CN104525158A - Heavy metal ion adsorbent and preparation method thereof - Google Patents
Heavy metal ion adsorbent and preparation method thereof Download PDFInfo
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- CN104525158A CN104525158A CN201510015436.2A CN201510015436A CN104525158A CN 104525158 A CN104525158 A CN 104525158A CN 201510015436 A CN201510015436 A CN 201510015436A CN 104525158 A CN104525158 A CN 104525158A
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- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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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
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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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
- C02F2101/00—Nature of the contaminant
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Abstract
The invention provides a heavy metal ion adsorbent which contains nucleuses, polyamidoamine dendrimers grafted to the nucleuses through a silane compound and polyanions absorbed to the polyamidoamine dendrimers. The nucleuses are silicon dioxide coated ferroferric oxide. In the heavy metal ion adsorbent, the polyamidoamine dendrimers are absorbed with a layer of polyanions through electrostatic attraction, polyanions and especially the configuration of DNA is not changed, it is ensured that the outermost-layer polyanions can produce strong chelation with heavy metal ions during absorption, and accordingly the heavy metal ions in a water body are effectively removed. The heavy metal ion adsorbent is small in particle size and large in specific surface area. Furthermore, the polyamidoamine dendrimers with spherical structures can be further grafted to the polyamidoamine dendrimers and then the polyanions are absorbed to the polyamidoamine dendrimers, so that the heavy metal ion adsorbent is good in absorption effect and high in repeating utilization rate. In addition, the nucleuses in the heavy metal ion adsorbent are magnetic, so that separation is facilitated.
Description
Technical field
The present invention relates to water treatment field, particularly a kind of adsorbent for heavy metal and preparation method thereof.
Background technology
Heavy metal refers to the atom of atomic weight between 63.5 and 200.6, and their proportion is generally greater than 5.0g/cm
3.Heavy metal is non-degradable in the environment, and often accumulates in vivo, and therefore the improvement of heavy metal receives much concern.Many heavy metal ion have been proved to be poisonous or carcinogen.Such as, the copper of excess intake will bring serious poisoning problem, and as vomiting, spasm, twitches, even dead; The exemplary of mercury poisoning is minamata disease; Lead can cause central nervous system, kidney, the infringement of liver and reproductive system.
In water, the minimizing technology of heavy metal has chemical precipitation method, ion-exchange, membrane filtration, coagulation-flocculence, electrochemical method and absorption method etc.Wherein absorption method have efficiently, the feature such as cheap, convenient, being considered to remove heavy metal in water has the method for application prospect most.The removal effect of absorption method heavy metal pollutant depends primarily on the structures and characteristics of adsorbent, therefore finds cheapness, and efficiently, the adsorbent being easy to practical application is the Main way of current water treatment research.
DNA (Deoxyribonucleic acid, is abbreviated as DNA) is a kind of molecule guiding biological development and vital functions to operate, and in neutral conditions, the carboxyl ionization on DNA molecular, forms polyanion.Stronger interaction can be there is in this polyanion with metal ion.DNA is rich content in animal body, and DNA does not have toxicity, therefore has the research being applied to remove heavy metal ion in water.(the Changsheng Zhao such as Zhao, Ling Shi, Xingyi Xie, Shudong Sun, Xiangdong Liu, Motoyoshi Nomizuand Norio Nishi:Adsorption Science & Technology Vol.23No.52005, 387-398) at Polysulfone microspheres surface coating last layer DNA solution film, but because DNA molecular is water miscible, and the active force of DNA and microsphere surface is very weak, be dissolved in water in heavy-metal ion removal process to prevent DNA and run off, they make DNA polymerization reaction take place by the method for ultraviolet irradiation, microsphere surface is made to generate one deck DNA film parcel microballoon.The shortcoming of this method is, because the DNA after polymerization is hydrophobicity, the metal ion in water fully can not act on DNA molecular; And after irradiating, the configuration of the DNA molecular of polymerization reaction take place changes, and affects the chelating between itself and metal ion.Therefore the ability of this microballoon removal metal ion is affected.It is reported, the heavy metal ion residual concentration after this ion adsorbent purification is higher, and lead ion residual concentration reaches 1.28mg/L, and copper ion residual concentration reaches 2.38mg/L, and higher than drinking water maximum level index, (Pb is 0.015mg/L all far away; Cu is 1.3mg/L).
Summary of the invention
The technical problem that the present invention solves is to provide a kind of adsorbent for heavy metal and preparation method thereof, and described adsorbent for heavy metal can remove the heavy metal in water body effectively, easily.
The invention discloses a kind of adsorbent for heavy metal, comprising: core, the polyanion grafting on the Polyamidoamine Dendrimers on described core by silane compound and be adsorbed on described Polyamidoamine Dendrimers;
Described core is the tri-iron tetroxide of coated with silica.
Preferably, also comprise between described Polyamidoamine Dendrimers and polyanion, the space structure grafted on described Polyamidoamine Dendrimers is spherical Polyamidoamine Dendrimers;
It is on spherical Polyamidoamine Dendrimers that described polyanion is adsorbed in described space structure.
Preferably, described polyanion is DNA or polyanion cellulose.
Preferably, described core, Polyamidoamine Dendrimers and space structure are the gross mass of spherical Polyamidoamine Dendrimers and the mass ratio of polyanion is 1:1 ~ 20:1.
The invention also discloses a kind of preparation method of adsorbent for heavy metal, comprise the following steps:
By by the core of Polyamidoamine Dendrimers in silane compound grafting ultrasonic disperse in containing the cushioning liquid of polyanion, then leave standstill, obtain adsorbent for heavy metal;
Described core is the tri-iron tetroxide of coated with silica.
Preferably, in described grafting, the preparation method of the core of Polyamidoamine Dendrimers is:
After core is mixed in organic solvent with silane compound, react, obtain the core of 0 PAMAM dendrimer in grafting;
Described silane compound is 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxy silicon, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyltriethoxy dimethoxy silicon, N-β (aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyltriethoxy diethoxy silane or aminoethylaminopropyl trimethoxy silane.
Preferably, in described grafting, the preparation method of the core of Polyamidoamine Dendrimers also comprises:
The core of 0 PAMAM grafting is obtained the core of the PAMAM of different algebraically in grafting through the amidation process of Michael addition reaction or ester group.
Preferably, in grafting Polyamidoamine Dendrimers core ultrasonic disperse before, also comprise: by the core of Polyamidoamine Dendrimers in grafting and space structure be spherical PAMAM in organic solvent lucifuge react.
Preferably, the time of described ultrasonic disperse is 5 ~ 20 minutes, and described time of repose is 5 ~ 30 minutes.
Preferably, in described grafting, the core of Polyamidoamine Dendrimers and space structure are the mass ratio of spherical PAMAM is 0.5 ~ 5:1.
Compared with prior art, adsorbent for heavy metal of the present invention, comprising: core, the polyanion being grafted on the Polyamidoamine Dendrimers on described core by silane compound and be adsorbed on described Polyamidoamine Dendrimers; Described core is the tri-iron tetroxide of coated with silica.In adsorbent for heavy metal of the present invention, Polyamidoamine Dendrimers is by electrostatic attraction absorption last layer polyanion, the configuration of polyanion particularly DNA class can not be changed, ensure that when adsorbing, can there is strong chelation with heavy metal ion in outermost polyanion, thus remove the heavy metal ion in water body effectively, easily.This kind of material particle size is little, and specific area is large.Further, the present invention can also grafting space structure be spherical Polyamidoamine Dendrimers on Polyamidoamine Dendrimers, the upper polyanion of absorption, and adsorption effect is better, and recycling rate of waterused is high.In addition, the nucleus band in adsorbent of the present invention is magnetic, and is convenient to be separated.
Accompanying drawing explanation
Fig. 1 is the Capillary Electrophoresis figure after sorbent treatment water sample of the present invention;
Fig. 2 is the structural representation of adsorbent prepared by embodiment 5.
Detailed description of the invention
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of adsorbent for heavy metal, comprising: core, the polyanion grafting on the Polyamidoamine Dendrimers on described core by silane compound and be adsorbed on described Polyamidoamine Dendrimers;
Described core is the tri-iron tetroxide of coated with silica.
Adsorbent for heavy metal of the present invention is with the tri-iron tetroxide of coated with silica for core, and it has magnetic, is convenient to the separation of adsorbent.The present invention is not particularly limited for the source of the tri-iron tetroxide of coated with silica, prepares according to method well known to those skilled in the art.
Described core is grafted with Polyamidoamine Dendrimers by silane compound, and the present invention is not particularly limited for the macromolecular grafting method of polyamide-amide shape, as carried out in accordance with the following methods:
After core is mixed in organic solvent with silane compound, react, obtain the core of 0 PAMAM grafting;
Described silane compound is 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxy silicon, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyltriethoxy dimethoxy silicon, N-β (aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyltriethoxy diethoxy silane or aminoethylaminopropyl trimethoxy silane.
Core and the methyl acrylate of described 0 PAMAM dendrimer grafting react, and obtain the core of 0.5 PAMAM dendrimer grafting;
The core of described 0.5 PAMAM dendrimer grafting and ethylenediamine obtain the core of 1 PAMAM dendrimer grafting through the amidation process of ester group;
Core and the methyl acrylate of described 1 PAMAM dendrimer grafting react, and obtain the core of 1.5 PAMAM dendrimer grafting.
The preparation method of the core of the Polyamidoamine Dendrimers grafting in whole generation or half generation all can be prepared according to above method.The described Polyamidoamine Dendrimers grafted on described core by silane compound can be whole PAMAM dendrimer also can be half PAMAM dendrimer.The algebraically of described Polyamidoamine Dendrimers was preferably for 1 ~ 10 generation, was more preferably for 1.5 ~ 5 generations.
Owing to being subject to the impact of nuclear space structure, described Polyamidoamine Dendrimers is dendritic, and on described Polyamidoamine Dendrimers, be preferably also grafted with space structure is spherical Polyamidoamine Dendrimers.Described space structure is that to be preferably the space structure in whole generation be spherical Polyamidoamine Dendrimers for spherical Polyamidoamine Dendrimers, and its surface is amino.
The space structure in described whole generation is the preparation method of spherical Polyamidoamine Dendrimers:
Methanol solution to ethylenediamine is slowly added dropwise to half generation spherical Polyamidoamine Dendrimers, room temperature reaction 64 hours, and obtaining take amido as whole generation of periphery spherical Polyamidoamine Dendrimers.Product with methylalcohol washing purifying, removes unnecessary ethylenediamine with Rotary Evaporators, obtains spherical Polyamidoamine Dendrimers of whole generation.
Described half for the preparation method of spherical Polyamidoamine Dendrimers is:
Methyl acrylate is dissolved in methyl alcohol, slowly drips (ethylenediamine was considered as 0 generation) methanol solution of whole generation dendritic macromole, at room temperature reacts 24 hours, occur Michael addition reaction obtain with ethylenediamine be core half for dendritic macromole.Revolve and steam removing unnecessary methyl acrylate and solvent, obtain thick half for spherical Polyamidoamine Dendrimers.
Described space structure is that spherical Polyamidoamine Dendrimers was preferably for 1 ~ 10 generation, is more preferably for 2 ~ 5 generations.
Spherical Polyamidoamine Dendrimers specific area is large, by the more polyanion of Electrostatic Absorption, increases the adsorption effect of adsorbent for heavy metal.And to be grafted with space structure on Polyamidoamine Dendrimers be again that the adsorbent for heavy metal of spherical Polyamidoamine Dendrimers can be reused.
According to the present invention, the polyanion in described adsorbent for heavy metal is adsorbed on described Polyamidoamine Dendrimers.When preferably: when Polyamidoamine Dendrimers to be grafted with space structure be spherical polyamide-amine dendrimer, it is on spherical Polyamidoamine Dendrimers that described polyanion is adsorbed in described space structure.Described polyanion is preferably DNA or polyanion cellulose.Described core, Polyamidoamine Dendrimers and space structure are that the gross mass of spherical Polyamidoamine Dendrimers and the mass ratio of polyanion are preferably 1:1 ~ 20:1.
The invention also discloses a kind of preparation method of adsorbent for heavy metal, comprise the following steps:
By by the core of Polyamidoamine Dendrimers in silane compound grafting ultrasonic disperse in containing the cushioning liquid of polyanion, then leave standstill, obtain adsorbent for heavy metal;
Described core is the tri-iron tetroxide of coated with silica.
The time of described ultrasonic disperse is preferably 5 ~ 20 minutes, and the described standing time is preferably 5 ~ 30 minutes,
According to the present invention, preferably, in grafting Polyamidoamine Dendrimers core ultrasonic disperse before, also comprise: by by the core of Polyamidoamine Dendrimers in silane compound grafting and space structure be spherical PAMAM in organic solvent lucifuge react.Reacted by described lucifuge, space structure is that spherical Polyamidoamine Dendrimers is grafted on Polyamidoamine Dendrimers.The time of described lucifuge reaction is preferably 24 ~ 96 hours, is more preferably 40 ~ 50 hours; The temperature of described lucifuge reaction is preferably room temperature, and described organic solvent is preferably methyl alcohol, ethanol or toluene.In described grafting, the core of Polyamidoamine Dendrimers and space structure are the mass ratio of spherical PAMAM is 0.5 ~ 5:1.Preferably, product and the polyanion of described lucifuge reaction react, and obtain adsorbent for heavy metal.The described product of lucifuge reaction and the mass ratio of heavy metal ion are preferably 1:1 ~ 20:1.
According to the present invention, in described grafting, the preparation method of the core of Polyamidoamine Dendrimers preferably carries out according to following steps:
After core is mixed in organic solvent with silane compound, react, obtain the core of 0 PAMAM grafting;
Described silane compound is 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxy silicon, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyltriethoxy dimethoxy silicon, N-β (aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyltriethoxy diethoxy silane or aminoethylaminopropyl trimethoxy silane.
Core and the methyl acrylate of described 0 PAMAM dendrimer grafting react, and obtain the core of 0.5 PAMAM dendrimer grafting;
The core of described 0.5 PAMAM dendrimer grafting and ethylenediamine obtain the core of 1 PAMAM dendrimer grafting through the amidation process of ester group;
Core and the methyl acrylate of described 1 PAMAM dendrimer grafting react, and obtain the core of 1.5 PAMAM dendrimer grafting.
The preparation method of the core of the Polyamidoamine Dendrimers grafting in whole generation or half generation all can be prepared according to above method.The described Polyamidoamine Dendrimers grafted on described core by silane compound can be whole PAMAM dendrimer also can be half PAMAM dendrimer.The algebraically of described Polyamidoamine Dendrimers was preferably for 1 ~ 10 generation, was more preferably for 1.5 ~ 5 generations.
Owing to being subject to the impact of nuclear space structure, described Polyamidoamine Dendrimers is dendritic, and on described Polyamidoamine Dendrimers, be preferably also grafted with space structure is spherical Polyamidoamine Dendrimers.Described space structure is that to be preferably the space structure in whole generation be spherical Polyamidoamine Dendrimers for spherical Polyamidoamine Dendrimers, and its surface is amino.
The space structure in described whole generation is the preparation method of spherical Polyamidoamine Dendrimers:
Methanol solution to ethylenediamine is slowly added dropwise to half generation spherical Polyamidoamine Dendrimers, room temperature reaction 64 hours, and obtaining take amido as whole generation of periphery spherical Polyamidoamine Dendrimers.Product with methylalcohol washing purifying, removes unnecessary ethylenediamine with Rotary Evaporators, obtains spherical Polyamidoamine Dendrimers of whole generation.
Described half for the preparation method of spherical Polyamidoamine Dendrimers is:
Methyl acrylate is dissolved in methyl alcohol, slowly drips (ethylenediamine was considered as 0 generation) methanol solution of whole generation dendritic macromole, at room temperature reacts 24 hours, occur Michael addition reaction obtain with ethylenediamine be core half for dendritic macromole.Revolve and steam removing unnecessary methyl acrylate and solvent, obtain thick half for spherical Polyamidoamine Dendrimers.
Described space structure is that spherical Polyamidoamine Dendrimers was preferably for 1 ~ 10 generation, is more preferably for 2 ~ 5 generations.
Spherical Polyamidoamine Dendrimers specific area is large, by the more polyanion of Electrostatic Absorption, increases the adsorption effect of adsorbent for heavy metal.And to be grafted with space structure on Polyamidoamine Dendrimers be again that the adsorbent for heavy metal of spherical Polyamidoamine Dendrimers can be reused.
In order to understand the present invention further, be described adsorbent for heavy metal provided by the invention and preparation method thereof below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
At 25 DEG C, first by 5.4g FeSO
47H
2o and 6.8g FeCl
3(mol ratio: Fe (III)/Fe (II)=2:1) is dissolved in the water of 130mL high-purity argon gas deoxygenation, stirs and dropwise adds concentrated ammonia liquor (about 60mL) until pH is 10.0.Then, then heat 50min at 65 DEG C, collect magnetic Nano material with magnet contacting container outer wall, the black powder thing obtained, spend deionized water magnetic Nano material 3 times to neutral.Under nitrogen protection, by the magnetic Fe synthesized by 2g
3o
4nano material is scattered in absolute ethyl alcohol, adds 60mL ammoniacal liquor and 4mL tetraethyl orthosilicate (TEOS, Si (OC in ice-water bath after ultrasonic 15min successively
2h
5)
4).Continue in ice-water bath after ultrasonic 2h, collect product with magnet contacting container wall, with absolute ethanol washing 3 times, dry (70 DEG C, about 12h) under vacuum, obtain the magnetic nano-particle (Fe of Silica-coated
3o
4@SiO
2).
Embodiment 2
By 0.5g Fe
3o
4@SiO
2particle, 30mL toluene and 5mL 3-aminopropyl triethoxysilane join in 50mL flask, after the ultrasonic 30min of mixture, at 110 DEG C, react 8h.After reaction with magnet by product and fluid separation applications, after absolute ethanol washing 5 times (each 5mL), products obtained therefrom is vacuum drying 24h at 50 DEG C.Described product is 0 PAMAM graft (Fe
3o
4@SiO
2@PADD G0).
By 0.3g Fe
3o
4@SiO
2@PADD G0 and 10mL methyl alcohol join in round-bottomed flask, and ultrasonic 30min makes Fe
3o
4@SiO
2@PADD G0 disperses, and is then slowly joined in flask by 0.1mL methyl acrylate, at 50 DEG C, reacts 48h.After reaction with magnet by product and fluid separation applications, after washing 5 times (each 2mL) with absolute methanol, products obtained therefrom is vacuum drying 24h at 50 DEG C, and product is Fe
3o
4@SiO
2@PADD G0.5.
By 0.3g Fe
3o
4@SiO
2@PADD G0.5 and 10mL methyl alcohol join in round-bottomed flask, and ultrasonic 30min makes nano material disperse, and are then slowly joined in flask by 0.2mL ethylenediamine, and after mixture reacts 48h under the condition of 50 DEG C, namely purifying obtains 1 PAMAM graft (Fe
3o
4@SiO
2@PADD G1.0).
By 0.3g Fe
3o
4@SiO
2@PADD G1.0 and 10mL methyl alcohol join in round-bottomed flask, and ultrasonic 30min makes nano material disperse, and are then slowly joined in flask by 0.1mL methyl acrylate, and react 48h at 50 DEG C after, namely purifying obtains 1.5 PAMAM graft (Fe
3o
4@SiO
2@PADD G1.5).
The graft of thermogravimetric analysis (TGA) technology to synthesis is adopted to characterize.TGA carries out on TGA/DSC1 thermogravimetric analyzer (plum Teller-Tuo benefit, Switzerland), is added to by 1-3mg sample in alumina sample dish, under the protection of nitrogen, is heated to 600 DEG C with the programming rate of 20 DEG C/min from 25 DEG C.Fe
3o
4@SiO
2the percent grafting of the upper dendritic PADD of@PADD G0.5, G1.0, G1.5 is respectively 8.4%, 9.3% and 12.1%.
Embodiment 3
By Fe prepared by 0.5g embodiment 2
3o
4@SiO
2product, in 50mL methyl alcohol, after lucifuge places 48h at normal temperatures, is separated with solution with magnet, then uses methanol wash product 5 times by@PADD G1.5 and 0.3gg-PADD G4.0 ultrasonic disperse, obtains the magnetic Nano material Fe that surface is modified for spherical g-PADD G4.0
3o
4@SiO
2@PADDG1.5@g-PADD G4.0.
Thermal gravimetric analysis results shows, and the percent grafting of g-PADD G4.0 is 24.0%.
5mg herring sperm dna (Beijing Ding Guo Bioisystech Co., Ltd) is dissolved in the cushioning liquid (pH 7.0) of 20mL10mM sodium dihydrogen phosphate/10mM sodium hydrogen phosphate, adds 20mg Fe
3o
4@SiO
2@PADD G1.5@g-PADD G4.0, ultrasonic 10min dispersion, leaves standstill 5 minutes afterwards, then with magnet by nano material (Fe
3o
4@SiO
2@PADDG1.5@g-PADD G4.0@DNA) and solution separate, spend deionized water nano material 5 times, obtain adsorbent.
The nuclear magnetic resonance (Bruker AdvanceIII-400MHz, Rheinstetten, Germany) of spherical g-PADD of whole generation involved in the present invention characterizes as follows:
g-PADD G4.0(400MHz,D
2O):δ2.29(m,248H,J＝5.44Hz,NCH
2CH
2CONH),2.49(s,1,124H,NCH
2CH
2N+CONHCH
2CH
2N),2.60(s,1,128H,CONHCH
2CH
2NH
2),2.69(s,1,248H,NCH
2CH
2NH),3.16(m,248H,J＝6.24Hz CONHCH
2).
Take from water 100mL and be placed in 200mL beaker, in running water sample, add Hg
2+, Pb
2+and Cu
2+, make its concentration be respectively 10mg/L.By 20mg Fe
3o
4@SiO
2@PADDG1.5@g-PADD G4.0@DNA or 20mg Fe
3o
4@SiO
2@PADDG1.5@g-PADD G4.0 is scattered in 5mL deionized water, then nano material dispersion liquid is transferred to running water sample, shakes up, and leaves standstill and nano material is separated with water sample with magnet after 2 minutes.The concentration of heavy metal ion residual in mark-on running water sample is detected with capillary electrophoresis method.
Heavy metal ion residual concentration contrast (unit: mg/L) in mark-on running water after table 1 processes
| DNA process a) | Without DNA b) | |
| Hg 2+ | ≤0.3 | 2.08 |
| Pb 2+ | ≤0.01 | 1.32 |
| Cu 2+ | ≤0.007 | 0.06 |
a)for Fe
3o
4@SiO
2@PADD G1.5@g-PADD G4.0@DNA
b)for Fe
3o
4@SiO
2@PADD G1.5@g-PADD G4.0
Embodiment 4
By Fe prepared by 0.5g embodiment 2
3o
4@SiO
2product, in 50mL methyl alcohol, after lucifuge places 48h at normal temperatures, is separated with solution with magnet, then uses methanol wash product 5 times by@PADD G1.5 and 0.3gg-PADD G4.0 ultrasonic disperse, obtains the magnetic Nano material Fe that surface is modified for spherical g-PADD G4.0
3o
4@SiO
2@PADDG1.5@g-PADD G4.0.
Thermal gravimetric analysis results shows, and the percent grafting of g-PADD G4.0 is 24.0%.
6mg polyanion cellulose (PAC-LV-1, Nantong Hui Cai cellulose Science and Technology Ltd.) is dissolved in the cushioning liquid (pH 7.0) of 20mL 10mM sodium dihydrogen phosphate/10mM sodium hydrogen phosphate, adds 20mg Fe
3o
4@SiO
2@PADD G1.5@g-PADD G4.0, ultrasonic 10min dispersion, leaves standstill 5 minutes afterwards, then with magnet by nano material (Fe
3o
4@SiO
2@PADD G1.5@g-PADD G4.0@PAC) and solution separate, spend deionized water nano material 5 times, obtain adsorbent.
The ability of the adsorbent heavy-metal ion removal that embodiment 3 and embodiment 4 obtain is assessed,
With running water sample for blank;
With mark-on running water for model, the spiked levels in mark-on running water: Hg
2+(2mg/L), Pb
2+(2mg/L), Cu
2+(0.5mg/L);
Respectively with sorbent treatment mark-on running water prepared by embodiment 3 and embodiment 4, carry out Capillary Electrophoresis to these four kinds of water samples, result is the Capillary Electrophoresis figure after sorbent treatment water sample of the present invention see Fig. 1, Fig. 1.In Fig. 1, A is running water sample; B is mark-on running water sample, spiked levels: Hg
2+(2mg/L), Pb
2+(2mg/L), Cu
2+(0.5mg/L); C is Fe
3o
4@SiO
2the mark-on running water sample of@PADD G1.5@g-PADD G4.0@DNA process; D is Fe
3o
4@SiO
2the mark-on running water sample of@PADD G1.5@g-PADD G4.0@PAC process.Peak is pointed out: 1 is Hg
2+; 2 is Pb
2+; 3 is Cu
2+.
As can be seen from the figure, in the mark-on running water after process, inspection does not measure heavy metal ion peak, therefore can think that the detectability that heavy metal ion residual concentration is less than instrument (is respectively: Hg
2+, 0.3mg/L; Pb
2+, 0.01mg/L; Cu
2+, 0.007mg/L).
Comparative example 1
Adopt document Changsheng Zhao, Ling Shi, Xingyi Xie, Shudong Sun, Xiangdong Liu, Motoyoshi Nomizu and Norio Nishi:Adsorption Science & Technology Vol.23No.52005, the sorbent treatment mark-on running water in 387-398, the spiked levels in mark-on running water: Hg
2+(2mg/L), Pb
2+(2mg/L), Cu
2+(0.5mg/L);
After process mark-on running water, the heavy metal ion residual concentration contrast in water is see table 2.
Heavy metal ion residual concentration contrast (unit: mg/L) in mark-on running water after table 2 processes
As can be seen from experimental result, performance of the adsorbent of the present invention is far superior to the performance of the adsorbent (table 2) in document.And different types of polyanion DNA and PAC does not have obvious difference in removal of heavy metal ions efficiency.In addition, the material in document effectively can not remove mercury ion.
Embodiment 5
By Fe prepared by 0.5g embodiment 2
3o
4@SiO
2product, in 50mL methyl alcohol, after lucifuge places 48h at normal temperatures, is separated with solution with magnet, then uses methanol wash product 5 times by@PADD G1.5 and 0.3gg-PADD G2.0 ultrasonic disperse, obtains the magnetic Nano material Fe that surface is modified for spherical g-PADD G2.0
3o
4@SiO
2@PADDG1.5@g-PADD G2.0.
Thermal gravimetric analysis results shows, and the percent grafting of g-PADD G2.0 is 14.0%.
5mg herring sperm dna (Beijing Ding Guo Bioisystech Co., Ltd) is dissolved in the cushioning liquid (pH 7.0) of 20mL10mM sodium dihydrogen phosphate/10mM sodium hydrogen phosphate, adds 20mg Fe
3o
4@SiO
2@PADD G1.5@g-PADD G2.0, ultrasonic 10min dispersion, leaves standstill 5 minutes afterwards, then with magnet by nano material (Fe
3o
4@SiO
2@PADDG1.5@g-PADD G2.0@DNA) and solution separate, spend deionized water nano material 5 times, obtain adsorbent.
The nuclear magnetic resonance (Bruker AdvanceIII-400MHz, Rheinstetten, Germany) of spherical g-PADD of whole generation involved in the present invention characterizes as follows:
PADD G2.0(400MHz,D
2O):δ2.29(m,56H,J＝6.08Hz,NCH
2CH
2CONH),2.49(m,28H,J＝7.88Hz,NCH
2CH
2N+CONHCH
2CH
2N),2.58(m,32H,J＝5.88Hz,CONHCH
2CH
2NH
2),2.69(m,56H,J＝5.76Hz,NCH
2CH
2NH),3.13(m,56H,J＝6.16Hz,CONHCH
2)。
Fig. 2 is the structural representation of adsorbent prepared by embodiment 5.
Take from water 100mL and be placed in 200mL beaker, in running water sample, add Hg
2+, Pb
2+and Cu
2+, make its concentration be respectively 10mg/L.By 20mg Fe
3o
4@SiO
2@PADDG1.5@g-PADD G2.0@DNA or 20mg Fe
3o
4@SiO
2@PADDG1.5@g-PADD G2.0 is scattered in 5mL deionized water, then nano material dispersion liquid is transferred to running water sample, shakes up, and leaves standstill and nano material is separated with water sample with magnet after 2 minutes.The concentration of heavy metal ion residual in mark-on running water sample is detected with capillary electrophoresis method.
Heavy metal ion residual concentration contrast (unit: mg/L) in mark-on running water after table 3 processes
| DNA process a) | Without DNA b) | |
| Hg 2+ | ≤0.3 | 2.54 |
| Pb 2+ | ≤0.01 | 2.97 |
| Cu 2+ | ≤0.007 | 0.40 |
a) be Fe
3o
4@SiO
2@PADD G1.5@g-PADD G2.0@DNA
b)for Fe
3o
4@SiO
2@PADD G1.5@g-PADD G2.0
Embodiment 6
By Fe prepared by 0.5g embodiment 2
3o
4@SiO
2product, in 50mL methyl alcohol, after lucifuge places 48h at normal temperatures, is separated with solution with magnet, then uses methanol wash product 5 times by@PADD G1.5 and 0.3g g-PADDG3.0 ultrasonic disperse, obtains the magnetic Nano material Fe that surface is modified for spherical g-PADDG3.0
3o
4@SiO
2@PADD G1.5@g-PADD G3.0.
Thermal gravimetric analysis results shows, and the percent grafting of g-PADD G3.0 is 19.6%.
5mg herring sperm dna (Beijing Ding Guo Bioisystech Co., Ltd) is dissolved in the cushioning liquid (pH 7.0) of 20mL10mM sodium dihydrogen phosphate/10mM sodium hydrogen phosphate, adds 20mg Fe
3o
4@SiO
2@PADD G1.5@g-PADD G3.0, ultrasonic 10min dispersion, leaves standstill 5 minutes afterwards, then with magnet by nano material (Fe
3o
4@SiO
2@PADDG1.5@g-PADD G3.0@DNA) and solution separate, spend deionized water nano material 5 times, obtain adsorbent.
The nuclear magnetic resonance (Bruker AdvanceIII-400MHz, Rheinstetten, Germany) of spherical g-PADD of whole generation involved in the present invention characterizes as follows:
PADD G3.0(400MHz,D
2O):δ2.20(m,120H,J＝6.64Hz,NCH
2CH
2CONH),2.41(m,60H,J＝6.68Hz,NCH
2CH
2N+CONHCH
2CH
2N),2.51(s,1,64H,CONHCH
2CH
2NH
2),2.59(m,120H,J＝7.02Hz,NCH
2CH
2NH),3.08(m,120H,J＝6.44Hz,CONHCH
2).
Take from water 100mL and be placed in 200mL beaker, in running water sample, add Hg2+, Pb2+ and Cu2+, make its concentration be respectively 10mg/L.By 20mg Fe
3o
4@SiO
2@PADDG1.5@g-PADD G3.0@DNA or 20mg Fe
3o
4@SiO
2@PADDG1.5@g-PADD G3.0 is scattered in 5mL deionized water, then nano material dispersion liquid is transferred to running water sample, shakes up, and leaves standstill and nano material is separated with water sample with magnet after 2 minutes.The concentration of heavy metal ion residual in mark-on running water sample is detected with capillary electrophoresis method.
Heavy metal ion residual concentration contrast (unit: mg/L) in mark-on running water after table 4 processes
| DNA process a) | Without DNA b) | |
| Hg 2+ | ≤0.3 | 2.64 |
| Pb 2+ | ≤0.01 | 1.92 |
| Cu 2+ | ≤0.007 | 0.06 |
A) be Fe
3o
4@SiO
2@PADD G1.5@g-PADD G3.0@DNA
B) be Fe
3o
4@SiO
2@PADD G1.5@g-PADD G3.0
Above result display, the increase of the algebraically of the spherical dendrimer modified along with skin, does not have the removal efficiency of the material heavy metal ion of adsorption of DNA to have the trend of enhancing; But when after composite skin absorption last layer DNA, the removal efficiency for heavy metal ion increases substantially, to such an extent as to the amount of residual heavy metal ion (is respectively: Hg lower than the detectability of analytical method in the present invention
2+, 0.3mg/L; Pb
2+, 0.01mg/L; Cu
2+, 0.007mg/L).
To embodiment 3, surface prepared by embodiment 5 and embodiment 6 is the magnetic Nano material Fe that spherical g-PADD modifies
3o
4@SiO
2the ability of the opposing extreme condition of@PADD G1.5 is tested:
The present invention is respectively by 20mg Fe
3o
4@SiO
2@PADD G1.5@g-PADD G4.0, Fe
3o
4@SiO
2@PADD G1.5@g-PADD G2.0 and Fe
3o
4@SiO
2@PADDG1.5@g-PADD G3.0 pH value is the 30mM borax process 8 hours of 9.2, adds respectively in 5mL 20mg/L herring sperm dna, make its adsorption last layer DNA with after pure water washing.Take from water 100mL and be placed in 200mL beaker, in running water sample, add Hg
2+, Pb
2+and Cu
2+, make its concentration be respectively 10mg/L.By heavy metal ion in the materials adsorption mark-on running water of above-mentioned condition process, detect the concentration of heavy metal ion residual in sample with capillary electrophoresis method.Result is as following table:
Table 5 contrasts (unit: mg/L) to heavy metal ion residual concentration in mark-on running water after the nano material adsorption of DNA that the different algebraically g-PADD of extreme condition process modify
| g-PADD 2.0 | g-PADD 3.0 | g-PADD 4.0 | |
| Hg 2+ | 1.42 | 0.88 | ≤0.3 |
| Pb 2+ | 1.57 | 0.15 | ≤0.01 |
| Cu 2+ | 0.13 | 0.15 | ≤0.007 |
The above results shows, and the nano material that the spherical dendrimer of high algebraically is modified is stronger to the protective capability of silica, is more suitable for the removal of heavy metal ions under harsh conditions.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. an adsorbent for heavy metal, comprising: core, the polyanion being grafted on the Polyamidoamine Dendrimers on described core by silane compound and be adsorbed on described Polyamidoamine Dendrimers;
Described core is the tri-iron tetroxide of coated with silica.
2. adsorbent for heavy metal according to claim 1, it is characterized in that, also comprise between described Polyamidoamine Dendrimers and polyanion, the space structure grafted on described Polyamidoamine Dendrimers is spherical Polyamidoamine Dendrimers;
It is on spherical Polyamidoamine Dendrimers that described polyanion is adsorbed in described space structure.
3. adsorbent for heavy metal according to claim 2, is characterized in that, described polyanion is DNA or polyanion cellulose.
4. adsorbent for heavy metal according to claim 3, is characterized in that, described core, Polyamidoamine Dendrimers and space structure are the gross mass of spherical Polyamidoamine Dendrimers and the mass ratio of polyanion is 1:1 ~ 20:1.
5. a preparation method for adsorbent for heavy metal, comprises the following steps:
By by the core of Polyamidoamine Dendrimers in silane compound grafting ultrasonic disperse in containing the cushioning liquid of polyanion, then leave standstill, obtain adsorbent for heavy metal;
Described core is the tri-iron tetroxide of coated with silica.
6. preparation method according to claim 5, is characterized in that, in described grafting, the preparation method of the core of Polyamidoamine Dendrimers is:
After core is mixed in organic solvent with silane compound, react, obtain the core of 0 PAMAM dendrimer in grafting;
Described silane compound is 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxy silicon, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyltriethoxy dimethoxy silicon, N-β (aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyltriethoxy diethoxy silane or aminoethylaminopropyl trimethoxy silane.
7. preparation method according to claim 6, is characterized in that, in described grafting, the preparation method of the core of Polyamidoamine Dendrimers also comprises:
The core of 0 PAMAM in grafting is obtained the core of the PAMAM of different algebraically in grafting through the amidation process of Michael addition reaction or ester group.
8. preparation method according to claim 5, it is characterized in that, in grafting Polyamidoamine Dendrimers core ultrasonic disperse before, also comprise: by the core of Polyamidoamine Dendrimers in grafting and space structure be spherical PAMAM in organic solvent lucifuge react.
9. preparation method according to claim 5, is characterized in that, the time of described ultrasonic disperse is 5 ~ 20 minutes, and described time of repose is 5 ~ 30 minutes.
10. preparation method according to claim 8, is characterized in that, in described grafting, the core of Polyamidoamine Dendrimers and space structure are the mass ratio of spherical PAMAM is 0.5 ~ 5:1.
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