CN101992067B - Preparation method and use of loofah sponge surface lead ion imprinted absorbing material - Google Patents
Preparation method and use of loofah sponge surface lead ion imprinted absorbing material Download PDFInfo
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- CN101992067B CN101992067B CN2010102937805A CN201010293780A CN101992067B CN 101992067 B CN101992067 B CN 101992067B CN 2010102937805 A CN2010102937805 A CN 2010102937805A CN 201010293780 A CN201010293780 A CN 201010293780A CN 101992067 B CN101992067 B CN 101992067B
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- dithizone
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Abstract
The invention discloses a preparation method of a loofah sponge surface lead ion imprinted absorbing material and the use of the loofah sponge surface lead ion imprinted absorbing material in metal ion absorption and belongs to natural high polymer material modification. In the method, the loofah sponge natural high polymer material is used as a support, and the surface of the material is modified with a lead ion imprinted polymer. The main technical characteristics of the method include: adding acylated loofah sponge, lead-dithizone complex, 4-vinylpyridine, ethylene dimethacrylate and azodiisobutyronitrile into a chloroform medium, removing oxygen by argon in a certain proportion; introducing argon to expel oxygen; reacting in a water bath at a constant temperature of 50 to 70 DEG C, filtering and washing; and performing Soxhlet extraction by using 0.10mol/L solution of HNO3 for 12 hours, removing template lead ions, washing, drying and obtaining the material. The material has specific lead ion identification capacity, high selectivity, high absorption speed and high desorption capacity, is widely available and biodegradable, can be prepared by a simple process and has regeneration capacity and the advantages of environmental friendliness and the like.
Description
Technical field
The present invention relates to the preparation method and the application technology of the sorbing material of metal ion in the aqueous systems, the preparation method and the application technology of particularly a kind of luffa surface lead ion trace sorbing material belong to the natural macromolecular material modification.
Background technology
High selectivity material with molecular recognition function receives people's attention always.Molecular imprinting is one of main method of current preparation high selectivity material.Molecularly imprinted polymer according to this technology preparation shows predetermined, single-minded recognition performance owing to the stereochemical structure to microsphere has " memory " function, and very wide application prospect is arranged in fields such as separation science, biosimulation science.Along with the fast development of science and technology, people require also increasingly high to the separation determination of metal ion.Preparation has the material of ion selectivity adsorption function, optionally removes or measure metal ion, has important practical significance.
Ion imprinted polymer (Ion Imprinted Polymer, IIP) similar with molecularly imprinted polymer, the structure with molecular engram is imitated advantages such as foreseeability, specific recognition property and suit property, and just its template has become ion by molecule.The first metal ion species imprinted polymer was prepared by Kabanov and Nishide research group in 1989; The function monomer that this group at first can match with metal ion is processed line polymer; Form complex compound with metal ion then; Form the metal ion imprinted polymer with the monomer crosslinked polymerization of skeleton, remove the trace ion, promptly obtain the metal ion imprinted polymer through post processings such as pickling.
The traditional preparation process method of imprinted polymer is: template molecule (or ion), function monomer, crosslinking agent and initator are dissolved in the solvent (pore-foaming agent) according to a certain ratio, obtain block highly cross-linked rigid polymer under proper condition behind the initiated polymerization; The particle that obtains being of the required size through pulverizing, sieving then.The required device of the method is simple, and universality is strong, but has problem usually: (1) poor controllability in process of lapping, produce some irregular particles inevitably, and destroy part trace point simultaneously.The qualified particle that after screening, obtains generally is lower than 50%, causes obvious waste; (2) have that template molecule (or ion) embedding is dark excessively, to be difficult to wash-out, template seepage and mechanical performance low; (3) the imprinted sites skewness one, and a part is on the particle hole wall, and its mass transfer rate is very fast; And other are embedded among the polymer body, receive steric influence, and accessibility is poor; Combine the speed of template molecule (or ion) slow again, thereby reduced the utilization rate of imprinted sites.In order to address the above problem the surface imprinted focus that is called research as a kind of new method in recent years.So-called surface molecular (or ion) trace is exactly to take certain measure to be combined in all binding sites on the surface with good accessibility, thereby helps removing and combination again of template molecule (or ion).So select desirable support very important, application number is that disclosing a kind of in 200410072308.3 the patent is the cadmium ion trace sorbing material of support material with the silicon ball.
Shortage of resources and environmental pollution have become two big subject matters of the world today, therefore, utilize natural reproducible resource, friendly type product of development environment and the technological inexorable trend that will become sustainable development.Luffa is the profuse regenerated resources of the earth, has that light weight is inexpensive, characteristics such as degradable and environmental friendliness, and its possess hydrophilic property, also have abundant dentate, be easy to carry out chemical modification, and be the ideal polymer support.Domestic luffa is as the application of adsorbent in adsorption of metal ions, and application number is to disclose luffa as the application of adsorbent in adsorption of metal ions in 200810034734.6 the patent, and wherein luffa is to Cu
2+And Zn
2+Desorption rate all about 40%, luffa is to Cu
2+Adsorbance be respectively 10.2mg/g, to Zn
2+Adsorbance be about 25.5mg/g, in pH was 1 system, desorption rate was respectively 46%, 47%; In application number is 200810034735.0 patent, disclose the alkalization modifying method and the application thereof of luffa, wherein the alkali treatment luffa is to Zn
2+Adsorbance than Cu
2+Height, and the adsorbance gap is bigger, to Cu
2+Adsorbance be about 7～8mg/g, to Zn
2+Adsorbance be about 21～22mg/g; In application number is the patent of 200810034737.X, disclose the preparation method of etherized luffa and the application in adsorption of metal ions thereof, wherein etherized luffa is to Fe
3+Maximal absorptive capacity be 27.4mg/g.To Zn
2+Maximal absorptive capacity be 36.3mg/g.
Luffa chemical modification and absorption property are also had research abroad, it is fixation support that Nasreen etc. have studied the employing luffa, adheres to the microballoon algae that metal ion is had special adsorption function, contains Cd in order to processing
2+Sewage, through static and dynamic adsorption experiment, the result shows that the not immobilized chlorella adsorption capacity of employing is 33.5mg/g, and after immobilized is 39.2mg/g, Cd
2+Dynamic maximum adsorption capacity can reach 192mg/g.
More than adopt the adsorbance of the adsorbent of metal ion in the aqueous systems that luffa or luffa chemical modification obtain less, and its selectivity is relatively poor.
Summary of the invention
One of the object of the invention provides the preparation method of a kind of luffa surface lead ion imprinted material, mainly is with the surface imprinted lead ion of luffa, the synthetic sorbing material that lead ion is had high selectivity, recognition capability.
The object of the invention is realized through following technical scheme.
The preparation method of a kind of luffa surface lead ion imprinted material is characterised in that this method has following processing step:
(1) alkali treatment of luffa: with natural material luffa and an amount of mass percentage concentration is that 5～10% NaOH ethanolic solution mixes, and forms alkaline mixed system, reacts 24h under the room temperature; Mixed system azeotropic reaction 0.5～2h spends deionised water to neutral after the cooling, 60 ℃ of oven dry behind the suction filtration, and luffa must alkalize.
(2) acylated of luffa is handled: the luffa after will alkalizing adds chloroform in reactor, under the protection of argon gas, stirs 10min, dropwise adds acryloyl chloride with constant pressure funnel.Drip off the back and stir 10min, (addition adds by the following mass percent of forming, alkalization luffa: 5～10% dropwise to add triethylamine with constant pressure funnel again; Chloroform: 75～85%; Acryloyl chloride: 3～6%, triethylamine: 6～10%).After dropwising, stir 24～30h under the room temperature, filter, use chloroform, methanol wash successively, drying obtains the acylated luffa.
(3) lead-dithizone complex is synthetic: press dithizone: plumbous=(1.7～1.9): 1 mol ratio adds, and dithizone is dissolved in the ammonia spirit of 0.6mol/L, and at room temperature, stirring dropwise adds Pb (Ac) fast
23H
2O solution generates deposition, is washed till neutrality with deionized water, filters, and 40 ℃ of oven dry, obtains lead-dithizone complex.
(4) luffa surface lead ion imprinted material preparation: add the acylated luffa by the following mass percent of forming: 8～15%, lead-dithizone complex: 1.5～3.0%; Chloroform: 50～60%, 4-vinylpridine: 2.5～5%, ethylene glycol dimethacrylate: 30～40%; Azodiisobutyronitrile: 0.7～1.0%, feed argon gas 5min and remove oxygen; Sealing is isolated with air, in 50～70 ℃ of waters bath with thermostatic control, reacts 18～24h, filtration washing.
(5) removing of template ion: with the HNO of 0.1mol/L
3Solution soxhlet extraction 12h (promptly not having template molecule), it is clean to spend deionised water again, filters, and places 60 ℃ of vacuum drying chamber drying for standby.
Another object of the present invention provides luffa surface lead ion trace sorbing material in the identification of lead ion and the application in the absorption.Be characterized as: with the luffa for preparing surface lead ion trace sorbing material directly in water quality, by static method absorption; Can also the luffa surface lead ion trace sorbing material that prepare be made into adsorption column, by dynamic method absorption.
Advantage of the present invention and effect are:
(1) to obtain selective absorbent be to contain luffa surface lead ion trace sorbing material in the present invention; With the 4-vinylpridine is monomer; With lead-dithizone complex be microsphere; Luffa is a support, and the method that adds crosslinking agent employing polymerisation in bulk again prepares luffa surface lead ion trace sorbing material.The lead ion imprinted polymer that this method makes has specific hole, and lead ion is had special recognition capability, and selectivity is higher, and other ion is not adsorbed.
(2) to prepare process simple for luffa of the present invention surface lead ion trace sorbing material, and condition is easy to control, and production cost is low.
(3) the present invention prepares luffa surface lead ion trace sorbing material; Owing to be ion imprinted polymer in the luffa finishing, its adsorption site helps template ion absorption and wash-out all on the surface of adsorbent; Elution time is short; High adsorption capacity, efficient are high, and it is 335mg/g to the lead ion maximum adsorption capacity, and high adsorption rate can reach 95%.
(4) the present invention prepares luffa surface lead ion trace sorbing material; Used raw material luffa wide material sources; Biodegradable, and be regenerated resources, a large amount of uses can drive the especially agricultural industrialization process in backward area of China's agricultural; Improve peasant's income, have economical and social double benefit.
(5) the present invention prepares luffa surface lead ion trace sorbing material, and good physical and chemical stability and excellent mechanical stability are arranged, and is simple to the lead ion adsorption operations.
(6) have power of regeneration simultaneously, can use repeatedly more than 10 times.
Description of drawings
Fig. 1 luffa surface lead ion trace sorbing material is to the absorption of various ions
(ordinate Q is an adsorption rate, and adsorption conditions is at room temperature, pH 9.5, dynamically consistent with the Static Adsorption result)
Fig. 2 pH value is to the lead ion Adsorption Effect
(ordinate Q is an adsorption rate, and is dynamically consistent with the Static Adsorption result)
The specific embodiment
Embodiment 1
(1) luffa preliminary treatment: luffa derives from the sponge gourd fruit, obtains through the peeling stoning, and the luffa clear water that is cut into small pieces is cleaned, and pulverizes after the vacuum drying, with 80 purpose sieve;
(2) luffa of pulverizing is pressed 50% of gross mass; Use concentration is 5% NaOH solution and 20% ethanolic solution mixing submergence azeotropic 0.5h; During azeotropic, constantly add NaOH solution and alcohol mixeding liquid, to keep liquor capacity constant, spend after the cooling deionised water to pH be 7; Dry the luffa that obtains alkalizing behind the suction filtration down at 60 ℃.
(3) acylated luffa: in the triangular flask of tool plug, add 2g alkalization luffa and 40mL chloroform, under the protection of argon gas, stir 10min, dropwise add the 2mL acryloyl chloride with constant pressure funnel.Drip off the back and stir 10min, dropwise add the 3.5mL triethylamine with constant pressure funnel again.After dropwising, stir 24h under the room temperature, filter, use chloroform, methanol wash successively, drying obtains the acylated luffa.
(4) lead-dithizone complex is synthetic: take by weighing the 2.0506g dithizone in beaker, with the ammonia solvent of 300mL0.6mol/L, at room temperature, stirring dropwise adds lead acetate solution (1.6303g Pb (Ac) fast
23H
2O is dissolved in the 100mL water), generate deposition, be washed till neutrality with deionized water, filter, 40 ℃ of oven dry, obtain lead-dithizone complex.
(5) luffa surface lead ion imprinted material preparation: take by weighing 2g acylated luffa, 0.25g lead-dithizone complex, 12mL chloroform; Mix, add the 0.60g 4-vinylpridine, the 6mL ethylene glycol dimethacrylate; 0.1g azodiisobutyronitrile feeds argon gas 5min and removes oxygen, sealing is isolated with air; In 70 ℃ of waters bath with thermostatic control, react 18h, filtration washing.
(6) with the HNO of 0.1mol/L
3Solution soxhlet extraction 12h (promptly not having template molecule), it is clean to spend deionised water again, filters, and places 60 ℃ of vacuum drying chamber drying for standby.
Embodiment 2
(1) luffa preliminary treatment: luffa derives from the sponge gourd fruit, obtains through the peeling stoning, and the luffa clear water that is cut into small pieces is cleaned, and pulverizes after the vacuum drying, with 80 purpose sieve;
(2) luffa of pulverizing is pressed 50% of gross mass; Use concentration is 5% NaOH solution and 20% ethanolic solution mixing submergence azeotropic 0.5h; During azeotropic, constantly add NaOH solution and alcohol mixeding liquid, to keep liquor capacity constant, spend after the cooling deionised water to pH be 7; Dry the luffa that obtains alkalizing behind the suction filtration down at 60 ℃.
(3) acylated luffa: in the triangular flask of tool plug, add 2g alkalization luffa and 40mL chloroform, under the protection of argon gas, stir 10min, dropwise add the 2mL acryloyl chloride with constant pressure funnel.Drip off the back and stir 10min, dropwise add the 3.5mL triethylamine with constant pressure funnel again.After dropwising, stir 24h under the room temperature, filter, use chloroform, methanol wash successively, drying obtains the acylated luffa.
(4) lead-dithizone complex is synthetic: take by weighing the 2.0506g dithizone in beaker, with the ammonia solvent of 300mL0.6mol/L, at room temperature, stirring dropwise adds lead acetate solution (1.6303g Pb (Ac) fast
23H
2O is dissolved in the 100mL water), generate deposition, be washed till neutrality with deionized water, filter, 40 ℃ of oven dry, obtain lead-dithizone complex.
(5) luffa surface lead ion imprinted material preparation: take by weighing 2g acylated luffa, 0.3g lead-dithizone complex, 12mL chloroform; Mix, add the 0.8g 4-vinylpridine, the 8mL ethylene glycol dimethacrylate; 0.15g azodiisobutyronitrile feeds argon gas 5min and removes oxygen, sealing is isolated with air; In 60 ℃ of waters bath with thermostatic control, react 24h, filtration washing.
(6) with the HNO of 0.1mol/L
3Solution soxhlet extraction 12h (promptly not having template molecule), it is clean to spend deionised water again, filters, and places 60 ℃ of vacuum drying chamber drying for standby.
Embodiment 3
(1) luffa preliminary treatment: luffa derives from the sponge gourd fruit, obtains through the peeling stoning, and the luffa clear water that is cut into small pieces is cleaned, and pulverizes after the vacuum drying, with 80 purpose sieve;
(2) luffa of pulverizing is pressed 50% of gross mass; Use concentration is 5% NaOH solution and 20% ethanolic solution mixing submergence azeotropic 0.5h; During azeotropic, constantly add NaOH solution and alcohol mixeding liquid, to keep liquor capacity constant, spend after the cooling deionised water to pH be 7; Dry the luffa that obtains alkalizing behind the suction filtration down at 60 ℃.
(3) acylated luffa: in the triangular flask of tool plug, add 2g alkalization luffa and 40mL chloroform, under the protection of argon gas, stir 10min, dropwise add the 2mL acryloyl chloride with constant pressure funnel.Drip off the back and stir 10min, dropwise add the 3.5mL triethylamine with constant pressure funnel again.After dropwising, stir 24h under the room temperature, filter, use chloroform, methanol wash successively, drying obtains the acylated luffa.
(4) lead-dithizone complex is synthetic: take by weighing the 2.0506g dithizone in beaker, with the ammonia solvent of 300mL0.6mol/L, at room temperature, stirring dropwise adds lead acetate solution (1.6303g Pb (Ac) fast
23H
2O is dissolved in the 100mL water), generate deposition, be washed till neutrality with deionized water, filter, 40 ℃ of oven dry, obtain lead-dithizone complex.
(5) luffa surface lead ion imprinted material preparation: take by weighing 2g acylated luffa, 0.3g lead-dithizone complex, 15mL chloroform; Mix, add the 0.6g 4-vinylpridine, the 7mL ethylene glycol dimethacrylate; 0.12g azodiisobutyronitrile feeds argon gas 5min and removes oxygen, sealing is isolated with air; In 65 ℃ of waters bath with thermostatic control, react 20h, filtration washing.
(6) with the HNO of 0.1mol/L
3Solution soxhlet extraction 12h (promptly not having template molecule), it is clean to spend deionised water again, filters, and places 60 ℃ of vacuum drying chamber drying for standby.
Luffa surface lead ion imprinted material application process: the luffa surface lead ion imprinted material for preparing is soaked 6h with deionized water, by a kind of be static adsorptive method, another kind is a dynamic adsorption method, and adsorption of metal ions is used.
Measure absorption property with static adsorptive method; Get the metal ion solution 20mL of variable concentrations; The luffa surface lead ion imprinted material that adds equivalent under the same conditions; Concussion absorption 4h gets clear liquid, with the concentration of metal ion in the atomic absorption detecting clear liquid, calculates adsorption rate according to metal ion solution change in concentration before and after the absorption.
Measure absorption property with dynamic method; With a certain amount of luffa surface lead ion imprinted material adsorption column of packing into; Get the metal ion solution of variable concentrations, regulate the pH value, pass through adsorption column with the flow velocity of 1.0mL/min with diluted acid and diluted alkaline; Measure the amount of metal ion of adsorbing on filtered fluid and the post, calculate adsorption rate thus.
Prepare the application of luffa surface lead ion imprinted material in adsorption of metal ions as stated above.Luffa of the present invention surface lead ion imprinted material the adsorption of metal ions field be applied as directly to water body in the absorption and the wash-out of each metal ion species.Its method is:
(1) for containing K
+,Na
+, Ca
2+, Mg
2+, Cu
2+, Zn
2+, Cd
2+, Fe
3+, Ag
+, Co
2+, Ni
2+, Pb
2+, Pt
4+, Pd
2+, Au
3+In one or more staying water system; Adopt luffa surface lead ion trace sorbing material to carry out water treatment with the method for Static Adsorption; Promptly get luffa surface lead ion trace sorbing material and be immersed in the staying water system, concussion absorption 4h, its Adsorption law is following:
A. at room temperature, the pH value is 9.5 o'clock, for alkali metal and alkaline-earth metal if any K
+, Na
+, Ca
2+, Mg
2+Deng not adsorbing, do not influence the absorption property of luffa surface lead ion trace sorbing material when having alkali metal and alkaline-earth metal in the sample thus.
B. at room temperature, the pH value is 9.5 o'clock, sees Fig. 1 for noble metal and heavy metal ion ionic adsorption performance, and as can beappreciated from fig. 1 luffa surface lead ion trace sorbing material is adsorbed with obvious selectivity and recognition capability to lead ion.
Adsorption capacity is relevant with the pH value factors such as (the pH value are seen Fig. 2 to the lead ion Adsorption Effect) of concentration of metal ions, luffa surface lead ion trace sorbing material consumption, adsorption temp, solution system.
(2) for containing K
+, Na
+, Ca
2+, Mg
2+, Cu
2+, Zn
2+, Cd
2+, Fe
3+, Ag
+, Co
2+, Ni
2+, Pb
2+, Pt
4+, Pd
2+, Au
3+In one or more staying water system; Adopt luffa surface lead ion trace sorbing material to carry out water treatment with the method for dynamically absorption; The rule of its absorption is the same, and the pH value of adsorption capacity and concentration of metal ions, luffa surface lead ion trace sorbing material consumption, adsorption temp, solution system, the factors such as flow velocity of solution are relevant.
The luffa surface lead ion trace sorbing material that obtains is 335mg/g to the lead ion maximum adsorption capacity, and high adsorption rate can reach 95%, and to the absorption hardly of other ion, it is to the selective absorption of lead ion thus.
Claims (3)
1. the preparation method of luffa surface lead ion imprinted material is characterized in that: be that this method has following processing step:
(1) alkali treatment of luffa: with natural material luffa and an amount of mass percentage concentration is that 5～10% NaOH ethanolic solution mixes; Form alkaline mixed system; React 24h under the room temperature, alkaline mixed system azeotropic reaction 0.5～2h spends deionised water to neutral after the cooling; 60 ℃ of oven dry behind the suction filtration, luffa must alkalize;
(2) acylated of luffa is handled: the luffa that will alkalize adds chloroform in reactor; Under the protection of argon gas, stir 10min; Dropwise add acryloyl chloride with constant pressure funnel, drip off the back and stir 10min, dropwise add triethylamine with constant pressure funnel again; Addition adds by the following mass percent of forming, alkalization luffa: 5～10%; Chloroform: 75～85%; Acryloyl chloride: 3～6%, triethylamine: 6～10%, after dropwising, stir 24～30h under the room temperature, filter, use chloroform, methanol wash successively, drying obtains the acylated luffa;
(3) lead-dithizone complex is synthetic: press dithizone: plumbous=(1.7～1.9): 1 mol ratio adds, and dithizone is dissolved in the ammonia spirit of 0.6mol/L, at room temperature; Stirring dropwise adds lead acetate solution fast; Generate deposition, be washed till neutrality, filter with deionized water; 40 ℃ of oven dry, obtain lead-dithizone complex;
(4) luffa surface lead ion imprinted material preparation: add the acylated luffa by the following mass percent of forming: 8～15%, lead-dithizone complex: 1.5～3.0%; Chloroform: 50～60%, 4-vinylpridine: 2.5～5%, ethylene glycol dimethacrylate: 30～40%; Azodiisobutyronitrile: 0.7～1.0%; Each constituent content sum is absolutely, feeds argon gas 5min and removes oxygen, and sealing is isolated with air; In 50～70 ℃ of waters bath with thermostatic control, react 18～24h, filtration washing;
(5) removing of template ion: with the HNO of 0.1mol/L
3Solution soxhlet extraction 12h, it is clean to spend deionised water again, filters, and places 60 ℃ of vacuum drying chamber drying for standby.
2. the preparation method of luffa according to claim 1 surface lead ion imprinted material, it is characterized in that: lead ion and dithizone are prepared into complex, and then carry out polymerisation.
3. according to the application of the surperficial lead ion imprinted material of the luffa of claim 1 preparation in lead ion absorption.
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| CN102247813B (en) * | 2011-05-13 | 2013-12-04 | 中国科学院合肥物质科学研究院 | Modifying method and application of natural loofah |
| CN102600813B (en) * | 2012-04-06 | 2013-11-20 | 济南大学 | Preparation method and application of surface artemisinin molecule imprinting adsorbing material of vegetable sponge |
| CN102626611B (en) * | 2012-04-11 | 2014-03-26 | 哈尔滨工程大学 | Method for preparing metal ion imprinting adsorbent with underwater selective recognition performance |
| CN102814168A (en) * | 2012-09-18 | 2012-12-12 | 济南大学 | Preparation method and application of loofah sponge surface malachite green molecular imprinting adsorbing material |
| CN104084143A (en) * | 2014-07-23 | 2014-10-08 | 武汉理工大学 | Preparation method of function material in biomass water treatment environment |
| CN105214617B (en) * | 2015-09-10 | 2017-06-23 | 南京大学 | Surface imprinted chitosan microball of high efficiency selected heavy metal ion and preparation method thereof |
| CN107126938B (en) * | 2017-05-25 | 2019-02-22 | 济南大学 | A kind of preparation method of luffa surface procyanidine molecular engram adsorbent material |
| CN110746538B (en) * | 2019-09-19 | 2021-08-03 | 江苏大学 | Preparation method and application of loofah sponge-based imprinted membrane material with reinforced concrete-like structure |
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