CN101020589A - Prepn and application of free radical stabilizer - Google Patents
Prepn and application of free radical stabilizer Download PDFInfo
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- CN101020589A CN101020589A CN 200610007232 CN200610007232A CN101020589A CN 101020589 A CN101020589 A CN 101020589A CN 200610007232 CN200610007232 CN 200610007232 CN 200610007232 A CN200610007232 A CN 200610007232A CN 101020589 A CN101020589 A CN 101020589A
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Abstract
The present invention discloses preparation process and application of free radical stabilizer, and features that in water solution and under neutral condition, peroxy acid or its salt and ketone are reacted to produce free radical stabilizer for activating and stabilizing electron transferring reaction of free radical, especially electrophilic substitution reaction on unsaturated group and phenol type or non-phenol type benzene ring. The free radical stabilizer has ideal effect on oxygen-containing free radical, nitrogen-containing free radical, etc, and is suitable for the organic waste water treatment with free hydroxyl radical and the bleaching of paper, fiber, etc with H2O2, O2, O3, etc. The preparation process has low cost, no pollution and other features.
Description
Technical field
A kind of free radical stabilizer preparation method and application thereof relate to fields such as green organic chemistry, highly difficult treatment of Organic Wastewater, cleaning pulping bleaching, textile fibres bleaching and environment protection.
Background technology
Along with the continuous enhancing of countries in the world to environmental protection consciousness, every environmental legislation is gradually improved.Highly difficult treatment of Organic Wastewater turned to gradually with ozone oxidation, photochemical catalytic oxidation, electrochemical oxidation, ultrasonic technique, wet oxidation etc. be representative fast, high-level oxidation technology (AOPs) cheaply; Traditional bleaching process also turns to element-free chlorine (ECF) such as oxygen delignification and hydrogen peroxide bleaching and ozone bleaching and one after another completely without chlorine (TCF) bleaching technology in paper industry and the field of textiles.Above-mentioned technology has a common essence: promptly under given conditions; make oxygen, hydrogen peroxide, ozone etc. change into bioactive molecule-free radical that character is very active, have stronger chemical attack ability by different approaches (electrocatalysis, irradiation etc.), as hydroxyl radical free radical (OH), ultra-oxygen anion free radical
Perhydroxyl radical (HOO) etc.
The mechanism of action of high-level oxidation technology is the process that produces hydroxyl radical free radical by different approaches.Hydroxyl radical free radical has the higher standard electropotential than other common oxygenant, and oxidation capacity is strong, and character is very active.Hydroxyl radical free radical can bring out a series of radical chain reaction in case form, and does not almost have all contaminations in the directtissima water body selectively, until being degraded to CO
2, H
2O and other mineral salt.Therefore, advanced oxidation processes is a sign to produce hydroxyl radical free radical, and the development course of advanced oxidation processes is exactly the process that improves constantly OH production rate and utilization ratio.
Intermediate product hydroxyl radical free radical (OH), ultra-oxygen anion free radical in the reaction process such as oxygen delignification, hydrogen peroxide bleaching and ozone bleaching
And perhydroxyl radical (HOO) has significant effects to the degraded of delignification reaction, paper pulp and textile fibres bleaching, carbohydrate.Studies show that, consumption by pH value, pressure, temperature and reagent in the control reaction process, can make full use of above-mentioned free radical different bars with under selectivity, the happening part and the concentration of control free radical, thereby the reasonable use free radical reaction improves delignification and whitening capacity, and the acquisition bleaching speed is fast, bleaching process short, float the high good result of back whiteness.
As everyone knows, the active height of free radical reaction, strong, the speed of response fast (10 of chemical attack ability
6L/MolS-10
10L/MolS).But the free radical that existing method obtains all exists concentration low, the life-span short (survival time is less than 1 μ s), thereby increased the difficulty of research and limited the industrial applications of free radical reaction in wastewater treatment, paper pulp and weaving bleaching field.Therefore, the generation rule and the stable mechanism of further investigation free radical, adopt various means effectively to prolong radical life, to pollutent in the water body control difficult degradation organic waste particularly efficient degradation, " green " bleaching of paper pulp and textile fibres etc. is had crucial meaning.
Summary of the invention
The objective of the invention is to overcome free radical instability, short deficiency of life-span, provide that a kind of cost is low, flow process short, the preparation method of easy-operating free radical stabilizer.This free radical stabilizer can improve the stability of various free radicals and effectively prolong the life-span of free radical, has promoted the application of free radical reaction in fields such as highly difficult wastewater treatment, paper pulp and textile fibres bleachings.
The patent applicant discovers that repeatedly the compound that peroxy acid or its salt and ketone produce is the good free radical stabilizer of a class (FRS) under specified conditions in the aqueous solution, can effectively prolong the life-span of various free radicals; Simultaneously, this FRS is again the strong close electrooxidation reagent of a class, can shift by Sauerstoffatom in the process of stabilized radical and carry out selectable oxidizing reaction.For example, it can with a large amount of aliphatic structures that exist in the lignin and the two key generation cationoid reactions of the C=C in the aromatic structure, thereby cause the degraded of lignin, and in the slurry Mierocrystalline cellulose and hemicellulose part owing to there is not this double bond structure, therefore above-mentioned reaction does not take place with them in FRS, thereby has guaranteed the intensity of paper pulp.FRS and own patent " oxygen delignification and bleaching integration reactor " (number of patent application: CN1621609A) be used, can further improve ultra-oxygen anion free radical
Stability and prolong its life-span, shorten delignification and bleaching time thereby reach, further improve output, guarantee the purpose of pulping process cleaner production and non-secondary pollution simultaneously.FRS and patent CN1621609A are used the every technical indicator of gained paper pulp and all reach or be better than national standard.This technology fundamentally confirmed without highly basic, fear quinone etc. also can obtain
Free radical, thus paper industry, textile industry and sewage disposal industry are produced great technique influence.
The typical production of free radical stabilizer is among the present invention: a certain proportion of acetone and water are mixed in reactor, utilize sodium hydrogen carbonate solution to regulate the pH value and be 3.8-9.3, add peroxide one sulfuric acid by feed hopper, in certain vacuum degree, 5-10 ℃ reaction down, with nitrogen is carrier, utilizes efficient duplex condenser to collect FRS, and its concentration is 0.04-O.1mol/L, product is dissolved in extracting repeatedly in the methylene dichloride, makes FRS concentration bring up to 0.4mol/L.In addition, also can carry out in-situ preparing (seeing a kind of method 2 of embodiment) according to different needs.
Its reaction mechanism is: when peroxide one sulfuric acid (or its salt) reacts with ketone, introduce superfluous Sauerstoffatom effectively in the carbonyl of ketone, thereby obtain containing the FRS of the triatomic ring structure that two Sauerstoffatoms and carbon atom form, this ring texture makes that FRS is a kind of strong active close electrooxidation agent and free radical stabilizer.In the entire reaction journey, ketone only plays catalyst action, can recycle.Reaction formula is as follows:
R
1, R
2, R
3, R
4, R
5Be various straight-chain paraffins and ring-type aromatic group
Embodiment
Embodiment 1
Method 1
With concentration is that the FRS of 0.4mol/L drops into and to add in " oxygen delignification and the bleaching integration reactor " of honest material; rotating speed is 0.5m/s; softening temperature of charge is stabilized in 100 ℃; 0.35MPa depressing, oxygen adds 0.1% sal epsom, 0.5% water glass and 0.5% hydrogen peroxide Mierocrystalline cellulose protective material; reaction 30min; with wash hollander repetitive scrubbing secondary in 60 ℃ of deionized waters, detected result sees attached list 1.
Method 2
Dry pulp is dropped in proportion in " oxygen delignification and bleaching integration reactor "; rotating speed is 0.5m/s; softening temperature of charge is stabilized in 100 ℃; 0.35MPa depressing, oxygen adds oxygen one sulfuric acid, acetone, 0.1% sal epsom, 0.5% water glass and 0.5% hydrogen peroxide Mierocrystalline cellulose protective material; reaction 30min; with wash hollander repetitive scrubbing secondary in 60 ℃ of deionized waters, detected result sees attached list 1.
Embodiment 2
With the dull and stereotyped iron of nickel plating is anode, and porous carbon electrodes is a negative electrode, and the apparent area of anode and cathode respectively is 100cm
2Pass to oxygen or air at negative electrode, add certain printworks waste liquid in electrolyzer, the FRS of 0.4mol/L stirs, to reduce the Fe that anode and cathode generates
2+And H
2O
2Concentration polarization in the solution transmission course is with Na
2SO
4Be supporting electrolyte (20g/L).After handling 1h, waste liquid all becomes transparent, and the COD clearance reaches more than 75%.
Embodiment 3
With the dull and stereotyped iron of nickel plating is anode, and porous carbon electrodes is a negative electrode, and the apparent area of anode and cathode respectively is 100cm
2Pass to oxygen or air at negative electrode, add certain pulp mill's waste liquid in electrolyzer, the FRS of 0.4mol/L stirs with Na
2SO
4Be supporting electrolyte (20g/L).After handling 1.5h, the COD clearance reaches more than 70%.
Embodiment 4
Under the following conditions dried cotton is bleached: 60 ℃ of washing procedures, each wash(ing)cycle 6 kilograms of calico samples, the FRS that adds water glass, sodium sulfate, carboxymethyl cellulose and good antiscale property agent, 0.4mol/L in proportion behind the 10min, can obtain whiteness and be 78.6% bleaching cloth specimen.
Subordinate list 1: slurry experimental result
Claims (7)
- A kind of preparation of free radical stabilizer and application thereof,1, utilize peroxy acid (or its salt) and ketone under neutrallty condition in the aqueous solution, to prepare a kind of method of free radical stabilizer and in the application in highly difficult wastewater treatment and paper pulp, fiber bleached field.
- 2, according to right 1 requirement, described peroxy acid is peroxide one sulfuric acid etc., and its salt is peroxide one vitriolate of tartar, peroxide one sodium sulfate etc., and ketone is various ketone such as acetone, pentanone, cyclopentanone.
- 3, according to right 1 requirement, described neutrallty condition is to regulate as buffer reagent with sodium bicarbonate (potassium), sodium pyrosulfate (potassium) etc.
- 4,, adopt the method for solvent extraction to improve the concentration of FRS in organic solvent according to right 1 requirement.The FRS solution of free radicals such as this solvent extraction method is applicable to oxygen radical, contains nitrogen free radical, quinone free radical and superoxide-dismutase.
- 5, according to right 4 requirements, described extraction solvent is chloroform, methylene dichloride etc.
- 6, according to right 1 requirement, free radical stabilizer is used in highly difficult wastewater treatment, weaving bleaching and " oxygen delignification and bleaching integration reactor ", when carrying out delignification and bleaching operation, is applicable to the various free radicals in the claim 4.
- 7, according to right 3 requirements, described " oxygen delignification and bleaching integration reactor " passes through (number of patent application: CN1621609A) for own patent of invention, this patent first trial.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610007232 CN101020589A (en) | 2006-02-14 | 2006-02-14 | Prepn and application of free radical stabilizer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610007232 CN101020589A (en) | 2006-02-14 | 2006-02-14 | Prepn and application of free radical stabilizer |
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| Publication Number | Publication Date |
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| CN101020589A true CN101020589A (en) | 2007-08-22 |
Family
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| CN 200610007232 Pending CN101020589A (en) | 2006-02-14 | 2006-02-14 | Prepn and application of free radical stabilizer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621799A (en) * | 2020-12-10 | 2022-06-14 | 株式会社神户制钢所 | Method for producing ashless coal |
-
2006
- 2006-02-14 CN CN 200610007232 patent/CN101020589A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621799A (en) * | 2020-12-10 | 2022-06-14 | 株式会社神户制钢所 | Method for producing ashless coal |
| CN114621799B (en) * | 2020-12-10 | 2024-02-09 | 株式会社神户制钢所 | Method for producing ashless coal |
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Open date: 20070822 |