CN103033574A - 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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- CN103033574A CN103033574A CN2012105457090A CN201210545709A CN103033574A CN 103033574 A CN103033574 A CN 103033574A CN 2012105457090 A CN2012105457090 A CN 2012105457090A CN 201210545709 A CN201210545709 A CN 201210545709A CN 103033574 A CN103033574 A CN 103033574A
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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 the food safety detection field, refer in particular to the method for dissolvent residual in a kind of edible oil and fat product that adopts gas chromatography fast detecting Propane fluid extraction, the method can be grease production enterprise and Safety of Food Quality testing agency supplying method foundation.
Background technology
Subcritical fluids refer to some compound be higher than its boiling point but be lower than critical temperature and the condition of emergent pressure under, the material that exists with fluid form.The subcritical fluid extraction technology then is as solvent take subcritical fluids or its mixed solution, from natural products, extract a kind of new technology of target components, be particularly suitable for the extraction of volatile oil in the natural products, grease or liposoluble constituent, having normal temperature leaching, low temperature desolventizing, do not destroy the outstanding advantage of thermal sensitivity composition, is an environmental protection, the change technology that has a extensive future.
The subcritical fluids that is usually used in the extraction of valuable grease production or effective components from natural materials 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. wherein are most widely used with propane, butane, LPG.China Ministry of Public Health included propane in the food processing aid catalogue in 2008, yet because it has hypotoxicity 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, the propane residue detection there is no unified national standard in the grease of Propane extraction.Because not enough to its attention degree, so far not relevant for the research of the detection method of propane in the grease, and the mensuration of dissolvent residual is with being most widely used of headspace gas chromatography in the vegetable oil products of conventional solvent extraction, and GB5009.37-2003 just adopts this method to detect the residual quantity of No. six solvents.But because be gaseous state under the propane normal temperature and pressure, and normal hexane is in a liquid state, and compares with it, and it can not dissolve each other preferably with grease, so that can't accurately prepare the standard oil solution of propane, thus hindered the quantitative detection of residual propane in the grease.
The people such as Xu Yun have reported with infrared spectrophotometer and Headspace-Gas Chromatography Analysis and have measured the propane in the waste water, the method for butane.Although this method determines the content of propane in the waste water, butane.But the researchist is not with the propane standard items that are mixed with soluble in water, but directly use the Standard Gases sample introduction of variable concentrations, the matrix of standard items and testing sample is inconsistent, causes the inaccurate of measurement, compare simultaneously the matrix that contains propane from grease different, so method is inadvisable.
For this reason, must solve two key technical problems when adopting headspace gas chromatography to detect in the Propane extracted products dissolvent residual: at first, when preparation standard solution, propane can dissolve each other well with matrix oil, could accurately 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 of head space gas just has comparability after both balances.
In order to solve above-mentioned two key technical problems, the present invention first the propane calibrating gas is passed into oil phase to be measured with matrix oil (not containing propane) in, it is fully absorbed, then above-mentioned propane solution is carried out uncovered be placed to stable, with its dilution, obtain a series of propane standard oil solution thereby prepare again.
Summary of the invention
The present invention solves the technical scheme that its detection technique adopts: take by weighing the product oil that does not contain propane, propane is passed in this product oil, stop to pass into propane gas after a period of time, the quality of weighing product oil obtains the concentration of propane in this oil after a period of stabilisation; Then a certain amount of above-mentioned propane solution is diluted with product oil, to prepare the propane oil solution of a series of concentration, place balance a period of time under the head space bottle uniform temperature, get that head space gases carries out head space gas chromatography in the bottle, the record peak area, the drawing standard curve; With the testing sample of same amount, under the same conditions, carry out head space gas chromatography again, the record peak area contrasts above-mentioned typical curve, obtains the content of propane in the head space gases; Be converted at last the content of propane in the testing sample.
Above-mentioned purpose of the present invention realizes by following steps: the detection method of dissolvent residual in the Propane fluid extraction product, carry out according to following step:
(1) preparation of standard reserving solution:Take by weighing the product oil quality m that does not contain propane
1(20.0000～200.0000 g) passes into 10～60 min in this oil with propane gas, preferred 20～40 min wherein, after stop to pass into propane gas, ambient-temp-stable 12～96 h then, wherein behind preferred 48～84 h, the quality of weighing oil is m again
2, the weight of increase is the quality that passes into propane gas, obtains the concentration of propane in oil:
X
1=1000(m
2－m
1)/?m
1
In the formula:
X
1--the concentration of propane in oil, unit is milligram every gram (mg/g);
m
1--do not contain the quality of propane product oil, unit is gram (g);
m
2--pass into the quality of oil behind the propane, unit is gram (g).
(2) preparation of series standard solution:Pipette storing solution stable in the step that quality is m ' (1) in the tool plug head space bottle of cleaning drying, close plug obtains the quality (mg) of propane in product oil: m ' * X
1, add the product oil that do not contain propane to the quality of oil in this bottle and be m(5.00～50.00g), close plug, mixed preparing obtains the titer of a series of different propane concentrations, concentration be (m ' * X
1)/m
In the 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:Fat solution with the different propane concentrations of (m) identical in quality in the step (2), rotating speed with 500 rpm in 40～70 ℃ of thermostat water baths stirs balance 10～60 min, insert immediately microsyringe or syringe and pipette gasification bottle top tank air 100 μ L, carry out head space gas chromatography, write down peak area, take peak area as ordinate, propane concentration is horizontal ordinate, the drawing standard curve; Wherein GC conditions is: preferred column HP-PLOT Al
2O
3-S(15m*0.53 mm*15.00 μ m), flame ionization ditector (FID), 40～100 ℃ of column temperatures, 150～250 ℃ of the temperature of vaporizer and detecting device, carrier gas (N
2) 7.2 mL/min, hydrogen 50 mL/min, air 500 mL/min, the testing sample that pipettes (m) identical in quality is deposited in the tool plug head space bottle of volume same as described above, close plug under the same conditions, carries out head space gas chromatography, write down the peak area (a plurality of chromatographic peak normalization method) that component is measured, the contrast standard opisometer is calculated propane content (mg/kg): X=1000X in the testing sample
2
In the formula:
X
2--the content of propane in the testing sample, unit are milligram every gram (mg/g);
The content of propane in the X--testing sample, unit are every kilogram (mg/kg) of milligram.
(4) evaluation of method accuracy:Testing sample (oil and fat product of propane extraction) is carried out parallel replication 6 times by head space equilibrium condition and the GC conditions of step (3), calculate dissolvent residual in the sample according to typical curve, and calculate relative standard deviation (RSD)≤5.5%; This sample is carried out the recovery of standard addition test again, add the standard items (high, normal, basic concentration) of three levels, average recovery of standard addition is that 95 ~ 110%, RSD is 1 ~ 5.5%.
The product oil that does not contain propane of the present invention refers to that same oil plant or natural products adopt No. 6 solvents, sherwood oil, supercritical CO
2Or the grease that obtains of the extraction such as milling process, perhaps the product oil with the Propane extraction carries out 100 ℃ of heating 12～24 h, drains propane wherein.
Advantage of the present invention:
(1) the present invention gives sufficient inflationtime and suitable stable standing time and accurately weighing to the product oil that does not contain propane, product oil can be absorbed well to the propane calibrating gas to dissolve each other and reaches certain balance, having overcome the propane calibrating gas is injected directly in the grease, the deficiency of its dissolubility and poor stability, the accuracy that has improved the propane residue detection;
(2) the present invention's employing is matrix oil with oil phase to be measured oil together, propane is identical with oily interaction power to be measured with matrix oil, there is identical adsorption-desorption mobile equilibrium, therefore when the headspace gas chromatography sample introduction, the final equilibrium system of propane oil solution does not change, and the experimental data that records is accurate;
(3) the present invention's content of adopting headspace gas chromatography to detect propane in the valuable grease has that cost is low, easy and simple to handle, specificity strong and instrument system is polluted the advantages such as little.
Description of drawings
Fig. 1 is that concentration is the propane soybean embryo fat/oil standard solution gas chromatogram of 0.0021 mg/g in the example 1,
The soybean embryo fat/oil product gas chromatogram of propane extraction to be measured in Fig. 2 example 1,
The propane typical curve that makes in Fig. 3 example 1.
Embodiment
Below in conjunction with embodiment the present invention is further elaborated.
Get commercially available No. 6 solvent-extracted soybean embryo fat/oil 50.0000 g, in the 150ml ventilation bottle (comprising plastic bottle with cover, draft tube and gas outlet) of the homemade clean dried constant weight of packing into.The propane calibrating gas is stored in the steel cylinder, there is the valve of control flow the steel cylinder top, communicate with the external world with rubber tube, other gets one section rubber tube and communicates with the rubber tube of steel cylinder by emulsion tube, gross mass 110.3620 g of oil and air-breather, open cylinder valve, slowly pass into the propane calibrating gas in the product oil, 0.5 valve-off behind the h, the gross mass of weighing oil solution and air-breather is 111.3323 g, static placement 72h under the room temperature, the gross mass of weighing product oil and air-breather again, its steady quality does not change in 110.3624(1h), the quality that relatively increases before and after the ventilation is the quality of fat absorption propane, thereby obtains the standard inventory solution that concentration is 0.0080mg/g; Get the standard inventory solution of certain mass and do not contain the soybean embryo fat/oil mixed diluting of propane quantitatively to 10.00 g, make the propane concentration of standard solution and be 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 with its series standard solution close plug in 135 mL head space bottles, rotating speed with 500 rpm stirs balance 15 min in 50 ℃ of thermostat water baths respectively, from the head space bottle, extract 100 μ L top tank airs with microsyringe immediately, by gas chromatographic analysis, write down the component peaks area, with peak area propane concentration is carried out linear regression, getting regression equation is y=565377x-57.101, correlation coefficient r=0.9991, the range of linearity are 0.0002～0.0041 mg/g.Get the soybean germ oil product (laboratory makes) of 10.00 g Propanes extraction, close plug in 135 mL head space bottles, at 50 ℃ of lower water bath with thermostatic control 15 min, from bottle, extract 100 μ L with micro syringe immediately and analyze headspace gas chromatography, write down each component peaks area, the comparison typical curve, the residual quantity that calculates propane in the soybean embryo fat/oil of Propane extraction is 0.22mg/kg.
Gas chromatography reference conditions wherein:
Chromatographic column: HP-PLOT Al
2O
3-S (15m*0.53mm*15.00 μ m)
Detecting device: FID
Column temperature: 70 ℃
Temperature of vaporization chamber: 180 ℃
Detector temperature: 210 ℃
Carrier gas (N
2): 7.2 mL/min
Hydrogen: 50 mL/min
Air: 500 mL/min
Get supercritical CO
2Wheat-germ oil 100.0000 g of extraction are in the 150ml ventilation bottle of the homemade clean dried constant weight of packing into.The propane calibrating gas is stored in the steel cylinder, there is the valve of control flow the steel cylinder top, communicate with the external world with rubber tube, other gets one section rubber tube and communicates with the rubber tube of steel cylinder by emulsion tube, gross mass 160.3453 g of oil and air-breather, open cylinder valve, slowly pass into the propane calibrating gas in the product oil, valve-off behind 1 h, the gross mass of weighing oil and air-breather is 161.9173 g, static placement 84h under the room temperature, the gross mass of weighing product oil and air-breather again, its steady quality does not change in 160.3467(1h), the quality that relatively increases before and after the ventilation is the quality of fat absorption propane, thereby obtains the standard inventory solution that concentration is 0.0140mg/g; Get the standard inventory solution of certain mass and do not contain the wheat-germ oil mixed diluting of propane quantitatively to 10.00 g, make the propane concentration of standard solution and be 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 with its series standard solution close plug in 135 mL head space bottles, rotating speed with 500 rpm stirs balance 15 min in 50 ℃ of thermostat water baths respectively, from the head space bottle, extract 100 μ L top tank airs with microsyringe immediately, by gas chromatographic analysis, write down peak area, with peak area propane concentration is carried out linear regression, getting regression equation is y=507627x-36.541, correlation coefficient r=0.9997, the range of linearity are 0.0001～0.0070 mg/g.Get the wheat embryo oil product (commercially available) of 10.00 g Propanes extraction, close plug in 135 mL head space bottles, at 50 ℃ of water bath with thermostatic control 15 min, from bottle, extract 100 μ L with micro syringe immediately and analyze headspace gas chromatography, write down the component peaks area, compare above-mentioned typical curve, calculate that solvent residual amount does not detect in the wheat-germ oil of Propane extraction.
Gas chromatography reference conditions wherein:
Chromatographic column: HP-PLOT Al
2O
3-S (15m*0.53mm*15.00 μ m)
Detecting device: FID
Column temperature: 40 ℃
Temperature of vaporization chamber: 150 ℃
Detector temperature: 250 ℃
Carrier gas (N
2): 7.2 mL/min
Hydrogen: 50 mL/min
Air: 500 mL/min
Get commercially available No. 6 solvent-extracted rice bran oil 50.0000 g, in the 150ml ventilation bottle (comprising plastic bottle with cover, draft tube and gas outlet) of the homemade clean dried constant weight of packing into.The propane calibrating gas is stored in the steel cylinder, there is the valve of control flow the steel cylinder top, communicate with the external world with rubber tube, other gets one section rubber tube and communicates with the rubber tube of steel cylinder by emulsion tube, gross mass 110.3620 g of oil and air-breather, open cylinder valve, slowly pass into the propane calibrating gas in the product oil, 0.5 valve-off behind the h, the gross mass of weighing oil solution and air-breather is 111.3329 g, static placement 72 h of difference under the room temperature, the gross mass of weighing product oil and air-breather again, its steady quality does not change in 110.3625(1h), the quality that relatively increases before and after the ventilation is the quality of fat absorption propane, thereby obtains the standard inventory solution that concentration is 0.0100mg/g; The standard inventory solution of getting certain mass respectively with the rice bran oil mixed diluting that does not contain propane quantitatively to 10.00 g, make the propane concentration of standard solution and be 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 with its series standard solution close plug in 135 mL head space bottles, rotating speed with 500 rpm stirs balance 15 min in 50 ℃ of thermostat water baths respectively, from the head space bottle, extract 100 μ L top tank airs with microsyringe immediately, by gas chromatographic analysis, write down component and record peak area, with peak area propane concentration is carried out linear regression, getting regression equation is y=565468x-168.261, correlation coefficient r=0.9991, the range of linearity are 0.0003～0.0050 mg/g.Get the rice bran oil product (laboratory makes) of 10.00 g Propanes extraction, close plug in 135 mL head space bottles, at 50 ℃ of lower water bath with thermostatic control 15 min, from bottle, extract 100 μ L top tank airs with micro syringe immediately and analyze headspace gas chromatography, write down the component peaks area, compare above-mentioned typical curve, calculate that solvent residual amount does not detect in the rice bran oil of Propane extraction.
Gas chromatography reference conditions wherein:
Chromatographic column: HP-PLOT Al
2O
3-S (15m*0.53mm*15.00 μ m)
Detecting device: FID
Column temperature: 70 ℃
Temperature of vaporization chamber: 180 ℃
Detector temperature: 210 ℃
Carrier gas (N
2): 7.2 mL/min
Hydrogen: 50 mL/min
Air: 500 mL/min.
Claims (2)
1. the detection method of dissolvent residual in the Propane fluid extraction product is characterized in that carrying out according to following step:
(1) preparation of standard reserving solution:Take by weighing the product oil quality m that does not contain propane
1, propane gas is passed into 10～60 min in this oil, after stop to pass into propane gas, ambient-temp-stable 12～96 h then, the quality of weighing oil is m again
2, the weight of increase is the quality that passes into propane gas, obtains the concentration of propane in oil:
X
1=1000(m
2－m
1)/?m
1
In the formula:
X
1--the concentration of propane in oil, unit is the every gram of milligram;
m
1--do not contain the quality of propane product oil, unit is gram;
m
2--pass into the quality of oil behind the propane, unit is gram;
(2) preparation of series standard solution:Pipette storing solution stable in the step that quality is m ' (1) in the tool plug head space bottle of cleaning drying, close plug obtains the quality of propane in product oil: m ' * X
1, adding the product oil that do not contain propane to the quality of oil in this bottle is m, close plug, mixed preparing obtains the titer of a series of different propane concentrations, concentration be (m ' * X
1)/m
In the 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:Fat solution with different propane concentrations identical in quality in the step (2), rotating speed with 500 rpm in 40～70 ℃ of thermostat water baths stirs balance 10～60 min, insert immediately microsyringe or syringe and pipette gasification bottle top tank air 100 μ L, carry out head space gas chromatography, write down peak area, take peak area as ordinate, propane concentration is horizontal ordinate, the drawing standard curve; Pipetting testing sample identical in quality deposits in the tool plug head space 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, a plurality of chromatographic peak normalization methods, contrast standard opisometer are calculated propane content in the testing sample, and unit is milligram every gram: X=1000X
2
In the formula:
X
2--the content of propane in the testing sample, unit are the every gram of milligram;
The content of propane in the X--testing sample, unit are every kilogram of milligram;
(4) evaluation of method accuracy:Be that the oil and fat product of propane extraction carries out parallel replication by the head space equilibrium condition of step (3) 6 times with GC conditions to testing sample, calculate dissolvent residual in the sample according to typical curve, and calculate relative standard deviation RSD≤5.5%; This sample is carried out the recovery of standard addition test, the standard items that add three levels are high, normal, basic concentration again, and average recovery of standard addition is that 95 ~ 110%, RSD is 1 ~ 5.5%.
2. the detection method of dissolvent residual in the Propane fluid extraction product according to claim 1 is characterized in that
Wherein GC conditions is: chromatographic column HP-PLOT Al
2O
3-S(15m*0.53 mm*15.00 μ m), flame ionization ditector (FID), 40～100 ℃ of column temperatures, 150～250 ℃ of the temperature of vaporizer and detecting device, carrier gas (N
2) 7.2 mL/min, hydrogen 50 mL/min, air 500 mL/min.
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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 |
| CN109374804A (en) * | 2018-10-31 | 2019-02-22 | 内蒙古中煤蒙大新能源化工有限公司 | The chromatogram analysis method of bromopropane product in a kind of production of MTO technology |
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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 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN109374804A (en) * | 2018-10-31 | 2019-02-22 | 内蒙古中煤蒙大新能源化工有限公司 | The chromatogram analysis method of bromopropane product in a kind of production of MTO technology |
| 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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