CN104117344A - Preparation method of novel chitosan metal ion adsorbent - Google Patents
Preparation method of novel chitosan metal ion adsorbent Download PDFInfo
- Publication number
- CN104117344A CN104117344A CN201410384391.1A CN201410384391A CN104117344A CN 104117344 A CN104117344 A CN 104117344A CN 201410384391 A CN201410384391 A CN 201410384391A CN 104117344 A CN104117344 A CN 104117344A
- Authority
- CN
- China
- Prior art keywords
- humic acid
- metal ion
- chitosan
- shitosan
- ion adsorbent
- 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.)
- Granted
Links
Abstract
The invention relates to a preparation method of a novel chitosan metal ion adsorbent. The preparation method comprises the following steps: (1) preparing unsolvable humic acid; (2) crashing the unsolvable humic acid to obtain unsolvable humic acid powder; (3) dissolving chitosan in an ethylic acid solution; adding epichlorohydrin; stirring for 3-5 hours, adding the unsolvable humic acid powder and stirring for 30 minutes to obtain uniform mash; (4) dropwise adding the mash to an NaOH solution placed on a magnetic stirrer by virtue of a peristaltic pump; washing with distilled water until the solution is neutral after placing for 20-26 hours, thus obtaining the chitosan metal ion adsorbent. The chitosan metal ion adsorbent is immerged in deionized water and sealed in room temperature. The preparation method is low in cost, efficient and easy for industrial production.
Description
Technical field
The present invention relates to water-treatment technology field, relate in particular to the preparation method of novel chitosan metal ion adsorbent.
Background technology
The most outstanding with heavy metal in inorganic pollution in water.Heavy metal is difficult to Bei Shuizhong Institute of Micro-biology degraded, is easily converted into the alkyl compound that toxicity is larger, so by food chain at people's body accumulation, serious harm health.Although toxicity is different, the allowance in environment water quality standard and drinking water quality standard is also not quite similar, and can only move or produce the variation on form and valence state after entering water environment, belongs to persistent pollutant.Conventional processing method has chemical precipitation method, ion-exchange, electrolysis etc. at present, but all exist as complex process, cost is high or produce secondary pollution problems, so seek efficient cheap heavy metal ion water treatment agent, becomes the requirement that people are urgent.
Shitosan (Chitosan), chemistry (Isosorbide-5-Nitrae)-2-amido-2-deoxidation-B-D-glucose by name, is called for short CTS, is the product of chitin deacetylase base.It is a kind of line style natural polymer, contains a large amount of hydroxyls, amino on its macromolecular chain, and metal ion is had to certain absorption and coordination.Shitosan is natural biological high molecular polymer, can not cause secondary pollution to environment, and from environment sustainable development, tool is of great significance and causes the increasing interest of people.But the amino in chitosan molecule is used under the lower condition of pH value, is turned to-NH by proton
3 +and cause loss by dissolution, poor stability.For shitosan can be widely used in Treatment of Industrial Water, it need to be made to cross-linking products, conventional crosslinking agent has glutaraldehyde, formaldehyde, epoxychloropropane etc.Chitosan resin after crosslinked not swelling, do not run off, mechanical strength is good, reusable.
Humic acid is the product after the residual body of natural plant decomposes through rotting, the natural macromolecular that is a kind of complexity is organic, its molecule contains the various active functional groups such as carbonyl, carboxyl, alcoholic extract hydroxyl group and phenolic hydroxyl group, thereby can interact with many metal ions, forms stable chelate.In recent years, there are reports to the research of heavy metal ion adsorbed characteristic for relevant humic acid.But humic acid itself is exactly a kind of pollutant, be the precursor of many water body harmful chemicals, and water soluble under certain condition.Although therefore humic acid and heavy metal ion have very strong complexing power, still can not directly it be applied as adsorbent.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of efficient, preparation method of being easy to the novel chitosan metal ion adsorbent of suitability for industrialized production.
For addressing the above problem, the preparation method of novel chitosan metal ion adsorbent of the present invention, comprises the following steps:
(1) prepare insoluble humic acid:
Humic acid heats after 0.5 ~ 1.5 h at the temperature of 320 ~ 340 ℃, is immersed in 2 mol/L CaCl
21 ~ 3 h in solution, then filters, and obtains solids, and this solids is used 1 mol/L NaNO successively
3after solution and first water cyclic washing, be dried to constant weight through 70 ~ 90 ℃, obtain insoluble humic acid;
(2) described insoluble humic acid is crushed to 100 ~ 200 orders, obtains insoluble humic acid powder;
(3) shitosan is dissolved in to volumetric concentration and is in 5% acetum, then add epoxychloropropane, add described insoluble humic acid powder after stirring 3 ~ 5 h with the speed of 1100 ~ 1300rpm, continue to stir 30 min with identical speed and make even pastel; Wherein: the ratio of described shitosan and described acetum is 1 g:10 ~ 30 mL; The ratio of described shitosan and described epoxychloropropane is 1 g:0.2 ~ 0.8 mL; The ratio of described shitosan and described insoluble humic acid powder is 1 g:0.2 ~ 0.8 g;
(4) described pastel is added drop-wise to the 0.2 mol/L NaOH solution being placed on magnetic stirring apparatus by peristaltic pump, after placing 20 ~ 26 h, be washed with distilled water to neutrality, obtain chitosan-metal ion adsorbent, this chitosan-metal ion adsorbent is immersed in deionized water, normal temperature lower seal.
The present invention compared with prior art has the following advantages:
1, the present invention be take epoxychloropropane as crosslinking agent, prepare coccoid shitosan/insoluble humic acid (calcium humate) adsorbent, prepared adsorbent shows through the JSM-5610 of Hitachi, Ltd. ESEM, this adsorbent is single-size spheroid and rough surface (referring to Fig. 1), its internal structure is more loose, and there is porous network structure (referring to Fig. 2), and meanwhile, the controlled and narrowly distributing (referring to table 1) of particle diameter.
The adsorbent physical property test that table 1 the present invention is prepared
2, Tensor 27 Fourier infrared spectrographs of insoluble humic acid, shitosan, chitosan crosslinked insoluble humic acid bead (being the prepared adsorbent of the present invention), chitosan crosslinked insoluble humic acid bead absorption Pb (II) being produced by German BRUKER company are at 4000 ~ 400 cm
-1spectral region, after KBr compressing tablet, sample is carried out to examination of infrared spectrum demonstration (referring to Fig. 3):
(1) each peak ownership of insoluble humic acid infrared spectrogram is as follows: 3500cm
-1~ 3300cm
-1place is carboxyl, phenol and alcoholic extract hydroxyl group (OH) stretching vibration absworption peak, 1705cm
-1neighbouring is the C=O stretching vibration absworption peak of carboxyl, 1600cm
-1~ 1580cm
-1for aromatic ring C=C stretching vibration absworption peak.
(2) each peak ownership of shitosan infrared spectrogram is as follows: 2933cm
-1be-CH
2vibration peak, 1603cm
-1be-NH
2vibration peak and N-C=O stretch mixing peak, peak, 1402cm
-1for the absworption peak of N-H, 1306cm
-1for C-N absworption peak.
(3) the characteristic peak that chitosan crosslinked insoluble humic acid bead infrared spectrogram has comprised shitosan and insoluble humic acid.
(4) adsorb Pb
2+after the infrared spectrogram of chitosan crosslinked insoluble humic acid bead, except having there is the characteristic peak of chitosan crosslinked insoluble humic acid bead, the asymmetric stretching vibration of C-O key is by original 1085cm
-1move to 1105cm
-1, show that the secondary hydroxyl on shitosan participates in Pb
2+coordination.1402cm
-1n-H absworption peak die down and to lower wave number migration, this be due to and N atom between form coordinate bond, N Atomic Electron Cloud is shifted to the required energy of N-H key deformation vibration is reduced, and illustrates that the amino in chitosan molecule has participated in Pb
2+coordination.
Assignment of Infrared Spectrum result shows, bead is to Pb
2+suction-operated on the secondary hydroxyl and amino of shitosan, there is chemisorbed.
3, the prepared adsorbent of the present invention is changed with the characteristics of energy spectrum peak that the twin cathode (MgKa/AIKa) that VGScieniific Escalab210-UKX-ray photoelectricity energy disperse spectroscopy is measured has recorded before and after adsorbent absorption Pb (II), can (BEs) all being take in cls peak in all combinations is benchmark in 285.0eV calibration.Test result shows (referring to Fig. 4): in absorption Pb (II) xps energy spectrum before, there is C 1s, and N 1s,, after absorption, there is Pb 4f characteristic peak in O 1s, and the elemental characteristic peak such as Ca 2p3, the characteristic peak such as Ca 2p3 disappears simultaneously.
4, the present invention compared with prior art, has efficient adsorption rate (referring to table 2).
The adsorbent that table 2 the present invention is prepared and the contrast test of prior art
5, the present invention is with low cost, is easy to suitability for industrialized production.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is the whole SEM photo that amplifies 35 times of the present invention.
Fig. 2 is that the present invention cuts in half, and wherein half amplifies the SEM photo of 2000 times.
Fig. 3 is infrared spectrogram.Wherein: a is insoluble humic acid, b is shitosan, and c is chitosan crosslinked insoluble humic acid bead, after d is chitosan crosslinked insoluble humic acid bead absorption Pb (II).
Fig. 4 is the XPS collection of illustrative plates that Pb (II) front and back are adsorbed in the present invention.Wherein: a is for before adsorbing, and b is for after adsorbing.
The specific embodiment
embodiment 1the preparation method of novel chitosan metal ion adsorbent, comprises the following steps:
(1) prepare insoluble humic acid:
Humic acid heats after 1.5 h at the temperature of 320 ℃, is immersed in 2 mol/L CaCl
21 h in solution, then filters, and obtains solids, and this solids is used 1 mol/L NaNO successively
3after solution and first water cyclic washing, be dried to constant weight through 70 ℃, obtain insoluble humic acid.
(2) insoluble humic acid is crushed to 100 orders, obtains insoluble humic acid powder.
(3) shitosan is dissolved in to volumetric concentration and is in 5% acetum, then add epoxychloropropane, add insoluble humic acid powder after stirring 5 h with the speed of 1100rpm, continue to stir 30 min with identical speed and make even pastel.
Wherein:
The ratio of shitosan and acetum is 1 g:10 mL; The ratio of shitosan and epoxychloropropane is 1 g:0.2 mL; The ratio of shitosan and insoluble humic acid powder is 1 g:0.2 g.
(4) pastel is added drop-wise to the 0.2 mol/L NaOH solution being placed on magnetic stirring apparatus by peristaltic pump, after placing 20 h, be washed with distilled water to neutrality, obtain chitosan-metal ion adsorbent, this chitosan-metal ion adsorbent is immersed in deionized water, normal temperature lower seal.
embodiment 2the preparation method of novel chitosan metal ion adsorbent, comprises the following steps:
(1) prepare insoluble humic acid:
Humic acid heats after 0.5 h at the temperature of 340 ℃, is immersed in 2 mol/L CaCl
23 h in solution, then filter, and obtain solids, and this solids is used 1 mol/L NaNO successively
3after solution and first water cyclic washing, be dried to constant weight through 90 ℃, obtain insoluble humic acid.
(2) insoluble humic acid is crushed to 200 orders, obtains insoluble humic acid powder.
(3) shitosan is dissolved in to volumetric concentration and is in 5% acetum, then add epoxychloropropane, add insoluble humic acid powder after stirring 3 h with the speed of 1300rpm, continue to stir 30 min with identical speed and make even pastel.
Wherein:
The ratio of shitosan and acetum is 1 g:30 mL; The ratio of shitosan and epoxychloropropane is 1 g:0.8 mL; The ratio of shitosan and insoluble humic acid powder is 1 g:0.8 g.
(4) pastel is added drop-wise to the 0.2 mol/L NaOH solution being placed on magnetic stirring apparatus by peristaltic pump, after placing 26 h, be washed with distilled water to neutrality, obtain chitosan-metal ion adsorbent, this chitosan-metal ion adsorbent is immersed in deionized water, normal temperature lower seal.
embodiment 3the preparation method of novel chitosan metal ion adsorbent, comprises the following steps:
(1) prepare insoluble humic acid:
Humic acid heats after 1.0h at the temperature of 330 ℃, is immersed in 2 mol/L CaCl
22 h in solution, then filter, and obtain solids, and this solids is used 1 mol/L NaNO successively
3after solution and first water cyclic washing, be dried to constant weight through 80 ℃, obtain insoluble humic acid.
(2) insoluble humic acid is crushed to 150 orders, obtains insoluble humic acid powder.
(3) shitosan is dissolved in to volumetric concentration and is in 5% acetum, then add epoxychloropropane, add insoluble humic acid powder after stirring 4 h with the speed of 1200rpm, continue to stir 30 min with identical speed and make even pastel.
Wherein:
The ratio of shitosan and acetum is 1 g:20 mL; The ratio of shitosan and epoxychloropropane is 1 g:0.5 mL; The ratio of shitosan and insoluble humic acid powder is 1 g:0.5 g.
(4) pastel is added drop-wise to the 0.2 mol/L NaOH solution being placed on magnetic stirring apparatus by peristaltic pump, after placing 23 h, be washed with distilled water to neutrality, obtain chitosan-metal ion adsorbent, this chitosan-metal ion adsorbent is immersed in deionized water, normal temperature lower seal.
Claims (1)
1. the preparation method of novel chitosan metal ion adsorbent, comprises the following steps:
(1) prepare insoluble humic acid:
Humic acid heats after 0.5 ~ 1.5 h at the temperature of 320 ~ 340 ℃, is immersed in 2 mol/L CaCl
21 ~ 3 h in solution, then filters, and obtains solids, and this solids is used 1 mol/L NaNO successively
3after solution and first water cyclic washing, be dried to constant weight through 70 ~ 90 ℃, obtain insoluble humic acid;
(2) described insoluble humic acid is crushed to 100 ~ 200 orders, obtains insoluble humic acid powder;
(3) shitosan is dissolved in to volumetric concentration and is in 5% acetum, then add epoxychloropropane, add described insoluble humic acid powder after stirring 3 ~ 5 h with the speed of 1100 ~ 1300rpm, continue to stir 30 min with identical speed and make even pastel; Wherein: the ratio of described shitosan and described acetum is 1 g:10 ~ 30 mL; The ratio of described shitosan and described epoxychloropropane is 1 g:0.2 ~ 0.8 mL; The ratio of described shitosan and described insoluble humic acid powder is 1 g:0.2 ~ 0.8 g;
(4) described pastel is added drop-wise to the 0.2 mol/L NaOH solution being placed on magnetic stirring apparatus by peristaltic pump, after placing 20 ~ 26 h, be washed with distilled water to neutrality, obtain chitosan-metal ion adsorbent, this chitosan-metal ion adsorbent is immersed in deionized water, normal temperature lower seal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410384391.1A CN104117344B (en) | 2014-08-06 | 2014-08-06 | The preparation method of novel chitosan metal ion adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410384391.1A CN104117344B (en) | 2014-08-06 | 2014-08-06 | The preparation method of novel chitosan metal ion adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104117344A true CN104117344A (en) | 2014-10-29 |
| CN104117344B CN104117344B (en) | 2016-04-06 |
Family
ID=51763114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410384391.1A Expired - Fee Related CN104117344B (en) | 2014-08-06 | 2014-08-06 | The preparation method of novel chitosan metal ion adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104117344B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597699A (en) * | 2016-01-29 | 2016-05-25 | 四川农业大学 | Modified wormcast micro-ball for efficiently adsorbing Cu<2+>, preparation method and application |
| CN106040185A (en) * | 2016-06-01 | 2016-10-26 | 兰州城市学院 | Method for preparing magnetic adsorbent for methylene blue wastewater treatment |
| CN109092267A (en) * | 2018-09-30 | 2018-12-28 | 湖北工程学院 | Hydroxypropyl chitosan phytic acid porous composite film and the method for removing metal impurities |
| CN109989051A (en) * | 2019-04-03 | 2019-07-09 | 盐城工学院 | A kind of method of Modification of Cotton Fabric and electroless copper |
| CN112588277A (en) * | 2020-11-06 | 2021-04-02 | 兰州城市学院 | Preparation method of solid-phase micro-extraction fiber based on nanogold/chitosan coating |
| CN113019332A (en) * | 2021-03-01 | 2021-06-25 | 齐鲁工业大学 | Chitosan/ZIF-8 composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6143692A (en) * | 1995-08-15 | 2000-11-07 | Arctech, Inc. | Adsorbent |
| CN101797496A (en) * | 2010-01-07 | 2010-08-11 | 北京林业大学 | Preparation method of inorganic-organic compound-type adsorbent based on clinoptilolite and application for removing Cr(VI) in industrial waste water |
| CN102443186A (en) * | 2011-09-30 | 2012-05-09 | 浙江省海洋开发研究院 | Preparation method of epoxy chloropropane cross-linked chitosan microspheres |
-
2014
- 2014-08-06 CN CN201410384391.1A patent/CN104117344B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6143692A (en) * | 1995-08-15 | 2000-11-07 | Arctech, Inc. | Adsorbent |
| CN101797496A (en) * | 2010-01-07 | 2010-08-11 | 北京林业大学 | Preparation method of inorganic-organic compound-type adsorbent based on clinoptilolite and application for removing Cr(VI) in industrial waste water |
| CN102443186A (en) * | 2011-09-30 | 2012-05-09 | 浙江省海洋开发研究院 | Preparation method of epoxy chloropropane cross-linked chitosan microspheres |
Non-Patent Citations (2)
| Title |
|---|
| 方金鹏: "复合吸附剂吸附水中六价铬的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 王学刚 等: "交联壳聚糖吸附处理低浓度含铀废水", 《金属矿山》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597699A (en) * | 2016-01-29 | 2016-05-25 | 四川农业大学 | Modified wormcast micro-ball for efficiently adsorbing Cu<2+>, preparation method and application |
| CN105597699B (en) * | 2016-01-29 | 2018-07-13 | 四川农业大学 | A kind of efficient absorption Cu2+Modification wormcast microballoon, preparation method and application |
| CN106040185A (en) * | 2016-06-01 | 2016-10-26 | 兰州城市学院 | Method for preparing magnetic adsorbent for methylene blue wastewater treatment |
| CN109092267A (en) * | 2018-09-30 | 2018-12-28 | 湖北工程学院 | Hydroxypropyl chitosan phytic acid porous composite film and the method for removing metal impurities |
| CN109989051A (en) * | 2019-04-03 | 2019-07-09 | 盐城工学院 | A kind of method of Modification of Cotton Fabric and electroless copper |
| CN112588277A (en) * | 2020-11-06 | 2021-04-02 | 兰州城市学院 | Preparation method of solid-phase micro-extraction fiber based on nanogold/chitosan coating |
| CN113019332A (en) * | 2021-03-01 | 2021-06-25 | 齐鲁工业大学 | Chitosan/ZIF-8 composite material and preparation method and application thereof |
| CN113019332B (en) * | 2021-03-01 | 2023-01-20 | 齐鲁工业大学 | Chitosan/ZIF-8 composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104117344B (en) | 2016-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104117344A (en) | Preparation method of novel chitosan metal ion adsorbent | |
| WO2016187796A1 (en) | Preparation method and use of heavy metal ion adsorbent | |
| CN103447013B (en) | A kind of preparation method of Graphene/chitosan absorbent and application process thereof | |
| Heidari et al. | Selective adsorption of Pb (II), Cd (II), and Ni (II) ions from aqueous solution using chitosan–MAA nanoparticles | |
| Song et al. | Recovery of lithium (I), strontium (II), and lanthanum (III) using Ca–alginate beads | |
| Zhou et al. | Adsorption behavior of Cd2+, Pb2+, and Ni2+ from aqueous solutions on cellulose-based hydrogels | |
| Saber-Samandari et al. | Removal of mercury (II) from aqueous solution using chitosan-graft-polyacrylamide semi-IPN hydrogels | |
| CN105498707A (en) | Preparation method and application of modified graphene oxide/chitosan composite material | |
| KR102150430B1 (en) | Hybrid bead using persimmon leaf and chitosan for the treatment of aqueous solution contaminated with toxic heavy metal ions and method of the same | |
| CN103769058A (en) | Preparation method of carbonized chitosan adsorbent, adsorbent and application method of absorbent | |
| CN106824113B (en) | Preparation and application of imidazole ionic liquid modified chitosan adsorbent | |
| Chen et al. | Preparation and characteristics of anion exchanger from corn stalks | |
| CN108514870A (en) | Hydrotalcite-poly m-phenylene diamine composite material and preparation method and application | |
| CN114522672B (en) | Biomass functional material for antibiotic adsorption and preparation method thereof | |
| Bertagnolli et al. | Synthesis and application of a novel sorbent (tannic acid-grafted-polyethyleneimine encapsulated in alginate beads) for heavy metal removal | |
| CN113976050A (en) | Preparation method of magnetic cellulose-graphene oxide high-adsorbability aerogel | |
| CN107413314B (en) | Method for removing chromium in wastewater | |
| Mahmoud et al. | A novel cellulose-dioctyl phthate-baker's yeast biosorbent for removal of Co (II), Cu (II), Cd (II), Hg (II) and Pb (II) | |
| Tian et al. | Preparation and performance of dimethyl-acetoxy-(2-carboxymethyl ether)-lignin ammonium chloride amphoteric surfactant | |
| Liu et al. | Removal of copper by modified chitosan adsorptive membrane | |
| Zhang et al. | Decoration of sodium carboxymethylcellulose gel microspheres with modified lignin to enhanced methylene blue removal | |
| CN103785361A (en) | Method for preparing heavy metal ion absorbent through xanthation of granule sludge | |
| CN115254059B (en) | Chitosan/EDTA/polypyrrole adsorption material for efficiently removing hexavalent chromium ions in wastewater and preparation method thereof | |
| CN103073600A (en) | Method for preparing water soluble chitosan oligosaccharide | |
| CN109647356A (en) | A kind of preparation method and its application in removal waste water in anions and canons dyestuff at the same time of both sexes adsorbent material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160406 Termination date: 20160806 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |