CN103864231B - Chitosan multiple-effect water treatment medicine and preparation method thereof - Google Patents

Chitosan multiple-effect water treatment medicine and preparation method thereof Download PDF

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Publication number
CN103864231B
CN103864231B CN201410087203.9A CN201410087203A CN103864231B CN 103864231 B CN103864231 B CN 103864231B CN 201410087203 A CN201410087203 A CN 201410087203A CN 103864231 B CN103864231 B CN 103864231B
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chitosan
water treatment
maleic anhydride
isopropylene
ammonium chloride
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CN103864231A (en
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张秀华
刘全华
万振涛
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Shandong Taihe Technology Co ltd
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Shandong Taihe Water Treatment Co Ltd
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Abstract

The invention discloses a chitosan multiple-effect water treatment medicine which comprises the following components in percentage by mass: 1-15% of chitosan, 5-20% of dimethyl diallyl ammonia chloride, 10-80% of isopropylene phosphonic acid and 10-60% of hydrolysis maleic anhydride. The synthesis method specifically comprises steps of adding chitosan into an acetic acid diluted solution, stirring to dissolve, adding dimethyl diallyl ammonium chloride, isopropylene phosphonic acid and hydrolysis maleic anhydride, stirring and heating, dropping an initiator solution, after the dropping, keeping the temperature and continuously reacting till the final point.

Description

A kind of chitosan multiple-effect water treatment agent and preparation method thereof
Technical field
The present invention relates to a kind of water treatment agent field, particularly relate to a kind of chitosan multiple-effect water treatment agent.
Background technology
Industrial enterprise belongs to the rich and influential family of water consumption and sewage discharge, how to reduce water consumption and the wastewater disposition amount of industrial enterprise, has become the focus of entire society's growing interest.Wherein to the water coolant accounting for industrial water consumption 70 ~ 80% carry out recirculation use be a water saving, reduction of discharging, energy-conservation, lower consumption effective measure.Because water is reusing in process series of problems such as there is fouling, etching apparatus and pipeline, foundry loam, bacterium algae, if not can solve, then recirculated water cannot run at all.Exploitation advanced Water Treatment Chemicals and utilisation technology reliably, not only significantly can reduce water consumption and the wastewater disposition of industrial enterprise, and fully can ensure safe, efficient, the macrocyclic operation of production equipment, make enterprise obtain very considerable economic benefit while obtaining obvious social benefit.Therefore, the exploitation of Treatment of Industrial Water chemical and utilisation technology has become the focus of social and economic development, more and more causes the great attention of each department of country.
The new type water treatment chemicals with in inhibition, scale inhibition and sterilization three kinds of performances two kinds or over-all properties is the direction that many Water Treatment Chemicals workers make great efforts always.The comprehensive water treatment agent of potion multiple-effect, low cost, safety and low toxicity, environment-friendly biodegradable, is subject to the most attention of various countries day by day.
Chitosan-phospholipid complex has good anti-microbial activity, can suppress the growth and breeding of some fungies, bacterium and virus.And chitosan wide material sources, have nontoxic, tasteless, alkaline-resisting, heat-resisting, corrosion-resistant, defy advantages such as damaging by worms, be widely used in the fields such as printing and dyeing, weaving, food, medicine, water treatment, be especially a class excellent property, nontoxic, nuisanceless, biodegradable novel water-treatment medicament in water treatment.
The bactericidal property that quaternary ammonium salt has a broad-spectrum high efficacy effectively can control breeding and the foundry loam growth of bacterium algae in water, meanwhile, has good corrosion inhibition, for the anticorrosion of circulating water system pipeline and pickling inhibition protection.
Organic phosphoric acid is a class non-chemically equivalent Scale inhibitors, has obvious threshold effect.When them and other water conditioner compound uses, synergistic effect can be shown.To many metal ions (as calcium, magnesium, copper, zinc etc.), there is excellent sequestering power, also have deactivation to inorganic salts such as calcium sulfate, the calcium carbonate etc. of these metals.It is the rising medicament of a class.
Existing multiple-effect water treatment agent is compound product mostly, because various component different batches product performance are not quite similar, makes the performance inconsistency of compound product larger; And Component comparison too increases transport and storage cost more; In using, operation is loaded down with trivial details simultaneously, and labor force is large, and error property increases relatively.
Summary of the invention
The object of this invention is to provide that a kind of cost is low, dosing operation is few, a kind of chitosan multiple-effect water treatment agent of the comprehensive water treatment of applied range, potion multiple-effect.
For achieving the above object, the technical solution used in the present invention is: a kind of chitosan multiple-effect water treatment agent, is characterized in that: comprise chitosan and dimethyl diallyl ammonium chloride, isopropylene and phosphonic acid, hydrolyzed maleic anhydride, and the mass ratio of each component is:
Chitosan 1 ~ 15%;
Dimethyl diallyl ammonium chloride 5 ~ 20%;
Isopropylene and phosphonic acid 10 ~ 80%;
Hydrolyzed maleic anhydride 10 ~ 60%,
Its concrete synthetic method is for join stirring and dissolving in dilute solution of acetic acid by chitosan; Add dimethyl diallyl ammonium chloride, isopropylene and phosphonic acid, hydrolyzed maleic anhydride stirring heating; Drip initiator solution; Dropwise, keep temperature to continue reaction to terminal.
In this product, the mass ratio of described chitosan and dimethyl diallyl ammonium chloride, isopropylene and phosphonic acid, each component of hydrolyzed maleic anhydride is:
Chitosan 5 ~ 12%;
Dimethyl diallyl ammonium chloride 10 ~ 15%;
Isopropylene and phosphonic acid 30 ~ 60%;
Hydrolyzed maleic anhydride 20 ~ 50%.
In this product, the concentration of described dilute solution of acetic acid is 0.1 ~ 1.0%.
In this product, described copolymerization temperature is 60 ~ 100 DEG C, and the time of copolyreaction is 4 ~ 12h.
In this product, described initiator is superoxide or persulphate, and initiator add-on is 0.2 ~ 5% of total monomer quality, and initiator time for adding is 1 ~ 3h.
In this product, 208kg chitosan is joined stirring and dissolving in the dilute solution of acetic acid of 1000kg0.1%; Add 312kg dimethyl diallyl ammonium chloride, 1170kg isopropylene and phosphonic acid, 910kg hydrolyzed maleic anhydride stir, open and be heated to 80 DEG C; Drip the aqueous solution of 26kg Sodium Persulfate, keep 2h to dropwise; Temperature is kept to continue reaction 8h.
In this product, 196kg chitosan is joined stirring and dissolving in the dilute solution of acetic acid of 500kg0.5%; Add 280kg dimethyl diallyl ammonium chloride, 1344kg isopropylene and phosphonic acid, 980kg hydrolyzed maleic anhydride stir, open and be heated to 75 DEG C; Drip the aqueous solution of 56kg benzoyl peroxide, keep 3h to dropwise; Temperature is kept to continue reaction 5h.
In this product, 252kg chitosan is joined stirring and dissolving in the dilute solution of acetic acid of 1000kg0.1%; Add 308kg dimethyl diallyl ammonium chloride, 1316kg isopropylene and phosphonic acid, 924kg hydrolyzed maleic anhydride stir, open and be heated to 73 DEG C; Drip the aqueous solution of 22.4kg ceric ammonium nitrate, keep 1h to dropwise; Temperature is kept to continue reaction 8h.
In this product, 336kg chitosan is joined stirring and dissolving in the dilute solution of acetic acid of 1200kg0.5%; Add 252kg dimethyl diallyl ammonium chloride, 1204kg isopropylene and phosphonic acid, 1008kg hydrolyzed maleic anhydride stir, open and be heated to 85 DEG C; Drip the aqueous solution of 98kg benzoyl peroxide, keep 3h to dropwise; Temperature is kept to continue reaction 5h.
In this product, 338kg chitosan is joined stirring and dissolving in the dilute solution of acetic acid of 1200kg0.1%; Add 442kg dimethyl diallyl ammonium chloride, 936kg isopropylene and phosphonic acid, 884kg hydrolyzed maleic anhydride stir, open and be heated to 80 DEG C; Drip the aqueous solution of 26kg ceric ammonium nitrate, keep 2h to dropwise; Temperature is kept to continue reaction 11h.
Advantageous effect of the present invention is: due to this formula of the present invention and preparation method, so product disclosed in the present invention has potion multiple-effect have scale inhibition, inhibition, sterilization, antibacterial excellent characteristics simultaneously, cost-saving in water treatment applications, saves operation; There is low-phosphorous, nontoxic, nuisanceless, environment-friendly biodegradable; The few water per ton of this product add-on only needs the pharmaceutical quantities of 20 ~ 30ppm; And be applicable to high salt, high-alkali severe rugged environment.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1
208kg chitosan is joined stirring and dissolving in the dilute solution of acetic acid of 1000kg0.1%; Add 312kg dimethyl diallyl ammonium chloride, 1170kg isopropylene and phosphonic acid, 910kg hydrolyzed maleic anhydride stir, open and be heated to 80 DEG C; Drip the aqueous solution of 26kg Sodium Persulfate, keep 2h to dropwise; Temperature is kept to continue reaction 8h.
Embodiment 2
196kg chitosan is joined stirring and dissolving in the dilute solution of acetic acid of 500kg0.5%; Add 280kg dimethyl diallyl ammonium chloride, 1344kg isopropylene and phosphonic acid, 980kg hydrolyzed maleic anhydride stir, open and be heated to 75 DEG C; Drip the aqueous solution of 56kg benzoyl peroxide, keep 3h to dropwise; Temperature is kept to continue reaction 5h.
Embodiment 3
252kg chitosan is joined stirring and dissolving in the dilute solution of acetic acid of 1000kg0.1%; Add 308kg dimethyl diallyl ammonium chloride, 1316kg isopropylene and phosphonic acid, 924kg hydrolyzed maleic anhydride stir, open and be heated to 73 DEG C; Drip the aqueous solution of 22.4kg ceric ammonium nitrate, keep 1h to dropwise; Temperature is kept to continue reaction 8h.
Embodiment 4
336kg chitosan is joined stirring and dissolving in the dilute solution of acetic acid of 1200kg0.5%; Add 252kg dimethyl diallyl ammonium chloride, 1204kg isopropylene and phosphonic acid, 1008kg hydrolyzed maleic anhydride stir, open and be heated to 85 DEG C; Drip the aqueous solution of 98kg benzoyl peroxide, keep 3h to dropwise; Temperature is kept to continue reaction 5h.
Embodiment 5
338kg chitosan is joined stirring and dissolving in the dilute solution of acetic acid of 1200kg0.1%; Add 442kg dimethyl diallyl ammonium chloride, 936kg isopropylene and phosphonic acid, 884kg hydrolyzed maleic anhydride stir, open and be heated to 80 DEG C; Drip the aqueous solution of 26kg ceric ammonium nitrate, keep 2h to dropwise; Temperature is kept to continue reaction 11h.

Claims (10)

1. a chitosan multiple-effect water treatment agent, is characterized in that: comprise chitosan and dimethyl diallyl ammonium chloride, isopropylene and phosphonic acid, hydrolyzed maleic anhydride, and the mass ratio of each component is:
Chitosan 1 ~ 15%;
Dimethyl diallyl ammonium chloride 5 ~ 20%;
Isopropylene and phosphonic acid 10 ~ 80%;
Hydrolyzed maleic anhydride 10 ~ 60%,
Its concrete synthetic method is for join stirring and dissolving in dilute solution of acetic acid by chitosan; Add dimethyl diallyl ammonium chloride, isopropylene and phosphonic acid, hydrolyzed maleic anhydride stirring heating; Drip initiator solution; Dropwise, keep temperature to continue reaction to terminal.
2. a kind of chitosan multiple-effect water treatment agent according to claim 1, is characterized in that: the mass ratio of described chitosan and dimethyl diallyl ammonium chloride, isopropylene and phosphonic acid, each component of hydrolyzed maleic anhydride is:
Chitosan 5 ~ 12%;
Dimethyl diallyl ammonium chloride 10 ~ 15%;
Isopropylene and phosphonic acid 30 ~ 60%;
Hydrolyzed maleic anhydride 20 ~ 50%.
3. a kind of chitosan multiple-effect water treatment agent according to claim 2, is characterized in that: the concentration of described dilute solution of acetic acid is 0.1 ~ 1.0%.
4. a kind of chitosan multiple-effect water treatment agent according to claim 3, it is characterized in that: described insulation reaction temperature is 60 ~ 100 DEG C, the reaction times is 4 ~ 12h.
5. a kind of chitosan multiple-effect water treatment agent according to claim 4, it is characterized in that: described initiator is superoxide or persulphate, initiator add-on is 0.2 ~ 5% of total monomer quality, and initiator time for adding is 1 ~ 3h.
6. a kind of chitosan multiple-effect water treatment agent according to claim 1, is characterized in that: 208kg chitosan is joined stirring and dissolving in the dilute solution of acetic acid of 1000kg0.1%; Add 312kg dimethyl diallyl ammonium chloride, 1170kg isopropylene and phosphonic acid, 910kg hydrolyzed maleic anhydride stir, open and be heated to 80 DEG C; Drip the aqueous solution of 26kg Sodium Persulfate, keep 2h to dropwise; Temperature is kept to continue reaction 8h.
7. a kind of chitosan multiple-effect water treatment agent according to claim 1, is characterized in that: 196kg chitosan is joined stirring and dissolving in the dilute solution of acetic acid of 500kg0.5%; Add 280kg dimethyl diallyl ammonium chloride, 1344kg isopropylene and phosphonic acid, 980kg hydrolyzed maleic anhydride stir, open and be heated to 75 DEG C; Drip the aqueous solution of 56kg benzoyl peroxide, keep 3h to dropwise; Temperature is kept to continue reaction 5h.
8. a kind of chitosan multiple-effect water treatment agent according to claim 1, is characterized in that: 252kg chitosan is joined stirring and dissolving in the dilute solution of acetic acid of 1000kg0.1%; Add 308kg dimethyl diallyl ammonium chloride, 1316kg isopropylene and phosphonic acid, 924kg hydrolyzed maleic anhydride stir, open and be heated to 73 DEG C; Drip the aqueous solution of 22.4kg ceric ammonium nitrate, keep 1h to dropwise; Temperature is kept to continue reaction 8h.
9. a kind of chitosan multiple-effect water treatment agent according to claim 1, is characterized in that: 336kg chitosan is joined stirring and dissolving in the dilute solution of acetic acid of 1200kg0.5%; Add 252kg dimethyl diallyl ammonium chloride, 1204kg isopropylene and phosphonic acid, 1008kg hydrolyzed maleic anhydride stir, open and be heated to 85 DEG C; Drip the aqueous solution of 98kg benzoyl peroxide, keep 3h to dropwise; Temperature is kept to continue reaction 5h.
10. a kind of chitosan multiple-effect water treatment agent according to claim 1, is characterized in that: 338kg chitosan is joined stirring and dissolving in the dilute solution of acetic acid of 1200kg0.1%; Add 442kg dimethyl diallyl ammonium chloride, 936kg isopropylene and phosphonic acid, 884kg hydrolyzed maleic anhydride stir, open and be heated to 80 DEG C; Drip the aqueous solution of 26kg ceric ammonium nitrate, keep 2h to dropwise; Temperature is kept to continue reaction 11h.
CN201410087203.9A 2014-03-11 2014-03-11 Chitosan multiple-effect water treatment medicine and preparation method thereof Active CN103864231B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4536292A (en) * 1984-03-26 1985-08-20 Calgon Corporation Carboxylic/sulfonic/quaternary ammonium polymers for use as scale and corrosion inhibitors
CN101284693A (en) * 2008-05-26 2008-10-15 董超平 Natural organic polymer composite flocculant, method for preparing the same and applications
CN103012619A (en) * 2013-01-11 2013-04-03 河北工业大学 Water-soluble sulfonated/quaternized chitosan and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4536292A (en) * 1984-03-26 1985-08-20 Calgon Corporation Carboxylic/sulfonic/quaternary ammonium polymers for use as scale and corrosion inhibitors
CN101284693A (en) * 2008-05-26 2008-10-15 董超平 Natural organic polymer composite flocculant, method for preparing the same and applications
CN103012619A (en) * 2013-01-11 2013-04-03 河北工业大学 Water-soluble sulfonated/quaternized chitosan and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
《DMDAAC壳聚糖接枝共聚物的制备及其应用》;张荣等;《中国造纸学报》;20071231;第22卷(第1期);第46-50页 *
一种新型缓蚀阻垢剂的制备及性能初探;赵彦生等;《水处理技术》;19960229;第22卷(第1期);第48-51页 *

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Owner name: SHANGDONG TAIHE WATER TREATMENT TECHNOLOGIES CO.,

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Address after: Shandong Hong Village 277100 Zaozhuang City District Xi Wang Zhuang Xiang

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