CN103570112A - Preparation method of pre-gelatinized starch-chitosan grafted copolymer flocculating agent for removing heavy metal ions in industrial wastewater - Google Patents
Preparation method of pre-gelatinized starch-chitosan grafted copolymer flocculating agent for removing heavy metal ions in industrial wastewater Download PDFInfo
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- CN103570112A CN103570112A CN201210271453.9A CN201210271453A CN103570112A CN 103570112 A CN103570112 A CN 103570112A CN 201210271453 A CN201210271453 A CN 201210271453A CN 103570112 A CN103570112 A CN 103570112A
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Abstract
The invention relates to a pre-gelatinized starch-chitosan grafted copolymer flocculating agent and a preparation method thereof. The flocculating agent and the preparation method are characterized in that a modified starch/ chitosan copolymer flocculating agent is synthesized under the conditions that pre-gelatinized starch and chitosan are utilized as raw materials, ceric ammonium nitrate is used as an initiator, and the pH (Potential of Hydrogen) is 9, wherein the mass ratio of modified starch to chitosan is (2-5): 1; the reaction temperature is 30 to 60 DEG C; the reaction lasts for 8 hours; and the initiator used accounts for 0.1 to 1% based on the total mass of the system. The pre-gelatinized starch-chitosan grafted copolymer flocculating agent prepared by the method has the characteristics of being high in effect, low in cost, able to remove heavy metal ions, and environment-friendly; and compared with the conventional flocculating agent, the pre-gelatinized starch-chitosan grafted copolymer flocculating agent enables the removal rate of heavy metals in different wastewater to reach 90% with less dose.
Description
Technical field
The present invention relates to a kind of flocculation agent that utilizes heavy-metal ion removal and preparation method thereof, be specifically related to a kind of pre-gelatinized starch-chitosan graft graft copolymer flocculation agent for the treatment of metal ion in dyeing waste water, belong to water treatment flocculation technique field.
Background technology
Conventional water treatment flocculant is mainly 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, makes its hydrolysate agglomeration, the flocculation of building bridge forms can sedimentation or filtrable throw out, to reach the object purifying water.But inorganic flocculating agent all has colourity removal efficiency low, easily has the defects such as metal residual is detrimental to health.Therefore inorganic flocculating agent inherent defect is limited in limited scope.In order to make up the defect of inorganic flocculating agent, organic polymer coargulator is widely used and studies.Organic floculant refers to the organic molecule material natural or synthetic that can produce throwing out, and it is mainly water-soluble linear macromolecule material, such as protein or polysaccharide compound etc., most of ionizable in water, forms polymer electrolyte.But in actual use, organic floculant exists instantly-soluble poor, waste residue water ratio is high, is easily subject to the impact of coexisting ion in water, pH value and temperature, and the problem such as price is more expensive.And inorganic flocculating agent or organic floculant are all to the Cr in dyeing waste water
2+, Pb
2+, Hg
2+removal efficiency etc. heavy metal ion is all lower.
Chitosan claims again chitin, chitose, is a kind of natural polymer straight-chain polysaccharide, is that chitin is hydrolyzed and sloughs the derivative generating after part ethanoyl under alkaline condition.Chitin is that occurring in nature reserves are only second to cellulosic second largest organic resource, originates very abundant.Chitosan can form the molecule of similar cage shape by hydrogen bond and ionic linkage, heavy metal ion is had to stronger adsorptive power.But chitosan is when being used as flocculation agent, the pH value scope of application is narrower, and dissolved solution degree is lower, flocculating property relatively a little less than.
Starch is green plants by carbonic acid gas and water through the synthetic natural plant polyose of photosynthesis; Starch as a kind of natural polymer not only there is low price, renewable, source is wide and can be biodegradable completely, but also has the advantages such as nontoxic, molecular weight distribution is wide and active group is many.To starch and derivative thereof, by chemical treatment, can strengthen it to the seizure of particulate matter in suspension system and throwing out.The pre-gelatinization of starch, refers to starch small grain effect of swelling, division, the even pasty state solution of formation in water under proper temperature.Gelatinization is for the hydrogen bond between the starch molecule of orderly in starch small grain and unordered (crystalloid and amorphousness) state is disconnected, be dispersed in water and become colloidal solution, make full use of its backbone, flexible structure and rigid structure, strengthen reactivity and the solvability of starch granules.
Along with China's environmental stress is day by day huge, country has formulated more and more tighter emission standard to the discharge of industrial sewage, and the heavy-metal residual problem in dyeing waste water is badly in need of a kind of efficient and cheap method and is solved.Starch and chitosan are natural macromolecular material, and it has wide material sources, cheap, and the complete biodegradable feature of product, can form benign cycle at occurring in nature.And starch and chitosan are all deposited the deficiencies such as at room temperature solubleness is lower, flocculating property is poor, so we will process rear use to the two conventionally, make it add corresponding group, reach the function of removal heavy metal pollutent.
Summary of the invention
The object of the invention is to the defect existing for prior art, the preparation method of a kind of efficient by having, inexpensive, eco-friendly pre-gelatinized starch and chitosan copolymerization flocculating agent is provided.
For achieving the above object, the present invention adopts following technical scheme:
This pre-gelatinized starch-chitose graft copolymer flocculation agent is that to take pre-gelatinized starch and chitosan be raw material, ceric ammonium nitrate is initiator, under alkaline condition, synthetic pre-gelatinized starch-chitosan graft graft copolymer, and with infrared spectra, polymer architecture is characterized.
The present invention relates to following aspect:
1. the preparation method of pre-gelatinized starch-chitose graft copolymer flocculation agent, it is characterized in that, it is that to take pre-gelatinized starch and chitosan be raw material, take ceric ammonium nitrate as initiator, under alkaline condition, synthetic pre-gelatinized starch/chitose graft copolymer flocculation agent.
2. the preparation method of pre-gelatinized starch described in 1, is characterized in that, starch small grain is that 105-150 ℃, high-pressure steam pressure are under 20-100 normal atmosphere conditions in temperature, by continous way jet cooking device, by high pressure steam, with starch milk, mixes and makes it gelatinization.
3. pre-gelatinized starch-chitose graft copolymer flocculation agent preparation method described in 1, it is characterized in that, in above-mentioned synthesis step, in pH value, be 9, the mass ratio of pre-gelatinized starch and chitosan is (2-5): 1, temperature of reaction is 30-60 ℃, and the reaction times is 8h, and initiator amount accounts for the 0.1-1% of system total mass.
4. the starch-chitosan graft copolymer flocculation agent described in 1 and 2, is characterized in that selected starch native starch is selected from natural phant root starch, tuber starch, cereal starch, legume starch or its mixture.
5. above-mentioned described pre-gelatinized starch-chitose graft copolymer flocculation agent, wherein said chitosan is chemical modification deacetylation chitin, its pH value is 3～5 (in water, concentration 1%), deacetylation > 70%.
For different environments for use, select different pre-gelatinized starches and chitosan graft copolymerization.Pre-gelatinized starch and chitosan owing to thering is good dispersiveness and a large amount of hydroxyls on pre-gelatinized starch, and on chitosan molecule chain, there is a large amount of primary aminos, so can attract to form graft copolymer by positive and negative charge.And, the feature such as it is wide that the starch-chitosan graft copolymer after modification has molecular weight distribution, and active group is many, and structure is various.And starch and chitosan all to have source abundant, cheap feature, the most important thing is that two kinds of main raw materials all come from natural, safety non-toxic.And can complete biodegradable, there is good environment friendly.
The requirements such as that pre-gelatinized starch-chitose graft copolymer flocculation agent meets is just efficient, nontoxic, environmental protection, suitability are strong, are applicable to complicated trade effluent decolouring and sedimentation.And this copolymerization flocculating agent has good environment friendly, can be biodegradable completely, can not cause secondary pollution.
Through experiment, pre-gelatinized starch and chitosan are 2: 1 at mass ratio, temperature of reaction is 60 ℃, initiator ceric ammonium nitrate quality accounts for whole system quality 0.5%, reaction times is while being 8 hours, graft copolymer flocculation agent can reach more than 90% general industry heavy metals ion decreasing ratio, is optimum reaction condition.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention, rather than limitation of the present invention.
The present embodiment indication " pre-gelatinized starch " refers to native starch, be selected from natural phant root starch, tuber starch, cereal starch, legume starch or its mixture, by carrying out pre-gelatinization by means such as jet cooking devices, especially non-ionic type, cationic, anionic or amphoteric starch.Indication " chitosan " is to utilize deacetylation chitin, as cm-chitosan.
Embodiment mono-, pre-gelatinized starch: chitosan mass ratio is 2: 1, at 60 ℃, reaction 8h initiator ceric ammonium nitrate consumption account for total mass 0.1% time, preparation generates, and dries that to be crushed to 200 orders standby.The situation that reaches 50% quality that heavy metal removing rate adds by the conventional textile printing and dyeing wastewater decolouring that is 1g/L to 1L dyestuff content is in Table 1.
Embodiment bis-, pre-gelatinized starch: chitosan mass ratio is 3: 1, at 50 ℃, reaction 8h, initiator initiator ceric ammonium nitrate consumption account for total mass 0.5% time, preparation generates, and dries that to be crushed to 200 orders standby.By the trade effluent that is 1g/L to 1L heavy metal ion content, reach the situation of 75% heavy metal removal quality that degree adds in Table 2.
Embodiment tri-, pre-gelatinized starch: chitosan mass ratio is 4: 1, at 45 ℃, reaction 8h, initiator ceric ammonium nitrate consumption account for total mass 1% time, preparation generates, and dries that to be crushed to 200 orders standby.By the trade effluent that is 1g/L to 1L heavy metal ion content, reach the situation of 90% heavy metal removal quality that degree adds in Table 3.
By above-described embodiment, with conventional inorganic flocculating agent and organic floculant contrast, in to the removal of heavy metal ions of sample waste water, water, the removal of suspended substance all has obvious advantage; With simple pre-gelatinized starch, chitosan flocculant and PAM contrast, copolymer flocculant makes its effect separately obtain better coordination performance, effectively removes the common heavy metal in sample waste water.
Claims (5)
1. the preparation method of pre-gelatinized starch-chitose graft copolymer flocculation agent, it is characterized in that, it is that to take pre-gelatinized starch and chitosan be raw material, take ceric ammonium nitrate as initiator, under alkaline condition, synthetic pre-gelatinized starch/chitose graft copolymer flocculation agent.
2. the preparation method of pre-gelatinized starch described in 1, it is characterized in that, analytical pure starch small grain is that 105-150 ℃, high-pressure steam pressure are under 20-100 normal atmosphere conditions in temperature, by continous way jet cooking device, by high pressure steam, with starch milk, mixes and makes it gelatinization.
3. pre-gelatinized starch-chitose graft copolymer flocculation agent preparation method described in 1, it is characterized in that, in above-mentioned synthesis step, the mass ratio of pre-gelatinized starch and chitosan is (2-5): 1, temperature of reaction is 30-60 ℃, reaction times is 8h, and initiator amount accounts for the 0.1-1% of system total mass.
4. the starch-chitosan graft copolymer flocculation agent described in 1 and 3, is characterized in that selected starch native starch is selected from natural phant root starch, tuber starch, cereal starch, legume starch or its mixture.
5. above-mentioned described pre-gelatinized starch-chitose graft copolymer flocculation agent, wherein said chitosan is chemical modification deacetylation chitin, its pH value is 3～5 (in water, concentration 1%), deacetylation > 70%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430395A (en) * | 2016-08-27 | 2017-02-22 | 武汉理工大学 | Method of using hydrogel to adsorb heavy metals in water |
| 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 |
| CN110498514A (en) * | 2019-09-02 | 2019-11-26 | 浙江海洋大学 | A method of purification waste water |
-
2012
- 2012-08-01 CN CN201210271453.9A patent/CN103570112A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106430395A (en) * | 2016-08-27 | 2017-02-22 | 武汉理工大学 | Method of using hydrogel to adsorb heavy metals in water |
| CN110498514A (en) * | 2019-09-02 | 2019-11-26 | 浙江海洋大学 | A method of purification waste water |
| CN110498514B (en) * | 2019-09-02 | 2021-11-09 | 浙江海洋大学 | Method for purifying waste water |
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Application publication date: 20140212 |