CN105251452A - Chitosan-silica gel hybridized magnetic adsorbent as well as preparation method and application thereof - Google Patents
Chitosan-silica gel hybridized magnetic adsorbent as well as preparation method and application thereof Download PDFInfo
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- CN105251452A CN105251452A CN201510685850.4A CN201510685850A CN105251452A CN 105251452 A CN105251452 A CN 105251452A CN 201510685850 A CN201510685850 A CN 201510685850A CN 105251452 A CN105251452 A CN 105251452A
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Abstract
The invention belongs to the technical field of chitosan applications, and particularly relates to a chitosan-silica gel hybridized magnetic adsorbent as well as a preparation method and an application thereof. The adsorbent comprises chitosan, silica gel, magnetic seeds and a binder in the mass ratio being 1: (4-10): (0.05-0.5): (0.1-3) and is prepared with a method including steps of blending, spray deposition modeling and medium-temperature drying. The chitosan-silica gel hybridized magnetic adsorbent has the advantages of good acid resistance, high mechanical strength, easiness in solid-liquid separation, high adsorption speed, good recyclability and the like. The preparation technological process of the adsorbent is simple, the cost is low, and the adsorbent is environment-friendly and can be applied to harmless utilization and resource utilization of low-concentration heavy metal ions in wastewater.
Description
Technical field
The invention belongs to shitosan applied technical field, particularly a kind of shitosan-silica gel hybridization magnetic adsorbent and its preparation method and application.
Background technology
At present, along with industrial expansion, the industries such as metallurgy, plating, mine, chemical industry produce a large amount of waste water containing heavy metal.Increasing heavy metal enters in natural water body and soil, and works the mischief to human body.Heavy metal pollution of water body to have become in world wide an environmental problem urgently to be resolved hurrily greatly.How to reduce and to control the hot issue that heavy metal pollution is world's field of Environment Protection always.
The kind of heavy metal ions in wastewater, content and existing forms thereof are different with different production kind.The method of removal heavy metal from the aqueous solution conventional at present mainly comprises chemical precipitation method, hyperfiltration, absorption method, membrane separation process, Coagulation Method, ion-exchange, electrochemical process etc.Wherein, absorption method is the most effective and the most widely used method.Compared with other sorbing material, active carbon and chelating resin use more and more extensive in Treatment of Industrial Water, but active carbon and business chelating resin material expensive, cost are too high.Therefore, the shitosan deriving from biomaterial of low cost is considered to the ideal material processing heavy metal wastewater thereby.
Shitosan is a kind of natural biological polymeric compound, in molecule containing much active can with the amino of heavy metal ion generation complexing and hydroxyl, can as the high performance heavy metal capturing agent of one.But, due to shitosan itself exist be insoluble in water, easily swelling, affect the shortcomings such as excessive by pH, make it must carry out suitably modifiedly could being applied in wastewater treatment better.Silica gel has larger specific area, chemical inertness, biocompatibility and heat endurance, by chitosan loaded on silica gel, generating chitosan-silica gel hybridization material, so not only can increase specific area and the proportion of shitosan, also overcome shitosan as other shortcomings existed during adsorbent simultaneously.Meanwhile, adsorbent is magnetic, directly can add wastewater disposal basin and carry out large-area Dynamic Adsorption, also can be used for processing the waste water containing non magnetic solid matter, has expanded the range of application of chitosan-based adsorbent.
The invention provides a kind of shitosan-silica gel hybridization magnetic adsorbent, acid resistance is good, mechanical strength is high, Separation of Solid and Liquid is easy, the rate of adsorption is fast, can be recycled.Simple, the with low cost and environmental friendliness of the preparation process of this adsorbent, can be applicable to the innoxious and resource of low-concentration heavy metal ions in waste water.
Summary of the invention
The object of the present invention is to provide a kind of shitosan-silica gel hybridization magnetic adsorbent and preparation method thereof.For achieving the above object, by the following technical solutions:
A kind of shitosan-silica gel hybridization magnetic adsorbent, described adsorbent is made up of shitosan, silica gel, magnetic kind and binding agent, and the mass ratio of four kinds of compositions is 1:(4-10): (0.05-0.5): (0.1-3).
Further, the deacetylation of described shitosan is 80-95%, and molecular weight is 30-60 ten thousand.
Further, described silica gel is powdery chromatographic silica gel, and granularity is 40-100 order.
Further, described magnetic kind is rare earth magnetic material, natural magnetite or magnetic ferrites.
Further, described binding agent is one or more in glutaraldehyde, epoxychloropropane, tetraethoxysilane, tetramethoxy-silicane, KH-560 silane coupler and KH-570 silane coupler.
The preparation method of shitosan as above-silica gel hybridization magnetic adsorbent, adopts droplet generator jet deposition shaping, comprises the following steps:
(1) pretreatment of raw material: preparation chitosan solution; Silica gel is activated 1-2h in 100-120 DEG C of thermostatic drying chamber, and magnetic kind is finely ground to below 0.043mm;
(2) blended: in the chitosan solution of step (1), to add activated silica gel, magnetic kind and binding agent successively, blended 2-5h; Wherein, the mass ratio of shitosan, activated silica gel, magnetic kind and binding agent is 1:(4-10): (0.05-0.5): (0.1-3);
(3) jet deposition is shaping: blended liquid is by droplet generator injection molding, and deposition, aging 2h in alkali lye, form microballoon;
(4) middle temperature is dried: by shaping microballoon Magneto separate from alkali lye, deionized water is washed, and is dried to moisture-free, obtains shitosan-silica gel hybridization magnetic adsorbent.
In step (1) described chitosan solution, solvent is aqueous formic acid, acetic acid aqueous solution or watery hydrochloric acid, and the mass percent of solute shitosan is 1-5%.
Step (3) described alkali lye is sodium hydroxide solution or potassium hydroxide solution.
The application of shitosan as above-silica gel hybridization magnetic adsorbent in absorption heavy metal ions in wastewater.
Further, the concentration of described heavy metal ion is 5-500mg/L, and described heavy metal ion is one or more in copper, lead, zinc, nickel, cadmium, mercury and chromium.
Further, described shitosan-silica gel hybridization magnetic adsorbent is filled in adsorption column or adsorption tower as Stationary liquid, directly adds wastewater disposal basin, or arranges the grid of filling adsorbent at wastewater outlet, Dynamic Adsorption of Heavy Metal Ions.
The present invention adopts shitosan as the organic functional molecular of Adsorption of Heavy Metal Ions, activated silica gel is as inorganic carrier, and fine grinding magnetic powder, as magnetic kind, is aided with binding agent, by blended-jet deposition shaping-method of middle temperature is dried, obtain a kind spherical adsorbent.
Due to have adsorbing chitosan material in the form of a film uniform load on silica gel particle, adsorbent speed prepared by the present invention is fast, to the absorption of heavy metal ion in solution only 30min can reach capacity, this rate of adsorption is that general polymeric adsorbent is incomparable.
Shitosan prepared by the present invention-silica gel hybridization magnetic adsorbent, using silica gel as central support, has very excellent mechanical strength; There is excellent acid resistance, there is good stability in strong acid solution.
Shitosan prepared by the present invention-silica gel hybridization magnetic adsorbent, has good reproducibility and reusability.To adsorbent wash-out, the regeneration of heavy metal ion be adsorbed, then dry to neutral rear middle temperature with deionized water rinsing, namely reusable.
Shitosan prepared by the present invention-silica gel hybridization magnetic adsorbent, can be conveniently used in the process of low concentration heavy metal-containing waste water, simple to operate, do not cause secondary pollution.This magnetic adsorbent can be used as Stationary liquid and is filled in adsorption column or adsorption tower, Dynamic Adsorption of Heavy Metal Ions, also directly can add wastewater disposal basin or arrange the grid of filling adsorbent at wastewater outlet, can carry out Separation of Solid and Liquid after having adsorbed conveniently by magnetic method.
The preparation method of adsorbent provided by the invention, raw material sources are extensive, preparation technology is simple, with low cost, can be recycled and environmental friendliness, magnetic method solid-liquor separation can be adopted, be easy to commercial Application, can be applicable to the innoxious and resource of low-concentration heavy metal ions in waste water, have a extensive future, there is important economy and environment protection significance.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of shitosan-silica gel hybridization magnetic adsorbent prepared by the embodiment of the present invention 1.
Fig. 2 is the energy spectrogram of shitosan-silica gel hybridization magnetic adsorbent prepared by the embodiment of the present invention 1.
Detailed description of the invention
Embodiment 1
1. shitosan-silica gel hybridization magnetic adsorbent preparation process:
(1) take 4g shitosan, add the acetic acid aqueous solution 100ml that concentration expressed in percentage by volume is 2% wherein, leave standstill after stirring and all dissolve to shitosan, obtain chitosan solution; Taking 30g silica gel (60-100 order), in 110 DEG C of thermostatic drying chambers, activate 2h for subsequent use; Magnetite powder is finely ground to below 0.043mm, takes 0.2g for subsequent use; Measure tetramethoxy-silicane binding agent 2ml for subsequent use;
(2) in the above-mentioned chitosan solution prepared, silica gel, magnetic kind, the binding agent of activation is added successively, blended 4h;
(3) by the blended liquid that mixes by droplet generator injection molding, then proceed in the sodium hydroxide solution of 2mol/L deposit, aging 2h;
(4) with magnet piece, shaping sorbent microspheres is separated from alkali lye, then spends deionized water to neutral, under 50 DEG C of conditions, be dried to moisture-free, obtain shitosan-silica gel hybridization magnetic adsorbent.
2. adsorbent is to Cu
2+static Adsorption:
Get 50ml containing Cu
2+the laboratory obtained aqueous solution of 10.0mg/L, pH value is 5.5, adds 2.0g shitosan-silica gel hybridization magnetic adsorbent.Under the condition of rotating speed 170rpm, temperature 25 DEG C, be placed in gas bath constant-temperature table and adsorb 1h.After absorption terminates, isolate with magnet piece and adsorbed metal biosorption agent, the remaining liquid atomic absorption spectrum after absorption records Cu
2+concentration is 0.26mg/L, reaches discharging standards.
Embodiment 2
1. shitosan-silica gel hybridization magnetic adsorbent preparation process:
(1) take 5g shitosan, add the aqueous formic acid 100ml that concentration expressed in percentage by volume is 2% wherein, leave standstill after stirring and all dissolve to shitosan, obtain chitosan solution; Taking 20g silica gel (60-100 order), in 100 DEG C of thermostatic drying chambers, activate 1h for subsequent use; Magnetite powder is finely ground to below 0.043mm, takes 0.4g for subsequent use; Measure KH-570 binding agent 5ml for subsequent use;
(2) in the above-mentioned chitosan solution prepared, silica gel, magnetic kind, the binding agent of activation is added successively, blended 4h;
(3) by the blended liquid that mixes by droplet generator injection molding, then proceed in the sodium hydroxide solution of 2mol/L deposit, aging 2h;
(4) with magnet piece, shaping sorbent microspheres is separated from alkali lye, then spends deionized water to neutral, under 50 DEG C of conditions, be dried to moisture-free, obtain shitosan-silica gel hybridization magnetic adsorbent.
2. adsorbent is to the process of acid wastewater in mine:
Get 50ml acid wastewater in mine, wherein containing Cu
2+9.11mg/L, Zn
2+250.0mg/L, Pb
2+5.0mg/L, Ni
2+9.6mg/L, then adds 4.0g shitosan-silica gel hybridization magnetic adsorbent.Under the condition of rotating speed 170rpm, temperature 25 DEG C, be placed in gas bath constant-temperature table and adsorb 1h.After absorption terminates, isolate with magnet piece and adsorbed metal biosorption agent, each ion concentration of remaining liquid Atomic Absorption Spectrometry after absorption, measurement result is respectively Cu
2+0.52mg/L, Zn
2+3.34mg/L, Pb
2+0.89mg/L, Ni
2+2.16mg/L, reaches discharging standards.
Embodiment 3
1. shitosan-silica gel hybridization magnetic adsorbent preparation process:
(1) take 3g shitosan, add the acetic acid aqueous solution 100ml that concentration expressed in percentage by volume is 2% wherein, leave standstill after stirring and all dissolve to shitosan, obtain chitosan solution; Taking 20g silica gel (60-100 order), in 120 DEG C of thermostatic drying chambers, activate 1h for subsequent use; Magnetite powder is finely ground to below 0.043mm, takes 0.3g for subsequent use; Measure epoxychloropropane binding agent 4ml for subsequent use;
(2) in the above-mentioned chitosan solution prepared, silica gel, magnetic kind, the binding agent of activation is added successively, blended 4h;
(3) by the blended liquid that mixes by droplet generator injection molding, then proceed in the sodium hydroxide solution of 2mol/L deposit, aging 2h;
(4) with magnet piece, shaping sorbent microspheres is separated from alkali lye, then spends deionized water to neutral, under 50 DEG C of conditions, be dried to moisture-free, obtain shitosan-silica gel hybridization magnetic adsorbent.
2. adsorbent is to Zn
2+absorption:
Get five parts containing Zn
2+for the laboratory obtained aqueous solution 50ml of 325.0mg/L, add 1.0g shitosan-silica gel hybridization magnetic adsorbent.Under the condition of rotating speed 170rpm, temperature 25 DEG C, be placed in gas bath constant-temperature table and adsorb 10min, 20min, 30min, 1h, 4h respectively.After absorption terminates, isolate with magnet piece and adsorbed metal biosorption agent, the remaining liquid atomic absorption spectrum after absorption surveys Zn
2+concentration, calculates the adsorption capacity of adsorbent under each condition.Result of the test is: be respectively the condition of 10min, 20min, 30min, 1h, 4h at adsorption time under, equilibrium adsorption capacities is respectively 9.64mg/g, 10.08mg/g, 10.48mg/g, 10.48mg/g, 10.48mg/g.Result show this adsorbent to the absorption of Zn ion in solution only 30min can reach capacity.
Claims (9)
1. shitosan-silica gel hybridization magnetic adsorbent, it is characterized in that, described adsorbent is made up of shitosan, silica gel, magnetic kind and binding agent, and the mass ratio of four kinds of compositions is 1:(4-10): (0.05-0.5): (0.1-3).
2. shitosan according to claim 1-silica gel hybridization magnetic adsorbent, is characterized in that, the deacetylation of described shitosan is 80-95%, and molecular weight is 30-60 ten thousand; Described silica gel is powdery chromatographic silica gel, and granularity is 40-100 order.
3. shitosan according to claim 1-silica gel hybridization magnetic adsorbent, is characterized in that, described magnetic kind is rare earth magnetic material, natural magnetite or magnetic ferrites.
4. shitosan according to claim 1-silica gel hybridization magnetic adsorbent, it is characterized in that, described binding agent is one or more in glutaraldehyde, epoxychloropropane, tetraethoxysilane, tetramethoxy-silicane, KH-560 silane coupler and KH-570 silane coupler.
5. the preparation method of the shitosan according to any one of claim 1-4-silica gel hybridization magnetic adsorbent, is characterized in that, adopts droplet generator jet deposition shaping, comprises the following steps:
(1) pretreatment of raw material: preparation chitosan solution; Silica gel is activated 1-2h in 100-120 DEG C of thermostatic drying chamber, and magnetic kind is finely ground to below 0.043mm;
(2) blended: in the chitosan solution of step (1), to add activated silica gel, magnetic kind and binding agent successively, blended 2-5h; Wherein, the mass ratio of shitosan, activated silica gel, magnetic kind and binding agent is 1:(4-10): (0.05-0.5): (0.1-3);
(3) jet deposition is shaping: blended liquid is by droplet generator injection molding, and deposition, aging 2h in alkali lye, form microballoon;
(4) middle temperature is dried: by shaping microballoon Magneto separate from alkali lye, deionized water is washed, and is dried to moisture-free, obtains shitosan-silica gel hybridization magnetic adsorbent.
6. preparation method according to claim 5, is characterized in that, in step (1) described chitosan solution, solvent is aqueous formic acid, acetic acid aqueous solution or watery hydrochloric acid, and the mass percent of solute shitosan is 1-5%.
7. the application of the shitosan according to any one of claim 1-4-silica gel hybridization magnetic adsorbent in absorption heavy metal ions in wastewater.
8. application according to claim 7, is characterized in that, the concentration of described heavy metal ion is 5-500mg/L, and described heavy metal ion is one or more in copper, lead, zinc, nickel, cadmium, mercury and chromium.
9. application according to claim 7, it is characterized in that, described shitosan-silica gel hybridization magnetic adsorbent is filled in adsorption column or adsorption tower as Stationary liquid, directly adds wastewater disposal basin, or the grid of filling adsorbent is set at wastewater outlet, Dynamic Adsorption of Heavy Metal Ions.
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| CN106824131A (en) * | 2017-03-01 | 2017-06-13 | 辽宁大学 | A kind of chitosan-modified mesoporous material and its preparation method and application |
| CN106944002A (en) * | 2017-04-15 | 2017-07-14 | 嘉兴德扬生物科技有限公司 | A kind of preparation of compound modified silica gel of end-group alkyne and the application of mercury ion absorption |
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| WO2019085137A1 (en) * | 2017-11-02 | 2019-05-09 | 重庆大学 | Method for preparing multi-group magnetic coagulant and application thereof |
| CN111530434A (en) * | 2020-05-13 | 2020-08-14 | 鲁东大学 | Silica gel adsorbent for adsorbing heavy metal ions and preparation method thereof |
| CN114988542A (en) * | 2022-06-15 | 2022-09-02 | 江苏中电创新环境科技有限公司 | Preparation method of magnetic flocculant for high-speed sedimentation of chemical mixed sludge |
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2015
- 2015-10-21 CN CN201510685850.4A patent/CN105251452B/en not_active Expired - Fee Related
Non-Patent Citations (2)
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| 傅明连等: "磁性壳聚糖微球的制备及其吸附行为研究", 《化工新型材料》 * |
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Cited By (8)
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| CN106824131A (en) * | 2017-03-01 | 2017-06-13 | 辽宁大学 | A kind of chitosan-modified mesoporous material and its preparation method and application |
| CN106824131B (en) * | 2017-03-01 | 2019-04-09 | 辽宁大学 | A kind of chitosan-modified mesoporous material and its preparation method and application |
| CN106944002A (en) * | 2017-04-15 | 2017-07-14 | 嘉兴德扬生物科技有限公司 | A kind of preparation of compound modified silica gel of end-group alkyne and the application of mercury ion absorption |
| WO2019085137A1 (en) * | 2017-11-02 | 2019-05-09 | 重庆大学 | Method for preparing multi-group magnetic coagulant and application thereof |
| CN108795138A (en) * | 2018-05-25 | 2018-11-13 | 安徽华辉塑业科技股份有限公司 | A kind of blue tangerine line waterproof powdery paints applied on electric appliance |
| CN111530434A (en) * | 2020-05-13 | 2020-08-14 | 鲁东大学 | Silica gel adsorbent for adsorbing heavy metal ions and preparation method thereof |
| CN114988542A (en) * | 2022-06-15 | 2022-09-02 | 江苏中电创新环境科技有限公司 | Preparation method of magnetic flocculant for high-speed sedimentation of chemical mixed sludge |
| CN114988542B (en) * | 2022-06-15 | 2023-05-16 | 江苏中电创新环境科技有限公司 | Preparation method of magnetic flocculant for high-speed sedimentation of chemical mixed sludge |
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