CN102539551A - Method for detecting restaurant and kitchen waste oil mixed in edible vegetable oil - Google Patents
Method for detecting restaurant and kitchen waste oil mixed in edible vegetable oil Download PDFInfo
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Abstract
The invention provides a method for detecting restaurant and kitchen waste oil mixed in an edible vegetable oil. The method comprises the following step of: detecting the content of oxidized triglyceride polymer (TGP) in the edible vegetable oil. The characteristic index selected for the detection method provided by the invention has strong specificity, and the magnitude range fully represents the characteristics of restaurant and kitchen waste oil. The method is suitable for detection and judgment of all secondary oils including gutter oil, swill oil (hogwash oil) and frying oil, with high accuracy rate.
Description
Technical field
The present invention relates to the food inspection field, be specifically related to mix the detection method of edible vegetable oil Chinese meal kitchen waste oil.
Background technology
One, meal kitchen waste oil brief introduction
Meal kitchen waste oil, promptly the waste oil of broad sense mainly comprises three major types: cloaca oil (waste oil that refers to narrow sense), swill oil (hogwash fat), the old oil of frying.Cloaca oil is meant the greasy floating thing of fishing in the trench oil interceptors such as hotel, restaurant, is pitchy liquid paste, and the sour foul odour is arranged.Swill oil is meant the upper strata oil slick after leftovers, leftovers (common name swill) are collected, and is golden yellow to kermesinus through refining, and the sour flavor is arranged.Fry old oil and be meant and at high temperature be used for fried food repeatedly, bad change takes place, can not continue the grease that eats again.
Three types of meal kitchen waste oils all can be processed through refining to some extent and change its organoleptic properties and physicochemical property.
The refining processing technology of meal kitchen waste oil is simple, and the meal kitchen waste oil (water, slag, oil mixture) that generally will collect earlier heats, takes off slag, becomes coarse wool oil.Through heating and decolouring (acticarbon, carclazyte, oxydol etc.), become bleached oil again.Bleached oil passes through the high temperature deodorization again, becomes deodorised oil.
With meal kitchen waste oil is the coarse wool oil of raw material processing, and through the bleached oil and the deodorised oil of refining processing in various degree, in this patent, all is called secondary oil.Through refining processing meal kitchen waste oil; The secondary oil of deodorization particularly; Organoleptic indicators such as its color and luster, smell, flavour, and physical and chemical indexs such as acid value and peroxide value are approaching or reach country's " edible vegetable oil hygienic standard " fully (GB2716-2005), are difficult to and the differentiation of qualified edible vegetable oil.
Secondary oil is different because of waste oil source, meal kitchen, the refining processing stage is different; Essential fatty acid such as linoleic acid, leukotrienes not only; Grease such as plant sterol, tocopherol accompaniment content significantly reduces; Nutritive value significantly reduces, but also poisonous and harmful elements such as the heavy metal that residual amount does not wait, mycotoxin, Oxidation of Fat and Oils thing.After this oil is eaten, particularly long-term or a large amount of edible, unfavorable to health.
Two, blending meal kitchen waste oil in the qualified edible oil
The alleged here meal kitchen waste oil that mixes in the edible vegetable oil refers to the above-mentioned secondary oil that comes from meal kitchen waste oil.
Meal kitchen waste oil is many, and peopleware is low in simple and crude individual workship's processing, and environmental health is poor, and equipment reagent does not meet food production requirement etc.Secondary oil is compared with soybean oil, rapeseed oil, the common edible vegetable oil of corn wet goods, and raw material is cheap, processing cost is low.Therefore, the price of secondary oil is far below common soybean wet goods edible vegetable oil.Manage the lawless person of secondary oil, be with the secondary oil blending to edible vegetable oil, palm off qualified edible vegetable oil and sell.
Mix meal kitchen waste oil in the edible oil, generally directly coarse wool oil is not mixed in qualified edible oil, normally bleached oil or deodorised oil after the refining processing are sneaked in the qualified edible vegetable oil by a certain percentage, palm off qualified edible vegetable oil and sell profit.Usually be difficult to from organoleptic indicators such as color and lusters, even physical and chemical index such as acid value differentiates whether be mixed with secondary oil in the qualified edible vegetable oil, the secondary oil of the deodorization of particularly mixing.
Three, the detection technique and the deficiency of existing meal kitchen waste oil
For the detection method of meal kitchen waste oil, existing more report is lifted eight examples as follows.Existing the whole bag of tricks all exists the characteristic index selectivity not strong without exception, and perhaps detection sensitivity is not high, and perhaps detection accuracy is not high, and the detection that only can be suitable for the meal kitchen waste oil of particular type is within the specific limits judged.
Method one: conventional fat physical and chemical index method
Quality and the health national standard relevant according to present all kinds of edible vegetable oils, the multiple conventional physical and chemical index of detection grease is like acid number, peroxide value, carbonyl valency etc.If have one or more detection data not meet the mandatory provisions of national standard in these conventional physical and chemical indexs, judge that then this grease is meal kitchen waste oil.The major technique defective of present technique: the one, meal kitchen waste oil can be through refining, and the conventional physical and chemical index of each item can reach and meet fully or approaching national all kinds of quality and health national standard.The 2nd, in production and processing, storage transportation and the use of edible oil and fat, multiple different factor is arranged, can make the conventional physical and chemical index of grease not meet national standard, conventional physical and chemical index is not up to standard may not to be meal kitchen waste oil.
Method two: cholesterol level criterion
Only contain the extremely cholesterol of trace (being lower than 50PPM) in the general vegetable oil, and contain a large amount of cholesterol in the animal oil.Meal kitchen waste oil often is that the discarded edible oil and fat of multiple separate sources mix, and often contains animal fat.The major technique defective of present technique is: do not contain animal oil in the food and beverage waste oil and grease that has, as be used for the old wet goods of frying of deep fried noodles goods.This method is representative not enough, can cause erroneous judgement.And the main method of cholesterol level is a gas chromatographic technique in the present domestic detection grease, and its detection sensitivity is lower.When the meal kitchen waste oil ratio of mixing in the edible vegetable oil is less than 10%, be difficult to detect cholesterol wherein.
Method three: thin-layer chromatography detects polarity thing method
The thin-layer chromatography technology is carried out separation detection to the secondary oxidation product aldehyde of meal kitchen waste oil, ketone etc.The major technique defective of present technique is: the polar component aldehyde of meal kitchen waste oil, letones are in degree of depth refining (like the deodorization) process of grease; Can major part be removed; And the sensitivity of thin-layer chromatography technology for detection is extremely low, is inappropriate for the meal kitchen waste oil that detects degree of depth refining.
Method four: electrical conductivity method
Meal kitchen waste oil can be sneaked into a large amount of water-soluble substanceses, like flavouring such as salt, washing agent etc., and this type material electrical conductivity of water that can raise significantly, and water-soluble substances content is extremely low in the normal edible oil and fat.The major technique defective of present technique is: through degree of depth refining, can the water-soluble substances of the overwhelming majority in the waste oil of meal kitchen be removed, not be suitable for degree of depth refining meal kitchen waste oil.
Method five: the volatile ingredient of head space-gas chromatography coupling Mass Spectrometer Method grease
This method adopts head space sampling technique or headspace solid-phase microextraction sampling technique, collects the micromolecule volatile matter that meal kitchen waste oil oxidation produces, and the promoting the circulation of qi matter of going forward side by side coupling detects.The major technique defective of present technique is: through the deodorization refining, the volatile ingredient major part in the grease has all been removed, and is not suitable for degree of depth refining meal kitchen waste oil.
Method six: the relative degree of unsaturation of fatty acid (U/S value)
Natural edible vegetable oil contains the unsaturated fatty acid of high-load, therefore has than the relative degree of unsaturation of higher fatty acid (U/S value), generally between 4～6.2.Yet for saturated fatty acid, the thermal stability of unsaturated fatty acid is poor, and at high temperature the speed of its oxygenolysis is far faster than saturated fatty acid, and the U/S value of vegetable oil can constantly reduce.The major technique defective of present technique is: the U/S value of the meal kitchen waste oil of separate sources changes greatly; The U/S value of different types of vegetable oil itself changes also greatly; If at the bigger vegetable oil of U/S (like sunflower oil; U/S is about 6) in to mix a U/S be about 3 meal kitchen waste oil, even incorporation reaches 50% like this, the U/S value of final mixed oil also can reach about 4.5; And the U/S basically identical of this U/S value and normal edible peanut oil and edible blend oil just is difficult to judge.
Method seven: survey the mycotoxin method
The major technique defective is: in not all meal kitchen waste oil mycotoxin is arranged all, and just wherein a part of by the meal kitchen waste oil that mycotoxin pollutes.And, through degree of depth refining, can the mycotoxin of the overwhelming majority in the grease be removed.
Method eight: the residual method of surfactant
The major technique defective of present technique is: all have surfactant residual in not all meal kitchen waste oil.And, through degree of depth refining, can be with most surfactant residue removal in the grease.
In a word, because meal kitchen waste oil is not the changeless material of a kind of chemical composition, because of the difference of originating, refining processing stage difference, its inherent material composition can present difference more or less.Therefore, comprise above existing meal kitchen waste oil detection technique of giving an example, all fail to detect judgement that the judgement of testing result all can not be suitable for all types of meal kitchen waste oil to exclusive characteristic index and the value thereof of meal kitchen waste oil.
In theory, study and set up a perfect meal kitchen waste oil discrimination method, two keys are arranged.The first, the characteristic component of meal kitchen waste oil or the establishment of selectivity index, this index demonstrates fully the characteristic of meal kitchen waste oil, and with qualified edible vegetable oil significant difference is arranged.The second, the meal kitchen waste oil sample of research usefulness is representative.Meal kitchen waste oil sample component is changeable, no matter which kind of classification, source, refining processing stage, it is just representative all to possess its distinctive sample, in view of the above the data of research just tool be worth.
One of factor of restriction meal kitchen waste oil detection technique research is that sampling is difficult.Disguised and the underworld rule of the processing of meal kitchen waste oil and many tools of concluding the business, research institution is difficult to get the refining meal kitchen waste oil in the true sale, says nothing of the requirement of satisfying the large sample amount.Usually the researchist is the processing method of refining of simulation meal kitchen waste oil factory; Utilize breadboard condition; Meal kitchen waste oil crude oil to gathering carries out paper filtration, carclazyte or activated carbon decolorizing, washing, vacuum deodorization, makes the meal kitchen waste oil sample of experiment usefulness at different levels by oneself.Even if self-control meal kitchen waste oil sample, the statistics report of the result of study of also rare large sample amount.
The factor of another puzzlement meal kitchen waste oil detection technique research is that its component is changeable.In depth, extract the research work of the common feature and the value thereof of secondary oil, do not see breakthrough all the time the component system analysis and the statistics of the meal kitchen waste oil of the various sources of large sample and refined.Meal kitchen waste oil sample used in the research is all representative by supposition.
Therefore, just be understood that also that present existing meal kitchen waste oil detection method is only effective within the specific limits, lack extensive applicability, the problem of more or less expose erroneous judgement during application, failing to judge.
Summary of the invention
The objective of the invention is to overcome defective of the prior art, a kind of detection method of mixing edible vegetable oil Chinese meal kitchen waste oil is provided.
Qualified edible oil because of the influence of tableware, flavoring, pond, trench, storage-transport vessel, refining processing link, causes waste oil to receive heterogeneity, exogenous pollution in various degree in becoming the process of secondary oil.Comprise six kinds of main heavy metals (Pb, Cu, Fe, Zn, Mn, Cr), sodium dodecylsulphonate, cholesterol, mycotoxin etc.And the variation of physical and chemical index such as the acid value that causes because of oxidation, peroxide value, color and luster, smell.Because exogenous pollution has the variability of pollution source and the otherness of pollution level, all exogenous indexs all are difficult to become the desirable specific index of meal kitchen waste oil.And, through the also uncomfortable characteristic index of the easy physical and chemical index that improves of refining as meal kitchen waste oil.
Know-why of the present invention is following: the meal kitchen waste oil of which kind of type no matter; The old oil of cloaca oil or swill oil (hogwash fat) or frying; As secondary oil, all must experience or high temperature or air contact or rayed, so edible vegetable oil and fat is subjected to the oxidation of higher degree.As the triglyceride of edible vegetable oil and fat principal ingredient, especially undersaturated triglyceride very easily is oxidized to oxidation glyceride (principal ingredient is the oxidation triglyceride).And oxidation glyceride is under the condition of high temperature aerobic; The further polymerization reaction take place of meeting between the oxidation glyceride; Form polyglycerol ester (mainly being meant the oxidation triglyceride polymkeric substance that produces by the oxidation glyceride polymerization in the vegetable oil) (triglyceride oxidation universal law is as shown in Figure 1); The general obvious molecular weight of its molecular weight, and polyglycerol ester is in case form greater than normal triglyceride, be difficult to through come unstuck, oil and fat refining processing backs such as depickling, decolouring, deodorization remove.Its content, qualified edible vegetable oil can significantly be lower than meal kitchen waste oil.When confirming the desirable characteristic index of meal kitchen waste oil, should show great attention to the food plant main body of oil---the changes of chemical structures of triglyceride (content is about more than 95% in the GB first-grade edible oil) in oxidizing process.This variation has following characteristics: the first, endogenous is not influenced by or not the outside contamination source.The second, ubiquity, irrelevant with the classification of swill oil, cloaca oil, the old oil of frying, so long as edible vegetable oil.Therefore, probe into endogenic triglyceride has specificity and stability (being difficult to refining removes) concurrently in oxidizing process product, be expected to obtain to eat the desirable characteristic index of kitchen waste oil.
On the basis of having disclosed above-mentioned know-why, the invention discloses a kind of detection method of mixing the meal kitchen waste oil in the edible vegetable oil, comprise and detect polyglycerol ester (oxidized triglyceride polymer, content TGP) in the edible vegetable oil.
The molecular weight of oxidation glyceride generally about 700～1200 dalton (about 45～70 carbon atoms) in the said edible vegetable oil.
In the said edible vegetable oil molecular weight of polyglycerol ester general >=1500 dalton (80 more than the carbon atom).
The described meal kitchen waste oil that mixes in the edible vegetable oil is meant that all come from the secondary oil of meal kitchen waste oil; The coarse wool that mainly to comprise with cloaca oil, swill oil (hogwash fat, hogwash oil) or the old oil of frying be the raw material processing is oily, and by these coarse wool oil warp refining and meal kitchen waste oil of processing in various degree again.
Further, said detection method of mixing the meal kitchen waste oil in the edible vegetable oil also comprise detect below each or multinomial:
1) oxidation glyceride (oxidized triglyceride, content ox-TG) in the edible vegetable oil;
2) content of low carbon number (C≤14) fatty acid in the edible vegetable oil.
The content of said low carbon number (C≤14) fatty acid is meant that carbon number is not higher than the total content of 14 fatty acid.
Because the triglyceride of edible vegetable oil and fat principal ingredient, especially undersaturated triglyceride, in case oxidation forms oxidation glyceride, be difficult to through come unstuck, oil and fat refining processing backs such as depickling, decolouring, deodorization remove.Research shows, its content, qualified edible vegetable oil can significantly be lower than meal kitchen waste oil, so the content of oxidation glyceride also is suitable as the detected object that mixes edible vegetable oil Chinese meal kitchen waste oil.
Because triglyceride is through oxidation; Also degraded produces the fatty acid of low carbon number (C≤14); Be difficult for Ex-all in refining processing; As the low carbon number fatty acid total amount, meal kitchen waste oil is significantly higher than qualified edible oil, so the content of low carbon number (C≤14) fatty acid also is suitable as the detected object that mixes edible vegetable oil Chinese meal kitchen waste oil.
Best, said detection method of mixing the meal kitchen waste oil in the edible vegetable oil comprises the content separately that detects oxidation glyceride, polyglycerol ester and low carbon number (C≤14) fatty acid in the edible vegetable oil.
The core of aforementioned techniques scheme has been to disclose the application in polyglycerol ester mixes meal kitchen waste oil in detecting edible vegetable oil as characteristic index the detection method; Further, also can with in the content of oxidation glyceride, low carbon number (C≤14) fatty acid any one or multiplely be used for detecting in the detection method that edible vegetable oil mixes meal kitchen waste oil as characteristic index.The detection of mixing the meal kitchen waste oil in the edible vegetable oil is generally qualitative detection, but does not also get rid of detection by quantitative.
On the basis of preceding method; After deliberation; The present invention has confirmed to identify the method that whether is mixed with Residual oil meal kitchen waste oil in the edible vegetable oil; Whether comprise the content that detects polyglycerol ester in the edible vegetable oil more than or equal to certain specific value, the scope of the value that this is specific is the arbitrary numerical value (quality percentage composition) among the 1.0%-1.5%, as is 1.0%, 1.5%.When detecting the vegetable oil of high oil product, can adopt strict index as 1.0%, when detecting the vegetable oil of general oil product, can adopt looser index as 1.5%.
Further, the method that whether is mixed with Residual oil meal kitchen waste oil in the said evaluation edible vegetable oil also comprise detect below each or multinomial:
1) whether the quality percentage composition of low carbon number (C≤14) fatty acid is more than or equal to certain specific value in the edible vegetable oil, and this specific value is the arbitrary numerical value between 0.5%～4.5%, like 0.5% (quality percentage composition);
2) whether the quality percentage composition of oxidation glyceride is more than or equal to certain specific value in the edible vegetable oil, and this specific value is the arbitrary numerical value between 2.0%～5.0%, like 2.0% (quality percentage composition).
When aforementioned condition meets at least one, judge to be mixed with meal kitchen waste oil in the sample.
Optimum, whether be mixed with the method for meal kitchen waste oil in the said evaluation edible vegetable oil, whether comprise the content that detects polyglycerol ester in the edible vegetable oil more than or equal to certain specific value, the scope of the value that this is specific is the arbitrary numerical value among the 1.0%-1.5%; Whether the quality percentage composition of oxidation glyceride is more than or equal to certain specific value, and this specific value is the arbitrary numerical value in 2.0%～5.0%; Whether the quality percentage composition of low carbon number (C≤14) fatty acid is more than or equal to certain specific value, and this specific value is the arbitrary numerical value in 0.5%～4.5%; When aforementioned condition has one, two or three to meet, judge to be mixed with meal kitchen waste oil in the sample.
Detection to the content of polyglycerol ester in the edible vegetable oil generally comprises the following step:
1) from edible vegetable oil, separates polyglycerol ester;
2) the isolated polyglycerol ester of detection by quantitative, thus the content of polyglycerol ester in edible vegetable oil obtained.
Preferably, the content detection of polyglycerol ester can comprise the following steps: in the edible vegetable oil
1) polar component in the employing normal phase column chromatography separation and Extraction food plant oil samples.Said polar component mainly comprises polyglycerol ester and oxidation glyceride, and further, said polar component also comprises diglyceride, free fatty acid and sterol and other grease polarity accompaniment;
2) adopt the GPC technology from the polar component that step 1) obtains, to separate the also content of quantitative measurement polyglycerol ester.
Further, when adopting the polar component in the normal phase column chromatography separation and Extraction food plant oil samples, the column packing that is adopted is: silica gel, magnesium silicate or aluminium oxide; The sample dissolution liquid that is adopted is: the mixed liquor of one or more compositions in sherwood oil (being selected from 30～60 ℃ and 60～90 ℃ of boiling ranges), normal hexane, cyclohexane or the chloroform; Cleansing solution is the mixed liquor of sherwood oil and ether, and is preferable, and in the mixed liquor, the percent by volume of ether is 20%～0.5%, optimum, the number percent of ether is 13%; Eluent is: ether, tetrahydrofuran, methyl tert-butyl ether or methylene chloride; Collect eluent.
Further; During can adopting, said normal phase column chromatography presses quick preparative liquid chromatography method, among the present invention, when pressing quick preparative liquid chromatography method in the employing; Pressure control is 1～25PSI, and flow speed control is the separation preparative liquid chromatography technology of 2～60mL/min.
Further, when adopting the content of GPC (gel permeation chromatography) technology quantitative measurement oxidation glyceride from the polar component that step 1) obtains, the column packing that is adopted is: styrene-divinylbenzene crosslink gel copolymer; Moving phase is: the mixed liquor of one or more compositions in chloroform, tetrahydrofuran, dimethyl formamide, acetone, toluene, methyl tert-butyl ether, methylene chloride or the ethyl acetate.
Detection to the content of oxidation glyceride in the edible vegetable oil generally comprises the following step:
1) separation of oxygenated glyceride from edible vegetable oil;
2) the isolated oxidation glyceride of detection by quantitative, thus the content of oxidation glyceride in edible vegetable oil obtained.
Preferably, the content detection of oxidation glyceride specifically can comprise the following steps: in the edible vegetable oil
1) polar component in the employing normal phase column chromatography separation and Extraction food plant oil samples.Said polar component mainly comprises polyglycerol ester and oxidation glyceride, and further, said polar component also comprises diglyceride, free fatty acid and sterol and other grease polarity accompaniment;
2) adopt the GPC technology from the polar component that step 1) obtains, to separate the also content of quantitative measurement oxidation glyceride.
Further, when adopting the polar component in the normal phase column chromatography separation and Extraction food plant oil samples, the column packing that is adopted is: silica gel, magnesium silicate or aluminium oxide; The sample dissolution liquid that is adopted is: the mixed liquor of one or more compositions in sherwood oil, normal hexane, cyclohexane or the chloroform; Cleansing solution is the mixed liquor of sherwood oil and ether, and is preferable, and in the mixed liquor, the percent by volume of ether is 20%～0.5%, optimum, the percent by volume of ether is 13%; Eluent is: the mixed liquor of one or more compositions in ether, tetrahydrofuran, methyl tert-butyl ether or the methylene chloride; Collect eluent.Said sherwood oil is selected from the sherwood oil of 30～60 ℃ of boiling ranges and the sherwood oil of 60～90 ℃ of boiling ranges.
Further, press quick preparative liquid chromatography method during said normal phase column chromatography can adopt.
Further, when adopting the content of GPC (gel permeation chromatography) technology quantitative measurement oxidation glyceride from the polar component that step 1) obtains, the column packing that is adopted is: styrene-divinylbenzene crosslink gel copolymer; Moving phase is: the mixed liquor of one or more compositions in chloroform, tetrahydrofuran, dimethyl formamide, acetone, toluene, methyl tert-butyl ether, methylene chloride or the ethyl acetate.
Separation and detection oxidation glyceride and polyglycerol ester can carry out simultaneously.
To low carbon number in the edible vegetable oil (≤C14) mensuration of content of fatty acid can comprise the following steps:
1) glyceride hydrolysis and methyl esters are turned to free fatty acid methyl ester;
2) with capillary gas chromatography or mass-spectrometric technique different types of fatty acid methyl ester is carried out separation determination, final accumulative total draws the total content of low carbon number fatty acid methyl ester.
Low carbon number in the edible vegetable oil (≤C14) mensuration of content of fatty acid specifically can be according to national standard---and GB/T17377-2008 " gas chromatographic detection of animal and plant fat fatty acid methyl ester ", detect low carbon number (≤C14) fatty acid.
The described glyceride of step 1) refers to be present in the material with glyceride structure in the vegetable oil, mainly comprises various triglyceride and derivant thereof.
Further; In the mensuration of low carbon number in to edible vegetable oil (C≤14) content of fatty acid; Before the step 1); Adopt the polar component in the normal phase column chromatography separation and Extraction food plant oil samples like detection earlier, and after step 1) is converted into free fatty acid methyl ester with the glyceride type material in the polar component.
Utilize the separable extraction oil sample of normal phase column chromatography Semi-polarity composition.The physicochemical property of oxidation glyceride and molecular weight are close with normal triglyceride; Unique between the two significant difference is; Oxidation glyceride has certain polarity, under certain conditions, can by polar solid adsorbent (like silica gel, magnesium silicate, aluminium oxide etc.) sluggishness or absorption; And normal triglyceride polarity extremely a little less than, can not or adsorb by polar solid adsorbent institute's sluggishness.Polyglycerol ester also can by the polar solid adsorbent sluggishness or absorption, but the general obvious molecular weight of its molecular weight greater than normal triglyceride.
Adopt the GPC technology further to separate and quantitative measurement with polyglycerol ester to oxidation glyceride.Through the normal phase column chromatography of polar solid adsorbent as the solid absorption phase, oxidation glyceride, polyglycerol ester are separated with normal triglyceride and are extracted out.The polar material potpourri of separation and Extraction---oxidation glyceride and polyglycerol ester adopts efficient volume exclusion gel chromatography (GPC) technology further to separate.
The GPC technology is a kind of special high performance liquid chromatography (HPLC) technology, is that material to be detected is dissolved in the solution, injects the totally enclosed compartment analysis type chromatographic column that is filled with solid-phase adsorbent to sample solution with the mode of high pressure again.Because the chemical property of different material is different; Character, the speed of their absorption on solid-phase adsorbent and desorption are also different, and then are separated from each other different material and come, and successively elute from chromatographic column; Finally detected, and be converted into numerical information by the relevant detection device.In the GPC technology, the absorption of material to be detected on chromatographic column and the character of desorption, irrelevant with the chemical property of this material, only the molecular weight by this material determines.The molecular weight of material is big more, and is more difficult adsorbed by the GPC chromatographic column, just more early gone out the peak by wash-out.
The chemical property of oxidation glyceride and polyglycerol ester is more approaching, and the HPLC technology with general is difficult to they separation determinations.But adopt the GPC technology, because the molecular weight of polyglycerol ester is much larger than oxidation glyceride, so polyglycerol ester is very easy is separated with oxidation glyceride, and the wash-out that takes the lead in goes out the peak.Triglyceride monomer with standard is the standard quantitative material, can distinguish quantitatively according to the peak area of polyglycerol ester and oxidation glyceride.
Core of the present invention has been to disclose getting in touch between polyglycerol ester and the edible vegetable oil Chinese meal kitchen waste oil, thereby the detection of polyglycerol ester content is applied to the detection of edible vegetable oil Chinese meal kitchen waste oil.
Further, with polyglycerol ester, oxidation glyceride and low carbon number (C≤14) fatty acid characteristic index as meal kitchen waste oil, with the combination value that detects these indexs as judging the foundation that whether contains meal kitchen waste oil in the sample.Preferred authentication method of the present invention is the characteristics according to meal kitchen waste oil and refining processing back secondary oil thereof; With the characteristic index of polyglycerol ester, oxidation glyceride and low-carbon (LC) (C≤14) fatty acid as meal kitchen waste oil; Adopt normal phase column efficient volume exclusion exclusion chromatography of chromatography (GPC-ELSD/RI) and gas chromatography (GC) method, gas chromatography combined with mass spectrometry technology (GC/MS), respectively to three characteristic index detection by quantitative of meal kitchen waste oil.(A: polyglycerol ester content is more than or equal to certain specific value, and the scope of the value that this is specific is the arbitrary numerical value among the 1.0%-1.5% when having one, two or three to meet among three of the following A, B, C; B: the oxidation glyceride content is more than or equal to certain specific value, and this specific value is the arbitrary numerical value in 2.0%～5.0%; C: low carbon number (C≤14) content of fatty acid is more than or equal to certain specific value, and this specific value is the arbitrary numerical value in 0.5%～4.5%), promptly be mixed with meal kitchen waste oil in the decidable sample.This method is compared with the detection method of existing meal kitchen waste oil; The characteristic index selectivity of selecting for use is strong; The value scope demonstrates fully the characteristic of meal kitchen waste oil, is applicable to the detection and the judgement of all secondary oil that comprise cloaca oil, swill oil (hogwash fat), the old oil of frying.
Description of drawings
Fig. 1. triglyceride is oxidized to oxidation glyceride and polyglycerol ester
Fig. 2 .HPLC-GPC-RI chromatogram
Fig. 3: bleached oil processing reactive system
Embodiment
Below give an example embodiment with further elaboration the present invention, and should understand instance is not to be used to limit protection scope of the present invention.
Embodiment 1
The comparison of polyglycerol ester content in the different samples.
The polyglycerol ester content detecting method:
One), the extraction of grease polar component
Method 1) common column chromatography: accurately claim oil sample 2.5 grams (M) earlier; After dissolving fully with the sherwood oil of 30～60 ℃ of boiling ranges of 20mL; Sherwood oil with 30～60 ℃ of boiling ranges is settled to 50mL again; (internal diameter is the glass column of 21mm, long 450mm to get silica gel column chromatography on the 20mL sample solution; Interior filling 25 grams, water cut are 5% 100～200 purpose silica gel), with the cleansing solution (sherwood oil of 30～60 ℃ of boiling ranges: ether=87: 13), discard cleansing solution of 150mL with 2～2.5mL/ minute flow velocity flushing silica gel column chromatography; The ether of using 150mL again is with 2～2.5mL/ minute flow velocity eluting silica gel chromatographic column, and (quality of blank flask has been M in the flask of the 250mL that weighs of constant weight in one to collect whole ether eluents
1Gram), be not higher than under 60 ℃ the temperature, with behind the whole ether of Rotary Evaporators evaporate to dryness again constant weight weigh, the gross mass that obtains residue and flask at this moment is M
2Gram, (M
2-M
1)/M * 100% is residue---and polar component is the quality percentage composition in oil sample, uses [(M again
2-M
1) * 100] the tetrahydrofuran dissolving polar component of mL, polar component solution carries out efficient volume exclusion gel chromatography (HPLC-GPC is equipped with ELSD detecting device or RI detecting device) and detects after filtering through the nylon leaching film of 0.45um.
Method 2) press quick preparative liquid chromatography in: (internal diameter is the glass column of 30mm, long 115mm to get 2 new preparation type FLASH posts; Interior filling 20 gram particles directly are 40～60um, the amorphous silica gel of aperture for
); Up and down after the series connection; Connect in the solvent pipe of pressing quick liquid phase production purification system, with the cleansing solution (sherwood oil of 30～60 ℃ of boiling ranges: the FLASH post of ether=87: 13) connecting with 25mL/ minute flow velocity flushing balance 10～12 minutes.Claim oil sample 1.0 gram (M) then, after dissolving fully with the sherwood oil of 30～60 ℃ of boiling ranges of 5mL, the liquid inlet of injecting the FLASH post of connecting with the syringe of 10mL is again located.With the cleansing solution (sherwood oil of 30～60 ℃ of boiling ranges: ether=87: 13) with the FLASH post of 25mL/ minute flow velocity washing series connection 20 minutes; Discard cleansing solution; Again with ether with the FLASH post of 25mL/ minute flow velocity wash-out series connection 25 minutes, (quality of blank flask has been M in the flask of the 500mL that weighs of constant weight in one to collect whole ether eluents
1Gram), be not higher than under 60 ℃ the temperature, with behind the whole ether of Rotary Evaporators evaporate to dryness again constant weight weigh, the gross mass that obtains residue and flask at this moment is M
2Gram, (M
2-M
1)/M * 100% is residue---and polar component is the quality percentage composition in oil sample, uses [(M again
2-M
1) * 100] the tetrahydrofuran dissolving polar component of mL, polar component solution carries out efficient volume exclusion gel chromatography (HPLC-GPC is equipped with ELSD detecting device or RI detecting device) and detects after filtering through the nylon leaching film of 0.45um.
Two) detection of polyglycerol ester
Efficient volume exclusion gel chromatography detected parameters is following:
Chromatographic column: efficient volume exclusion gel chromatographic columns, internal diameter is 7.6mm, the stainless steel column of long 300mm, in to be filled with the aperture be that 10nm, particle diameter are high resolving power styrene-divinylbenzene crosslink gel copolymer of 5um, the twin columns coupling.Moving phase: chromatographically pure tetrahydrofuran.Flow velocity: 0.8mL/ minute.Column temperature: 35 ℃.Detecting device: (carrier gas: purity is greater than 99% nitrogen for EISD (ELSD); Gas flow rate 8mL/ minute; 90 ℃ of evaporation tube temperature) or differential refraction detector (RI) (35 ℃ of detection cell temperature).Sample size: 10ul.
Molecular weight with the triglyceride monomer of standard is reference; Analyze detecting the efficient volume exclusion gel chromatography figure that obtains, the chromatographic peak of every molecular weight overgauge triglyceride monomer molecule amount (molecular weight is about 800～900 dalton) is the chromatographic peak (except the solvent peak) of polyglycerol ester.Adopt peak area normalization quantitative technique; Promptly to account for all number percents that go out peak material total peak area be the quality percentage composition of polyglycerol ester in polar component with the peak area that goes out of polyglycerol ester chromatographic peak in the gained chromatogram; This quality percentage composition multiply by the quality percentage composition of polar component in edible vegetable oil again, can calculate the quality percentage composition that obtains polyglycerol ester in the edible vegetable oil.
By above method; Each sample carries out the detection of 5 polyglycerol ester content continuously; I.e. 5 collimation test experience; The relative standard deviation (RSD) that requires the result that these 5 collimations detect is less than 12%, and the mean value of 5 collimation testing results that meets certain sample of this condition is the final measured value of this sample.
Sample detection:
Cloaca oil: from certain restaurant's oil interceptor
Swill oil: from the hogwash in certain restaurant, separate obtaining
The old oil of frying: from the frying oil pot in certain restaurant
One, coarse wool oil sample preparation originally:
1) preparation of swill oil coarse wool oil
Elder generation puts into 40 ℃～60 ℃ constant temperature oven with swill crude oil, heats several hours, melts fully until swill crude oil to be in a liquid state.With a Buchner funnel, wherein funnel bottom is filled up last 3 layers of middling speed qualitative filter paper earlier, spreads the thick zeyssatite of one deck 0.5cm more above that, on diatomite layer, fills up 1 layer of middling speed qualitative filter paper at last again.With the mode of suction filtration, the swill crude oil to fusing filters while hot, and collects oil strain, is swill oil coarse wool oil.
2) preparation of cloaca oil coarse wool oil
Elder generation puts into 40 ℃～60 ℃ constant temperature oven with cloaca oil crude oil, heats several hours, melts fully until cloaca oil crude oil to be in a liquid state.With a Buchner funnel, wherein funnel bottom is filled up last 3 layers of middling speed qualitative filter paper earlier, spreads the thick zeyssatite of one deck 0.5cm more above that, on diatomite layer, fills up 1 layer of middling speed qualitative filter paper at last again.With the mode of suction filtration, the cloaca oil crude oil to fusing filters while hot, and collects oil strain, is cloaca oil coarse wool oil.
3) preparation of the old oily coarse wool oil of frying
To fry old oily crude oil earlier and put into 40 ℃～60 ℃ constant temperature oven, heat several hours, and melt fully and be in a liquid state until the old oily crude oil of frying.With a Buchner funnel, wherein funnel bottom is filled up last 3 layers of middling speed qualitative filter paper earlier, spreads the thick zeyssatite of one deck 0.5cm more above that, on diatomite layer, fills up 1 layer of middling speed qualitative filter paper at last again.With the mode of suction filtration, the old oily crude oil of frying to fusing filters while hot, and collects oil strain, is the old oily coarse wool oil of frying.
Two, the preparation of bleached oil sample:
1) preparation of swill oil bleached oil sample
The swill oil coarse wool oil that takes by weighing 150～300 grams is poured in 2 250mL pear shape separatory funnels in the beaker of 600mL equably, washs 2 times the distilled water of each 100mL, jolting 2～3 minutes with the distilled water jolting that is heated to 70～95 ℃.After each jolting washing, standing demix discards the washings of lower floor.The phosphate aqueous solution of preparation 0.5～5%, and be heated to 70～95 ℃.The hot phosphoric acid solution that in every separating funnel, adds 100mL, shake well be after 2～3 minutes, and standing demix discards the aqueous acid of lower floor, adds 70～95 ℃ new phosphate aqueous solution again, and pickling is 3 times so repeatedly.And then wash with 70～95 ℃ distilled water, go into the hot distilled water of 100mL at every turn, shake well is after 2～3 minutes; Standing demix; Discard the rinsing solution of lower floor, wash repeatedly 3～4 times, the pH value of using the wide pH value test paper to measure up to the lower layer of water dilution is about 4～7.Swill oil coarse wool oil after the washing is all poured in the there-necked flask of a 500mL, and the acquisition oil of weighing is heavy.After the flask sealing, the distillation condenser pipe reconnects vacuum pump in the connection, is placed on there-necked flask on the heating head of Temperature Control Type magnetic helical stir well heater again, forms an airtight reactive system (seeing shown in Figure 3).Speed with 300～800rpm/min stirs, and is heated to 50～70 ℃ to oily temperature while stirring, opens vacuum pump simultaneously, keeps the negative pressure state of entire reaction system 700～740 mm Hg.At this moment, the bubble that has a large amount of boilings in the oil produces (being water vapour), keeps heating and vacuum state, in oil, does not have tangible bubble again and produces.Close vacuum pump, remove the vacuum state of reactive system.Keeping under the state of stirring, be heated to 50～70 ℃ to swill oil coarse wool oil, in the swill oil of there-necked flask, adding the atlapulgite of oil quality 1%～5% and the acticarbon of oil quality 1%～5% then.Sealed reaction system, the open vacuum pump is kept the negative pressure state of system's 700～740 mm Hg, and stirring rate transfers to 300～800rpm/min, keeps 50～70 ℃ oil temperature, reaction 15～50 clocks.Then, swill oil coarse wool oil is heated to 75～105 ℃, continues reaction 15～50 minutes.Reaction is closed vacuum pump, condensate water, stirring and heating after finishing.Take off the there-necked flask that swill oil decolouring potpourri is housed, potpourri is wherein poured in the Buchner funnel that is lined with three metafiltration paper, carry out suction filtration.Oil strain under the suction filtration is collected in the bottle,suction of a 500mL.After for the first time suction filtration is accomplished, pour in the same Buchner funnel again the oil strain that obtains into suction filtration again and once collect oil strain in a new 500mL bottle,suction, be the decolouring swill oil.
2) preparation of cloaca oil decolorization oil samples
The cloaca oil coarse wool oil that takes by weighing 150～300 grams is poured in 2 250mL pear shape separatory funnels in the beaker of 600mL equably, washs 2 times the distilled water of each 100mL, jolting 2～3 minutes with the distilled water jolting that is heated to 70～95 ℃.After each jolting washing, standing demix discards the washings of lower floor.The phosphate aqueous solution of preparation 0.5～5%, and be heated to 70～95 ℃.The hot phosphoric acid solution that in every separating funnel, adds 100mL, shake well be after 2～3 minutes, and standing demix discards the aqueous acid of lower floor, adds 70～95 ℃ new phosphate aqueous solution again, and pickling is 3 times so repeatedly.And then wash with 70～95 ℃ distilled water, go into the hot distilled water of 100mL at every turn, shake well is after 2～3 minutes; Standing demix; Discard the rinsing solution of lower floor, wash repeatedly 3～4 times, the pH value of using the wide pH value test paper to measure up to the lower layer of water dilution is about 4～7.Cloaca after washing oil coarse wool oil is all poured in the there-necked flask of a 500mL, and the acquisition oil of weighing is heavy.After the flask sealing, the distillation condenser pipe reconnects vacuum pump in the connection, is placed on there-necked flask on the heating head of Temperature Control Type magnetic helical stir well heater again, forms an airtight reactive system (seeing shown in Figure 3).Speed with 300～800rpm/min stirs, and is heated to 50～70 ℃ to oily temperature while stirring, opens vacuum pump simultaneously, keeps the negative pressure state of entire reaction system 700～740 mm Hg.At this moment, the bubble that has a large amount of boilings in the oil produces (being water vapour), keeps heating and vacuum state, in oil, does not have tangible bubble again and produces.Close vacuum pump, remove the vacuum state of reactive system.Keeping under the state of stirring, be heated to 50～70 ℃ to cloaca oil coarse wool oil, in the oil coarse wool oil of the cloaca of there-necked flask, adding the atlapulgite of oil quality 1%～5% and the acticarbon of oil quality 1%～5% then.Sealed reaction system, the open vacuum pump is kept the negative pressure state of system's 700～740 mm Hg, and stirring rate transfers to 300～800rpm/min, keeps 50～70 ℃ oil temperature, reaction 15～50 clocks.Then, cloaca oil coarse wool oil is heated to 75～105 ℃, continues reaction 15～50 minutes.Reaction is closed vacuum pump, condensate water, stirring and heating after finishing.Take off the there-necked flask that cloaca oil decolorization potpourri is housed, potpourri is wherein poured in the Buchner funnel that is lined with three metafiltration paper, carry out suction filtration.Oil strain under the suction filtration is collected in the bottle,suction of a 500mL.After for the first time suction filtration is accomplished, pour in the same Buchner funnel again the oil strain that obtains into suction filtration again and once collect oil strain in a new 500mL bottle,suction, be decolouring cloaca oil.
3) preparation of the old oil decolorization oil samples of frying
The old oily coarse wool oil of frying that takes by weighing 150～300 grams is poured in 2 250mL pear shape separatory funnels in the beaker of 600mL equably, washs 2 times the distilled water of each 100mL, jolting 2～3 minutes with the distilled water jolting that is heated to 70～95 ℃.After each jolting washing, standing demix discards the washings of lower floor.The phosphate aqueous solution of preparation 0.5～5%, and be heated to 70～95 ℃.The hot phosphoric acid solution that in every separating funnel, adds 100mL; Behind the shake well 2～3 minutes, standing demix, emulsion layer may occur at top layer oil reservoir and bottom sour water interlayer this moment; Discard the sour water layer and close emulsion layer; The oil reservoir that keeps top layer as far as possible adds 70～95 ℃ new phosphate aqueous solution again, and pickling is 3 times so repeatedly.And then wash with 70～95 ℃ distilled water, go into the hot distilled water of 100mL at every turn, shake well is after 2～3 minutes; Standing demix; Discard the rinsing solution of lower floor, wash repeatedly 3～4 times, the pH value of using the wide pH value test paper to measure up to the lower layer of water dilution is about 4～7.The old oily coarse wool oil of frying after the washing is all poured in the there-necked flask of a 500mL, and the acquisition oil of weighing is heavy.After the flask sealing, the distillation condenser pipe reconnects vacuum pump in the connection, is placed on there-necked flask on the heating head of Temperature Control Type magnetic helical stir well heater again, forms an airtight reactive system (seeing shown in Figure 3).Speed with 300～800rpm/min stirs, and is heated to 50～70 ℃ to oily temperature while stirring, opens vacuum pump simultaneously, keeps the negative pressure state of entire reaction system 700～740 mm Hg.At this moment, the bubble that has a large amount of boilings in the oil produces (being water vapour), keeps heating and vacuum state, in oil, does not have tangible bubble again and produces.Close vacuum pump, remove the vacuum state of reactive system.Keeping under the state of stirring, be heated to 50～70 ℃ to the old oily coarse wool oil of frying, in the old oily coarse wool oil of the frying of there-necked flask, adding the atlapulgite of oil quality 1%～5% and the acticarbon of oil quality 1%～5% then.Sealed reaction system, the open vacuum pump is kept the negative pressure state of system's 700～740 mm Hg, and stirring rate transfers to 300～800rpm/min, keeps 50～70 ℃ oil temperature, reaction 15～50 clocks.Then, will fry old oily coarse wool oil and be heated to 75～105 ℃, continue reaction 15～50 minutes.Reaction is closed vacuum pump, condensate water, stirring and heating after finishing.Take off the there-necked flask that the old oil decolorization potpourri of frying is housed, potpourri is wherein poured in the Buchner funnel that is lined with three metafiltration paper, carry out suction filtration.Oil strain under the suction filtration is collected in the bottle,suction of a 500mL.After for the first time suction filtration is accomplished, pour in the same Buchner funnel again the oil strain that obtains into suction filtration again and once collect oil strain in a new 500mL bottle,suction, being the old oil of decolouring frying.
Three, the preparation of deodorised oil sample
1) preparation of swill oil deodorised oil sample
The decolouring swill oil is poured in the new 500mL there-necked flask, and flask is put into the Temperature Control Type heating jacket.After the flask sealing, the distillation condenser pipe reconnects vacuum pump in the connection, forms airtight reactive system.Open vacuum pump and condensate water, keep the negative pressure state of system's 700～740 mm Hg.Open heating jacket then,, keep vacuum state, reacted 2～5 hours oily temperature rise to 170～250 ℃.After reaction finishes, there-necked flask is taken out from heating jacket, be cooled to room temperature after, close vacuum pump and condensate water, promptly obtain the deodorization swill oil.
2) preparation of cloaca oil deodorised oil sample
Decolouring cloaca oil is poured in the new 500mL there-necked flask, and flask is put into the Temperature Control Type heating jacket.After the flask sealing, the distillation condenser pipe reconnects vacuum pump in the connection, forms airtight reactive system.Open vacuum pump and condensate water, keep the negative pressure state of system's 700～740 mm Hg.Open heating jacket then,, keep vacuum state, reacted 2～5 hours oily temperature rise to 170～250 ℃.After reaction finishes, there-necked flask is taken out from heating jacket, be cooled to room temperature after, close vacuum pump and condensate water, promptly obtain deodorization cloaca oil.
3) preparation of the old oily deodorised oil sample of frying
The old oil of decolouring frying is poured in the new 500mL there-necked flask, and flask is put into the Temperature Control Type heating jacket.After the flask sealing, the distillation condenser pipe reconnects vacuum pump in the connection, forms airtight reactive system.Open vacuum pump and condensate water, keep the negative pressure state of system's 700～740 mm Hg.Open heating jacket then,, keep vacuum state, reacted 2～5 hours oily temperature rise to 170～250 ℃.After reaction finishes, there-necked flask is taken out from heating jacket, be cooled to room temperature after, close vacuum pump and condensate water, promptly obtain the old oil of deodorization frying.
Sample and testing result:
| The content of polyglycerol ester (%) | |
| The coarse wool oil of cloaca oil preparation | 14.5 |
| The bleached oil of cloaca oil preparation | 17.3 |
| The deodorised oil of cloaca oil preparation | 22.1 |
| The coarse wool oil of swill oil preparation | 14.0 |
| The bleached oil of swill oil preparation | 15.6 |
| The deodorised oil of swill oil preparation | 18.8 |
| The coarse wool oil of the old oil preparation of frying | 15.9 |
| The bleached oil of the old oil preparation of frying | 18.2 |
| The deodorised oil of the old oil preparation of frying | 24.4 |
| The GB one-level leaches soybean oil | 1.1 |
| GB one-level squeezing corn oil | 1.0 |
| GB one-level squeezing rapeseed oil | 1.0 |
| GB one-level squeezing peanut oil | 0.9 |
| GB one-level squeezing sunflower oil | 1.2 |
Interpretation of result:
Therefore; No matter be the secondary oil in which kind of source; The content of its polyglycerol ester is all far above the content in the edible vegetable oil, and the content of polyglycerol ester is lower than 1.5% in the edible vegetable oil, and the content of polyglycerol ester far surpasses 1.5% in the secondary oil; With the content of polyglycerol ester is 1.5% as detecting index, can detect meal kitchen waste oil.For more high-quality oil, the content of polyglycerol ester can lower (being lower than 1.0%) in the edible vegetable oil, therefore, under the strict situation, also can be 1.0% as detecting index with the content of polyglycerol ester.
Embodiment 2
The comparison of oxidation glyceride content in the different samples.
The detection method of oxidation glyceride content:
One), the extraction of grease polar component
Method 1) common column chromatography: accurately claim oil sample 2.5 grams (M) earlier; After dissolving fully with the sherwood oil of 30～60 ℃ of boiling ranges of 20mL; Sherwood oil with 30～60 ℃ of boiling ranges is settled to 50mL again; (internal diameter is the glass column of 21mm, long 450mm to get silica gel column chromatography on the 20mL sample solution; Interior filling 25 grams, water cut are 5% 100～200 purpose silica gel), with the cleansing solution (sherwood oil of 30～60 ℃ of boiling ranges: ether=87: 13), discard cleansing solution of 150mL with 2～2.5mL/ minute flow velocity flushing silica gel column chromatography; The ether of using 150mL again is with 2～2.5mL/ minute flow velocity eluting silica gel chromatographic column, and (quality of blank flask has been M in the flask of the 250mL that weighs of constant weight in one to collect whole ether eluents
1Gram), be not higher than under 60 ℃ the temperature, with behind the whole ether of Rotary Evaporators evaporate to dryness again constant weight weigh, the gross mass that obtains residue and flask at this moment is M
2Gram, (M
2-M
1)/M * 100% is residue---and polar component is the quality percentage composition in oil sample, uses [(M again
2-M
1) * 100] the tetrahydrofuran dissolving polar component of mL, polar component solution carries out efficient volume exclusion gel chromatography (HPLC-GPC is equipped with ELSD detecting device or RI detecting device) and detects after filtering through the nylon leaching film of 0.45um.
Method 2) press quick preparative liquid chromatography in: (internal diameter is the glass column of 30mm, long 115mm to get 2 new preparation type FLASH posts; Interior filling 20 gram particles directly are 40～60um, the amorphous silica gel of aperture for
); Up and down after the series connection; Connect in the solvent pipe of pressing quick liquid phase production purification system, with the cleansing solution (sherwood oil of 30～60 ℃ of boiling ranges: the FLASH post of ether=87: 13) connecting with 25mL/ minute flow velocity flushing balance 10～12 minutes.Claim oil sample 1.0 gram (M) then, after dissolving fully with the sherwood oil of 30～60 ℃ of boiling ranges of 5mL, the liquid inlet of injecting the FLASH post of connecting with the syringe of 10mL is again located.With the cleansing solution (sherwood oil of 30～60 ℃ of boiling ranges: ether=87: 13) with the FLASH post of 25mL/ minute flow velocity washing series connection 20 minutes; Discard cleansing solution; Again with ether with the FLASH post of 25mL/ minute flow velocity wash-out series connection 25 minutes, (quality of blank flask has been M in the flask of the 500mL that weighs of constant weight in one to collect whole ether eluents
1Gram), be not higher than under 60 ℃ the temperature, with behind the whole ether of Rotary Evaporators evaporate to dryness again constant weight weigh, the gross mass that obtains residue and flask at this moment is M
2Gram, (M
2-M
1)/M * 100% is residue---and polar component is the quality percentage composition in oil sample, uses [(M again
2-M
1) * 100] the tetrahydrofuran dissolving polar component of mL, polar component solution carries out efficient volume exclusion gel chromatography (HPLC-GPC is equipped with ELSD detecting device or RI detecting device) and detects after filtering through the nylon leaching film of 0.45um.
Efficient volume exclusion gel chromatography detected parameters is following:
Chromatographic column: efficient volume exclusion gel chromatographic columns, internal diameter is 7.6mm, the stainless steel column of long 300mm, in to be filled with the aperture be that 10nm, particle diameter are high resolving power styrene-divinylbenzene crosslink gel copolymer of 5um, the twin columns coupling.Moving phase: chromatographically pure tetrahydrofuran.Flow velocity: 0.8mL/ minute.Column temperature: 35 ℃.Detecting device: (carrier gas: purity is greater than 99% nitrogen for EISD (ELSD); Gas flow rate 8mL/ minute; 90 ℃ of evaporation tube temperature) or differential refraction detector (RI) (35 ℃ of detection cell temperature).Sample size: 10ul.
Molecular weight with the triglyceride monomer of standard is reference; Efficient volume exclusion gel chromatography figure to detect obtaining analyzes, and every molecular weight is equivalent to or the chromatographic peak that approaches standard triglyceride monomer molecule amount (molecular weight is about 800～900 dalton) is the chromatographic peak of oxidation glyceride.Adopt peak area normalization quantitative technique; Promptly to account for all number percents that go out peak material total peak area be the quality percentage composition of oxidation glyceride in polar component with the peak area that goes out of oxidation glyceride chromatographic peak in the gained chromatogram; This quality percentage composition multiply by the quality percentage composition of polar component in edible vegetable oil again, can calculate the quality percentage composition that obtains oxidation glyceride in the edible vegetable oil.
By above method; Each sample carries out the detection of 5 oxidation glyceride contents continuously; I.e. 5 collimation test experience; The relative standard deviation (RSD) that requires the result that these 5 collimations detect is less than 12%, and the mean value of 5 collimation testing results that meets certain sample of this condition is the final measured value of this sample.
Sample detection:
The preparation of coarse wool oil, bleached oil, deodorised oil sample is with embodiment 1.
Sample and testing result:
| The content of oxidation glyceride (%) | |
| The coarse wool oil of cloaca oil preparation | 52.3 |
| The bleached oil of cloaca oil preparation | 39.9 |
| The deodorised oil of cloaca oil preparation | 29.2 |
| The coarse wool oil of swill oil preparation | 34.4 |
| The bleached oil of swill oil preparation | 25.5 |
| The deodorised oil of swill oil preparation | 19.7 |
| The coarse wool oil of the old oil preparation of frying | 36.2 |
| The bleached oil of the old oil preparation of frying | 25.9 |
| The deodorised oil of the old oil preparation of frying | 20.0 |
| The GB one-level leaches soybean oil | 1.6 |
| GB one-level squeezing corn oil | 1.4 |
| GB one-level squeezing rapeseed oil | 1.3 |
| GB one-level squeezing peanut oil | 1.5 |
| GB one-level squeezing sunflower oil | 1.6 |
Interpretation of result:
Therefore, no matter be the secondary oil in which kind of source, the content of its oxidation glyceride is all far above the content in the edible vegetable oil; And after the processing; Oxidation glyceride is not removed, and the content of oxidation glyceride all is lower than 2.0% in the edible vegetable oil, and the content of oxidation glyceride far surpasses 2.0% in the secondary oil; With the content of oxidation glyceride is 2.0% as detecting index, can detect meal kitchen waste oil.
Embodiment 3
Low carbon number (≤C14) the comparison of content of fatty acid in the different samples.
Low carbon number (≤C14) detection method of content of fatty acid:
One), the extraction of grease polar component
Method 1) common column chromatography: accurately claim oil sample 2.5 grams (M) earlier; After dissolving fully with the sherwood oil of 30～60 ℃ of boiling ranges of 20mL; Sherwood oil with 30～60 ℃ of boiling ranges is settled to 50mL again; (internal diameter is the glass column of 21mm, long 450mm to get silica gel column chromatography on the 20mL sample solution; Interior filling 25 grams, water cut are 5% 100～200 purpose silica gel), with the cleansing solution (sherwood oil of 30～60 ℃ of boiling ranges: ether=87: 13), discard cleansing solution of 150mL with 2～2.5mL/ minute flow velocity flushing silica gel column chromatography; The ether of using 150mL again is with 2～2.5mL/ minute flow velocity eluting silica gel chromatographic column, and (quality of blank flask has been M in the flask of the 250mL that weighs of constant weight in one to collect whole ether eluents
1Gram), be not higher than under 60 ℃ the temperature, with behind the whole ether of Rotary Evaporators evaporate to dryness again constant weight weigh, the gross mass that obtains residue and flask at this moment is M
2Gram, (M
2-M
1)/M * 100% is residue---and polar component is the quality percentage composition in oil sample.
Method 2) press quick preparative liquid chromatography in: (internal diameter is the glass column of 30mm, long 115mm to get 2 new preparation type FLASH posts; Interior filling 20 gram particles directly are 40～60um, the amorphous silica gel of aperture for
); Up and down after the series connection; Connect in the solvent pipe of pressing quick liquid phase production purification system, with the cleansing solution (sherwood oil of 30～60 ℃ of boiling ranges: the FLASH post of ether=87: 13) connecting with 25mL/ minute flow velocity flushing balance 10～12 minutes.Claim oil sample 1.0 gram (M) then, after dissolving fully with the sherwood oil of 30～60 ℃ of boiling ranges of 5mL, the liquid inlet of injecting the FLASH post of connecting with the syringe of 10mL is again located.With the cleansing solution (sherwood oil of 30～60 ℃ of boiling ranges: ether=87: 13) with the FLASH post of 25mL/ minute flow velocity washing series connection 20 minutes; Discard cleansing solution; Again with ether with the FLASH post of 25mL/ minute flow velocity wash-out series connection 25 minutes, (quality of blank flask has been M in the flask of the 500mL that weighs of constant weight in one to collect whole ether eluents
1Gram), be not higher than under 60 ℃ the temperature, with behind the whole ether of Rotary Evaporators evaporate to dryness again constant weight weigh, the gross mass that obtains residue and flask at this moment is M
2Gram, (M
2-M
1)/M * 100% is residue---and polar component is the quality percentage composition in oil sample.
Two), the detection of the esterification of polar component and low carbon number fatty acid
Get the polar component about 0.2 gram earlier; Method according to GB/T 17376-2008 " preparation of animal and plant fat fatty acid methyl ester " is carried out esterification to oil sample; Obtain the esterification polarity grease of this oil sample, by the method for GB/T 17377-2008 " gas chromatographic detection of animal and plant fat fatty acid methyl ester " fatty acid of esterification grease is formed again and measured.Finally with the peak area normalization method to low carbon number (≤C14) total percentage composition of fatty acid carries out quantitatively; The (≤C14) percentage composition in polar component of fatty acid of low carbon number in the oil sample; Again this percentage composition multiply by polar component quality percentage composition in oil sample, get final product the low carbon number (≤C14) percentage composition of fatty acid in oil sample.
By above method; Each sample carries out 5 low carbon number (≤C14) detections of content of fatty acid continuously; I.e. 5 collimation test experience; The relative standard deviation (RSD) that requires the result that these 5 collimations detect is less than 12%, and the mean value of 5 collimation testing results that meets certain sample of this condition is the final measured value of this sample.
Sample detection:
The preparation of coarse wool oil, bleached oil, deodorised oil sample is with embodiment 1.
Sample and testing result:
| Low carbon number (<=C14) the content of fatty acid (%) | |
| The coarse wool oil of cloaca oil preparation | ?10.7 |
| The bleached oil of cloaca oil preparation | ?13.3 |
| The deodorised oil of cloaca oil preparation | ?10.8 |
| The coarse wool oil of swill oil preparation | ?9.6 |
| The bleached oil of swill oil preparation | ?10.8 |
| The deodorised oil of swill oil preparation | ?9.8 |
| The coarse wool oil of the old oil preparation of frying | ?9.9 |
| The bleached oil of the old oil preparation of frying | ?12.9 |
| The deodorised oil of the old oil preparation of frying | ?10.2 |
| The GB one-level leaches soybean oil | ?0.1 |
| GB one-level squeezing corn oil | ?0.3 |
| GB one-level squeezing rapeseed oil | ?0.1 |
| GB one-level squeezing peanut oil | ?0.1 |
| GB one-level squeezing sunflower oil | ?0.1 |
| The GB one-level leaches big | The bleached oil (%) of swill oil preparation | Low carbon number (<=C14) fatty acid |
| Soya-bean oil (%) | Content (%) | ||
| Sample 1 | 100％ | 0 | 0.1 |
| Sample 2 | 95 | 5 | 0.6 |
| Sample 3 | 90 | 10 | 1.1 |
| Sample 4 | 80 | 20 | 2.3 |
| Sample 5 | 60 | 40 | 4.3 |
| Sample 6 | 40 | 60 | 6.4 |
| Sample 7 | 0 | 100％ | 10.8 |
Interpretation of result:
Therefore; No matter be the secondary oil in which kind of source; Its low carbon number (≤C14) content of fatty acid is far above the content in the edible vegetable oil, low carbon number in the edible vegetable oil (≤C14) content of the content of fatty acid is lower than 0.5%, and low carbon number in the secondary oil (≤C14) content of the content of fatty acid far surpasses 0.5%; With low carbon number (≤C14) content of fatty acid is 0.5% as detecting index, can detect meal kitchen waste oil.
Embodiment 4
Pattern detection
Sample source: from the frying oil pot in certain restaurant
Detection method:
The first step: the detection by quantitative of polyglycerol ester and oxidation glyceride in the sample
One), the extraction of grease polar component
Method 1) common column chromatography: accurately claim oil sample 2.5 grams (M) earlier; After dissolving fully with the sherwood oil of 30～60 ℃ of boiling ranges of 20mL; Sherwood oil with 30～60 ℃ of boiling ranges is settled to 50mL again; (internal diameter is the glass column of 21mm, long 450mm to get silica gel column chromatography on the 20mL sample solution; Interior filling 25 grams, water cut are 5% 100～500 purpose silica gel), with the cleansing solution (sherwood oil of 30～60 ℃ of boiling ranges: ether=87: 13), discard cleansing solution of 150mL with 2～2.5mL/ minute flow velocity flushing silica gel column chromatography; The ether of using 150mL again is with 2～2.5mL/ minute flow velocity eluting silica gel chromatographic column, and (quality of blank flask has been M in the flask of the 250mL that weighs of constant weight in one to collect whole ether eluents
1Gram), be not higher than under 60 ℃ the temperature, with behind the whole ether of Rotary Evaporators evaporate to dryness again constant weight weigh, the gross mass that obtains residue and flask at this moment is M
2Gram, (M
2-M
1)/M * 100% is residue---and polar component is the quality percentage composition in oil sample, uses [(M again
2-M
1) * 100] the tetrahydrofuran dissolving polar component of mL, polar component solution carries out efficient volume exclusion gel chromatography (HPLC-GPC is equipped with ELSD detecting device or RI detecting device) and detects after filtering through the nylon leaching film of 0.45um.
Method 2) press quick preparative liquid chromatography in: (internal diameter is the FLASH post of 30mm, long 115mm to get 2 new preparation type FLASH posts; Interior filling 20 gram particles directly are 40～60um, the amorphous silica gel of aperture for
); Up and down after the series connection; Connect in the solvent pipe of pressing quick liquid phase production purification system, with the cleansing solution (sherwood oil of 30～60 ℃ of boiling ranges: the FLASH post of ether=87: 13) connecting with 25mL/ minute flow velocity flushing balance 10～12 minutes.Claim oil sample 1.0 gram (M) then, after dissolving fully with the sherwood oil of 30～60 ℃ of boiling ranges of 5mL, the liquid inlet of injecting the FLASH post of connecting with the syringe of 10mL is again located.With the cleansing solution (sherwood oil of 30～60 ℃ of boiling ranges: ether=87: 13) with the FLASH post of 25mL/ minute flow velocity washing series connection 20 minutes; Discard cleansing solution; Again with ether with the FLASH post of 25mL/ minute flow velocity wash-out series connection 25 minutes, (quality of blank flask has been M in the flask of the 500mL that weighs of constant weight in one to collect whole ether eluents
1Gram), be not higher than under 60 ℃ the temperature, with behind the whole ether of Rotary Evaporators evaporate to dryness again constant weight weigh, the gross mass that obtains residue and flask at this moment is M
2Gram, (M
2-M
1)/M * 100% is residue---and polar component is the quality percentage composition in oil sample, uses [(M again
2-M
1) * 100] the tetrahydrofuran dissolving polar component of mL, polar component solution carries out efficient volume exclusion gel chromatography (HPLC-GPC is equipped with ELSD detecting device or RI detecting device) and detects after filtering through the nylon leaching film of 0.45um.
Two) detection of polyglycerol ester and oxidation glyceride
Efficient volume exclusion gel chromatography detected parameters is following:
Chromatographic column: efficient volume exclusion gel chromatographic columns, internal diameter is 7.6mm, the stainless steel column of long 300mm, in to be filled with the aperture be that 10nm, particle diameter are high resolving power styrene-divinylbenzene crosslink gel copolymer of 5um, the twin columns coupling.Moving phase: chromatographically pure tetrahydrofuran.Flow velocity: 0.8mL/ minute.Column temperature: 35 ℃.Detecting device: (carrier gas: purity is greater than 99% nitrogen for EISD (ELSD); Gas flow rate 8mL/ minute; 90 ℃ of evaporation tube temperature) or differential refraction detector (RI).Sample size: 10～20ul.
Molecular weight with the triglyceride monomer of standard is reference; Analyze detecting the efficient volume exclusion gel chromatography figure that obtains, the chromatographic peak of every molecular weight overgauge triglyceride monomer molecule amount (molecular weight is about 800～900 dalton) is the chromatographic peak (except the solvent peak) of polyglycerol ester; Every molecular weight is equivalent to or the chromatographic peak that approaches standard triglyceride monomer molecule amount (molecular weight is about 800～900 dalton) is the chromatographic peak of oxidation glyceride.Adopt peak area normalization quantitative technique at last; Promptly to account for all number percents that go out peak material total peak area be the quality percentage composition of polyglycerol ester in polar component with the peak area that goes out of polyglycerol ester chromatographic peak in the gained chromatogram; This quality percentage composition multiply by the quality percentage composition of polar component in edible vegetable oil again, can calculate the quality percentage composition that obtains polyglycerol ester in the edible vegetable oil.Same; To account for all number percents that go out peak material total peak area be the quality percentage composition of oxidation glyceride in polar component with the peak area that goes out of oxidation glyceride chromatographic peak in the gained chromatogram; This quality percentage composition multiply by the quality percentage composition of polar component in edible vegetable oil again, can calculate the quality percentage composition that obtains oxidation glyceride in the edible vegetable oil.The content that last quantitative Analysis goes out polyglycerol ester is 13.3%; The content of oxidation glyceride is 6.2%.As shown in Figure 2.
Second step: the (≤C14) detection of fatty acid of low carbon number in the sample
One), the extraction of grease polar component
Method 1) common column chromatography: accurately claim oil sample 2.5 grams (M) earlier; After dissolving fully with the sherwood oil of 30～60 ℃ of boiling ranges of 20mL; Sherwood oil with 30～60 ℃ of boiling ranges is settled to 50mL again; (internal diameter is the glass column of 21mm, long 450mm to get silica gel column chromatography on the 20mL sample solution; Interior filling 25 grams, water cut are 5% 100～200 purpose silica gel), with the cleansing solution (sherwood oil of 30～60 ℃ of boiling ranges: ether=87: 13), discard cleansing solution of 150mL with 2～2.5mL/ minute flow velocity flushing silica gel column chromatography; The ether of using 150mL again is with 2～2.5mL/ minute flow velocity eluting silica gel chromatographic column, and (quality of blank flask has been M in the flask of the 250mL that weighs of constant weight in one to collect whole ether eluents
1Gram), be not higher than under 60 ℃ the temperature, with behind the whole ether of Rotary Evaporators evaporate to dryness again constant weight weigh, the gross mass that obtains residue and flask at this moment is M
2Gram, (M
2-M
1)/M * 100% is residue---and polar component is the quality percentage composition in oil sample.
Method 2) press quick preparative liquid chromatography in: (internal diameter is the glass column of 30mm, long 115mm to get 2 new preparation type FLASH posts; Interior filling 20 gram particles directly are 40～60um, the amorphous silica gel of aperture for
); Up and down after the series connection; Connect in the solvent pipe of pressing quick liquid phase production purification system, with the cleansing solution (sherwood oil of 30～60 ℃ of boiling ranges: the FLASH post of ether=87: 13) connecting with 25mL/ minute flow velocity flushing balance 10～12 minutes.Claim oil sample 1.0 gram (M) then, after dissolving fully with the sherwood oil of 30～60 ℃ of boiling ranges of 5mL, the liquid inlet of injecting the FLASH post of connecting with the syringe of 10mL is again located.With the cleansing solution (sherwood oil of 30～60 ℃ of boiling ranges: ether=87: 13) with the FLASH post of 25mL/ minute flow velocity washing series connection 20 minutes; Discard cleansing solution; Again with ether with the FLASH post of 25mL/ minute flow velocity wash-out series connection 25 minutes, (quality of blank flask has been M in the flask of the 500mL that weighs of constant weight in one to collect whole ether eluents
1Gram), be not higher than under 60 ℃ the temperature, with behind the whole ether of Rotary Evaporators evaporate to dryness again constant weight weigh, the gross mass that obtains residue and flask at this moment is M
2Gram, (M
2-M
1)/M * 100% is residue---and polar component is the quality percentage composition in oil sample.
Two), the detection of the esterification of polar component and low carbon number fatty acid
Get the polar component about 0.2 gram earlier; Method according to GB/T 17376-2008 " preparation of animal and plant fat fatty acid methyl ester " is carried out esterification to oil sample; Obtain the esterification polarity grease of this oil sample, by the method for GB/T 17377-2008 " gas chromatographic detection of animal and plant fat fatty acid methyl ester " fatty acid of esterification grease is formed again and measured.Finally with the peak area normalization method to low carbon number (≤C14) total percentage composition of fatty acid carries out quantitatively; Low carbon number in the oil sample (≤C14) percentage composition in polar component of fatty acid multiply by polar component quality percentage composition in oil sample with this percentage composition again.Get final product low carbon number (≤C14) percentage composition of fatty acid in oil sample is 2.5%.
The 3rd step: the result judges
A, polyglycerol ester content: 6.2% >=1.5%
B, oxidation glyceride content: 13.3% >=2.0%
C, low carbon number (≤C14) content of fatty acid: 2.5%>=0.5%
Because the A of oil sample to be detected, B, C index all above index, are mixed with meal kitchen waste oil so judge this oil sample.
Claims (19)
1. a detection method of mixing the meal kitchen waste oil in the edible vegetable oil comprises the content that detects polyglycerol ester in the edible vegetable oil.
2. mix the detection method of the meal kitchen waste oil in the edible vegetable oil according to claim 1, it is characterized in that, also comprise detect below each or multinomial:
1) content of oxidation glyceride in the edible vegetable oil;
2) content of low carbon number (C≤14) fatty acid in the edible vegetable oil.
3. mix the detection method of the meal kitchen waste oil in the edible vegetable oil according to claim 1, it is characterized in that,
Detection to the content of polyglycerol ester in the edible vegetable oil comprises the following steps:
1) polar component in the employing normal phase column chromatography separation and Extraction food plant oil samples;
2) adopt the GPC technology from the polar component that step 1) obtains, to separate the also content of quantitative measurement polyglycerol ester.
4. like the said detection method of mixing the meal kitchen waste oil in the edible vegetable oil of claim 2, it is characterized in that the content detection of oxidation glyceride specifically comprises the following steps: in the edible vegetable oil
1) polar component in the employing normal phase column chromatography separation and Extraction food plant oil samples;
2) adopt the GPC technology from the polar component that step 1) obtains, to separate the also content of quantitative measurement oxidation glyceride.
5. like claim 3 or 4 said detection methods of mixing the meal kitchen waste oil in the edible vegetable oil; It is characterized in that; Said employing GPC technology is separated from the polar component that step 1) obtains and during the content of quantitative measurement oxidation glyceride or polyglycerol ester, the column packing that is adopted is styrene-divinylbenzene crosslink gel copolymer; Moving phase is: the mixed liquor of one or more compositions in chloroform, tetrahydrofuran, dimethyl formamide, acetone, toluene, methyl tert-butyl ether, methylene chloride or the ethyl acetate.
6. like the said detection method of mixing the meal kitchen waste oil in the edible vegetable oil of claim 2, it is characterized in that, the mensuration of low carbon number in the edible vegetable oil (C≤14) content of fatty acid is comprised the following steps:
1) glyceride hydrolysis and methyl esters are turned to free fatty acid methyl ester;
2) with capillary gas chromatography or mass-spectrometric technique different types of fatty acid methyl ester is carried out separation determination, final accumulative total draws the total content of low carbon number fatty acid methyl ester.
7. like the said detection method of mixing the meal kitchen waste oil in the edible vegetable oil of claim 6; It is characterized in that; In the mensuration of low carbon number in to edible vegetable oil (C≤14) content of fatty acid; Before the step 1), adopt the polar component in the normal phase column chromatography separation and Extraction food plant oil samples earlier, and after step 1) is converted into free fatty acid methyl ester with the glyceride type material in the polar component.
8. like claim 3,4 or 7 said detection methods of mixing the meal kitchen waste oil in the edible vegetable oil; It is characterized in that; During polar component in the said employing normal phase column chromatography separation and Extraction food plant oil samples, the column packing that is adopted is selected from silica gel, magnesium silicate or aluminium oxide; The sample dissolution liquid that is adopted is: the mixed liquor of one or more compositions in sherwood oil, normal hexane, cyclohexane or the chloroform; Cleansing solution is the mixed liquor of sherwood oil and ether; Eluent is: the mixed liquor of one or more compositions in ether, tetrahydrofuran, methyl tert-butyl ether or the methylene chloride.
9. like the said detection method of mixing the meal kitchen waste oil in the edible vegetable oil of claim 8, it is characterized in that said normal phase column chromatography adopts common column chromatography or the quick preparative liquid chromatography method of middle pressure.
10. identify the method that whether is mixed with meal kitchen waste oil in the edible vegetable oil for one kind; Comprise that whether the quality percentage composition that detects polyglycerol ester in the edible vegetable oil is more than or equal to certain specific value; The scope of the value that this is specific is the arbitrary numerical value in 1.0%～1.5%; When testing result is eligible, judge to be mixed with meal kitchen waste oil in the sample.
11. as whether being mixed with the method for meal kitchen waste oil in the said evaluation edible vegetable oil of claim 10, it is characterized in that, also comprise detect below each or multinomial:
1) whether the quality percentage composition of low carbon number (C≤14) fatty acid is more than or equal to certain specific value in the edible vegetable oil, and this specific value is the arbitrary numerical value in 0.5%～4.5%;
2) whether the quality percentage composition of oxidation glyceride is more than or equal to certain specific value in the edible vegetable oil, and this specific value is the arbitrary numerical value in 2.0%～5.0%;
3) when at least one testing result is eligible, judge to be mixed with meal kitchen waste oil in the sample.
12. as whether being mixed with the method for meal kitchen waste oil in the said evaluation edible vegetable oil of claim 11; It is characterized in that; Comprise that whether the quality percentage composition that detects polyglycerol ester in the edible vegetable oil is more than or equal to certain specific value; The scope of the value that this is specific is the arbitrary numerical value in 1.0%～1.5%; Whether the quality percentage composition of oxidation glyceride is more than or equal to certain specific value, and this specific value is the arbitrary numerical value in 2.0%～5.0%; Whether the quality percentage composition of low carbon number (C≤14) fatty acid is more than or equal to certain specific value, and this specific value is the arbitrary numerical value in 0.5%～4.5%; When aforementioned condition meets one, two or three, judge to be mixed with meal kitchen waste oil in the sample.
13. as whether being mixed with the method for meal kitchen waste oil in the said evaluation edible vegetable oil of claim 10, it is characterized in that,
Detection to the content of polyglycerol ester in the edible vegetable oil comprises the following steps:
1) polar component in the employing normal phase column chromatography separation and Extraction food plant oil samples;
2) adopt the GPC technology from the polar component that step 1) obtains, to separate the also content of quantitative measurement polyglycerol ester.
14., it is characterized in that the content detection of oxidation glyceride specifically comprises the following steps: in the edible vegetable oil as whether being mixed with the method for meal kitchen waste oil in the said evaluation edible vegetable oil of claim 11
1) polar component in the employing normal phase column chromatography separation and Extraction food plant oil samples;
2) adopt the GPC technology from the polar component that step 1) obtains, to separate the also content of quantitative measurement oxidation glyceride.
15. as whether being mixed with the method for meal kitchen waste oil in claim 13 or the 14 said evaluation edible vegetable oils; It is characterized in that; Said employing GPC technology is separated from the polar component that step 1) obtains and during the content of quantitative measurement oxidation glyceride or polyglycerol ester, the column packing that is adopted is styrene-divinylbenzene crosslink gel copolymer; Moving phase is: the mixed liquor of one or more compositions in chloroform, tetrahydrofuran, dimethyl formamide, acetone, toluene, methyl tert-butyl ether, methylene chloride or the ethyl acetate.
16. as whether being mixed with the method for meal kitchen waste oil in the said evaluation edible vegetable oil of claim 11, it is characterized in that, to low carbon number in the edible vegetable oil (≤C14) mensuration of content of fatty acid comprises the following steps:
1) glyceride hydrolysis and methyl esters are turned to free fatty acid methyl ester;
2) with capillary gas chromatography or mass-spectrometric technique different types of fatty acid methyl ester is carried out separation determination, final accumulative total draws the total content of low carbon number fatty acid methyl ester.
17. as whether being mixed with the method for meal kitchen waste oil in the said evaluation edible vegetable oil of claim 16; It is characterized in that; In the mensuration of low carbon number in to edible vegetable oil (C≤14) content of fatty acid; Before the step 1), adopt the polar component in the normal phase column chromatography separation and Extraction food plant oil samples earlier, and after step 1) is converted into free fatty acid methyl ester with the glyceride type material in the polar component.
18. as whether being mixed with the method for meal kitchen waste oil in claim 13, the 14 or 17 said evaluation edible vegetable oils; It is characterized in that; During polar component in the said employing normal phase column chromatography separation and Extraction food plant oil samples, the column packing that is adopted is selected from silica gel, magnesium silicate or aluminium oxide; The sample dissolution liquid that is adopted is: the mixed liquor of one or more compositions in sherwood oil, normal hexane, cyclohexane or the chloroform; Cleansing solution is the mixed liquor of sherwood oil and ether; Eluent is: the mixed liquor of one or more compositions in ether, tetrahydrofuran, methyl tert-butyl ether or the methylene chloride.
19., it is characterized in that said normal phase column chromatography adopts common column chromatography or the quick preparative liquid chromatography method of middle pressure as whether being mixed with the method for meal kitchen waste oil in the said evaluation edible vegetable oil of claim 18.
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| CN103439420A (en) * | 2013-08-14 | 2013-12-11 | 广东省食品药品检验所 | Method for identifying inferior edible oil |
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| CN108872449A (en) * | 2018-09-19 | 2018-11-23 | 新疆维吾尔自治区产品质量监督检验研究院 | The measuring method of gutter oil is adulterated in edible vegetable oil |
| CN110196292A (en) * | 2019-05-16 | 2019-09-03 | 暨南大学 | A kind of method of twin columns detection grease deterioration product assay |
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