CN103864991A - Preparation method of chitosan grafted copolymer flocculation-bactericide - Google Patents
Preparation method of chitosan grafted copolymer flocculation-bactericide Download PDFInfo
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- CN103864991A CN103864991A CN201410044923.7A CN201410044923A CN103864991A CN 103864991 A CN103864991 A CN 103864991A CN 201410044923 A CN201410044923 A CN 201410044923A CN 103864991 A CN103864991 A CN 103864991A
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Abstract
The invention provides a chitosan grafted copolymer flocculation-bactericide for treating water bodies such as circulating cooling water, papermaking sewage, printing and dyeing sewage, domestic sewage, drilling fluid and the like. The bactericide is a compound agent which can kill the plankton such as viruses, bacteria, algae and the like in the water body and settles along with the colloid and suspended particles in the water body. The bactericide provided by the invention is prepared by graft copolymerization of chitosan and dimethyl diallyl ammonium salt and acrylamide triggered under the nitrogen protection.
Description
Technical field
The invention belongs to water treatment agent field, a kind of preparation method of chitose graft copolymer flocculation-sterilant is provided.
Background technology
Chemical flocculation is the conventional important method of processing the industrial sewages such as some papermaking, sugaring, printing and dyeing, oil production and sanitary sewage.Conventional flocculation agent has take Tai-Ace S 150, aluminum chloride, ferric sulfate, iron(ic) chloride and polymkeric substance thereof as main inorganic flocculating agent, the organic polymer coargulator of polyacrylamide, quaternary ammonium salt etc., microbial flocculant etc.Flocculation agent is added in utilization in sink drainage can effectively make colloid, the suspended particle flocculating settling in water.Cause organic fine particles in a lot of industrial production of reason of water pollution muddiness, greasy dirt, microorganism, mineral colloid etc.Chemical floc can effectively make more than 90% suspended particle in water body, colloid flocculating settling.But the factor that causes water body muddiness is all much microorganism in some water bodys, bacterium, algae etc. constantly grows up into the biotic pollution that is suspended in the microbe granular in water body, so want will first control this part microbial growth from the problem of basic solution water pollution muddiness, first will carry out sterilization.
Water treatment purification process traditionally, flocculation is the two procedures of separating with sterilization, in the process of water treatment, flocculation is two interdependences with sterilization, interactional process.In flocculation process, residual organic floculant easily reacts with the oxidizing bactericide in sterilization process and produces toxic substance, and the bacterium dirt that independent sterilization process produces can not be removed in time, wherein microorganism remains, algae etc. are one of important factors causing water pollution.Therefore, if two procedures can have flocculation and sterilization double-effect concurrently simultaneously, and synergy is the quantum jump that water treatment purifies mutually.
Summary of the invention
Can not synchronize the problem of carrying out for the flocculation occurring in existing water cleaning section and sterilization, the invention provides a kind of preparation method of chitose graft copolymer flocculation-sterilant, its existing good throwing out has again strong bactericidal property.The present invention has reduced water treatment operation, and potion economic benefits and social benefits have been saved cost, and the pollution of having avoided lower molecular weight Fungicide residue to cause, and the flocculation dirt that can once remove in water body by the effect of sterilant can play the effect of putting things right once and for all.
To achieve these goals, the way that the present invention takes is take chitosan, dimethyl diallyl ammonium chloride, acrylamide as raw material, under nitrogen protection, and take persulphate as initiator, initiation grafting copolymerization; Concrete operation steps is:
(1) chitosan is joined in reactor, and add aqueous acetic acid, be stirred to chitosan and all dissolve;
(2) dimethyldiallylammonium salt and two kinds of monomers of acrylamide are joined in reactor to hierarchy of control monomer concentration;
(3) control reactor temperature, in reactor, pass into nitrogen, under nitrogen protection, drip initiator persulphate, dropwise rear insulation reaction;
(4) stop heating reaction product is poured in ethanol, have and faint yellowly separate out to brown solid, rinse solid with the mixing solutions of second alcohol and water, then vacuum-drying, grinds to form small-particle.
Chitosan molecule amount described in above-mentioned steps (1) is 20 ~ 500,000, and deacetylation is 40% ~ 80%.
The mol ratio of the chitosan described in above-mentioned steps (1) and (2) and dimethyldiallylammonium salt, acrylamide is 1:2 ~ 8:2 ~ 8.
The described reaction system monomer concentration of above-mentioned steps (2) is 30 ~ 60%.
The described temperature of reaction system of above-mentioned steps (3) is 50 ~ 90 ℃.
The described persulfate initiator of above-mentioned steps (3) is selected from Sodium Persulfate, ammonium persulphate, Potassium Persulphate one wherein.
The dripping quantity of the initiator described in above-mentioned steps (3) is 0.5 ~ 10% of monomer total mass per-cent.
The described initiator of above-mentioned steps (3) dropwises at 1 ~ 3h.
The time of the insulation reaction described in above-mentioned steps (3) is 2 ~ 5h.
The described vacuum drying temperature of above-mentioned steps (4) is 80 ℃.
The advantage of patented product of the present invention is: (1) this invention product, with flocculation and sterilization double-effect effect, can be killed the biological pollutions such as bacterium algae in water body in flocculating.Simplify water-purifying process process, reduced costs; (2) natural high molecular substance chitosan is nontoxic, and readily biodegradable can not produce secondary pollution to environment, environmental protection; (3) effect that chitosan not only can play flocculating and purifying sewage can also catch the Hg in water
+, Ni
2+, Pb
2+, Cd
2+etc. heavy metal ion, for recovery and the harm of minimizing heavy metal to living things system of precious metal; (4) technological reaction mild condition of the present invention, percentage of grafting is high, and raw material is cheap and easy to get.
Embodiment
The present invention is through a large amount of orthogonal experiments, and application experiment checking, obtains serial qualified product within the scope of above-mentioned parameter.
Embodiment 1(most preferred embodiment)
(1) chitosan (molecular-weight average 380000, deacetylation 63%) is added in reactor, add aqueous acetic acid, be stirred to chitosan and all dissolve;
(2), in chitosan: dimethyldiallylammonium salt: the ratio that acrylamide mol ratio is 1:6:4 joins dimethyldiallylammonium salt and acrylamide monomer in reactor, adding water management reaction system monomer concentration is 40%;
(3) control 60 ℃ of reactor temperatures, in reactor, pass into nitrogen, drip monomer total mass 3% initiator potassium persulfate under nitrogen protection, 1.5h dropwises, insulation reaction 3h;
(4) stop heating reaction product is poured in ethanol, have and faint yellowly separate out to brown solid, rinse solid with the mixing solutions of second alcohol and water, then 80 ℃ of vacuum-dryings, grind to form small-particle.
Embodiment 2
(1) by chitosan (molecular-weight average 250000, deacetylation 60%), add in reactor, add aqueous acetic acid, be stirred to chitosan and all dissolve;
(2), in chitosan: dimethyldiallylammonium salt: the ratio that acrylamide thing mol ratio is 1:4:6 joins dimethyldiallylammonium salt and acrylamide monomer in reactor, adding water management reaction system monomer concentration is 40%;
(3) control 75 ℃ of reactor temperatures, in reactor, pass into nitrogen, drip monomer total mass 5% initiator Sodium Persulfate under nitrogen protection, 1h dropwises, insulation reaction 5h;
(4) stop heating reaction product is poured in ethanol, have and faint yellowly separate out to brown solid, rinse solid with the mixing solutions of second alcohol and water, then 80 ℃ of vacuum-dryings, grind to form small-particle.
Embodiment 3
(1) by chitosan (molecular-weight average 500000, deacetylation 42%), add in reactor, add aqueous acetic acid, be stirred to chitosan and all dissolve;
(2), in chitosan: dimethyldiallylammonium salt: the ratio that acrylamide thing mol ratio is 1:3:8 joins dimethyldiallylammonium salt and acrylamide monomer in reactor, adding water management reaction system monomer concentration is 50%;
(3) control 65 ℃ of reactor temperatures, in reactor, pass into nitrogen, drip monomer total mass 7% initiator potassium persulfate under nitrogen protection, 2h dropwises, insulation reaction 4h;
(4) stop heating reaction product is poured in ethanol, have and faint yellowly separate out to brown solid, rinse solid with the mixing solutions of second alcohol and water, then 80 ℃ of vacuum-dryings, grind to form small-particle.
Embodiment 4
(1) by chitosan (molecular-weight average 380000, deacetylation 63%), add in reactor, add aqueous acetic acid, be stirred to chitosan and all dissolve;
(2), in chitosan: dimethyldiallylammonium salt: the ratio that acrylamide mol ratio is 1:8:3 joins dimethyldiallylammonium salt and acrylamide monomer in reactor, adding water management reaction system monomer concentration is 40%;
(3) control 80 ℃ of reactor temperatures, in reactor, pass into nitrogen, drip monomer total mass 3% initiator ammonium persulfate under nitrogen protection, 3h dropwises, insulation reaction 2h;
(4) stop heating reaction product is poured in ethanol, have and faint yellowly separate out to brown solid, rinse solid with the mixing solutions of second alcohol and water, then 80 ℃ of vacuum-dryings, grind to form small-particle.
Claims (10)
1. a preparation method for chitose graft copolymer flocculation-sterilant, is characterized in that, take chitosan, dimethyl diallyl ammonium chloride, acrylamide as raw material, and under nitrogen protection, take persulphate as initiator, initiation grafting copolymerization; Concrete operation steps is:
(1) chitosan is joined in reactor, and add aqueous acetic acid, be stirred to chitosan and all dissolve;
(2) dimethyldiallylammonium salt and two kinds of monomers of acrylamide are joined in reactor to hierarchy of control monomer concentration;
(3) control reactor temperature, in reactor, pass into nitrogen, under nitrogen protection, drip initiator persulphate, dropwise rear insulation reaction;
(4) stop heating reaction product is poured in ethanol, have and faint yellowly separate out to brown solid, rinse solid with the mixing solutions of second alcohol and water, then vacuum-drying, grinds to form small-particle.
2. the preparation method of a kind of chitose graft copolymer flocculation-sterilant according to claim 1, is characterized in that, the chitosan molecule amount described in step (1) is 20 ~ 500,000, and deacetylation is 40% ~ 80%.
3. the preparation method of a kind of chitose graft copolymer flocculation-sterilant according to claim 1, it is characterized in that, the mol ratio of the chitosan described in step (1) and (2) and dimethyldiallylammonium salt, acrylamide is 1:2 ~ 8:2 ~ 8.
4. the preparation method of a kind of chitose graft copolymer flocculation-sterilant according to claim 1, is characterized in that, the described reaction system monomer concentration of step (2) is 30 ~ 60%.
5. the preparation method of a kind of chitose graft copolymer flocculation-sterilant according to claim 1, is characterized in that, the described temperature of reaction system of step (3) is 50 ~ 90 ℃.
6. the preparation method of a kind of chitose graft copolymer flocculation-sterilant according to claim 1, is characterized in that, the described persulfate initiator of step (3) is selected from Sodium Persulfate, ammonium persulphate, Potassium Persulphate one wherein.
7. the preparation method of a kind of chitose graft copolymer flocculation-sterilant according to claim 1, is characterized in that, the dripping quantity of the described initiator of step (3) is 0.5 ~ 10% of monomer total mass per-cent.
8. the preparation method of a kind of chitose graft copolymer flocculation-sterilant according to claim 1, is characterized in that, the described initiator of step (3) dropwises at 1 ~ 3h.
9. the preparation method of a kind of chitose graft copolymer flocculation-sterilant according to claim 1, is characterized in that, the time of the described insulation reaction of step (3) is 2 ~ 5h.
10. the preparation method of a kind of chitose graft copolymer flocculation-sterilant according to claim 1, is characterized in that, the described vacuum drying temperature of step (4) is 80 ℃.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261540A (en) * | 2014-10-09 | 2015-01-07 | 成都冠禹科技有限公司 | Flocculating agent for treating electroplating wastewater, preparation method and application of flocculating agent |
| CN104692506A (en) * | 2015-03-24 | 2015-06-10 | 山东中移能节能环保科技股份有限公司 | Preparation method and application of composite flocculant for treating coking strong-salt wastewater |
| CN105175636A (en) * | 2015-10-27 | 2015-12-23 | 安徽工业大学 | Method for nano modification of polyacrylamide flocculant |
| CN105622848A (en) * | 2016-03-21 | 2016-06-01 | 南京工业大学 | Preparation method and application of plasma-initiated synthesized turbidity-removing agent |
| CN105622847A (en) * | 2016-03-21 | 2016-06-01 | 南京工业大学 | Synthesis method and application of water soluble chitosan-based flocculant |
| CN105770941A (en) * | 2014-12-18 | 2016-07-20 | 浙江澳兴生物科技有限公司 | Sterilization method of chitosan and chitosan derivatives |
| CN104774290B (en) * | 2015-03-27 | 2017-10-10 | 南京师范大学 | A kind of pH, temperature dual sensitiveness chitosan flocculant and its preparation method and application |
| CN108264610A (en) * | 2016-12-30 | 2018-07-10 | 中国石油化工股份有限公司 | A kind of chitosan flocculant and its preparation method and application |
| CN108633879A (en) * | 2018-04-20 | 2018-10-12 | 袁杰 | A kind of circulating water sterilizing agent |
| CN109049210A (en) * | 2018-09-25 | 2018-12-21 | 安徽省汉甲机电设备科技有限公司 | A kind of modified wicker wicker plaiting article of chitosan graft |
| CN109907069A (en) * | 2019-03-25 | 2019-06-21 | 天津市郁峰化工有限公司 | A kind of hypochlorous acid thimerosal and preparation method thereof |
| CN111441095A (en) * | 2020-03-27 | 2020-07-24 | 安徽瑞和新材料有限公司 | Fiber flocculation material for removing pollutants and sterilizing and disinfecting and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1654497A (en) * | 2005-01-14 | 2005-08-17 | 华南理工大学 | Chitosan graft ternary polymerization polymeric flocculant and its preparation method and use |
| CN102774947A (en) * | 2012-07-25 | 2012-11-14 | 华南理工大学 | Biological compound flocculant and application thereof |
-
2014
- 2014-02-07 CN CN201410044923.7A patent/CN103864991A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1654497A (en) * | 2005-01-14 | 2005-08-17 | 华南理工大学 | Chitosan graft ternary polymerization polymeric flocculant and its preparation method and use |
| CN102774947A (en) * | 2012-07-25 | 2012-11-14 | 华南理工大学 | Biological compound flocculant and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| 唐春红: "《天然防腐剂与抗氧化剂》", 31 May 2010, 中国轻工业出版社 * |
| 李群等: "《天然产物在绿色纺织品生产中的应用》", 31 March 2008, 化学工业出版社 * |
| 汪多仁: "《现代高分子材料生产及应用手册》", 31 May 2002, 中国石化出版社 * |
| 谢宇: "《壳聚糖及其衍生物制备与应用》", 31 July 2010, 中国水利水电出版社 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261540A (en) * | 2014-10-09 | 2015-01-07 | 成都冠禹科技有限公司 | Flocculating agent for treating electroplating wastewater, preparation method and application of flocculating agent |
| CN105770941B (en) * | 2014-12-18 | 2018-04-20 | 浙江澳兴生物科技有限公司 | The sterilizing methods of chitosan and chitosan derivatives |
| CN105770941A (en) * | 2014-12-18 | 2016-07-20 | 浙江澳兴生物科技有限公司 | Sterilization method of chitosan and chitosan derivatives |
| CN104692506A (en) * | 2015-03-24 | 2015-06-10 | 山东中移能节能环保科技股份有限公司 | Preparation method and application of composite flocculant for treating coking strong-salt wastewater |
| CN104774290B (en) * | 2015-03-27 | 2017-10-10 | 南京师范大学 | A kind of pH, temperature dual sensitiveness chitosan flocculant and its preparation method and application |
| CN105175636A (en) * | 2015-10-27 | 2015-12-23 | 安徽工业大学 | Method for nano modification of polyacrylamide flocculant |
| CN105622848A (en) * | 2016-03-21 | 2016-06-01 | 南京工业大学 | Preparation method and application of plasma-initiated synthesized turbidity-removing agent |
| CN105622847A (en) * | 2016-03-21 | 2016-06-01 | 南京工业大学 | Synthesis method and application of water soluble chitosan-based flocculant |
| CN105622848B (en) * | 2016-03-21 | 2018-08-17 | 南京工业大学 | A kind of plasma causes the preparation method and applications of synthesis clearer |
| CN108264610A (en) * | 2016-12-30 | 2018-07-10 | 中国石油化工股份有限公司 | A kind of chitosan flocculant and its preparation method and application |
| CN108633879A (en) * | 2018-04-20 | 2018-10-12 | 袁杰 | A kind of circulating water sterilizing agent |
| CN109049210A (en) * | 2018-09-25 | 2018-12-21 | 安徽省汉甲机电设备科技有限公司 | A kind of modified wicker wicker plaiting article of chitosan graft |
| CN109907069A (en) * | 2019-03-25 | 2019-06-21 | 天津市郁峰化工有限公司 | A kind of hypochlorous acid thimerosal and preparation method thereof |
| CN111441095A (en) * | 2020-03-27 | 2020-07-24 | 安徽瑞和新材料有限公司 | Fiber flocculation material for removing pollutants and sterilizing and disinfecting and preparation method thereof |
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Address after: Shandong Hong Village 277100 Zaozhuang City District Xi Wang Zhuang Xiang Applicant after: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES CO., LTD. Address before: Shandong Hong Village 277100 Zaozhuang City District Xi Wang Zhuang Xiang Applicant before: Shandong Taihe Water Treatment Co., Ltd. |
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Application publication date: 20140618 |