CN103335878B - The preprocess method of phthalic ester plasticizer in a kind of edible oil - Google Patents
The preprocess method of phthalic ester plasticizer in a kind of edible oil Download PDFInfo
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- CN103335878B CN103335878B CN201310162847.5A CN201310162847A CN103335878B CN 103335878 B CN103335878 B CN 103335878B CN 201310162847 A CN201310162847 A CN 201310162847A CN 103335878 B CN103335878 B CN 103335878B
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Abstract
The invention discloses the preprocess method of phthalic ester plasticizer in a kind of edible oil, it is by the edible oil organic solvent extraction of certain mass; Extract is carried out extracting liq after freezing ungrease treatment; Extract is purified through solid phase extraction column; Scavenging solution after purification is carried out wash-out and dries up constant volume process.With the pre-treating method ratio in GB, inspection process of the present invention is short, easy to operate, and extraction efficiency is high, reproducible, solvent few, cost of determination is low, method is highly sensitive, can detect the content of 5 kinds of common phthalic esters in edible oil simultaneously, have good application prospect.
Description
Technical field
The present invention relates to Safety of Food Quality detection technique field, a kind of pretreated method of several frequently seen phthalic ester plasticizer in edible oil is provided.
Background technology
Plasticiser, or plastifier are a kind of adjuvants that can increase the characteristic such as material softness, elasticity, are widely used in the every field of national industry.Plasticiser mainly refers to phthalate material (PAEs).Research shows, though the anxious toxic action of PAEs is not obvious, can cause the poisoning of many organization systems such as liver, kidney, lung and heart, reproduction etc., wherein obvious with male reproductive system infringement.Phthalate material is all successively listed in the blacklist of priority pollutants by EFSA, the U.S., Japan, China, and the harm of PAEs substances on human health has caused the extensive concern in the world as can be seen here.
For these reasons, PAEs pollutes the great attention being subject to countries in the world.PAEs is all listed in the blacklist of priority monitoring by the U.S., Japan and European many countries, has listed 6 kinds of phthalic esters in the pollutant blacklist of EPA's 129 kinds of priority controls in: phthalic acid two (2-ethylhexyl) ester (DEHP), repefral (DMP), dibutyl phthalate (DBP), diethyl phthalate (DEP), di-n-octyl phthalate (DnOP), phthalic acid butyl ester (BBP); N-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, phthalic acid two (2-ethylhexyl) ester, diisoheptyl phthalate, diisooctyl phthalate are listed in emphasis environmental surveys material list by Japan, and China has also listed DMP, DBP, DEHP in priority pollutants blacklist in water.
Edible oil, as the important component part of food, is the required flavouring of people's daily life.Wherein, phthalate material (diethyl phthalate (DEP), dibutyl phthalate (DBP), phthalic acid butyl ester (BBP), phthalic acid two (2-ethylhexyl) ester (DEHP), di-n-octyl phthalate (DnOP)), not to be connected with plastic polymer by chemical bond because of PAEs and to be liposoluble substance, be easy to pollute edible oil.Due to the complicacy of edible oil matrix and the low content of PAEs, the PAEs detection limit of a lot of bibliographical information is higher and comparatively large by impurity interference, and detect more difficult, the PAEs for low concentration cannot detect especially.And the quality that detection limit height and interfering material are removed topmostly affects the pretreatment process that step is sample, so pre-treatment is the key ensureing that low content plasticiser is detected.
Summary of the invention
The object of this part is some aspects of general introduction embodiments of the invention and briefly introduces some preferred embodiments.May do in the specification digest and denomination of invention of this part and the application a little simplify or omit with avoid making this part, specification digest and denomination of invention object fuzzy, and this simplification or omit and can not be used for limiting the scope of the invention.
In view of Problems existing in the preprocess method of phthalic ester plasticizer in above-mentioned and/or existing edible oil, propose the present invention.
Therefore, the object of the invention is the deficiency for existing method of operating, there is provided the preprocess method of phthalic ester plasticizer in a kind of edible oil, in this edible oil, the preprocess method of phthalic ester plasticizer can make phthalic ester plasticizer accuracy of detection in edible oil significantly promote; Meanwhile, the shortcoming that the present invention can overcome prior art, with not enough, provides that a kind of extraction and cleaning is easy, interfering material removal effect is good, equipment simple, cost of determination reduction process method.
For solving the problems of the technologies described above, the invention provides following technical scheme: the preprocess method of phthalic ester plasticizer in a kind of edible oil, by the edible oil organic solvent extraction of certain mass; Extract is carried out extracting liq after freezing ungrease treatment; Extract is purified through solid phase extraction column; Scavenging solution after purification is carried out wash-out and dries up constant volume process.
As a kind of preferred version of the preprocess method of phthalic ester plasticizer in edible oil of the present invention, wherein: described organic solvent extraction, by organic solvent and edible oil vortex mixed 2 ~ 3min, the then centrifugal 3 ~ 5min of 4000 ~ 6000rpm.
As a kind of preferred version of the preprocess method of phthalic ester plasticizer in edible oil of the present invention, wherein: described organic solvent is one or more in acetonitrile, ethanol, ethyl acetate and normal hexane.
As a kind of preferred version of the preprocess method of phthalic ester plasticizer in edible oil of the present invention, wherein: described freezing ungrease treatment, be that extract is left standstill 1 ~ 2h, then extracting liq part under the condition of-10 ° of C ~-20 ° C.
As a kind of preferred version of the preprocess method of phthalic ester plasticizer in edible oil of the present invention, wherein: described extracting liq part, first the solid liquid phase of stratification is separated, then liquid part nitrogen stream under the condition of 40 ° of C ~ 45 ° C blows near dry, finally extracts with normal hexane mixing.
As a kind of preferred version of the preprocess method of phthalic ester plasticizer in edible oil of the present invention, wherein: its filler of described solid phase extraction column comprises primary secondary amine.
As a kind of preferred version of the preprocess method of phthalic ester plasticizer in edible oil of the present invention, wherein: described scavenging solution carries out wash-out process, be by scavenging solution first through normal hexane wash-out, then use acetone-normal hexane (V:V) wash-out of acetone and/or normal hexane and/or 4% ~ 10% again.
As a kind of preferred version of the preprocess method of phthalic ester plasticizer in edible oil of the present invention, wherein: described scavenging solution carries out drying up process, be that eluent nitrogen stream under the condition of 40 ° of C ~ 45 ° C is dried up.
As a kind of preferred version of the preprocess method of phthalic ester plasticizer in edible oil of the present invention, wherein: described scavenging solution carries out constant volume process, be eluent normal hexane constant volume after being dried up by nitrogen stream.
Beneficial effect of the present invention:
(1) object of the present invention adopts organic solvent extraction, freezing ungrease treatment and solid phase pillar purified treatment, not only ensure that the recovery but also effectively eliminate impurity, belongs to pioneering research;
(2) with the pre-treating method ratio in GB, inspection process of the present invention is short, easy to operate, and extraction efficiency is high, reproducible, solvent few, cost of determination is low, method is highly sensitive, can detect the content of 5 kinds of common phthalic esters in edible oil simultaneously, have good application prospect.
Embodiment
Below in conjunction with specific embodiment, the method for the invention is described in detail.
Be described below in detail embodiments of the invention, the example of described embodiment illustrates, wherein same or similar label represents same or similar composition or has component that is identical or similar functions from start to finish.The following examples are exemplary, only for explaining the present invention, and can not be interpreted as limitation of the present invention.
Embodiment 1
One, extract
Accurately take one-level soybean oil 1g(and be accurate to 0.001g) in 10mL glass centrifuge tube, add the acetonitrile of 5mL, vortex mixing 2min, 4000rpm, centrifugal 3min, acetonitrile layer is taken out in layering, repeats above operation 3 times, merges 3 extracts.
The present embodiment adopts the PAEs in the method extraction edible oil of liquid-liquid extraction, and extraction solvent is acetonitrile.Mixed with acetonitrile by a certain amount of edible oil, centrifugal after vortex oscillation, acetonitrile layer is on upper strata, and grease is in lower floor.
Extraction times is too much or very fewly all can produce certain influence to measurement result.Extraction times is very few, and the recovery of standard addition of object is lower does not reach analysis requirement; The more meeting of the more impurity extracted in the lump of extraction times causes interference to subsequent analysis, and waste reagent and time.
Two, extracting liq after freezing ungrease treatment
After extract is placed 2h at-20 DEG C, transfer to rapidly in another clean test tube.40 DEG C, nitrogen stream blows near dry.Add 2mL normal hexane again, mix to be clean.
Although acetonitrile and grease do not dissolve each other, the inevasible amount of grease that has of leaching process is in acetonitrile layer.If do not removed, after purification, more grease can be remained, carry out polluting or blocking chromatographic column, so grease must be removed when GC-MS detects.5 kinds of PAEs, the solidifying point of DEP, BBP, DBP, DEHP, DOP is respectively :-40 DEG C ,-35 DEG C ,-35 DEG C ,-55 DEG C ,-25 DEG C, and the solidifying point of grease is more much higher than the fusing point of PAEs, so under the condition of-20 DEG C, grease can crystallize out, be deposited in bottom, and 5 kinds of PAEs are still in acetonitrile layer, this experiment utilizes this principle to carry out degreasing, research finds substantially to remove in acetonitrile layer the greases such as sweet three esters, DAG by the method, substantially increases the sensitivity that in edible oil and fat, plasticiser detects.Meanwhile, freezing processing can also remove partial pigment molecule, effectively prevent solid phase extraction column overload, has saved cost.
Three, solid phase extraction column purification
Liquid to be clean is comprised the solid phase extraction column purification of primary secondary amine and silica gel by filler.
It is that the solid phase extraction column of main stuffing purifies that the present invention finally screens with primary secondary amine, and its predominant intermolecular forces is polarity, anion exchange.This solid phase extraction column has two amidos, has higher exchange capacity (1.4mep/kg).And its anion exchange capacity compares NH
2be eager to excel, its functional group is a good binary ligand, and this makes primary secondary amine be good chelating material.Its many carbon structure makes the nonpolar action force rate NH of primary secondary amine
2be eager to excel.Containing pigment, fatty acid, alcohols isopolarity material in edible oil, when extracting with acetonitrile, part can be proposed in the lump, and these materials can cause certain interference to mensuration, therefore must remove these compounds.Object PAEs is a kind of low pole material, be adsorbed on the solvent elution strengthened successively by polarity after on this solid phase extraction column, first object is eluted, and the material that pigment, fatty acid isopolarity are strengthened can be retained on pillar, thus well achieve object and realize being separated with interfering material.
Four, wash-out dries up constant volume process
Scavenging solution is collected, first use 5mL hexane, then 5mL acetone, normal hexane, 4% acetone-normal hexane (V:V), 8% acetone-normal hexane (V:V), 10% acetone-normal hexane (V:V) wash-out is used respectively, the eluent of collection 40 DEG C of nitrogen streams are dried up, then be settled to 2mL with normal hexane, analyze for GC-MS.
The recovery of different eluting solvents to object has considerable influence.Eluant, eluent polarity is weak, can not by object from solid phase pillar elute or wash-out incomplete; Eluant, eluent polarity is too strong, can elute a lot of impurity in the lump, cause certain interference to follow-up analysis, so tackle different eluant, eluents to carry out com-parison and analysis, determine best eluting solvent.
Embodiment 2
Embodiment 2 is that sample is tested with peanut oil
Accurately take peanut oil 1g(and be accurate to 0.001g) in 10mL glass centrifuge tube, divide 2 extractions with 10mL(respectively), 15mL(divides 3 extractions), 20mL(divides 4 extractions) normal hexane extraction.After extract is placed 3h at-20 DEG C, transfer to rapidly in another clean test tube.45 DEG C, nitrogen stream blows near dry, then adds 2mL normal hexane, mixes to be clean.
Be the solid phase extraction column purification of primary secondary amine by filler by liquid to be clean, collect efflux, first use 5mL hexane, then 5mL8% acetone-normal hexane (V:V) wash-out is used, the eluent of collection is dried up at 40 DEG C of nitrogen, is settled to 2mL with normal hexane, analyze for GC-MS.
Embodiment 3
Embodiment 3 is that sample is tested with olive oil
Accurately take olive oil 1g(and be accurate to 0.001g) in 10mL glass centrifuge tube, divide 2 extractions with 10mL(respectively), 15mL(divides 3 extractions), 20mL(divides 4 extractions) acetonitrile extraction.After extract is placed 3h at-20 DEG C, transfer to rapidly in another clean test tube.45 DEG C, nitrogen stream blows near dry, then adds 2mL normal hexane, mixes to be clean.
Be the solid phase extraction column purification of primary secondary amine by filler by liquid to be clean, collect efflux, first use 5mL hexane, then 5mL8% acetone-normal hexane (V:V) wash-out is used, the eluent of collection is dried up at 42 DEG C of nitrogen, is settled to 2mL with normal hexane, analyze for GC-MS.
Embodiment proves, after above-mentioned preprocess method, GC-MS Accurate Analysis can to go out in edible oil plasticizer loading in the situation of below 1.5mg/kg.This preprocess method shows with existing methodical check analysis:
1, the detection limit of edible oil higher (1.5mg/kg) in GB, the plastifier for low content cannot detect.Plasticiser can at people's cylinder accumulation, if the edible oil that human body is taken in for a long time containing lower content plasticiser finally also can damage human body.And preprocess method provided by the invention accurately can detect that content of plasticizing agent is lower than the plasticiser situation in the edible oil of 1.5mg/kg;
2, process the gel permeation chromatograph adopted at present and have a lot of plastic components (as drawn the plastic tube etc. of mobile phase), during the membrane filtration of this external application 0.45 μm, filter membrane edge is plastics.These all measurement result may bring error.
The principle of the gel permeation chromatography 3, adopted in GB is separated according to potpourri molecular size, a lot of interfering material is as similar with plasticizer molecule size in fatty acid, pigment, a sweet ester etc., therefore these materials can be separated in the lump, can cause matrix interference effect when detecting with GC-MS.
4, existing method detects high for equipment requirement, and the cost of input is comparatively large, and a lot of laboratory or research institution can not complete independentlies.
Pretreatment process of the present invention can effectively go deimpurity interference by the extraction of solvent, solid phase extraction column purification, organic reagent elution step.With much lower than the detection limit in GB of signal to noise ratio (S/N ratio) (S/N) to be the 10 Supreme Procuratorate's rising limits calculated be 100 μ g/kg.
It should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (5)
1. the preprocess method of phthalic ester plasticizer in edible oil, is characterized in that:
By the edible oil organic solvent extraction of certain mass, described organic solvent extraction is by organic solvent and edible oil vortex mixed 2 ~ 3min, the then centrifugal 3 ~ 5min of 4000 ~ 6000rpm;
Extract being carried out extracting liq after freezing ungrease treatment, described freezing ungrease treatment, is that extract is left standstill 1 ~ 2h, then extracting liq part under the condition of-10 DEG C ~-20 DEG C;
Extract is purified through solid phase extraction column;
Scavenging solution after purification is carried out wash-out and dries up constant volume process, described scavenging solution carries out drying up process, be dried up by eluent nitrogen stream under the condition of 40 DEG C ~ 45 DEG C, described scavenging solution carries out constant volume process, is the eluent normal hexane constant volume after being dried up by nitrogen stream.
2. the preprocess method of phthalic ester plasticizer in edible oil according to claim 1, is characterized in that: described organic solvent is one or more in acetonitrile, ethanol, ethyl acetate and normal hexane.
3. the preprocess method of phthalic ester plasticizer in edible oil according to claim 1, it is characterized in that: described extracting liq part, first the solid liquid phase of stratification is separated, then liquid part nitrogen stream under the condition of 40 DEG C ~ 45 DEG C blows near dry, finally extracts with normal hexane mixing.
4. the preprocess method of phthalic ester plasticizer in edible oil according to claim 1, is characterized in that: its filler of described solid phase extraction column comprises primary secondary amine.
5. the preprocess method of phthalic ester plasticizer in edible oil according to claim 1, it is characterized in that: described scavenging solution carries out wash-out process, first through hexane by scavenging solution, then again with counting by volume, acetone and/or normal hexane and/or 4% ~ 10% acetone-hexane.
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| CN103242953A (en) * | 2013-05-20 | 2013-08-14 | 广州理和健康产品科技有限公司 | Method for removing plasticizer from fructus schizandrae oil or ganoderma spore oil |
| CN104569218B (en) * | 2013-10-29 | 2016-06-29 | 中国石油化工股份有限公司 | For extracting the compound extract of phthalic acid ester in polypropylene material |
| CN103588744B (en) * | 2013-10-31 | 2016-01-13 | 宁波大红鹰生物工程股份有限公司 | Remove the method for fluidizer in natural VE |
| CN104178337A (en) * | 2014-05-05 | 2014-12-03 | 中粮屯河股份有限公司 | Method for separating phthalate esters from seabuckthorn seed oil |
| CN104071460A (en) * | 2014-07-07 | 2014-10-01 | 扬州大学 | Method for removing plasticizer in liquid food |
| CN105572364A (en) * | 2014-10-11 | 2016-05-11 | 江苏维赛科技生物发展有限公司 | Making method and detection method of kit for detecting di-n-butyl phthalate |
| CN104560358A (en) * | 2014-12-27 | 2015-04-29 | 华南农业大学 | Removal and extraction method for low phthalic acid ester compounds in schisandra chinensis oil |
| CN111366658A (en) * | 2020-04-15 | 2020-07-03 | 广汉市迈德乐食品有限公司 | Method for rapidly detecting plasticizer in beef tallow |
| CN115389679B (en) * | 2022-09-28 | 2023-03-21 | 成都圣恩生物科技股份有限公司 | Method for detecting plasticizer in oil-containing compound seasoning |
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