CN105968261A - Method for synthesizing Cu2+ adsorbing resin by using carboxymethyl potato starch as raw material - Google Patents

Method for synthesizing Cu2+ adsorbing resin by using carboxymethyl potato starch as raw material Download PDF

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Publication number
CN105968261A
CN105968261A CN201610479553.9A CN201610479553A CN105968261A CN 105968261 A CN105968261 A CN 105968261A CN 201610479553 A CN201610479553 A CN 201610479553A CN 105968261 A CN105968261 A CN 105968261A
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China
Prior art keywords
potato starch
carboxymethyl potato
concentration
acrylic acid
resin
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Pending
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CN201610479553.9A
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Chinese (zh)
Inventor
温国华
张建平
张静
刘广华
李媛
陈超
宋健
宋丽君
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Inner Mongolia University
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Inner Mongolia University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Analytical Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a method for synthesizing Cu2+ adsorbing resin by using carboxymethyl potato starch as a raw material through hydrogen peroxide oxidation and by using a one-pot method. The method is mainly characterized in that hydrogen peroxide oxidized carboxymethyl potato starch is not separated, washed or purified, the carboxymethyl potato starch as well as acrylic acid without a polymerization inhibitor and sodium salt of the acrylic acid are heated by water bath under protection of nitrogen to synthesize the Cu2+ adsorbing resin by the one-pot method, the adsorption quantity of the product synthesized under the optimum condition to Cu2+ with the concentration of 5 ppm is 15.19 mg/g, the adsorption quantity to Cu2+ with the concentration of 50 ppm is 128.72 mg/g, and the removal rate to Cu2+ with the concentration of 5-50 ppm is 48.12%-48.52%. The method has the advantages that the hydrogen peroxide oxidized carboxymethyl potato starch is not required to be separated, purified or washed as the traditional oxidized carboxymethyl potato starch, polymerization can be realized without extra initiators, the prepared product has large adsorption quantity to Cu2+ with low concentration and Cu2+ with high concentration, therefore, a process of synthesizing the Cu2+ adsorbing resin is simple, the cost is low, large-scale production is easy to realize, and because adsorption quantity to Cu2+ is quite high, the product has good application prospect in aspects of treatment of Cu2+-containing sewage, soil restoration and the like.

Description

With carboxymethyl potato starch for Material synthesis Adsorption of Cu2+The method of resin
Technical field
The invention discloses a kind of novel Adsorption of Cu2+Resin and preparation method thereof, is particularly used for containing Cu2+Sewage The aspects such as process, soil and Discussion On Measures of Rivers Pollution Treatment, belong to environment functional material field.
Background technology
The process of industrialization and urbanization is increasingly faster, and trade effluent, mining industry waste water, municipal sewage etc. are without effectively processing Directly to environmental emission, thus cause the heavy metal pollution in waters, meanwhile, along with these water also pollutes substantial amounts of for irrigation Ploughing, at present, the processing method of nationwide heavy metal ion mainly includes neutralization precipitation method, sulfide precipitation, chemistry also Former method, electrochemical reducing, ion exchange, biologic treating technique, but said method all exists certain in actual applications Limitation, the neutralization precipitation method removal of heavy metal ions less effective to low concentration, sulfide precipitation can produce H2The secondary such as S Pollutant, electrochemistry removal method cost is high, and ion exchange investment is big, floor space is big, and biologic treating technique processes the cycle too Long etc..
Owing to heavy metal has enriching and stability, it is difficult to the feature degraded in the environment, therefore dirty relative to other Dye, heavy metal pollution has become as the great environmental problem threatening human development.In smelting, intermetallic composite coating, machine manufacture, organic The waste water of synthesis and other industry all contains copper, wherein the highest with intermetallic composite coating, electroplating facility institute effluent copper content, every liter Waste water cupric tens is to hundreds of milligram.This waste water enters water body, can affect the quality of water.In water, copper content reaches 0.01mg/L Time, the self-purification of water is had obvious inhibitory action；More than 3.0mg/L, abnormal flavour can be produced;More than 15mg/L, just cannot drink. If using copper-containing wastewater irrigated farmland, copper is accumulated in soil and crops, can cause crops particularly Oryza sativa L. and barley growth Bad, and grain seed can be polluted.In some little korneforos, copper staining was once occurred to cause hydrobiological acute poisoning event；? Seashore and Gulf Region, once occurred copper staining to cause Carnis ostreae to turn green event.
Herein with hydrogen peroxide and carboxymethyl potato starch as raw material, one pot process one is used to be applicable to absorption and go Except Cu2+New functional macromolecule material, be mainly characterized in that resin structure is three-dimensional network type, have and can accommodate Cu2+Crosslinking Site；Containing groups such as-COOH ,-COONa, can be with Cu2+There is complexing；Specific surface area is big, beneficially quick adsorption.
Summary of the invention
The invention provides that a kind of technique is simple, synthesis low cost, adsorb and remove Cu2+The new type resin product that ability is strong And preparation method thereof.
Its method and step are as follows:
(1) hydrogen peroxide of carboxymethyl potato starch with deionized water, 30% is mixed by the mass ratio of 1:6～15:0.04～0.8 Close, at 30-60 DEG C, then aoxidize 0.5-3h；Weigh carboxymethyl potato starch quality 3～the acrylic acid of 12 times, weigh propylene The sodium hydroxide of acid quality 0.11-0.444 times, with NaOH mass 3～the above-mentioned sodium hydroxide of deionized water dissolving of 12 times；At ice Water-bath cooling is lower with in above-mentioned sodium hydroxide solution and acrylic acid.
(2) by the carboxymethyl potato starch solution after above-mentioned oxidation with in sodium hydroxide and rear prepared acrylic acid and Its saline solution is sufficiently mixed, and adds containing carboxymethyl potato starch the quality 0.04～N of 0.24%, N ＇-methylene bisacrylamide acyl Amine makees cross-linking agent, and stirring is allowed to uniform, is passed through nitrogen, is slowly heated, make temperature of reaction system be stepped up, and reaction to be polymerized is opened After beginning, stop stirring, continue slowly to heat up, at 80 DEG C, be incubated 2h, drying, pulverize and i.e. obtain Adsorption of Cu2+Resin.
Advantages of the present invention:
(1) carboxymethyl potato starch water solublity is strong, and the preparation of resin need not gelatinization process；
(2) present invention uses one pot process Adsorption of Cu first2+Resin, technique is simple, easily operated.
(3) add initiator i.e. polymerizable without extra during synthetic resin, impurity, low cost will not be introduced.
(4) hydrogen peroxide catabolite is water and oxygen, pollution-free, products obtained therefrom excellent performance simultaneously.
(5) resin is to Cu2+High adsorption capacity, no matter low concentration or high concentration all have bigger adsorbance, to concentration be 5ppmCu2+Adsorbance be 15.19mg/g, be 50ppmCu to concentration2+Adsorbance be 128.72mg/g.
Accompanying drawing explanation
Fig. 1 carboxymethyl potato starch synthesis Adsorption of Cu2+The process chart of resin
Fig. 2 Adsorption of Cu2+Resin is to variable concentrations Cu2+Adsorbance
Fig. 3 is carboxymethyl potato starch with monomer ratio to Cu2+The influence curve of adsorbance
Fig. 4 is that acrylic acid degree of neutralization is to Cu2+The influence curve of adsorbance
Fig. 5 is that the consumption of cross-linking agent is to Cu2+The influence curve of adsorbance
Fig. 6 is that reaction system total Water is to Cu2+The influence curve of adsorbance
Fig. 7 is Adsorption of Cu2+The Orthogonal experiment results of the synthesis condition of resin.
Detailed description of the invention
Hydrogen peroxide at 50 DEG C, aoxidize 1h, measure 20g (19.1ml) acrylic acid, weighing sodium hydroxide 5.6g is dissolved in In 30ml deionized water, under ice-water bath cools down, neutralize acrylic acid by above-mentioned prepared NaOH solution, by the acrylic acid become reconciled And the carboxymethyl potato starch solution after sodium salt solution and oxidation is sufficiently mixed uniformly, addition 4ml concentration is 2.5mg/ml N, N ＇-methylene-bisacrylamide solution, at N2Under protection, it is slowly heated and makes system temperature be stepped up, reaction to be polymerized Stop stirring after beginning, continue slowly to heat up, at 80 DEG C, be incubated 2h, product drying, pulverize and i.e. obtain product, by the present embodiment Obtained product in the solution that concentration is 20ppm to Cu2+Adsorbance be 57.89mg/g.
Water aoxidizes 1h at 50 DEG C, measures 20g (19.1ml) acrylic acid, weighing sodium hydroxide 5.6g be dissolved in 20ml go from Sub-water, neutralizes acrylic acid with above-mentioned prepared sodium hydroxide solution under ice-water bath cools down, by the acrylic acid become reconciled and salt thereof Carboxymethyl potato starch solution after solution and oxidation is sufficiently mixed uniformly, and adding 6ml concentration is the N of 2.5mg/ml, N ＇-Asia Bisacrylamide solution, at N2Under protection, it is slowly heated and makes system temperature be stepped up, after reaction to be polymerized starts, stop Only stirring, continues slowly to heat up, and is incubated 2h at 80 DEG C, drying, pulverizes and i.e. obtains product.By the product obtained by the present embodiment It is 30ppm Cu in concentration2+Solution in Cu2+Adsorbance be 98.26mg/g.
Water aoxidizes 1h at 50 DEG C, measures 20g (19.1ml) acrylic acid, weighing sodium hydroxide 5.6g be dissolved in 20ml go from Sub-water, neutralizes acrylic acid with above-mentioned prepared sodium hydroxide solution under ice-water bath cools down, by the acrylic acid become reconciled and sodium thereof Saline solution with oxidation after carboxymethyl potato starch solution be sufficiently mixed uniformly, addition 4ml concentration be the N of 2.5mg/ml, N ＇- Methylene-bisacrylamide solution, at N2Under protection, it is slowly heated and makes system temperature be stepped up, after reaction to be polymerized starts, Stop stirring, continue slowly to heat up, at 80 DEG C, be incubated 2h, drying, pulverize and i.e. obtain product.By the product obtained by the present embodiment Product are 10ppm Cu in concentration2+Solution in Cu2+Adsorbance be 28.88mg/g.
Embodiment 4: through L9 (34) orthogonal experiment obtained synthesis Adsorption of Cu2+The optimum condition of resin, specific embodiment As follows:
Weigh 5g carboxymethyl potato starch to mix homogeneously with 40ml deionized water, add 6ml hydrogen peroxide at 50 DEG C, aoxidize 1h, Measuring 20g (19.05ml) acrylic acid, weighing sodium hydroxide 5.6g is dissolved in 20ml deionized water, by above-mentioned prepared hydroxide Sodium solution neutralizes acrylic acid under ice-water bath cools down, by carboxymethyl horse after the acrylic acid become reconciled and sodium salt solution thereof and oxidation Bell sweet potato starch solution is sufficiently mixed uniformly, and adding 1ml concentration is the N of 2.5mg/ml, N ＇-methylene-bisacrylamide solution, N2Under protection, it is slowly heated and makes system temperature be stepped up, after reaction to be polymerized starts, stop stirring, continue slowly to heat up, It is incubated 2h at 80 DEG C, drying, pulverizes and i.e. obtain product, the product obtained by the present embodiment be the Cu of 5ppm in concentration2+Solution To Cu2+High adsorption capacity be 15.19mg/g.

Claims (3)

1. with carboxymethyl potato starch for Material synthesis Adsorption of Cu2+The method of resin, is characterised by that its method and step are:
(1) hydrogen peroxide of carboxymethyl potato starch with deionized water, 30% is mixed by certain mass ratio, then necessarily At a temperature of aoxidize；Take acrylic acid and the sodium hydroxide of certain mass, with the above-mentioned sodium hydroxide of a certain amount of deionized water dissolving；? Ice-water bath cooling is lower with in above-mentioned sodium hydroxide and acrylic acid；
(2) by the carboxymethyl potato starch solution after above-mentioned oxidation with in sodium hydroxide and rear prepared acrylic acid and sodium thereof Saline solution is sufficiently mixed, and adds N, the N ＇-methylene-bisacrylamide containing carboxymethyl potato starch certain mass ratio and hands over Connection agent, stirring is allowed to uniform, is passed through nitrogen, is slowly heated, make temperature of reaction system be stepped up, after reaction to be polymerized starts, Stop stirring, continue slowly to heat up, at 80 DEG C, be incubated 2h, drying, pulverize and i.e. obtain Adsorption of Cu2+Resin.
The most according to claim 1 with carboxymethyl potato starch for Material synthesis Adsorption of Cu2+The method of resin, most preferably synthesizes Technique is: m (carboxymethyl potato starch): m (acrylic acid): m (N,N methylene bis acrylamide): m(sodium hydroxide): m (deionized water): m (hydrogen peroxide)=1:4:0.0004:1.12:12:1.33, oxidization time 1h, oxidizing temperature is 60 DEG C, this condition The lower product prepared is 5ppmCu to concentration2+Adsorbance be 15.19mg/g, be the Cu of 50ppm to concentration2+Adsorbance be 128.72mg/g。
The most according to claim 1 with carboxymethyl potato starch for Material synthesis Adsorption of Cu2+The method of resin, N, N ＇-Asia The concentration of bisacrylamide solution is 2.5 mg/mL, and the mass fraction of hydrogen peroxide is 30%.
CN201610479553.9A 2016-06-28 2016-06-28 Method for synthesizing Cu2+ adsorbing resin by using carboxymethyl potato starch as raw material Pending CN105968261A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1667007A (en) * 2005-04-01 2005-09-14 大连民生环保科技有限公司 Starch-base macromolecules environmental protection flocculant, process for preparing same and use thereof
CN103613709A (en) * 2013-09-30 2014-03-05 内蒙古大学 Method for synthesizing special heavy metal absorption ion resin by using potato starch xanthate as raw material
CN104177545A (en) * 2014-07-08 2014-12-03 内蒙古大学 Method for preparing super absorbent resin through graft polymerization of hydrogen peroxide-oxidized potato starch

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1667007A (en) * 2005-04-01 2005-09-14 大连民生环保科技有限公司 Starch-base macromolecules environmental protection flocculant, process for preparing same and use thereof
CN103613709A (en) * 2013-09-30 2014-03-05 内蒙古大学 Method for synthesizing special heavy metal absorption ion resin by using potato starch xanthate as raw material
CN104177545A (en) * 2014-07-08 2014-12-03 内蒙古大学 Method for preparing super absorbent resin through graft polymerization of hydrogen peroxide-oxidized potato starch

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
冯玉杰等主编: "《环境工程中的功能材料》", 31 July 2003, 化学工业出版社 *
张思思等: "羧甲基淀粉基高吸水树脂去除重金属离子研究", 《功能材料与器件学报》 *

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Application publication date: 20160928