CN105251452B - A kind of chitosan-silica gel hybridization magnetic adsorbent and its preparation method and application - Google Patents
A kind of chitosan-silica gel hybridization magnetic adsorbent and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to chitosan applied technical field, more particularly to a kind of chitosan-silica gel hybridization magnetic adsorbent and its preparation method and application.The adsorbent is made of chitosan, silica gel, magnetic kind and binder, and the mass ratio of four kinds of ingredients is 1:(4-10)：(0.05-0.5)：(0.1-3)；It is prepared by the method for blending-jet deposition molding-middle temperature is dried.Chitosan of the present invention-silica gel hybridization magnetic adsorbent has many advantages, such as that good acid resistance, high mechanical strength, separation of solid and liquid is easy, the rate of adsorption is fast, recycling is good.The preparation process of adsorbent is simple, of low cost and environmental-friendly, can be applied to the innoxious and recycling of low-concentration heavy metal ions in waste water.
Description
Technical field
The invention belongs to chitosan applied technical field, more particularly to a kind of chitosan-silica gel hybridization magnetic adsorbent and
Preparation method and application.
Background technology
Currently, with the development of industry, the industries such as metallurgy, plating, mine, chemical industry generate the largely waste water containing heavy metal.
More and more heavy metals enter in natural water body and soil, and do harm to huamn body.Heavy metal pollution of water body has become
A big environmental problem urgently to be resolved hurrily in world wide.How to reduce and control heavy metal pollution is always world's field of environment protection
Hot issue.
Type, content and its existing forms of heavy metal ions in wastewater are different with different production types.It is currently used
Go the methods of removing heavy metals from aqueous solution mainly and include chemical precipitation method, hyperfiltration, absorption method, membrane separation process, Coagulation Method,
Ion-exchange, electrochemical process etc..Wherein, absorption method is most effective and most widely used method.With other sorbing material phases
Than, activated carbon and chelating resin using more and more extensive in Treatment of Industrial Water, but activated carbon and business chelating resin material are high
It is expensive, cost is too high.Therefore, the inexpensive chitosan from biomaterial is considered as the ideal material for handling heavy metal wastewater thereby
Material.
Chitosan is a kind of natural biological polymeric compound, in molecule containing it is many it is active can with heavy metal from
The amino and hydroxyl that son is complexed, can be used as a kind of high performance heavy metal capturing agent.But due to chitosan sheet
Be insoluble in existing for body water, easily swelling, by pH influenced the shortcomings of excessive, make its have to carry out it is appropriate it is modified could preferably
Applied in wastewater treatment.Silica gel has larger specific surface area, chemical inertness, biocompatibility and thermal stability, and shell is gathered
Sugar is carried on silica gel, is generated chitosan-silica gel hybridization material, not only can be increased the specific surface area and ratio of chitosan
Again, existing other shortcomings when while also overcoming chitosan as adsorbent.Meanwhile adsorbent is magnetic, can directly be added
Enter the Dynamic Adsorption that wastewater disposal basin carries out large area, it can also be used to which waste water of the processing containing non magnetic solid matter has expanded chitosan
The application range of base adsorbent.
The present invention provides a kind of chitosan-silica gel hybridization magnetic adsorbent, and acid resistance is good, high mechanical strength, separation of solid and liquid
It is easy, the rate of adsorption is fast, can be recycled.The preparation process of the adsorbent is simple, of low cost and environmental-friendly, can answer
Innoxious and recycling for low-concentration heavy metal ions in waste water.
Invention content
The purpose of the present invention is to provide a kind of chitosan-silica gel hybridization magnetic adsorbents and preparation method thereof.To realize
Above-mentioned purpose, using following technical scheme：
A kind of chitosan-silica gel hybridization magnetic adsorbent, the adsorbent is by chitosan, silica gel, magnetic kind and binder group
At the mass ratio of four kinds of ingredients is 1:(4-10)：(0.05-0.5)：(0.1-3).
Further, the deacetylation of the chitosan is 80-95%, and molecular weight is 30-60 ten thousand.
Further, the silica gel is powdery chromatographic silica gel, and granularity is 40-100 mesh.
Further, the magnetic kind is rare earth magnetic material, natural magnetite or magnetic ferrites.
Further, the binder is glutaraldehyde, epoxychloropropane, tetraethoxysilane, tetramethoxy-silicane, KH-
One or more in 560 silane coupling agents and KH-570 silane coupling agents.
The preparation method of chitosan-silica gel hybridization magnetic adsorbent as described above, using droplet generator jet deposition
Molding, includes the following steps：
(1) pretreatment of raw material：Prepare chitosan solution；Silica gel is activated into 1-2h, magnetic in 100-120 DEG C of thermostatic drying chamber
Kind is finely ground to 0.043mm or less；
(2) it is blended：Activated silica gel, magnetic kind and binder are sequentially added into the chitosan solution of step (1), and 2- is blended
5h；Wherein, the mass ratio of chitosan, activated silica gel, magnetic kind and binder is 1:(4-10)：(0.05-0.5)：(0.1-3)；
(3) jet deposition is molded：By droplet generator injection molding, deposition, aging 2h in lye are formed blended liquid
Microballoon；
(4) middle temperature is dried：Magneto separate, deionized water washing from lye by molding microballoon, and dry to moisture-free,
Obtain chitosan-silica gel hybridization magnetic adsorbent.
In step (1) described chitosan solution, solvent is aqueous formic acid, acetic acid aqueous solution or dilute hydrochloric acid, and solute shell is poly-
The mass percent of sugar is 1-5%.
Step (3) described lye is sodium hydroxide solution or potassium hydroxide solution.
Application of the chitosan-silica gel hybridization magnetic adsorbent in terms of adsorbing heavy metal ions in wastewater as described above.
Further, a concentration of 5-500mg/L of the heavy metal ion, the heavy metal ion be copper, lead, zinc, nickel,
One or more in cadmium, mercury and chromium.
Further, the chitosan-silica gel hybridization magnetic adsorbent is filled in adsorption column or adsorption tower as stationary phase,
It is directly added into wastewater disposal basin, or the grid of filling adsorbent, Dynamic Adsorption of Heavy Metal Ions are set in wastewater outlet.
Organic functional molecular of the present invention using chitosan as absorption heavy metal ion, activated silica gel are used as without airborne
Body, fine grinding magnetic powder are aided with binder as magnetic kind, by the method for blending-jet deposition molding-middle temperature is dried, obtain
A kind of spherical adsorbent.
Since for uniform load on silica gel particle, prepared by the present invention in the form of a film for the chitosan material with suction-operated
The adsorbent rate of adsorption it is fast, i.e., saturation can reach to the absorption only 30min of heavy metal ion in solution, this rate of adsorption is
General absorption resin is incomparable.
Chitosan prepared by the present invention-silica gel hybridization magnetic adsorbent, the supporter centered on silica gel have very excellent
Different mechanical strength；With excellent acid resistance, there is good stability in strong acid solution.
Chitosan prepared by the present invention-silica gel hybridization magnetic adsorbent has preferable reproducibility and reusability.It will
Adsorbent elution, the regeneration of heavy metal ion are adsorbed, then medium temperature is dried after being rinsed to neutrality with deionized water, you can repetition makes
With.
Chitosan prepared by the present invention-silica gel hybridization magnetic adsorbent can be conveniently used in low concentration and contain heavy metal
The processing of waste water, it is easy to operate, do not cause secondary pollution.The magnetic adsorbent can be used as stationary phase and be filled in adsorption column or absorption
Tower, Dynamic Adsorption of Heavy Metal Ions can also be directly added into wastewater disposal basin or the grid of filling adsorbent are arranged in wastewater outlet, inhale
It can be separated by solid-liquid separation conveniently by magnetic method after the completion of attached.
The preparation method of adsorbent provided by the invention, raw material sources are extensive, preparation process is simple, it is of low cost, can follow
Ring use and it is environmental-friendly, magnetic method solid-liquor separation can be used, be easy to commercial Application, can be applied to low-concentration heavy metal in waste water
The innoxious and recycling of ion, has a extensive future, and has important economical and environmentally friendly meaning.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of chitosan-silica gel hybridization magnetic adsorbent prepared by the embodiment of the present invention 1.
Fig. 2 is the energy spectrum diagram of chitosan-silica gel hybridization magnetic adsorbent prepared by the embodiment of the present invention 1.
Specific implementation mode
Embodiment 1
1. chitosan-silica gel hybridization magnetic adsorbent preparation process：
(1) 4g chitosans are weighed, the acetic acid aqueous solution 100ml that concentration expressed in percentage by volume is 2% is added thereto, stirs evenly
After stand to chitosan all dissolve, obtain chitosan solution；30g silica gel (60-100 mesh) is weighed in 110 DEG C of thermostatic drying chambers
Middle activation 2h is spare；Magnetite powder is finely ground to 0.043mm hereinafter, to weigh 0.2g spare；Measure tetramethoxy-silicane binder
2ml is spare；
(2) silica gel, magnetic kind, the binder of activation are sequentially added into above-mentioned prepared chitosan solution, and 4h is blended；
(3) then uniformly mixed blended liquid is transferred to 2mol/L sodium hydroxide by droplet generator injection molding
Deposition, aging 2h in solution；
(4) molding sorbent microspheres are detached with magnet piece from lye, then be washed with deionized to neutrality, 50
It is dried to moisture-free under the conditions of DEG C, obtains chitosan-silica gel hybridization magnetic adsorbent.
2. adsorbent is to Cu2+Static Adsorption：
50ml is taken to contain Cu2+It is miscellaneous that 2.0g chitosans-silica gel is added in the laboratory obtained aqueous solution of 10.0mg/L, pH value 5.5
Change magnetic adsorbent.Under conditions of rotating speed 170rpm, 25 DEG C of temperature, it is placed in gas bath constant-temperature table and adsorbs 1h.Absorption terminates
Afterwards, the adsorbent for having adsorbed metal ion is isolated with magnet piece, the extraction raffinate after absorption measures Cu with atomic absorption spectrum2+Concentration
For 0.26mg/L, reach discharging standards.
Embodiment 2
1. chitosan-silica gel hybridization magnetic adsorbent preparation process：
(1) 5g chitosans are weighed, the aqueous formic acid 100ml that concentration expressed in percentage by volume is 2% is added thereto, stirs evenly
After stand to chitosan all dissolve, obtain chitosan solution；20g silica gel (60-100 mesh) is weighed in 100 DEG C of thermostatic drying chambers
Middle activation 1h is spare；Magnetite powder is finely ground to 0.043mm hereinafter, to weigh 0.4g spare；It is standby to measure KH-570 binders 5ml
With；
(2) silica gel, magnetic kind, the binder of activation are sequentially added into above-mentioned prepared chitosan solution, and 4h is blended；
(3) then uniformly mixed blended liquid is transferred to 2mol/L sodium hydroxide by droplet generator injection molding
Deposition, aging 2h in solution；
(4) molding sorbent microspheres are detached with magnet piece from lye, then be washed with deionized to neutrality, 50
It is dried to moisture-free under the conditions of DEG C, obtains chitosan-silica gel hybridization magnetic adsorbent.
2. processing of the adsorbent to acid wastewater in mine：
50ml acid wastewater in mine is taken, wherein containing Cu2+9.11mg/L、Zn2+250.0mg/L、Pb2+5.0mg/L、Ni2+
Then 4.0g chitosans-silica gel hybridization magnetic adsorbent is added in 9.6mg/L.Under conditions of rotating speed 170rpm, 25 DEG C of temperature,
It is placed in gas bath constant-temperature table and adsorbs 1h.After absorption, the adsorbent for having adsorbed metal ion is isolated with magnet piece, is adsorbed
Each ion concentration of extraction raffinate Atomic Absorption Spectrometry afterwards, measurement result is respectively Cu2+0.52mg/L、Zn2+3.34mg/L、
Pb2+0.89mg/L、Ni2+2.16mg/L reaches discharging standards.
Embodiment 3
1. chitosan-silica gel hybridization magnetic adsorbent preparation process：
(1) 3g chitosans are weighed, the acetic acid aqueous solution 100ml that concentration expressed in percentage by volume is 2% is added thereto, stirs evenly
After stand to chitosan all dissolve, obtain chitosan solution；20g silica gel (60-100 mesh) is weighed in 120 DEG C of thermostatic drying chambers
Middle activation 1h is spare；Magnetite powder is finely ground to 0.043mm hereinafter, to weigh 0.3g spare；Measure epoxychloropropane binder 4ml
It is spare；
(2) silica gel, magnetic kind, the binder of activation are sequentially added into above-mentioned prepared chitosan solution, and 4h is blended；
(3) then uniformly mixed blended liquid is transferred to 2mol/L sodium hydroxide by droplet generator injection molding
Deposition, aging 2h in solution；
(4) molding sorbent microspheres are detached with magnet piece from lye, then be washed with deionized to neutrality, 50
It is dried to moisture-free under the conditions of DEG C, obtains chitosan-silica gel hybridization magnetic adsorbent.
2. adsorbent is to Zn2+Absorption：
Five parts are taken to contain Zn2+For the laboratory obtained aqueous solution 50ml of 325.0mg/L, 1.0g chitosans-silica gel hybridization is added
Magnetic adsorbent.Under conditions of rotating speed 170rpm, 25 DEG C of temperature, be placed in gas bath constant-temperature table adsorb respectively 10min,
20min,30min,1h,4h.After absorption, the adsorbent for having adsorbed metal ion is isolated with magnet piece, it is remaining after absorption
Liquid surveys Zn with atomic absorption spectrum2+Concentration, the adsorption capacity of adsorbent under the conditions of calculating respectively.Test result is：In adsorption time
Respectively under conditions of 10min, 20min, 30min, 1h, 4h, equilibrium adsorption capacities be respectively 9.64mg/g, 10.08mg/g,
10.48mg/g,10.48mg/g,10.48mg/g.The result shows that absorption only 30min of the adsorbent to Zn ions in solution
Reach saturation.
Claims (8)
1. a kind of preparation method of chitosan-silica gel hybridization magnetic adsorbent, which is characterized in that heavy using droplet generator injection
Product molding, includes the following steps：
（1）Pretreatment of raw material：Prepare chitosan solution；Silica gel is activated into 1-2h in 100-120 DEG C of thermostatic drying chamber, magnetic kind is thin
It is milled to 0.043mm or less；
（2）It is blended：To step（1）Chitosan solution in sequentially add activated silica gel, magnetic kind and binder, 2-5h is blended；Its
In, chitosan, activated silica gel, magnetic kind and binder mass ratio be 1: (4-10) ：(0.05-0.5) ：(0.1-3)；Institute
The mass percent for stating solute chitosan is 1-5%；
The binder is glutaraldehyde, epoxychloropropane, tetraethoxysilane, tetramethoxy-silicane, KH-560 silane coupling agents
One or more of with KH-570 silane coupling agents；
（3）Jet deposition is molded：By droplet generator injection molding, deposition, aging 2h in lye are formed micro- blended liquid
Ball；
（4）Middle temperature is dried：Magneto separate, deionized water washing from lye by molding microballoon, and drying is obtained to moisture-free
Chitosan-silica gel hybridization magnetic adsorbent.
2. preparation method according to claim 1, which is characterized in that step（1）Described in the deacetylation of chitosan be
80-95%, molecular weight are 30-60 ten thousand；The silica gel is powdery chromatographic silica gel, and granularity is 40-100 mesh.
3. preparation method according to claim 1, which is characterized in that step（1）Described in magnetic kind be rare earth magnetic material,
Natural magnetite or magnetic ferrites.
4. preparation method according to claim 1, which is characterized in that step（1）In the chitosan solution, solvent is first
Aqueous acid, acetic acid aqueous solution or dilute hydrochloric acid.
5. chitosan-silica gel hybridization magnetic adsorbent prepared by any one of the claim 1-4 preparation methods.
6. chitosan-silica gel hybridization magnetic adsorbent answering in terms of adsorbing heavy metal ions in wastewater described in claim 5
With.
7. application according to claim 6, which is characterized in that a concentration of 5-500mg/L of the heavy metal ion, it is described
Heavy metal ion is one or more of copper, lead, zinc, nickel, cadmium, mercury and chromium.
8. application according to claim 6, which is characterized in that the chitosan-silica gel hybridization magnetic adsorbent is as solid
It is fixed to be mutually filled in adsorption column or adsorption tower, it is directly added into wastewater disposal basin, or the grid of filling adsorbent, dynamic are set in wastewater outlet
Adsorb heavy metal ion.
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| 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 |
| CN107555569B (en) * | 2017-11-02 | 2021-03-23 | 重庆大学 | Preparation method and application of multi-group magnetic coagulant |
| 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 |
| 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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| 高压静电法制备多孔磁性壳聚糖微球;胡巧玲等;《高等学校化学学报》;20080831;第29卷(第8期);1660-1664 * |
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