CN1353083A - Process for preparing ClO2 - Google Patents
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- CN1353083A CN1353083A CN 00132247 CN00132247A CN1353083A CN 1353083 A CN1353083 A CN 1353083A CN 00132247 CN00132247 CN 00132247 CN 00132247 A CN00132247 A CN 00132247A CN 1353083 A CN1353083 A CN 1353083A
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Abstract
A process for preparing ClO2 features that under the existance of proton catalyst and the aqueous solution of strong inorganic acid, the chloride acid and hydrogen peroxide take part in reaction at 30-95 deg.C under stirring condition to generate ClO2. Its advantages include high reaction speed and conversion rate, no discharge of waste liuqid and dregs, cyclic use of proteon catalyst and low cost.
Description
The present invention relates to the production method of chlorine oxides, the production method of the dioxide peroxide of more specifically saying so.
See dioxide peroxide ClO from chemical terms
2Chemical property very active, be strong oxidizer.Dioxide peroxide can with the reaction of the enzyme system (SH-yl) of microorganism, even can oxygenolysis fall the corpse of microorganism.It can with the radical reaction that adds lustre to of coloring matter, can with the reaction of the reducing substances of sulfur-bearing, phosphorus, nitrogen, can and CN
-, ArOH, Fe
2+, Mn
+ 2Deng reaction.Thereby, from application point, ClO
2Be strong sterilization, sterilizing agent, mould inhibitor, reodorant, SYNTHETIC OPTICAL WHITNER, the preservation agent of a broad-spectrum high efficacy, it integrates multiple function.
Common chlorinated product, for example Cl as sterilization, sterilization, SYNTHETIC OPTICAL WHITNER
2, NaOCl, chlorinated lime etc., in its use, can generate the halohydrocarbon series derivates with the organic substance reaction.But with CHX
3For many halohydrocarbon of representative have carcinogenic, cause tumour, clastogenic " three cause " effect, HUMAN HEALTH has been brought potential harm.And the reaction of dioxide peroxide and organic substance does not generate the material of " three cause " effect, and human body and higher animal are had the security of height, is confirmed as the safe sterilant of A1 level by the World Health Organization, is the optimal chemical bactericide of generally acknowledging in the world.Number of research projects proof dioxide peroxide all has killing action rapidly and thoroughly to bacterial propagule, fungal spore, virus, algae, and does not see resistance so far.
Since the late nineteen eighties, corresponding regulations has all been issued in many in the world developed countries and area, at extensive fields mandatory use dioxide peroxide.At American-European and Asia developed country and the waterworks application ClO of regional thousands of families
2Replaced the liquid chlorine sterilization process.The association with pulp bleaching great majority in the U.S., Canada, Northern Europe have adopted ClO
2Bleaching process.Various technical fields such as that dioxide peroxide can also be used for is fiber bleached, grease bleaching, bleaching of flour, industrial circulating cooling water processing, sewage and waste water processing, melon and fruit storage fresh-keeping, fishery products storage fresh-keeping, oil production plugging removal and stimulation, refining of petroleum, its purposes is very extensive, has enormous and latent market.
The production method of dioxide peroxide has electrochemical process, chemical synthesis and their combined method.Present business-like chlorine dioxide generation major part is with sodium chlorate (NaClO
3) be raw material, in the strong inorganic acid medium, prepare dioxide peroxide with reductive agent reduction sodium chlorate.The reductive agent that adopts in the production has chlorion (Cl
-) source, sulfurous gas (SO
2) or S-WAT (Na
2SO
3) or sodium bisulfite (NaHSO
3), methyl alcohol (CH
3OH) or other organism.The strong inorganic acid that adopts mainly is sulfuric acid (H
2SO
4) or hydrochloric acid (HCl).Adopt the greatest drawback of chloride-ion source reductive agent to be, when generating dioxide peroxide, generated a large amount of chlorine (Cl
2), as previously mentioned, chlorine is objectionable constituent, not chloride dioxide peroxide is produced in environmental requirement.Adopt the subject matter of methyl alcohol reductive agent to be, because its volatility has not only reduced its utilization ratio, and the volatile intermediate of methyl alcohol and generation thereof enters in the gaseous mixture, reduced the production efficiency of dioxide peroxide.When adopting sulfurous gas or sulfur-bearing reductive agent, because the speed of reaction of they and sodium chlorate is slow, cause chlorine dioxide production efficiency to reduce, in order to improve speed of reaction, often need to add small amount of chloride and augmenting response liquid acidity, thereby often contain small amounts of chlorine in the feasible dioxide peroxide that generates, and increased the burden that reactivity liquid is handled.In order to overcome the defective of above-mentioned reductive agent, in chlorine dioxide production technical literature recently, proposed with hydrogen peroxide (H
2O
2) be reductive agent and sodium chlorate reaction, under lower acidity, can obtain higher speed of reaction, generate the dioxide peroxide that does not contain organism, is substantially free of chlorine.But still exist generate sodium sulfate and (or) the waste reaction solution problem of sodium pyrosulfate, though these be liquid or the solid refuse all must from reactor, remove away, not only need to increase the liquid waste disposal investment, and these regenerants there is no much economic worths.
The another kind of method of commercially producing dioxide peroxide is with Textone NaClO
2Be raw material and HCl or Cl
2Reaction generates ClO
2The advantage of this method is, can be in normal-temperature reaction, need not heat, speed of reaction is fast, and the transformation efficiency of Textone is respectively up to more than 80% and 95%, and process unit is simple, easy-to-operate, easily realize control automatically, but its shortcoming is that raw material Textone price is much more expensive than sodium chlorate, thereby the cost that makes this method produce dioxide peroxide increases greatly.
American documentation literature US5486344 proposes: in order to reduce and to avoid generating alkali-metal vitriol or/and the hydrosulfate byproduct adopts chloric acid (HClO
3) alternate base metal chlorate prepares dioxide peroxide, promptly is raw material with chloric acid, hydrogen peroxide is that reductive agent is produced ClO
2Method.This method is a chloric acid and as the hydrogen peroxide of reductive agent, does not particularly have sulfuric acid at other mineral acids that do not have except chloric acid basically, does not also have to be added in the reaction system under the condition of alkalimetal ion, and chloric acid is reduced into dioxide peroxide.The concentration of raw material chloric acid is 0.5-12M, and its temperature of reaction is 15 ℃-100 ℃.The speed of reaction of this method is than other system, and the significant reaction ground that for example produces dioxide peroxide in oxymuriate-methyl alcohol-sulfuric acid system or oxymuriate-hydrogen peroxide-sulfuric acid system is fast, and does not generate sodium sulfate or/and sodium pyrosulfate.But this method is to use electrolytic process, obtain be the mixing solutions of chloracid-sodium chlorate as raw material, prepare dioxide peroxide with hydroperoxidation, unreacted sodium chlorate is recycled to the electrolyzer from reactor.This method equipment complexity, and restricted by current efficiency, the efficient that the electrolysis sodium chlorate changes into chloric acid is not high, simultaneously, the present invention discovers that by experiment the speed of reaction and the transformation efficiency of chloric acid and hydrogen peroxide generation dioxide peroxide neither be very high, and the transformation efficiency of its chloric acid only is 60-72%.
Purpose of the present invention just is to work out that a kind of used equipment is simple, speed of reaction is faster, transformation efficiency is higher, do not produce sodium sulfate and (or) method of the production high-pure chlorinedioxide of sodium pyrosulfate byproduct.
The production method of a kind of dioxide peroxide of the present invention, be in the presence of the proton catalyst strong inorganic acid aqueous solution, join simultaneously in the proton catalyst strong inorganic acid aqueous solution with raw material chloric acid with as the hydrogen peroxide of reductive agent in the stirring, under 30-95 ℃ temperature, make chloric acid and hydroperoxidation generate dioxide peroxide.
Said proton catalyst strong inorganic acid is sulfuric acid, perchloric acid, phosphoric acid, the sulfuric acid of any mol ratio and mixing acid a kind of acid wherein of phosphoric acid.For well, the concentration of perchloric acid is the 2-6 mol to proton catalyst vitriolic concentration with the 1-12 mol, and concentration of phosphoric acid is the 3-12 mol, and the concentration of the mixing acid of the sulfuric acid of mol ratio and phosphoric acid is the 3-12 mol arbitrarily.The concentration of raw material chloric acid is the 5-45% weight percentage, the concentration of chloric acid is less than 5% weight percentage, it is too slow that reaction is carried out, and during greater than 45% weight percentage, poor stability, so the concentration of raw material chloric acid is advisable with the 20-40% weight percentage, the purity of chloric acid is being good (with pure chloric acid) more than or equal to 98%, chloric acid has day green environment engineering limited liability company sale in Beijing, and the chloric acid that can also produce with the ion exchange method of U.S. Pat 3810969 or US4798715 is raw material.The purity of chloric acid is high more good more.If the purity of chloric acid is not high, wherein contain impurity component, for example contain metal ion, need to handle after then using some cycles.The concentration of reductive agent hydrogen peroxide (hydrogen peroxide) is the 5-35% weight percentage, and the hydrogen peroxide of general commercial goods is for containing H
2O
2The 27-35% weight percentage.The concentration of reductive agent hydrogen peroxide is good with 27-35%.When chloric acid and hydrogen peroxide reacted, the mol ratio of chloric acid and hydrogen peroxide (hydrogen peroxide) is 1: 0.2-2.0, again with 1: 0.5-1.8 was good.In order to make hydrogen peroxide more stable, preferably stablizer is joined in the reductive agent hydrogen peroxide (hydrogen peroxide), hydrogen peroxide and stablizer are pre-mixed evenly.The amount of the stablizer in the hydrogen peroxide that joins is 0.01～2% of reductive agent hydrogen peroxide (hydrogen peroxide) weight, again with the 0.1-1% of hydrogen peroxide (hydrogen peroxide) weight for well.The stablizer that is added is 1-hydroxy ethylene-1-di 2 ethylhexyl phosphonic acid, 1-ethylamine-1, and wherein a kind of of 1-di 2 ethylhexyl phosphonic acid amino three (methylene phosphonic acid), diethylenetriamine five (methylene phosphonic acid) seen U.S. Pat 5486344 for details.
At first proton catalyst strong inorganic acid solution is placed reaction vessel, the amount that the proton catalyst strong inorganic acid aqueous solution joins in the reaction vessel is the 1-70% (V/V) of reaction vessel volume, again with the 1-50% (V/V) of reaction vessel volume for well.In the presence of proton catalyst strong inorganic acid solution, the temperature of reaction of chloric acid and hydrogen peroxide is 30-95 ℃, and when its temperature of reaction was lower than 30 ℃, speed of reaction was slow, and when temperature of reaction was higher than 95 ℃, poor stability was so its temperature of reaction is good with 65-85 ℃.Proton catalyst strong inorganic acid solution is heated to 30-95 ℃, again to be heated to 65-85 ℃ for well.Under agitation can add chloric acid and hydrogen peroxide simultaneously in proton catalyst strong inorganic acid solution, the inlet amount of reaction mass is according to the throughput of dioxide peroxide being determined under experiment condition, the flow of the adding of its chloric acid is 230～800 Grams Per Hours, H
2O
2Adding inbound traffics is the 90-234 Grams Per Hour.Be injected into continuously in the proton catalyst strong inorganic acid solution after also raw material chloric acid and hydrogen peroxide (as reductive agent) can being pre-mixed and react.The size of the stirring velocity when stirring has no significant effect reaction, exactly proton catalyst strong inorganic acid solution, chloric acid, hydrogen peroxide is mixed, and its alr mode can be an induction stirring, also can stir or the alternate manner stirring with stirring arm.
The reaction of chloric acid and hydrogen peroxide can be carried out under the condition of malleation or negative pressure.Overflowing from reaction vessel for fear of the product dioxide peroxide that is generated, is good with the reaction of carrying out chloric acid and hydrogen peroxide (hydrogen peroxide) under the condition of negative pressure, and its pressure range is 8Kpa～66.5Kpa (being the 60-500mmHg post).For the reaction that makes chloric acid and hydrogen peroxide is carried out more safely, can be in reaction vessel bubbling air or nitrogen, play the effect of the chlorine dioxide concentration that bubbling stirred reaction mixture and dilution generate.Under negative-pressure operation, make the product dioxide peroxide of generation and the gaseous mixture of air or nitrogen and the water vapor that evaporation generates in reaction process, transfer out reactive system.The air that is fed or the flow of nitrogen make the content of the dioxide peroxide in gaseous mixture less than 10% percent by volume.The gaseous mixture water of product dioxide peroxide that transports out continuously from reaction vessel and air or nitrogen and the water vapor that generates in reaction process absorbs or is passed in the processed system and is applied.The proton catalyst strong inorganic acid aqueous solution that is added in the reaction of chloric acid and hydrogen peroxide does not consume, and can recycle.When but low or other reasons is introduced impurity in reaction raw materials purity, then need to handle.After stopping charging, after continuing again to react one suitable period, can be according to ClO in the national standard method assaying reaction device inner proton catalyzer strong inorganic acid of GB/T1618-1995
3 -Content, its measured value approaches zero.
The advantage of chlorine dioxide generation of the present invention just is:
1. the present invention has adopted proton catalyst, makes chloric acid and hydrogen peroxide generate the speed of reaction of dioxide peroxide, increases substantially when existing than no proton catalyst, and the transformation efficiency of its chloric acid is higher.Reaction only generates dioxide peroxide, oxygen and water.Do not detect chlorine and generated, more do not had the organism by product.Thereby the method for pressing the production dioxide peroxide of the present invention's proposition, can produce chlorine dioxide with high purity, do not contain harmful ingredients.
2. proton catalyst strong inorganic acid of the present invention does not consume in reaction process, can recycle.Chlorine dioxide generation proposed by the invention, do not have in process of production vitriol or (with) the hydrosulfate by product generates, promptly reactionless waste liquid generates, and does not more have waste liquid, waste sludge discharge problem.Be that chlorine dioxide generation proposed by the invention is a cleaning procedure.
3. the chlorine dioxide generation that proposes of the present invention, its operational condition can be the reacting by heating aqueous solution under condition of negative pressure, make the reaction and the evaporation carry out simultaneously, but and bubbling air or nitrogen, make the chlorine dioxide concentration in the reactor diluted, thereby can guarantee safe production.
4. the chlorine dioxide generation of the present invention's proposition applicable to batch production and continuity production, and is applicable to for example various types of reactors such as still formula, tubular type.Process unit is simple, and is easy to operate, and easily control is controlled and shaken in realization automatically, and throughput is changeable.
5. the chlorine dioxide generation that proposes of the present invention, its production cost is more much lower than the cost that with the Textone is the raw material production dioxide peroxide.And fundamentally overcome with NaClO
3With with NaClO
2Waste reaction solution problem for raw material.
Below the production method of dioxide peroxide of the present invention is further described with following indefiniteness embodiment; to help further understanding to the present invention and advantage thereof; and not as the qualification to protection scope of the present invention, protection scope of the present invention is decided by claim.
Embodiment 1
Present embodiment is to be that the aqueous sulfuric acid of 7.5 mol joins in the reaction vessel with its concentration of proton catalyst sulfuric acid, said reaction vessel is 2000 milliliters a reaction flask, and the concentration that is added is that the amount of the aqueous sulfuric acid of 7.5 mol is 10% (V/V) of the volume of reaction vessel.Proton catalyst concentration be 7.5 mol aqueous sulfuric acid in the presence of in the stirring at magnetic stirring apparatus be the chloric acid of 38% weight percentage and be that the hydrogen peroxide of 31% weight percentage joins simultaneously and fills in the sulphuric acid soln that proton catalyst concentration is 7.5 mol as the concentration of reductive agent with material concentration, stir with magnetic stirring apparatus, make proton catalyst aqueous sulfuric acid, raw material chloric acid, hydrogen peroxide mix the formation mixing solutions, keep mixing solutions under 83 ± 1 ℃ temperature, to react.The inbound traffics that add of raw material chloric acid are 374 Grams Per Hours, the inbound traffics that add of reductive agent hydrogen peroxide (hydrogen peroxide) are 120 Grams Per Hours, the purity of raw material chloric acid is 98%, the raw material chloric acid that is added and the mol ratio of reductive agent hydrogen peroxide 1: 0.65, make the pressure in the reaction vessel remain on 35Kpa with Venturi tube, make the product dioxide peroxide produced, oxygen, water vapor etc. from reaction vessel, transport out water absorption product ClO continuously
2Stop charging after 10 minutes, measure ClO in the proton catalyst aqueous sulfuric acid with the measuring method of GB/T-1618-1995 regulation
3 -Remaining quantity calculate the transformation efficiency 99.8% of chloric acid, near 100%.The continuous iodometric determination of dioxide peroxide absorption liquid does not detect chlorine and exists.
Embodiment 2
Its working method of present embodiment and device are substantially the same manner as Example 1, only different is, the amount that the proton catalyst aqueous sulfuric acid joins in the reaction vessel is 5% of a reaction vessel volume, in reductive agent hydrogen peroxide (hydrogen peroxide) water, added stablizer diethylenetriamine five (methylene phosphonic acid), the amount of its adding is 0.5% of reductive agent hydrogen peroxide (hydrogen peroxide) weight, it is 7.8% percent by volume that bubbling air in reaction vessel, the flow of the air that is fed make the content of dioxide peroxide in the gaseous mixture of product dioxide peroxide, water vapor.
Embodiment 3
Its working method of present embodiment and device are substantially the same manner as Example 1, only different is, the amount that the proton catalyst aqueous sulfuric acid joins in the reaction vessel is 70% (V/V) of reaction vessel volume, feed nitrogen in reaction vessel, it is 7.9% percent by volume that the flow of the nitrogen that feeds makes the content of dioxide peroxide in the gas phase mixture of product dioxide peroxide, water vapor.
Embodiment 4
Its working method of present embodiment and device are substantially the same manner as Example 1, only different is, the concentration of proton catalyst aqueous sulfuric acid is 12 mol, the amount that the proton catalyst aqueous sulfuric acid is added in the reaction vessel is 40% (V/V) of reaction vessel volume, the concentration of raw material chloric acid is 5% weight percentage, the concentration of reductive agent hydrogen peroxide (hydrogen peroxide) is 10% weight percentage, keep proton catalyst sulfuric acid, chloric acid, the temperature of mixed solution of hydrogen peroxide is 78 ℃, the flow that adds chloric acid is 447 Grams Per Hours, the flow that adds hydrogen peroxide (hydrogen peroxide) is 90 Grams Per Hours, the purity of raw material chloric acid is 98.6%, the mol ratio of raw material chloric acid that is added and reductive agent hydrogen peroxide (hydrogen peroxide) is 1: 0.50, add stablizer diethylenetriamine five (methylene phosphonic acids) in reductive agent hydrogen peroxide (hydrogen peroxide), the amount of its adding is 0.1% of a hydrogen peroxide weight.The pressure that keeps in the reaction vessel is 8Kpa, and the flow of the air that is fed is that to make the content of dioxide peroxide in the gaseous mixture of product dioxide peroxide, oxygen, water vapor be 8.2% percent by volume, transformation efficiency 99.9%.
Embodiment 5
Its working method of present embodiment and device are substantially the same manner as Example 1, only different is, the concentration of proton catalyst aqueous sulfuric acid is 3 mol, the amount that the proton catalyst aqueous sulfuric acid is added in the reaction vessel is 60% (V/V) of reaction vessel volume, the concentration of raw material chloric acid is 45% weight percentage, the concentration of reductive agent hydrogen peroxide is 35% weight percentage, keep the proton catalyst aqueous sulfuric acid, raw material chloric acid, the temperature of reductive agent hydrogen peroxide (hydrogen peroxide) mixing solutions is 30 ℃, the flow that adds raw material chloric acid is 230 Grams Per Hours, the flow that adds reductive agent hydrogen peroxide (hydrogen peroxide) is 211 Grams Per Hours, and the mol ratio of raw material chloric acid that is added and reductive agent hydrogen peroxide (hydrogen peroxide) is 1: 1.8.In reductive agent hydrogen peroxide (hydrogen peroxide), add stablizer diethylenetriamine five (methylene phosphonic acids), its add-on is 0.8% of a hydrogen peroxide weight, the pressure that keeps in the reaction vessel is 65Kpa, and the flow of the air that is fed is that to make the content of dioxide peroxide in the gas phase mixture of product dioxide peroxide, oxygen, water vapor be 8.9% percent by volume.
Embodiment 6
Its working method of present embodiment and device are substantially the same manner as Example 1, only different is, the concentration of proton catalyst aqueous sulfuric acid is 6 mol, the amount that the proton catalyst aqueous sulfuric acid is added in the reaction vessel is 10% (V/V) of reaction vessel volume, the concentration of raw material chloric acid is 20% weight percentage, the concentration of reductive agent hydrogen peroxide (hydrogen peroxide) is 27.5% weight percentage, keep the proton catalyst aqueous sulfuric acid, raw material chloric acid, the temperature of reductive agent mixed solution of hydrogen peroxide is 85 ± 1 ℃, the flow that adds chloric acid is 389 Grams Per Hours, and the flow that adds hydrogen peroxide (hydrogen peroxide) is 110 Grams Per Hours.The raw material chloric acid that is added and the mol ratio of reductive agent hydrogen peroxide are 1.0: 1.0, add stablizer diethylenetriamine (methylene phosphonic acid) in the reductive agent hydrogen peroxide, and its add-on is hydrogen peroxide (H
2O
2) weight 0.6%, keep-uping pressure in the reaction vessel is that it is 8.0% percent by volume that 15Kpa, the flow of the air that is fed make the content of dioxide peroxide in the gas phase mixture of product dioxide peroxide, oxygen, water vapor.The transformation efficiency of chloric acid is 99.3%.
Embodiment 7
Its working method of present embodiment and device are substantially the same manner as Example 1, only different is, the concentration of proton catalyst aqueous sulfuric acid is 8.5 mol, the amount that the proton catalyst aqueous sulfuric acid is added in the reaction vessel is 20% (V/V) of reaction vessel volume, the concentration of raw material chloric acid is 40% weight percentage, the concentration of reductive agent hydrogen peroxide is 25% weight percentage, keep the proton catalyst aqueous sulfuric acid, raw material chloric acid, the temperature of the mixing solutions of reductive agent hydrogen peroxide is 75 ± 1 ℃, the flow that adds chloric acid is 454 Grams Per Hours, the flow that adds hydrogen peroxide is 234 Grams Per Hours, and the raw material chloric acid that is added and the mol ratio of reductive agent hydrogen peroxide are 1: 0.8.In the reductive agent hydrogen peroxide, add stablizer diethylenetriamine (methylene phosphonic acid), its add-on is 0.45% of a hydrogen peroxide weight, keep-uping pressure in the reaction vessel is 50Kpa, and it is 8.9% percent by volume (V/V) that the flow of institute's bubbling air makes the content of dioxide peroxide in the gas phase mixture of product dioxide peroxide, oxygen, water vapor.Stop charging after 15 minutes, measure ClO in the proton catalyst aqueous sulfuric acid
3 -Remaining quantity, the transformation efficiency of chloric acid is 99.9%, does not find Cl
2Generation.
Embodiment 8
Its working method of present embodiment and device are substantially the same manner as Example 1, only different is that used proton catalyst is the high chloro acid solution, high chloro acid solution's concentration is 4.5 mol, the amount that the proton catalyst high chloro acid solution is added in the reaction vessel is 6% (V/V) of reaction vessel volume, the concentration of raw material chloric acid is 30% weight percentage, the concentration of reductive agent hydrogen peroxide is 25% weight percentage, keep the proton catalyst high chloro acid solution, raw material chloric acid, the temperature of the mixed aqueous solution of reductive agent hydrogen peroxide is 70 ± 1 ℃, the flow that adds chloric acid is 296 Grams Per Hours, the flow that adds the reductive agent hydrogen peroxide is 100 Grams Per Hours, the raw material chloric acid that is added and the mol ratio of reductive agent hydrogen peroxide are 1: 0.7, add stablizer diethylenetriamine (methylene phosphonic acid) in the reductive agent hydrogen peroxide, its add-on is 0.62% of a hydrogen peroxide weight.It is 8.2% percent by volume (V/V) that the 41Kpa that keep-ups pressure in the reaction vessel, the flow of the air that is fed make the content of dioxide peroxide in the gas phase mixture of product dioxide peroxide, oxygen, water vapor etc.Stop charging after 10 minutes, measure ClO among the proton catalyst high chloro acid solution
3 -Remaining quantity, the transformation efficiency of chloric acid is 97.7%, does not find Cl
2Generation.
Embodiment 9
Its working method of present embodiment and device are substantially the same manner as Example 1, and only different is that used proton catalyst is the aqueous solution of phosphoric acid, and concentration of phosphoric acid is 6 mol in the proton catalyst phosphate aqueous solution.
Embodiment 10
Its working method of present embodiment and device are substantially the same manner as Example 1, only different is that used proton catalyst is the mixing aqueous acid of sulfuric acid and phosphoric acid, the concentration of the mixed acid aqueous solution of sulfuric acid and phosphoric acid is 7 mol, the mol ratio of sulfuric acid and phosphoric acid is 1: 1, the amount that proton catalyst sulfuric acid and phosphoric acid mixing aqueous acid are added in the reaction vessel is 25% (V/V) of reaction vessel volume, the concentration of raw material chloric acid is 27% weight percentage, the concentration of reductive agent hydrogen peroxide is 30% weight percentage, the mixed acid aqueous solution that keeps proton catalyst sulfuric acid and phosphoric acid, raw material chloric acid, the temperature of the mixed aqueous solution of reductive agent hydrogen peroxide is 70 ± 1 ℃, the flow that adds chloric acid is 460 Grams Per Hours, the flow that adds hydrogen peroxide is 125 Grams Per Hours, and the raw material chloric acid that is added and the mol ratio of reductive agent hydrogen peroxide are 1: 0.75.Add stablizer diethylenetriamine (methylene phosphonic acid) in the reductive agent hydrogen peroxide, its add-on is 0.71% of a hydrogen peroxide weight.35Kpa keep-ups pressure in the reaction vessel, it is 7.5% percent by volume (V/V) that the flow of the air that is fed makes the content of dioxide peroxide in the gas phase mixture of product dioxide peroxide, oxygen, water vapor etc., stops charging and measures ClO in proton catalyst sulfuric acid and the phosphoric acid mixed acid aqueous solution after 10 minutes
3 -Residual volume, the transformation efficiency of chloric acid is 95.8%, does not find Cl
2Generation.
Embodiment 11
Its working method of present embodiment and device are substantially the same manner as Example 10, and in the mixed acid aqueous solution of only different is used proton catalyst sulfuric acid and phosphoric acid, the mol ratio of sulfuric acid and phosphoric acid is 1: 9.
Embodiment 12
Its working method of present embodiment and device are substantially the same manner as Example 10, and in the mixed acid aqueous solution of only different is used proton catalyst sulfuric acid and phosphoric acid, the mol ratio of sulfuric acid and phosphoric acid is 9: 1.
Claims (17)
1. the production method of a dioxide peroxide, it is characterized in that, in the presence of the proton catalyst strong inorganic acid aqueous solution, join simultaneously in the proton catalyst strong inorganic acid aqueous solution with raw material chloric acid with as the hydrogen peroxide of reductive agent in the stirring, under 30-95 ℃ temperature, make chloric acid and hydroperoxidation generate dioxide peroxide.
2. according to the production method of a kind of dioxide peroxide of claim 1, it is characterized in that said proton catalyst strong inorganic acid is sulfuric acid, perchloric acid, phosphoric acid, the sulfuric acid of mol ratio and mixing acid a kind of acid wherein of phosphoric acid arbitrarily.
3. according to the production method of a kind of dioxide peroxide of claim 2, it is characterized in that vitriolic concentration is the 1-12 mol, the concentration of perchloric acid is the 2-6 mol, concentration of phosphoric acid is the 3-12 mol, and the concentration of the mixing acid of the sulfuric acid of mol ratio and phosphoric acid is the 3-12 mol arbitrarily.
4. according to the production method of a kind of dioxide peroxide of claim 1, it is characterized in that the concentration of raw material chloric acid is the 5-45% weight percentage.
5. according to the production method of a kind of dioxide peroxide of claim 4, it is characterized in that the concentration of raw material chloric acid is the 20-40% weight percentage.
6. according to the production method of a kind of dioxide peroxide of claim 4 or 5, it is characterized in that the purity of chloric acid is more than or equal to 98%.
7. according to the production method of a kind of dioxide peroxide of claim 1, it is characterized in that the concentration of reductive agent hydrogen peroxide is the 5-35% weight percentage.
8. according to the production method of a kind of dioxide peroxide of claim 7, it is characterized in that the concentration of reductive agent hydrogen peroxide is the 27-35% weight percentage.
9. according to the production method of a kind of dioxide peroxide of claim 1, it is characterized in that the mol ratio of chloric acid and hydrogen peroxide is 1: 0.2-2.0.
10. according to the production method of a kind of dioxide peroxide of claim 9, it is characterized in that the mol ratio of chloric acid and hydrogen peroxide is 1: 0.5-1.8.
11. the production method according to a kind of dioxide peroxide of claim 7 or 8 is characterized in that stablizer is joined in the reductive agent hydrogen peroxide, and its add-on is the 0.01-2.0% of hydrogen peroxide weight.
12. production method according to a kind of dioxide peroxide of claim 11, it is characterized in that stablizer is 1-hydroxy ethylene-1-di 2 ethylhexyl phosphonic acid, 1-ethylamine-1, wherein a kind of of 1-di 2 ethylhexyl phosphonic acid amino three (methylene phosphonic acid), diethylenetriamine five (methylene phosphonic acid).
13. the production method according to a kind of dioxide peroxide of claim 1 is characterized in that the amount that the proton catalyst strong inorganic acid aqueous solution joins in the reaction vessel is the 1-70% of reaction vessel volume, V/V.
14. the production method according to a kind of dioxide peroxide of claim 13 is characterized in that the amount that the proton catalyst strong inorganic acid aqueous solution joins in the reaction vessel is the 1-50% of reaction vessel volume, V/V.
15. the production method according to a kind of dioxide peroxide of claim 1 is characterized in that the temperature of reaction of chloric acid and hydrogen peroxide is 65-85 ℃.
16. the production method according to a kind of dioxide peroxide of claim 1 is characterized in that carry out the reaction of chloric acid and hydrogen peroxide under condition of negative pressure, its pressure range is 8Kpa-66.5Kpa.
17. the production method according to a kind of dioxide peroxide of claim 13 is characterized in that bubbling air or nitrogen in reaction vessel, the flow of institute's bubbling air or nitrogen make the content of the dioxide peroxide in the gas phase mixture less than 10% percent by volume.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103145101A (en) * | 2013-03-20 | 2013-06-12 | 广西轻工业科学技术研究院 | Sugar manufacturing process-based high-purity chlorine dioxide preparation method |
| CN106645576A (en) * | 2016-12-16 | 2017-05-10 | 山东省计量科学研究院 | Method for preparing chlorine dioxide standard material in nitrogen |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103145101A (en) * | 2013-03-20 | 2013-06-12 | 广西轻工业科学技术研究院 | Sugar manufacturing process-based high-purity chlorine dioxide preparation method |
| CN103145101B (en) * | 2013-03-20 | 2015-06-03 | 广西轻工业科学技术研究院 | Sugar manufacturing process-based high-purity chlorine dioxide preparation method |
| CN106645576A (en) * | 2016-12-16 | 2017-05-10 | 山东省计量科学研究院 | Method for preparing chlorine dioxide standard material in nitrogen |
| 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 |
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