CN103121742A - Inorganic-modified chitosan composite type polymeric flocculant - Google Patents
Inorganic-modified chitosan composite type polymeric flocculant Download PDFInfo
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- CN103121742A CN103121742A CN2012104541197A CN201210454119A CN103121742A CN 103121742 A CN103121742 A CN 103121742A CN 2012104541197 A CN2012104541197 A CN 2012104541197A CN 201210454119 A CN201210454119 A CN 201210454119A CN 103121742 A CN103121742 A CN 103121742A
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Abstract
The invention relates to an inorganic-modified chitosan composite type polymeric flocculant. The inorganic-modified chitosan composite type polymeric flocculant is characterized in that a method for preparing the composite type polymeric flocculant comprises the following steps of: taking polyacrylamide-modified chitosan as a raw material and methacryloyloxyethyl trimethyl ammonium chloride, maleic acid and ceric ammonium nitrate as initiators, synthesizing a modified chitosan copolymer under a faintly acidic condition and blending the modified chitosan copolymer with polymerized ferric chloride and polymerized aluminium chloride to obtain the inorganic-modified chitosan composite type polymeric flocculant. According to the steps, the mass ratio of modified starch to the chitosan is (1-2): 1, the reaction temperature is 50-60 DEG C, the reaction time is 2-3 hours, and the use amount of the initiators accounts for 0.02 part of the total mass of the system. The inorganic-modified chitosan composite type polymeric flocculant prepared by using the method has the characteristics of high efficiency, low cost and low secondary pollution to environment; and aiming at different sludges, compared with a conventional flocculant, the inorganic-modified chitosan composite type polymeric flocculant disclosed by the invention has the advantages that the wastewater decoloring rate and the wastewater deturbidity rate can reach more than 99 percent under the condition of low use amount.
Description
Technical field
The present invention relates to a kind of inorganic-the modified chitosan composite type polymeric flocculant, belong to water treatment flocculation technique field.
Background technology
Domestic water treatment flocculant commonly used mainly is divided into inorganic flocculating agent and the large class of organic floculant two.Inorganic flocculating agent is mainly that polymerize aluminum chloride, poly-ferric chloride are main flocculation agent, and its principle is by the collision of coagulation solid, but to make its hydrolysate agglomeration, bridge formation flocculation form sedimentation or filtrable throw out, to reach the purpose that purifies water.Bring iron ion into system but contain ferric flocculant, easily cause the corrosion of equipment, and after processing in water with the trace iron ion, have certain colourity.Contain the aluminium flocculating agent processing relatively slightly good than swage flocculation agent treatment effect, but the high residue of aluminum ion in water can cause secondary pollution, especially enters human body and can bring out senile dementia, aluminium osteopathy, anemia etc.Therefore the inorganic flocculating agent inherent defect is limited in it in limited scope.In order to make up the defective of inorganic flocculating agent, organic polymer coargulator is widely used and studies.Organic floculant refers to produce natural or organic molecule material synthetic of throwing out, and it is mainly water-soluble linear macromolecule material, and is most of ionizable in water such as protein or polysaccharide compound etc., forms polymer electrolyte.But in actual use, organic floculant exists instantly-soluble poor, and the waste residue water ratio is high, and certain remaining toxicity is arranged, and easily is subject to the impact of coexisting ion in water, pH value and temperature, and the problem such as price is more expensive.
Chitosan is natural macromolecular material, and it has wide material sources, and is cheap, and the complete biodegradable characteristics of product, can form benign cycle at occurring in nature.And chitosan is deposited the deficiencies such as at room temperature solubleness is lower, flocculating property is poor, so we will use after modification both carrying out usually.Along with China's environmental stress is day by day huge, country has formulated more and more tighter emission standard to the discharging of industrial sewage, thereby is badly in need of a kind of environmental friendliness flocculation agent with the characteristics such as simple, that the speed that takes effect is fast, cost is low of exploitation.
Summary of the invention
The object of the invention is to the defective that exists for prior art, provide a kind of efficient by having, inexpensive, eco-friendly inorganic-the modified chitosan composite type polymeric flocculant.
For achieving the above object, the present invention adopts following technical scheme:
This inorganic-modified chitosan composite type polymeric flocculant is that chitosan, polyacrylamide and poly-ferric chloride and polymerize aluminum chloride are raw material, take MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, toxilic acid and ceric ammonium nitrate as initiator, under solutions of weak acidity, become inorganic-modified high-molecular flocculation agent by graft copolymerization synthesis modification chitosan and with polymerize aluminum chloride and polymerize aluminum chloride blend.
1. inorganic-modified chitosan composite type polymeric flocculant, it is characterized in that: described organic composite type polymeric flocculant is light yellow viscous liquid, and density is 1.10～1.30g/ml in the time of 20 ℃, and the pH value is 5～6;
The raw material weight proportioning of inorganic organic composite type polymeric flocculant is as follows:
Modified chitosan: 1 part～2 parts
Polyacrylamide: 1 part～2 parts
Polymerize aluminum chloride: 0.2 part～0.5 part
Poly-ferric chloride: 0.2 part～0.5 part
Initiator: 0.01 part～0.02 part
Conditioning agent: 0.02～0.05 part
Water: 100 parts
Described chitosan is chemical modification deacetylation chitin, and its pH value is 3～5 (in water, concentration 1%), deacetylation＞85%;
Described polyacrylamide can be cationic-type polyacrylamide, anion-polyacrylamide and amphoteric polyacrylamide, and molecular-weight average is 2,000,000～1,000 ten thousand;
Described conditioning agent is 1% dilute hydrochloric acid;
Under 50 ℃～60 ℃ conditions, add successively chitosan, polyacrylamide, initiator and water according to mass fraction in reactor, drip conditioning agent and regulate pH value to 5, reacted 2～3 hours, under agitation condition, add polymerize aluminum chloride and poly-ferric chloride in system, fully mix, obtain inorganic-modified chitosan composite type polymeric flocculant.
2. item 1 is described, a kind of inorganic-preparation method of modified chitosan composite type polymeric flocculant, it is characterized in that: described preparation method's step is as follows: under 50 ℃～60 ℃ conditions, add successively chitosan according to mass fraction in reactor, polyacrylamide, ceric ammonium nitrate, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, toxilic acid and water, drip conditioning agent and regulate pH value to 5, graft copolymerization 2～3 hours occur, under agitation condition, add polymerize aluminum chloride and poly-ferric chloride in system, fully mix, obtain inorganic-modified chitosan composite type polymeric flocculant.
3. 1 described, a kind of inorganic-preparation method of modified chitosan composite type polymeric flocculant, it is characterized in that: chitosan is chemical modification deacetylation chitin, its pH value is 3～5 (in water, concentration 1%), deacetylation＞85%;
4. item 1 is described, a kind of inorganic-preparation method of modified chitosan composite type polymeric flocculant, it is characterized in that: polyacrylamide can be cationic-type polyacrylamide, anion-polyacrylamide and amphoteric polyacrylamide, and molecular-weight average is 2,000,000～1,000 ten thousand;
5. 1 described, a kind of inorganic-preparation method of modified chitosan composite type polymeric flocculant, it is characterized in that: initiator is for formulated according to 2 parts of ceric ammonium nitrates of mass fraction, 1 part of ammonium persulphate, 1 part of sodium bisulfite;
6. 1 described, a kind of inorganic-preparation method of modified chitosan composite type polymeric flocculant, it is characterized in that: described application is that described flocculation agent is applied in that treatment of dyeing and printing, colourity are high, in the organic waste water that contains active group;
7. 6 described, a kind of inorganic-preparation method of modified chitosan composite type polymeric flocculant, it is characterized in that: in described application, the add-on of described flocculation agent accounts for 0.2%～0.5% of whole system for handling.
For different environments for use, select different modified polyacrylamide and chitin modified, and coordinate the inorganic polymer flocculant of different concns.Owing to having a large amount of hydroxyls and primary amino on chitosan molecular chain after modification, so modified chitosan can attract to form polyelectrolyte by positive and negative charge.And, have molecular weight distribution through the chitin copolymer after modification wide, the characteristics such as active group is many, and structure is various.And chitosan to have a source abundant, cheap characteristics the most important thing is that two kinds of main raw materials all come from natural, safety non-toxic.And can complete biodegradable, have good environment friendly.
The requirements such as that the modified chitosan copolymer flocculant meets just is efficient, nontoxic, environmental protection, suitability are strong are fit to complicated trade effluent decolouring and sedimentation.And this copolymerization flocculating agent has good environment friendly, and is most of biodegradable, causes secondary pollution few, improves the service efficiency of the inorganic flocculating agent of knowing clearly.Through experiment, modified inorganic-modified chitosan composite type polymeric flocculant reaches more than 99% common decolorizing printing and dyeing waste water rate and turbidity removal rate.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention
The present embodiment indication " modified chitosan " refers to the deacetylation chitosan, and after polyacrylamide carries out modification by graft copolymerization, is prepared from a small amount of polymerize aluminum chloride and poly-ferric chloride blend.
Embodiment one, take by with acrylamide: the chitosan mass ratio is as 2: 1, under 50 ℃, reaction 3h, the initiator amount of quoting accounts for 0.02 part of solid total mass, preparation generates stoste.During use, with 10 times of stoste dilutions, and with isocyatic conventional flocculation agent contrast, the situation that the conventional textile printing and dyeing wastewater decolouring that is 100mg/L to 1L dyestuff content reaches 90% color removal quality that degree adds sees Table 1.
Table 1
Table 2
By above-described embodiment, with the contrast of conventional inorganic flocculating agent and organic floculant, the removal of suspended substance all has obvious advantage in to the removing of the colourity of waste water, water; With simple chitosan flocculant contrast, copolymer flocculant is better coordinated its effect separately, effectively improves flocculating effect, and decolouring, turbidity removal are had obvious effect.
Claims (7)
1. inorganic-modified chitosan composite type polymeric flocculant, it is characterized in that: described organic composite type polymeric flocculant is light yellow viscous liquid, and density is 1.10～1.30g/ml in the time of 20 ℃, and the pH value is 5～6;
The raw material weight proportioning of inorganic organic composite type polymeric flocculant is as follows:
Modified chitosan: 1 part～2 parts
Polyacrylamide: 1 part～2 parts
Polymerize aluminum chloride: 0.2 part～0.5 part
Poly-ferric chloride: 0.2 part～0.5 part
Initiator: 0.01 part～0.02 part
Conditioning agent: 0.02～0.05 part
Water: 100 parts
Described chitosan is chemical modification deacetylation chitin, and its pH value is 3～5 (in water, concentration 1%), deacetylation＞85%;
Described polyacrylamide can be cationic-type polyacrylamide, anion-polyacrylamide and amphoteric polyacrylamide, and molecular-weight average is 2,000,000～1,000 ten thousand;
Described conditioning agent is 1% dilute hydrochloric acid;
Under 50 ℃～60 ℃ conditions, add successively chitosan, polyacrylamide, initiator and water according to mass fraction in reactor, drip conditioning agent and regulate pH value to 5, reacted 2～3 hours, under agitation condition, add polymerize aluminum chloride and poly-ferric chloride in system, fully mix, obtain inorganic-modified chitosan composite type polymeric flocculant.
2. according to claim 1, a kind of inorganic-preparation method of modified chitosan composite type polymeric flocculant, it is characterized in that: described preparation method's step is as follows: under 50 ℃～60 ℃ conditions, add successively chitosan according to mass fraction in reactor, polyacrylamide, cerous nitrate, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, toxilic acid and water, drip conditioning agent and regulate pH value to 5, graft copolymerization 2～3 hours occur, under agitation condition, add polymerize aluminum chloride and poly-ferric chloride in system, fully mix, obtain inorganic-modified chitosan composite type polymeric flocculant.
3. according to claim 1, a kind of inorganic-preparation method of modified chitosan composite type polymeric flocculant, it is characterized in that: chitosan is chemical modification deacetylation chitin, its pH value is 3～5 (in water, concentration 1%), deacetylation＞85%.
4. according to claim 1, a kind of inorganic-preparation method of modified chitosan composite type polymeric flocculant, it is characterized in that: polyacrylamide can be cationic-type polyacrylamide, anion-polyacrylamide and amphoteric polyacrylamide, and molecular-weight average is 2,000,000～1,000 ten thousand.
5. according to claim 1, a kind of inorganic-preparation method of modified chitosan composite type polymeric flocculant, it is characterized in that: initiator is for formulated according to 2 parts of ceric ammonium nitrates of mass fraction, 1 part of ammonium persulphate, 1 part of sodium bisulfite.
6. according to claim 1, a kind of inorganic-preparation method of modified chitosan composite type polymeric flocculant, it is characterized in that: described application is that described flocculation agent is applied in that treatment of dyeing and printing, colourity are high, in the organic waste water that contains active group.
7. according to claim 6, a kind of inorganic-preparation method of modified chitosan composite type polymeric flocculant, it is characterized in that: in described application, the add-on of described flocculation agent accounts for 0.2%～0.5% of whole system for handling.
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Cited By (22)
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| CN103232100A (en) * | 2013-05-31 | 2013-08-07 | 滁州友林科技发展有限公司 | Organic and inorganic mixed flocculant |
| CN103965377A (en) * | 2014-05-14 | 2014-08-06 | 东南大学 | Method for preparing synanthrin from jerusalem artichoke |
| 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 |
| CN104447007A (en) * | 2014-12-06 | 2015-03-25 | 杨雪飞 | Biological organic compound fertilizer as well as preparation method and application thereof |
| CN105129944A (en) * | 2015-09-02 | 2015-12-09 | 武汉宏安伟立科技有限公司 | Inorganic and modified chitosan composite polymer flocculant |
| CN106335988A (en) * | 2015-07-06 | 2017-01-18 | 迪建东 | Composite high polymer flocculant for coking wastewater and preparation method thereof |
| CN106477701A (en) * | 2015-09-02 | 2017-03-08 | 武汉宏安伟立科技有限公司 | A kind of preparation method of the pre-gelatinized starch-chitose graft copolymer flocculant for removing heavy metals in industrial wastewater ion |
| CN106824137A (en) * | 2017-03-21 | 2017-06-13 | 中国海洋大学 | A kind of preparation method for heavy metal ion adsorbed poly graft crosslinking chitosan microball |
| CN106986396A (en) * | 2017-05-04 | 2017-07-28 | 浙江清天地环境工程有限公司 | A kind of modification of chitosan and preparation method thereof |
| CN107840430A (en) * | 2017-12-18 | 2018-03-27 | 李进宅 | A kind of high efficiency sewage treating agent and its preparation method and application |
| CN108002503A (en) * | 2018-01-12 | 2018-05-08 | 常州华禹环保科技有限公司 | Composite flocculant and preparation method thereof |
| CN108394976A (en) * | 2018-03-30 | 2018-08-14 | 浙江大学 | A kind of floating type flocculant and preparation method thereof |
| CN108585155A (en) * | 2018-03-30 | 2018-09-28 | 浙江大学 | Polyaluminum ferric chloride-（Chitose-acrylic amide-magnesium lignosulfonate graft copolymer）Composite flocculation agent and preparation method thereof |
| CN109319895A (en) * | 2018-10-23 | 2019-02-12 | 四川意德康环保科技有限公司 | A kind of aluminium polychloride and preparation method thereof that Nano chitosan is modified |
| WO2019051743A1 (en) * | 2017-09-14 | 2019-03-21 | 谢超 | Method for preparing polyaluminum chloride-chitosan composite flocculant |
| CN110294521A (en) * | 2019-06-26 | 2019-10-01 | 江西师范大学 | It is a kind of for removing the high polymer coagulant of sewage heavy metal |
| CN111115782A (en) * | 2020-01-09 | 2020-05-08 | 江西省地质环境监测总站(鄱阳湖生态环境研究所) | Sewage treatment flocculant and preparation method thereof |
| CN111573801A (en) * | 2020-04-30 | 2020-08-25 | 广西夏阳环保科技有限公司 | Organic composite aluminum sulfate water treatment agent and preparation method thereof |
| CN112358022A (en) * | 2020-11-18 | 2021-02-12 | 浙江九环环境科技有限公司 | Flocculating agent and preparation method thereof |
| CN112624291A (en) * | 2020-12-31 | 2021-04-09 | 江西挺进环保科技有限公司 | Wastewater treatment flocculant and wastewater treatment method |
| CN112811656A (en) * | 2020-12-29 | 2021-05-18 | 科之杰新材料集团有限公司 | Flocculating agent for sand washing water and preparation method thereof |
| CN114249407A (en) * | 2021-12-28 | 2022-03-29 | 河北正润环境科技有限公司 | Method for recycling pickling waste liquid in steel finishing |
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Addressee: Wuhan Sloan Electric Co., Ltd. Document name: Notification that Application Deemed to be Withdrawn |
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Application publication date: 20130529 |