CN104209102A - Heavy metal ion adsorbent for grafting glycine to chloromethylated polystyrene, preparation method and application thereof - Google Patents
Heavy metal ion adsorbent for grafting glycine to chloromethylated polystyrene, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a heavy metal ion adsorbent for grating glycine to chloromethylated polystyrene, a preparation method and an application thereof, and belongs to the technical field of a solid-phase extraction agent. The technical solution of the invention is that: a heavy metal ion adsorbent for grafting glycine to chloromethylated polystyrene takes chloromethylated polystyrene and glycine as raw materials, and glycine is grafted on the chloromethylated polystyrene surface through one-step synthesis. The invention further discloses the preparation method of the heavy metal ion adsorbent for grating glycine to chloromethylated polystyrene and the application of taking the adsorbent as the solid-phase extraction agent to selectively separate and enrich trace Pb2+ from environmental samples. The heavy metal ion adsorbent is simple in a synthetic method, good in selectivity and high in sensitivity, nontoxic, easy to regenerate and recyclable.
Description
Technical field
The invention belongs to solid extracting agent technical field, be specifically related to a kind of glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal and its preparation method and application.
Background technology
The waste water that production, metallurgy, machine-building etc. that in environment, lead contamination mainly comes from coating produce.Lead is a kind of cumulative toxicant, non-degradable after entered environment, due to non-degradable and the cumulative bad of lead, make Environmental Trace lead can enter human body by the absorption of food chain enrichment, water and breathing, the hemopoietic system of human body, nervous system, cardiovascular system, Genitourinary, bone are caused serious harm, especially cannot eliminate the infringement of upgrowth and development of children.Therefore, for Determination of Trace Lead in Environmental Samples ion detection and remove significant.
Heavy metal ion content in environmental sample is general very low, add that environmental sample composition itself is complicated, Matrix effects is serious, when directly it being measured and remove, common analytical method and removal technology are often difficult to realize, even if select highly sensitive detection means such as Atomic absorption, inductivity coupled plasma mass spectrometry, ion exchange resin etc. to be also difficult to reach desirable detection and removal effect.Therefore, to the mensuration of trace heavy metal ion, the pre-treatment of sample just seems particularly crucial.Can exclusive PCR component by pretreatment technologies such as separation and concentrations, enrichment component to be measured, thus improve the sensitivity and the degree of accuracy analyzing and detect.Conventional traditional method for separating and concentrating has precipitation-coprecipitation, liquid-liquid extraction method, cloud point extraction method etc., and these methods have complicated operation in use, and length consuming time, organic solvent consumption is large, be difficult to shortcomings such as recycling.Solid phase extraction techniques is development in recent years a kind of Sample Pretreatment Technique rapidly, compared with conventional method, it is fast that it has balancing speed, cost is low, and the rate of recovery is high, selective good, easy to operate, to be separated and enrichment a step advantage such as can to complete, be in current sample treatment technology a kind of simple and direct, efficiently, means flexibly, therefore a kind of Sample Pretreatment Technique of Chang Zuowei is for the compartment analysis of heavy metal ion in environmental sample.Meanwhile, this technology also can remove the heavy metal ion of trace in water body, is applicable to purification of water quality.
The core of solid phase extraction techniques is the selection of packed column solid extracting agent, and the selection of solid extracting agent determines the sensitivity height of quality to the selective absorption of target heavy metal ion and detection.Therefore constantly research and development, for the important research direction that heavy metal ion has high sensitivity, high selectivity and the high novel solid extracting agent of stability are still environmental sample pre-treatment field, have great Research Significance and application prospect.The solid extracting agent for separation of heavy metal ions enrichment reported in current document comprises active carbon, chelating resin, silica gel, molecularly imprinted polymer and novel nano-material etc.
Wherein be used for heavy metal ion adsorbed pertinent literature with amino acid grafted support synthetic adsorbent also few, the prior art related to the present invention retrieved is as follows:
Publication number be CN103041784A patent discloses a kind of glycine graft crosslinking chitosan microball adsorbent for heavy metal; take shitosan as initial feed; first be polymerized to obtain glutaraldehyde cross-linking chitosan microball with glutaraldehyde as cross linker by inverse suspension crosslinking; after add glycine solution and stir under nitrogen protection, at the uniform velocity drip Carbodiimides dehydrating agent in the most backward solution and react to obtain end product.In this technical scheme, the synthesis of adsorbent need through multistep reaction, and synthesis cycle is long, preparation process complicated operation, not easily realize, need in synthesis to use a large amount of organic solvent, toxicity is comparatively large, and does not have the adsorbent synthesized by investigation in this technical scheme for the selective absorption performance of heavy metal ion.
Publication number is the preparation method that patent discloses a kind of Spherical amino acid resin sorbent of CN1476908A, this technical scheme comprises ball shaped cellulose, agar, agarose, glucan, shitosan, Arabic gum, gelatin or starch for carrier with natural polymer, the amino acid aglucon being fixed with effective amount after Epichlorohydrin activation obtains, and wherein said amino acid aglucon comprises arginine, lysine, glutamic acid, serine, TYR, leucine, isoleucine, phenylalanine, tryptophan, cysteine or histidine.Ball type carrier selected in this technical scheme need through four step pre-treatment and activation processes, complex operation, and a large amount of organic solvent such as carbon disulfide, toluene, chloroform, formaldehyde need be used, carrying capacity of environment is large, also need after ball type carrier after Epichlorohydrin activation and amino acid react in the basic conditions to add 1M ethanolamine solutions reaction 1-3h to close residual epoxy radicals, increase workload.
Huang Wenqiang, this will bosom etc. use nBu by the solution of 3-polystyrene sulfonyl expoxy propane and glycine in dioxane solution
4nI is that phase transfer catalyst has synthesized N-(3-polystyrene sulfonyl-2-hydroxypropyl) glycine adsorbent, and investigated synthesized adsorbent to Cu
2+complex performance (ion-exchange and absorption, 1997,13(3); 307-312); the dioxane solution toxicity selected in this technology is comparatively large, and selected 3-polystyrene sulfonyl expoxy propane determines synthesized adsorbent and contains hydroxyl and carboxyl structure, and synthetic material is for Cu
2+demonstrate good selective absorption performance.
Lv Zhe, Shen Ziyue etc. have synthesized fixed amino acid cationic ion-exchange resin, and have investigated synthesized resin for Ca
2+and Mg
2+absorption property (chemistry and bioengineering, 2012,29 (12), 43-47), the carrier selected in this technology is Sephadex G-25 gel, belong to inert carrier, need first by after Epichlorohydrin activation again with glycine reactant 24h, the adsorption mechanism proposed in document is by the H on carboxyl aglucon
+with metal ion exchanged and adsorbing metal ions.According to hsab theory, due to RCOO
-for hard base, so for the Ca belonging to hard acid
2+and Mg
2+show good absorption property, this adsorbent is less than 90% to metal biosorption rate after 5 recyclings, recycles rate lower, is unfavorable for applying in actual environment sample.
Li Jiang, Du Kaifeng etc. have synthesized a kind of glycine and have modified macroporous cellulose microballoon, and have investigated it to Cr
3+, Fe
3+absorption property (Treatment of Industrial Water, 2011,31(5), 58-61), first synthetic cellulose microballoon is needed during the synthesis of this adsorbent, take calcium carbonate granule as pore-foaming agent, adopt PUR conversion method synthesis macroporous cellulose microballoon, the rear glycine solution with adding a certain amount of NaOH reacts 17h and obtains end product.Relate to absorbent cotton alkalization in synthesis step, aging, the operation such as be heating and curing, complicated operation, not easily realize, and time of equilibrium adsorption needed for this adsorbent is 270min, equilibration time is long, can not regenerate realization to recycle, therefore this adsorbent is unfavorable for the process of heavy metal ion in actual water sample.
Meng Guanhua, Ou Chenghui etc. have synthesized the chelating absorption resin that a kind of L-TYR is modified, and have studied it to Cu
2+absorption property (applied chemistry, 2009,26(12), 1450-1455), in this technology, the synthesis of material comprises two parts, first be that chlorine ball and L-TYR react 5h and obtain L-TYR chelating resin in the aqueous solution adding pyridine, after by swelling for the resin nitrobenzene obtained, then add ZnCl
2reaction 8h, apparatus,Soxhlet's extracting 8h obtains end product.Because the L-TYR selected contains benzene ring structure, comparatively large with steric hindrance during metallic ion coordination, containing a large amount of-OH and-COOH structure, for Cu
2+show good absorption property, the synthesis of this adsorbent comprises more than two steps and reacts, and operation relates to more than surname extraction 8h, and synthesis cycle is long, operates not easy, to Cu
2+time of equilibrium adsorption reach 24h, equilibration time is long, and without regeneration tests, is unfavorable for process actual environment water sample.
He Ping Lin, Wang Wen have synthesized the asymmetric resin (Nature Journal of polystyrene-divinylbenzene of a series of alpha-amido acid functional groups on an equal basis, 1982,5(7), 557), the synthesis of the asymmetric resin of the glycine mentioned in this technology comprises two-step reaction, first by chloromethyl polystyrene resin and DMA Reactive Synthesis anline resin, rear anline resin and amino acid Reactive Synthesis.Course of reaction is comparatively complicated, and synthesized resin is for splitting various a-amino acid racemic mixture.
Above technology is amino acid by the synthesis of different modes grafting different carriers adsorbent and application, can find out by analyzing, above the deficiencies in the prior art part is: preparation process complicated operation, selective good not, time of equilibrium adsorption is longer, because selected carrier is different, amino acid grafting method is different, the adsorbent prepared also has different structures, the mechanism of thus adsorbing is different, thus demonstrates different selective absorption performances for different metal ions.
Up to the present, also do not find to select glycine by the adsorbent for heavy metal of single step reaction grafting chloromethyl polystyrene resin and for Pb
2+selective separation enrichment and the report of removal.
Summary of the invention
The technical problem that the present invention solves there is provided a kind of glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal, and this adsorbent for heavy metal is to trace Pb in environmental sample
2+have good adsorption selectivity, the rate of adsorption is fast, is easy to regeneration, can repeatedly recycles, and is a kind of desirable for trace Pb in environmental sample
2+the solid extracting agent of selective separation enrichment.
It is gentle that another technical problem that the present invention solves there is provided a kind of synthesis condition, easy and simple to handle and be easy to the preparation method of the glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal realized.
The technical problem that the present invention also solves is that this glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal is as solid extracting agent trace Pb in environmental sample
2+application in selective separation enrichment.
Technical scheme of the present invention is: a kind of glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal, it is characterized in that: with chloromethyl polystyrene resin and glycine for raw material, by one-step synthesis reaction, glycine be grafted on chloromethyl polystyrene resin surface and formed.
The preparation method of glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal of the present invention, it is characterized in that concrete steps are: will be transferred in reaction vessel after swelling for chloromethyl polystyrene resin ethanolic solution 12-24h activation, then ethanol and the solution containing glycine and triethylamine is added successively, in 60-90 DEG C of concussion reaction 8-24h, cooled and filtered products therefrom, use ethanol successively, deionized water washing to filtrate is neutral, 60 DEG C of vacuum drying 12-24h, finally obtain faint yellow product glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal.
Concrete reaction equation in the preparation method of glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal of the present invention is:
。
Glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal of the present invention is as solid extracting agent trace Pb in environmental sample
2+application in selective separation enrichment.
Glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal of the present invention is as solid extracting agent trace Pb in environmental sample
2+application in selective separation enrichment, is characterized in that mainly through realizing with under type: regulate containing Pb with salpeter solution or sodium hydroxide solution
2+the pH of water sample is 3-6, then by water sample with the flow velocity of 0.1-0.5ml/min by being filled with the solid-phase extraction column of glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal, can separation and concentration containing Pb
2+the Pb of trace in water sample
2+.
Of the present invention containing Pb
2+pb in water sample
2+concentration limit be 0.005 μ g/ml.
Absorption Pb of the present invention
2+solid-phase extraction column can be that the acetum of 0.05-2mol/L or hydrochloric acid zeolite regeneration Posterior circle use by molar concentration.
Solid-phase extraction column absorption Pb of the present invention
2+after, can be the acetum of 0.05-2mol/L or the Pb of hydrochloric acid wash-out SPE on-column enrichment by molar concentration
2+, be then neutral with deionized water rinsing solid-phase extraction column to efflux, thus realize SPE column regeneration Posterior circle and use.
When adsorbent for heavy metal of the present invention prepares solid-phase extraction column as solid extracting agent, to the Pb in sample solution
2+desirable separation and concentration effect can be reached, Pb
2+minimal detectable concentration can be low to moderate 0.005 μ g/mL, and enrichment multiplying power can reach 333 times, and the solid-phase extraction column after adsorption equilibrium uses by acetum or hydrochloric acid zeolite regeneration Posterior circle.Compared with prior art, adsorbent for heavy metal of the present invention have simple synthetic method, selective good, highly sensitive, nontoxic, be easy to regeneration and the advantage such as to can be recycled.
Accompanying drawing explanation
fig. 1 is the infared spectrum of empty chloromethyl polystyrene resin of the present invention and glycine grafting chloromethyl polystyrene resin.
Detailed description of the invention
Be described in further details foregoing of the present invention by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
Take 1g chloromethyl polystyrene resin, with proceeding in conical flask after the swelling 12h of ethanolic solution, add 10mL ethanol, after add the aqueous solution that 80mL is dissolved with 4.67g glycine and 13mL triethylamine, after sealing, synthetic reaction 12h is shaken under 80 DEG C of conditions, room temperature is cooled to after end of synthesis, filter, use ethanol successively, deionized water washing to filtrate is neutral, vacuum drying 12h under 60 DEG C of conditions, finally obtain faint yellow product and be glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal, product is sealed in bottle, be stored in drier for subsequent use.
Glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal synthesized by the present invention, structure contains N, O coordination atom, and according to hsab theory, the reagent hardness containing N, O coordination structure is less than O, the hardness of O coordination, and RCOO
-belong to typical hard base, and the existence of N coordination atom reduces the hardness of reagent, improve the selective of this adsorbent, Pb (II) belongs to acid of having a common boundary, experiment proves, synthesized adsorbent for heavy metal demonstrates good selective absorption performance for Pb (II), and does not substantially adsorb other metal ion or adsorb seldom.
Fig. 1 is the infared spectrum of blank chloromethyl polystyrene resin and glycine grafting chloromethyl polystyrene resin, wherein CMPS is the infared spectrum of blank chloromethyl polystyrene resin, and CMPS-Gly is the infared spectrum of glycine grafting chloromethyl polystyrene resin.Blank chloromethyl polystyrene resin infared spectrum shows, 670.12cm
-1place is C-Cl key stretching vibration peak on chloromethyl polystyrene resin, 699.13cm
-1place is C-H out-of-plane bending vibration peak on monosubstituted phenyl ring, 1264.34cm
-1place is CH on resin
2the in-plane bending vibration to H on disubstituted benzenes ring of Cl strengthening.Chloromethyl polystyrene resin infared spectrum after the grafting of contrast glycine, 670.12cm
-1the stretching vibration peak of place's display C-Cl key obviously disappears, 1264.34cm
-1place's display CH
2on the phenyl ring of Cl strengthening, the flexural vibrations peak of H obviously disappears, and 699.13cm
-1place represents that on monosubstituted phenyl ring, C-H flexural vibrations peak does not disappear, prove C-Cl bond fission on Chloromethyl polystyrene branch in synthetic reaction, thus cause characteristic peak obviously to disappear, and the overall monosubstituted structure of resin does not change, and proves that this course of reaction is chemical bonding process thus.Contrast blank resin collection of illustrative plates, at fingerprint region 1392.46cm on the chloromethyl polystyrene resin infared spectrum after glycine grafting
-1having there is the new peak that blank resin does not have in place, is-NH by this peak of the long position judgment of this spike
2with CH
2the characteristic absorption peak of the new key of-C-N-generated after Cl reaction.1583.80cm
-1-C=O key after the peak value located is glycine grafting in-COOH affects by benzene ring structure conjugation on resin, moves the characteristic absorption peak of formation to shortwave number, proves thus to have synthesized glycine grafting chloromethyl polystyrene resin.
(1) solid extracting agent is to the adsorptive selectivity of metal ion and other material
The adsorbent for heavy metal taken obtained by 0.1g is filled in solid-phase extraction column, make SPE microtrabeculae (column internal diameter 3mm, post height 20mm), get the sample solution containing a certain amount of metal ion, pH value of solution is regulated to be 4.0 with the salpeter solution of 0.1mol/L and sodium hydroxide solution, with the flow velocity of 0.3mL/min by the SPE microtrabeculae of loading by preparation, measure adsorbent to the adsorption rate of each ion.SPE microtrabeculae is to Pb
2+with the selective absorption performance parameter of other metal ion and some common coexisting substances in table 1 and table 2.
Table 1 glycine grafting chloromethyl polystyrene resin is to the adsorption rate of different metal ion
Table 2 coexisting ion allows interference multiplying power
| Interfering ion | Allow multiplying power | Interfering ion | Allow multiplying power |
| K + | 2500 | Na + | 2800 |
| Ca 2+ | 1400 | Mg 2+ | 1500 |
| Co 2+ | 100 | Cd 2+ | 100 |
| Ni 2+ | 100 | Mn 2+ | 100 |
| Zn 2+ | 85 | Cu 2+ | 90 |
| Hg 2+ | 20 | Cr 3+ | 100 |
| Fe 3+ | 100 | Al 3+ | 15 |
| Cl - | 1000 | CO 3 2- | 500 |
| SO 4 2- | 150 | Glucose | 1500 |
| Soluble starch | 1800 |
As can be seen from Table 1, in the metal ion situation adding identical amount, the Pb in sample solution
2+100% enrichment can be reached on solid-phase extraction column, and except Al
3+outside other metal biosorption rate be far smaller than Pb
2+, each coexistent metallic ion and molecule allow the interference multiplying power of existence as shown in table 2, and common ion is as K
+, Na
+, CO
3 2-, Cl
-deng and other metal ion and the macromolecular existence of neutrality do not disturb solid-phase extraction column selective absorption Pb
2+, above experimental result shows that prepared adsorbent for heavy metal has good selective absorption performance to Pb (II).
(2) to trace Pb
2+absorption sensitivity
Get the Pb of 5 μ g
2+be dissolved in the aqueous solution of different volumes, sample solution pH is regulated to be 4 with the salpeter solution of 0.1mol/L, with the flow velocity of 0.3mL/min by solid-phase extraction column, then select the flow velocity wash-out of acetum 1.5mL with 0.4mL/min of 0.1mol/L, measure Pb in eluent
2+concentration.Experimental result shows, when loading volume is 500mL, and Pb
2+the rate of recovery be 90.4%, now enrichment multiplying power is 333 times, shows that synthesized adsorbent for heavy metal is to trace Pb
2+have good concentration effect, the solid extracting agent synthesized by explanation is to the trace Pb in sample solution
2+there is good absorption property, and can be used for underwater trace Pb
2+removal.
In concentration limit experiment, be 4.0 pH respectively, concentration is the Pb of 0.015 μ g/mL, 0.010 μ g/mL, 0.005 μ g/mL
2+solution, with the SPE microtrabeculae of the flow velocity of 0.3mL/min by preparation, measures solid-phase extraction column to Pb with ICP-MS
2+adsorption rate.Result shows, when containing Pb
2+when the concentration of sample is low to moderate 0.005 μ g/mL, solid-phase extraction column is to Pb
2+adsorption rate still can reach 91.8%, and this concentration requires Pb lower than country-level water environment quality standard
2+standard limited value (0.01 μ g/mL), show that synthesized solid extracting agent is to Pb
2+absorption highly sensitive, can be used for trace Pb
2+detection and removal.
Select the acetum 1.5mL of 0.1mol/L with the elution flow rate of 0.4mL/min can wash-out solid-phase extraction column retain Pb
2+, with deionized water rinsing solid-phase extraction column until efflux is in neutral, this method can be used for the regeneration of solid-phase extraction column, reaches reusable object, and what regeneration tests had investigated synthesized adsorbent for heavy metal reuses number of times to Pb
2+the impact of the rate of recovery, experimental result is as shown in table 3.
Reusing and regenerability of table 3 CMPS-Gly resin
| Number of times reused by CMPS-Gly resin | 5 | 10 | 15 | 20 | 25 | 30 |
| Pb 2+The rate of recovery/% | 100 | 100 | 98 | 98 | 97 | 96 |
As can be seen from Table 3, the solid-phase extraction column of preparation more than the 30 times performances that can be recycled remain unchanged substantially, and the solid-phase extraction column prepared by explanation can be recycled, and recycling rate of waterused is high.
(3) adsorbent is to Pb in actual sample
2+removal and detect application
With the experimental technique in (1), the adsorbent for heavy metal of synthesis is used for Pb in actual environment water sample and pedotheque
2+removal and analyze detect, detect respectively with ICP-MS and belong to the concentration of ion by Gold Samples before and after solid-phase extraction column enrichment, experimental result is in table 4.
The analysis of table 4 actual sample
As can be seen from Table 4, prepared SPE microtrabeculae is to Pb
2+the rate of recovery can reach more than 93%, show that this solid-phase extraction column can to get rid of in actual environment sample complicated Matrix effects, be optionally separated the trace Pb removed in sample solution
2+, selective good, and highly sensitive, tool has significant practical applications.
Embodiment 2
Take 0.5g chloromethyl polystyrene resin, proceed in 100mL conical flask with after the swelling 12h of ethanolic solution, 8mL ethanol is added in conical flask, after add the aqueous solution that 40mL is dissolved with 2.34g glycine and 8mL triethylamine, after sealing, synthetic reaction 16h is shaken under 70 DEG C of conditions, room temperature is cooled to after end of synthesis, filter, use ethanol successively, deionized water washing to filtrate is neutral, vacuum drying 12h under 60 DEG C of conditions, finally obtain faint yellow product glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal, product is sealed in bottle, be stored in drier for subsequent use.
The adsorbent for heavy metal taken obtained by 0.1g is filled in solid phase splitter, makes SPE microtrabeculae (column internal diameter 3mm, post height 20mm).Get containing a certain amount of Pb
2+sample solution, with the HNO of 0.1mol/L
3the NaOH solution of solution and 0.1mol/L regulates pH value of solution to be 5, with the solid-phase extraction column of the flow velocity of 0.4mL/min by preparation, and the Pb in sample solution
2+100% enrichment can be reached on solid-phase extraction column, and except Al
3+outside other metal biosorption rate be far smaller than Pb
2+, common ion is as K
+, Na
+, CO
3 2-, Cl
-deng and other metal ion and the macromolecular existence of neutrality do not disturb solid-phase extraction column selective absorption Pb
2+.
Can the Pb that retains of wash-out solid-phase extraction column with the elution flow rate of 0.4mL/min with the acetum 1mL of 2mol/L
2+, with deionized water rinsing solid-phase extraction column until efflux is in neutral, this method can be used for the regeneration of solid-phase extraction column, reaches the object recycled.Experiment proves, the solid-phase extraction column of preparation more than the 30 times performances that can be recycled remain unchanged substantially, and the solid-phase extraction column prepared by explanation can be recycled, and recycling rate of waterused is high.
Embodiment 3
Take 1g chloromethyl polystyrene resin, proceed in 250ml conical flask with after the swelling 12h of ethanolic solution, 10mL ethanol is added in conical flask, after add the aqueous solution that 80mL is dissolved with 9.35g glycine and 13mL triethylamine, after sealing, synthetic reaction 24h is shaken under 60 DEG C of conditions, room temperature is cooled to after end of synthesis, filter, use ethanol successively, deionized water washing to filtrate is neutral, vacuum drying 24h under 60 DEG C of conditions, finally obtain faint yellow product glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal, product is sealed in bottle, be stored in drier for subsequent use.
The adsorbent for heavy metal taken obtained by 0.2g is filled in solid phase splitter, makes SPE microtrabeculae (column internal diameter 3mm, post height 40mm), gets containing a certain amount of Pb
2+sample solution, with the HNO of 0.1mol/L
3the NaOH solution of solution and 0.1mol/L regulates pH value of solution to be 6, with the solid-phase extraction column of the flow velocity of 0.5mL/min by preparation, and the Pb in sample solution
2+100% enrichment can be reached on solid-phase extraction column, and except Al
3+outside other metal biosorption rate be far smaller than Pb
2+, common ion is as K
+, Na
+, CO
3 2-, Cl
-deng and other metal ion and the macromolecular existence of neutrality do not disturb solid-phase extraction column selective absorption Pb
2+.
Can the Pb that retains of wash-out solid-phase extraction column with the elution flow rate of 0.4mL/min with the hydrochloric acid 1mL of 0.1mol/L
2+, with deionized water rinsing solid-phase extraction column until efflux is in neutral, this method can be used for the regeneration of solid-phase extraction column, reaches the object recycled.Experiment proves, the solid-phase extraction column of preparation more than the 30 times performances that can be recycled remain unchanged substantially, and the solid-phase extraction column prepared by explanation can be recycled, and recycling rate of waterused is high.
Embodiment 4
Take 1g chloromethyl polystyrene resin, proceed in 250ml conical flask with after the swelling 12h of ethanolic solution, 12mL ethanol is added in conical flask, after add the aqueous solution that 80mL is dissolved with 4.67g glycine and 13mL triethylamine, after sealing, synthetic reaction 8h is shaken under 90 DEG C of conditions, room temperature is cooled to after end of synthesis, filter, use ethanol successively, deionized water washing to filtrate is neutral, vacuum drying 12h under 60 DEG C of conditions, finally obtain faint yellow product glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal, product is sealed in bottle, be stored in drier for subsequent use.
The adsorbent for heavy metal taken obtained by 0.1g is filled in solid phase splitter, makes SPE microtrabeculae (column internal diameter 3mm, post height 20mm), gets containing a certain amount of Pb
2+sample solution, with the HNO of 0.1mol/L
3the NaOH solution of solution and 0.1mol/L regulates pH value of solution to be 5, with the solid-phase extraction column of the flow velocity of 0.2mL/min by preparation, and the Pb in sample solution
2+100% enrichment can be reached on solid-phase extraction column, and except Al
3+outside other metal biosorption rate be far smaller than Pb
2+, common ion is as K
+, Na
+, CO
3 2-, Cl
-deng and other metal ion and the macromolecular existence of neutrality do not disturb solid-phase extraction column selective absorption Pb
2+.
Select the hydrochloric acid 1mL of 0.05mol/L with the elution flow rate of 0.4mL/min can wash-out solid-phase extraction column retain Pb
2+, live with deionized water rinsing SPE until efflux is in neutral, this method can be used for the regeneration of solid-phase extraction column, reaches the object of recycling.Experiment proves, the solid-phase extraction column of preparation more than the 30 times performances that can be recycled remain unchanged substantially, and the solid-phase extraction column prepared by explanation can be recycled, and recycling rate of waterused is high.
Embodiment 5
Take 1g chloromethyl polystyrene resin, proceed in 250ml conical flask with after the swelling 12h of ethanolic solution, 15mL ethanol is added in conical flask, after add the aqueous solution that 80mL is dissolved with 6.23g glycine and 13mL triethylamine, after sealing, synthetic reaction 24h is shaken under 80 DEG C of conditions, room temperature is cooled to after end of synthesis, filter, use ethanol successively, deionized water washing to filtrate is neutral, vacuum drying 12h under 60 DEG C of conditions, finally obtain faint yellow product glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal, product is sealed in bottle, be stored in drier for subsequent use.
The adsorbent for heavy metal taken obtained by 0.15g is filled in solid phase splitter, makes SPE microtrabeculae (column internal diameter 3mm, post height 30mm), gets containing a certain amount of Pb
2+sample solution, use 0.1mol/L HNO
3solution and 0.1mol/L NaOH solution regulate pH value of solution to be 3, with the solid-phase extraction column of the flow velocity of 0.1mL/min by preparation, and the Pb in sample solution
2+100% enrichment can be reached on solid-phase extraction column, and except Al
3+outside other metal biosorption rate be far smaller than Pb
2+, common ion is as K
+, Na
+, CO
3 2-, Cl
-deng and other metal ion and the macromolecular existence of neutrality do not disturb solid-phase extraction column selective absorption Pb
2+.
Select the acetum 1.5mL of 0.1mol/L with the elution flow rate of 0.4mL/min can wash-out solid-phase extraction column retain Pb
2+, live with deionized water rinsing SPE until efflux is in neutral, this method can be used for the regeneration of solid-phase extraction column, reaches the object of recycling.Experiment proves, the solid-phase extraction column of preparation more than the 30 times performances that can be recycled remain unchanged substantially, and the solid-phase extraction column prepared by explanation can be recycled, and recycling rate of waterused is high.
Embodiment 6
Take 0.5g chloromethyl polystyrene resin, proceed in 100mL conical flask with after the swelling 24h of ethanolic solution, 10mL ethanol is added in conical flask, after add the aqueous solution that 40mL is dissolved with 3.89g glycine and 8mL triethylamine, after sealing, synthetic reaction 10h is shaken under 60 DEG C of conditions, room temperature is cooled to after end of synthesis, filter, use ethanol successively, deionized water washing to filtrate is neutral, vacuum drying 12h under 60 DEG C of conditions, finally obtain faint yellow product glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal, product is sealed in bottle, be stored in drier for subsequent use.
The adsorbent for heavy metal taken obtained by 0.1g is filled in solid phase splitter, makes SPE microtrabeculae (column internal diameter 3mm, post height 20mm), gets containing a certain amount of Pb
2+sample solution, use 0.1mol/L HNO
3solution and 0.1mol/L NaOH solution regulate pH value of solution to be 4.5, with the solid-phase extraction column of the flow velocity of 0.4mL/min by preparation, and the Pb in sample solution
2+100% enrichment can be reached on solid-phase extraction column, and except Al
3+outside other metal biosorption rate be far smaller than Pb
2+, common ion is as K
+, Na
+, CO
3 2-, Cl
-deng and other metal ion and the macromolecular existence of neutrality do not disturb solid-phase extraction column selective absorption Pb
2+.
Select the acetum 1mL of 1mol/L with the elution flow rate of 0.4mL/min can wash-out solid-phase extraction column retain Pb
2+, live with deionized water rinsing SPE until efflux is in neutral, this method can be used for the regeneration of solid-phase extraction column, reaches the object of recycling.Experiment proves, the solid-phase extraction column of preparation more than the 30 times performances that can be recycled remain unchanged substantially, and the solid-phase extraction column prepared by explanation can be recycled, and recycling rate of waterused is high.
Embodiment above describes general principle of the present invention, principal character and advantage; the technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and description just illustrates principle of the present invention; under the scope not departing from the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of the invention.
Claims (8)
1. a glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal, is characterized in that: with chloromethyl polystyrene resin and glycine for raw material, by one-step synthesis reaction, glycine is grafted on chloromethyl polystyrene resin surface and is formed.
2. the preparation method of a glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal according to claim 1, it is characterized in that concrete steps are: will be transferred in reaction vessel after swelling for chloromethyl polystyrene resin ethanolic solution 12-24h activation, then ethanol and the solution containing glycine and triethylamine is added successively, in 60-90 DEG C of concussion reaction 8-24h, cooled and filtered products therefrom, use ethanol successively, deionized water washing to filtrate is neutral, 60 DEG C of vacuum drying 12-24h, finally obtain faint yellow product glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal.
3. the preparation method of glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal according to claim 2, is characterized in that the concrete reaction equation in preparation method is:
。
4. glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal according to claim 1 is as solid extracting agent trace Pb in environmental sample
2+application in selective separation enrichment.
5. glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal according to claim 4 is as solid extracting agent trace Pb in environmental sample
2+application in selective separation enrichment, is characterized in that mainly through realizing with under type: regulate containing Pb with salpeter solution and sodium hydroxide solution
2+the pH of water sample is 3-6, then by water sample with the flow velocity of 0.1-0.5ml/min by being filled with the solid-phase extraction column of glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal, can separation and concentration containing Pb
2+the Pb of trace in water sample
2+.
6. glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal according to claim 5 is as solid extracting agent trace Pb in environmental sample
2+application in selective separation enrichment, is characterized in that: described contains Pb
2+pb in water sample
2+concentration limit be 0.005 μ g/ml.
7. glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal according to claim 5 is as solid extracting agent trace Pb in environmental sample
2+application in selective separation enrichment, is characterized in that: absorption Pb
2+solid-phase extraction column can be that the acetum of 0.05-2mol/L or hydrochloric acid zeolite regeneration Posterior circle use by molar concentration.
8. glycine grafting chloromethyl polystyrene resin adsorbent for heavy metal according to claim 5 is as solid extracting agent trace Pb in environmental sample
2+application in selective separation enrichment, is characterized in that: described solid-phase extraction column absorption Pb
2+after, can be the acetum of 0.05-2mol/L or the Pb of hydrochloric acid wash-out SPE on-column enrichment by molar concentration
2+, be then neutral with deionized water rinsing solid-phase extraction column to efflux, thus realize SPE column regeneration Posterior circle and use.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107233871A (en) * | 2017-07-18 | 2017-10-10 | 河南师范大学 | Immobilized methylimidazole bromide solid extracting agent of 1 amine ethyl 3 of chloromethyl polystyrene resin and its preparation method and application |
| CN108392853A (en) * | 2018-04-12 | 2018-08-14 | 淮海工学院 | A kind of solid-phase extraction column and the preparation method and application thereof |
| CN110152629A (en) * | 2019-06-04 | 2019-08-23 | 南京信息工程大学 | A kind of adsorbent and its application for water process |
| CN110451701A (en) * | 2019-07-29 | 2019-11-15 | 苏州飞辉环境科技有限公司 | The minimizing technology of heavy metal in a kind of flying ash leachate |
| CN111422942A (en) * | 2020-03-23 | 2020-07-17 | 浙江工业大学 | Method for synchronously reducing and adsorbing hexavalent chromium in water by using ethylenediamine-based resin |
| CN112010448A (en) * | 2019-05-28 | 2020-12-01 | 宝山钢铁股份有限公司 | Method and system for removing total organic carbon and magnesium ions in cold-rolling nanofiltration concentrated water |
| CN115073804A (en) * | 2022-07-21 | 2022-09-20 | 河北利江生物科技有限公司 | Preparation method and application of amino acid loaded high-molecular resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2005122817A (en) * | 2005-07-18 | 2007-01-27 | Государственное образовательное учреждение высшего профессионального образовани "Воронежска государственна технологическа академи " (RU) | TEST METHOD FOR DETERMINING THE DEGREE OF OXIDATIVE PROCUREMENT OF ANIMAL FAT |
| CN103041784A (en) * | 2012-12-24 | 2013-04-17 | 青岛盛瀚色谱技术有限公司 | Heavy metal ion adsorbent of glycine grafted crosslinked chitosan microsphere |
-
2014
- 2014-09-29 CN CN201410507475.XA patent/CN104209102B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2005122817A (en) * | 2005-07-18 | 2007-01-27 | Государственное образовательное учреждение высшего профессионального образовани "Воронежска государственна технологическа академи " (RU) | TEST METHOD FOR DETERMINING THE DEGREE OF OXIDATIVE PROCUREMENT OF ANIMAL FAT |
| CN103041784A (en) * | 2012-12-24 | 2013-04-17 | 青岛盛瀚色谱技术有限公司 | Heavy metal ion adsorbent of glycine grafted crosslinked chitosan microsphere |
Non-Patent Citations (2)
| Title |
|---|
| R.S. PRAVEEN ET AL.: "Solid phase extractive preconcentration of uranium(VI) using quinoline-8-ol anchored chloromethylated polymeric resin beads", 《TALANTA》 * |
| 张健等: "水杨酸型螯合树脂对Fe(III)离子的螯合吸附行为", 《物理化学学报》 * |
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| CN107233871B (en) * | 2017-07-18 | 2019-11-22 | 河南师范大学 | Immobilized 1- amine ethyl-3-methylimidazole bromide solid extracting agent of chloromethyl polystyrene resin and its preparation method and application |
| CN108392853A (en) * | 2018-04-12 | 2018-08-14 | 淮海工学院 | A kind of solid-phase extraction column and the preparation method and application thereof |
| CN108392853B (en) * | 2018-04-12 | 2021-01-19 | 淮海工学院 | Solid phase extraction column and preparation method and application thereof |
| CN112010448A (en) * | 2019-05-28 | 2020-12-01 | 宝山钢铁股份有限公司 | Method and system for removing total organic carbon and magnesium ions in cold-rolling nanofiltration concentrated water |
| CN112010448B (en) * | 2019-05-28 | 2022-10-21 | 宝山钢铁股份有限公司 | Method and system for removing total organic carbon and magnesium ions in cold-rolling nanofiltration concentrated water |
| CN110152629A (en) * | 2019-06-04 | 2019-08-23 | 南京信息工程大学 | A kind of adsorbent and its application for water process |
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