CN203370327U - Automatically dynamic hollow fiber membrane liquid-liquid-liquid microextraction device - Google Patents
Automatically dynamic hollow fiber membrane liquid-liquid-liquid microextraction device Download PDFInfo
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- CN203370327U CN203370327U CN201320460000.0U CN201320460000U CN203370327U CN 203370327 U CN203370327 U CN 203370327U CN 201320460000 U CN201320460000 U CN 201320460000U CN 203370327 U CN203370327 U CN 203370327U
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Abstract
The utility model provides an automatically dynamic hollow fiber membrane liquid-liquid-liquid microextraction device. The microextraction device comprises a magnetic stirring apparatus, an extraction bottle, a polypropylene fiber membrane and a flow injection instrument, wherein connectors are arranged at two sides of the middle part of an extraction bottle body, the polypropylene fiber membrane is fixed on the connectors at two sides of the middle part of the extraction bottle body by a quartz capillary tube, the flow injection instrument is provided with two pumps and one automatic switching valve, one end of the pump I is connected with a sample bottle, a cleaning bottle and a waste liquid bottle I by the automatic switching valve, a pipeline I and a pipeline I respectively, the other end of the pump I is connected with the extraction bottle, one end of the pump II is connected with a waste liquid bottle II by the automatic switching valve, and the other end of the pump II is connected with an organic solvent bottle, an acceptor phase bottle and a sample introduction bottle by the quartz capillary tube, a pipeline III and a pipeline IV. The microextraction device can extract methyl mercury, phenyl mercury and inorganic mercury simultaneously, and has the advantages of simple structure, rapidness in analysis, high automation degree, good repeatability and strong purifying capacity of sample matrixes.
Description
Technical field
The utility model relates to a kind of extraction equipment, the dynamic hollow-fibre membrane liquid of especially a kind of automation liquid-liquid micro-extraction device.Background technology
Liquid-phase micro-extraction (LPME) is a kind of microminiaturization, the eco-friendly Sample Pretreatment Technique grown up on liquid-phase extraction (LLE) basis, has the device cheapness, analyzes quick, simple operation and other advantages.According to the extraction mode division, LPME can be divided into single micro-extraction (SDME), hollow fiber membrane liquid-phase micro extraction (HF-LPME), disperse phase liquid phase extraction (DLLME), suspend and solidify single micro-extraction (SFODME) and electrolemma extraction (EME) etc.Wherein, HF-LPME has enrichment times height and the strong remarkable advantage of matrix detergent power, is one of most widely used a kind of LPME extraction pattern.HF-LPME generally adopts that physicochemical properties are stable, the compatible good polypropylene fibre film of organic solvent is as extraction organic solvent support membrane, and film hole diameter is 0.2 μ m.A desirable LPME extraction system should have following characteristics: 1. can be efficiently, the selective extraction target analytes; 2. there is extraction kinetics faster; 3. reduce manually-operated, improve the automaticity of extraction.For reaching above-mentioned requirements, can be from following several respects effort: 1. explore the LPME system that is applicable to the target analytes extraction; 2. building or improve the LPME extraction equipment accelerates or the reinforcement of extraction automaticity the LPME extraction kinetics.
At metallic element and form (as mercury shape) analysis field thereof, find efficient and there is optionally LPME system and have certain difficulty.Main cause is that most metals element and form thereof exist with ionic species except the less organo-metallic compound of minority solubility, generally can not realize direct LPME extraction.At present, most of report about LPME extracting metals element and form thereof is to realize extraction by selecting suitable complexometric reagent and metal target element or its form to generate hydrophobic metal complex.But alternative complexometric reagent kind is very limited, and many complexometric reagents lack selective.Pena-Pereira etc. are usingd dithizone (dithizonates) as complexometric reagent, and ionic liquid 1-hexyl-3-methylimidazole hexafluorophosphoric acid, as the extraction organic solvent, adopts two-phase SDME to realize methyl mercury (MeHg
+), ethyl mercury (EtHg
+), phenyl mercury (PhHg
+) and inorganic mercury (Hg
2+) time extraction.In addition, when LPME and high performance liquid chromatography (HPLC) or Capillary Electrophoresis (CE) coupling, for back-ground electolyte (BGE) coupling of the mobile phase with HPLC, CE, usually need to adopt three-phase LPME extraction pattern.Three-phase LPME requires the solubility of object element form in organic solvent to be greater than the solubility in sample solution, and is greater than the solubility in organic solvent in the solubility of accepting phase.Therefore, be suitable for the more difficult acquisition of three-phase LPME system of metallic element and morphological analysis.By in accepting mutually, add to mercury have strong affinity containing SR as sodium thiosulfate, thiocarbamide, L-half Guang ammonia etc. as reextraction reagent, can be in the situation that do not use complexometric reagent to realize the three-phase LPME extraction to the organic mercury form; But while extracting when LPME is used for inorganic mercury and organic mercury form, except needs, use sodium thiosulfate as reextraction reagent, also need to use the extraction complexometric reagent as 1,2-pyridylazo beta naphthal (PAN).
Increasing the extraction kinetics of LPME and the automaticity of raising LPME is the important directions of LPME development.Design dynamic LPME extraction equipment and can effectively accelerate the LPME extraction kinetics, thereby obtain higher enrichment times in shorter extraction time.The automaticity that improves dynamic LPME not only can make analytical work person free from loaded down with trivial details operation, and can improve the experiment reappearance.Dynamically the LPME extraction comprises the dynamic LPME extraction of two-phase and two kinds of patterns of three-phase LPME dynamic extraction.In the dynamic LPME of two-phase, organic solvent moves back and forth, and in each dynamic extraction circulation, all can produce new organic solvent thin layer (OSF).Target analytes is mass transfer between organic solvent thin layer and sample solution (directly submergence extraction) or gas phase (headspace extraction), and than static extracting, its mass transfer is more prone to.Dynamically, in three-phase LPME, accept phase solution and move back and forth, thereby accelerated target analytes at the extraction organic solvent and the mass transfer between accepting mutually.But, when static three-phase LPME extraction, by the mode stirred, can only make the mass transfer of target analytes between sample solution and extraction organic solvent accelerate, and the mass transfer between organic solvent and acceptance mutually can only rely on diffusion, causes mass transfer slower.Therefore, than static LPME, dynamic extraction has extraction kinetics faster.Early stage dynamically LPME device is realized by manual extracting syringe shank.Manually operated shortcoming is that experimental error is larger, and complex operation.Subsequently, the dynamic extraction device that has developed the dynamic extraction device auxiliary by the sequencing syringe pump or other particular design to be to realize organic solvent or to accept the automation of the shuttling movement step of phase, but need to, by means of special equipment, operate easy not enough.
The utility model content
In order to overcome the deficiencies in the prior art, the purpose of this utility model is to provide the dynamic hollow-fibre membrane liquid of a kind of automation liquid-liquid micro-extraction device, the advantages such as this apparatus structure is simple, analyze fast, favorable reproducibility, sample substrate detergent power are strong, applicable to the analysis of methyl mercury, phenyl mercury and inorganic mercury form in actual environment and biological sample.
The purpose of this utility model is achieved through the following technical solutions:
The dynamic hollow-fibre membrane liquid of a kind of automation liquid-liquid micro-extraction device, comprise magnetic stirring apparatus, extraction flask, polypropylene fibre film and flow injection instruments, and both sides, extraction flask body middle part have interface one and interface two; Polypropylene fibre film one end is inserted with quartz capillary one, and the other end is inserted with quartz capillary two; Quartz capillary one and quartz capillary two seal by sealing compound respectively with the overlapping position of polypropylene fibre film; The polypropylene fibre film is placed in extraction flask, and makes quartz capillary one through the interface one of extraction flask, the interface two that quartz capillary two passes extraction flask; Interface one and interface two by sealing compound, seal respectively and make quartz capillary one be fixed on interface one, quartz capillary two is fixed on interface two; Described flow injection instruments is the flow injection instruments with pump one, pump two and an automatic switching valve; One end of pump one is connected with pipeline two with pipeline one respectively by automatic switching valve, and pipeline one connects respectively sample bottle and washer bottle by hand-operated valve one, and pipeline two connects waste liquid bottle one; The other end of pump one is connected with extraction flask; One end of pump two is connected with waste liquid bottle two by automatic switching valve; The other end of pump two is connected with quartz capillary one, and quartz capillary two is connected with pipeline four with pipeline three respectively, and pipeline three is connected with the organic solvent bottle, and the pipeline four-way is crossed hand-operated valve two and connected respectively acceptance bottle and sample injection bottle mutually.
Described polypropylene fibre film is preferably polypropylene hollow fiber membrane, and polypropylene hollow fiber membrane is placed in extraction flask, and the polypropylene hollow fiber membrane two ends contact with extraction flask.
Described flow injection instruments is preferably FIA-3110 type flow injection instruments (Beijing Jitian Instrument Co., Ltd.'s product).
The utility model can extract methyl mercury, phenyl mercury and inorganic mercury simultaneously, for analyzing human hair sample and environmental water sample methyl mercury, phenyl mercury and inorganic mercury form; Have device simple, analyze the advantage such as change fast and automatically that degree is high, favorable reproducibility, sample substrate detergent power are strong, applicable to the analysis of methyl mercury, phenyl mercury and inorganic mercury form in actual environment and biological sample; With static extracting, compare, extraction kinetics of the present utility model is faster, and the required extraction equilibrium time is shorter, and can obtain lower detection limit and higher enrichment times.
The accompanying drawing explanation
Fig. 1 is the structural representation of the dynamic hollow-fibre membrane liquid of automation liquid-liquid micro-extraction device, wherein: the 1-magnetic stirring apparatus, the 2-extraction flask, 2-1-interface one, 2-2-interface two, 3-polypropylene fibre film, 3-1-quartz capillary one, 3-2-quartz capillary two, the 4-flow injection instruments, P1-pump one, P1-pump two, the EV-automatic switching valve, 5-stream one, 6-stream two, 7-pipeline one, 8-pipeline two, 9-hand-operated valve one, the S-sample bottle, the W1-washer bottle, W2-waste liquid bottle one, 10-pipeline three, 11-pipeline four, 12-hand-operated valve two, O-organic solvent bottle, A-accepts bottle mutually, the E-sample injection bottle, W2 '-waste liquid bottle two.
Fig. 2 is 2 valve position switching schematic diagrames of 16 hole eight passage automatic switching valves, a: sample bits, and b: the injection position, wherein: 5-stream one, 6-stream two, the 2-extraction flask, O-organic solvent bottle, A-accepts bottle mutually, E-sample injection bottle, W2-waste liquid bottle one, W2 '-waste liquid bottle two, S-sample bottle, W1-washer bottle.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing, the utility model is done to further detailed description, but embodiment of the present utility model is not limited to this.
Embodiment 1
The dynamic hollow-fibre membrane liquid of a kind of automation liquid-liquid micro-extraction device, as shown in Figure 1, comprise magnetic stirring apparatus 1, extraction flask 2, polypropylene fibre film 3 and flow injection instruments 4, and extraction flask 1 both sides, body middle part have interface one 2-1 and interface two 2-2; Polypropylene fibre film 3 one ends are inserted with quartz capillary one 3-1, and the other end is inserted with quartz capillary two 3-2; The overlapping position of quartz capillary one 3-1 and quartz capillary two 3-2 and polypropylene fibre film 3 seals by sealing compound respectively; Polypropylene fibre film 3 is placed in extraction flask, and makes quartz capillary one 3-1 pass interface two 2-2 of extraction flask through interface one 2-1, quartz capillary two 3-2 of extraction flask; Interface one 2-1 and interface two 2-2 by sealing compound, seal respectively and make quartz capillary one 3-1 be fixed on interface one 2-1, quartz capillary two 3-2 are fixed on interface two 2-2; Described flow injection instruments 4 is the flow injection instruments with pump one P1, pump two P2 and an automatic switching valve EV; The end of pump one P1 is connected with pipeline 28 with pipeline 1 respectively by automatic switching valve EV, and pipeline 1 connects respectively sample bottle S and washer bottle W1 by hand-operated valve 1, and pipeline 28 connects waste liquid bottle one W2; The other end of pump one P1 is connected with extraction flask 2; The end of pump two P2 is connected with waste liquid bottle two W2 ' by automatic switching valve EV; The other end of pump two P2 is connected with quartz capillary one 3-1, and quartz capillary two 3-2 are connected with pipeline 4 11 with pipeline 3 10 respectively, and pipeline 3 10 is connected with organic solvent bottle O, and pipeline 4 11 connects respectively and accepts bottle A and sample injection bottle E mutually by hand-operated valve 2 12.
Wherein: magnetic stirring apparatus 1 is the 85-2A digital display constant temperature magnetic stirring apparatus (Jintan City, Jiangsu Province high honour instrument manufacturing Co., Ltd product) that tests the speed, in whole use procedure all in opening.
The stream of the dynamic hollow-fibre membrane liquid of automation liquid-liquid micro-extraction device is coupled together by pump line and the interface of polyfluortetraethylene pipe, organic solvent-resistant.
The use procedure of the dynamic hollow-fibre membrane liquid of automation liquid-liquid micro-extraction device is as follows: the first step, and eight logical valves are switched to a position (as shown in Figure 2 a), and stream 1 meets sample bottle S, and stream 26 is connected to machine solvent bottle O; Pump one P1 with-160rpm(is counterclockwise) speed rotate 40s, the 6mL sample solution is pumped in extraction flask 2; Simultaneously, pump two P2 with+3rpm(is clockwise) speed by organic solvent by polypropylene hollow fiber membrane, make fenestra be full of organic solvent.Second step, pump two P2 get rid of the organic solvent in the hollow-fibre membrane chamber with the speed operation 20s of-20rpm.The 3rd step, eight logical valve EV are switched to b position (as shown in Figure 2 b), and stream 26 is accepted bottle A mutually, and pump two P2 rotate 5s with the speed of+6rpm, and the 12 μ L liquid pump of accepting to mix is entered in hollow-fibre membrane.The 4th step and the 5th step are the dynamic extraction step, and the 4th step pump two P2 first rotate 5s with the speed of+3rpm, then rotate 5s with the speed of-3rpm, promote to accept phase solution and move back and forth, and realize dynamic extraction.The FIA – 3110 flow injection instruments single operations of using due to experiment mostly are 99 times most, therefore, reach the extraction of 20min, need to adopt twice circulation, single operation 60 times.Thereby, the 6th step is set, be about to pump one P1 and pump two P2 and stop 1s, program is reappeared and forward the 4th step to.The 7th step, change the acceptance of stream 26 a phase bottle A into sample injection bottle E, and stream 1 meets waste liquid bottle one W2; Pump two P2 enter the liquid pump that mixes of the acceptance after extraction in sample injection bottle E with the speed of-6rpm, and for the analysis of Capillary Electrophoresis (CE) sample introduction; Simultaneously, pump one P1 rotates 40s with the speed of+160rpm, and the sample solution after extraction is pumped in waste liquid bottle one W2.The 8th step, be switched to a position by eight logical valves, the machine that the is connected to solvent bottle O of stream 26, and stream 1 meets washer bottle W1; Pump one P1 rotates 40s with the speed of-160rpm, and ultra-pure water is pumped in sample bottle S, cleans sample bottle S and stream; Simultaneously, pump two P2 pump into organic solvent in tunica fibrosa with the speed of+3rpm, clean tunica fibrosa, to eliminate memory effect.The 9th step, be switched to the b position by eight logical valves, and stream 1 meets waste liquid bottle one W2, and the waste liquid of cleaning is pumped.If analyte concentration excessive (being greater than 500 μ g/L), can repeat cleaning step 8 and 9 once, to eliminate the memory effect of sample bottle.
In whole extraction process, except the time of extraction, the whole operating time is 175s, can complete loading, clean sample bottle, hollow-fibre membrane and pipeline, the overall processes such as sample analysis.And adopt manual extraction pattern, generally need the time of cost 5-10min to complete this process; In addition, in extraction process, except will manually changing several times reagent bottle, without other manually-operateds, can realize most of automation of whole extraction process.
The dynamic hollow-fibre membrane of table 1 automation-liquid liquid-liquid micro-extraction programmed instruction
+: ， – clockwise circulates: counterclockwise circulation, *: when the concentration of target analytes, during higher than 500 μ g/L, rinsing step (8 and 9) will repeat 2 times.
At the dynamic hollow-fibre membrane liquid of AD-HF-LLLME(automation liquid-liquid micro-extraction) above-mentioned experiment condition under, investigate the dynamic hollow-fibre membrane liquid of automation liquid-liquid micro-extraction Capillary Electrophoresis ultraviolet and detected the analytical performance that (AD-HF-LLLME-CE/UV) analyzes methyl mercury, phenyl mercury and inorganic mercury form, the results are shown in table 2 and table 3.As can be seen from the table, the relative standard deviation (RSDs, n=5) of calibration peak area (peak area/transit time), between 3.79-8.01%, shows to test reappearance better; Detection limit (LODs) is (S/N=3) in 1.59-3.80 μ g/L scope; Enrichment times (EFs) is 235-281 times.And, under identical extraction conditions, the LODs that adopts AS-HF-LLLME-CE/UV to obtain is 1.82-5.99 μ g/L, EFs is 149-253 times.Therefore, can find out, adopt the dynamic extraction pattern, the LODs obtained is lower, and EFs is higher.Bulk sample is piled up to (LVSS) technology and the dynamic hollow-fibre membrane liquid of automation liquid-liquid micro-extraction (AD-HF-LLLME) combination, after two step enrichments, the LOD that the method is analyzed phenyl mercury, methyl mercury and inorganic mercury is respectively 0.21,0.75 and 1.09 μ g/L; EF is respectively 2195,1307 and 820 times; RSDs is in the 8.13-12.97% scope.
The utility model can obtain the distributed intelligence of organic mercury and inorganic mercury form in sample simultaneously, and the extraction equilibrium time is short.With other dynamic extraction patterns, compare, the utility model adopts simple instrument can realize most of automation of dynamic extraction step, and common laboratory can realize.The extraction equilibrium time of the present utility model shorter (25min), extraction kinetics is very fast, and enrichment times is higher.In addition, by increasing flow pumps, control the modes such as stream, simplicity of design interface, the AD-HF-LLLME of design is expected to realize on-line coupling with the instrument such as commercialization HPLC.
The range of linearity, coefficient correlation and the relative standard deviation of table 2AD-HF-LLLME and AD-HF-LLLME-LVSS
a: sample solution: phenyl mercury concentration is that 50 μ g/L, methyl mercury and inorganic mercury are all 100 μ g/L
b, sample solution: phenyl mercury concentration is that 10 μ g/L, methyl mercury and inorganic mercury are all 20 μ g/L.
Table 3AS-HF-LLLME, AD-HF-LLLME and AD-HF-LLLME-LVSS detection limit and enrichment times
aeF=CE/UV method detection limit/AS-HF-LLLME-CE/UV method detection limit;
beF=CE/UV method detection limit/AD-HF-LLLME-CE/UV method detection limit;
ceF=CE/UV method detection limit/AD-HF-LLLME-LVSS-CE/UV method detection limit.
The operating condition of automatic Static hollow-fibre membrane liquid liquid-liquid micro-extraction (AS-HF-LLLME) and AD-HF-LLLME is as follows: organic solvent: chlorobenzene; Sample pH value is 4.5; Stir speed (S.S.): 700rpm; Pump speed: 3rpm; Extraction time: 25min; Accept phase: 0.1% unithiol (m/v); Give phase: 0.4%18-is preced with-6 (m/v)+15%NaCl (m/v).
For the accuracy of verification method, the utility model, for standard reference materials---the analysis of spiny dogfish musculature standard substance (DORM-2) mercury shape, has been found methyl mercury and inorganic mercury in standard substance DORM-2, does not detect phenyl mercury.The content of methyl mercury is 4369.1 ± 230.2ng/g, with standard value 4470 ± 320ng/g, coincide better, and inorganic mercury can not be quantitative.
Analysis by the utility model for environmental water sample and human hair sample methyl mercury, phenyl mercury and inorganic mercury form, experimental result is listed in table 4.Phenyl mercury and inorganic mercury form do not detected in the human hair sample, the content of methyl mercury is 419.3-631.7ng/g; Three kinds of target mercury shapes all do not detected in East Lake Water, Wuhan and Yangtze River Water.Actual sample has been carried out to recovery testu, and recovery of standard addition is between 87.9-110.7%.The electrophoretogram that actual sample is analyzed is cleaner, has strong matrix detergent power.
The content of the methyl mercury in table 4 human hair and environmental water sample, phenyl mercury and inorganic mercury
anD: do not detect;
bnQ: can't be quantitative;
cwater sample 1: East Lake Water, Wuhan;
dwater sample 2: Yangtze River Water;
e: in the sample of surveying, the scalar that adds of methyl mercury, phenyl mercury and inorganic mercury is all 10 μ g/L, and the rate of recovery=(concentration of surveying in the mark-on sample-by the mark-on sample, surveyed concentration) * 100/ adds scalar.
Above-described embodiment is preferably embodiment of the utility model; but embodiment of the present utility model is not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present utility model and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection domain of the present utility model.
Claims (3)
1. the dynamic hollow-fibre membrane liquid of an automation liquid-liquid micro-extraction device is characterized in that: comprise magnetic stirring apparatus, extraction flask, polypropylene fibre film and flow injection instruments, both sides, extraction flask body middle part have interface one and interface two; Polypropylene fibre film one end is inserted with quartz capillary one, and the other end is inserted with quartz capillary two; Quartz capillary one and quartz capillary two seal by sealing compound respectively with the overlapping position of polypropylene fibre film; The polypropylene fibre film is placed in extraction flask, and makes quartz capillary one through the interface one of extraction flask, the interface two that quartz capillary two passes extraction flask; Interface one and interface two by sealing compound, seal respectively and make quartz capillary one be fixed on interface one, quartz capillary two is fixed on interface two; Described flow injection instruments is the flow injection instruments with pump one, pump two and an automatic switching valve; One end of pump one is connected with pipeline two with pipeline one respectively by automatic switching valve, and pipeline one connects respectively sample bottle and washer bottle by hand-operated valve one, and pipeline two connects waste liquid bottle one; The other end of pump one is connected with extraction flask; One end of pump two is connected with waste liquid bottle two by automatic switching valve; The other end of pump two is connected with quartz capillary one, and quartz capillary two is connected with pipeline four with pipeline three respectively, and pipeline three is connected with the organic solvent bottle, and the pipeline four-way is crossed hand-operated valve two and connected respectively acceptance bottle and sample injection bottle mutually.
2. the dynamic hollow-fibre membrane liquid of automation according to claim 1 liquid-liquid micro-extraction device, it is characterized in that: described polypropylene fibre film is polypropylene hollow fiber membrane, polypropylene hollow fiber membrane is placed in extraction flask, and the polypropylene hollow fiber membrane two ends contact with extraction flask.
3. the dynamic hollow-fibre membrane liquid of automation according to claim 1 liquid-liquid micro-extraction device, it is characterized in that: described flow injection instruments is FIA-3110 type flow injection instruments.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105920875A (en) * | 2016-06-29 | 2016-09-07 | 中华人民共和国济宁出入境检验检疫局 | Hollow fiber extracting device |
| CN106442816A (en) * | 2016-11-30 | 2017-02-22 | 中国人民解放军63977部队 | Dynamic headspace liquid-phase micro-extraction method based on extracting solvent evaporation |
-
2013
- 2013-07-30 CN CN201320460000.0U patent/CN203370327U/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105920875A (en) * | 2016-06-29 | 2016-09-07 | 中华人民共和国济宁出入境检验检疫局 | Hollow fiber extracting device |
| CN106442816A (en) * | 2016-11-30 | 2017-02-22 | 中国人民解放军63977部队 | Dynamic headspace liquid-phase micro-extraction method based on extracting solvent evaporation |
| CN106442816B (en) * | 2016-11-30 | 2019-05-07 | 中国人民解放军63977部队 | A kind of Dynamic headspace liquid-phase microextraction method based on extractant volatilization |
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Granted publication date: 20140101 Termination date: 20170730 |