CN103657601A - Preparation method of porous chitosan - Google Patents
Preparation method of porous chitosan Download PDFInfo
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- CN103657601A CN103657601A CN201310626458.3A CN201310626458A CN103657601A CN 103657601 A CN103657601 A CN 103657601A CN 201310626458 A CN201310626458 A CN 201310626458A CN 103657601 A CN103657601 A CN 103657601A
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Abstract
The invention discloses a preparation method of porous chitosan. The preparation method comprises the following steps: ultrasonically dispersing Fe3O4 nanoparticles into de-ionized water, adding ZrOCl2, fully mixing, heating, reacting to generate ZrO2/Fe3O4 compound metal oxide nanospheres, adding into chitosan, dissolving in a 4% acetic acid solution to form sol-gel, dropwise filling 2 mol/L of a NaOH solution with the sol-gel through a peristaltic pump to form monodisperse microspheres, and performing freeze-drying to form a porous chitosan microsphere-loaded ZrO2/Fe3O4 metal oxide. An adsorbent in the method is easy to prepare, convenient to operate, low in cost, remarkable in treatment effect and good in reproducibility, and can be quickly subjected to magnetic separation.
Description
Technical field
The invention belongs to water body purification processing technology field, be specifically related to a kind of preparation method with the boehmite of micro-nano hierarchy.
Background technology
Humic acid is the chief component of dissolved organic matter in natural water body, it is the large molecule poly-ring aromatic compounds of the multiple functional groups such as a kind of phenolic hydroxy group, carboxyl, alcoholic extract hydroxyl group, be mainly derived from the biodegradation of nature animals and plants chip, account for 50% ~ 90% of total organic matter in water.In water body, the existence of humic acid can cause the series of problems such as health and environment, in water body, humic acid existence is the main cause of water body chroma and stink, humic acid is easy to complex in water, greatly increase the stability of colloid, increase water treatment difficulty, in chlorination of drinking water disinfecting process, humic acid can react with chlorhexidine-containing disinfectant, produce chloroform, the DBPs such as halogen acetic acid, human body is had carcinogenic, teratogenesis, mutagenic effect, in addition, humic acid may disturb human body to the absorption of inorganic elements and metabolic balance, can cause large osteopathy, therefore, how efficiently to remove humic acid in water and become the focus that current water treatment field is paid close attention to.
At present, in water body, the acid-treated method of humic mainly contains: coagulation assisted, membrane filter technique, advanced oxidation processes and absorption method etc., coagulation assisted method and membrane filter technique are conventional methods, but the humic acid poor removal effect of enhanced coagulation to low concentration, although membrane filter technique removal effect is good, but easily cause membrane pollution problem, there is the problems such as operating cost is high, device is complicated, treating capacity is limited in advanced oxidation processes, absorption method is as low energy consumption, high security, treatment process simple to operate, there is good application prospect, become the focus of current environment research.
Absorption is a kind of mass transport process occurring on material surface, mainly that interaction between adsorption molecule and adsorbent surface molecule realizes, be divided into physical absorption and chemisorbed, humic acid has phenolic hydroxyl group, carboxyl, the large molecule poly-ring aromatic compounds of the multiple functional group such as alcoholic extract hydroxyl group, research shows, the adsorbent of amido class has good adsorption effect to humic acid, it mainly relies on adsorbent surface amido to be combined by electrostatic interaction with carboxyl and the alcoholic extract hydroxyl group of humic acid dissociation, amido class adsorbent for adsorbed water body humic acid mainly contains shitosan at present, polypyrrole, amino modified polyacrylonitrile etc., this type of adsorbent is better to humic acid removal effect in water body, but after absorption, adsorbent separation difficulty has limited its application.
Summary of the invention
The object of this invention is to provide that a kind of technique is simple, low production cost, be highly suitable for the preparation method of the high-quality boehmite micro-nano hierarchy of suitability for industrialized production.
Chitosan molecule is formed by connecting by amido glucose unit, therefore has the special functional groups such as a large amount of hydroxyls, amido, can be used for removing the humic acid in water body.In order to improve adsorption efficiency, can improve pore structure, carried magnetic particle can improve separative efficiency, and carrying transition metal oxide can strengthen the joint efficiency with humic acid.
In order to solve existing problem in background technology, the present invention adopts technical scheme to comprise that step is as follows:
By iron oxide (Fe
3o
4) nano particle is ultrasonic is distributed in deionized water, adds zirconium oxychloride (ZrOCl
2) abundant agitating heating reaction generation ZrO
2/ Fe
3o
4composite metal oxide nanosphere, joining afterwards shitosan is dissolved in 4% acetum, form sol-gel, again this sol-gel is dropwise injected in 2mol/L NaOH solution and is become single many microballoons that disperse by peristaltic pump, by freeze drying, form Porous Chitosan Microspheres load ZrO
2/ Fe
3o
4metal oxide.
The present invention is with Porous Chitosan Microspheres load ZrO
2/ Fe
3o
4metal oxide is adsorbent, to humic acid pollutants Adsorption in water body, absorption can adopt dynamic process and static process, the water body that the present invention processes is faintly acid or (preferred pH=4 ~ 8, neutral left and right, most preferably 5 ~ 7) containing the micro-polluted water of humic acids, in water body, humic acid initial concentration scope is 5 ~ 150 mg/L, and water temperature is 20 ~ 40 ℃.Porous Chitosan Microspheres load ZrO
2/ Fe
3o
4the concrete grammar that metal oxide is removed humic acid pollutants in water body is: this adsorbent is joined by a certain percentage in the water body that contains humic acids micropollutants, the consumption of adsorbent can regulate as the case may be, preferred adsorbent and micro-polluted water mass ratio are 1:2000 ~ 10000, fully stir 1 ~ 24h, after adsorption equilibrium, under additional magnetic fields, the adsorbent after absorption reclaims, and reaches the object of removing humic acid in water body.
The present invention has following beneficial effect:
Porous Chitosan Microspheres load ZrO2/Fe3O4 metal oxide has well water-soluble, because containing abundant amido, adsorbent is easy to humic acids molecule combination in water body, and the metallic iron on surface and zirconium can produce complexing with humic acid molecule, the synergy of these factors, greatly strengthen the absorption to humic acid, its absorption property is obviously better than other sorbing material.The adsorbance of Porous Chitosan Microspheres load ZrO2/Fe3O4 metal oxide maximum is 194.8mg/g, and polyaniline maximal absorptive capacity is 126.58mg/g, active carbon maximal absorptive capacity, be that 2.51mg/g, amination mesoporous silicon maximal absorptive capacity are that 117.6mg/g, amination polypropylene fibre film maximal absorptive capacity are 16.22mg/g, and this inventive method is simple to operate, with low cost.
Can be under additional magnetic fields after adsorption equilibrium, rapid magnetic is separated, and effectively separation and recovery adsorbent, utilize 0.1mol/L NaOH solution to carry out the desorption of adsorbent, then recycles; And desorption and regeneration rate is 99% for the first time, loop adsorption and desorption regeneration tests, to regenerate after 6 times, desorption and regeneration rate is 80%.
In addition, it is simple that Porous Chitosan Microspheres load ZrO2/Fe3O4 metal oxide adsorbs required equipment for humic acids, and reaction condition is gentle, consuming time short, has better improved production efficiency.Therefore, the present invention is used for removing micropollutant water humic acid pollutants by Porous Chitosan Microspheres load ZrO2/Fe3O4 metal oxide, has good economy and environment benefit.
The specific embodiment
Embodiment 1
By 2.43g diameter, be the Fecl of 100 nm
3.6H
2o joins and in 72ml ethylene glycol solution, fully stirs into clear solution, then transfers in 100ml reactor after adding 6.48g and 1.8g polyethylene glycol, this mixed solution fully to stir 30min, and 200 ℃ of reaction 10h, obtain Fe
3o
4nanosphere Magnetic Isolation, then uses washed with de-ionized water, afterwards, and Fe
3o
4nanosphere is re-dispersed in deionized water, then dropwise adds 12.5ml0.5mol/L ZrOCl
2solution, making the mol ratio of iron oxide and zirconates is 2:1, pH is adjusted to 8,120 ℃ of reaction 2h under nitrogen protection.End product washed with de-ionized water, dries in 60 ℃ of air, obtains ZrO
2/ Fe
3o
4composite metal oxide nanosphere.
A certain amount of shitosan is dissolved in 400ml4% acetum and fully stirs, and the mol ratio that makes iron oxide and acetic acid is 1:7, then by a certain amount of magnetic ZrO
2/ Fe
3o
4composite metal oxide nanosphere joins and in shitosan sol solution, stirs 3h and form collosol and gel, the mass ratio that makes described iron oxide and shitosan is 1:5, again this sol-gel is dropwise injected in 2mol/L NaOH solution and is become single many microballoons that disperse by peristaltic pump, by freeze drying, form Porous Chitosan Microspheres load ZrO
2/ Fe
3o
4metal oxide.
The Porous Chitosan Microspheres load ZrO that this legal system is standby
2/ Fe
3o
4metal oxide sorbents particle size is about the microballoon of 3mm, and BET specific area is 50.2041m
2/ g, mean pore size is 41.7347, total pore volume is 0.052381cm
3/ g, is suitable as adsorbent, chitosan microball load ZrO
2/ Fe
3o
4the intensity of magnetization that metal oxide has is 17.14 emu/g, can be separated fast under outside magnetic field effect.
Above-mentioned synthetic Porous Chitosan Microspheres load ZrO
2/ Fe
3o
4metal oxide is adsorbent, process the micro-polluted water containing humic acid, in closed container, carry out adsorption experiment, 25 ℃ of adsorption temps, adsorption time 24h, humic acid initial concentration is 100ml/L, quantity of sorbent is 1g/L, pH is 6 o'clock, and the adsorbance that records humic acid is 85mg/g, and humic acid clearance is 80%.
Embodiment 2
By 2.43g diameter, be the Fecl of 120 nm
3.6H
2o joins and in 72ml ethylene glycol solution, fully stirs into clear solution, then transfers in 100ml reactor after adding 6.48g and 1.8g polyethylene glycol, this mixed solution fully to stir 30min, and 200 ℃ of reaction 10h, obtain Fe
3o
4nanosphere Magnetic Isolation, then uses washed with de-ionized water, afterwards, and Fe
3o
4nanosphere is re-dispersed in deionized water, then dropwise adds 20ml0.5mol/L ZrOCl
2solution, making the mol ratio of iron oxide and zirconates is 3.2:1, pH is adjusted to 8,120 ℃ of reaction 2h under nitrogen protection, end product washed with de-ionized water, dries in 60 ℃ of air, obtains ZrO
2/ Fe
3o
4composite metal oxide nanosphere.
A certain amount of shitosan is dissolved in 400ml4% acetum and fully stirs, and the mol ratio that makes iron oxide and acetic acid is 1:5, then by a certain amount of magnetic ZrO
2/ Fe
3o
4composite metal oxide nanosphere joins and in shitosan sol solution, stirs 3h and form collosol and gel, the mass ratio that makes described iron oxide and shitosan is 1:7, again this sol-gel is dropwise injected in 2mol/L NaOH solution and is become single many microballoons that disperse by peristaltic pump, by freeze drying, form Porous Chitosan Microspheres load ZrO
2/ Fe
3o
4metal oxide.
The Porous Chitosan Microspheres load ZrO that this legal system is standby
2/ Fe
3o
4metal oxide sorbents particle size is about the microballoon of 2mm, and BET specific area is 72.0028m
2/ g, mean pore size is 46.4354, total pore volume is 0.060255cm
3/ g, is suitable as adsorbent, chitosan microball load ZrO
2/ Fe
3o
4the intensity of magnetization that metal oxide has is 16.81emu/g, can be separated fast under outside magnetic field effect.
Embodiment 3
By 2.43g diameter, be the Fecl of 150 nm
3.6H
2o joins and in 72ml ethylene glycol solution, fully stirs into clear solution, then transfers in 100ml reactor after adding 6.48g and 1.8g polyethylene glycol, this mixed solution fully to stir 30min, and 200 ℃ of reaction 10h, obtain Fe
3o
4nanosphere Magnetic Isolation, then uses washed with de-ionized water, afterwards, and Fe
3o
4nanosphere is re-dispersed in deionized water, then dropwise adds 25ml0.5mol/L ZrOCl
2solution, making the mol ratio of iron oxide and zirconates is 4:1, pH is adjusted to 8,120 ℃ of reaction 2h under nitrogen protection, end product washed with de-ionized water, dries in 60 ℃ of air, obtains ZrO
2/ Fe
3o
4composite metal oxide nanosphere.
A certain amount of shitosan is dissolved in 400ml4% acetum and fully stirs, and the mol ratio that makes iron oxide and acetic acid is 1:9, then by a certain amount of magnetic ZrO
2/ Fe
3o
4composite metal oxide nanosphere joins and in shitosan sol solution, stirs 3h and form collosol and gel, the mass ratio that makes described iron oxide and shitosan is 1:3, again this sol-gel is dropwise injected in 2mol/L NaOH solution and is become single many microballoons that disperse by peristaltic pump, by freeze drying, form Porous Chitosan Microspheres load ZrO
2/ Fe
3o
4metal oxide.
The Porous Chitosan Microspheres load ZrO that this legal system is standby
2/ Fe
3o
4metal oxide sorbents particle size is about the microballoon of 5mm, and BET specific area is 46.8832m
2/ g, mean pore size is 40.2579, total pore volume is 0.04906cm
3/ g, is suitable as adsorbent, chitosan microball load ZrO
2/ Fe
3o
4the intensity of magnetization that metal oxide has is 17.01emu/g, can be separated fast under outside magnetic field effect.
Claims (4)
1. a preparation method for porous chitosan, is characterized in that comprising the steps:
By iron oxide (Fe
3o
4) nano particle is ultrasonic is distributed in deionized water, adds zirconium oxychloride (ZrOCl
2) abundant agitating heating reaction generation ZrO
2/ Fe
3o
4composite metal oxide nanosphere, joining afterwards shitosan is dissolved in 4% acetum, form sol-gel, again this sol-gel is dropwise injected in 2mol/L NaOH solution and is become single many microballoons that disperse by peristaltic pump, by freeze drying, form Porous Chitosan Microspheres load ZrO
2/ Fe
3o
4metal oxide.
2. method according to claim 1, is characterized in that, the diameter of described ferric oxide nanometer particle is 100 ~ 150 nm.
3. method according to claim 1, is characterized in that, the mol ratio of described iron oxide and zirconates is 2 ~ 4:1.
4. method according to claim 1, is characterized in that, the mol ratio of described iron oxide and acetic acid is 1:5 ~ 9.
Method according to claim 1, is characterized in that, the mass ratio of described iron oxide and shitosan is 1:3 ~ 7.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103894159A (en) * | 2014-04-11 | 2014-07-02 | 华东理工大学 | Dye adsorbent capable of effectively removing anions from wastewater and preparation method of dye adsorbent |
| CN103962106A (en) * | 2014-06-03 | 2014-08-06 | 湖南大学 | Method for removing lead in wastewater by virtue of chitosan/humic acid-modified magnetic adsorbent |
| CN108505322A (en) * | 2018-06-05 | 2018-09-07 | 安徽龙安消防工程有限责任公司 | A kind of high temperature resistant fire-fighting quipment and preparation method thereof that fireman uses |
| CN110339818A (en) * | 2019-03-13 | 2019-10-18 | 广西中连智浩科技有限公司 | A kind of preparation method of modified magnetic chitosan absorbent |
| CN111732148A (en) * | 2020-06-29 | 2020-10-02 | 河海大学 | System for retrieve phosphate in follow surface eutrophic water |
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|---|---|---|---|---|
| CN102172498A (en) * | 2011-01-24 | 2011-09-07 | 上海交通大学医学院附属瑞金医院 | Three-dimensional porous chitosan/gelatine microsphere, preparation method thereof and application in liver cell culture |
| CN102614840A (en) * | 2012-04-12 | 2012-08-01 | 南昌航空大学 | Preparation method for magnetic nano material for efficiently removing phosphate radicals and nitrates |
| CN102850576A (en) * | 2012-09-07 | 2013-01-02 | 中国科学技术大学 | Nanometer composite scaffolds assembled by adopting chitosan scaffold, preparation method and applications thereof |
-
2013
- 2013-12-02 CN CN201310626458.3A patent/CN103657601A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102172498A (en) * | 2011-01-24 | 2011-09-07 | 上海交通大学医学院附属瑞金医院 | Three-dimensional porous chitosan/gelatine microsphere, preparation method thereof and application in liver cell culture |
| CN102614840A (en) * | 2012-04-12 | 2012-08-01 | 南昌航空大学 | Preparation method for magnetic nano material for efficiently removing phosphate radicals and nitrates |
| CN102850576A (en) * | 2012-09-07 | 2013-01-02 | 中国科学技术大学 | Nanometer composite scaffolds assembled by adopting chitosan scaffold, preparation method and applications thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103894159A (en) * | 2014-04-11 | 2014-07-02 | 华东理工大学 | Dye adsorbent capable of effectively removing anions from wastewater and preparation method of dye adsorbent |
| CN103962106A (en) * | 2014-06-03 | 2014-08-06 | 湖南大学 | Method for removing lead in wastewater by virtue of chitosan/humic acid-modified magnetic adsorbent |
| CN108505322A (en) * | 2018-06-05 | 2018-09-07 | 安徽龙安消防工程有限责任公司 | A kind of high temperature resistant fire-fighting quipment and preparation method thereof that fireman uses |
| CN110339818A (en) * | 2019-03-13 | 2019-10-18 | 广西中连智浩科技有限公司 | A kind of preparation method of modified magnetic chitosan absorbent |
| CN110339818B (en) * | 2019-03-13 | 2022-12-09 | 广西中连智浩科技有限公司 | Preparation method of modified magnetic chitosan adsorbent |
| CN111732148A (en) * | 2020-06-29 | 2020-10-02 | 河海大学 | System for retrieve phosphate in follow surface eutrophic water |
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Application publication date: 20140326 |