, and avoids the elemental chlorine of formation reaction (7) (8).Reaction (9) is very fast, so the elemental chlorine that reaction (7) (8) produce is reduced into chlorion very soon.Chlorion is the catalyzer that generates the reaction (6) of dioxide peroxide.
By reaction mechanism, can be clear that muriate is reduced into chlorion (Cl soon through several steps after reacting with reductive agent
–), thereby promoted carrying out smoothly of entire reaction, constantly generate dioxide peroxide.So, the generation of chlorion and to replenish be one of essential condition of avoiding in the chlorine dioxide reaction abortive response.
The inventive method adopts by the reasonably combined combined reducing agent of forming of methyl alcohol, hydrogen peroxide, hydrochloric acid or sodium-chlor, under strong acid, certain temperature, vacuum condition in titanium vessels reduction sodium chlorate continuous production chlorine dioxide with high purity and the acid saltcake of byproduct, ClO
2Gas absorbs with cryogenic freezing water after cooling off, and obtains having finite concentration ClO
2Solution reclaims byproduct simultaneously.
The combined reducing agent that the inventive method is used is the mixed solution of the rational methyl alcohol of collocation, hydrogen peroxide, hydrochloric acid or sodium-chlor, produce dioxide peroxide than producing the transformation efficiency 3-6% that dioxide peroxide can effectively improve sodium chlorate with the inventive method, continuously replenish the stability that chlorion is kept chemical reaction with single reductive agent.Because sodium chlorate accounts for most ratios in the production cost of dioxide peroxide, so that production cost has reduced is many, ClO 2 solution neutralization simultaneously significantly reduces from the amount of chlorine of dioxide peroxide absorption tower tail gas discharged.
Description of drawings
Fig. 1 is technological process of production figure of the present invention.
Embodiment
The technical process of the inventive method is by shown in Figure 1, the vitriol oil is extracted out from the sulfuric acid storage tank and injection producer after the sulfuric acid strainer filters, the sodium chlorate solution is extracted out and injection producer after the sodium chlorate strainer filters from the sodium chlorate storage tank, the vitriol oil and sodium chlorate form reaction mother liquor, are circulating in the producer circulating line under the effect of recycle pump.Comprise reboiler in the circulating line, reboiler heats to reaction mother liquor keeps the required temperature of reaction.Methyl alcohol is extracted out from the methyl alcohol storage tank and logical nozzle injection producer after the methyl alcohol strainer filters.Hydrochloric acid of extracting out from hydrochloric acid or sodium-chlor storage tanks or sodium-chlor filter the back through filter and inject producer.From the hydrogen peroxide storage tanks, extract hydrogen peroxide out and inject producer reaction generation dioxide peroxide with nozzle.The mixed gas of dioxide peroxide and water vapour enters inter cooler and enters the dioxide peroxide absorption tower through after cooling, and absorbs the formation aqueous solution of chlorine dioxide and is transported to the storage tank storage with refrigerated water in the tower.With the mother liquor of pump extraction in the producer bottom, utilize filter to leach the acid saltcake of byproduct, the mother liquor that leaches returns producer.Along with continuous adding NaClO
3Solution, the vitriol oil and combined reducing agent, ClO
2Gas constantly reacts generation.Vacuum is aspirated vacuum Venturi by two with middle pressure steam and is produced.
Hydrochloric acid or sodium-chlor, methyl alcohol and hydrogen peroxide add some optimization, and promptly hydrochloric acid or sodium-chlor are added on before the recycle pump, and methyl alcohol and hydrogen peroxide are added on after the reboiler.It is preceding in methyl alcohol adding point that hydrogen peroxide adds point.
Material benzenemethanol in the combined reducing agent, hydrogen peroxide, hydrochloric acid or sodium-chlor all adopt technical pure.
Embodiment 1:
With weight concentration is that 98% vitriol oil 108kg and weight concentration are that 30% sodium chlorate solution 547kg filters the back and injects producer and form reaction mother liquor, in circulation and make reaction mother liquor keep acidity 8.0～8.2N and sodium chlorate content 158～266g/l in the producer circulating line under the effect of recycle pump.Steam conducts heat to the reaction mother liquor heating by reboiler and keeps 68～78 ℃ of temperature.Be respectively 20% methyl alcohol, weight with weight 52.5kg concentration for 12.5kg concentration be 30% hydrogen peroxide and weight for 2.5kg concentration be that 30% hydrochloric acid injects producer with nozzle and makes reaction produce dioxide peroxide.Producer keeps vacuum condition, and pressure is the 120mm mercury column, and vacuum is aspirated vacuum Venturi by two with middle pressure steam and produced.Under condition of negative pressure, from the gas dioxide peroxide of producer derivation and the mixed gas temperature of water vapour is 57～68 ℃, tentatively cool 38～45 ℃ by inter cooler, gas enters dioxide peroxide and absorbs in the Tata, absorbs to form aqueous solution of chlorine dioxide and be transported to storage tank with 4～10 ℃ of refrigerated water sprays and stores.Reacting surplus liquid and byproduct forms crystal with reaction and constantly separates out, the solid volume percent content is 18～23% in the maintenance producer, extract mother liquor in the producer bottom out with pump and utilize filter to leach the acid saltcake of byproduct, the mother liquor that leaches returns producer.Along with continuous adding NaClO
3Solution, the vitriol oil and combined reducing agent, ClO
2Gas constantly reacts generation.
Embodiment 2:
With weight concentration is that 98% vitriol oil 108kg and weight concentration are that 30% sodium chlorate solution 547kg filters the back and injects producer and form reaction mother liquor, in circulation and make reaction mother liquor keep acidity 8.0～8.2N and sodium chlorate content 158～266g/l in the producer circulating line under the effect of recycle pump.Steam conducts heat to the reaction mother liquor heating by reboiler and keeps 68～78 ℃ of temperature.Be respectively 20% methyl alcohol, weight with weight 67.5kg concentration for 3.5kg concentration be 30% hydrogen peroxide and weight for 1.5kg concentration be that 30% hydrochloric acid injects producer with nozzle and makes reaction produce dioxide peroxide.Producer keeps vacuum condition, and pressure is the 120mm mercury column, and vacuum is aspirated vacuum Venturi by two with middle pressure steam and produced.Under condition of negative pressure, from the gas dioxide peroxide of producer derivation and the mixed gas temperature of water vapour is 57～68 ℃, tentatively cool 38～45 ℃ by inter cooler, gas enters dioxide peroxide and absorbs in the Tata, absorbs to form aqueous solution of chlorine dioxide and be transported to storage tank with 4～10 ℃ of refrigerated water sprays and stores.Reacting surplus liquid and byproduct forms crystal with reaction and constantly separates out, the solid volume percent content is 18～23% in the maintenance producer, extract mother liquor in the producer bottom out with pump and utilize filter to leach the acid saltcake of byproduct, the mother liquor that leaches returns producer.Along with continuous adding NaClO
3Solution, the vitriol oil and combined reducing agent, ClO
2Gas constantly reacts generation.
Embodiment 3:
With weight concentration is that 98% vitriol oil 108kg and weight concentration are that 30% sodium chlorate solution 547kg filters the back and injects producer and form reaction mother liquor, in circulation and make reaction mother liquor keep acidity 8.0～8.2N and sodium chlorate content 158～266g/l in the producer circulating line under the effect of recycle pump.Steam conducts heat to the reaction mother liquor heating by reboiler and keeps 68～78 ℃ of temperature.Be respectively 20% methyl alcohol, weight with weight 64.5kg concentration for 5kg concentration be 30% hydrogen peroxide and weight for 2kg concentration be that 30% hydrochloric acid injects producer with nozzle and makes reaction produce dioxide peroxide.Producer keeps vacuum condition, and pressure is the 120mm mercury column, and vacuum is aspirated vacuum Venturi by two with middle pressure steam and produced.Under condition of negative pressure, from the gas dioxide peroxide of producer derivation and the mixed gas temperature of water vapour is 57～68 ℃, tentatively cool 38～45 ℃ by inter cooler, gas enters dioxide peroxide and absorbs in the Tata, absorbs to form aqueous solution of chlorine dioxide and be transported to storage tank with 4～10 ℃ of refrigerated water sprays and stores.Reacting surplus liquid and byproduct forms crystal with reaction and constantly separates out, the solid volume percent content is 18～23% in the maintenance producer, extract mother liquor in the producer bottom out with pump and utilize filter to leach the acid saltcake of byproduct, the mother liquor that leaches returns producer.Along with continuous adding NaClO
3Solution, the vitriol oil and combined reducing agent, ClO
2Gas constantly reacts generation.
Claims (2)
1. method that adopts combined reducing agent to produce chlorine dioxide with high purity, it is characterized in that: at first the vitriol oil, sodium chlorate solution are injected producer and form reaction mother liquor, and make reaction mother liquor keep acidity 8.0-8.2N, sodium chlorate content 158-266g/l, keep 68-78 ℃ of temperature, add the reductive agent reaction then and produce chlorine dioxide and the acid saltcake of byproduct, chlorine dioxide cryogenic freezing water with 4-10 ℃ after cooling off absorbs, obtain aqueous solution of chlorine dioxide, simultaneously byproduct is reclaimed;
The combined reducing agent that described reductive agent is made up of methyl alcohol, hydrogen peroxide, hydrochloric acid or sodium-chlor, the add-on of this combined reducing agent are the 9-10% that adds sodium chlorate weight;
Methyl alcohol in this combined reducing agent and hydrogen peroxide, hydrochloric acid or sodium-chlor mixture ratio by weight percent are: methyl alcohol 70-90%: hydrogen peroxide 7-25%: hydrochloric acid or sodium-chlor 3-5%.
2. employing combined reducing agent according to claim 1 is produced the method for chlorine dioxide with high purity, and it is characterized in that: methyl alcohol in the combined reducing agent and hydrogen peroxide, hydrochloric acid or sodium-chlor optimum ratio by weight percentage is: methyl alcohol 86%: hydrogen peroxide 10%: hydrochloric acid or sodium-chlor 4%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101146387A CN101746731B (en) | 2009-12-16 | 2009-12-16 | Method for producing chlorine dioxide with high purity by adopting combined reducing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101146387A CN101746731B (en) | 2009-12-16 | 2009-12-16 | Method for producing chlorine dioxide with high purity by adopting combined reducing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101746731A CN101746731A (en) | 2010-06-23 |
| CN101746731B true CN101746731B (en) | 2011-09-14 |
Family
ID=42474442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101146387A Active CN101746731B (en) | 2009-12-16 | 2009-12-16 | Method for producing chlorine dioxide with high purity by adopting combined reducing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101746731B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439091B (en) * | 2015-12-02 | 2017-11-17 | 广西大学 | The peroxide passivation chlorine dioxide preparation method and equipment of environment-friendly type |
| CN105439096B (en) * | 2015-12-02 | 2017-11-17 | 广西大学 | Environment-friendly type peroxide passivation chlorine dioxide technique prepares the method and apparatus of sodium chlorite |
| CN105726469A (en) * | 2016-03-08 | 2016-07-06 | 刘学武 | Chlorine dioxide containing injection and preparation method thereof |
| CN105752931A (en) * | 2016-05-03 | 2016-07-13 | 广西大学 | Method for producing high-purity chlorine dioxide |
| CN110382409A (en) * | 2018-08-30 | 2019-10-25 | 广西博世科环保科技股份有限公司 | A kind of methanol combines the method that reduction prepares chlorine dioxide with high purity with hydrogen peroxide |
| CN109704282B (en) * | 2019-01-30 | 2022-05-27 | 广东至诚紫光新材料有限公司 | Chlorine dioxide solution for removing formaldehyde and preparation method and application thereof |
| CN109678116B (en) * | 2019-01-30 | 2022-05-27 | 广东至诚紫光新材料有限公司 | Chlorine dioxide solution for sewage treatment and preparation method and application thereof |
-
2009
- 2009-12-16 CN CN2009101146387A patent/CN101746731B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101746731A (en) | 2010-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101746731B (en) | Method for producing chlorine dioxide with high purity by adopting combined reducing agent | |
| CN105752931A (en) | Method for producing high-purity chlorine dioxide | |
| CN101659426A (en) | Method for preparing sodium bromide by continuous multi-stage air blow | |
| CN101544354A (en) | A method for preparing clo2 using combined BSC reducing reagent | |
| CN104086362A (en) | Method for recycling organic solvents of wastewater generated in synthesis of hydrazine hydrate by ketazine method | |
| CN101519189A (en) | Method and device for preparing basic magnesium hypochlorite by using waste chlorine | |
| CN104261350A (en) | Preparation method of chlorine dioxide without production of solids | |
| CN105439095A (en) | Method and device for preparing sodium chlorite through comprehensive method chlorine dioxide process | |
| CN103641748B (en) | A kind of recycle by-product hydrochloric acid prepares the method for methylsulphonic acid | |
| CN113321186B (en) | Method for producing chlorine dioxide by reducing sodium chlorate with calcium peroxide in sodium bisulfate solution environment | |
| CN101544384B (en) | Method for reclaiming the accessory product acidic mirabilite when producing chlorine dioxide | |
| US9776163B1 (en) | Method and system for the integral chlorine dioxide production with relatively independent sodium chlorate electrolytic production and chlorine dioxide production | |
| CN101982404B (en) | Equipment and method for preparing chlorine dioxide solution | |
| AU2010305879B2 (en) | Process for production of chlorine dioxide | |
| AU2010261878B2 (en) | Process for the production of chlorine dioxide | |
| CN1261051A (en) | Process for preparing stable ClO2 solution based on hydrochloric acid | |
| CA2116427C (en) | Acidity control in chlorine dioxide manufacture | |
| EP3845488A1 (en) | Method for preparing high-purity chlorine dioxide using combination of methyl alcohol and hydrogen peroxide as reducing agent | |
| CN101712479B (en) | Method for preparing sodium sulfite by utilizing total alkali in hydrazine hydrate | |
| CN204981135U (en) | No spent acid discharges dioxygen water law chlorine dioxide generator | |
| JPH0621004B2 (en) | Chlorine dioxide manufacturing method | |
| CA2734867C (en) | Process for producing chlorine dioxide using waste glycerol from a biodiesel plant | |
| CN220951197U (en) | System for preparing caustic soda by recycling natural alkali tail liquid | |
| CN209957373U (en) | Equipment for producing sodium chlorite based on chloric acid and hydrogen peroxide | |
| CN102530876B (en) | Method for producing sodium chlorite by sulfur method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhou Maoxian Inventor after: Xu Cuisheng Inventor after: LAN Yun Fei Inventor before: Zhou Maoxian Inventor before: Xu Cuisheng Inventor before: Zhan Lei Inventor before: Li Xusheng Inventor before: Nong Bin Inventor before: Nong Guangzai Inventor before: LAN Yun Fei |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: ZHOU MAOXIAN XU CUISHENG ZHAN LEI LI XUSHENG NONG BIN NONG GUANGZAI LAN YUNFEI TO: ZHOU MAOXIAN XU CUISHENG LAN YUNFEI |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for producing chlorine dioxide with high purity by adopting combined reducing agent Effective date of registration: 20171013 Granted publication date: 20110914 Pledgee: Bank of Communications Ltd. the Guangxi Zhuang Autonomous Region branch Pledgor: GUANGXI BOSSCO ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Registration number: 2017450000009 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20191119 Granted publication date: 20110914 Pledgee: Bank of Communications Ltd. the Guangxi Zhuang Autonomous Region branch Pledgor: GUANGXI BOSSCO ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Registration number: 2017450000009 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for producing chlorine dioxide with high purity by adopting combined reducing agent Effective date of registration: 20191121 Granted publication date: 20110914 Pledgee: Nanning Urban Rural Credit Cooperative Association Pledgor: GUANGXI BOSSCO ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Registration number: Y2019450000023 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20201119 Granted publication date: 20110914 Pledgee: Nanning Urban Rural Credit Cooperative Association Pledgor: GUANGXI BOSSCO ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Registration number: Y2019450000023 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: Intersection of Dongcheng Avenue and Dongcheng Road in Heli Park, Ningguo Economic and Technological Development Zone, Ningguo City, Xuancheng City, Anhui Province Patentee after: Anhui Boshike Environmental Protection Technology Co.,Ltd. Country or region after: China Address before: 530007, No. two, No. 1, hi tech Zone, the Guangxi Zhuang Autonomous Region, Nanning Patentee before: GUANGXI BOSSCO ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Country or region before: China |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20240430 Address after: Intersection of Dongcheng Avenue and Dongcheng Road in Heli Park, Ningguo Economic and Technological Development Zone, Ningguo City, Xuancheng City, Anhui Province Patentee after: Anhui Boshike Environmental Protection Technology Co.,Ltd. Country or region after: China Patentee after: Guangxi Boshike Environmental Technology Co.,Ltd. Address before: Intersection of Dongcheng Avenue and Dongcheng Road in Heli Park, Ningguo Economic and Technological Development Zone, Ningguo City, Xuancheng City, Anhui Province Patentee before: Anhui Boshike Environmental Protection Technology Co.,Ltd. Country or region before: China |
|
| TR01 | Transfer of patent right |