CN100562488C - The production method and the equipment that contain the aqueous solution of dioxide peroxide - Google Patents
The production method and the equipment that contain the aqueous solution of dioxide peroxide Download PDFInfo
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- CN100562488C CN100562488C CNB2005800345379A CN200580034537A CN100562488C CN 100562488 C CN100562488 C CN 100562488C CN B2005800345379 A CNB2005800345379 A CN B2005800345379A CN 200580034537 A CN200580034537 A CN 200580034537A CN 100562488 C CN100562488 C CN 100562488C
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Abstract
The present invention relates to produce the continuation method of dioxide peroxide, this method comprises the following step of carrying out continuously: a) feeding acid in reactor (1), hydrogen peroxide and alkaline metal chlorate; B) make alkaline metal chlorate and acid and hydroperoxidation, comprise the product stream (2) of dioxide peroxide, oxygen and an alkali metal salt that should acid with formation; C) this product stream is delivered to injector (3) from reactor, and it is mixed with motion water in being fed into injector, form diluted product stream thus; D) from diluted product stream, remove deoxidation; E) before removing the step of deoxidation, in the process or afterwards, take out part diluted product stream (9); F) in the diluted product stream part of not taking out, add entry (11) to form recirculation flow (12); And g) recirculation flow (12) is delivered to injector, and be fed into wherein as motion water (4).The invention still further relates to the production unit that is used to produce the aqueous solution that contains dioxide peroxide.
Description
Technical field
The present invention relates to be used to produce the method and the production unit of the aqueous solution that contains dioxide peroxide.
Background technology
Dioxide peroxide is used for various application, for example association with pulp bleaching, fatty bleaching, desalt and remove organic substance from industrial waste.Because dioxide peroxide is not a stable storing, so common produce in situ.
In large-scale methods, by being reacted, alkaline metal chlorate and reductive agent produce dioxide peroxide usually in water-containing reacting medium.As in for example United States Patent (USP) 5091166,5091167 and European patent 612686 described methods, can from reaction medium, take out dioxide peroxide with gas form.Usually, then chlorine dioxide is absorbed in the water to form its aqueous solution.These large-scale methods are very effective, but need big processing unit (plant) and instrument.
For in small scale equipment, producing dioxide peroxide, for example use or little bleaching facility for desalt, advantageously from reaction medium, do not separate dioxide peroxide, but randomly after dilute with water, from reactor, directly take out the solution that contains dioxide peroxide.These methods commercialization in recent years is for example in United States Patent (USP) 2833624,4534952,5895638,6387344,6790427 and No. the 2004/0175322nd, U.S. Patent Application Publication with disclose in No. 2003/0031621 and described these methods.Required processing unit (plant) and instrument are than much smaller in the above-mentioned large-scale methods.But, still need further improvement.
From reactor, directly take out in the method based on the alkaline metal chlorate of the solution that contains dioxide peroxide the solution of (paper that for example circulates bleaching, bagasse bleaching or association with pulp bleaching) the on a small scale desired high concentration of chlorine dioxide that is difficult to obtain to have many application therein.
Summary of the invention
The purpose of this invention is to provide can the direct production high concentration of chlorine dioxide aqueous solution simple method.
Another object of the present invention provides the production unit that carries out this method.
Be surprisingly found out that can satisfy these purposes by the continuation method of producing dioxide peroxide is provided, this method comprises the following step of carrying out continuously:
A) feeding acid, hydrogen peroxide and alkaline metal chlorate in reactor;
B) make alkaline metal chlorate and acid and hydroperoxidation, comprise the product stream of dioxide peroxide, oxygen and an alkali metal salt that should acid with formation;
C) this product stream is delivered to injector from reactor, and it is mixed with motion water in being fed into injector, form diluted product stream thus;
D) from diluted product stream, remove deoxidation;
E) before removing the step of deoxidation, in the process or afterwards, take out the part diluted product stream;
F) in the diluted product stream part of not taking out, add entry to form recirculation flow; With
G) recirculation flow is delivered to injector, and be fed into wherein as motion water.
No. the 2004/0175322nd, document United States Patent (USP) 2833624,4534952,5895638,6387344,6790427 and U.S. Patent Application Publication and disclose described in No. 2003/0031621 and come operant response device and injector as previously mentioned, these documents are incorporated into herein by reference.
Suitably the alkaline metal chlorate is fed to reactor with aqueous solution form.Basic metal can be for example sodium, potassium or its mixture, and wherein sodium is most preferred.This acid is preferably mineral acid, for example sulfuric acid, hydrochloric acid, nitric acid, perchloric acid or its mixture, and wherein sulfuric acid is most preferred.Be fed to the H of reactor
2O
2With ClO
3 -Mol ratio be about 0.2 suitably: about 2: 1 of 1-, preferred about 0.5: about 1.5: 1 of 1-, most preferably 0.5: about 1: 1 of 1-.The alkaline metal chlorate always comprises some muriates as impurity, but the more muriate of feeding also is fully possible as metal chloride or hydrochloric acid in reactor.But, for the formation that makes chlorine minimizes, preferably keep the low amount that is fed into the chlorion in the reactor, be lower than ClO suitably
3 -About 1mol%, preferably be lower than about 0.1mol%, more preferably less than about 0.05mol%, most preferably be lower than the Cl of about 0.02mol%
-(comprising in the oxymuriate) as the muriate of impurity and the muriate of the extra interpolation of choosing wantonly.
Under the situation of sulfuric acid as the charging of reactor, vitriolic concentration is preferably the about 98wt% of about 60-, and the most preferably from about about 85wt% of 70-, and temperature is preferably about 80 ℃ of about 0-, and most preferably from about 20-is about 60 ℃.Produce every kgClO
2The about 7kgH of the about 2-of preferred feedstock
2SO
4, the about 5kg H of 3-most preferably from about
2SO
4In order to use the sulfuric acid of high density, preferred dilution and the cooling scheme that adopts described in No. the 2004/0175322nd, U.S. Patent Application Publication.
In particularly preferred embodiments, alkaline metal chlorate and hydrogen peroxide are fed into reactor with the form of the premix aqueous solution, for example as US 6387344 described compositions.This composition can be the aqueous solution that comprises following substances: about 6.5 mol of about 1-; the alkaline metal chlorate of preferred about 6 mol of about 3-; about 7 mol of about 1-; the hydrogen peroxide of preferred about 5 mol of about 3-; with protective colloid, radical scavenger or at least a based in the phosphonic complexing agent; wherein the pH of this aqueous solution is about 4 for about 0.5-suitably, and preferably about 1-is about 3.5, and more preferably from about 1.5-about 3.Preferably, exist at least a based on the phosphonic complexing agent, the amount of existence be preferably about 5 mmoles of about 0.1-/liter, most preferably from about about 3 mmoles of 0.5-/liter.If there is protective colloid, then its concentration is preferably about 0.5 mol of about 0.001-, most preferably from about about 0.05 mol of 0.02-.If there is radical scavenger, then its concentration is preferably about 1 mol of about 0.01-, most preferably from about about 0.2 mol of 0.02-.Particularly preferred composition comprise at least a be selected from following substances based on the phosphonic complexing agent: 1-hydroxy ethylene-1, the 1-di 2 ethylhexyl phosphonic acid, 1-ethylamine-1, the 1-di 2 ethylhexyl phosphonic acid, amino three (methylene phosphonic acids), ethylenediamine tetraacetic (methylene phosphonic acid), hexamethylene-diamine four (methylene phosphonic acid), diethylenetriamine five (methylene phosphonic acid), diethylenetriamine six (methylene phosphonic acid), 1-amino alkane-1,1-di 2 ethylhexyl phosphonic acid (morpholino methanebisphosphonic acid for example, N, N-dimethylamino dimethyl di 2 ethylhexyl phosphonic acid, aminomethyl diphosphonic acid), and reaction product and salt, particular certain cancers.Useful protective colloid comprises tin compound, for example alkali metal stannate, particularly sodium stannate (Na
2(Sn (OH)
6).Useful radical scavenger comprises pyridine carboxylic acid, for example 2, and dipicolimic acid 2.Suitably, the amount of chlorion be lower than about 300 mmoles/liter, preferably be lower than about 50 mmoles/liter, more preferably less than about 5 mmoles/liter, most preferably be lower than about 0.5 mmole/liter.
Temperature in the reactor remains below reactant suitably and product flows at that time the boiling point under (prevailing) pressure, is preferably about 80 ℃ of about 20-, most preferably from about 30-60 ℃.The pressure that keeps in the reactor is preferably the about 100kPa absolute pressure of about 30-, most preferably from about the about 95kPa absolute pressure of 65-suitably a shade below normal atmosphere.
Reactor can comprise one or several container, for example vertical, level or be obliquely installed.Reactant can directly or by independent mixing equipment be fed into reactor.Suitably, reactor is preferably through-flow container of piped or pipe basically, most preferably comprises being used for the uniform device of mode mixed reactant basically.This mixing for example discloses in No. the 2004/0175322nd, US 6790427 and U.S. Patent Application Publication with device.
Reactor used length (on main flow direction) is preferably the about 1500mm of about 150-, the most preferably from about about 900mm of 300-.Have been found that and advantageously use piped reactor basically, its internal diameter is the about 300mm of about 25-, the about 150mm of preferably about 50-.Particularly advantageously use piped reactor basically, its length is preferably about 12 with the ratio of internal diameter: about 1: 1 of 1-, most preferably from about 8: about 4: 1 of 1-.Suitable mean residence time in most of the cases is about 60 seconds of about 1-in reactor, about 20 seconds of preferably about 3-.
The reaction of alkaline metal chlorate, acid and hydrogen peroxide causes forming product stream in reactor, the circulation of this product often comprises liquid and foam, and comprises dioxide peroxide, oxygen, this sour an alkali metal salt and some residual unreacted feed chemicals in most cases.Dioxide peroxide and oxygen can be dissolved in the liquid and gas foamy form exists.If use sulfuric acid, then an alkali metal salt is a vitriol.Have been found that the alkaline metal chlorate that can obtain about 75%-100% is converted into the transformation efficiency of dioxide peroxide, preferably about 80-100%, most preferably from about 95-100%.
The end that this feed chemicals that comprises acid, alkaline metal chlorate and reductive agent preferably approaches reactor provides, and product stream preferably takes out at the other end of reactor.
Preferably will deliver to injector from the product stream that reactor takes out, comprise any liquid, foam and gas in this product stream by the suction that produces by injector.Product stream is mixed, to form diluted product stream with the motion water that is fed into injector.Can use the injector of any kind, yet especially preferably use, wherein make motion water so that the form of small part spiral (spiral) or spiral (helical) flows as US 6790427 described injectors.
The diluted product stream that obtains from injector still comprises dioxide peroxide, oxygen and an alkali metal salt that should acid.Should remove at least some oxygen by any suitable means, for example by having the cyclonic separator of venting port, large diameter pipe with vent valve has the separator of tank level control and automatic exhaust steam valve, perhaps is used for separating from liquid flow any other existing apparatus of rare gas element such as air.In a preferred embodiment, diluted product stream is delivered to aeration tank, wherein it is kept the sufficiently long time, so that at least some oxygen break away from from liquid.In order to make the loss minimum of dioxide peroxide, the temperature in jar is preferably maintained in the range of from about about 20 ℃ of 1-, and most preferably from about 4-is about 10 ℃.
Take out the part diluted product stream, preferably about 10-is about 90%, and most preferably from about 20-is about 80%, and particularly most preferably from about 30-is about 70%, and it constitutes the actual product of this method, promptly contains the aqueous solution of dioxide peroxide, and its concentration is preferably greater than 4g/l.This can be before removing deoxidation, carry out in the process or afterwards.If in aeration tank, remove deoxidation, preferably from same jar, take out the part of the diluted product stream that constitute actual product.
Add entry in the part of the diluted product stream of not taking out, forming recirculation flow, the add-on of water makes that preferably the concentration of dioxide peroxide is the about 12g/l of about 2-, the most preferably from about about 6g/l of 3-in the recirculation flow.The water that adds preferably has enough low temperature, so that the temperature of recirculation flow is lower than about 20 ℃, preferably is lower than about 15 ℃, most preferably is lower than about 10 ℃, particularly most preferably is lower than about 5 ℃.Also can use other refrigerating unit, for example interchanger etc.There is not lowest temperature, as long as it is not less than freezing point.Then recirculation flow is fed into injector as motion water, and mixes with the product stream that comes autoreactor therein.
Method of the present invention is particularly suitable for producing on a small scale dioxide peroxide, the about 250kg ClO of for example about 0.5-
2/ hr, the about 150kg ClO of preferably about 10-
2/ hr.Do not use method of independent absorption tower operation different with other based on oxymuriate, the ClO 2 solution that method of the present invention can the production high density, the about 10g/l of for example about 4-or more than.
Typical small-scale production unit of the present invention only comprises a reactor usually, but several reactors can be set, for example up to about 15 or more parallel reactor, for example the form setting to restrain.
The invention still further relates to the production unit that is used to produce the aqueous solution that contains dioxide peroxide, described equipment comprises:
A) be equipped with one or more reactors that are used for acid, hydrogen peroxide and alkaline metal chlorate's feed entrance;
B) be connected to the injector of reactor, its be equipped with the inlet of motion water and mix use device, this device to be used in the future the product stream of autoreactor mixes with motion water, with the acquisition diluted product stream;
C) be used for from remove the device of deoxidation by the diluted product stream of injector acquisition;
D) be used to take out the device of part diluted product stream;
E) be used for adding entry to obtain the device of recirculation flow to the diluted product stream part of not taking out; With
F) be used for recirculation flow is fed into as motion water the device of injector.
About the preferred feature of this production unit, with reference to the description of above method.
Embodiment
Embodiments of the present invention are described below with reference to the accompanying drawings.But scope of the present invention is not limited to this embodiment.
Accompanying drawing schematically shows process program of the present invention.
With reference to the accompanying drawings, the premixed aqueous solution with sulfuric acid and sodium chlorate and hydrogen peroxide is fed into Vertical through-flow tubular reactor 1, and they are reacted therein is to form liquid and foam Product stream 2, this product stream comprise chlorine dioxide, oxygen, sodium sulphate and sulfuric acid that some are residual and Sodium chlorate. Injector 3 is supplied with motion water 4, and produces slightly lower than atmospheric pressure, This pressure makes product stream flow out into the injector 3 from reactor 1, in injector 3 Product stream mixes with motion water, to form the product stream 5 of dilution, the product stream 5 that dilutes is sent To tank 6. Take out the product stream of part dilution as end product 9, namely with pump 8 from this tank The aqueous solution that contains chlorine dioxide. Tank 6 provides the oxygen row who will emit from diluted product stream wherein The exhaust blower 7 that goes out. The part of the cut back solution that will not take out with pump 10 is taken out from tank 6, And make it to mix with cold water 11, to form recirculation flow 12, the temperature of this cold water 11 is for example Be about 20 ℃ of about 1-, preferably about 4-is about 10 ℃. The gas of discharging from tank 6 also can comprise Chlorine dioxide, and in order to make its loss reduction, available water is washed this gas to absorb major part The chlorine dioxide (not shown), and make in its product stream or recirculation flow that turns back to dilution. Make recirculation flow 12 turn back to injector, and be fed into wherein as motion water 4. Producing 6g ClO2In the method of/l product solution 9, according to the efficient of injector, can add suitably enough water and comprise the about 4.5g ClO of about 3-to obtain every liter2Recirculation flow 12. For life Produce 10g ClO2/ l product solution 9 can add suitably enough water and comprise about 7g ClO to obtain every liter2Recirculation flow 12.
The process equipment that comprises reactor 1, injector 3 and tank 6 is connect by tolerating them suitably The material manufacturing of the chemicals that touches, this chemicals for example be hydrogen peroxide, sodium chlorate, sulfuric acid and In the chlorine dioxide one or more. This material comprises for example glass, tantalum, titanium, glass fibers The plastics that dimension strengthens, fluoroplastics such as PVDF (poly-inclined to one side vinylidene fluoride), CPVC (chlorination Polyvinyl chloride), PTFE (polytetrafluoroethylene (PTFE)), PFA (perfluoroalkoxy), ECTFE (ethene CTFE) or FEP (PEP) perhaps use these materials to do Lining material for structural material such as steel or stainless steel. Suitable fluoroplastics are with trade (brand) name
Or
Sell.
To further specify the present invention by following examples, but this embodiment is not intended to limit the scope of the invention.Except as otherwise noted, all umber and per-cents are meant weight part and weight percentage.
Embodiment: in equipment as described in Figure, produce dioxide peroxide by the mixture of sulfuric acid and sodium chlorate and hydrogen peroxide.Began back 1 hour, and observed following condition:
Operating speed: 45kg/hr ClO
2
The concentration of product solution (9): 5.9g/l ClO
2
The flow of product solution (9): 7m
3/ hr
The flow of recirculation flow (12): 26m
3/ hr
The flow of cold water (11): 7.5m
3/ hr
The temperature of cold water (11): 10 ℃
Temperature in the jar (6): 14 ℃.
Claims (12)
1. produce the method for the aqueous solution that contains dioxide peroxide, described method comprises the following step of carrying out continuously:
(a) feeding mineral acid, hydrogen peroxide and alkaline metal chlorate in reactor;
(b) make alkaline metal chlorate and acid and hydroperoxidation, comprise the product stream of dioxide peroxide, oxygen and an alkali metal salt that should acid with formation;
(c) this product stream is delivered to injector from reactor, and it is mixed with motion water in being fed into injector, form diluted product stream thus;
(d) from diluted product stream, remove deoxidation;
(e) before removing the step of deoxidation, in the process or afterwards, take out the part diluted product stream;
(f) in the diluted product stream part of not taking out, add entry to form recirculation flow; With
(g) recirculation flow is delivered to injector, and be fed into wherein as motion water.
2. the method for claim 1 wherein has enough low temperature for forming the glassware for drinking water that recirculation flow adds, so that the temperature of recirculation flow is lower than 20 ℃.
3. method as claimed in claim 1 or 2 wherein makes that for the add-on that forms the water that recirculation flow adds the concentration of dioxide peroxide is 2g/1-12g/1 in the recirculation flow.
4. method as claimed in claim 1 or 2 is wherein delivered to aeration tank with diluted product stream, in this aeration tank it is kept the sufficiently long time, so that at least some oxygen leave.
5. method as claimed in claim 4 is wherein taken out the part diluted product stream of taking out in step (e) from aeration tank.
6. method as claimed in claim 4, wherein the temperature in the aeration tank remains on 1-20 ℃.
7. method as claimed in claim 1 or 2, the diluted product stream of wherein in step (e), taking out 10-90%.
8. method as claimed in claim 1 or 2, wherein diluted product stream comprises the dioxide peroxide greater than 4g/l.
9. method as claimed in claim 1 or 2, wherein acid is sulfuric acid.
10. method as claimed in claim 1 or 2, wherein reactor is through-flow container or pipe.
11. method as claimed in claim 1 or 2, wherein acid, alkaline metal chlorate and the hydrogen peroxide end that approaches reactor provides, and product stream takes out at the other end of reactor.
12. be used to produce the production unit of the aqueous solution that contains dioxide peroxide, described equipment comprises:
(a) be equipped with one or more reactors that are used for mineral acid, hydrogen peroxide and alkaline metal chlorate's feed entrance;
(b) be connected to the injector of reactor, its be equipped with the inlet of motion water and mix use device, this device to be used in the future the product stream of autoreactor mixes with motion water, with the acquisition diluted product stream;
(c) be used for from remove the device of deoxidation by the diluted product stream of injector acquisition;
(d) be used to take out the device of part diluted product stream;
(e) be used for adding entry to obtain the device of recirculation flow to the diluted product stream part of not taking out; With
(f) be used for recirculation flow is fed into as motion water the device of injector.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63313004P | 2004-12-06 | 2004-12-06 | |
| US60/633,130 | 2004-12-06 | ||
| EP05100143.6 | 2005-01-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101039872A CN101039872A (en) | 2007-09-19 |
| CN100562488C true CN100562488C (en) | 2009-11-25 |
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|---|---|---|---|
| CNB2005800345379A Active CN100562488C (en) | 2004-12-06 | 2005-11-11 | The production method and the equipment that contain the aqueous solution of dioxide peroxide |
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| CN (1) | CN100562488C (en) |
| ZA (1) | ZA200702526B (en) |
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| CN105169913B (en) * | 2015-08-16 | 2018-01-05 | 南京理工大学 | A kind of denitration of boiler smoke Chlorine Dioxide Oxidation agent feed system and its technique |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4744956A (en) * | 1986-02-12 | 1988-05-17 | Quantum Technologies, Inc. | Continuous reaction of gases with liquids |
-
2005
- 2005-11-11 CN CNB2005800345379A patent/CN100562488C/en active Active
- 2005-11-11 ZA ZA200702526A patent/ZA200702526B/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4744956A (en) * | 1986-02-12 | 1988-05-17 | Quantum Technologies, Inc. | Continuous reaction of gases with liquids |
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|---|---|
| ZA200702526B (en) | 2008-11-26 |
| CN101039872A (en) | 2007-09-19 |
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