CN105170107B - A kind of preparation method of green heavy metal chelating agent - Google Patents
A kind of preparation method of green heavy metal chelating agent Download PDFInfo
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- CN105170107B CN105170107B CN201510672269.9A CN201510672269A CN105170107B CN 105170107 B CN105170107 B CN 105170107B CN 201510672269 A CN201510672269 A CN 201510672269A CN 105170107 B CN105170107 B CN 105170107B
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Abstract
The invention discloses a kind of preparation method of green heavy metal chelating agent; calcium chloride and chitosan are dispersed in dilute acetic acid solution by this method; chitosan/calcium complex is formed after being completely dissolved; amino in chitosan is protected by; react to form gel by glutaraldehyde cross-linking again, pore-creating is then carried out by freeze-drying, hydrochloric acid is eventually adding and washes away calcium ion; amino is discharged, the porous chitin modified material rich in amino is obtained.Green heavy metal chelating agent heavy metal Cu, Cd and Ni etc. have good adsorption effect made from this method.Green heavy metal chelating agent of the present invention is using wide material sources, with low cost and environment amenable chitosan as raw material, and preparation method is easy, and occupation mode is simple, is had broad application prospects in sewage disposal especially heavy metal containing wastewater treatment field.
Description
Technical field
Processing the present invention relates to a kind of preparation method of green heavy metal chelating agent and its for heavy metal wastewater thereby, belongs to
Field of environment protection.
Background technology
Heavy metal has enriching and toxicity big in itself, and it is difficult to degrade only to be purified by naturally, in general water containing 1~
100mg/L will cause evil；Some heavy metals toxicity in the presence of microorganism can be reinforced；Heavy metal is sufficiently stable in water,
Be difficult to be degraded, and can by food chain in organism enrichment method, human body is then entered by food chain, in human body
Savings gets up to cause slow poisoning in some organs, is detrimental to health.The method of wastewater treatment of current development and application is main
There are three kinds：The first is chemical method, and heavy metal in water is removed by chemically reacting includes chemical reduction method, neutralisation, electrification
Learn reducing process etc.；Second is physical method, i.e., under conditions of chemical form is not changed heavy metal adsorbed, concentrated,
Separation, so that the purpose of removing heavy metals is reached, including absorption, extraction, ion exchange etc., the third is biological treatment, that is, is borrowed
The method for helping the effect such as flocculation, absorption, accumulation, enrichment of microorganism or plant to remove heavy metal in waste water, including bioflocculation,
Biological adsorption, phytoremediation etc..The processing methods such as chemical precipitation method, electrolysis, liquid membrane separating method, for a huge sum of money for different characteristics
The shortcomings of belonging to waste water, achieve certain achievement, but there is big, the cost height that consumes energy, be also easy to produce secondary pollution, by contrast, inhale
Attached technology is processing heavy metal polluted waste water more preferably industrial technology, because adsorption technology has simple to operate, economic height
Effect, advantages of environment protection.Absorption method is it is crucial that selected adsorbent, traditional adsorbent such as activated carbon and zeolite is all present
The shortcomings of adsorption capacity is relatively low, regeneration cost is high after Adsorption of Heavy Metals.Therefore, it is good and economical and easily available to continue to seek absorption property
The sorbing material of Adsorption of Heavy Metals ion is popular research direction in recent years.
Chitosan, with abundant raw material, it is nontoxic, be readily biodegradable the features such as, have broad application prospects.Chitosan
Because heavy metal material has stronger Adsorption effect containing abundant hydroxyl and amino, it can be used for returning for heavy metal
Receive and the processing containing heavy metal industrial effluent.But chitosan dissolves in the inorganic acids such as dilute hydrochloric acid, nitric acid and most of organic
Acid, has that pH accommodations are narrow, poor to low-concentration metallic ionic adsorption, adsorptive selectivity is poor, time of equilibrium adsorption is longer
Shortcoming, these shortcomings limit application of the chitosan in terms of wastewater treatment.Therefore need to be modified chitosan, improve shell
Glycan physics, chemical property, improve its absorption property, and the present invention is exactly to a chitin modified Beneficial.
The content of the invention
It is an object of the invention to provide a kind of preparation method of green heavy metal chelating agent, it is therefore intended that provides a kind of acidproof
Alkali, heavy metal ionic adsorption performance be good and segregative heavy metal chelating agent.
The purpose of the present invention technical scheme is that：A kind of preparation side of green heavy metal chelating agent
Method, it is characterised in that described green heavy metal chelating agent passes through amido protecting, crosslinking, pore-creating, amino using chitosan as raw material
The steps such as release are made, specific as follows：
(1) amido protecting：In 5wt% acetic acid solutions, chitosan and calcium chloride, chitosan and acetic acid solution used are added
Mass ratio is 1:20~1:80, the mass ratio of chitosan and calcium chloride is 2:1~1:1, magnetic agitation 3h.
(2) it is crosslinked：5% glutaraldehyde solution is slowly added dropwise in step (1) resulting solution, glutaraldehyde and chitosan used
Mass ratio is 1:5~1:2, continue stir about 4h, it is 8~10 to be adjusted with 20wt% sodium hydroxide solution to pH, forms solidifying
Glue, is cleaned and suction filtration repeatedly with distilled water and ethanol；
(3) pore-creating：Gel is moved into 4 DEG C of refrigerators and stands 6h, -10 DEG C of freezings are put into after refrigeration；Frozen samples are carried out cold
Dry (- 50 DEG C, ＜ 20Pa) are freezed to complete dehydration, porous material is obtained；
(4) amino discharges：Obtained porous material is eluted to after no calcium ion detection with 0.1M hydrochloric acid, is washed with deionized water
Wash to neutrality, dry, obtain product.
The application method of green heavy metal chelating agent：In heavy metal wastewater thereby solution, appropriate green heavy metals trapping is added
Agent, 2~8h of stirring or concussion, after staticly settling.
Beneficial effects of the present invention：
Chitosan because amino is dissociated in an acidic solution and it is soluble, improve its acid resistance by cross-linking modified, but
Crosslinking can occupy active site position especially amino and decline its adsorption capacity.Therefore this experiment is first using calcium trace protection amino,
Reuse glutaraldehyde to be crosslinked it, its specific surface area and porosity is then improved using desivac pore-creating, improve absorption property, system
It is standby go out novel heavy metal trapping agent.
The method of usual chitosan protection amino is to use schiff base reaction, and the course of reaction uses a large amount of organic solvents,
High risks are caused to environment and operator's health, found in the research of early stage, ion blotting method can also protect amino,
And it is simple to operate, but it is general using object ion as trace ion, during can produce heavy metal pollution, the present invention uses nothing
The calcium ion of poison protects amino, improves the absorption property of heavy metal as trace ion, and process does not produce shadow to environment
Ring.
For increase trapping agent specific surface area, the absorption property of heavy metal is improved, pore-creating is carried out using freeze-drying, should
Method is to be chilled to water-containing materials below freezing, water is changed into ice, so as a kind of cheap and flexible template null method
The drying means that ice is changed into steam and removed under high vacuum afterwards.It can not only assign material morphology controllable porous
Structure, and economic, environmental sound.
Therefore the inventive method has many advantages, such as environmental protection and technique simplicity are easily industrialized, in sewage disposal especially
Heavy metal containing wastewater treatment has broad application prospects in field, has important meaning to the high-valued and industrial applications of chitosan
Justice.
Brief description of the drawings
Fig. 1 is the electron-microscope scanning figure of glutaraldehyde cross-linking chitosan.
Fig. 2 is the electron-microscope scanning figure of green heavy metal chelating agent.
Embodiment
For ease of understanding, with reference to specific embodiment, the present invention will be further described.
Embodiment 1
(1) 1.00g chitosans are dissolved in 40mL, 5% acetic acid solution in triangular flask.Treat that it is completely dissolved, into solution
Add the stirring of 0.50g calcium chloride, isothermal vibration 3 hours.
(2) 10mL, 5wt% glutaraldehyde solution is slowly added dropwise into there-necked flask, continues stir about 4h after completion of dropping, and drip
Plus 20wt% NaOH solution, regulation pH value of solution is between 8-10.Gel is formed, is cleaned and taken out repeatedly with distilled water and ethanol
Filter.
(3) gel is moved into 4 DEG C of refrigerators and stands 6h, -10 DEG C of freezings are put into after refrigeration；Frozen samples are freeze-dried
(- 50 DEG C, ＜ 20Pa) obtain porous material to complete dehydration.
(4) obtained porous material is eluted to after no calcium ion detection with 0.1M hydrochloric acid, is washed with deionized to neutrality,
Dry, obtain product.
From experiment, directly add chitosan and adsorbed, be difficult to be separated from the water after the completion of reaction, and glutaraldehyde is handed over
The chitosan of connection is then settled from water quickly, is illustrated crosslinking to the shaping of chitosan and is separated very necessary；Pass through infrared spectrum
Scanning is understood, directly with the chitosan of glutaraldehyde cross-linking in 1599cm-1Neighbouring δ (N-H) flexural vibrations absworption peak substantially weakens,
Protected with calcium ion after amino again with the chitosan of glutaraldehyde cross-linking in 1599cm-1Neighbouring δ (N-H) flexural vibrations absworption peak base
This is constant, in 1599cm after product Adsorption of Heavy Metals-1Neighbouring δ (N-H) flexural vibrations absworption peak substantially weakens, and illustrates that amino exists
Played an important role during Adsorption of Heavy Metals, amino can be taken during glutaraldehyde cross-linking, can effectively protected using calcium ion blotting
Protect amino；By ESEM, product is loose porous, shows that freeze-drying pore-creating works well, can effectively improve suction
Subordinate list face, as shown in Figure 1 and Figure 2.
Embodiment 2
The electroplating effluent of certain factory's electroplating workshop plating line and manual groove, main cupric, nickel, cadmium ion add implementation
Green heavy metal chelating agent 20g/L prepared by example 1, stirring, reaction 200min, after staticly settling, takes supernatant, former using flame
Sub- absorption process carries out quantitative analysis to its concentration of heavy metal ion, as a result as shown in table 1：
The heavy metal out of electroplating wastewater content of the green heavy metal chelating agent of table 1 before and after the processing
| Determine element | Before processing (mg/L) | After processing (mg/L) |
| Cu2+ | 56.420 | 0.015 |
| Ni2+ | 63.350 | 0.020 |
| Cd2+ | 26.230 | 0.010 |
Water outlet reaches discharging standards.
Embodiment 3
General cleaning waste water during certain company production printed circuit board (PCB), main cupric, the concentration of copper ion reaches 15mg/
L, adds the green heavy metal chelating agent 2g/L of the preparation of embodiment 1, stirring, reaction 120min, after staticly settling, takes supernatant,
Analyzed using flame atomic absorption spectrometry, content of copper ion is 0.04mg/L.
It should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, although ginseng
The present invention is described in detail according to previous embodiment, for those skilled in the art, it still can be to preceding
State the technical scheme described in embodiment to modify, or which part technical characteristic is replaced on an equal basis.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc., should be included in
Within protection scope of the present invention.
Claims (1)
1. a kind of preparation method of green heavy metal chelating agent, it is characterised in that described green heavy metal chelating agent is with chitosan
For raw material, it is made, is comprised the following steps that by amido protecting, crosslinking, pore-creating, amino release steps：
Step (1) amido protecting：In 5wt% acetic acid solutions, chitosan and calcium chloride, chitosan and acetic acid solution used are added
Mass ratio is 1:20~1:80, the mass ratio of chitosan and calcium chloride is 2:1~1:1, magnetic agitation 3h；
Step (2) is crosslinked：5% glutaraldehyde solution is slowly added dropwise in step (1) resulting solution, glutaraldehyde and chitosan used
Mass ratio is 1:5~1:2, continue to stir 4h, it is 8~10 to be adjusted with 20wt% sodium hydroxide solution to pH, forms gel,
Cleaned repeatedly with distilled water and ethanol and suction filtration；
Step (3) pore-creating：Gel is moved into 4 DEG C of refrigerators and stands 6h, -10 DEG C of freezings are put into after refrigeration；By frozen samples -50
DEG C, it is freeze-dried under the conditions of ＜ 20Pa to complete dehydration, obtains porous material；
Step (4) amino discharges：Obtained porous material is eluted to after no calcium ion detection with 0.1M hydrochloric acid, deionized water is used
Washing is dried to neutrality, obtains green heavy metal chelating agent product.
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| CN107216496B (en) * | 2017-06-14 | 2020-11-06 | 北京大学口腔医学院 | Amino-content-controllable chitosan material and preparation method thereof |
| CN113023812B (en) * | 2021-03-02 | 2022-03-11 | 中国矿业大学 | Copper-containing carbon-based composite efficient photothermal conversion material and preparation method thereof |
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| US8877907B2 (en) * | 2010-06-07 | 2014-11-04 | The Johns Hopkins University | Molecularly imprinted polymers |
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| CN101301604A (en) * | 2008-06-04 | 2008-11-12 | 哈尔滨工程大学 | Method for preparing magnetic powder heavy metal ion blotting chitosan compound adsorbing agent |
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