CN103623784B - The preparation method of copper ion blotting chitosan composite - Google Patents
The preparation method of copper ion blotting chitosan composite Download PDFInfo
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- CN103623784B CN103623784B CN201310624839.8A CN201310624839A CN103623784B CN 103623784 B CN103623784 B CN 103623784B CN 201310624839 A CN201310624839 A CN 201310624839A CN 103623784 B CN103623784 B CN 103623784B
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- copper ion
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- ion blotting
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 53
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 131
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 131
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- 239000010949 copper Substances 0.000 claims abstract description 56
- 230000000694 effects Effects 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 14
- 238000000151 deposition Methods 0.000 claims abstract description 14
- 230000008021 deposition Effects 0.000 claims abstract description 14
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 14
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 14
- 238000002444 silanisation Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 33
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- 150000002500 ions Chemical class 0.000 claims description 14
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- 239000000203 mixture Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 9
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- 235000011158 Prunus mume Nutrition 0.000 description 6
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
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- 239000003446 ligand Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
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- 230000007423 decrease Effects 0.000 description 2
- LICVGLCXGGVLPA-UHFFFAOYSA-N disilanyl(disilanylsilyl)silane Chemical compound [SiH3][SiH2][SiH2][SiH2][SiH2][SiH3] LICVGLCXGGVLPA-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
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- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
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- 241001465754 Metazoa Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to imprinted polymer, and in particular to a kind of preparation method of copper ion blotting chitosan composite.The preparation method of the present invention is comprised the following steps：(1)Al2O3Surface activity SiO2The deposition of layer；(2) to deposited surface activity SiO2The Al of layer2O3Silanization；(3) prepare Cu2+Chitosan complex；(4) prepare copper ion blotting chitosan composite material template；(5) eluting, washing, drying.Operation is simple for the present invention, and the composite of preparation can effectively remove the Cu in waste water2+, and energy consumption is low, no secondary pollution.
Description
Technical field
The present invention relates to imprinted polymer, and in particular to a kind of preparation method of copper ion blotting chitosan composite.
Background technology
With electronics industry and the development of metallurgical industry, the waste water of substantial amounts of copper ions is generated.This heavy metal species gives up
When water is discharged, even if concentration very little, also serious harm can be caused to environment and human body.Heavy metal poison is not degraded by microorganisms,
Can only mutually conversion, the dispersion between different shape.And its toxicity is so that in the presence of ionic state, the most seriously, this form is easily by ligand
Ligand complex is adsorbed by negatively charged colloid, is drifted with the tide and is migrated everywhere.Heavy metal contaminants are difficult to administer, in water body
In run up to certain limit serious harm will be produced to water body and aquatic animals and plants system, and affected by drinking-water and food chain
To the health of mankind itself.After heavy metal enters human body, can act on vivo biodistribution polymer substance and be allowed to lose activity, together
When be accumulated in some organs of human body, cause chronic toxicity, when serious can burst disease, ultimately result in death.
As most heavy metal ion, when copper ion is present in excess in human body or environment, can serious harm people
The ecosystem of the life and health and surrounding of body.Therefore need to be effectively treated the copper ion in waste water, excluding and
Reduce the infringement to human body and environment.
The processing method of copper-containing wastewater mainly has using the sedimentation method and electrolysis at present.The advantage of the sedimentation method is equipment investment
Less, process is simple and convenient to operate safety etc..But the acidity of generally heavy metal wastewater thereby is big, needs to add substantial amounts of precipitant, needs
What is produced in constantly consuming chemical materialss, and precipitation process is difficult to process containing poisonous heavy metal compound sludge.On the other hand,
Often contain various anion ligands in copper-containing wastewater, these ligands generate the metal compound of solubility with metal ion
Thing so as to be trapped in waste water, is difficult to be reacted with precipitant, causes treatment effeciency to decline, while being also easy to produce secondary pollution.
Electrolysis is that copper-containing wastewater is electrolysed, Cu2+Separate out to cathodic migration and in electrode surface, so as to reduce system for handling
In Cu2+.But electrolysis is easy to pollution, and energy consumption is big, processing cost is high.
The content of the invention
In order to solve the disadvantages mentioned above of prior art, the present invention provides a kind of system of copper ion blotting chitosan composite
Preparation Method, the composite can effectively remove the Cu in waste water2+, and energy consumption is low, no secondary pollution.
The technical scheme for being adopted that the present invention solves the above problems for：A kind of copper ion blotting chitosan composite
Preparation method, the preparation method of copper ion blotting chitosan composite, the method are comprised the following steps：
(1)Al2O3Surface activity SiO2The deposition of layer
In Al2O3Surface deposits SiO2Layer, then obtains activity Si-OH, drying for standby with dilute hydrochloric acid immersion；
(2) to deposited surface activity SiO2The Al of layer2O3Silanization
By deposition SiO obtained by step (1)2The Al of active layer2O3In 3～7 grams of addition round-bottomed flasks of powder, 20 are added
～30mL silane coupler KH-560, are diluted with 20～30mL acetone, in 60～80 DEG C of 8～12h of back flow reaction, obtain silanization
Al2O3；
(3) prepare Cu2+- chitosan complex
Weigh 0.2～0.3g CuSO4·5H2O and 2.5～3.5g shitosans are dissolved in the acetic acid of 120～180mL0.1mol/L
Solution, in constant temperature blender with magnetic force, 20～30 DEG C of 1.5～2.5h of reaction make shitosan and Cu2+Fully reaction generates Cu2+-
Chitosan complex；
(4) prepare copper ion blotting chitosan composite material template
By the Al of step (2) hexasilane2O3It is added to Cu obtained in step (3)2+In-chitosan complex, 20～
30 DEG C of 4～6h of stirring reaction obtain copper ion blotting chitosan composite material template；After reaction terminates, the copper ion of gained is printed
Mark Chitosan Composites template is placed in baking oven and is dried 12～48h；
(5) eluting, washing, drying
Drying sample grind into powder, acetone and ethanol are respectively washed 2～3 times with mortar, deionized water wash 3～4 times,
Vacuum drying；Then with the HCl eluted template ions of 0.5～0.7mol/L, sucking filtration；Then again with 0.05～0.15mol/L's
NaOH solution is washed, and is then washed with deionized repeatedly to cleaning mixture in neutrality, and 40～60 DEG C of vacuum drying are sieved, obtained
Cu2+Blotting chitosan composite IIP/Al2O3。
Preferably, step (1) Al2O3Surface activity SiO2The deposition of layer, its technique is：Weigh appropriate Al2O3Powder,
Acetone soak 10h；Then with the process of 3mol/L NaOH solutions, deionized water wash, filtration, drying；Then will dry
Al2O3It is placed in crucible, 600 DEG C of roasting 7h in Muffle furnace；After natural cooling, 15h is soaked with dilute HCl, deionized water wash is into
Property, filter, be put into dry for standby in vacuum drying oven；Then a certain amount of above-mentioned dried sample is taken, is added equipped with appropriate 1/
In the round-bottomed flask of 10 TEOS/ ethanol solution, 70 DEG C of back flow reaction 30h, then by reacted sample filtering, move into Muffle
550 DEG C of calcining 3h, natural cooling in stove；The HCl immersion 24h of 0.1mol/L are added after deionized water wash, activity Si- is obtained
OH；Finally it is washed with deionized to neutrality, 80 DEG C of drying for standby.
Preferably, step (2) is to deposited surface activity SiO2The Al of layer2O3The technique of silanization is：By step (1) institute
Deposition SiO for obtaining2The Al of active layer2O3In 5 grams of addition round-bottomed flasks of powder, 25mL silane coupler KH-560 are added, used
25mL acetone dilutes, and in 70 DEG C of back flow reaction 10h, obtains the Al of silanization2O3。
Preferably, step (3) prepares Cu2+The technique of-chitosan complex is：Weigh 0.25gCuSO4·5H2O and 3.0g
Shitosan is dissolved in the acetum of 150mL0.1mol/L, and in constant temperature blender with magnetic force, 25 DEG C of reaction 2h make shitosan and Cu2+
Fully reaction generates Cu2+- chitosan complex.
Preferably, the technique that step (4) prepares copper ion blotting chitosan composite material template is：By step (2) own silicon
The Al of alkanisation2O3It is added to Cu obtained in step (3)2+In-chitosan complex, copper ion print is obtained in 25 DEG C of stirring reactions 5h
Mark Chitosan Composites template；After reaction terminates, the copper ion blotting chitosan composite material template of gained is placed in into baking oven
In be dried 24h.
Preferably, step (5) eluting, washing, drying process are：Dry copper ion blotting chitosan is combined with mortar
Respectively washing 2 times of material pattern grind into powder, acetone and ethanol, deionized water wash 3 times are vacuum dried 8h；Then use
The HCl eluted template ions of 0.6mol/L, sucking filtration；Then washed with the NaOH solution of 0.1mol/L again, then deionized water
Repeatedly to cleaning mixture in neutrality, 50 DEG C of vacuum drying 8h cross 80 mesh sieves, obtain Cu for washing2+Blotting chitosan composite IIP/
Al2O3。
Operation is simple for the present invention, and the composite of preparation can effectively remove the Cu in waste water2+, and energy consumption
It is low, no secondary pollution.
Description of the drawings
Fig. 1 is Al2O3, Al after deposition reaction2O3, shitosan, IIP/Al2O3And NIP/Al2O3) infrared spectrogram；
Fig. 2 is influence curve figure of the pH value to adsorbance；
Fig. 3 is influence curve figure of the initial concentration to adsorbance；
Fig. 4 is IIP/Al2O3And NIP/Al2O3The selectivity comparison diagram adsorbed by Cu (II)；
Fig. 5 is IIP/Al2O3With NIP/Al2O3Breakthrough curve figure.
Specific embodiment
Some embodiments of the present invention presented below, to help further understanding the present invention, but protection scope of the present invention
It is not limited in these embodiments.
Experimental raw and instrument
(1) main agents
Shitosan (deacetylation 85～95%, Chemical Reagent Co., Ltd., Sinopharm Group)；
(analysis is pure, and Chinese medicines group chemical reagent is limited for γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane (KH-560)
Company)；
Glacial acetic acid (analyzes pure, Xilong Chemical Co., Ltd)；
Tetraethyl orthosilicate (TEOS) (analyzes pure, Xilong Chemical Co., Ltd)；
Acetone (analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group)；
Dehydrated alcohol (analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group)；
Hydrochloric acid, sodium hydroxide are pure for analysis；Experimentation water is deionized water.
Copper sulfate (analyzes pure, Xilong Chemical Co., Ltd)；
(2) key instrument
Electron scanning Electronic Speculum (JSM-6380LV, NEC)；
Infrared spectrometer (Nicolet-6700, power ＆ light company of the U.S.)；
TG-DTA analysis instrument (WCT-1D, Beijing Optical Instrument Factory)；
Energy dispersion X-ray spectrogrph (EDX-GP, Japanese Shimadzu Corporation)；
Atomic Absorption Spectrometer (AA-670, Japanese Shimadzu Corporation)；
Spectrophotometry instrument (UV-2550, Japanese Shimadzu Corporation)；
Muffle furnace (SRJX-4-9, Changsha experimental electric furnace factory)；
Vacuum drying oven (DZF-6050, the grand experimental facilitiess company limited of upper Nereid)；
Laboratory pH meter (FE20, prunus mume (sieb.) sieb.et zucc. Teller-support benefit Instrument Ltd.)；
Heat collecting type constant-temperature heating magnetic stirring apparatus (DF-101S, Yu Hua Instrument Ltd. of Gongyi City)
Electronic balance (AL204, prunus mume (sieb.) sieb.et zucc. Teller-support benefit Instrument Ltd.)
Vacuum pump using circulatory water (SHB-B88, Yu Hua Instrument Ltd. of Gongyi City)
Embodiment 1
1st, the preparation of imprinted polymer
(1)Al2O3Surface activity SiO2The deposition of layer
Weigh appropriate Al2O3Powder, acetone soak 10h.Processed with 3mol/L NaOH solutions, deionized water wash, filtration,
Drying.By the Al dried2O3It is placed in crucible, 600 DEG C of roasting 7h in Muffle furnace.After natural cooling, 15h is soaked with dilute HCl,
Deionized water wash is filtered, is put into dry for standby in vacuum drying oven to neutrality；A certain amount of above-mentioned dried sample is taken, plus
Enter in the round-bottomed flask equipped with appropriate 1/10 TEOS/ ethanol solution, 70 DEG C of back flow reaction 30h, then by reacted sample
Filter, move into 550 DEG C of calcining 3h in Muffle furnace, natural cooling.The HCl immersion 24h of 0.1mol/L are added after deionized water wash,
Obtain activity Si-OH.Finally it is washed with deionized to neutrality, 80 DEG C of drying for standby.
(2) to deposited surface activity SiO2The Al of layer2O3Silanization
By deposition SiO obtained by step (1)2The Al of active layer2O3In 5 grams of addition round-bottomed flasks of powder, 25mL silicon is added
Alkane coupling agent KH-560, is diluted with 25mL acetone, in 70 DEG C of back flow reaction 10h, obtains the Al of silanization2O3。
(3) prepare Cu2+- chitosan complex
Weigh 0.25g CuSO4·5H2O and 3.0g shitosans are dissolved in the acetum of 150mL0.1mol/L, in constant temperature magnetic
In power agitator, 25 DEG C of reaction 2h make shitosan and Cu2+Fully reaction generates Cu2+- chitosan complex.
(4) prepare copper ion blotting chitosan composite material template
By the Al of step (2) hexasilane2O3It is added to Cu obtained in step (3)2+In-chitosan complex, at 25 DEG C
Stirring reaction 5h obtains copper ion blotting chitosan composite material template；After reaction terminates, the copper ion trace shell of gained is gathered
Sugared composite material template is placed in baking oven and is dried 24h.
(5) eluting, washing, drying process
Dry copper ion blotting chitosan composite material template grind into powder, acetone and ethanol are respectively washed with mortar
2 times, deionized water wash 3 times is vacuum dried 8h；Then with the HCl eluted template ions of 0.6mol/L, sucking filtration；Then use again
The NaOH solution washing of 0.1mol/L, is then washed with deionized repeatedly to cleaning mixture in neutrality, 50 DEG C of vacuum drying 8h, mistake
80 mesh sieves, obtain Cu2+Blotting chitosan composite IIP/Al2O3。
Course of reaction：
Then, except being not added with Cu2+Outward, additive method is same as described above, prepares non-trace composite (NIP/Al2O3) conduct
Contrast material.
2nd, performance test is carried out to obtained copper ion blotting chitosan composite
(1) infrared spectrum characterization
Fig. 1 is Al2O3, Al after deposition reaction2O3, shitosan, IIP/Al2O3And NIP/Al2O3Infrared spectrogram.
Al2O3Infrared spectrum 1634 and 958cm-1There are two peaks, correspond to Si-O bendings and asymmetric stretching vibration peak (figure respectively
1.a).After deposition reaction, in 943cm-1Place occurs in that the Si-O stretching vibration peaks (Fig. 1 .b) being remarkably reinforced, and this peak exists
IIP/Al2O3Transfer has been moved to 909cm-1Place (Fig. 1 .d), shows in Al2O3Surface has defined reactive silica silicon layer.Shell gathers
Sugared 1081cm-1The C-O flexural vibrations peaks (Fig. 1 .c) at place are in IIP/Al2O3(Fig. 2 .d) and NIP/Al2O3Turn in (Fig. 1 .e) respectively
Have been moved to 1079cm-1And 1040cm-1Place；Shitosan 3430cm-1N-H the and O-H stretching vibrations peak at place is in IIP/Al2O3And NIP/
Al2O3It is middle to be transferred to 3384cm respectively-1And 3458cm-1Place, this shows：In imprinted polymer preparation process, the N-H of shitosan
Complexation reaction may be participated in O-H.Shitosan 1651cm-1The N-H flexural vibrations peaks at place and 1382cm-1The C-N at place is asymmetric to be stretched
Contracting vibration peak is in IIP/Al2O3It is middle to be transferred to 1732cm respectively-1And 1397cm-1.Additionally, in IIP/Al2O3In spectrogram,
2925cm-1And 2870cm-1There are two obvious C-H stretching vibration peaks at place, and this is due to IIP/Al2O3In occur in that and carry out self-crosslinking
- the CH of agent KH-5603Group.It can be seen that, imprinted polymer has been grafted to Al2O3Surface.With surface imprinted and crosslinking technology it is
Basis, in modified Al2O3Surface grafting Cu2+Blotting chitosan, is prepared for novel C u2+Blotting chitosan composite.
(2) copper ion blotting chitosan composite static adsorption
Raw material and instrument
Zinc sulfate
Nickel sulfate
Hydrochloric acid, sodium hydroxide are pure for analysis；Experimentation water is deionized water.
Copper sulfate (analyzes pure, Xilong Chemical Co., Ltd)；
Laboratory pH meter (FE20, prunus mume (sieb.) sieb.et zucc. Teller-support benefit Instrument Ltd.)；
Heat collecting type constant-temperature heating magnetic stirring apparatus (DF-101S, Yu Hua Instrument Ltd. of Gongyi City)
Electronic balance (AL204, prunus mume (sieb.) sieb.et zucc. Teller-support benefit Instrument Ltd.)
Vacuum pump using circulatory water (SHB-B88, Yu Hua Instrument Ltd. of Gongyi City)
Thermostat water bath
Selective Separation experimentation
According to Ni2+、Zn2+With Cu2+Raw matter, structure size are similar, select to study IIP/Al both as competing ions2O3It is multiple
Condensation material is to Cu2+Selective absorption behavior.
Prepare Ni2+、Zn2+With Cu2+Concentration is the mixed solution of 250mg/L, and it is 5 to adjust pH value of solution, is subsequently adding 0.5g
Cu2+IIP/Al2O3Polymeric material or NIP/Al2O3Polymeric material, standing 60min, take supernatant liquid filtering with a ultraviolet vis spectroscopy
Photometer determines the equilibrium concentration of each ion respectively.Simultaneously respectively with following formula calculation of distribution coefficient, selectivity factor and relative choosing
Select property coefficient.
The zeolite regeneration and estimation of stability of adsorbent
HCl solution eluting target Cu of this experiment using 0.6mol/L2+.At room temperature, multiple agitator treating, until washing
Cu is can't detect in liquid2+, then washed with the NaOH solution of 0.1mol/L, solution is then repeatedly washed in neutrality, with 50 DEG C
Dry in vacuum drying oven.Repeat absorption-elution process 10 times, evaluate IIP/Al2O3Stability.
The effects pH between 2.0～5.5 pH value to IIP/Al2O3Equilibrium adsorption capacities impact.As a result as schemed
Shown in 2, IIP/Al2O3To Cu (II) (Cu (II), 500mg L-1；T, 298K) equilibrium adsorption capacity with solution ph increase and it is fast
Speed increases, and reaches maximum in pH5.5.Therefore adsorbance changes of the pH on imprinted polymer affects larger, mainly due to Cu
And H (II)+Competitive Adsorption.When pH is relatively low, H+Concentration is big, and competitiveness strengthens, IIP/Al2O3Upper a large amount of avtive spots are by H+
Occupy, so when IIP/Al2O3There is relatively low adsorption capacity to Cu (II).With the increase of pH value of solution, H+Competitiveness is reduced,
IIP/Al2O3Upper enough avtive spots adsorbed target Cu (II), therefore, equilibrium adsorption capacity gradually increases.During pH ＞ 6, due to
Cu (II) is hydrolyzed, the change of the form generation of ion, investigates IIP/Al2O3Meaning has been lost to Cu (II) equilibrium adsorption capacity.
Impact of Cu (II) initial concentrations to polymeric material equilibrium adsorption capacity
Experiment have studied impact of Cu (II) initial concentrations to polymeric material equilibrium adsorption capacity using static method, such as Fig. 3 institutes
Show, be that 5, Cu (II) initial concentration is 10-600mg L in pH-1When, the IIP/Al of unit mass2O3And NIP/Al2O3Adsorption of Cu
(II) equilibrium adsorption capacity increases with the increase of Cu (II) initial concentration, until absorption reaches saturation.Obviously, relatively low
During Cu (II) initial concentration, IIP/Al2O3To the rate of rise of the equilibrium adsorption capacity of Cu (II) quickly, mainly due to now
IIP/Al2O3Enough avtive spots can be provided to adsorbed target Cu (II).When initial concentration reaches 300mg L-1When,
IIP/Al2O3To increaseing slowly for the equilibrium adsorption capacity of Cu (II), this is mainly due to the increase of initial concentration, IIP/
Al2O3The avtive spot and hole relative deficiency of Adsorption of Cu (II), until adsorption site reaches saturation, therefore, reach in initial concentration
For 500mg L-1Adsorption equilibrium quantity tends to certain value afterwards, i.e. absorption reaches saturation,.By calculating IIP/Al2O3And NIP/Al2O3
30.42 and 11.49mg/g are respectively to the static saturated adsorption capacity of Cu (II), it is evident that IIP/Al2O3To target Cu (II)
Saturated adsorption capacity be far above NIP/Al2O3.This explanation is in IIP/Al2O3In adsorption to Cu (II), printing process rises
Important effect is arrived.
Selectivity is tested
IIP/Al2O3And NIP/Al2O3It is as shown in Figure 4 to the result of the adsorption rate of Cu (II), Ni (II) and Zn (II).Very
Substantially, IIP/Al2O371.5% is up to the adsorption rate of Cu (II), and the adsorption rate of Ni (II), Zn (II) is only near to
20%.On the other hand, NIP/Al2O3Relatively low adsorption rate is only shown to all of metal ion.IIP/Al2O3And NIP/
Al2O3To the selectivity parameter of metal ion such as：Distribution ratio, selectivity factor and relative selectivity coefficient can be tried to achieve according to following formula：
Qe=(C0-Ce)V/W (1)
D=Qe/Ce (2)
α=DCu/DX (3)
α '=αIP/αNP (4)
In formula：QeIt is equilibrium adsorption capacities (mg g-1)；C0And CeMetal ion initial concentration and equilibrium concentration are represented respectively
(mg L-1), V is the volume (mL) of metal ion solution；W is the quality (g) of adsorbent；D, α and α ' represent distribution ratio (mL respectively
g-1), selectivity factor and relative selectivity coefficient；DCuAnd DXRepresent the distribution ratio of Cu (II) and other competing ions；αIPAnd αNP
It is IIP/Al respectively2O3Selectivity factor and NIP/Al2O3Selectivity factor.
As shown in Table 1, IIP/Al2O3It is very high to the selectivity factor value of target Cu (II), show IIP/Al2O3To Cu
(II) there is very high identification selection, and to Ni (II) and the no Selective recognitions of Zn (II), even if they have similar change
Learn property；Review NIP/Al2O3, it is then relatively low to the selectivity factor value of target Cu (II), it is meant that NIP/Al2O3To target Cu
(II) it is sufficiently close to the absorbability of competing ions, almost no selectivity.Relative to Ni (II) and Zn (II), to Cu (II)
Relative selectivity coefficient value be 6.90 and 7.72 respectively, illustrate IIP/Al2O3NIP/ is about to the selectivity of Cu (II)
Al2O37 times, i.e., relative to NIP/Al2O3, IIP/Al2O3Target Cu (II) selectivity is greatly improved.This is mainly
Due to IIP/Al2O3Preparation process in trace effect generate special avtive spot for Selective recognition target Cu
(II)。
Table 1IIP/Al2O3And NIP/Al2O3Selectivity parameter to Cu (II)
In addition, Jing tests, under identical condition, using same IIP/Al2O3, after repeating ten absorption-elution processes,
IIP/Al2O3Adsorption capacity only decline 2%.This shows, under the experiment condition studied, IIP/Al2O3Show good
Stability and the repeatable characteristic for utilizing.
The Study on dynamic adsorption of copper ion trace composite
Experimental raw and instrument
Zinc sulfate
Nickel sulfate
Copper sulfate (analyzes pure, Xilong Chemical Co., Ltd)；
Hydrochloric acid, sodium hydroxide are pure for analysis；Experimentation water is deionized water
Organic glass column 120mm*3.2mm,
Vacuum drying oven (DZF-6050, the grand experimental facilitiess company limited of upper Nereid)；
Laboratory pH meter (FE20, prunus mume (sieb.) sieb.et zucc. Teller-support benefit Instrument Ltd.)；
Heat collecting type constant-temperature heating magnetic stirring apparatus (DF-101S, Yu Hua Instrument Ltd. of Gongyi City)
Electronic balance (AL204, prunus mume (sieb.) sieb.et zucc. Teller-support benefit Instrument Ltd.)
Vacuum pump using circulatory water (SHB-B88, Yu Hua Instrument Ltd. of Gongyi City)
Thermostat water bath
Dosing pump
Right cylinder dynamic adsorption is tested
By 0.5,0.75 and 1.0g IIP/Al2O3Or NIP/Al2O3Load in the glass column of internal diameter 3.2mm, corresponding post
It is high to be respectively 25,37.25 and 50mm, with 2mLmin-1The deionized water rinsing glass column 30min of flow velocity so that IIP/Al2O3
Or NIP/Al2O3It is fully swelling, pH value is adjusted with hydrochloric acid and sodium acetate buffer solution；At 25 DEG C of temperature, by finite concentration (50,
100、200mg·L-1), pH value (2,3,4,5) and flow velocity (0.5,1.0,1.5,2.0mLmin-1) CuSO4Solution flows through
IIP/Al2O3Or NIP/Al2O3Adsorption column, every 10min in the sampling of absorption column bottom, is flowed out with atomic absorption spectrometry
Liquid Cu2+Concentration, until its concentration is equal with entrance concentration, draws breakthrough curve, when measure is penetrated at the end of total effluent, experiment
The Cu of total effluent2+Concentration, calculating penetrate adsorbance and equilibrium adsorption capacity；IIP/Al under the conditions of research trends2O3Or NIP/
Al2O3To Cu2+Selective absorption behavior, with Ni2+、Zn2+And Cu2+Mixed solution is object of study, and three kinds of ion concentrations are
100mg·L-1, pH value is 5；After adsorption column adsorption saturation, with 0.6molL-1HCl solution eluting metal ion, then with go from
After sub- water washing, adsorption column is reused.
The optimization of elution requirement
The eluting effect of target metal ions and the property of functional complexes and eluting in metal ion imprinted polymer
The elution requirements such as the species of liquid, flow velocity, the amount of eluent are related.Target copper ion is washed using the method for pickling herein
It is de-.Experimental technique is specific as follows：IIP/Al2O3Residual copper ion solution in post is extracted out up to after adsorption saturation by packed column, is used
Deionized water rinses pillar 5min with the flow velocity of 2mL/min, and different eluant (H are then respectively adopted2SO4、HNO3And HCl),
The HCl (0.1mol/L, 0.6mol/L and 1.0mol/L) of variable concentrations, 0.6mol/L HCl different in flow rate (0.5mL/min,
1.0mL/min and 2.0mL/min) the adsorbed copper ion of eluting, constant operating temperature is 25 DEG C, to adsorbing column bottom eluent
Sample every 1min, determine the concentration of copper ion in eluent, until Cu is can't detect in cleaning mixture2+, terminate experiment.Drafting is washed
De- curve, calculates eluting rate, optimizes elution parameters.
The reproducibility of trace packed column
In order to determine the regenerability of trace packed column, the same packed column of this experiment repeats absorption-elution process 5 times,
IIP/Al2O3Loading is 0.75g, and pillar height is 37.25mm, and initial concentration solution 100mg/L, pH=5.0, solution pass through filling
The flow velocity of post：1.0mL/min, temperature：25 DEG C, the HCl solution of 0.6mol/L is adopted with flow velocity eluting target Cu of 1mol/L2+,
The leakage capacity of experiment, saturated adsorption capacity and clearance every time are determined, the stability of trace packed column is evaluated.
Experimental result
The research of breakthrough curve
In filling column inlet Cu2+Concentration is 100mg/L, IIP/Al2O3Or NIP/Al2O3Quality be 0.75g, pillar height is
37.25mm, flow velocity is 1.0mL/min and pH value is, under 5, to study IIP/Al2O3With NIP/Al2O3Breakthrough curve, as a result as scheme
Shown in 5, Fig. 5 is IIP/Al2O3With NIP/Al2O3Breakthrough curve.Time of break-through, adsorbance and clearance are shown in Table 2.
Dynamic adsorbance is calculated with formula (1) and (2) and is obtained：
Qtotal=(C0-Ctotal)vttotal (1)
Q in formulatotalFor the Cu being adsorbed in packed column2+Total amount (mg)；C0、CtAnd CtotalRespectively Cu2+Initial concentration, t
Moment fills column outlet Cu2+Concentration and total effluent Cu2+Concentration (mg/L)；V is flow velocity (mL/min)；ttotalDuring to test total
Between (min)；qeqFor dynamic adsorbance (mg/g)；Quality (g) of the M for adsorbent.From Fig. 5 and Biao 2 as can be seen that IIP/Al2O3
And NIP/Al2O3Packed column is to Cu2+The equilibrium adsorption time (define Ct/C0When=0.95 corresponding time was equilibrium adsorption
Between[13]) it is respectively 215min and 120min, and IIP/Al2O3To Cu2+Dynamic adsorbance be far above NIP/Al2O3.Simultaneously can
Know, IIP/Al2O3Packed column is to Cu2+Time of break-through (define Ct/C0=0.05 corresponding time was time of break-through[13]) about
In 31min, break through volume is about 4.03mg/g, and NIP/Al2O3Packed column is to Cu2+The adsorption penetration time be 0min.
Cu2+Clearance is defined as follows：
In formula, RP is Cu2+Clearance (%)；mtotalFor the Cu in working solution2+Total amount (mg).Can be obtained by table 2, experiment condition
Under, IIP/Al2O3Packed column compares NIP/Al2O3Packed column is to Cu2+Clearance high nearly 20%, i.e. IIP/Al2O3Packed column pair
Cu2+Adsorption efficiency be far above NIP/Al2O3Packed column.It can be seen that, printing process not only have impact on IIP/Al2O3Adsorption capacity,
Also which is affected to Cu2+Adsorption process.
2 operating parameter of table is to IIP/Al2O3The impact of post dynamic adsorption
Table 3Thomas fitting data
From under the conditions of in table 3, data can be seen that different operating, the relative coefficient R of Thomas model equations fitting2
Close to 1, and by the calculated maximal absorptive capacity q of model equation0calWith experiment value qexpIt is also very close to, shows given
Experiment condition under, Thomas models are especially suitable for for simulating the post absorption behavior.On the other hand, by the IIP/ of chapter 3
Al2O3The Adsorption thermodynamics conclusion of copper ion is understood, IIP/Al2O3It is that chemisorbed is made to the adsorption process of target copper ion
With, and Thomas models are based on a kind of model that this adsorption mechanism is set up, therefore this model and reality under the system
Testing data has very high degree of fitting.
As can be known from Table 3, with increase Thomas speed constants K of ion concentrationThIt is gradually reduced, and saturated extent of adsorption
qexpIncrease, it may be possible to due in liquid phase during the increase of copper ion initial concentration, IIP/Al2O3Around avtive spot, positive charge increases
It is many, repulsive interaction increase, the rate of adsorption and reduce, but with the increase of concentration, IIP/Al2O3Surface is dense with copper ion in liquid phase
Degree gradient increase, mass transfer driving force increase, overcome sterically hindered so that more avtive spots produce absorption to copper ion and make
With, therefore saturated extent of adsorption increases.On the other hand, under high flow rate, mass transfer rate is larger, therefore Thomas speed constants KThAnd with
The increase of flow velocity and increase.
The selectivity and estimation of stability of packed column
Due to Ni2+、Zn2+、Cu2+Property is similar, herein with Ni2+、Zn2+And Cu2+The mixed solution of three kinds of ions is research
Object, is 25 DEG C in temperature, IIP/Al2O3Or NIP/Al2O3Quality is 0.75g, and pillar height is 37.25mm, three kinds in mixed solution
Ion concentration is 100mgL-1, pH=5.0 and flow velocity are 1.0mLmin-1Under, investigate IIP/Al2O3And NIP/Al2O3It is right
Cu2+Selective absorption behavior, it is found that IIP/Al2O3To Cu2+Adsorption rate is up to 40.6%, to Ni2+And Zn2+Adsorption rate point
Wei 5.1% and 3.4%；NIP/Al2O3Three metal ion species are shown with very low adsorption rate.It can be seen that, IIP/Al2O3Post pair
Cu2+Have compared with high selectivity.
Using 0.6molL-1Hydrochloric acid solution is eluent, in 1.0mLmin-1Cu under flow velocity in eluting packed column2+,
Identical packed column repeats the single Cu of absorption-eluting2+5 times, by the time of break-through of each experiment, penetrate adsorbance, dynamic adsorption capacity
It is listed in Table 3 below with clearance.After 3 absorption-elution experiments, IIP/Al2O3The time of break-through of post and to penetrate adsorbance basic
Constant, equilibrium adsorption capacity and clearance are declined slightly；After 5 absorption-elution experiments, IIP/Al2O3Post penetrate adsorbance and
Dynamic adsorption capacity only declines 5.2% and 3.0% respectively, it is seen then that IIP/Al2O3Post has preferable stability and regenerability.
Table 4IIP/Al2O3The circulation absorption data of post
Conclusion
(1) Kinetic penetration curve shows, IIP/Al2O3Post is to Cu2+Adsorption efficiency is far above NIP/Al2O3Post, i.e. trace row
To affect dynamic adsorption process；Filling column inlet Cu2+Concentration, pillar height, flow velocity and pH value appreciable impact IIP/Al2O3The dynamic of post
Absorption property, adequate operation parameter is：C0=100mgL-1, h=37.25mm, v=1.0 or 1.5mLmin-1And pH=5.
(2) temperature be 25 DEG C, IIP/Al2O3Quality is 0.75g, and pillar height is 37.25mm, fills column inlet Cu2+Concentration
For 100mgL-1, pH=5.0 and flow velocity are 1.0mLmin-1Under, K is obtained by Thomas Equation for CalculatingTh=0.3429 × 10- 3L·mg-1·min-1And q0, cal=15.76mgg-1, theoretical adsorbance with experiment adsorbance closely, theoretical curve and reality
Test data degree of agreement larger, IIP/Al2O3Post dynamic adsorption behavior meets Thomas models.
(3)IIP/Al2O3Post is to Cu2+Adsorption rate is far above competing ions Ni2+And Zn2+, with higher Cu2+Selectivity, 5
After secondary repetition absorption-eluting, penetrate adsorbance and equilibrium adsorption capacity only reduces 5.2% and 3.0%, IIP/Al respectively2O3Post
Can be stable, reproducibility is good.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any spirit without departing from the present invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (6)
1. the preparation method of copper ion blotting chitosan composite, is characterized in that, comprise the following steps：
(1)Al2O3Surface activity SiO2The deposition of layer
In Al2O3Surface deposits SiO2Layer, then obtains activity Si-OH, drying for standby with dilute hydrochloric acid immersion；
(2) to deposited surface activity SiO2The Al of layer2O3Silanization
By deposition SiO obtained by step (1)2The Al of active layer2O3In 3～7 grams of addition round-bottomed flasks of powder, add 20～
30mL silane coupler KH-560, are diluted with 20～30mL acetone, in 60～80 DEG C of 8～12h of back flow reaction, obtain silanization
Al2O3；
(3) prepare Cu2+- chitosan complex
Weigh 0.2～0.3g CuSO4·5H2The acetic acid that O and 2.5～3.5g shitosans are dissolved in 120～180mL0.1mol/L is molten
Liquid, in constant temperature blender with magnetic force, 20～30 DEG C of 1.5～2.5h of reaction make shitosan and Cu2+Fully reaction generates Cu2+- shell
Polysaccharide coordination compound；
(4) prepare copper ion blotting chitosan composite material template
By the Al of step (2) silanization2O3It is added to Cu obtained in step (3)2+In-chitosan complex, stir at 20～30 DEG C
Mix 4～6h of reaction and obtain copper ion blotting chitosan composite material template；After reaction terminates, the copper ion trace shell of gained is gathered
Sugared composite material template is placed in baking oven and is dried 12～48h；
(5) eluting, washing, drying
Drying sample grind into powder, acetone and ethanol are respectively washed 2～3 times with mortar, deionized water wash 3～4 times, vacuum
It is dried；Then with the HCl solution eluted template ion of 0.5～0.7mol/L, sucking filtration；Then again with 0.05～0.15mol/L's
NaOH solution is washed, and is then washed with deionized repeatedly to cleaning mixture in neutrality, and 40～60 DEG C of vacuum drying are sieved, obtained
Cu2+Blotting chitosan composite IIP/Al2O3。
2. the preparation method of copper ion blotting chitosan composite according to claim 1, is characterized in that, the step
(1)Al2O3Surface activity SiO2The deposition of layer, its technique is：Weigh appropriate Al2O3Powder, acetone soak 10h；Then use 3mol/
The process of L NaOH solutions, deionized water wash, filtration, drying；Then by the Al dried2O3It is placed in crucible, in Muffle furnace
600 DEG C of roasting 7h；After natural cooling, 15h is soaked with dilute HCl solution, deionized water wash to neutrality is filtered, and is put into vacuum and is done
Dry for standby in dry case；Then a certain amount of above-mentioned dried sample is taken, is added equipped with appropriate 1/10 TEOS/ ethanol solution
In round-bottomed flask, 70 DEG C of back flow reaction 30h, then by reacted sample filtering, move into 550 DEG C of calcining 3h in Muffle furnace, from
So cool down；The HCl solution immersion 24h of 0.1mol/L is added after deionized water wash, activity Si-OH is obtained；Deionization is used finally
Water washing to neutrality, 80 DEG C of drying for standby.
3. the preparation method of copper ion blotting chitosan composite according to claim 1, is characterized in that, step (2) is right
Deposited surface activity SiO2The Al of layer2O3The technique of silanization is：By deposition SiO obtained by step (1)2Active layer
Al2O3In 5 grams of addition round-bottomed flasks of powder, 25mL silane coupler KH-560 are added, diluted with 25mL acetone, flowed back at 70 DEG C
Reaction 10h, obtains the Al of silanization2O3。
4. the preparation method of copper ion blotting chitosan composite according to claim 1, is characterized in that, step (3) system
Standby Cu2+The technique of-chitosan complex is：Weigh 0.25gCuSO4·5H2O and 3.0g shitosans are dissolved in 150mL 0.1mol/L
Acetum, in constant temperature blender with magnetic force, 25 DEG C reaction 2h, make shitosan and Cu2+Fully reaction generates Cu2+- shitosan
Coordination compound.
5. the preparation method of copper ion blotting chitosan composite according to claim 1, is characterized in that, step (4) system
The technique of standby copper ion blotting chitosan composite material template is：By the Al of step (2) silanization2O3It is added to step (3) system
The Cu for obtaining2+In-chitosan complex, copper ion blotting chitosan composite material template is obtained in 25 DEG C of stirring reactions 5h；Reaction
After end, the copper ion blotting chitosan composite material template of gained is placed in baking oven and is dried 24h.
6. the preparation method of copper ion blotting chitosan composite according to claim 1, is characterized in that, step (5) is washed
De-, washing, drying process are：With mortar by dry copper ion blotting chitosan composite material template grind into powder, acetone
With ethanol respectively washing 2 times, deionized water wash 3 times, vacuum drying 8h；Then with the HCl solution eluted template of 0.6mol/L from
Son, sucking filtration；Then washed with the NaOH solution of 0.1mol/L again, be then washed with deionized repeatedly to cleaning mixture in neutrality,
50 DEG C of vacuum drying 8h, cross 80 mesh sieves, obtain Cu2+Blotting chitosan composite IIP/Al2O3。
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| CN109464991A (en) * | 2018-12-23 | 2019-03-15 | 陕西省石油化工研究设计院 | A kind of preparation method of chitosan absorption silver ion ion blotting |
| CN110508259B (en) * | 2019-09-03 | 2022-02-15 | 晋江瑞碧科技有限公司 | Preparation method of copper ion imprinted composite magnetic hollow microsphere |
| CN110975325A (en) * | 2019-10-23 | 2020-04-10 | 武汉科技大学 | Method for evaluating adsorption stability of heavy metal ion adsorbent based on solid-phase extraction |
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