CN107140711A - A kind of method for removing the dye of positive ion - Google Patents
A kind of method for removing the dye of positive ion Download PDFInfo
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- CN107140711A CN107140711A CN201710458746.0A CN201710458746A CN107140711A CN 107140711 A CN107140711 A CN 107140711A CN 201710458746 A CN201710458746 A CN 201710458746A CN 107140711 A CN107140711 A CN 107140711A
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Abstract
The invention discloses a kind of method for removing the dye of positive ion.This method is with anion frame [NC2H8]4[CuI 5(BTT)3] xG (hereinafter referred to as Cu BTT) as adsorbent to dye of positive ion Adsorption.The present invention using simple hydro-thermal method it is synthetically prepared go out the Cu BTT with anion frame, dye of positive ion methylene blue (MB) in aqueous solution, rhodamine B (RhB), safranine T (ST) and crystal violet (CV) are adsorbed with neutral dye phenol red (PR) mixed solution using it at ambient temperature, the sorbing material only has absorption to the dye of positive ion, and centering dyestuff is without absorption.For the absorption of methylene blue, maximal absorptive capacity is 590mg/g at ambient temperature.
Description
Technical field
The invention belongs to administer water pollution field, relate to the use of and dyestuff is harmful in the novel absorption material Adsorption aqueous solution
Method.
Background technology
Metal-organic framework materials (MOFs) are that the one kind newly risen in the last few years has before great development space and application
The porous material of scape.Due to high-specific surface area and porosity, duct controllability and chemistry can be carried out according to target
The features such as modification, MOFs be widely used in gas storage with separating, the field such as drug delivery, photism.Wherein, MOFs is applied to
The research of Dye Adsorption just gradually attracts attention in solution.It is well known that most of dyestuffs all have light stable or inoxidizability,
Therefore it is extremely difficult to the purpose degraded to dyestuff using luminescence method or oxidizing process in the industry.Because many dyestuffs all have
Toxicity even carcinogenicity, including China, the fast-developing industry of many countries, such as medicine, weaving, leather, printing and modeling
Material, has resulted in a large amount of industry byproducts comprising a variety of dyestuffs and is discharged into domestic water, cause serious environment
Pollution, the life and health to the mankind causes very big threat.Find rapidly and effectively method from sewage transferred dyes into
Nowadays a worldwide critically important target and challenge.
At present, it is contemplated that economic competitiveness and validity, many chemistry, physics, biotechnology be proposed into
Row Dye Adsorption.However, common adsorption process is often along with some problems, such as adsorption capacity is low, poor selectivity, prepared
Journey is complicated and is difficult to regenerate, and selection for dye molecule there is high absorption capacity and the adsorbent of high selectivity to be heavy to closing
Want.MOFs materials possess many advantages as a kind of dye sorbent, such as possess abundant topological structure and can basis
Simple designs carry out pore properties regulation and control.Wherein non-electroneutral MOFs materials have more unique advantage, and they can pass through
Main-object electronic action or visitor-object electronic action reaches the purpose of selective absorption cation or anionic dye, structure
In duct and cavity dye ions can further be absorbed.
Haque et al. have studied absorption of the MOF-235 to anionic dye methyl orange and dye of positive ion methylene blue,
It was found that the neutral backbone material all has good Adsorption effect to both yin, yang dyestuffs, maximal absorptive capacity reaches respectively
477mg/g and 187mg/g are arrived.Nickerl team is using cation matrix material to four kinds of dyestuff Nile red/Nile blue/first
Base is red/and fluorescein carries out absorption research, and Nile red and Nile blue are closely similar in structure, but adsorbent is not inhaled to Nile red
It is attached, it can also be desorbed after only having absorption, and absorption to Nile blue.Dyestuff methyl red and fluorescein produce corresponding through deprotonation
It can also be adsorbed after anion, but because methyl red/fluorescein is to be trapped in by electrostatic interaction in skeleton duct
Portion, or end hydrone is instead of, neutral framework is formd, so the desorption of dyestuff can not be realized.Test result indicates that,
Ionic MOFs has selective absorption to ionic dyes, and the dyestuff adsorbed by electrostatic force is difficult to realize de-
It is attached.In addition, because the phenomenon of selective absorption occurs in dimensional effect during MOFs absorption dyestuffs.In Wang et al. uses
Property MOFs framework materials adsorb several various sizes of dyestuffs：(rhodamine B size is more than for methylene blue, rhodamine B and methyl orange
Other two kinds of dyestuffs).Experimental result shows that methylene blue and methyl orange are all absorbed, and larger-size rhodamine B not by
Absorb, embody influence of the dyestuff dimensional effect to MOFs selective absorptions.What article was reported mostly occurs greatly on Dye Adsorption
In cation matrix material or neutral backbone material, these materials can adsorb polytype dyestuff, and adsorptive selectivity is poor, inhale
Attached effect is also uneven, the even no systematic research of absorption to the dye of positive ion.At present, many is on MOFs materials
In the research in terms of Dye Adsorption carried out in organic solvent system, and the Dye Adsorption carried out in water solution system,
More have a wide range of applications, there is to be developed.
The content of the invention
The present invention provides a kind of method for removing the dye of positive ion, and the present invention is open using having containing anion MOFs
Presence can carry out visitor in anion frame structure, duct-the sky of dimethylamine cation, dimensional effect and nanometer that visitor exchanges
Chamber, uses it as selective absorption of the adsorbent investigation to mixed dye cationic dyestuff.
The technical solution adopted in the present invention is：Under room temperature condition, anion MOFs will be contained as adsorbent and put into sun
In ionic dye, absorption is stirred using constant temperature blender with magnetic force.Adsorbent is solid particle, and solid-liquid point is carried out after absorption
From.
In the present invention, the MOFs contains anion frame structure.
In the present invention, described dye of positive ion adjoining dimensions, and can pass freely through containing anion MOFs holes
Road.
In the present invention, mixed dye solvent volume is 50mL, and cation identical with neutral dye concentration is 15ppm.
Preferably, constant temperature blender with magnetic force regulation controls temperature to be 25 DEG C, and regulation mixing speed is 800r/min.
In order to optimize technical scheme, following experiment has been carried out：
1) containing anion MOFs to four groups of mixed dye solution methylene blues (MB), rhodamine B (RhB), safranine T
(ST) mixed with neutral dye phenol red (PR) isoconcentration with crystal violet (CV) and carry out Dye Adsorption experiment.
2) adsorption experiment is carried out to the MB aqueous solution under the conditions of various concentrations containing anion MOFs, probes into the framework material
Maximal absorptive capacity.
The characteristics of present invention process is：
1) Dye Adsorption experiment is carried out using containing anion MOFs, makes full use of it mutual between the dye of positive ion
Electrostatic force, and lar nanometric cavities present in skeleton can be further by Dye Adsorption in duct.
2) selective absorption that MB/RhB/ST/CV and PR mixed solution is carried out is tested, what is utilized is anion frame
To the selectivity of the dye of positive ion, and four kinds of cations are due to having differences property of size, and adsorbent MB less to size inhales
It is attached most fast, and most slow is adsorbed to larger-size RhB.
3) Cu-BTT maximal absorptive capacity is probed into the absorption to MB by determining different dyes initial concentration.
4) adsorbent equipment is simple, and experiment condition is gentle, and adsorbent amount needed for experiment is less and experimentation is inhaled for physics
Attached process, will not produce side reaction and accessory substance.
Step 2 of the present invention) in, prepare respectively the MB of the identical mass concentrations of 100mL and PR, RhB and PR, ST and PR with
And CV and PR mixed solution, under identical stirring condition, add 30mg adsorbents and carry out adsorption experiment, pass through ultraviolet spectrometry light
Degree meter determines corresponding absorbance respectively.
The step 3) in, the 100mL mass concentrations 200ppm MB aqueous solution is prepared, 10mg adsorbents is added, utilizes purple
Outer spectrophotometer carries out absorbance measurement Dye Adsorption situation, calculates the corresponding adsorbance of adsorption process.
Anion frame Cu-BTT used is the crystal (DOI that this seminar early stage is synthesized and characterized in the present invention:
10.1039/c4cc10002f), its synthesis is that hydro-thermal reaction is generated under the conditions of 140 DEG C, and the material has good water stable
Property and the features such as high temperature resistant, resistance to acids and bases, solve that the solvent occurred in adsorption reaction is inapplicable, acid-base property it is inapplicable with
And a series of problems, such as Dye Adsorption poor selectivity.
Brief description of the drawings
Fig. 1 is that MB changes over time curve with PR mixed solution adsorption process absorbances；
Fig. 2 is that RhB changes over time curve with PR mixed solution adsorption process absorbances；
Fig. 3 is that ST changes over time curve with PR mixed solution adsorption process absorbances；
Fig. 4 is that CV changes over time curve with PR mixed solution adsorption process absorbances；
Fig. 5 is Cu-BTT to four kinds of dye of positive ion adsorbances and time curve；
Fig. 6 is that Cu-BTT adsorbs molal weight and time curve to four kinds of dyes of positive ion；
Fig. 7 is that Cu-BTT changes over time curve to MB adsorbances when initial concentration is 200ppm.
Embodiment
For a better understanding of the present invention, the skill of the present invention is illustrated by specific embodiment below in conjunction with the accompanying drawings
Art scheme.
Embodiment 1
Draw standard dye solution concentration and absorbance relation curve：The accurate MB for weighing 200mg, uses deionized water constant volume
To 500mL, the MB solution that mass concentration is 400ppm is configured to.Mother liquor is diluted successively, and a series of mass concentration degree are prepared respectively
For 20ppm, 15ppm, 10ppm, 5ppm, 3ppm, 1ppm, 0.5ppm aqueous solution of methylene blue, ultraviolet specrophotometer is utilized
(UV) absorbance curve tested respectively under each concentration, and obtain a length of 665nm of the maximum absorption wave of methylene blue.In maximum
Under absorbing wavelength, A-C curve is drawn using the absorbance (A) corresponding to mass concentration (C), linear equation is set up.
RhB/ST/CV/PR concentration of polymer solution and the standard curve of absorbance are drawn respectively according to above-mentioned identical step.
Embodiment 2
Prepare and stirred under MB and the PR mixed solution that 100mL mass concentrations are 15ppm, room temperature condition, add 30mg
Cu-BTT carries out adsorption experiment, and absorbance measurement is carried out with ultraviolet specrophotometer in certain period of time, draws absorbance-
Time graph, calculates the corresponding adsorbance of adsorption process and draws adsorbance-time graph.
With above-mentioned experimental method identical, prepare respectively RhB and PR, ST and PR that 100mL mass concentrations are 15ppm,
CV and PR mixed solution, carries out corresponding absorbance-the time, adsorbance-drafting of time graph.Compare Cu-BTT to four
The otherness of Cation adsorption is planted, influence of the dimensional effect to Dye Adsorption is probed into.
Embodiment 3
The 100mL mass concentrations 200ppm MB aqueous solution is prepared, the addition of 10mg adsorbents is accurately weighed, what is be stirred continuously
Under the conditions of carry out Dye Adsorption experiment, using ultraviolet specrophotometer carry out absorbance measurement, calculate adsorption process accordingly adsorb
Measure and draw adsorbance-time graph.
Test result analysis：
Fig. 1/2/3/4 is selectivity of the Cu-BTT to MB and PR, RhB and PR, ST and PR, CV and PR mixed solution respectively
Situation map is adsorbed, as can be seen from the figure Cu-BTT is to the selective absorption of the dye of positive ion in mixed solution, and centering
Dyestuff is not adsorbed.
Fig. 5/6 are adsorbance data of the Cu-BTT to mixed dye cationic dyestuff respectively, can be with from adsorbance curve
Find out, within the 160min times, four kinds of dyes of positive ion are nearly all adsorbed；Absorption is can be seen that from absorption mole data
Effect is influenceed by dye molecule size, and dye molecule size is smaller (MB ＜ ST ＜ CV ＜ RhB), and absorption molal quantity is more.
Fig. 7 is that 10mg adsorbents Cu-BTT is that 200ppm MB adsorption from aqueous solution amounts are changed over time to 100mL mass concentrations
Curve map, it can be seen that maximal absorptive capacity is 590mg/g when absorption of the Cu-BTT to MB reaches adsorption saturation, it is seen that
There are very big potentiality to MB Adsorption.
Claims (4)
1. a kind of method for removing the dye of positive ion, it is characterised in that under room temperature condition, regard the MOFs for containing anion as suction
In attached dose of input dye of positive ion solution, absorption is stirred using constant temperature blender with magnetic force.
2. in accordance with the method for claim 1, it is characterised in that the MOFs contains anion frame structure.
3. in accordance with the method for claim 1, it is characterised in that described cation is methylene blue, rhodamine B, alkalescence
Safranine T and crystal violet.
4. in accordance with the method for claim 1, it is characterised in that constant temperature blender with magnetic force regulation controls temperature to be 25 DEG C, adjusts
Section mixing speed is 800r/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110538638A (en) * | 2019-08-23 | 2019-12-06 | 江苏理工学院 | Magnetic composite adsorption material and preparation method and application thereof |
| CN111788468A (en) * | 2018-06-01 | 2020-10-16 | 费德里科·圣玛丽亚技术大学 | Kit and method for evaluating adsorption performance of material surface |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102774949A (en) * | 2012-08-10 | 2012-11-14 | 山西大学 | Method for decolorizing cationic dye waste water |
| CN102921383A (en) * | 2012-11-26 | 2013-02-13 | 四川大学 | Absorbent for cationic dyes in waste water and preparation method of absorbent |
-
2017
- 2017-06-16 CN CN201710458746.0A patent/CN107140711A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102774949A (en) * | 2012-08-10 | 2012-11-14 | 山西大学 | Method for decolorizing cationic dye waste water |
| CN102921383A (en) * | 2012-11-26 | 2013-02-13 | 四川大学 | Absorbent for cationic dyes in waste water and preparation method of absorbent |
Non-Patent Citations (1)
| Title |
|---|
| 卜凡艳 等: ""[CuI5(BTT)3]4-阴离子框架材料对染料的选择性吸附研究"", 《中国化学会第30届学术年会摘要集-第三十二分会：多孔功能材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111788468A (en) * | 2018-06-01 | 2020-10-16 | 费德里科·圣玛丽亚技术大学 | Kit and method for evaluating adsorption performance of material surface |
| CN110538638A (en) * | 2019-08-23 | 2019-12-06 | 江苏理工学院 | Magnetic composite adsorption material and preparation method and application thereof |
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Application publication date: 20170908 |