CN102649045A - Method for preparing attapulgite clay composite gel adsorption microsphere by spray drying - Google Patents
Method for preparing attapulgite clay composite gel adsorption microsphere by spray drying Download PDFInfo
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- CN102649045A CN102649045A CN2011100468200A CN201110046820A CN102649045A CN 102649045 A CN102649045 A CN 102649045A CN 2011100468200 A CN2011100468200 A CN 2011100468200A CN 201110046820 A CN201110046820 A CN 201110046820A CN 102649045 A CN102649045 A CN 102649045A
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- attapulgite clay
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- plural gel
- microballoon
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Abstract
The invention discloses a method for preparing an attapulgite clay composite gel adsorption microsphere by spray drying. The method comprises the following steps of: preparing attapulgite clay and chitosan or chitosan derivative into suspension and gel solution respectively; adding the attapulgite clay suspension into the chitosan or chitosan derivative gel solution; adding a cross-linking agent; reacting at room temperature for 1-4 hours; and preparing the composite gel adsorption microsphere by a spray drying method. The prepared composite gel adsorption microsphere has the advantages of simple process, large specific surface and high adsorption and can be applied to the fields of wastewater treatment, drug slow release and the like.
Description
Technical field
The present invention relates to a kind of preparation method of attapulgite clay plural gel absorption microballoon.Be specially and adopt spray drying method for preparation plural gel absorption microballoon, belong to nonmetallic ore deep processing field.
Background technology
Adsorption separation technology has obtained extensive use aspect water pollution control, but the adsorbent that generally uses at present or cost an arm and a leg, select adsorptivity poor, or adsorbance is little, non-renewable and environment is unfriendly.How can reach the wastewater treatment purpose, to utilize again by secondary again, become the focus of present concern.Therefore, exploitation cheapness, environmental friendliness and the water treatment absorbent that utilizes again will be important directions of absorption research.
In numerous material for water treatment exploitations, organic/inorganic composite material has received great concern in recent years.After discovering that clay and macromolecular material are compound, have the not available property of clay, combination property is greatly improved.So, clay and vinyl monomer are carried out polymerization exploitation compound water treatment adsorbent become present important development direction.
Compound adsorbent mainly is to adopt the solution polymerization process preparation at present, and the colloid that is synthesized will pass through steps such as prebake, granulation and oven dry just can obtain product, and the process energy consumption is higher, and handling procedure is numerous and diverse.How to realize that one-step method prepares that organic-inorganic is compound to attach agent, directly obtaining pelletized product after the finishing polymerization is desired destination.For this reason, we go on foot to have prepared through aqueous solution dispersin polymerization one has the compound absorption microballoon of three-dimensional net structure granular organic and inorganic (CN101664666), but finds that in the process of industrialization technology is succinct not enough.Therefore, seek simple and convenient preparation method and become the important directions that can the compound absorption microballoon of organic-inorganic be used.
Spray-drying is to utilize droplet rapid dry balling-up under the effect of hot-air of atomizing.The method can make microballoon have good flowability through the moment volatilization of solvent; And can control the size of microballoon through the different parameters in the control procedure, for example the pressure of the speed of the size of nozzle, spraying, atomizing, the temperature that gets into air and crosslinking degree etc.The spray drying process technical process is simple, and a step balling-up need not microballoon is carried out post processing, is fit to large-scale commercial production.
Summary of the invention
In view of plural gel absorption microballoon in the prior art prepares existing problem, the purpose of this invention is to provide a kind of low cost, plural gel absorption method for preparing microsphere that serviceability is good.
Principle of the present invention is to utilize the gel-forming property of linear polymer chitosan of cation and derivative thereof; Interact with attapulgite clay with cation interchangeability; Under formaldehyde or glutaraldehyde effect; Utilize schiff base reaction,, form plural gel absorption microballoon with three-dimensional net structure through spray drying process.For this reason, we have selected the attapulgite clay of unique properties for use, and shitosan or chitosan derivatives be raw material, with formaldehyde or glutaraldehyde as cross linker, and the attapulgite clay base plural gel absorption microballoon that adopted spray drying method for preparation.
The present invention at first processes suspension and gel solution respectively with attapulgite clay and shitosan or chitosan derivatives; Then attapulgite clay suspension is added in shitosan or the chitosan derivative gel solution; Add crosslinking agent again; After at room temperature reacting 1～4 hour, make plural gel absorption microballoon through spray drying process.
A kind of spray-drying prepares the method for attapulgite clay plural gel absorption microballoon, it is characterized in that this method prepares through the following step successively:
The preparation of A attapulgite clay suspension: under stirring, attapulgite clay is added in the entry, process the suspension of concentration at 5-15wt%;
The preparation of B gel solution: under stirring, shitosan or chitosan derivatives are dissolved in the acetic acid solution, process shitosan or chitosan derivative gel solution that concentration is 1-5wt%;
The preparation of C plural gel liquid: under stirring, attapulgite clay suspension is added in shitosan or the chitosan derivative gel solution, add crosslinking agent formaldehyde or glutaraldehyde again after continuing to stir 30-60min, at room temperature reacted 1～4 hour;
The preparation of D plural gel absorption microballoon: with above-mentioned plural gel liquid; Is under the 10-15mL/min condition at inlet temperature 140-160 ℃ with feed rate; Adopt spray drying process to make plural gel absorption microballoon, the average grain diameter of plural gel absorption microballoon is 1～20 μ m.
Attapulgite clay is a kind of chain layer silicate mineral that contains Shuifu County's magnalium, has the duct of numerous nanoscales that are parallel to each other, and is natural monodimension nanometer material.Adopt high-speed stirred can make attapulgite clay form steady suspension.
Chitosan derivatives is a kind of in CMC, hydroxyethyl chitosan, the succinyl-chitosan or two kinds.
The mass ratio 1-5% of crosslinking agent and attapulgite clay.
The present invention is a raw material with attapulgite clay and shitosan or chitosan derivatives, with formaldehyde or glutaraldehyde as cross linker, adopts the attapulgite clay base plural gel absorption microballoon of spray drying method for preparation, has the following advantages:
1, the three-dimensional network microballoon that utilizes shitosan and derivative thereof and attapulgite clay to construct has the big and good advantage of absorption property of specific area, can be used for the absorption and the recovery of the dye of positive ion, heavy metal ion and ammonia nitrogen waste water.
2, adopt spray drying process technology simple, process is easy to control, the plural gel absorption microballoon homogeneous grain diameter that makes, constant product quality.Can be according to different demands, through regulating jet size, the plural gel absorption microballoon of preparation different-grain diameter.
3, the three-dimensional network microballoon that adopts crosslinking agent to construct has good mechanical strength and chemical stability, through the control cross-linked dosage, realizes the reusable of microballoon.
The specific embodiment
Embodiment 1
Under 1000 rev/mins, attapulgite clay is added in the entry, be mixed with the suspension that attapulgite clay concentration is 7wt%; Under 1000 rev/mins, shitosan is dissolved in the acetic acid solution of 1wt%, be mixed with the gel solution that chitosan concentration is 3wt%.Under 2500 rev/mins, attapulgite clay suspension is joined in the chitosan gel rubber solution, the mass ratio of adding and attapulgite clay is 2% formaldehyde behind the continuation stirring 30min, at room temperature reacts 2h.With above-mentioned plural gel liquid, be under the 12mL/min condition with feed rate for 150 ℃ in inlet temperature, adopt spray drying process to make plural gel absorption microballoon, the average grain diameter of plural gel absorption microballoon is at 2～5 μ m.
Embodiment 2
Under 1000 rev/mins, attapulgite clay is added in the entry, be mixed with the suspension that attapulgite clay concentration is 10wt%; Under 1000 rev/mins, CMC is dissolved in the acetic acid solution of 1wt%, be mixed with the gel solution that chitosan concentration is 2wt%.Under 2500 rev/mins, attapulgite clay suspension is joined in the CMC gel solution, the mass ratio of adding and attapulgite clay is 2% formaldehyde behind the continuation stirring 40min, at room temperature reacts 2h.With above-mentioned plural gel liquid, be under the 12mL/min condition with feed rate for 150 ℃ in inlet temperature, adopt spray drying process to make plural gel absorption microballoon, the average grain diameter of plural gel absorption microballoon is at 2～4 μ m.
Embodiment 3
Under 1000 rev/mins, attapulgite clay is added in the entry, be mixed with the suspension that attapulgite clay concentration is 12wt%; Under 1000 rev/mins, CMC is dissolved in the acetic acid solution of 1wt%, be mixed with the gel solution that chitosan concentration is 2wt%.Under 2500 rev/mins, attapulgite clay suspension is joined in the CMC gel solution, the mass ratio of adding and attapulgite clay is 1.5% glutaraldehyde behind the continuation stirring 40min, at room temperature reacts 3h.With above-mentioned plural gel liquid, be under the 13mL/min condition with feed rate for 155 ℃ in inlet temperature, adopt spray drying process to make plural gel absorption microballoon, the average grain diameter of plural gel absorption microballoon is at 4～8 μ m.
Embodiment 4
Under 1000 rev/mins, attapulgite clay is added in the entry, be mixed with the suspension that attapulgite clay concentration is 8wt%; Under 1000 rev/mins, succinyl-chitosan is dissolved in the acetic acid solution of 1wt%, be mixed with the gel solution that succinyl-chitosan concentration is 5wt%.Under 2500 rev/mins, attapulgite clay suspension is joined in the succinyl-chitosan gel solution, the mass ratio of adding and attapulgite clay is 1.5% glutaraldehyde behind the continuation stirring 40min, at room temperature reacts 2h.With above-mentioned plural gel liquid, be under the 12mL/min condition with feed rate for 150 ℃ in inlet temperature, adopt spray drying process to make plural gel absorption microballoon, the average grain diameter of plural gel absorption microballoon is at 5～7 μ m.
Embodiment 5
Under 1000 rev/mins, attapulgite clay is added in the entry, be mixed with the suspension that attapulgite clay concentration is 12wt%; Under 1000 rev/mins, hydroxyethyl chitosan is dissolved in the acetic acid solution of 1wt%, be mixed with the gel solution that hydroxyethyl chitosan concentration is 4wt%.Under 2500 rev/mins, attapulgite clay suspension is joined in the hydroxyethyl chitosan gel solution, the mass ratio of adding and attapulgite clay is 1% glutaraldehyde behind the continuation stirring 40min, at room temperature reacts 3h.With above-mentioned plural gel liquid, be under the 12mL/min condition with feed rate for 150 ℃ in inlet temperature, adopt spray drying process to make plural gel absorption microballoon, the average grain diameter of plural gel absorption microballoon is at 8～12 μ m.
Claims (3)
1. a spray-drying prepares the method that the attapulgite clay plural gel adsorbs microballoon, it is characterized in that this method prepares through the following step successively:
The preparation of A attapulgite clay suspension: under stirring, attapulgite clay is added in the entry, process the suspension of concentration at 5-15wt%;
The preparation of B gel solution: under stirring, shitosan or chitosan derivatives are dissolved in the acetic acid solution, process shitosan or chitosan derivative gel solution that concentration is 1-5wt%;
The preparation of C plural gel liquid: under stirring, attapulgite clay suspension is added in shitosan or the chitosan derivative gel solution, add crosslinking agent formaldehyde or glutaraldehyde again after continuing to stir 30-60min, at room temperature reacted 1～4 hour;
The preparation of D plural gel absorption microballoon: with above-mentioned plural gel liquid; Is under the 10-15mL/min condition at inlet temperature 140-160 ℃ with feed rate; Adopt spray drying process to make plural gel absorption microballoon, the average grain diameter of plural gel absorption microballoon is 1～20 μ m.
2. the method for claim 1 is characterized in that chitosan derivatives is a kind of in CMC, hydroxyethyl chitosan, the succinyl-chitosan or two kinds.
3. method as claimed in claim 1 is characterized in that the mass ratio 1-5% of crosslinking agent and attapulgite clay.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274509A (en) * | 2013-05-27 | 2013-09-04 | 天津市金鳞水处理科技有限公司 | Preparation method of composite flocculant capable of adsorbing heavy metal ions and composite flocculant product through |
| CN105642233A (en) * | 2016-01-06 | 2016-06-08 | 河南工业大学 | Method for preparing CMC/GO compound hydrogel microspheres by virtue of continuous method |
| CN106861644A (en) * | 2017-03-13 | 2017-06-20 | 苏州顶裕生物科技有限公司 | A kind of attapulgite loaded chitosan absorbent and preparation method thereof |
| CN109158058A (en) * | 2018-09-11 | 2019-01-08 | 淮阴工学院 | Recessed soil-chitosan plural gel and preparation method thereof |
| CN109942904A (en) * | 2019-02-28 | 2019-06-28 | 淮阴工学院 | A kind of attapulgite clay compounded chitosan gel rubber and preparation method thereof |
| CN110935406A (en) * | 2019-11-29 | 2020-03-31 | 中国石油大学(华东) | High-strength polysaccharide-nano-laponite composite microsphere and preparation method thereof |
| CN111282551A (en) * | 2020-02-14 | 2020-06-16 | 兰州大学 | Preparation method of ethylenediamine tetraacetic acid modified magnetic attapulgite-chitosan microspheres |
| CN111973751A (en) * | 2020-09-01 | 2020-11-24 | 湖北民族大学 | Chitosan composite microsphere and drug-loaded microsphere as well as preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337678A (en) * | 2008-08-08 | 2009-01-07 | 淮阴工学院 | Simple high-performance modification process for attapulgite clay |
| CN101347719A (en) * | 2008-09-10 | 2009-01-21 | 华南师范大学 | Chitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent and preparation method thereof |
-
2011
- 2011-02-24 CN CN2011100468200A patent/CN102649045A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337678A (en) * | 2008-08-08 | 2009-01-07 | 淮阴工学院 | Simple high-performance modification process for attapulgite clay |
| CN101347719A (en) * | 2008-09-10 | 2009-01-21 | 华南师范大学 | Chitosan/sheet silicate nano compound stephanoporate crosslinked microsphere sorbent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 殷竟洲等: "壳聚糖改性凹凸棒土对重金属离子的吸附", 《化工环保》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274509A (en) * | 2013-05-27 | 2013-09-04 | 天津市金鳞水处理科技有限公司 | Preparation method of composite flocculant capable of adsorbing heavy metal ions and composite flocculant product through |
| CN105642233A (en) * | 2016-01-06 | 2016-06-08 | 河南工业大学 | Method for preparing CMC/GO compound hydrogel microspheres by virtue of continuous method |
| CN105642233B (en) * | 2016-01-06 | 2018-09-14 | 河南工业大学 | A kind of method that continuity method prepares CMC/GO composite hydrogel microballoons |
| CN106861644A (en) * | 2017-03-13 | 2017-06-20 | 苏州顶裕生物科技有限公司 | A kind of attapulgite loaded chitosan absorbent and preparation method thereof |
| CN109158058A (en) * | 2018-09-11 | 2019-01-08 | 淮阴工学院 | Recessed soil-chitosan plural gel and preparation method thereof |
| CN109942904A (en) * | 2019-02-28 | 2019-06-28 | 淮阴工学院 | A kind of attapulgite clay compounded chitosan gel rubber and preparation method thereof |
| CN110935406A (en) * | 2019-11-29 | 2020-03-31 | 中国石油大学(华东) | High-strength polysaccharide-nano-laponite composite microsphere and preparation method thereof |
| CN111282551A (en) * | 2020-02-14 | 2020-06-16 | 兰州大学 | Preparation method of ethylenediamine tetraacetic acid modified magnetic attapulgite-chitosan microspheres |
| CN111973751A (en) * | 2020-09-01 | 2020-11-24 | 湖北民族大学 | Chitosan composite microsphere and drug-loaded microsphere as well as preparation method and application thereof |
| CN111973751B (en) * | 2020-09-01 | 2023-10-10 | 湖北民族大学 | Chitosan composite microsphere and drug-loaded microsphere as well as preparation methods and application thereof |
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Application publication date: 20120829 |