CN108579689A - A kind of beta cyclo dextrin polymer and preparation and the method for handling anionic dye waste water using it - Google Patents
A kind of beta cyclo dextrin polymer and preparation and the method for handling anionic dye waste water using it Download PDFInfo
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- CN108579689A CN108579689A CN201810356041.2A CN201810356041A CN108579689A CN 108579689 A CN108579689 A CN 108579689A CN 201810356041 A CN201810356041 A CN 201810356041A CN 108579689 A CN108579689 A CN 108579689A
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- beta
- methyl orange
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
A kind of method for handling waste water from dyestuff the invention discloses beta cyclodextrin polymer and its preparation and using it.Preparation method includes the following steps：In an inert atmosphere, by beta cyclodextrin (β CD), crosslinking agent (tetrafluoro terephthalonitrile, TFPN after), alkaline salt compound carries out polymerisation in organic solvent, resulting polymers are reacted with ethanol amine (EA) again, and reaction product obtains porous beta cyclodextrin (EA CDP).Porous beta cyclodextrin prepared by the present invention can quickly remove the anionic dyes pollutant such as methyl orange, methyl orange, acid blue 83, Indian yellow G in water removal, and adsorbing filament technique specific activity Carbon Materials are big and price is low.In addition, polymer can regenerate for several times in a mild condition, and performance loss very little.
Description
Technical field
The invention belongs to Dye Adsorption technical field in wastewater treatment, more particularly to prepared by a kind of anionic dye adsorbent
With the method for handling anionic dye waste water using it.
Background technology
Water pollution problems becomes increasingly conspicuous in recent years, and an important pollution sources of the waste water from dyestuff as water pollution are greatly endangered
Ecological environment and health, such as the anionic dyes such as common methyl orange, Congo red, acid blue 83, Indian yellow G have been done harm to,
Since its is difficult to degrade, bio-toxicity is high, being discharged into after water body not only can directly endanger the growth of aquatic animals and plants, destroy soil, and
And health can be damage by bioconcentration.Currently, mainly having absorption, chemistry heavy in the processing method of waste water from dyestuff
Shallow lake, UF membrane, bioanalysis etc., wherein the method for absorption and UF membrane due to it is efficient, simple for process, do not generate secondary pollution etc.
Feature has obtained the extensive concern of domestic and foreign scholars.
Go in water removal organic dye pollutant the most commonly used is activated carbon, but activated carbon has several defects, including absorption speed
Degree is slow, expensive, and is difficult to remove the micropollutants of many relative hydropathics.In addition, regeneration waste active carbon energy consumption is high, and
The absorption property of regenerated carbon is poor.
In conclusion in existing commercial Application technology, absorption method, which handles waste water from dyestuff, still has prodigious advantage, and inhales
Adsorbent used in during attached method processing waste water is still not up to ideal effect, the new dye absorption of excellent combination property
The research and development of agent are still the hot and difficult issue of the current technical field research work.
Cyclodextrin as second generation super molecular compound has inner cavity hydrophobic, and the hydrophilic special construction of outer rim makes it can
It is formed with many organic and inorganic molecule according to Van der Waals force, hydrophobic interaction power, the intermolecular matching effect of Subjective and Objective etc.
Inclusion compound and molecular assembled system become chemistry and the interested research object of chemical research person.This selective envelope is made
It is protected in Chemical Decomposition, organic synthesis and catalysis, drug control, food processing, environment with i.e. usually said molecular recognition function
It is used widely in the fields such as shield and nano material.Since the solubility of β-CD is smaller, in order to overcome cyclodextrin solubility itself
Defect, natural cyclodextrin is modified causes greatly to pay attention in recent years.Cyclodextrin is organic with being captured from gas, liquid
The ability of molecule and complexation of metal ions, the polymer material containing cyclodextrin is in terms of the environmental protection such as environmental monitoring and wastewater treatment
There is important application, thus prepares polymer using cyclodextrine derivatives and be expected to obtain the higher new material of stability.β-ring paste
Essence is a kind of cheap, reproducible glucose products, and micropollutants can be adsorbed from water.Beta-cyclodextrin can be formed with pollutant
Host-guest complex, but so far, compared with conventional activated carbon, the crosslinked beta cyclo dextrin polymer surface area reported
Low, absorption property is poor.
Invention content
It is an object of the invention to the deficiencies for existing beta cyclo dextrin polymer adsorbent, provide a kind of efficiently removal
The beta cyclo dextrin polymer sorbent preparation method of anionic dye and the side using its processing anionic dye waste water in waste water
Method.
The technical solution adopted by the present invention is as follows：Anionic dye adsorbent, the adsorbent are beta cyclo dextrin polymer,
Preparation includes the following steps：In nitrogen or argon gas, beta-cyclodextrin, crosslinking agent, alkali compounds are carried out in organic solvent
After polymerisation, resulting polymers are reacted with ethanol amine again, and reaction finishes to obtain the beta cyclo dextrin polymer (EA-
CDP)。
The crosslinking agent is for tetrafluoro terephthalonitrile or to itrile group ptfe pyridine；The alkali compounds is K2CO3Or
KHCO3；The solvent is the organic solvent that tetrahydrofuran mixes composition with N,N-dimethylformamide；The tetrahydrofuran and N,
The volume ratio of dinethylformamide is 7-10 ﹕ 1.
The mass ratio of the alkali compounds and beta-cyclodextrin is 3-5 ﹕ 1；The weight ratio of the beta-cyclodextrin and crosslinking agent
For 2-3 ﹕ 1；The weight ratio of the ethanol amine and beta-cyclodextrin is 1 ﹕ 1-3 or 1 ﹕ 2.
In the substitution reaction step, temperature is 80-100 DEG C；The time of first time substitution reaction is 24-48 hours；
The time of second secondary response is 24-48 hours；The substitution reaction carries out in argon gas or nitrogen atmosphere.
The method further includes following steps：After second of reaction step, reaction system is cooling, filtering,
After removing remaining alkali compounds, obtained solid is washed with deionized, is dried in vacuo and obtains flaxen powdered sample
Product.
It is a kind of using the anionic dye (methyl orange dye adsorbent) handle methyl orange dye waste water method its
It is characterized in that：Methyl orange dye adsorbent is added in the waste water solution containing methyl orange dye, is made using oscillator concussion
Methyl orange dye adsorbent fully adsorbs methyl orange, is then separated by filtration, and removes the beta cyclo dextrin polymer suction for having adsorbed dyestuff
Attached dose.
The purpose of the present invention is achieved through the following technical solutions：
One of the objects of the present invention is to provide a kind of beta cyclo dextrin polymers with good adsorption function for invention content.
Another object of the present invention is to provide the preparation methods of above-mentioned polymer.
The third object of the present invention is to provide application of the beta cyclo dextrin polymer in dying industrial wastewater processing.
The present invention realizes that process is as follows：It is prepared by beta cyclo dextrin polymer (EA-CDP) shown in FIG. 1.
The preparation method of beta cyclo dextrin polymer (EA-CDP) of the present invention includes：
1, the preparation of CDP；
2, the preparation of beta cyclo dextrin polymer (EA-CDP).
Preparation method includes the following steps：In an inert atmosphere, by beta-cyclodextrin (β-CD), (tetrafluoro is to benzene two for crosslinking agent
Nitrile, TFPN), after alkaline salt compound carries out polymerisation in organic solvent, resulting polymers again with ethanol amine (EA) progress
Reaction, reaction product obtain porous beta cyclo dextrin polymer (EA-CDP).In the above method, the crosslinking agent is tetrafluoro to benzene two
Formonitrile HCN or to formonitrile HCN base ptfe pyridine；The alkali compounds is K2CO3Or KHCO3；The solvent is tetrahydrofuran and dimethyl
The mixed solvent of formamide (DMF) composition；The volume ratio of the tetrahydrofuran and n,N-Dimethylformamide is 6-10 ﹕ 1, specifically
Can be 9 ﹕ 1.The mass ratio of the alkali compounds and beta-cyclodextrin is 3-5 ﹕ 1；The weight ratio of the beta-cyclodextrin and crosslinking agent
For 2-3 ﹕ 1.The tetrafluoro terephthalonitrile is 1 to the weight ratio of formonitrile HCN base ptfe pyridine and beta-cyclodextrin：1-3 specifically may be used
For 1 ﹕ 2；In the substitution reaction step, temperature is 60-120 DEG C, concretely 90 DEG C；The time of polymerisation is 24~48
Hour, concretely 24 hours；The reaction carries out in inert atmosphere such as nitrogen or argon gas atmosphere.Wherein, the removing
The method that remaining alkali compounds can use salt acid elution；The concentration of hydrochloric acid used concretely 1mol/L；The cleaning solvent
Selected from least one of deionized water, tetrahydrofuran and dichloromethane；Three kinds of solvents are washed with arbitrary tandem；Institute
It states and dry be followed successively by vacuum freeze drying and obtain faint yellow solid powder CDP；Wherein, in the freeze-drying step, drying temperature
Can be 77K；Concretely 15-30 minutes drying time more specifically can be 15 minutes.230mg is added in 100mL three-necked flasks
CDP, the ethanol amine of 20mL is injected in the environment of nitrogen, and 120 DEG C of reaction temperature stirs 48h.Ethyl alcohol stirring is added after reaction
15min, obtained product filters and uses distillation washing three times, and is put into vacuum drying chamber drying for 24 hours, obtains product EA modifications
Cyclodextrin (EA-CDP) in addition, the beta cyclo dextrin polymer being prepared according to the method described above and the polymer in water
Processing adsorpting anion ionic dye also belongs to protection scope of the present invention.
Compared with the prior art, the advantages of the present invention are as follows：(1) adsorbent provided by the invention has higher specific surface
Long-pending and lower cost, and environmental-friendly, it is with good stability under neutral or acid condition the features such as.(2) of the invention
The anionic dye adsorbent can be obviously improved the performance of its Adsorption anionic dye methyl orange, reach efficient removal
The purpose of methyl orange.Polymer material 3h can reach adsorption equilibrium, the removal rate of methyl orange dye up to 95.0% or more,
Maximal absorptive capacity is up to 290mg/g.(3) beta cyclo dextrin polymer adsorbent provided by the invention removes anionic dye methyl orange
Method have and be not necessarily to special installation, step is simple and efficient, will not introduce other harmful substances in processing procedure, the rate of adsorption compared with
Quickly, the features such as adsorption efficiency is high.
Description of the drawings
Beta cyclo dextrin polymer (EA-CDP) shown in FIG. 1 prepares figure.
Fig. 2 is the infared spectrum of 1 gained EA-CDP of embodiment.
Fig. 3 is the nuclear magnetic spectrogram of 1 gained EA-CDP of embodiment.
Fig. 4 is adsorption time under difference EA-CDP additions in the processing example of methyl orange anionic dye waste water and absorption
The graph of relation of amount.
Fig. 5 is the graph of relation of the methyl orange dye waste water for testing one handled in example between pH and adsorbance.
Fig. 6 is the absorption schematic diagram that beta cyclo dextrin polymer adsorbs methyl orange.
Specific implementation mode
With reference to specific embodiment, the present invention is further elaborated.The beta cyclo dextrin polymer adsorbent method is such as
No special instruction is conventional method.The raw material can obtain unless otherwise instructed from open commercial sources.
The method for handling the waste water solution containing methyl orange dye furthermore with beta cyclo dextrin polymer adsorbent：By β-ring
Dextrin polymer is added in the waste water solution containing methyl orange anionic dye, and shaken after mixing makes adsorbent fill for a period of time
Divide absorption methyl orange dye, be then separated by filtration, removes the beta cyclo dextrin polymer absorption for having adsorbed methyl orange anionic dye
Agent.Utilize the determination of methyl orange dye adsorbent Adsorption methyl orange anionic dye condition：By setting different absorption
Time, different adsorbent input amounts, adsorption temp, the initial concentration of methyl orange, draws the suction of adsorbent in Methyl Orange in Wastewater
Attached amount qtWith adsorption time t, initial concentration solution C0Etc. factors variation diagram, investigate beta cyclo dextrin polymer removal methyl orange
Optimal adsorption condition.When visible light photometry being used to measure a certain etching solution in wavelength for the absorbance A at 464nm, according to C=
KA calculates its concentration, and K is absorptivity (L/mol), the removal rate of methyl orange is then calculated according to (1) formula, according to (2) formula
Calculate the adsorbance of adsorbent.
Wherein：E is the removal rate of methyl orange, qtFor the adsorbance (mg/g) of adsorbent, C0For the initial dense of methyl orange solution
It spends (mg/L), CtFor the concentration (mg/L) of methyl orange in solution after absorption, V is the volume (L) of the methyl orange solution for absorption,
M is the quality (g) that beta cyclo dextrin polymer is added.
Embodiment 1 prepares beta cyclo dextrin polymer (EA-CDP)
By 0.962g beta-cyclodextrins, 0.5g crosslinking agent tetrafluoro terephthalonitriles and 1.23g basic salt compound Ks2CO3It is added to
27ml tetrahydrofurans (THF) and 3mlN, dinethylformamide (DMF) in the mixed solvent (VTHF:VDMF=9), lead to nitrogen 5 to divide
Clock carried out polymerisation after 48 hours at 85 DEG C, with the solid on 1mol/L salt acid elution filter paper, remove remaining K2CO3,
Until CO2Release finishes, and washs obtained solid with 20ml deionized waters, 20ml tetrahydrofurans, 20ml dichloromethane successively, then will
Solid is freeze-dried 10-20 minutes in high vacuum liquid nitrogen bath, is then dried in vacuo 2-3 days at room temperature, is obtained the first stepping
Beta cyclo dextrin polymer CDP after row substitution reaction.230mgCDP made from above-mentioned experiment is taken, is injected in the environment of nitrogen
The EA of 20mL, 120 DEG C of reaction temperature stir 48h.Ethyl alcohol is added after reaction and stirs 15min, obtained product, which filters, to be used in combination
Distillation washing three times, and is put into vacuum drying chamber drying for 24 hours, obtains the amine-modified cyclodextrin polymerization (EA-CDP) of product ethanol.
The infrared spectrum of the polymer is as shown in Fig. 2, nuclear magnetic spectrogram is as shown in Figure 3.As seen from the figure, the correct of the polymer architecture
Embodiment 2, EA-CDP absorption methyl orange experiments
1 gained beta cyclo dextrin polymer EA-CDP and 10ml initial concentration 30mg/l methyl orange solutions of 10mg embodiments are mixed
It closes, is placed in 30 DEG C of constant temperature water bath oscillator with 170rmin-1Speed shake 30 minutes.After concussion, use
0.2 μm of polytetrafluoroethylene (PTFE) filter paper filters separation solid and solution.Pass through first in UV-vis ultraviolet visible spectrometry determination samples
The residual concentration (measuring the absorbance A that wavelength is the places 464nm) of base orange, in 2 hours removable water Methylene Blue up to 95% with
On.Ultrasonic beta-cyclodextrin compound, renewable beta-cyclodextrin compound, experiment cycle 5 times, not having property of polymer are impregnated with ethyl alcohol
The loss of energy is smaller.
Embodiment 3, EA-CDP adsorb Congo Red test
The 1 Congo red solution of gained beta cyclo dextrin polymer EA-CDP and 10ml initial concentrations 30mg/l of 3mg embodiments is mixed
It closes, is placed in 30 DEG C of constant temperature water bath oscillator with 170rmin-1Speed shake 30 minutes.After concussion, use
0.2 μm of polytetrafluoroethylene (PTFE) filter paper filters separation solid and solution.By rigid in UV-vis ultraviolet visible spectrometry determination samples
The residual concentration (it is the absorbance A at 497nm to measure wavelength) of arnotto, can remove Congo red up to 95% or more in water in 2 hours.
Ultrasonic beta-cyclodextrin compound is impregnated with ethyl alcohol, renewable beta-cyclodextrin compound, experiment cycle 5 times, polymer does not have performance
Loss is smaller.
Embodiment 4, EA-CDP absorption acid blues 83 are tested
By 1 gained beta cyclo dextrin polymer EA-CDP of 3mg embodiments and 83 solution of 10ml initial concentration 30mg/l acid blues
Mixing, is placed in 30 DEG C of constant temperature water bath oscillator with 170rmin-1Speed shake 30 minutes.After concussion, use
0.2 μm of polytetrafluoroethylene (PTFE) filter paper filters separation solid and solution.By sour in UV-vis ultraviolet visible spectrometry determination samples
Property indigo plant 83 residual concentration (measuring the absorbance A that wavelength is the places 600nm), acid blue 8390% in removable water in 100 minutes.
Ultrasonic beta-cyclodextrin compound, the renewable polymer, experiment cycle 3 times, beta cyclo dextrin polymer adsorptivity are impregnated with ethyl alcohol
The loss of energy is smaller.
Embodiment 4, EA-CDP absorption Indian yellow G experiments
1 gained beta cyclo dextrin polymer EA-CDP and 10ml initial concentration 30mg/l Indian yellow G solution of 3mg embodiments is mixed
It closes, is placed in 30 DEG C of constant temperature water bath oscillator with 170rmin-1Speed shake 30 minutes.After concussion, use
0.2 μm of polytetrafluoroethylene (PTFE) filter paper filters separation solid and solution.By sour in UV-vis ultraviolet visible spectrometry determination samples
Property Huang G residual concentration (measuring the absorbance A that wavelength is the places 410nm), in 60 minutes in removable water Indian yellow G 95% with
On.Ultrasonic beta-cyclodextrin compound, the renewable polymer, experiment cycle 5 times, beta cyclo dextrin polymer absorption are impregnated with ethyl alcohol
Performance loss is smaller.
Claims (6)
1. anionic dye adsorbent, which is beta cyclo dextrin polymer, and preparation includes the following steps：In nitrogen or argon
In gas, after beta-cyclodextrin, crosslinking agent, alkali compounds are carried out polymerisation in organic solvent, resulting polymers again with second
Hydramine is reacted, and reaction finishes to obtain the beta cyclo dextrin polymer (EA-CDP).
2. anionic dye adsorbent according to claim 1, it is characterised in that：The crosslinking agent is tetrafluoro terephthaldehyde
Nitrile or to itrile group ptfe pyridine；The alkali compounds is K2CO3Or KHCO3；The solvent is tetrahydrofuran and N, N- dimethyl
The organic solvent of formamide mixing composition；The volume ratio of the tetrahydrofuran and N,N-dimethylformamide is 7-10 ﹕ 1.
3. the beta cyclo dextrin polymer preparation method according to claim 1-2, it is characterised in that：The alkali compounds with
The mass ratio of beta-cyclodextrin is 3-5 ﹕ 1；The weight ratio of the beta-cyclodextrin and crosslinking agent is 2-3 ﹕ 1；The ethanol amine and β-ring
The weight ratio of dextrin is 1 ﹕ 1-3 or 1 ﹕ 2.
4. according to any beta cyclo dextrin polymer preparation method in claim 1-3, it is characterised in that：The substitution is anti-
It answers in step, temperature is 80-100 DEG C；The time of first time substitution reaction is 24-48 hours；The time of second secondary response is
24-48 hours；The substitution reaction carries out in argon gas or nitrogen atmosphere.
5. beta cyclo dextrin polymer preparation method according to any one of claims 1-4, it is characterised in that：The method is also
Include the following steps：After second of reaction step, reaction system is cooling, filtering removes remaining alkaline chemical combination
After object, obtained solid is washed with deionized, is dried in vacuo and obtains flaxen powdered samples.
6. a kind of anionic dye using described in claim 5 handle the method for methyl orange dye waste water it is characterized in that：It will
Methyl orange dye adsorbent is added in the waste water solution containing methyl orange dye, so that methyl orange dye is inhaled using oscillator concussion
Attached dose fully adsorbs methyl orange, is then separated by filtration, and removes the beta cyclo dextrin polymer adsorbent for having adsorbed dyestuff.
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| CN109513430A (en) * | 2019-01-15 | 2019-03-26 | 天津市水利工程有限公司 | A kind of preparation method and application of supermolecule polymer adsorbent |
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Application publication date: 20180928 |