CN101597387B - Preparation method of polysaccharose nanometer antichlor for industrial water treatment - Google Patents
Preparation method of polysaccharose nanometer antichlor for industrial water treatment Download PDFInfo
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- CN101597387B CN101597387B CN2009100518240A CN200910051824A CN101597387B CN 101597387 B CN101597387 B CN 101597387B CN 2009100518240 A CN2009100518240 A CN 2009100518240A CN 200910051824 A CN200910051824 A CN 200910051824A CN 101597387 B CN101597387 B CN 101597387B
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Abstract
The invention relates to a preparation method of polysaccharose nanometer antichlor for industrial water treatment, comprising the following steps: (1), preparing soluble cationic starch to water solution; heating till the solution becomes clear; placing at room temperature; mixing with toluene and chloroform; adding surfactant Span80, stirring and mixing uniformly; adding starch hydrolysis liquid into the oil-phase emulsion, stirring; adding glyoxal, continuously stirring, washing, freeze-drying; (2), putting trimethyl amine into the container; placing in ice salt bath; adding epoxy chloropropane, stirring; putting refined lignin into the container; adding sodium hydroxide solution; adding the intermediate monomer after stirring, continuously stirring; (3) mixing cross-linked starch particles and lignin quaternary ammonium salt, obtaining the product. The polysaccharose nanometre antichlor obtained in the invention has more than 60% of average chlorine ion removal rate of the boiler after 3-year practical operation, the maximum removal rate being 80%; the chlorine-removing effect is obvious, and the requirements for the pressure container hydraulic test are satisfied.
Description
Technical field
The invention belongs to the Treatment of Industrial Water field, particularly relate to the preparation method of the polysaccharose nanometer antichlor that is used for Treatment of Industrial Water.
Background technology
The material of existing many pressurized vessels mostly is 304,316 stainless steels, and when hydraulic test of pressure vessel, the concentration of national standard chlorion is less than 25ppm.Because the chlorine ion concentration in the tap water is about 100ppm, so just can not adopt tap water to carry out the water test, therefore, present solution is carried out the water test for buying de-salted water, but the cost of this method is somewhat expensive comparatively speaking, and the price of de-salted water per ton is about 300 yuan.
Service water recycle system inner metal surfaces keeps good state that its safety and economic operation is had great significance.Yet because the inner water quality of water-steam system always contains foreign ion, make the metallic surface phenomenons such as burn into fouling usually occur, threatening the normal operation of unit.Harm with chlorion in the foreign ion is the most serious.It is very difficult adopting common inorganic chemical mode to remove chlorion, thus because of it compound mostly soluble in water being difficult to remove.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method of the polysaccharose nanometer antichlor that is used for Treatment of Industrial Water, the gained polysaccharose nanometer antichlor, through the actual motions in 3 years the average removal rate of boiler chlorine root is reached more than 60%, reach as high as 80%, the dechlorination effect is obvious, satisfies the requirement of hydraulic test of pressure vessel.
The preparation method who is used for the polysaccharose nanometer antichlor of Treatment of Industrial Water of the present invention comprises:
(1) preparation method of cross-linked cationic starch granules
Soluble cation starch (Changli County, Hebei province dragon rises economic and technological development zone Hao Rui Food Co., Ltd) 10-15 gram is made into the aqueous solution of 10%-15%, heats in the boiling water bath, and up to the solution clarification, room temperature is placed;
Measure toluene 30ml-40ml and chloroform 10ml-15ml and mix, add the tensio-active agent Span80 (sorbester p17, Shanghai flood Ji chemical industry company limited) that accounts for cumulative volume 0.7-0.8, stirring and evenly mixing forms the oil phase emulsion;
To mix in the above-mentioned starch hydrolyzate adding 5ml-8ml oil phase emulsion, continue to be stirred to the small emulsion of formation, add the linking agent oxalic dialdehyde that accounts for starch quality 0.2%-0.5%, continue stirring reaction 30min-1h, acetone and washing with alcohol emulsion 3-5 time, lyophilize can obtain the cross-linking starch particle;
(2) preparation of lignin quaternary:
Take by weighing trimethylamine solution 1-1.5 gram and place Erlenmeyer flask, flask to place cryosel to bathe, add epoxy chloropropane 0.7-1 gram, stirring reaction 1-2h, monomer in the middle of getting
Leave standstill;
To make with extra care xylogen (Henan Province Hui Kang industry main office) 2-3 gram and put into there-necked flask, place 70 ℃ of-90 ℃ of thermostat water baths, install reflux condensing tube, the 10%-20% sodium hydroxide solution that adds 20ml-30ml makes the lignin molecule activation as catalyzer, stir the back and add above-mentioned middle monomer, continue stirring reaction 3h, get brown viscous liquid, be lignin quaternary
(3) preparation of polysaccharose nanometer antichlor
The cross-linking starch particle of preparation is mixed with lignin quaternary, stir fast, form small emulsion droplet, crosslinking reaction just takes place with xylogen in starch in emulsion droplet, obtain nano level particle and form the surface charge of quaternary amine, obtain shell starch nano particle with strong positive charge.Because this particle has stronger positive charge can adsorbing chloride ions.
Adopt the biological nano technology, use macromolecule polysaccharide molecule, macromole dextrin to be raw material, and its functional group is recombinated and improves.
The destruction of chlorion mainly shows as and makes the metallic surface change active state into by passive state.Make metal change the mechanism of active state into about chlorion, two kinds of viewpoints arranged at present by passive state, phase film theory and adsorption theory.Become the viewpoint of phase film theory to think, because the chlorion radius is little, penetrativity is strong, so its easiest interior minimum hole of oxide film that penetrates arrives the metallic surface, and forms soluble compound with metal interaction, make the structure of oxide film change corroding metal.Adsorption theory then thinks, the basic reason of the disruptive oxidation film of chlorion be since chlorion have very strong can be by the ability of metal adsorption, they are preferentially by metal adsorption, and from the metallic surface oxygen are drained.Because oxygen is determining the passive state of metal, adsorption site on chlorion and the oxygen contention metallic surface, even can replace passivation ion in the absorption, form muriate with metal, the absorption of muriate and metallic surface is also unstable, formed soluble substance, the result generates the little pit that the aperture is 20～30 μ m on base metal, and these little pits are pitting nuclear.Adding under the anodic polarization condition, as long as contain a certain amount of chlorion in the medium, just may make erosion authorize the generate pit, thereby cause corrosive to quicken.
Beneficial effect
(1) gained polysaccharose nanometer antichlor of the present invention can make the average removal rate of boiler chlorine root reach more than 60% through the actual motions in 3 years, reaches as high as 80%, and the dechlorination effect is obvious;
(2) gained polysaccharose nanometer antichlor of the present invention, effective adsorbing chloride ions, thus satisfy the requirement of hydraulic test of pressure vessel.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) preparation method of cross-linked cationic starch granules
Soluble cation starch (Changli County, Hebei province dragon rises economic and technological development zone Hao Rui Food Co., Ltd) 10 grams are made into 10% the aqueous solution, heat in the boiling water bath, and up to the solution clarification, room temperature is placed;
Measure toluene 30ml and chloroform 10ml and mix, add the tensio-active agent Span80 (sorbester p17, Shanghai flood Ji chemical industry company limited) that accounts for cumulative volume 0.8, stirring and evenly mixing forms the oil phase emulsion;
To mix in the above-mentioned starch hydrolyzate adding 5ml oil phase emulsion, continue to be stirred to the small emulsion of formation, add the linking agent oxalic dialdehyde that accounts for starch quality 0.2%, continue stirring reaction 30min, acetone and washing with alcohol emulsion 3-5 time, lyophilize can obtain the cross-linking starch particle;
(2) preparation of lignin quaternary:
Take by weighing trimethylamine solution 1 gram and place Erlenmeyer flask, flask to place cryosel to bathe, add epoxy chloropropane 0.7 gram, stirring reaction 1-2h, monomer in the middle of getting
Leave standstill;
To make with extra care xylogen (Henan Province Hui Kang industry main office) 2 grams and put into there-necked flask, place 70 ℃ of thermostat water baths, install reflux condensing tube, add 20ml 10% sodium hydroxide solution and make the lignin molecule activation as catalyzer, stir the back and add above-mentioned middle monomer, continue stirring reaction 3h, get brown viscous liquid, be lignin quaternary
(3) preparation of polysaccharose nanometer antichlor
The cross-linking starch particle of preparation is mixed with lignin quaternary, stir fast, form small emulsion droplet, crosslinking reaction just takes place with xylogen in starch in emulsion droplet, obtain nano level particle and form the surface charge of quaternary amine, obtain shell starch nano particle with strong positive charge.
Embodiment 2
(1) preparation method of cross-linked cationic starch granules
Soluble cation starch (Changli County, Hebei province dragon rises economic and technological development zone Hao Rui Food Co., Ltd) 15 grams are made into 10% the aqueous solution, heat in the boiling water bath, and up to the solution clarification, room temperature is placed;
Measure toluene 30ml and chloroform 10ml and mix, add the tensio-active agent Span80 (sorbester p17, Shanghai flood Ji chemical industry company limited) that accounts for cumulative volume 0.7, stirring and evenly mixing forms the oil phase emulsion;
To mix in the above-mentioned starch hydrolyzate adding 8ml oil phase emulsion, continue to be stirred to the small emulsion of formation, add the linking agent oxalic dialdehyde that accounts for starch quality 0.3%, continue stirring reaction 1h, acetone and washing with alcohol emulsion 3-5 time, lyophilize can obtain the cross-linking starch particle;
(2) preparation of lignin quaternary:
Take by weighing trimethylamine solution 1.5 grams and place Erlenmeyer flask, flask to place cryosel to bathe, add epoxy chloropropane 0.7 gram, stirring reaction 1-2h, monomer in the middle of getting
Leave standstill;
To make with extra care xylogen (Henan Province Hui Kang industry main office) 2 grams and put into there-necked flask, place 70 ℃ of thermostat water baths, install reflux condensing tube, add 20ml 20% sodium hydroxide solution and make the lignin molecule activation as catalyzer, stir the back and add above-mentioned middle monomer, continue stirring reaction 3h, get brown viscous liquid, be lignin quaternary
(3) preparation of polysaccharose nanometer antichlor
The cross-linking starch particle of preparation is mixed with lignin quaternary, stir fast, form small emulsion droplet, crosslinking reaction just takes place with xylogen in starch in emulsion droplet, obtain nano level particle and form the surface charge of quaternary amine, obtain shell starch nano particle with strong positive charge.
Claims (1)
1. be used for the preparation method of the polysaccharose nanometer antichlor of Treatment of Industrial Water, comprise:
(1) soluble cation starch 10-15 gram is made into the aqueous solution of 10%-15%, heating, and up to the solution clarification, room temperature is placed;
Get toluene 30ml-40ml and chloroform 10ml-15ml and mix, add the tensio-active agent Span80 that accounts for cumulative volume 0.7-0.8, stirring and evenly mixing forms the oil phase emulsion;
With mixing in the above-mentioned starch hydrolyzate adding 5ml-8ml oil phase emulsion, stir, add the linking agent oxalic dialdehyde that accounts for starch quality 0.2%-0.5%, continue stirring reaction 30min-1h, acetone and washing with alcohol emulsion 3-5 time, lyophilize promptly obtains the cross-linking starch particle;
(2) get trimethylamine solution 1-1.5 gram and place container, place cryosel to bathe then, add epoxy chloropropane 0.7-1 gram, stirring reaction 1-2h, monomer leaves standstill in the middle of getting;
To make with extra care xylogen 2-3 gram and put into container, place 70 ℃ of-90 ℃ of waters bath with thermostatic control, add the 10%-20% sodium hydroxide solution of 20ml-30ml, stir the back and add above-mentioned middle monomer, continue stirring reaction 3-5h, get brown viscous liquid, be lignin quaternary;
(3) above-mentioned cross-linking starch particle is mixed with lignin quaternary, stir fast, promptly get the shell starch nano particle.
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| CN2009100518240A CN101597387B (en) | 2009-05-22 | 2009-05-22 | Preparation method of polysaccharose nanometer antichlor for industrial water treatment |
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| CN2009100518240A CN101597387B (en) | 2009-05-22 | 2009-05-22 | Preparation method of polysaccharose nanometer antichlor for industrial water treatment |
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| CN101597387B true CN101597387B (en) | 2011-12-07 |
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| CN110973142A (en) * | 2019-12-24 | 2020-04-10 | 甘肃泰升化工科技有限公司 | Power plant sterilization algicide and preparation method thereof |
| CN114349887B (en) * | 2021-12-29 | 2023-06-13 | 智仑超纯环氧树脂(西安)有限公司 | Epoxy resin chlorine removing agent and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1137491A (en) * | 1996-01-23 | 1996-12-11 | 石永湘 | Water quality treating chemicals |
| EP0860183A2 (en) * | 1997-02-24 | 1998-08-26 | Kabushiki Kaisha Meidensha | Noxious component removal process and noxious component removal agent therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1137491A (en) * | 1996-01-23 | 1996-12-11 | 石永湘 | Water quality treating chemicals |
| EP0860183A2 (en) * | 1997-02-24 | 1998-08-26 | Kabushiki Kaisha Meidensha | Noxious component removal process and noxious component removal agent therefor |
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