CN101376070B - Hollow fiber membrane type liquid phase micro-extraction apparatus and method of use thereof - Google Patents
Hollow fiber membrane type liquid phase micro-extraction apparatus and method of use thereof Download PDFInfo
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- CN101376070B CN101376070B CN2008101213940A CN200810121394A CN101376070B CN 101376070 B CN101376070 B CN 101376070B CN 2008101213940 A CN2008101213940 A CN 2008101213940A CN 200810121394 A CN200810121394 A CN 200810121394A CN 101376070 B CN101376070 B CN 101376070B
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Abstract
The invention provides with a hollow fibre membrance type liquid-phrase micro extractor, which comprises a horizontally mounted base, an extraction frame vertically fixed on the base, and a hollow fibre membrane fixing device fixed on the extraction frame. The invention is characterized in that the hollow fibre membrane type liquid-phrase micro extractor is further comprises a gas extraction device, which is positioned above the hollow fibre membrane fixing device and arranged on a fixing frame perpendicular to the base. The device of the invention and a method thereof have the beneficial effects that: 1. the required organic solvent amount is small (generally 10 to 40 Mu L), thereby greatly increasing mass transfer velocity of extraction, and reducing the extracting time; 2. after extraction, sample extract liquid can be taken out directly without static separation, thereby simplifying the process of sample processing; 3. interferences are decreased and analysis sensitivity is increased, thereby easily realizing purification and enrichment of samples; 4. and the device is simple and can carry out extracting effects comparison among different organic extracting solvents, thereby simplifying the operation and increasing the efficiency.
Description
(1) technical field
The present invention relates to a kind of doughnut membrane type liquid phase micro-extraction apparatus, and utilize it to carry out the method for residues of pesticides pre-treatment.
(2) background technology
The environmental toxicity problem that a large amount of use caused of chemical pesticide has caused people's great attention.China is the big country of pesticide producing and use, and especially based on chemical pesticide, again mainly based on organophosphorus pesticide, organophosphorus pesticide accounts for more than 70% of China's agricultural chemicals use amount in the chemical pesticide.
Reinforcement is to the detection and the environment toxicological study of persticide residue, for reasonable development and the correct chemical pesticide that uses, preserves the ecological environment, and ensures human health, avoids and reduce unnecessary agricultural losses etc. having important theory and practice significance.
At present, the pre-treating method of organophosphorus pesticide analysis has many, mainly contains: cable-styled extraction, the distribution of liquid liquid, column chromatography, SPE, SPME, supercritical fluid extraction, accelerated solvent extraction etc.But in these methods, have all more or less that extraction efficiency is low, organic solvent consumption is big, to shortcomings such as environment are unfriendly.Therefore develop a kind of low toxicity, simply quick, the easy to operate residual pre-treating method of organophosphor farming, can overcome this bottleneck technical problem of pre-treatment, can promote developing by leaps and bounds of chromatography again.
The liquid-liquid-liquid micro-extraction technique is a kind of advanced person's of growing up in nearly one or two years the residual new technology of extraction trace organic compound.It comprises feed liquid phase (sample), organic facies, accepts phase, and whole extraction process is as follows: the analyte in the feed liquid phase (sample) at first is extracted in the organic solvent, and is stripped into (as shown in Figure 1) in the acceptor.In different liquid phases, protonation and complexing have changed the chemical property of analyte, and drive its transfer.
Shortcomings such as can be seen, the liquid-liquid-liquid micro-extraction exists wayward from above-mentioned installation drawing, and the extraction time is long.
Because the liquid-liquid-liquid micro-extraction technique is the emerging pretreatment technology in a kind of world, domestic and international application pesticide residue analysis in beverage yet there are no report, if this advanced person's extracting method can be applied in many residue detection of organophosphorus pesticide in the beverage, will be the once pioneering research and the important innovations of this based food middle peasant medicine retention analysis.
(3) summary of the invention
The object of the invention is to solve the liquid-liquid-liquid micro-extraction and exists wayward, droplet easily to be broken up, be unfavorable for shortcomings such as operation, a kind of easy operating, extraction time weak point are provided, are easy to realize the doughnut membrane type liquid phase micro-extraction apparatus of sample purification enrichment, and utilize it to carry out the method for residues of pesticides pre-treatment.
The technical solution used in the present invention is:
A kind of doughnut membrane type liquid phase micro-extraction apparatus, mainly comprise horizontal positioned base, be vertically fixed on extraction support on the base, be fixed on the hollow-fibre membrane fixture on the extraction support, described doughnut membrane type liquid phase micro-extraction apparatus also comprises air extractor, described air extractor be positioned at the hollow-fibre membrane fixture the top, be arranged on the fixed support vertical with base, can move up and down along fixed support; Described fixed support can directly be fixedly connected on the base, when air extractor need move horizontally, described fixed support can be arranged on the affixed horizontally moving device of base on, move horizontally to realize it.
Described hollow-fibre membrane fixture is made of the locating rack of the hollow stationary pipes that is furnished with some both ends opens and the hollow-fibre membrane that releasably is fixed on the hollow stationary pipes, and hollow-fibre membrane is vertical separately with described base horizontal plane when being fixed on the described hollow stationary pipes; Described hollow stationary pipes external diameter can be slightly larger than the hollow-fibre membrane internal diameter, so that hollow-fibre membrane is fixed, does not break away from from the hollow stationary pipes with hollow-fibre membrane and is advisable.
Some syringe needles of bleeding constitute described air extractor on the hollow fixed bar by being connected with the fixedly connected fixture of fixed support, horizontally disposed hollow fixed bar, bleed syringe and the vertical fixing that are connected with the hollow fixed bar, described hollow fixed bar is connected with fixture, and described hollow fixed bar one end seals, syringe is bled in the dismountable connection of openend; The described syringe needle lower ending opening of bleeding, the hollow chamber of upper end and hollow fixed bar, the syringe of bleeding connect and airtight closing, and the described syringe needle arrangement pitches of bleeding is arranged with described hollow-fibre membrane and is matched.Described air extractor can be implemented in moving up and down on the fixed support by sleeve arrangement.
The cavity that the described hollow fixed bar hollow space and the syringe needle inside of bleeding are formed can not be too big, too big words can't be extracted the water extract in the hollow-fibre membrane out, common, described hollow fixed bar hollow space is an elongate conduit, be communicated with the syringe needle of bleeding and get final product.
Described hollow stationary pipes is in a row arranged, described hollow-fibre membrane is in a row arranged, the described syringe needle of bleeding layout in a row is arranged with described hollow-fibre membrane and is matched, when air extractor moves down by sleeve arrangement, the described syringe needle of bleeding can pass the cavity bottom that described hollow stationary pipes extends hollow-fibre membrane.
Described hollow stationary pipes is provided with the some row of cells that are parallel to each other, be parallel to each other between each row of cells of described hollow-fibre membrane, the fixture of described air extractor is provided with can be for the vertically mobile fixed muffle chute of hollow fixed bar, described hollow fixed bar can be connected in the chute of described fixture horizontally slidingly, and the described layout of syringe needle on the hollow fixed bar of bleeding matches with the arranging of hollow-fibre membrane of described row of cells.
Concrete, the hollow stationary pipes in the described hollow-fibre membrane fixture can be many rows, and the spacing between described same row's the hollow stationary pipes is identical.The syringe needle of bleeding in the described air extractor matches with single hollow stationary pipes, and described air extractor is provided with and moves horizontally sleeve arrangement, and utilization moves horizontally sleeve arrangement can realize the extraction of air extractor to water extract in each row's hollow-fibre membrane.
Preferably, described hollow-fibre membrane is a polypropylene hollow fiber membrane, internal diameter 0.7～1.0mm, wall thickness 0.05～0.2mm, membrane aperture 0.45 μ m.
A kind ofly use the method that described doughnut membrane type liquid phase micro-extraction apparatus carries out the residues of pesticides pre-treatment, described method is as follows:
(1) hollow-fibre membrane is cut into 4～6cm segment, soaks with benzinum and remove the hollow-fibre membrane surface impurity, drying and volatilizing is removed benzinum, put into the organic facies solvent and soak 2～3h, take out, seal an end, inject water to hollow space, blind end is not fixed on the hollow stationary pipes;
(2) container that will fill the organophosphorus pesticide testing sample solution places hollow-fibre membrane fixture below, make hollow-fibre membrane all immerse in the sample solution, behind extraction 1～2h, air extractor is moved down, the needle tubing of bleeding is inserted in first row's hollow-fibre membrane, in the syringe of bleeding with the water extract suction air extractor in the hollow-fibre membrane, then air extractor carries out horizontal movement by moving horizontally sleeve arrangement, insert in second row's hollow-fibre membrane and extract, until the extract in all hollow-fibre membranes is sucked, extract carries out next step Detecting Pesticide.
During extraction, but turn on agitator is to accelerate its rate of extraction, by selecting appropriate organic solvent, the organophosphorus pesticide determinand can optionally enter another recipient's solution from supplier's solution extraction, treat that extract is ionic condition in supplier's solution, combine the extraction activity form that forms the nonionic state with extraction solution, enter in the hollow-fibre membrane membrane aperture, enter recipient's solution by diffusion again, it also is the water acceptor in the hollow-fibre membrane, recover ionic condition again, promptly finish extraction.
Preferably, hollow stationary pipes in the described hollow-fibre membrane fixture is 3～6 rows, the syringe needle of bleeding in the described air extractor matches with single hollow stationary pipes, the fixture of described air extractor is provided with the fixedly chute that can supply the hollow fixed bar to move horizontally, and described hollow fixed bar can be connected in the chute of described fixture horizontally slidingly; The hollow-fibre membrane that is fixed in same row soaks with organic facies solvent of the same race, and after extraction finished, each each personal air extractor of water extract of arranging in the hollow-fibre membrane extracted collection.Like this, can carry out the comparison of different organic extraction solvent extraction effects simultaneously, simplify operation.
Described hollow-fibre membrane is a polypropylene hollow fiber membrane, internal diameter 0.7～1.0mm, wall thickness 0.05～0.2mm, membrane aperture 0.45 μ m.
It is one of following that described organophosphorus pesticide can be: parathion, parathion-methyl, Rogor, flolimat, malathion, DDVP, chlopyrifos.The present invention to the recovery of standard addition of above-mentioned organophosphorus pesticide is: 90.4%～98.9%; Minimum detects concentration: 0.10 * 10
-4Mg/kg～0.74 * 10
-3Mg/kg.
Method as claimed in claim 4 is characterized in that: described organic facies solvent is one of following or two or more mixture wherein: benzene, toluene, acetone, chloroform.
The inventive method is a kind of novel, efficient, environment amenable sample pre-treatments technology, and the sensitivity that compares favourably with the liquid-liquid-liquid micro-extraction can be provided, even higher concentration effect.This technology centralized procurement sample, extraction, simmer down to one have reduced the step of sample pre-treatments, make to have characteristics such as quick, easy, simple to operate.Compare with traditional pre-treating method, this method is because with an organic solvent considerably less, and the mass transfer velocity in the time of can improving extraction greatly shortens the extraction time, is a kind of efficient pre-treating method.Behind doughnut membrane type liquid phase micro-extraction apparatus, can effectively remove the interfering material in the organophosphorus pesticide, obtain higher selectivity and sensitivity.
The beneficial effect of apparatus of the present invention and method is mainly reflected in: 1, required consumption of organic solvent few (being generally 10～40 μ L), can significantly improve the mass transfer velocity of extraction, thereby shorten the extraction time; 2, after the extraction, sample extraction liquid can directly take out, need not standing separation, simplified the step of sample treatment; 3, reduce interference, raising sensitivity for analysis, be easy to realize the purifying and the enrichment of sample; 4, device is simple, can carry out the comparison of different organic extraction solvent extraction effects simultaneously, has simplified operation, has improved efficient.
(4) description of drawings
Fig. 1 is existing liquid-liquid-liquid micro-extraction device, and among the figure: 10-microsyringe, 11-sample bottle, 12-agitator, 13-stir magneton, and 14-extracts droplet, the 15-organic facies;
Fig. 2 is a doughnut membrane type liquid phase micro-extraction apparatus structural representation of the present invention; 1-base, 2-horizontally moving device, the 3-syringe of bleeding, the vertical moving sleeve device of 4-, 5-extracts support, 6-hollow fixed bar, the 7-syringe needle of bleeding, 8-locating rack, 9-hollow stationary pipes; The 16-fixed support;
Fig. 3 is a hollow-fibre membrane fixture schematic top plan view;
Fig. 4 is the air extractor elevational schematic view;
Fig. 5 is for base and move horizontally the sleeve arrangement schematic top plan view.
(5) specific embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
Referring to accompanying drawing 2～5, a kind of doughnut membrane type liquid phase micro-extraction apparatus mainly comprises base 1, the extraction support 5 vertical with base, is arranged at hollow-fibre membrane fixture, the air extractor on the extraction support and can makes air extractor carry out sleeve arrangement vertical and that move horizontally.
Described hollow-fibre membrane fixture is made of locating rack 8 and the hollow stationary pipes 9 that is arranged on a plurality of both ends opens on the locating rack, described hollow stationary pipes lower end is in order to fixing hollow-fibre membrane, described hollow stationary pipes external diameter is 1mm, internal diameter 0.8mm, length 2cm, and described hollow stationary pipes is independent and parallel with described extraction support separately; The hollow stationary pipes is designed to prong structure, so that hollow-fibre membrane is inserted in the hollow stationary pipes smoothly.
Described air extractor is made of hollow fixed bar 6 and a plurality of syringe needles 7 of bleeding that are arranged on the hollow fixed bar, described hollow fixed bar one end sealing, openend removably connect the syringe 3 of bleeding, described fixed bar hollow space (internal diameter 2mm) connects with the described syringe needle of bleeding, and the described syringe needle external diameter 0.5mm that bleeds, length are 8cm;
Described air extractor is positioned at described hollow-fibre membrane fixture top, described air extractor and described fixed support are slidingly connected by sleeve arrangement 4, when air extractor moves down, the described syringe needle of bleeding can pass the cavity bottom that described hollow stationary pipes extends hollow-fibre membrane.
Described hollow stationary pipes is 30 holes (6 holes * 5 row), the needle tubing of bleeding of described air extractor is 6 holes, matches with single hollow stationary pipes, described air extractor is provided with horizontally moving device 2, described fixed support 16 is vertically set on the horizontally moving device 2, described horizontally moving device adopts the sleeve arrangement design, can realize the extraction collection of air extractor to water extract in each row hollow-fibre membrane.
Embodiment 2:
Accurately take by weighing parathion-methyl (country mark thing center) standard items, be dissolved in the 10mL volumetric flask, with the methyl alcohol dissolving and be diluted to scale, shake up.The concentration of standard reference material is 10ug/mL, is stored in 4 ℃ of refrigerators standby.
Accurately measure 5,8,10,15,20,40,100uL standard reference material solution, be 5mL with the methyl alcohol dilution, being prepared into concentration is 10
-2, 1.6 * 10
-2, 2 * 10
-2, 3 * 10
-2, 4 * 10
-2, 8 * 10
-2, 2 * 10
-1Ug/mL standard reference material solution.
Adopt the device of embodiment 1, with hollow-fibre membrane (film research institute of University Of Tianjin) (internal diameter 0.8mm, wall thickness 0.1mm, membrane aperture 0.45 μ m) is cut into the segment of 5cm, totally six sections, soak with benzinum, remove the impurity on hollow-fibre membrane surface, drying and volatilizing is removed benzinum, drop into then and soak 2h in the toluene, take out, add heat-seal one end, inject 10uL water to hollow space, blind end is not fixed on the hollow stationary pipes.The hollow stationary pipes that will have hollow-fibre membrane is submerged in the standard reference material of the above-mentioned variable concentrations that makes, behind the extraction 1h, adopt mobile device, 6 hole air extractors of extract system are inserted the hollow-fibre membrane that is fixed on the hollow stationary pipes, mobile extract system, from top to bottom in the syringe with the water extract suction extract system in the hollow-fibre membrane, get 3ul extract sample introduction then, the record chromatographic peak, with the peak area is ordinate, with standard reference material concentration is abscissa, makes the calibration curve of parathion-methyl.
Get the sample solution of 100uL known content respectively, in the bottles of the different numberings of packing into, be diluted to 10mL with methyl alcohol after, add 3,5,8,10 successively, the 20uL reference substance solution.Calculate recovery of standard addition, be approximately 95.3%～98.7%, illustrate that thus 95% can diffuse into water by hollow-fibre membrane with the subscript product and is extracted, again the water extract is carried out organophosphorus pesticide and measure, owing to reduced the interference of impurity, therefore can obtain comparatively accurate data.
Embodiment 3:
Accurately take by weighing Rogor (country mark thing center) standard items, be dissolved in the 10mL volumetric flask, with the methyl alcohol dissolving and be diluted to scale, shake up.The concentration of standard reference material is 10ug/mL, is stored in 4 ℃ of refrigerators standby.
Accurately measure 10,20,30,50,100,150,250uL standard reference material solution, be 5mL with the methyl alcohol dilution, being prepared into concentration is 2 * 10
-2, 4 * 10
-2, 6 * 10
-2, 0.1,0.2,0.3,0.5ug/mL standard reference material solution.
Adopt the device of embodiment 1, hollow-fibre membrane is cut into the segment of 5cm, totally ten two sections, soak with benzinum, remove the impurity on hollow-fibre membrane surface, drying and volatilizing is removed benzinum, wherein soak 2h in six sections input toluene, remaining is immersed in the mixed solution of benzene and acetone, take out behind the 2h, add heat-seal one end, in hollow-fibre membrane, inject 3uL water, the hollow-fibre membrane that will soak in toluene is fixed on the first row hollow stationary pipes, and remaining six sections hollow-fibre membranes are fixed on the secondary series hollow stationary pipes.The hollow stationary pipes that will have hollow-fibre membrane is submerged in the standard reference material of the above-mentioned variable concentrations that makes, and behind the extraction 1h, gets 10uL water extract sample introduction, the record chromatographic peak, with the peak area is ordinate, is abscissa with standard reference material concentration, makes the calibration curve of Rogor.Get the sample solution of 100uL known content respectively, in the bottles of the different numberings of packing into, be diluted to 10mL with methyl alcohol after, add 3,5,8,10 successively, the 20uL reference substance solution.Calculate recovery of standard addition, be approximately 93.7%～96.5%, illustrate that thus 95% can diffuse into water by hollow-fibre membrane with the subscript product and is extracted, for the accurate mensuration of follow-up organophosphorus pesticide is laid a good foundation.
Embodiment 4:
Accurately take by weighing malathion (country mark thing center), Rogor, parathion-methyl standard items, be dissolved in the 10mL volumetric flask, with the methyl alcohol dissolving and be diluted to scale, shake up.The concentration of standard reference material is 10ug/mL, is stored in 4 ℃ of refrigerators standby.
Get three groups of solution, in the A group malathion, Rogor, parathion-methyl get 50,100 respectively, 150uL; In the B group malathion, Rogor, parathion-methyl get 100,50 respectively, 200uL; In the C group malathion, Rogor, parathion-methyl get 150,200 respectively, 100uL, all be diluted to 5mL with methyl alcohol.The concentration of malathion, Rogor, parathion-methyl sees the following form in each group:
Press the operation of embodiment 2, mixed solution A, B, C are carried out efficient gas phase analysis, the record chromatographic peak is an ordinate with the peak area, is abscissa with standard reference material concentration, makes the calibration curve of A, B, C.Get the parathion-methyl standard liquid (concentration is 10ug/mL) of three parts of 50uL preparations, put into A, B, C solution respectively, be diluted to 10mL with methyl alcohol then, adopt gas phase analysis, calculate recovery of standard addition, be approximately 92.9%～95.7%, illustrate that thus 95% can diffuse into water by hollow-fibre membrane with the subscript product and is extracted, for the accurate mensuration of follow-up organophosphorus pesticide is laid a good foundation.
Claims (10)
1. doughnut membrane type liquid phase micro-extraction apparatus, mainly comprise horizontal positioned base, be vertically fixed on extraction support on the base, be fixed on the hollow-fibre membrane fixture on the extraction support, it is characterized in that described doughnut membrane type liquid phase micro-extraction apparatus also comprises air extractor, described air extractor be positioned at the hollow-fibre membrane fixture the top, be arranged on the fixed support vertical with base;
Described hollow-fibre membrane fixture is made of the locating rack of the hollow stationary pipes that is furnished with both ends open and the hollow-fibre membrane that releasably is fixed on the hollow stationary pipes, and described hollow-fibre membrane is vertical with described base horizontal plane when being fixed on the described hollow stationary pipes;
Described air extractor constitutes by being connected the syringe needle of bleeding on the hollow fixed bar with the fixedly connected fixture of fixed support, horizontally disposed hollow fixed bar, bleed syringe and the vertical fixing that are connected with the hollow fixed bar, described hollow fixed bar is connected with fixture, described hollow fixed bar one end sealing, the dismountable syringe of bleeding that is connected with of openend, the described syringe needle lower ending opening of bleeding, upper end and the hollow chamber of hollow fixed bar, the syringe of bleeding connect and airtight closing, and the described syringe needle arrangement pitches of bleeding is arranged with described hollow-fibre membrane and matched.
2. doughnut membrane type liquid phase micro-extraction apparatus as claimed in claim 1 is characterized in that described hollow stationary pipes in a row arranges, described hollow-fibre membrane in a row arranges, the described syringe needle of bleeding is in a row arranged to arrange with described hollow-fibre membrane and matched.
3. doughnut membrane type liquid phase micro-extraction apparatus as claimed in claim 1, it is characterized in that described hollow stationary pipes is provided with the some row of cells that are parallel to each other, be parallel to each other between each row of cells of described hollow-fibre membrane, the fixture of described air extractor is provided with the fixedly chute that can supply the hollow fixed bar to move horizontally, described hollow fixed bar can be connected in the chute of described fixture horizontally slidingly, and the described layout of syringe needle on the hollow fixed bar of bleeding matches with the arranging of hollow-fibre membrane of described row of cells.
4. as claim 2 or 3 described doughnut membrane type liquid phase micro-extraction apparatus, it is characterized in that the spacing between described same row's the hollow stationary pipes is identical.
5. as the described doughnut membrane type of one of claim 1～3 liquid phase micro-extraction apparatus, it is characterized in that described hollow-fibre membrane is a polypropylene hollow fiber membrane, internal diameter 0.7～1.0mm, wall thickness 0.05～0.2mm, membrane aperture 0.45 μ m.
6. method that application rights requires 1 described doughnut membrane type liquid phase micro-extraction apparatus to carry out the residues of pesticides pre-treatment, described hollow stationary pipes is provided with the some row of cells that are parallel to each other, be parallel to each other between each row of cells of described hollow-fibre membrane, described method is as follows:
(1) hollow-fibre membrane is cut into 4～6cm segment, soaks with benzinum and remove the hollow-fibre membrane surface impurity, drying and volatilizing is removed benzinum, put into the organic facies solvent and soak 2～3h, take out, seal an end, inject water to hollow space, blind end is not fixed on the hollow stationary pipes;
(2) container that will fill the organophosphorus pesticide testing sample solution places hollow-fibre membrane fixture below, make hollow-fibre membrane all immerse in the sample solution, behind extraction 1～2h, air extractor is moved down, the needle tubing of bleeding is inserted in first row's hollow-fibre membrane, in the syringe of bleeding with the water extract suction air extractor in the hollow-fibre membrane, then air extractor carries out horizontal movement by moving horizontally sleeve arrangement, insert in second row's hollow-fibre membrane and extract, until the extract in all hollow-fibre membranes is sucked, extract carries out next step Detecting Pesticide.
7. method as claimed in claim 6, it is characterized in that: the hollow stationary pipes in the described hollow-fibre membrane fixture is 3～6 rows, the syringe needle of bleeding in the described air extractor matches with single hollow stationary pipes, the fixture of described air extractor is provided with the fixedly chute that can supply the hollow fixed bar to move horizontally, and described hollow fixed bar can be connected in the chute of described fixture horizontally slidingly; The hollow-fibre membrane that is fixed in same row soaks with organic facies solvent of the same race, and after extraction finished, each each personal air extractor of water extract of arranging in the hollow-fibre membrane extracted collection.
8. method as claimed in claim 6 is characterized in that described hollow-fibre membrane is a polypropylene hollow fiber membrane, internal diameter 0.7～1.0mm, wall thickness 0.05～0.2mm, membrane aperture 0.45 μ m.
9. method as claimed in claim 6 is characterized in that: described organophosphorus pesticide is one of following: parathion, parathion-methyl, Rogor, flolimat, malathion, DDVP, chlopyrifos.
10. method as claimed in claim 6 is characterized in that: described organic facies solvent is one of following or two or more mixture wherein: benzene, toluene, acetone, chloroform.
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| US9568460B2 (en) | 2014-08-28 | 2017-02-14 | King Fahd University Of Petroleum And Minerals | Simple method for the detection of sulfur compounds in crude oils and diesel |
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| CN102974127B (en) * | 2012-11-23 | 2017-12-08 | 中国计量学院 | A kind of hollow-fibre membrane micro-extraction apparatus and its application |
| CN103033582A (en) * | 2013-01-10 | 2013-04-10 | 广东珠江桥生物科技股份有限公司 | Probe coated with SPME coatings and used for collecting toxic substances and application of probe |
| CN109443900B (en) * | 2018-10-26 | 2021-10-26 | 宁波大学 | Method and device for strengthening liquid phase micro-extraction effect by combining electromagnetic field |
| CN110412174B (en) * | 2019-08-28 | 2022-06-14 | 福建中妆技术研究有限公司 | Headspace microdroplet extraction-chromatographic detection method for residual solvent in grease |
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| US9568460B2 (en) | 2014-08-28 | 2017-02-14 | King Fahd University Of Petroleum And Minerals | Simple method for the detection of sulfur compounds in crude oils and diesel |
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