CN106117436A - Cr is adsorbed for Material synthesis with carboxymethyl potato starch3+the method of resin - Google Patents
Cr is adsorbed for Material synthesis with carboxymethyl potato starch3+the method of resin Download PDFInfo
- Publication number
- CN106117436A CN106117436A CN201610479507.9A CN201610479507A CN106117436A CN 106117436 A CN106117436 A CN 106117436A CN 201610479507 A CN201610479507 A CN 201610479507A CN 106117436 A CN106117436 A CN 106117436A
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- CN
- China
- Prior art keywords
- potato starch
- carboxymethyl potato
- resin
- concentration
- adsorbance
- Prior art date
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Classifications
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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
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- 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
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- 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
Abstract
The invention discloses a kind of with carboxymethyl potato starch as raw material, use one pot process absorption Cr through hydrogen peroxide oxidation3+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 Cr thereof removing polymerization inhibitor3+Resin, under optimum condition, the product of synthesis is 5ppmCr to concentration3+Adsorbance be 23.95mg/g, be 55ppmCr to concentration3+Adsorbance is 245.9mg/g, to the Cr that concentration is 5 55ppm3+Clearance is 89.07% 94.86%；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 Cr to low concentration Yu high concentration3+Being respectively provided with bigger adsorbance, therefore, the present invention synthesizes absorption Cr3+Resin process is simple, low cost, be easier to large-scale production, due to Cr3+Having the highest adsorbance, product is containing Cr3+The aspect such as sewage disposal, soil remediation has good application prospect.
Description
Technical field
The invention discloses a kind of novel absorption Cr3+Resin and preparation method thereof, is particularly used for containing Cr3+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.Owing to weathering enters the chromium in soil, hold
The composite anion of oxidizable one-tenth solubility, is then transferred in the surface water or subsoil water by drip washing.When Chromium in Soil is too much,
The Nitrification of organic substance can be suppressed, and make chromium at plant body accumulation.Trivalent chromium has lethal effect to aquatile.Chromium
Very big to harm, drinking if eating by mistake, the poisoning symptom such as abdominal discomfort and diarrhoea can be caused, cause allergic dermatitis or eczema；
Entering if breathing, respiratory tract being had stimulation and corrosiveness, causes pharyngitis, bronchitis etc..The seriously polluted Area Inhabitants of water, warp
Often contact or Excess free enthalpy person, the rhinitis that is easy to get, tuberculosis, diarrhoea, bronchitis, dermatitis etc..
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 Cr3+New functional macromolecule material, be mainly characterized in that resin structure is three-dimensional network type, have and can accommodate Cr3+Crosslinking
Site；Containing groups such as-COOH ,-COONa, can be with Cr3+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 Cr3+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 sodium salt solution is sufficiently mixed, and adds containing carboxymethyl potato starch the quality 0.04～N of 0.24%, N ＇-methylene bisacrylamide
Amide 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, reaction to be polymerized
After beginning, stop stirring, continue slowly to heat up, at 80 DEG C, be incubated 2h, drying, pulverizes i.e. to obtain and adsorb Cr3+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 Cr first3+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 Cr3+High adsorption capacity, no matter low concentration or high concentration all have bigger adsorbance, to concentration be
5ppmCr3+Adsorbance be 23.95mg/g, be 55ppmCr to concentration3+Adsorbance be 245.9mg/g.
(6) clearance is higher, is the Cr of 5-55ppm to concentration3+Clearance is at 89.07%-94.86%.
Accompanying drawing explanation
Fig. 1 carboxymethyl potato starch synthesis absorption Cr3+The process chart of resin
Fig. 2 adsorbs Cr3+Resin is to variable concentrations Cr3+Adsorbance
Fig. 3 is carboxymethyl potato starch with monomer ratio to Cr3+The influence curve of adsorbance
Fig. 4 is that acrylic acid degree of neutralization is to Cr3+The influence curve of adsorbance
Fig. 5 is that the consumption of cross-linking agent is to Cr3+The influence curve of adsorbance
Fig. 6 is that reaction system total Water is to Cr3+The influence curve of adsorbance.
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 Cr3+Adsorbance be 113.1mg/g.
Embodiment 2: weigh 5g carboxymethyl potato starch and mix homogeneously with 50ml 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 50ml 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
Cr3+Solution in Cr3+Adsorbance be 157.68mg/g.
Embodiment 3: weigh 5g carboxymethyl potato starch and mix homogeneously with 50ml deionized water, adds 6ml hydrogen peroxide and exists
Aoxidizing 1h at 50 DEG C, measure 30g (28.57ml) acrylic acid, weighing sodium hydroxide 8.4g is dissolved in 50ml 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 5ppm by the product obtained by the present embodiment in concentration
Cr3+Solution in Cr3+Adsorbance be 23.95mg/g.
Claims (3)
1. adsorb Cr with carboxymethyl potato starch for Material synthesis3+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 salt thereof
Solution is sufficiently mixed, and adds N, the N ＇-methylene-bisacrylamide containing carboxymethyl potato starch certain mass ratio and cross-links
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
Only stirring, continues slowly to heat up, and is incubated 2h at 80 DEG C, drying, pulverizes i.e. to obtain and adsorbs Cr3+Resin.
Cr is adsorbed for Material synthesis the most according to claim 1 with carboxymethyl potato starch3+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)=1:6:0.002:1.68:20:1.33, oxidization time 1h, oxidizing temperature is 60 DEG C, this condition
The lower product prepared is 5ppmCr to concentration3+Adsorbance be 23.95mg/g.
Cr is adsorbed for Material synthesis the most according to claim 1 with carboxymethyl potato starch3+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%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610479507.9A CN106117436A (en) | 2016-06-28 | 2016-06-28 | Cr is adsorbed for Material synthesis with carboxymethyl potato starch3+the method of resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610479507.9A CN106117436A (en) | 2016-06-28 | 2016-06-28 | Cr is adsorbed for Material synthesis with carboxymethyl potato starch3+the method of resin |
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| CN106117436A true CN106117436A (en) | 2016-11-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610479507.9A Pending CN106117436A (en) | 2016-06-28 | 2016-06-28 | Cr is adsorbed for Material synthesis with carboxymethyl potato starch3+the method of resin |
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Citations (2)
| 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 |
-
2016
- 2016-06-28 CN CN201610479507.9A patent/CN106117436A/en active Pending
Patent Citations (2)
| 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)
| Title |
|---|
| 冯玉杰等: "《环境工程中的功能材料》", 31 July 2003 * |
| 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: 20161116 |