CN1552499A - Memberane extracting method for trace organic pollutant in water - Google Patents
Memberane extracting method for trace organic pollutant in water Download PDFInfo
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- CN1552499A CN1552499A CNA031383483A CN03138348A CN1552499A CN 1552499 A CN1552499 A CN 1552499A CN A031383483 A CNA031383483 A CN A031383483A CN 03138348 A CN03138348 A CN 03138348A CN 1552499 A CN1552499 A CN 1552499A
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Abstract
A membrane extraction method for the trace organic pollutant in water features that an amphoteric composite glyceride trioleatel cellulose acetate membrane is used to extract the trace agricultural chemical of organochlorine from water, and it is eluted only by less organic solvent, so decreasing environmental pollution.
Description
Technical field
The present invention relates to a kind of extracting process, particularly relate to a kind of membrane extraction method that is used for the underwater trace organic pollution.
Technical background
Because global Pollution by Chemicals is on the rise, persistence toxic organic pollutantses such as polycyclic aromatic hydrocarbon, organo-chlorine pesticide, Polychlorinated biphenyls, bioxin have potential ecology and health threat, the monitoring of this pollutant have been become a day-to-day work of environmental monitoring department.
SPE is because of using no or little organic solvent in extraction process, can not cause secondary pollution and receive much concern.SPE method commonly used comprises the film solid phase extraction, the flat film that this method uses macromolecular material such as the polytetrafluoroethylene (PTFE), polyvinyl chloride of porous network shape or glass fibre to form, the particulate that in film, has mixed various chemically bonded stationary phase fillers, or the Direct Bonding of film own multiple different functional groups, various organic pollutions are had strong adsorption capacity, and this absorption both may be physical absorption, also may be chemical bonding, thereby hold back object, reach effect of extracting; But this method cost is high, and needs additionaling power.What method material, target compound and principle were all approaching therewith is the column SPE, and this is to use columnar material to replace flat film, thereby sectional area is little, flow is low, stop up easily, increased, in the processing time especially to environmental sample, the cylindricality filler easily produces the slit, breakthrough volume dwindles, and reduces extraction efficiency, and selectivity is poor slightly, disturb morely, need additionaling power.
The concentration of trace toxic organic pollutants such as organo-chlorine pesticide in water is generally part per billion (μ g/L) or part per trillion (ng/L) even lower, and SPE is difficult to reach analysis purpose usually to the accumulation ability and the detection limit of this type of fat-soluble pollutant.In order to address the above problem, developed the membrane extraction technology in recent years.The method that the underwater trace organic pollution is carried out membrane extraction commonly used comprises: 1) hollow-fibre membrane: adopt macromolecular materials such as silicon rubber, capillary polypropylene to make hollow-fibre membrane, it has the tubulose geometry, can make the infiltration of the higher or volatile organic matter of Henry coefficient pass the fiber tube wall, thereby obtain separating purpose; But this method is only effective for volatile organic matter, and operating process is comparatively complicated, also needs additionaling power.2) prop up the carrier fluid film: adopt ptfe porous membrane to soak into and form " liquid film " as spe medium with the immiscible organic solvent of water, the reagent that is extracted the metal ion in the sample aqueous solution, acid organic matter isopolarity compound and adding generates neutral molecule, diffusion is assigned in organic liquid film then, thereby enters static extraction phase; This method has absorbed liquid/liquid extraction and has had the advantage of enrichment and selection, can effectively remove the strong point that matrix disturbs in conjunction with dialysis again, have advantages such as efficient, quick, easy, easy automation, but owing between object and extraction phase chemical reaction takes place, so the liquid film extraction device is had certain specification requirement, also needs additionaling power in addition.3) chromatographic membrane: the employing porous Teflon is a separating medium, and outsourcing one layer thickness is the microporous poly tetrafluoroethylene of 0.8mm, can extract polar molecule and gas molecule; This method complicated operation, with high content of technology, need additionaling power.
Summary of the invention
The objective of the invention is to overcome the complicated operation, with high content of technology and need the defective of additionaling power of prior art, thereby adopt a kind of neutral fats/cellulose acetate composite film material that fat-soluble organic matter is had higher accumulation ability, utilize the lipophilicity enrichment principle of hydrophobic organic pollutant and the characteristics that semipermeable membrane can stop colloidal solid and macromolecular substances (as humic acid) to enter, provide a kind of easy and simple to handle, with low cost and need not the membrane extraction method of additionaling power, the underwater trace toxic organic pollutant is extracted.
The objective of the invention is to be achieved through the following technical solutions:
The invention provides a kind of membrane extraction method that is used for the underwater trace organic pollution, comprise the steps:
1) prepares a kind of olein/cellulose acetate composite film material, this composite film material and preparation method have been open in 02142106.4 the patent at another application number of the inventor, for clarity sake, the step of existing concise and to the point narration its preparation method is as follows:
To gather cellulose acetate and be dissolved in dioxane and the acetone, add olein and magnesium perchlorate, and place 25～45 ℃ of dissolvings of baking oven evenly until the dissolving of film liquid; By weight percentage, described poly-cellulose acetate 18wt%, dioxane 10wt%, acetone 70wt%, magnesium perchlorate 2wt%, this film liquid of every 100g adds olein 1～5g; With liquid-solid phase conversion legal system film, 25～40 ℃ of its system film temperatures, evaporation time is 20～60 seconds, the cooling bath temperature is 15～25 ℃; The film water that makes is rinsed out remaining solvent, store in the distilled water; The composite film material that obtains is the structural framing material with poly-cellulose acetate, and olein drips evenly to be inlayed wherein, and the composite membrane top layer is pure cellulose acetate phase;
Obtained composite film material surface is the micropore compacted zone, and the aperture is 1～10nm, allows molecular weight to stride film less than 1000 pollutant and enters enrichment in the film, can prevent that the olein of film inside from revealing simultaneously again; Thickness 30～40 μ m, the specific area＞4000cm of triglycerides
2/ g;
2) amount that the composite film material that makes in the step 1) is handled volume 0.5～5L water body to be measured by every 0.1g gram composite film material places water body to be measured, stirred 12～24 hours, similar mixing between the fatty glyceride in the strong organic pollution of lipophilicity and the composite film material, produce difference in chemical potential, the diffusion of organic micro-pollutant Hue potential difference sees through the plain film of surface fibre and enters the fatty glyceride phase mutually, thereby the organic micro-pollutant in the water body is enriched in the composite film material; Described trace is a concentration 1～10 in water
3Ng/L;
3) with step 2) in be enriched with organic pollutants composite membrane place 10～20mL organic solvent/every 0.1g composite membrane, fully soak, organic pollution is eluted.
Described step 2) organic pollution is an organo-chlorine pesticide, comprise α-BHC (α-HCH), β-BHC (β-HCH), γ-BHC (γ-HCH), δ-BHC (δ-HCH), 4,4 '-dichloro-diphenyl-dichlorothane (p, p '-DDD), 4,4 '-drip to drip her (p, p '-DDE), 4,4 '-DDT (p, p '-DDT), drinox (Aldrin), dieldrite (Dieldrin), endrin (Endrin), 5a,6,9,9a-hexahydro-6,9-methano-2,4 I (Endosulfan I), 5a,6,9,9a-hexahydro-6,9-methano-2,4 II (Endosulfan II), 5a,6,9,9a-hexahydro-6,9-methano-2,4 sulfuric ester (Endosulfan sulfate), endrin aldehyde (Endrin aldehyde), heptachlor (Heptachlor), heptachlor epoxy (Heptachlor epoxide), methoxychlor (Methoxychlor) is totally 17 kinds of compounds.
The organic solvent of described step 3) comprises carrene, n-hexane, cyclohexane, acetone or their mixed solvent.
The membrane extraction method that is used for the underwater trace organic pollution that the present invention adopts, its principle are that employed composite film material is is the structural framing material with the cellulose acetate macromolecule, and neutral fats drips evenly to be inlayed wherein, and the composite membrane top layer is pure cellulose acetate phase.It is amphipathic that this structure of material has caused material to have: on the one hand because the hydrogen bond action between the cellulose hydroxyl, and this composite film material extexine highly-hydrophilic and water insoluble; On the other hand, the internal layer of this composite film material is that cellulose acetate-neutral fats mixes phase, inlay wherein neutral fats and drip and be lipophilicity, and these neutral fats drips the small one by one fat storehouse of formation, and fat-soluble pollutant is had high carrying capacity.The composite film material surface is the micropore compacted zone in addition, and the aperture is 1～10 nanometer, allows molecular weight to stride film less than 1000 pollutant and enters enrichment in the film, can prevent that again the neutral fats of film inside from dripping leakage simultaneously.In the Membrane Extraction, be dissolved in the toxic organic pollutant in the water body, because its different solubility and certain concentration difference is arranged in water and in neutral fats, can enter and be enriched in the ester along concentration difference by a large amount of micropores of film surface distributed, thereby reach the purpose that from water, extracts organic micro-pollutant.
Compare with existing membrane extraction and SPE, the advantage that is used for the membrane extraction method of underwater trace organic pollution provided by the invention is: 1) adopted to have amphipathic composite film material, being extracted is static phase mutually, so need not consider the phase required drive that flows; 2) film itself is waterproof, does not need to consider factors such as flow and transmitance; 3) organic pollution is to be distributed in the composite membrane by passive diffusion, thereby does not need additionaling power; 4) very high to persistence organic pollutant enrichment multiple, when every 100g casting solution adds neutral fats 1g, for logK
Ow(octanol-water partition coefficient logarithm) organic matter greater than 4, enrichment multiple be all more than 2000, even can be up to more than 30000; When every 100g casting solution interpolation neutral fats was brought up to 2g, the enrichment multiple had all reached more than 10000; 5) in the Membrane Extraction, as long as composite film material is hung on stirring in the pending water sample with superfine stainless steel wire, operating procedure and equipment are simple; 6) belong to solvent-free abstraction technique, only use a small amount of organic solvent to come wash-out in the processing procedure, reduce environmental pollution.
Description of drawings
Fig. 1. the gas chromatographic analysis spectrogram of the sample that extracts through composite film material among the embodiment 1;
Wherein 1 is that heptachlor, 2 is that drinox, 3 is that heptachlor epoxy, 4 is that α-5a,6,9,9a-hexahydro-6,9-methano-2,4,5 is that dieldrite, 6 is that endrin, 7 is that β-5a,6,9,9a-hexahydro-6,9-methano-2,4,8 is that endrin aldehyde, 9 is 5a,6,9,9a-hexahydro-6,9-methano-2,4 sulfate;
Fig. 2. nine kinds of organo-chlorine pesticides among the embodiment 1 are through the rate of recovery schematic diagram of composite film material extraction.
Specific embodiments
Below in conjunction with embodiment and accompanying drawing technical scheme of the present invention is further described.
Embodiment 1: cyclopentadiene replaces organo-chlorine pesticide in cellulose acetate-olein composite membrane extraction water
Cellulose acetate 18g is dissolved among dioxane 10g and the acetone 70g, adds magnesium perchlorate 2g and olein 1.5g, and 25 ℃ of dissolvings until the dissolving of film liquid evenly in baking oven; With liquid-solid phase conversion legal system film, casting film scraper gap 200 μ m, 25 ℃ of evaporating temperatures, evaporation time 60 seconds, 20 ℃ of gel bath temperatures, relative humidity 60% makes the thick cellulose acetate of 30～40 μ m-olein composite membrane.
With nine kinds of cyclopentadiene organo-chlorine pesticides stipulating in U.S. EPA 8080 methods, comprise that heptachlor, heptachlor epoxy, drinox, dieldrite, endrin, endrin aldehyde, α-5a,6,9,9a-hexahydro-6,9-methano-2,4, β-5a,6,9,9a-hexahydro-6,9-methano-2,4,5a,6,9,9a-hexahydro-6,9-methano-2,4 sulfate are made into a simulated water sample with 10ng/L concentration respectively.
The composite membrane that 0.1g is made places this simulated water sample 5L, stirs 24 hours; The composite membrane of target compound that taken out enrichment adds the 20ml carrene, and ultrasonic extraction 30min soaks 24h, and these organic pollutions are dissolved in the organic solvent.
With extract after the separation and purification of silica gel pillar, use gas chromatograph (HP6890)-
63The little pond of Ni electron capture detector (GC-μ ECD) (Agilent Technologies, the U.S.) carries out gas Chromatographic Determination, and used chromatographic column is the HP-5 capillary chromatographic column, 30m * 320 μ m * 0.25 μ m, carrier gas high-purity N
2Column cap constant voltage 20psi, injector temperature are 250 ℃, and detector temperature is 300 ℃, with 85 ℃ is initial column temperature, and keep 2min, with the speed temperature programming to 180 of 10 ℃/min ℃, keep 15min then in this temperature, then with the speed temperature programming to 280 of 20 ℃/min ℃, keep 3.5min again, adopt no split sampling 1 μ L and Agilent ChemStation for GCSystems (quantitative analysis software) analyzing and processing data.
Analysis of spectra is plotted in Fig. 1, this shows, use method of the present invention can enrichment from water body, extract nine kinds of organo-chlorine pesticides of simulation test.
The column schematic diagram of the rate of recovery that records is plotted in Fig. 2.As seen from the figure, have only the rate of recovery of two kinds of 5a,6,9,9a-hexahydro-6,9-methano-2,4s to be lower than 60%, the rate of recovery of other seven kinds of organo-chlorine pesticides is all 80～110%, nine kinds of organo-chlorine pesticides that use method of the present invention enrichment from water body fully effectively, extract simulation test are described, method of the present invention is a kind of very effective method for the extraction of common organo-chlorine pesticide.
Carry out repeatedly repeated experiments, the result shows that this composite film material has good stability, and its reappearance RSD%≤9.76% (RSD is the English symbol of relative standard deviation, the percentage of accurate deviation of index and mean value, data reappearance is analyzed in expression).
Embodiment 2: with settle out organo-chlorine pesticide in the water of the composite film material of embodiment 1 extraction Qinghe sewage treatment plant two
To use glass fiber filter (Whatman Co., GF/F, 150mm φ) to filter immediately from Qinghe sewage treatment plant two water sample that hydromining gets that settles out.
Cellulose acetate-olein composite membrane with embodiment 1 preparation extracts, and uses the 0.1g film to put into the 1L water sample at every turn, stirs 24h; The composite membrane of target compound that taken out enrichment adds the 20ml carrene, ultrasonic extraction 30min, soak 24h, will soak (wash-out) liquid and be concentrated into 1ml, through the little column purification of silica gel, n-hexane, carrene (v: v is 7: 3) mixed liquor wash-out, it is to be measured to be settled to 0.5ml with n-hexane at last.
Gas chromatograph (HP6890)-
63The little pond of Ni electron capture detector (GC-μ ECD) (AgilentTechnologies, the U.S.) is gone up and is analyzed, and method is with embodiment 1, and the result detects three kinds of organo-chlorine pesticides, and detected value is listed in table 1.
Comparative Examples 1: with settle out organo-chlorine pesticide in the water of HLB SPE column extracting Qinghe sewage treatment plant two
With the HLB solid-phase extraction column water sample identical among the embodiment 2 is extracted, concrete grammar is as follows:
Adopt the HLB solid-phase extraction column of 6cc, 200mg.Clean with carrene, methyl alcohol, each 5mL of distilled water successively before the use, keep 5min behind the liquid feeding, drive vavuum pump and extract liquid, handle the back pillar and be in the state of activation.Regulate vacuum, make water sample cross the constant flow rate of post at 5mL/min.Each pillar is handled 1L and is filtered water sample.After enrichment finishes, water being drained, is that eluent divides three drip washing with the carrene of 15mL, is eluted in the K-D inspissator, purifies that to be concentrated into 0.5ml to be measured.
Gas chromatograph (HP6890)-
63The little pond of Ni electron capture detector (GC-μ ECD) (AgilentTechnologies, the U.S.) is gone up and is analyzed, and the result detects three kinds of organo-chlorine pesticides, and detected value is listed in table 1.
The comparison of table 1.HLB post and cellulose acetate-two kinds of extracting process analysis results of olein composite membrane
Detect pollutant levels (ng/L)
The extraction of HLB column extracting composite membrane
α-HCH 2.88 2.08
B-HCH 7.90 8.37
γ-HCH 6.74 6.64
By table 1 as seen, the detected value of two kinds of methods is quite approaching, illustrates that this composite membrane can replace SPE to be used for underwater trace toxic organic pollutant sample pre-treatments.
With method preparation among the embodiment 1 be embedded with different olein content cellulose acetate-olein composite membrane, and the water body that contains different organo-chlorine pesticides extracted, it the results are shown in table 2.
Table 2
Real three oleic acid glycerine extraction water sample
Stir the target compound eluting solvent
Execute ester addition volume/0.1g rate of recovery (%)
Time and concentration and consumption
Example (every 100g film liquid) composite membrane
4,4 '-dichloro-diphenyl-dichlorothane, 1ng/L 38.0
4,4 '-droplet she, 1ng/L n-hexane or 39.4
3 1g 5L 24h
4,4 '-DDT, 1ng/L cyclohexane 20ml 80.3
Methoxychlor, 1ng/L 70.2
α-BHC, 1000ng/L 63.1
β-BHC, 1000ng/L 52.4
4 2g 0.5L 12h
Acetone 10ml
γ-BHC, 1000ng/L 105.6
δ-BHC, 1000ng/L 111.2
α-BHC, 50ng/L carrene, the third 60.1
β-BHC, 50ng/L ketone mixed liquor 50.1
5 5g 2L 16h
γ-BHC, 50ng/L (1: 1, v/v) 101.1
δ-BHC, 50ng/L 15ml 96.4
Claims (4)
1, a kind of membrane extraction method that is used for the underwater trace organic pollution comprises the steps:
1) prepares a kind of olein/cellulose acetate composite film material, obtained composite film material surface is the micropore compacted zone, the aperture is 1～10nm, allows molecular weight to stride film less than 1000 pollutant and enters enrichment in the film, can prevent that the olein of film inside from revealing simultaneously again; Thickness 30～40 μ m, the specific area＞4000cm of triglycerides
2/ g;
2) amount that the composite film material that makes in the step 1) is handled volume 0.5～5L water body to be measured by every 0.1g gram composite film material places water body to be measured, stirred 12～24 hours, similar mixing between the fatty glyceride in the strong organic pollution of lipophilicity and the composite film material, produce difference in chemical potential, the diffusion of organic micro-pollutant Hue potential difference sees through the plain film of surface fibre and enters the fatty glyceride phase mutually, thereby the organic micro-pollutant in the water body is enriched in the composite film material; Described trace is a concentration 1～10 in water
3Ng/L;
3) with step 2) in be enriched with organic pollutants composite membrane place 10～20mL organic solvent/every 0.1g composite membrane, fully soak, organic pollution is eluted.
2, by the described membrane extraction method that is used for the underwater trace organic pollution of claim 1, it is characterized in that: the preparation method of composite film material has been open in 02142106.4 the patent at another application number of the inventor in the described step 1), for clarity sake, the step of existing concise and to the point narration its preparation method is as follows:
To gather cellulose acetate and be dissolved in dioxane and the acetone, add olein and magnesium perchlorate, and place 25～45 ℃ of dissolvings of baking oven evenly until the dissolving of film liquid; By weight percentage, described poly-cellulose acetate 18wt%, dioxane 10wt%, acetone 70wt%, magnesium perchlorate 2wt%, this film liquid of every 100g adds olein 1～5g; With liquid-solid phase conversion legal system film, 25～40 ℃ of its system film temperatures, evaporation time is 20～60 seconds, the cooling bath temperature is 15～25 ℃; The film water that makes is rinsed out remaining solvent, store in the distilled water; The composite film material that obtains is the structural framing material with poly-cellulose acetate, and olein drips evenly to be inlayed wherein, and the composite membrane top layer is pure cellulose acetate phase.
3, by the described membrane extraction method that is used for the underwater trace organic pollution of claim 1, it is characterized in that: organic pollution described step 2) is an organo-chlorine pesticide, comprise α-BHC, β-BHC, γ-BHC, δ-BHC, 4,4 '-dichloro-diphenyl-dichlorothane, 4,4 '-drip to drip she, 4,4 '-DDT, drinox, dieldrite, endrin, 5a,6,9,9a-hexahydro-6,9-methano-2,4 I, 5a,6,9,9a-hexahydro-6,9-methano-2,4 II, 5a,6,9,9a-hexahydro-6,9-methano-2,4 sulfuric ester, endrin aldehyde, heptachlor, heptachlor epoxy, methoxychlor.
4, by the described membrane extraction method that is used for the underwater trace organic pollution of claim 1, it is characterized in that: the organic solvent of described step 3) comprises carrene, n-hexane, cyclohexane, acetone or their mixed solvent.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431690C (en) * | 2006-12-01 | 2008-11-12 | 山西大同大学 | Compound absorbent embedded lipid in cellulose acetate/cyanoethyl cellulose acetate commixture, its preparation method and application |
| CN1928527B (en) * | 2006-09-15 | 2010-12-08 | 东南大学 | Functional nano-fiber based method for extracting and enriching pollutants in water |
| CN103007902A (en) * | 2012-12-20 | 2013-04-03 | 重庆绿色智能技术研究院 | Biomimetic fat absorbing and dissolving material as well as preparation method and application thereof |
| CN103674668A (en) * | 2013-12-11 | 2014-03-26 | 南昌航空大学 | Online pre-separation and enrichment device for pollutants in large-volume water sample |
| CN108362808A (en) * | 2018-01-18 | 2018-08-03 | 大连民族大学 | A method of preventing Passive sampler penetration effect |
| CN109317108A (en) * | 2018-12-06 | 2019-02-12 | 环境保护部华南环境科学研究所 | A kind of magnetic composite nano material and its preparation method and application |
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2003
- 2003-05-27 CN CNA031383483A patent/CN1552499A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1928527B (en) * | 2006-09-15 | 2010-12-08 | 东南大学 | Functional nano-fiber based method for extracting and enriching pollutants in water |
| CN100431690C (en) * | 2006-12-01 | 2008-11-12 | 山西大同大学 | Compound absorbent embedded lipid in cellulose acetate/cyanoethyl cellulose acetate commixture, its preparation method and application |
| CN103007902A (en) * | 2012-12-20 | 2013-04-03 | 重庆绿色智能技术研究院 | Biomimetic fat absorbing and dissolving material as well as preparation method and application thereof |
| CN103674668A (en) * | 2013-12-11 | 2014-03-26 | 南昌航空大学 | Online pre-separation and enrichment device for pollutants in large-volume water sample |
| CN103674668B (en) * | 2013-12-11 | 2016-08-17 | 南昌航空大学 | Pollutant online pre-separation enriching apparatus in a kind of water sample with bulk mass |
| CN108362808A (en) * | 2018-01-18 | 2018-08-03 | 大连民族大学 | A method of preventing Passive sampler penetration effect |
| CN108362808B (en) * | 2018-01-18 | 2020-07-14 | 大连民族大学 | Method for preventing penetration effect of passive sampler |
| CN109317108A (en) * | 2018-12-06 | 2019-02-12 | 环境保护部华南环境科学研究所 | A kind of magnetic composite nano material and its preparation method and application |
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