CN103033574B - Method for detecting residual solvent in subcritical propane extraction product - Google Patents
Method for detecting residual solvent in subcritical propane extraction product Download PDFInfo
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- CN103033574B CN103033574B CN201210545709.0A CN201210545709A CN103033574B CN 103033574 B CN103033574 B CN 103033574B CN 201210545709 A CN201210545709 A CN 201210545709A CN 103033574 B CN103033574 B CN 103033574B
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Abstract
The invention relates to a method for detecting a residual solvent in a subcritical propane extraction product and relates to the field of food safety detection. The method comprises the following steps: firstly, filling propane standard gas into a refined oil product without propane, of which the oil type is the same with that of oil to be measured, sufficiently stabilizing the obtained product and accurately weighing to obtain concentration of stock solution; then diluting the stock solution to prepare a series of propane standard oil solution; placing 5.00 to 100.00 g of the series of propane standard oil solution into a headspace bottle with a volume of 135 mL; carrying out stirring balancing on the propane standard oil solution for 10 to 60min at a rotating speed of 500 rpm under the condition of thermostatic water bath of 40 to 70 DEG C; taking gas on the upper layer of the propane standard oil solution by a microsyringe to carry out headspace gas chromatographic analysis; under the same conditions, measuring a peak area of residual propane in the oil sample to be measured; and according to a standard curve, obtaining content of the residual propane in the oil sample to be measured. The method has the advantages of low cost, simplicity and convenience for operation, strong specificity and the like and can be widely applied to grain and oil quality inspection and control of grease subcritical fluid processing enterprises and grain and oil detection organizations.
Description
Technical field
The present invention relates to field of detection of food safety, refer in particular to a kind of method adopting gas chromatography to detect dissolvent residual in the edible oil and fat product of Propane fluid extraction fast, the method can be grease production enterprise and Safety of Food Quality testing agency supplying method foundation.
Background technology
Subcritical fluids refers to that some compound is higher than its boiling point but lower than under the condition of critical temperature and emergent pressure, the material existed with fluid form.Subcritical fluid extraction technology is then for solvent with subcritical fluids or its mixed solution, a kind of new technology of target components is extracted from natural products, be particularly suitable for the extraction of volatile oil in natural products, grease or liposoluble constituent, the change technology there is normal temperature leaching, low temperature desolventizing, do not destroy the outstanding advantage of heat-sensitive ingredients, be an environmental protection, having a extensive future.
The subcritical fluids being usually used in valuable grease production or effective components from natural materials extraction comprises: propane, butane, liquefied petroleum gas (LPG) (LPG), high-purity isobutane (R600a), 1,1,1,2-HFC-134a (R134a), dimethyl ether (DME) and sulfur hexafluoride etc., be wherein most widely used with propane, butane, LPG.The Ministry of Public Health of China includes propane in food processing aid catalogue in 2008, but has hypotoxicity due to it to nerve system of human body, so, be a food-safety problem that can not be ignored with dissolvent residual in the product of Propane extraction.
At present, Propane extraction grease in propane residue detection there is no unified national standard.Due to not enough to its attention degree, so far the research of the detection method about propane in grease is not had, and mensuration being most widely used with headspace gas chromatography of dissolvent residual in the vegetable oil products of conventional solvent extraction, GB5009.37-2003 just adopts this method to detect the residual quantity of No. six solvents.But because be gaseous state under propane normal temperature and pressure, and normal hexane is in a liquid state, and in contrast, it can not dissolve each other preferably with grease, makes the standard oil solution accurately cannot preparing propane, thus hinders the quantitative detection of residual propane in grease.
The people such as Xu Yun report the method with the propane in infrared spectrophotometer and Headspace-Gas Chromatography Analysis wastewater measurement, butane.Although this method determines the content of propane in waste water, butane.But researchist is not mixed with standard items by soluble in water for propane, but directly with the Standard Gases sample introduction of variable concentrations, the matrix of standard items and testing sample is inconsistent, causes the inaccurate of measurement, matrix simultaneously containing propane compared with grease is different, because the method is inadvisable.
For this reason, two key technical problems must be solved: first when adopting headspace gas chromatography to detect dissolvent residual in Propane extracted products, when preparation standard solution, propane can dissolve each other well with matrix oil, accurately could obtain variable concentrations (series) propane solution; Secondly, the matrix of standard solution must be consistent with the matrix of testing sample, and like this, the concentration that both balance rear headspace gas just has comparability.
In order to solve above-mentioned two key technical problems, propane calibrating gas first passes in the matrix oil (not containing propane) same with oil phase to be measured by the present invention, make it be fully absorbed, then above-mentioned propane solution is carried out uncovered be placed to stable, diluted again, thus preparation obtains a series of propane standard oil solution.
Summary of the invention
The present invention solves the technical scheme that its detection technique adopts: take not containing the product oil of propane, propane is passed in this product oil, stop after a period of time passing into propane gas, weigh the quality of product oil after a period of stabilisation, obtain the concentration of propane in this oil; Then a certain amount of above-mentioned propane solution product oil is diluted, to prepare the propane oil solution of a series of concentration, under being placed in ml headspace bottle uniform temperature, balance a period of time, get head space gases in bottle and carry out head space gas chromatography, record peak area, drawing standard curve; Again by the testing sample of identical amount, under the same conditions, carry out head space gas chromatography, record peak area, contrasts above-mentioned typical curve, obtains the content of propane in head space gases; Finally be converted to the content of propane in testing sample.
Above-mentioned purpose of the present invention is realized by following steps: the detection method of dissolvent residual in Propane fluid extraction product, carries out according to following step:
(1) preparation of standard reserving solution:take not containing the product oil quality m of propane
1(20.0000 ~ 200.0000 g), propane gas is passed into 10 ~ 60 min in this oil, wherein preferred 20 ~ 40 min, and rear stopping passes into propane gas, then ambient-temp-stable 12 ~ 96 h, and wherein preferably after 48 ~ 84 h, the quality again weighing oil is m
2, the weight of increase is the quality passing into propane gas, obtains the concentration of propane in oil:
X
1=1000(m
2－m
1)/?m
1
In formula:
X
1--the concentration of propane in oil, unit is milligram every gram (mg/g);
M
1--not containing the quality of propane product oil, unit is gram (g);
M
2--quality oily after passing into propane, unit is gram (g).
(2) preparation of series standard solution:pipette storing solution stable in the step (1) that quality is m ' in the tool plug ml headspace bottle of clean drying, close plug, obtains the quality of propane in product oil (mg): m ' × X
1, in this bottle, add the product oil not containing propane is m(5.00 ~ 50.00g to oily quality), close plug, mixed preparing obtains the titer of a series of different propane concentration, and concentration is (m ' × X
1)/m
In formula:
M '--pipette the amount of propane standard reserving solution, unit is gram (g);
M--is used for the oil sample amount of gas chromatographic detection, and unit is gram (g).
(3) head space gas chromatography:by the fat solution of the different propane concentrations of (m) identical in quality in step (2), balance 10 ~ 60 min is stirred with the rotating speed of 500 rpm in 40 ~ 70 DEG C of thermostat water baths, insertion microsyringe or syringe pipette gasification bottle top tank air 100 μ L immediately, carry out head space gas chromatography, write down peak area, take peak area as ordinate, propane concentration is horizontal ordinate, drawing standard curve; Wherein GC conditions is: preferred column HP-PLOT Al
2o
3-S(15m*0.53 mm*15.00 μm), flame ionization ditector (FID), column temperature 40 ~ 100 DEG C, the temperature of vaporizer and detecting device 150 ~ 250 DEG C, carrier gas (N
2) 7.2 mL/min, hydrogen 50 mL/min, air 500 mL/min, the testing sample pipetting (m) identical in quality is deposited in the tool plug ml headspace bottle of volume same as described above, close plug, under the same conditions, carries out head space gas chromatography, write down the peak area (multiple chromatographic peak normalization method) that component is measured, contrast standard opisometer calculates propane content in testing sample (mg/kg): X=1000X
2
In formula:
X
2--the content of propane in testing sample, unit is milligram every gram (mg/g);
The content of propane in X--testing sample, unit is milligrams per kilogram (mg/kg).
(4) evaluation of method accuracy:by head space equilibrium condition and the GC conditions of step (3), 6 parallel replications are carried out to testing sample (oil and fat product of propane extraction), calculates dissolvent residual in sample according to typical curve, and calculate relative standard deviation (RSD)≤5.5%; Again this sample is carried out recovery of standard addition test, add the standard items (high, normal, basic concentration) of three levels, average recovery of standard addition is 95 ~ 110%, RSD is 1 ~ 5.5%.
The product oil not containing propane of the present invention refers to that same oil plant or natural products adopt No. 6 solvents, sherwood oil, supercritical COs
2or the grease that the extraction such as milling process obtains, or the product oil that Propane extracts is carried out 100 DEG C of heating 12 ~ 24 h, drain propane wherein.
Advantage of the present invention:
(1) the present invention gives sufficient inflationtime and suitable stable standing time to the product oil not containing propane and weighs accurately, product oil is absorbed well to propane calibrating gas dissolve each other and reach certain balance, overcoming propane calibrating gas is injected directly in grease, the deficiency of its dissolubility and poor stability, improves the accuracy of propane residue detection;
(2) the present invention adopts the oil same with oil phase to be measured to be matrix oil, propane is identical with the Interaction Force of oil to be measured with matrix oil, there is identical adsorption-desorption mobile equilibrium, therefore when headspace gas chromatography sample introduction, the final equilibrium system of propane oil solution does not change, and the experimental data recorded is accurate;
(3) content that the present invention adopts headspace gas chromatography to detect propane in valuable grease has that cost is low, easy and simple to handle, specificity is strong and pollute the advantages such as little to instrument system.
Accompanying drawing explanation
Fig. 1 is that in example 1, concentration is the propane soybean embryo fat/oil standard solution gas chromatogram of 0.0021 mg/g,
The soybean embryo fat/oil product gas chromatogram of propane extraction to be measured in Fig. 2 example 1,
Propane typical curve obtained in Fig. 3 example 1.
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated.
embodiment 1
Get commercially available No. 6 solvent-extracted soybean embryo fat/oil 50.0000 g, the 150ml loading homemade clean dried constant weight ventilates in bottle (comprising plastic bottle with cover, draft tube and gas outlet).Propane calibrating gas is stored in steel cylinder, the valve controlling flow is had above steel cylinder, communicate with the external world with rubber tube, separately get one section of rubber tube to be communicated with the rubber tube of steel cylinder by emulsion tube, gross mass 110.3620 g of oil and air-breather, open cylinder valve, propane calibrating gas is slowly passed in product oil, valve-off after 0.5 h, the gross mass weighing oil solution and air-breather is 111.3323 g, standing at room temperature places 72h, again weigh the gross mass of product oil and air-breather, its steady quality does not change in 110.3624(1h), the quality relatively increased before and after ventilation is the quality of fat absorption propane, thus obtain the Standard Stock solutions that concentration is 0.0080mg/g, get the Standard Stock solutions of certain mass and soybean embryo fat/oil mixed diluting quantitatively to 10.00 g not containing propane, obtained propane concentration of standard solution is followed successively by 0.0041 mg/g, 0.00031 mg/g, 0.0021 mg/g, 0.0010 mg/g, 0.0008 mg/g, 0.0004 mg/g, 0.0002 mg/g, and by its series standard solution close plug in 135 mL ml headspace bottle, balance 15 min is stirred with the rotating speed of 500 rpm respectively in 50 DEG C of thermostat water baths, from ml headspace bottle, 100 μ L top tank airs are extracted immediately with microsyringe, pass through gas chromatographic analysis, write down component peaks area, with peak area, linear regression is carried out to propane concentration, obtaining regression equation is y=565377x-57.101, correlation coefficient r=0.9991, the range of linearity is 0.0002 ~ 0.0041 mg/g.Get the soybean germ oil product (laboratory obtains) of 10.00 g Propane extractions, close plug in 135 mL ml headspace bottle, water bath with thermostatic control 15 min at 50 DEG C, from bottle, extract 100 μ L with micro syringe immediately and carry out analysis headspace gas chromatography, write down each component peaks area, comparison typical curve, the residual quantity calculating propane in the soybean embryo fat/oil of Propane extraction is 0.22mg/kg.
Wherein gas chromatography reference conditions:
Chromatographic column: HP-PLOT Al
2o
3-S (15m*0.53mm*15.00 μm)
Detecting device: FID
Column temperature: 70 DEG C
Temperature of vaporization chamber: 180 DEG C
Detector temperature: 210 DEG C
Carrier gas (N
2): 7.2 mL/min
Hydrogen: 50 mL/min
Air: 500 mL/min
embodiment 2
Get supercritical CO
2wheat-germ oil 100.0000 g of extraction, the 150ml loading homemade clean dried constant weight ventilates in bottle.Propane calibrating gas is stored in steel cylinder, the valve controlling flow is had above steel cylinder, communicate with the external world with rubber tube, separately get one section of rubber tube to be communicated with the rubber tube of steel cylinder by emulsion tube, gross mass 160.3453 g of oil and air-breather, open cylinder valve, propane calibrating gas is slowly passed in product oil, valve-off after 1 h, the gross mass weighing oil and air-breather is 161.9173 g, standing at room temperature places 84h, again weigh the gross mass of product oil and air-breather, its steady quality does not change in 160.3467(1h), the quality relatively increased before and after ventilation is the quality of fat absorption propane, thus obtain the Standard Stock solutions that concentration is 0.0140mg/g, get the Standard Stock solutions of certain mass and wheat-germ oil mixed diluting quantitatively to 10.00 g not containing propane, obtained propane concentration of standard solution is followed successively by 0.0070 mg/g, 0.0053 mg/g, 0.0035 mg/g, 0.0028 mg/g, 0.0014 mg/g, 0.0006 mg/g, 0.0003 mg/g, 0.0001 mg/g, and by its series standard solution close plug in 135 mL ml headspace bottle, balance 15 min is stirred with the rotating speed of 500 rpm respectively in 50 DEG C of thermostat water baths, from ml headspace bottle, 100 μ L top tank airs are extracted immediately with microsyringe, pass through gas chromatographic analysis, write down peak area, with peak area, linear regression is carried out to propane concentration, obtaining regression equation is y=507627x-36.541, correlation coefficient r=0.9997, the range of linearity is 0.0001 ~ 0.0070 mg/g.Get the wheat embryo oil product (commercially available) of 10.00 g Propane extractions, close plug in 135 mL ml headspace bottle, at 50 DEG C of water bath with thermostatic control 15 min, from bottle, extract 100 μ L with micro syringe immediately and carry out analysis headspace gas chromatography, write down component peaks area, the above-mentioned typical curve of comparison, calculates solvent residual amount in the wheat-germ oil of Propane extraction and does not detect.
Wherein gas chromatography reference conditions:
Chromatographic column: HP-PLOT Al
2o
3-S (15m*0.53mm*15.00 μm)
Detecting device: FID
Column temperature: 40 DEG C
Temperature of vaporization chamber: 150 DEG C
Detector temperature: 250 DEG C
Carrier gas (N
2): 7.2 mL/min
Hydrogen: 50 mL/min
Air: 500 mL/min
embodiment 3
Get commercially available No. 6 solvent-extracted rice bran oil 50.0000 g, the 150ml loading homemade clean dried constant weight ventilates in bottle (comprising plastic bottle with cover, draft tube and gas outlet).Propane calibrating gas is stored in steel cylinder, the valve controlling flow is had above steel cylinder, communicate with the external world with rubber tube, separately get one section of rubber tube to be communicated with the rubber tube of steel cylinder by emulsion tube, gross mass 110.3620 g of oil and air-breather, open cylinder valve, propane calibrating gas is slowly passed in product oil, valve-off after 0.5 h, the gross mass weighing oil solution and air-breather is 111.3329 g, static placement 72 h of difference under room temperature, again weigh the gross mass of product oil and air-breather, its steady quality does not change in 110.3625(1h), the quality relatively increased before and after ventilation is the quality of fat absorption propane, thus obtain the Standard Stock solutions that concentration is 0.0100mg/g, the Standard Stock solutions getting certain mass respectively with rice bran oil mixed diluting quantitatively to 10.00 g not containing propane, obtained propane concentration of standard solution is followed successively by 0.0050 mg/g, 0.00038 mg/g, 0.0025 mg/g, 0.0020 mg/g, 0.0010 mg/g, 0.0005 mg/g, 0.0003 mg/g, and by its series standard solution close plug in 135 mL ml headspace bottle, balance 15 min is stirred with the rotating speed of 500 rpm respectively in 50 DEG C of thermostat water baths, from ml headspace bottle, 100 μ L top tank airs are extracted immediately with microsyringe, pass through gas chromatographic analysis, write down component and record peak area, with peak area, linear regression is carried out to propane concentration, obtaining regression equation is y=565468x-168.261, correlation coefficient r=0.9991, the range of linearity is 0.0003 ~ 0.0050 mg/g.Get the rice bran oil product (laboratory obtains) of 10.00 g Propane extractions, close plug in 135 mL ml headspace bottle, water bath with thermostatic control 15 min at 50 DEG C, from bottle, extract 100 μ L top tank airs with micro syringe immediately and carry out analysis headspace gas chromatography, write down component peaks area, the above-mentioned typical curve of comparison, calculates solvent residual amount in the rice bran oil of Propane extraction and does not detect.
Wherein gas chromatography reference conditions:
Chromatographic column: HP-PLOT Al
2o
3-S (15m*0.53mm*15.00 μm)
Detecting device: FID
Column temperature: 70 DEG C
Temperature of vaporization chamber: 180 DEG C
Detector temperature: 210 DEG C
Carrier gas (N
2): 7.2 mL/min
Hydrogen: 50 mL/min
Air: 500 mL/min.
Claims (1)
1. the detection method of dissolvent residual in Propane fluid extraction product, is characterized in that carrying out according to following step:
(1) preparation of standard reserving solution:take not containing the product oil quality m of propane
1, propane gas is passed into 10 ~ 60 min in this oil, rear stopping passes into propane gas, then ambient-temp-stable 12 ~ 96 h, and the quality again weighing oil is m
2, the weight of increase is the quality passing into propane gas, obtains the concentration of propane in oil:
X
1=1000(m
2－m
1)/?m
1
In formula:
X
1--the concentration of propane in oil, unit is milligram every gram;
M
1--not containing the quality of propane product oil, unit is gram;
M
2--pass into the quality of oil after propane, unit is gram;
(2) preparation of series standard solution:pipette storing solution stable in the step (1) that quality is m ' in the tool plug ml headspace bottle of clean drying, close plug, obtains the quality of propane in product oil: m ' × X
1, in this bottle, add the product oil not containing propane is m to oily quality, and close plug, mixed preparing obtains the titer of a series of different propane concentration, and concentration is (m ' × X
1)/m
In formula:
M '--pipette the amount of propane standard reserving solution, unit is gram;
M--is used for the oil sample amount of gas chromatographic detection, and unit is gram;
(3) head space gas chromatography:by the fat solution of different propane concentrations identical in quality in step (2), balance 10 ~ 60 min is stirred with the rotating speed of 500 rpm in 40 ~ 70 DEG C of thermostat water baths, insertion microsyringe or syringe pipette gasification bottle top tank air 100 μ L immediately, carry out head space gas chromatography, write down peak area, take peak area as ordinate, propane concentration is horizontal ordinate, drawing standard curve; Pipetting testing sample identical in quality deposits in the tool plug ml headspace bottle of volume same as described above, close plug, under the same conditions, carry out head space gas chromatography, write down the peak area that component is measured, multiple chromatographic peak normalization method, contrast standard opisometer calculates propane content in testing sample, and unit is milligram every gram: X=1000X
2
In formula:
X
2--the content of propane in testing sample, unit is milligram every gram;
The content of propane in X--testing sample, unit is milligrams per kilogram;
(4) evaluation of method accuracy:with GC conditions, 6 parallel replications are carried out by the head space equilibrium condition of step (3) to the oil and fat product of testing sample and propane extraction, calculates dissolvent residual in sample according to typical curve, and calculate relative standard deviation RSD≤5.5%; Again this sample is carried out recovery of standard addition test, add the standard items of three levels and high, normal, basic concentration, average recovery of standard addition is 95 ~ 110%, RSD is 1 ~ 5.5%;
Wherein GC conditions is: chromatographic column HP-PLOT Al
2o
3-S 15m*0.53 mm*15.00 μm, flame ionization ditector FID, column temperature 40 ~ 70 DEG C, the temperature of vaporizer and detecting device 150 ~ 250 DEG C, carrier gas N
27.2 mL/min, hydrogen 50 mL/min, air 500 mL/min.
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|---|---|---|---|
| CN201210545709.0A CN103033574B (en) | 2012-12-17 | 2012-12-17 | Method for detecting residual solvent in subcritical propane extraction product |
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| CN103033574B true CN103033574B (en) | 2014-12-24 |
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Families Citing this family (3)
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| CN103743829A (en) * | 2013-11-29 | 2014-04-23 | 山东省化工研究院 | Method for detecting purity of propane and hydrocarbon impurities in propane |
| CN108303479A (en) * | 2018-01-24 | 2018-07-20 | 吉林省百利生物科技有限公司 | The assay method of solvent residual amount in a kind of edible vegetable oil |
| CN109374804B (en) * | 2018-10-31 | 2020-11-03 | 内蒙古中煤蒙大新能源化工有限公司 | Chromatographic analysis method for propane product in methanol-to-olefin process production |
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| CN101858893A (en) * | 2009-04-07 | 2010-10-13 | 北京协和药厂 | Headspace gas chromatography detection method of residual solvents in macroporous resin extract |
| CN102288686A (en) * | 2010-06-17 | 2011-12-21 | 河北以岭医药研究院有限公司 | Method for measuring residual amount of organic solvent in traditional Chinese medicine freeze-drying injection |
| CN102323353A (en) * | 2011-08-16 | 2012-01-18 | 上海新先锋药业有限公司 | Method for detecting organic solvent residues in liposome medicines |
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Inventor after: Xu Bin Inventor after: Jiang Song Inventor after: Zhou Shilong Inventor after: Dong Ying Inventor after: Sun Jun Inventor after: Qi Kun Inventor after: Zhu Xinliang Inventor before: Xu Bin Inventor before: Jiang Song Inventor before: Zhou Shilong Inventor before: Dong Ying Inventor before: Sun Jun |
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Effective date of registration: 20160415 Address after: 455113, Henan, Anyang hi tech Zone, Henan Province, Chung song street, southern section of Hong 200 meters Patentee after: Henan Yalinjie Biological Technology Co., Ltd. Address before: Zhenjiang City, Jiangsu Province, 212013 Jingkou District Road No. 301 Patentee before: Jiangsu University |
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