CN102827380A - Preparation method for metal ion printing chitosan porous micro-spheres - Google Patents
Preparation method for metal ion printing chitosan porous micro-spheres Download PDFInfo
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Abstract
The invention discloses a preparation method for metal ion printing chitosan porous micro-spheres and belongs to the technical field of parting material preparation. The preparation method comprises the following steps of: using an acetic acid aqueous solution to dissolve chitosan and metal salt to serve as a dispersion phase, using an organic solvent immiscible to water to dissolve a surface active agent and a cross-linking agent to serve as a continuous phase, using a shear action of the continuous phase to disperse the dispersion phase to form micron order liquid drops in microstructural equipment, enabling the liquid drops to complete crosslinking and solidification to form micro-spheres after certain retention time, finally eluting the organic solvent, the surface active agent, uncreated cross-linking agent, the metal ion and the like in the micro-spheres, and drying to obtaining the metal ion printing chitosan porous micro-spheres. The method is simple, convenient and rapid, and prepared metal ion printing chitosan porous micro-spheres are even in size, keep good network structures and effective adsorption position points and have the characteristics of big adsorption capacity, high speed and the like. The preparation method provides an effective means for mass preparation of high-performance metal ion adsorbing materials.
Description
Technical field
The invention belongs to the parting material preparing technical field, be specifically related to the preparation method of a metal ion species blotting chitosan porous microsphere.
Background technology
Along with development of human society, water pollution more and more receives people's attention, and heavy metal contamination is one of maximum pollution of harm.Heavy metal contamination is mainly derived from the discharge of wastewater of chemical industry, plating, non-ferrous metal metallurgy, electronics industry, nuclear industry etc.Heavy metal ion has non-degradable, accumulation and transitivity in water, take in the food and the drinking-water that receive heavy metal contamination, can cause diseases such as angina abdominis, hepatitis, hypertension, peripheral neuropathy, toxic encephalitis and anaemia.Therefore, the heavy metal ion-containing waste water treatment technology of research and development highly economical is very urgent.
Absorption method is to handle the domestic method of effluent containing heavy metal ions, and its key problem in technology is to seek and study reproducible, environment amenable sorbing material.Chitosan becomes ideal biomass sorbing material with its unique characteristic.These characteristics comprise: hydroxyl and amino a large amount of in the chitosan molecule have good reaction activity, can carry out functional group grafting and modification easily; Chitosan possess hydrophilic property, biocompatibility and degradability etc.
Sheet or the little and dense non-porous of pulverous chitosan specific surface area are unfavorable for mass transfer, and it is a well selection that chitosan is processed porous microsphere.The microballoon size that traditional pin hole method prepares is in the millimeter level, and specific surface area is little, compact structure, and mass transfer velocity is slow.And, under acidic conditions, be prone to the shortcoming that dissolving is run off for overcoming chitosan, often adopt the intensity of the method enhancing chitosan microball of chemically crosslinked.For large size, the microballoon that has cured, the local association degree is difficult to control, and guarantee effectively to solidify just needs excessively relatedly, and this can cause crosslinked chitosan microsphere that the adsorptive power of heavy metal ion is significantly reduced.
The introducing of metals ion blotting can reduce amino excessively crosslinked possibility, and then the loading capacity of bigger raising microballoon.But the ion blotting legal system of existing report is equipped with chitosan microball; All be to utilize pin hole that the complex solution of chitosan and metals ion is dripped in the sodium hydroxide solution earlier; Drop solidifies balling-up, again ball is added carry out in the linking agents such as LUTARALDEHYDE, epoxy chloropropane crosslinked.In this process: 1) acid and the sodium hydroxide in the title complex drop neutralizes fast; Cause microsphere volume to be shunk rapidly; It is fine and close that inside becomes, and simultaneously, deformation takes place in contraction process the space structure that forms between amido and metals ion (avtive spot); Cause site activity to weaken, the microballoon adsorptive power descends; When 2) crosslinked because chitosan microball inside is fine and close, and cross-linker molecules is difficult to get into microballoon inside, and it is crosslinked that most of and microsphere surface take place, and finally forms fine and close reticulated structure on the surface, is unfavorable for mass transfer.Therefore develop chitosan porous microsphere technology of preparing and be still a challenging job with high adsorption activity.
Summary of the invention
Problems such as it is complicated to the objective of the invention is to overcome existing preparation process for chitosan microsphere, and pattern is difficult to regulation and control, and monodispersity is poor, and loading capacity is little, and adsorption time is long provide a kind of preparation method of ion blotting chitosan porous microsphere.
The preparation method of one metal ion species blotting chitosan porous microsphere, the method comprising the steps of as follows:
(1) use concentration to obtain disperse phase as the aqueous acetic acid dissolving chitosan of 1-5wt% and the mixture of metal-salt, the concentration of chitosan is 1-4wt% in the disperse phase, and the concentration of metal-salt is 0.1-1wt%;
(2) obtain external phase with organic solvent dissolution tensio-active agent and linking agent, the concentration of linking agent is 1-20wt% in the external phase, surfactant concentrations 1-5wt%;
(3) utilize two constant-flux pumps that above-mentioned disperse phase that makes and external phase are injected Microtraps pore structure or microchannel apparatus; Wherein the flow velocity of continuous phase fluid is 0.1-3.0m/s; The throughput ratio of external phase and disperse phase is 10-100:1; Utilize the shearing action of continuous phase fluid that dispersed phase fluid is dispersed into drop, simultaneously linking agent from external phase to the disperse phase mass transfer;
(4) drop that obtains in above-mentioned (3) is collected in the fixation bath, under the effect of linking agent, accomplished crosslinking curing through 10-120min, temperature of reaction is 25-70
oC obtains chitosan microball;
(5) wash microballoon with acetone or alcohol earlier, from microballoon, remove organic solvent, linking agent and tensio-active agent with water washing again; The metals ion that uses concentration to use as YD 30 (EDTA) the solution removal trace of 0.001M-0.5M then as Hydrogen chloride or the concentration of 0.01M-1M; Again through washing, drying, promptly obtain metals ion blotting chitosan porous microsphere at last.
The molecular weight of chitosan is 3-100 ten thousand described in the step (1), and deacetylation is 70%-100%.
Metal-salt is muriate, acetic acid, nitric acid, sulfuric acid or thiosulphate described in the step (1), and the positively charged ion in the metal-salt is Cu
2+, Co
2+, Ni
2+, Cd
2+, Cr
3+, Zn
2+, Pb
2+, Ag
+, Fe
3+Or Fe
2+
Organic solvent is the Fatty Alcohol(C12-C14 and C12-C18) of C4-C8 described in the step (2).
Tensio-active agent described in the step (2) is sodium lauryl sulphate (SDS), Tween 80 or Span80.
Said linking agent is LUTARALDEHYDE or epoxy chloropropane described in the step (2).
Microtraps hole or microchannel are of a size of 100 μ m-1000 μ m in the step (3).
Method beneficial effect of the present invention is: this method through metals ion trace, micro-fluidic method and linking agent crosslinked unite utilization, a step makes diameter at micron-sized porous chitosan microballoon.Compare and solidify the crosslinked again method of balling-up in the traditional preparation process technology earlier, this method is not only simple, easy handling, and has well kept the space structure and the avtive spot of microballoon, has increased the loading capacity of microballoon greatly.In addition, the microballoon specific surface area is bigger, has further increased the loading capacity of microballoon; Enough hole on the microballoon has greatly shortened absorption and has reached balance time; The introducing of microflow control technique has greatly improved the monodispersity of microballoon, has well realized the regulation and control to the microballoon pattern; The introducing of metals ion engram technology makes microballoon have selectivity preferably to metallic print ion.To sum up, it is complicated that this method has solved existing preparation process for chitosan microsphere, and pattern is difficult to regulation and control, and monodispersity is poor, and loading capacity is little, and adsorption time is long, problems such as poor selectivity.
Description of drawings
Fig. 1 is outward appearance, surface and the section of lead ion blotting chitosan porous microsphere.
Embodiment
To combine accompanying drawing and specific examples that the present invention is done further explanation below.
Embodiment 1
Present embodiment provides a kind of preparation method of lead ion blotting chitosan porous microsphere, and is specific as follows:
(1) 1g chitosan and 1.0g lead chloride are dissolved in the acetum that 100mL concentration is 1wt%, as disperse phase; The n-Octanol solution of Span80 of LUTARALDEHYDE and 1wt% that contains 1wt% is as external phase; Wherein, glutaraldehyde as cross linker, Span80 are tensio-active agent.
(2) utilize two constant-flux pumps that disperse phase that makes in above-mentioned (1) and external phase are injected Microtraps hole equipment, wherein the disperse phase flow is 0.5mL/min, and the external phase flow is 15mL/min, and flow velocity is 1m/s, Microtraps bore dia 200 μ m.
(3) drop that obtains in above-mentioned (2) is collected in the fixation bath, made the further crosslinking curing of drop, the chitosan microball of formation; Wherein, the fixation bath temperature is 25
oC, be 30min set time;
(4) the EDTA solution, deionized water of using acetone, 0.1M respectively are in temperature 20
oThe microballoon that washing above-mentioned (3) obtains under the condition of C is removed metals ion, intact LUTARALDEHYDE and the n-Octanol of unreacted on the microballoon.
(5) microballoon that above-mentioned (4) is obtained obtains the lead ion blotting chitosan microballoon of the about 80 μ m of median size after washing and vacuum-drying, as shown in Figure 1.
Embodiment 2
Present embodiment provides a kind of preparation method of cupric ion blotting chitosan porous microsphere, and is specific as follows:
(1) 2g chitosan and 0.2g copper sulfate are dissolved in the acetum that 100ml concentration is 2wt%, as disperse phase; The n-Octanol solution of Span80 of epoxy chloropropane and 1wt% that contains 10wt% is as external phase; Wherein, epoxy chloropropane is a linking agent, and Span80 is a tensio-active agent.
(2) utilize two constant-flux pumps disperse phase that makes in above-mentioned (1) and external phase to be injected Microtraps hole equipment, the preparation dispersed phase drop; Wherein, the disperse phase flow is 1mL/min, and the external phase flow is 100mL/min, and velocity of shear is 0.1m/s, Microtraps bore dia 400 μ m.
(3) drop that obtains in above-mentioned (2) is collected in the fixation bath, made the further crosslinking curing of drop, form chitosan microball; Wherein, the fixation bath temperature is 30
oC, be 40min set time.
(4) Hydrogen chloride, deionized water of using acetone, 0.1M respectively are in temperature 20
oThe microballoon that washing above-mentioned (3) obtains under the condition of C is removed metals ion, intact epoxy chloropropane and the n-Octanol of unreacted on the microballoon.
(5) microballoon that above-mentioned (4) is obtained obtains the cupric ion blotting chitosan microballoon of the about 400 μ m of mean diameter after washing and lyophilize.
Embodiment 3
Present embodiment provides a kind of preparation method of nickel ion blotting chitosan porous microsphere, and is specific as follows:
(1) 3g chitosan and 0.6g nickelous chloride are dissolved in the acetum that 100ml concentration is 3wt%, as disperse phase; The n-Heptyl alcohol solution of Span80 of epoxy chloropropane and 5wt% that contains 5wt% is as external phase; Wherein, epoxy chloropropane is a linking agent, and Span80 is a tensio-active agent.
(2) utilize the disperse phase and the external phase that make in two constant-flux pumps just above-mentioned (1) to inject Microtraps hole equipment, the preparation dispersed phase drop; Wherein, the disperse phase flow is 1mL/min, and the external phase flow is 30mL/min, and flow velocity is 0.5m/s, Microtraps bore dia 200 μ m.
(3) drop that obtains in above-mentioned (2) is collected in the fixation bath, made the further crosslinking curing of drop, form chitosan microball; Wherein, the fixation bath temperature is 30
oC, be 20min set time;
(4) the EDTA solution, deionized water of using acetone, 0.01M respectively are in temperature 20
oThe microballoon that washing above-mentioned (3) obtains under the condition of C is removed metals ion, intact epoxy chloropropane and the n-Octanol of unreacted on the microballoon.
(5) microballoon that above-mentioned (4) is obtained obtains the nickel ion blotting chitosan microballoon of the about 300 μ m of median size after washing and lyophilize.
Embodiment 4
Present embodiment provides a kind of preparation method of zinc ion imprinted chitosan porous microsphere, and is specific as follows:
(1) 4g chitosan and 0.8g zinc nitrate are dissolved in the acetum that 100ml concentration is 4wt%, as disperse phase; The Pentyl alcohol solution of SDS of epoxy chloropropane and 2wt% that contains 20wt% is as external phase.
(2) utilize the disperse phase and the external phase that make in two constant-flux pumps just above-mentioned (1) to inject Microtraps hole equipment, the preparation dispersed phase drop; Wherein, the disperse phase flow is 1mL/min, and the external phase flow is 10mL/min, and flow velocity is 2.0m/s, Microtraps bore dia 100 μ m.
(3) the chitosan drop that obtains in above-mentioned (2) is collected in the fixation bath, made the further crosslinking curing of drop, form the micron order chitosan microball; Wherein, the fixation bath temperature is 35
oC, be 30min set time.
(4) the EDTA solution, deionized water of using acetone, 0.4M respectively are in temperature 20
oThe microballoon that washing above-mentioned (3) obtains under the condition of C is removed metals ion, intact epoxy chloropropane and the Pentyl alcohol of unreacted on the microballoon.
(5) microballoon that above-mentioned (4) is obtained obtains the zinc ion imprinted chitosan microball of the about 200 μ m of median size after washing and lyophilize.
Embodiment 5
Present embodiment provides a kind of preparation method of chromium ion blotting chitosan porous microsphere, and is specific as follows:
(1) 4g chitosan and 1.0g chromium chloride are dissolved in the acetum that 100ml concentration is 5wt%, as disperse phase; The n-hexyl alcohol solution of Tween 80 of LUTARALDEHYDE and 2wt% that contains 20wt% is as external phase.
(2) utilize the disperse phase and the external phase that make in two constant-flux pumps just above-mentioned (1) to inject the microchannel, the preparation dispersed phase drop; Wherein, the disperse phase flow is 2mL/min, and the external phase flow is 100mL/min, and flow velocity is 3.0m/s, Microtraps bore dia 200 μ m.
(3) the chitosan drop that obtains in above-mentioned (2) is collected in the fixation bath, made the drop crosslinking curing, form the micron order chitosan microball; Wherein, the fixation bath temperature is 45
oC, be 10min set time;
(4) the EDTA solution, deionized water of using acetone, 0.05M respectively are in temperature 30
oThe microballoon that washing above-mentioned (3) obtains under the condition of C is removed metals ion, intact LUTARALDEHYDE and the n-Octanol of unreacted on the microballoon.
(5) microballoon that above-mentioned (4) is obtained obtains the chromium ion blotting chitosan microballoon of the about 200 μ m of median size after washing and lyophilize.
Embodiment 6
Present embodiment provides a kind of preparation method of cadmium ion blotting chitosan porous microsphere, and is specific as follows:
(1) 2g chitosan and 0.5g cadmium nitrate are dissolved in the acetum that 100mL concentration is 2wt%, as disperse phase; The butanol solution of Tween 80 of epoxy chloropropane and 2wt% that contains 20wt% is as external phase.
(2) utilize the disperse phase and the external phase that make in two constant-flux pumps just above-mentioned (1) to inject the microchannel, the preparation dispersed phase drop; Wherein, the disperse phase flow is 2mL/min, and the external phase flow is 60mL/min, and flow velocity is 1.5m/s, Microtraps bore dia 1000 μ m.
(3) drop that obtains in above-mentioned (2) is collected in the fixation bath, made the drop crosslinking curing, form chitosan microball; Wherein, the fixation bath temperature is 55 ℃, and be 120min set time;
(4) the EDTA solution, deionized water of using acetone, 0.5M respectively are in temperature 20
oThe microballoon that washing above-mentioned (3) obtains under the condition of C is removed metals ion, intact epoxy chloropropane and the Pentyl alcohol of unreacted on the microballoon.
(5) microballoon that above-mentioned (4) is obtained obtains the cadmium ion blotting chitosan microballoon of the about 600 μ m of median size after washing and lyophilize.
Claims (7)
1. the preparation method of a metal ion species blotting chitosan porous microsphere is characterized in that, the method comprising the steps of as follows:
(1) use concentration to obtain disperse phase as the aqueous acetic acid dissolving chitosan of 1-5wt% and the mixture of metal-salt, the concentration of chitosan is 1-4wt% in the disperse phase, and the concentration of metal-salt is 0.1-1wt%;
(2) obtain external phase with organic solvent dissolution tensio-active agent and linking agent, the concentration of linking agent is 1-20wt% in the external phase, surfactant concentrations 1-5wt%;
(3) utilize two constant-flux pumps that above-mentioned disperse phase that makes and external phase are injected Microtraps pore structure or microchannel apparatus; Wherein the flow velocity of continuous phase fluid is 0.1-3.0m/s; The throughput ratio of external phase and disperse phase is 10-100:1; Utilize the shearing action of continuous phase fluid that dispersed phase fluid is dispersed into drop, simultaneously linking agent from external phase to the disperse phase mass transfer;
(4) drop that obtains in above-mentioned (3) is collected in the fixation bath, under the effect of linking agent, accomplished crosslinking curing through 10-120min, temperature of reaction is 25-70
oC obtains chitosan microball;
(5) wash microballoon with acetone or alcohol earlier, from microballoon, remove organic solvent, linking agent and tensio-active agent with water washing again; The metals ion that uses concentration to use as the EDTA solution removal trace of 0.001M-0.5M then as Hydrogen chloride or the concentration of 0.01M-1M; Again through washing, drying, promptly obtain metals ion blotting chitosan porous microsphere at last.
2. preparation method according to claim 1 is characterized in that, the molecular weight of chitosan is 3-100 ten thousand described in the step (1), and deacetylation is 70%-100%.
3. preparation method according to claim 1 is characterized in that, metal-salt is muriate, acetic acid, nitric acid, sulfuric acid or thiosulphate described in the step (1), and the positively charged ion in the metal-salt is Cu
2+, Co
2+, Ni
2+, Cd
2+, Cr
3+, Zn
2+, Pb
2+, Ag
+, Fe
3+Or Fe
2+
4. preparation method according to claim 1 is characterized in that, organic solvent is the Fatty Alcohol(C12-C14 and C12-C18) of C4-C8 described in the step (2).
5. preparation method according to claim 1 is characterized in that, tensio-active agent described in the step (2) is SDS, Tween 80 or Span80.
6. preparation method according to claim 1 is characterized in that, said linking agent is LUTARALDEHYDE or epoxy chloropropane described in the step (2).
7. preparation method according to claim 1 is characterized in that, Microtraps hole or microchannel are of a size of 100 μ m-1000 μ m in the step (3).
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Cited By (11)
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|---|---|---|---|---|
| CN105170107A (en) * | 2015-10-16 | 2015-12-23 | 西安科技大学 | Preparation method for green heavy metal capturing agent |
| CN106861663A (en) * | 2017-03-06 | 2017-06-20 | 华东理工大学 | A kind of micro-fluidic synthesis trace adsorbent for copper-containing wastewater treatment |
| CN108816205A (en) * | 2018-07-09 | 2018-11-16 | 莆田学院 | A kind of preparation method of nickel ion imprinted crosslinked chitosan microballoon |
| CN108816204A (en) * | 2018-07-09 | 2018-11-16 | 莆田学院 | A kind of preparation method of copper ion imprinted crosslinked chitosan microballoon |
| CN108918613A (en) * | 2018-06-22 | 2018-11-30 | 江苏大学 | Based on gold nanoparticle/graphite alkene/chitosan trace cadmium ion electrochemical sensor, preparation method and its usage |
| CN109293976A (en) * | 2018-11-16 | 2019-02-01 | 武汉工程大学 | A kind of preparation method of Porous Chitosan Microspheres |
| CN109603766A (en) * | 2018-12-18 | 2019-04-12 | 黑龙江大学 | A kind of preparation method and its removal anionic surfactant of chitosan microball |
| CN109967050A (en) * | 2019-03-21 | 2019-07-05 | 海南大学 | A kind of Thermo-sensitive ion blotting adsorbent material and its preparation method and application based on polysaccharide |
| CN112169756A (en) * | 2020-09-29 | 2021-01-05 | 四川大学 | Microporous granular carbon and preparation method thereof |
| CN114669746A (en) * | 2022-03-07 | 2022-06-28 | 合肥工业大学 | Preparation method of porous metal microspheres for 3D printing |
| CN115007114A (en) * | 2022-06-02 | 2022-09-06 | 嘉兴学院 | Chitosan/gelatin composite microsphere and preparation method and application thereof |
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| CN105170107B (en) * | 2015-10-16 | 2017-11-07 | 西安科技大学 | A kind of preparation method of green heavy metal chelating agent |
| CN106861663A (en) * | 2017-03-06 | 2017-06-20 | 华东理工大学 | A kind of micro-fluidic synthesis trace adsorbent for copper-containing wastewater treatment |
| CN108918613A (en) * | 2018-06-22 | 2018-11-30 | 江苏大学 | Based on gold nanoparticle/graphite alkene/chitosan trace cadmium ion electrochemical sensor, preparation method and its usage |
| CN108816205A (en) * | 2018-07-09 | 2018-11-16 | 莆田学院 | A kind of preparation method of nickel ion imprinted crosslinked chitosan microballoon |
| CN108816204A (en) * | 2018-07-09 | 2018-11-16 | 莆田学院 | A kind of preparation method of copper ion imprinted crosslinked chitosan microballoon |
| CN109293976A (en) * | 2018-11-16 | 2019-02-01 | 武汉工程大学 | A kind of preparation method of Porous Chitosan Microspheres |
| CN109293976B (en) * | 2018-11-16 | 2021-06-01 | 武汉工程大学 | Preparation method of porous chitosan microspheres |
| CN109603766A (en) * | 2018-12-18 | 2019-04-12 | 黑龙江大学 | A kind of preparation method and its removal anionic surfactant of chitosan microball |
| CN109967050A (en) * | 2019-03-21 | 2019-07-05 | 海南大学 | A kind of Thermo-sensitive ion blotting adsorbent material and its preparation method and application based on polysaccharide |
| CN112169756A (en) * | 2020-09-29 | 2021-01-05 | 四川大学 | Microporous granular carbon and preparation method thereof |
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| CN115007114A (en) * | 2022-06-02 | 2022-09-06 | 嘉兴学院 | Chitosan/gelatin composite microsphere and preparation method and application thereof |
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