CN101597387B - Preparation method of polysaccharose nanometer antichlor for industrial water treatment - Google Patents

Preparation method of polysaccharose nanometer antichlor for industrial water treatment Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
starch
stirring
add
antichlor
polysaccharose
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.)
Expired - Fee Related
Application number
CN2009100518240A
Other languages
Chinese (zh)
Other versions
CN101597387A (en
Inventor
马宝全
朱祥
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Lanmiao Water Treatment Science & Technology Co Ltd
Original Assignee
Shanghai Lanmiao Water Treatment Science & Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai Lanmiao Water Treatment Science & Technology Co Ltd filed Critical Shanghai Lanmiao Water Treatment Science & Technology Co Ltd
Priority to CN2009100518240A priority Critical patent/CN101597387B/en
Publication of CN101597387A publication Critical patent/CN101597387A/en
Application granted granted Critical
Publication of CN101597387B publication Critical patent/CN101597387B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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

The preparation method who is used for the polysaccharose nanometer antichlor of Treatment of Industrial Water
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
Figure G2009100518240D00021
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
Figure G2009100518240D00022
(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
Figure G2009100518240D00041
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
Figure G2009100518240D00042
(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
Figure G2009100518240D00051
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.
CN2009100518240A 2009-05-22 2009-05-22 Preparation method of polysaccharose nanometer antichlor for industrial water treatment Expired - Fee Related CN101597387B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009100518240A CN101597387B (en) 2009-05-22 2009-05-22 Preparation method of polysaccharose nanometer antichlor for industrial water treatment

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009100518240A CN101597387B (en) 2009-05-22 2009-05-22 Preparation method of polysaccharose nanometer antichlor for industrial water treatment

Publications (2)

Publication Number Publication Date
CN101597387A CN101597387A (en) 2009-12-09
CN101597387B true CN101597387B (en) 2011-12-07

Family

ID=41418994

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009100518240A Expired - Fee Related CN101597387B (en) 2009-05-22 2009-05-22 Preparation method of polysaccharose nanometer antichlor for industrial water treatment

Country Status (1)

Country Link
CN (1) CN101597387B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
CN101597387A (en) 2009-12-09

Similar Documents

Publication Publication Date Title
CN103641245A (en) Papermaking wastewater treating agent and preparation method thereof
Chauhan et al. Novel polycarboxylated starch-based sorbents for Cu2+ ions
CN101597387B (en) Preparation method of polysaccharose nanometer antichlor for industrial water treatment
JPS5969151A (en) Spherical ion exchange resin and its production and adsorptive treatment
WO2021097663A1 (en) Nano-encapsulated binary composite phase change material
CN107501445A (en) A kind of synthetic method of low viscosity polyvinyl butyral resin
CN100999659A (en) Graft type fracturing fluid and preparation process thereof
CN102898580B (en) Method for preparing polyacrylamide
CN106825603B (en) A kind of preparation method of aluminium cladding titanium composite alloy powder
CN109482160A (en) Phosphate-based efficient uranium absorption agent of one kind and the preparation method and application thereof
CN103880782A (en) Method for preparing epoxy propane
CN105418774A (en) Method for preparing crosslinked starch by utilizing sodium trimetaphosphate crosslinking agent
CN105170122B (en) A kind of preparation method and applications based on the full interpenetrating film of quaternized polyvinyl alcohol class
CN107460484A (en) For polishing polishing reagent, the method and system of nickel-base alloy workpiece inner flow passage
CN101270312A (en) Coal combustion catalyst microcapsule and producing method thereof
US4014820A (en) Method of making a Raney copper catalyst and the catalyst so made
CN101024706B (en) Preparing method of composite catalytic solid-phase prepared hydroxypropyl starch
CN100348505C (en) Hydrogenation and deoxidization method for palladium ion type catalytic resin
CN115318345A (en) Manufacturing device and application of hypochlorous acid
CN113234101A (en) Gas-liquid two-phase synthesis method and reaction device of gamma-chloropropyltrichlorosilane
CN101497041B (en) Method for preparing palladium-carrying catalyst with nano Pd by suspension polymerization
Li et al. Solid–Liquid Stable Equilibrium of the Aqueous Quaternary System NH4SCN–(NH4) 2S2O3–(NH4) 2SO4–H2O at 303.15 K
Komissarenkov et al. Use of lignosulfonates in newsprint paper production
CN109465034A (en) It is a kind of for eliminating the catalyst and preparation method thereof of dissolved oxygen in liquid
CN101723463B (en) Method and device for preparing tungstic acid through closed type acid decomposition of wolframite

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20111207

CF01 Termination of patent right due to non-payment of annual fee