CN106117434A - Cd is adsorbed for Material synthesis with carboxymethyl potato starch2+the method of resin - Google Patents

Cd is adsorbed for Material synthesis with carboxymethyl potato starch2+the method of resin Download PDF

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Publication number
CN106117434A
CN106117434A CN201610479121.8A CN201610479121A CN106117434A CN 106117434 A CN106117434 A CN 106117434A CN 201610479121 A CN201610479121 A CN 201610479121A CN 106117434 A CN106117434 A CN 106117434A
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CN
China
Prior art keywords
potato starch
carboxymethyl potato
resin
concentration
adsorbance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610479121.8A
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Chinese (zh)
Inventor
温国华
张建平
刘广华
李媛
张静
李茹
柳青
刘力玮
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Inner Mongolia University
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Inner Mongolia University
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Priority to CN201610479121.8A priority Critical patent/CN106117434A/en
Publication of CN106117434A publication Critical patent/CN106117434A/en
Pending legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/18—Oxidised starch
    • C08B31/185—Derivatives of oxidised starch, e.g. crosslinked oxidised starch
    • 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
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates

Abstract

The invention discloses a kind of with carboxymethyl potato starch as raw material, use one pot process absorption Cd through hydrogen peroxide oxidation2+The method of resin, it is mainly characterized by hydrogen peroxide oxidation carboxymethyl potato starch, without isolation, washs, purifies, with acrylic acid and the sodium salt heating in water bath one pot process under nitrogen protection absorption Cd thereof removing polymerization inhibitor2+Resin, the product prepared under optimum condition is 5ppmCd to concentration2+Adsorbance be 24.25mg/g, be 55ppmCd to concentration2+Adsorbance is 87.46mg/g, to the Cd that concentration is 5 55ppm2+Clearance is 25.06% 41.55%；Advantage of the invention is that hydrogen peroxide oxidation carboxymethyl potato starch needs not move through the separation of conventional oxidation carboxymethyl potato starch, purifies, washs, it is not necessary to extra add initiator i.e. polymerizable, the prepared product Cd to low concentration Yu high concentration2+Being respectively provided with bigger adsorbance, therefore, the present invention synthesizes absorption Cd2+Resin process is simple, low cost, be easier to large-scale production, due to Cd2+Having the highest adsorbance, product is containing Cd2+The aspect such as sewage disposal, soil remediation has good application prospect.

Description

Cd is adsorbed for Material synthesis with carboxymethyl potato starch2+The method of resin
Technical field
The invention discloses a kind of novel absorption Cd2+Resin and preparation method thereof, is particularly used for containing Cd2+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.After environment is by cadmium pollution, cadmium can be at biology Internal enrichment, enters human body by food chain and causes chronic poisoning.After cadmium is absorbed by the body, form cadmium sulfoprotein, choosing in vivo Accumulate to selecting property in liver, kidney.Wherein, kidney can absorb the internal cadmium of nearly 1/3 of entrance, is cadmium poisoning " target organ ".Other is dirty Device such as spleen, pancreas, thyroid and hair etc. also have a certain amount of accumulation.Owing to cadmium damages renal tubules, there is glycosuria, albuminuria in patient And aminoaciduria.
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 Cd2+New functional macromolecule material, be mainly characterized in that resin structure is three-dimensional network type, have and can accommodate Cd2+Crosslinking Site；Containing groups such as-COOH ,-COONa, can be with Cd2+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 Cd2+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, pulverizes i.e. to obtain and adsorb Cd2+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 to adsorb Cd 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 Cd2+High adsorption capacity, no matter low concentration or high concentration all have bigger adsorbance, to concentration be 5ppmCd2+Adsorbance be 24.25mg/g, be 55ppmCd to concentration2+Adsorbance be 87.46mg/g.
Accompanying drawing explanation
Fig. 1 carboxymethyl potato starch synthesis absorption Cd2+The process chart of resin
Fig. 2 adsorbs Cd2+Resin is to variable concentrations Cd2+Adsorbance
Fig. 3 is carboxymethyl potato starch with monomer ratio to Cd2+The influence curve of adsorbance
Fig. 4 is that acrylic acid degree of neutralization is to Cd2+The influence curve of adsorbance
Fig. 5 is that the consumption of cross-linking agent is to Cd2+The influence curve of adsorbance
Fig. 6 is that reaction system total Water is to Cd2+The influence curve of adsorbance
Fig. 7 is absorption Cd2+The Orthogonal experiment results of the synthesis condition of resin.
Detailed description of the invention
Embodiment 1: weigh 5g carboxymethyl potato starch and mix homogeneously with 50ml deionized water, adds the dioxygen of 6ml30% Water aoxidizes 1h at 50 DEG C, measures 20g (19.1ml) acrylic acid, and weighing sodium hydroxide 5.6g is dissolved 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 sodium salt solution thereof and oxygen Carboxymethyl potato starch solution after change is sufficiently mixed uniformly, and adding 4ml concentration is the N of 2.5mg/ml, N ＇-di-2-ethylhexylphosphine oxide third Acrylamide solution, at N2Under protection, being slowly heated and make system temperature be stepped up, reaction to be polymerized stops stirring after starting, and continues Continuous slowly heat up, at 80 DEG C, be incubated 2h, product drying, pulverize and i.e. obtain product, by the product obtained by the present embodiment dense Spend in the solution for 25ppm Cd2+Adsorbance be 46.83mg/g.
Embodiment 2: weigh 5g carboxymethyl potato starch and mix homogeneously with 40ml deionized water, adds 6ml hydrogen peroxide and exists Aoxidizing 1h at 50 DEG C, measure 20g (19.1ml) acrylic acid, weighing sodium hydroxide 5.6g is dissolved in 20ml deionized water, with above-mentioned The sodium hydroxide solution prepared neutralizes acrylic acid under ice-water bath cools down, by after the acrylic acid become reconciled and saline solution thereof and oxidation Carboxymethyl potato starch solution be sufficiently mixed uniformly, add 6ml concentration be the N of 2.5mg/ml, N ＇-methylene bisacrylamide acyl Amine aqueous solution, at N2Under protection, it is slowly heated and makes system temperature be stepped up, after reaction to be polymerized starts, stop stirring, continue slow Slow heat up, at 80 DEG C, be incubated 2h, drying, pulverize and i.e. obtain product.It is 35ppm by the product obtained by the present embodiment in concentration Cd2+Solution in Cd2+Adsorbance be 63.97mg/g.
Embodiment 3: weigh 5g carboxymethyl potato starch and mix homogeneously with 40ml deionized water, adds 6ml hydrogen peroxide and exists Aoxidizing 1h at 50 DEG C, measure 20g (19.1ml) acrylic acid, weighing sodium hydroxide 5.6g is dissolved in 20ml deionized water, with above-mentioned The sodium hydroxide solution prepared neutralizes acrylic acid under ice-water bath cools down, by after the acrylic acid become reconciled and saline solution thereof and oxidation Carboxymethyl potato starch solution be sufficiently mixed uniformly, add 4ml concentration be the N of 2.5mg/ml, N ＇-methylene bisacrylamide acyl Amine aqueous solution, at N2Under protection, it is slowly heated and makes system temperature be stepped up, after reaction to be polymerized starts, stop stirring, continue slow Slow heat up, at 80 DEG C, be incubated 2h, drying, pulverize and i.e. obtain product.It is 15ppm by the product obtained by the present embodiment in concentration Cd2+Solution in Cd2+Adsorbance be 31.77mg/g.
Embodiment 4: through L9 (34) orthogonal experiment obtained synthesis absorption Cd2+The optimum condition of resin, specific embodiment As follows:
Weigh 5g carboxymethyl potato starch to mix homogeneously with 60ml 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 60ml 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 3.2ml concentration is 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, it is incubated 2h, drying, pulverizes and i.e. obtain product, the product obtained by the present embodiment be the Cd of 5ppm in concentration2+Molten Liquid is to Cd2+High adsorption capacity be 24.25mg/g.

Claims (3)

1. adsorb Cd with carboxymethyl potato starch for Material synthesis2+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, pulverizes i.e. to obtain and adsorb Cd2+Resin.
Cd is adsorbed for Material synthesis the most according to claim 1 with carboxymethyl potato starch2+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)=1:4:0.0016:1.12:24:1.33, oxidization time 1h, oxidizing temperature is 60 DEG C, this condition The lower product prepared is 5ppmCd to concentration2+Adsorbance be 24.25mg/g, be the Cd of 55ppm to concentration2+Adsorbance be 87.46mg/g。
Cd is adsorbed for Material synthesis the most according to claim 1 with carboxymethyl potato starch2+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%.
CN201610479121.8A 2016-06-28 2016-06-28 Cd is adsorbed for Material synthesis with carboxymethyl potato starch2+the method of resin Pending CN106117434A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101638458A (en) * 2009-09-14 2010-02-03 内蒙古大学 Method for preparing super absorbent resin by using carboxymethyl potato starch 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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101638458A (en) * 2009-09-14 2010-02-03 内蒙古大学 Method for preparing super absorbent resin by using carboxymethyl potato starch 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: "《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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CN106117434A (en) Cd is adsorbed for Material synthesis with carboxymethyl potato starch2+the method of resin

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