CN106117437A - Ni is adsorbed for Material synthesis with carboxymethyl potato starch2+the method of resin - Google Patents
Ni is adsorbed for Material synthesis with carboxymethyl potato starch2+the method of resin Download PDFInfo
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- CN106117437A CN106117437A CN201610479769.5A CN201610479769A CN106117437A CN 106117437 A CN106117437 A CN 106117437A CN 201610479769 A CN201610479769 A CN 201610479769A CN 106117437 A CN106117437 A CN 106117437A
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- CN
- China
- Prior art keywords
- potato starch
- carboxymethyl potato
- resin
- concentration
- acrylic acid
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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
-
- 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
Abstract
The invention discloses a kind of with carboxymethyl potato starch as raw material, use one pot process absorption Ni 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 Ni thereof removing polymerization inhibitor2+Resin, the product prepared under optimum condition is 5ppmNi to concentration2+Adsorbance be 18.63mg/g, be 55ppmNi to concentration2+Adsorbance is 58.45mg/g, to the Ni that concentration is 5 55ppm2+Clearance is 14.59% 33.45%；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 the extra initiator i.e. polymerizable that adds, therefore, the present invention synthesizes absorption Ni2+Resin process is simple, low cost, be easier to large-scale production, due to Ni2+Having higher adsorbance, product is containing Ni2+The aspect such as sewage disposal, soil remediation has good application prospect.
Description
Technical field
The invention discloses a kind of novel absorption Ni2+Resin and preparation method thereof, is particularly used for containing Ni2+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.Nickel contamination is very big to the harm of human body, generally has
Carcinogenesis.The carcinogenesis of carcinogenecity nickel, is found in 1933, as Wales, Britain south Ke Lidehe nickel smelter workman
In, suffer from a lot of of pulmonary carcinoma and tumor of nasal cavity.The R. Dorr of Britain equal to 1970 to participated in before this factory's nineteen forty-four refinery activities 5 years with
On 845 workmans carried out follow up survey, workman's cancer mortality situation is compared with general resident, find nineteen twenty-five with
Before the workman that works die from the observation number of pulmonary carcinoma, for 5～10 times of national residents lung cancer death same period expectation number；Extremely
Observation number in tumor of nasal cavity is about 100～900 times of national residents.In Canada, Norway, German Democratic Republic and day
The Epidemiological study that state such as this grade is carried out, also has similar discovery.Nickel contamination is longer for carcinogenic incubation period, and FEIAI PING is 27
Year, tumor of nasal cavity average out to 23 years.The history of China's Refining Nickel operation is shorter, does not also have the report that nickel contamination is carcinogenic.Herein with double
Oxygen water and carboxymethyl potato starch are raw material, use one pot process one to be applicable to Ni2+Absorption and the new function removed
Macromolecular material, is mainly characterized in that resin structure is three-dimensional network type, has and can accommodate Ni2+Crosslink sites；Containing-COOH ,-
The groups such as COONa, can be with Ni2+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 Ni2+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 Ni2+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 Ni 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 Ni2+High adsorption capacity, no matter low concentration or high concentration all have bigger adsorbance, to concentration be
5ppmNi2+Adsorbance be 18.63mg/g, be 55ppmNi to concentration2+Adsorbance be 58.45mg/g.
Accompanying drawing explanation
Fig. 1 carboxymethyl potato starch synthesis absorption Ni2+The process chart of resin
Fig. 2 adsorbs Ni2+Resin is to variable concentrations Ni2+Adsorbance
Fig. 3 is carboxymethyl potato starch with monomer ratio to Ni2+The influence curve of adsorbance
Fig. 4 is that acrylic acid degree of neutralization is to Ni2+The influence curve of adsorbance
Fig. 5 is that the consumption of cross-linking agent is to Ni2+The influence curve of adsorbance
Fig. 6 is that reaction system total Water is to Ni2+The influence curve of adsorbance
Fig. 7 is absorption Ni2+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 50ml 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 Ni2+Adsorbance be 31.21mg/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
Ni2+Solution in Ni2+Adsorbance be 38.79mg/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 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 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
Ni2+Solution in Ni2+Adsorbance be 27mg/g.
Embodiment 4: through L9 (34) orthogonal experiment obtained synthesis absorption Ni2+The optimum condition of resin, specific embodiment
As follows:
Weigh 5g carboxymethyl potato starch to mix homogeneously with 50ml deionized water, add 6ml hydrogen peroxide at 50 DEG C, aoxidize 1h,
Measuring 10g (9.5ml) acrylic acid, weighing sodium hydroxide 2.8g is dissolved in 50ml deionized water, with above-mentioned prepared sodium hydroxide
Solution neutralizes acrylic acid under ice-water bath cools down, by carboxymethyl Ma Ling after the acrylic acid become reconciled and sodium salt solution thereof and oxidation
Sweet potato starch solution is sufficiently mixed uniformly, and adding 1.6ml 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 Ni of 5ppm to concentration2+Solution
In to Ni2+High adsorption capacity be 18.63mg/g.
Claims (3)
1. adsorb Ni 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 after acrylic acid and sodium salt molten
Liquid is sufficiently mixed, and adds N, the N ＇-methylene-bisacrylamide containing carboxymethyl potato starch certain mass ratio and makees cross-linking 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, stops stirring
Mix, continue slowly to heat up, at 80 DEG C, be incubated 2h, drying, pulverizes i.e. to obtain and adsorb Ni2+Resin.
Ni 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)=1:2:0.0008:0.56:20:1.33, oxidization time 1h, oxidizing temperature is 60 DEG C, this condition
The lower product prepared is 5ppmNi to concentration2+Adsorbance be 18.63mg/g, be the Ni of 55ppm to concentration2+Adsorbance be
58.45mg/g。
Ni 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%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610479769.5A CN106117437A (en) | 2016-06-28 | 2016-06-28 | Ni is adsorbed for Material synthesis with carboxymethyl potato starch2+the method of resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610479769.5A CN106117437A (en) | 2016-06-28 | 2016-06-28 | Ni is adsorbed for Material synthesis with carboxymethyl potato starch2+the method of resin |
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| Publication Number | Publication Date |
|---|---|
| CN106117437A true CN106117437A (en) | 2016-11-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610479769.5A Pending CN106117437A (en) | 2016-06-28 | 2016-06-28 | Ni is adsorbed for Material synthesis with carboxymethyl potato starch2+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 CN201610479769.5A patent/CN106117437A/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, 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: 20161116 |