CN101279776B - Novel method for fast removing cupric ion with magnetic sorbent - Google Patents
Novel method for fast removing cupric ion with magnetic sorbent Download PDFInfo
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- CN101279776B CN101279776B CN2008100378096A CN200810037809A CN101279776B CN 101279776 B CN101279776 B CN 101279776B CN 2008100378096 A CN2008100378096 A CN 2008100378096A CN 200810037809 A CN200810037809 A CN 200810037809A CN 101279776 B CN101279776 B CN 101279776B
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Abstract
The present invention relates to a method for fast removing metal copper ions in waste water by a magnetic adsorbent, which comprises steps that: (1) a chitosan solution with the mass fraction of 16 percent is used to wrap a Fe3O4 magnetic powder to prepare magnetic nanometer particles; (2) an acetic acid buffer solution with a pH value of 5.6 is used for swelling the magnetic nanometer particles and carrying out the surface chemical modification so as to prepare a novel magnetic adsorbent; (3) a magnetic nano-adsorber of 10-120mg is used for adsorbing a copper ion solution with the volume of 10ml and concentration of 40-800ppm at a temperature of 22 DEG C and a speed of 100rpm, and the solution undergoes the elution by an eluant with the volume of 20ml and concentration of 100mmol/L, thereby obtaining the regenerative magnetic nano-adsorber; and (4) the adsorption conditions of the magnetic nano-adsorber are optimized through adjusting the adsorption conditions. The method has advantages of simple and convenient operation, short time consumption, allowing fast feeding, convenient and rapid elution and strong regenerative power.
Description
Technical field
The invention belongs to water-treatment technology field, particularly relate to the method that a kind of novel magnetic sorbent material is rapidly and efficiently removed metal copper ion in the waste water.
Background technology
Copper is a kind of valuable metal, is first subgroup element in periodic system, and it is of wide application.Also have important role in life, cupric is few in the natural water, and the copper in the water mainly is that the pollution by trade effluent causes, mainly from departments such as plating, smelting, five metals, chemical industry, minings.
Copper in the water body not only can not be by microbiological degradation, and on the contrary, organism can make its enrichment, and it is converted into the bigger heavy metal organic compound of toxicity.Copper seriously influences the self-purification of water body.In the water body environment of complexity, copper very easily causes river pollution if enter water body.For example, can make white fabrics painted when water body is polluted above 1.0mg/L by copper-containing wastewater, surpassing 1.5mg/L water has peculiar smell.The copper of higher concentration has toxicity equally to organism simultaneously, and its influence has bigger difference with organism kind difference.Sea grass and mollusk are responsive especially to copper, and their safe concentration is less than 10 μ g/L.Because the avidity of some tissue is big especially in copper and the human body, in conjunction with after understand the activity of inhibitory enzyme, thereby toxic action also can not be ignored to human body.The adult needs the about 2～3mg of copper every day, but surpasses 100mg/ during every day when taking in the copper amount, and the system that will stimulate digestion because of excessive copper causes stomachache, vomiting, if the long-term excessive liver cirrhosis that causes.In addition, copper also is very important valuable metal, also is a kind of wasting of resources in loss and the sewage.Therefore, pollute, preserve the ecological environment, detect and remove the cupric ion that pollutes in the waste water, and the recovery valuable metal just seems very important in order to reduce water.
At present the method for copper-containing wastewater industrial treatment mainly contains chemical coagulation-sedimentation method, ion exchange method, electrolytic process, reverse osmosis method, electroosmose process etc., yet all there is as cost high shortcoming such as clearance is low, complex operation, power consumption are big in these methods.
Summary of the invention
Technical problem to be solved by this invention provides the method that a kind of novel magnetic sorbent material is removed cupric ion fast, and this method is simple, and is easy to operate, mass-producing utilization easily, and can obtain high economic benefit.
A kind of novel magnetic sorbent material of the present invention is removed the method for cupric ion fast, comprising:
(1) chitosan solution with massfraction 16% wraps up Fe
3O
4Magnetic powder prepares magnetic nanometer particles;
(2) hac buffer of using pH=5.6 carries out the magnetic nanometer particles swelling surface chemical modification and makes the novel magnetic sorbent material that contains energy chelated mineral cupric ion active group;
(3) at 22 ℃, 100rpm, pH are 2.0～8.0 o'clock, are that the copper ion solution of 40～800ppm carries out absorption reaction 0～4h with 10-120mg magnetic Nano sorbent material and 10ml concentration, carry out wash-out with 20ml 100mmol/L eluent again, obtain regenerated magnetic Nano sorbent material;
(4), optimize the adsorption conditions of magnetic Nano sorbent material by the regulation and control adsorption conditions.
Magnetic nanometer particles biologically active in the described step (1), its diameter Distribution are about 20-40nm, and chitosan dissolves with the acetum of 25wt.%.
Coating materials in the described step (2) is a α-Tong Wuersuan.
Surface chemical modification in the described step (2) is the reaction that the chitosan of α-Tong Wuersuan and magnetic nanometer particles surface parcel carries out.
The solution that contains cupric ion in the described step (3) is copper-bath.
Eluent in the described step (3) is disodium ethylene diamine tetraacetate or citric acid.
Wash-out in the described step (3) is that the 50mg magnetic adsorbent is joined in disodium ethylene diamine tetraacetate or the citric acid solution, and reaction 10min separates with reaction solution under the effect of externally-applied magnetic field again.
The optimal adsorption condition of optimizing in the described step (4) is: the concentration of copper-bath is 200ppm, the consumption of magnetic Nano sorbent material is 50mg, pH value in reaction is 6.0, and the reaction times is 2h, and the ratio of the magnetic nano-particle of α-Tong Wuersuan and chitosan parcel is 50: 1mg/ml.
Beneficial effect
Characteristics such as 1) magnetic Nano sorbent material of the present invention has fast, high absorbability ability and regenerative power are strong;
2) product of the present invention easily separates from wastewater treatment system, recyclable repeated use, advantage such as the utilization ratio that improves sorbent material is arranged and reduce production costs;
3) the present invention is easy and simple to handle, and equipment is simple, and reaction temperature and weak point consuming time allow reinforced fast and simple and efficient wash-out, have greatly improved production efficiency;
4) compared with prior art, the magnetic Nano sorbent material of the present invention's preparation is easier to use of large-scale production, and mass-producing detects and remove the metal copper ion in the waste water.
Description of drawings
Fig. 1 is the Cu of different concns copper-bath
2+Adsorption curve;
Fig. 2 is the Cu of different magnetic Nano quantity of sorbent
2+Adsorption curve;
Fig. 3 is the Cu that changes with the pH value
2+Adsorption curve;
Fig. 4 is the Cu that changes with the reaction times
2+Adsorption curve;
Fig. 5 is the Cu with the magnetic-particle ratio vary of modifier and chitosan parcel
2+Adsorption curve.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With the preparation of the nano magnetic particle of chitosan parcel, concrete steps are as follows:
Under 50 ℃,, make the chitosan solution of 16wt.% with acetum (25wt.%) dissolving chitosan.
10ml Fe
3O
4Add the Span-80 of 1ml in the solution, more above-mentioned chitosan solution is poured into wherein, 1000r/min stirs 15min down.Sonic oscillation 30min stirs 30min down in 1000r/min more then.
Under the condition of magnetic field existence, use distilled water wash 3 times, finish settling process, collect and obtain magnetic nanometer particles.
Embodiment 2
With the α-Tong Wuersuan be coating materials the magnetic Nano preparation of adsorbent, concrete steps are as follows:
The nano magnetic particle that will wrap up chitosan with the hac buffer of pH=5.6 carries out swelling.
In above-mentioned solution, add the 0.25g α-Tong Wuersuan, regulate pH value to 4.5～5.0, slowly add 0.15g NaBH then with 5mol/l NaOH
4, regulate pH value to 6.5～7.0 with the HCl of 15wt.%, reaction 24h.
Use ethanol and the anhydrous diethyl ether of 100wt.% respectively, wash three times.
Embodiment 3
Magnetic Nano sorbent material with preparation is removed Cu
2+Adsorption experiment, concrete steps are as follows:
At 22 ℃, under the 100rpm condition, with 50mg magnetic Nano sorbent material and the certain density CuSO of 10ml
4Solution mixes, reaction 4h.
Under the effect of externally-applied magnetic field, the magnetic Nano sorbent material that reacts completely is separated with reaction solution.
EDTA with 25mmol/L is a sequestrant, uses remaining CuSO in the ultraviolet spectrophotometer test reaction liquid under the 740nm wavelength
4Concentration is calculated the CuSO in the absorption
4Amount.
Embodiment 4
Use Na
2EDTA carries out wash-out to the magnetic Nano sorbent material, and concrete steps are as follows:
After reaction finished, the magnetic Nano sorbent material that 50mg has been adsorbed cupric ion joined the Na of 20ml 100mmol/L
2In EDTA (disodium ethylene diamine tetraacetate) solution, reaction 10min carries out wash-out.Under the effect of externally-applied magnetic field, the magnetic Nano sorbent material is separated with reaction solution, under the 740nm wavelength, measure the elution amount of cupric ion, eluting rate is 100%.
Embodiment 5
With citric acid the magnetic Nano sorbent material is carried out wash-out, concrete steps are as follows:
After reaction finishes, with 50mg adsorbed cupric ion the magnetic Nano sorbent material join in the citric acid solution of 20ml 100mmol/L, reaction 10min carries out wash-out.Under the effect of externally-applied magnetic field, the magnetic Nano sorbent material is separated with reaction solution, under the 740nm wavelength, measure the elution amount of cupric ion, eluting rate is 61.2%.
Embodiment 6
To the adsorption conditions optimization of magnetic Nano adsorbents adsorb cupric ion reaction, concrete steps are as follows:
(1) determining of the initial copper-bath concentration of optimum response:
Get 11 groups of each 50mg magnetic Nano sorbent materials, adding concentration respectively is the 10ml CuSO of 40ppm, 60ppm, 80ppm, 100ppm, 120ppm, 140ppm, 160ppm, 180ppm, 200ppm, 400ppm, 800ppm
4In the solution, at 22 ℃, under the 100rpm condition, reaction 4h measures different initial CuSO
4The Cu of concentration
2+Adsorption curve.Experimental result as shown in Figure 1, optimal adsorption concentration is 200ppm CuSO
4Solution.
(2) determining of optimum response magnetic Nano quantity of sorbent:
Get 6 groups of different magnetic Nano quantity of sorbent, respectively with the CuSO of 6 groups of each 10ml 200ppm
4Solution mixes, and at 22 ℃, under the 100rpm condition, reaction 4h measures the Cu under the different magnetic adsorbent amount conditions
2+Adsorption curve, the amount of the magnetic Nano sorbent material of adding is respectively 10mg, 30mg, 50mg, 70mg, 90mg, 120mg.Experimental result as shown in Figure 2, the amount of optimum magnetic sorbent material is 50mg.
(3) determining of optimum response pH value of solution value:
Get 7 groups of each 50mg magnetic Nano sorbent materials, respectively with the CuSO of 7 groups of each 10ml 200ppm
4Solution mixes, at 22 ℃, and under the 100rpm condition, reaction 4h, the Cu of the different pH values of mensuration solution
2+Adsorption curve.CuSO
4The pH value of solution is respectively 2.0,3.0,4.0,5.0,6.0,7.0,8.0.Experimental result as shown in Figure 3 because pH is 6 more approaching neutrality, so optimum response pH value is chosen in 6.0.
(4) determining of optimum reacting time:
Get 8 groups of each 50mg magnetic Nano sorbent materials, respectively with the CuSO of 8 groups of each 10ml 200ppm
4Solution mixes, and at 22 ℃, 100rpm, pH are 6.0 o'clock, measures the Cu of differential responses time
2+Adsorption curve.Reaction times is respectively 2min, 10min, 20min, 30min, 60min, 120min, 180min, 360min.Experimental result as shown in Figure 4, the selection optimum reacting time is 240min.
(5) determining of the best ratio of the magnetic nanoparticle of chemical modifier (α-Tong Wuersuan) and chitosan parcel:
Get the magnetic Nano sorbent material that 6 groups of each 50mg contain different modifying dosage, respectively with the CuSO of 6 groups of each 10ml 200ppm
4Solution mixes, and at 22 ℃, 100rpm, pH are 6.0 o'clock, reaction 4h, the Cu under the different ratios of the magnetic nano-particle of mensuration chemical modifier and chitosan parcel
2+Adsorption curve.The ratio of the magnetic nanoparticle of α-Tong Wuersuan that adds and chitosan parcel (mg: ml) be respectively 10: 1,20: 1,30: 1,40: 1,50: 1 and 60: 1.The result who measures determines that the ratio of the magnetic nano-particle of best chemical modifier and chitosan parcel is 50: 1 as shown in Figure 5.
Claims (6)
1. a magnetic adsorbent is removed the method for cupric ion fast, comprising:
(1) chitosan solution with massfraction 16% wraps up Fe
3O
4Magnetic powder prepares magnetic nanometer particles;
(2) hac buffer of using pH=5.6 carries out the magnetic nanometer particles swelling surface chemical modification with α-Tong Wuersuan and makes the magnetic adsorbent that contains energy chelated mineral cupric ion active group;
(3) at 22 ℃, 100rpm, pH are 2.0～8.0 o'clock, are that the copper ion solution of 40～800ppm carries out absorption reaction 4h with 10-120mg magnetic adsorbent and 10ml concentration, carry out wash-out with 20ml 100mmol/L eluent again, obtain the regenerated magnetic adsorbent;
(4), optimize the adsorption conditions of magnetic adsorbent by the regulation and control adsorption conditions.
2. magnetic adsorbent according to claim 1 is removed the method for cupric ion fast, it is characterized in that: the surface chemical modification in the described step (2) is the reaction that the chitosan of α-Tong Wuersuan and magnetic nanometer particles surface parcel carries out.
3. magnetic adsorbent according to claim 1 is removed the method for cupric ion fast, it is characterized in that: the solution that contains cupric ion in the described step (3) is copper-bath.
4. magnetic adsorbent according to claim 1 is removed the method for cupric ion fast, it is characterized in that: the eluent in the described step (3) is disodium ethylene diamine tetraacetate or citric acid.
5. magnetic adsorbent according to claim 1 is removed the method for cupric ion fast, it is characterized in that: the wash-out in the described step (3) is that the 50mg magnetic adsorbent is joined in disodium ethylene diamine tetraacetate or the citric acid solution, reaction 10min separates with reaction solution under the effect of externally-applied magnetic field again.
6. magnetic adsorbent according to claim 1 is removed the method for cupric ion fast, it is characterized in that: the adsorption conditions of optimizing in the described step (4) is: copper-bath concentration is 200ppm, the consumption of magnetic adsorbent is 50mg, pH value in reaction is 6.0, reaction times is 4h, and the ratio of the magnetic nanometer particles of α-Tong Wuersuan and chitosan parcel is 50: 1mg/ml.
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| CN102107980B (en) * | 2011-01-18 | 2012-06-27 | 浙江大学 | Method for removing sulfonic-group-containing dye in alkaline waste water by using magnetic chitosan adsorbent |
| CN102153183A (en) * | 2011-04-22 | 2011-08-17 | 中国科学院生态环境研究中心 | Nano ferric oxide-cationic polyelectrolyte coupled multielement composite flocculant |
| CN102258981B (en) * | 2011-05-27 | 2012-12-26 | 清华大学 | Method for preparing magnetic chitosan nano particles and processing heavy metal wastewater |
| CN102600777A (en) * | 2012-03-14 | 2012-07-25 | 天津师范大学 | Stable easy-separation nanoscale iron ball, preparation method thereof and application thereof |
| CN103611503B (en) * | 2013-11-26 | 2016-02-24 | 湖南大学 | The chitosan magnetic of KG modification, preparation method and the application in cadmium wastewater process field thereof |
| CN103937779A (en) * | 2014-05-13 | 2014-07-23 | 清华大学 | Preparation and application method of magnetic chitosan biological immobilized particles |
| CN104525131A (en) * | 2015-01-05 | 2015-04-22 | 福州大学 | CDTA modified magnetic nano-adsorbent and preparation method and application thereof |
| CN104677976B (en) * | 2015-02-03 | 2017-06-16 | 武汉大学 | Magnetic powder adsorbent and the combination analysis method in normal pressure mass spectrum source |
| CN105153351B (en) * | 2015-07-31 | 2017-05-17 | 莆田学院 | Citric acid-polyacrylate magnetic hydrogel, preparation method and application thereof |
| CN105561943B (en) * | 2016-03-14 | 2017-12-15 | 武汉轻工大学 | A kind of preparation method and application of magnetic rape stalk sorbing material |
| CN105771912B (en) * | 2016-03-15 | 2019-03-29 | 中南大学 | A kind of multifunctional bio adsorbent material and preparation method thereof |
| CN106423074A (en) * | 2016-10-13 | 2017-02-22 | 济南大学 | Preparation method and application of magnetic thenoyltrifluoroacetone TTAaFe3O4 |
| CN107694528A (en) * | 2017-10-24 | 2018-02-16 | 当涂县瑞龙果树种植专业合作社 | A kind of heavy metal in water inorganic agent and preparation method thereof |
| CN114502753A (en) * | 2019-08-28 | 2022-05-13 | N9Ve自然海洋和价值有限公司 | Method and system for recovering rare earth elements and/or lithium using marine macroalgae |
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