CN103018369B - Detecting method for solvent residues in liquefied petroleum gas extraction products - Google Patents
Detecting method for solvent residues in liquefied petroleum gas extraction products Download PDFInfo
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Abstract
The invention relates to a detecting method for solvent residues in liquefied petroleum gas extraction products, in particular to the field of detection of food safety. The main components of n-butane, iso-butane and propane standard gases in the liquefied petroleum gas are introduced in finished oil which has the same type with oil to be detected and dose not contain the components, are fully stabilized, and are accurately weighed to obtain concentrations of three stock solutions; and then the three stock solutions are diluted to prepare a series of standard oil solutions; 5.00-100.00 g of the series of standard oil solutions are respectively taken to be placed in a headspace empty bottle of 135 mL, and are mixed and balanced for 10-60 minutes at the rotating speed of 500 rpm under the constant-temperature water bath comdition of 40-70 DEG C; upper layer gases of the oil solutions are taken by a microsyringe to realize the headspace gas chromatography; residual liquefied petroleum gas components in the oil sample to be detected are detected under the same conditions; and the contents of the residual solvent in the oil sample can be obtained according to corresponding standard curves. The method has the advantages of low cost, easiness in operation, strong specificity and the like.
Description
Technical field
The present invention relates to field of detection of food safety, refer in particular to a kind of using gas-chromatography quick detection subcritical fluids（Liquefied petroleum gas）The method of dissolvent residual in the edible oil and fat product of extraction, this method can be that grease production enterprise and Safety of Food Quality testing agency provide method foundation.
Background technology
Subcritical fluids refer to some compounds higher than its boiling point but less than under conditions of critical-temperature and critical pressure, the material existed with fluid form.And subcritical fluid extraction technology is then using subcritical fluids or its mixed solution as solvent, a kind of new technology of target components is extracted from natural products, it is particularly suitable for the extraction of volatile oil in natural products, grease or liposoluble constituent, with normal temperature leaching, low temperature desolventizing, the outstanding advantage for not destroying heat-sensitive ingredients, the change technology for be an environmental protection, having a extensive future.
Being usually used in the subcritical fluids of valuable grease production or effective components from natural materials extraction includes：Liquefied petroleum gas（LPG）, butane, propane, high-purity isobutane（R600a）, HFA 134a（R134a）, dimethyl ether（DME）With sulfur hexafluoride etc., wherein being most widely used with LPG, butane, propane.The Ministry of Public Health of China 2008 is by LPG（Main component normal butane, iso-butane and propane）Food processing aid catalogue is included, there is hypotoxicity to nerve system of human body yet with it, so, dissolvent residual is a food-safety problem that can not be ignored in the product extracted with liquefied petroleum gas.
At present, normal butane, iso-butane, propane residue detection there is no unified national standard in the grease of LPG extractions.Chen Qi et al. reports the detection method of No. four dissolvent residuals in cocoa butter, has mainly used for reference the assay method of No. six dissolvent residuals（GB5009.37-2003）, i.e., using headspace gas chromatography, butane is injected in matrix oil, is made after standard liquid, by headspace gas chromatography, recorded peak area, draw standard curve；Testing sample is after the same terms are handled, headspace sampling, records peak area, is compared with standard curve, obtain the content of butane in head space gases, be finally converted to the residual quantity of No. four solvents in testing sample.But the detection of butane residual is compared with n-hexane residue detection in No. six solvents, there is certain defect, it is gaseous state at normal temperatures and pressures that reason, which is mainly butane, and n-hexane is in a liquid state, after the n-hexane of liquid can preferably be dissolved each other with grease, and gaseous butane is injected in ml headspace bottle, it is full of in oily upper epidermis, because gas-liquid characteristic butane can not dissolve each other well with matrix oil so that can not accurately learn the butane quality being dissolved in grease；Simultaneously with oil phase ratio to be measured, equilibrium system disunity is adsorbed and desorbed between butane and oil therein, even if the amount of butane being injected directly into same matrix oil is identical with amount contained in oil to be measured, the two balanced under identical head space equilibrium condition after in ml headspace bottle head space gases butane content, the former is also greater than the latter, this just causes the latter made slope of standard curve of gas chromatographic detection bigger than reality, so that the Lower result of measurement.Therefore, butane standard liquid prepare can not with reference to n-hexane standard liquid compound method.
In addition, Xu Yun et al. reports the propane determined with infrared spectrophotometer and Headspace-Gas Chromatography Analysis in waste water, the method for butane.Although the method determines the content of propane in waste water, butane.But researcher is not inconsistent by the butane matrix soluble in water for being configured to standard liquid, i.e. standard liquid and testing sample, equally exists above-mentioned Chen Qi deficiency, along with the matrix containing butane, propane compared with grease is different, therefore this method is inadvisable.
The method that the content of butane in the expiratory air of people is determined for the use gas chromatography that Yan Li et al. is reported, although this method can measure the content of butane in the expiratory air of people, but the preparation of this method standard items is by clean air dilution standard butane gas, the matrix containing butane is different compared with grease, therefore the detection of residual solvent can not be with reference to this method in liquefied petroleum gas oil and grease extracting product.
In summary：Two key technical problems must be solved when detecting dissolvent residual in liquefied petroleum gas extracted products using headspace gas chromatography：First, when preparing standard liquid, liquefied petroleum gas（Principal component includes normal butane, iso-butane and propane）It can well be dissolved each other with matrix oil, could accurately obtain various concentrations（Series）Normal butane, iso-butane and propane solution；Secondly, the matrix of standard liquid must be consistent with the matrix of testing sample, so, and the concentration of headspace gas just has comparativity after both balances.
In order to solve above-mentioned two key technical problem, normal butane, iso-butane and propane calibrating gas are first each passed through and oily identical matrix oil to be measured by the present invention（Without liquefied petroleum gas components）In, them are fully absorbed, above-mentioned ventilation solution is then subjected to open placement to stable, three kinds of standard reserving solutions are made, then they are diluted respectively, so as to prepare a series of normal butane for obtaining concentration, iso-butane and propane standard oil solution.
The content of the invention
The present invention solves subcritical fluids（Liquefied petroleum gas）The technical scheme that dissolvent residual is used in oil and grease extracting is：Weigh the product oil without liquefied petroleum gas components, normal butane, iso-butane and propane Standard Gases are each passed through in the product oil respectively, stop being passed through calibrating gas after a period of time, weigh the quality of three kinds of product oils respectively after a period of stabilisation, the concentration of normal butane, iso-butane and propane in the oil is obtained, so that three kinds of standard reserving solutions are made；Then a certain amount of above-mentioned three kinds of storing solutions are diluted with product oil respectively, to prepare the normal butane, iso-butane and propane oil solution of a series of concentration, it is placed in ml headspace bottle under uniform temperature and balances a period of time, head space gases in bottle are taken to carry out head space gas chromatography, respective peak area is recorded, draws obtain three standard curves respectively；Again by same amount of testing sample, under the same conditions, head space gas chromatography is carried out, record each component peak area, above-mentioned three standard curves are contrasted respectively, the content of normal butane in head space gases, iso-butane and propane is obtained；Finally it is converted to the content of liquefied petroleum gas in testing sample.
The method of the present invention through the following steps that realize：The detection method of dissolvent residual in liquefied petroleum gas extracted products, is carried out as steps described below：
（1）The preparation of standard reserving solution：It is m to weigh three parts of finished product oil qualities without liquefied petroleum gas components0（20.0000~200.0000 g）, normal butane, iso-butane and propane gas are each led into 10~60 min in three parts of oil, wherein it is preferred that stopping being passed through three kinds of gases after 20~40 min, the then h of ambient-temp-stable 12~96, wherein it is preferred that the quality for weighing oil after 48~84 h respectively again is m1、m2And m3, increased weight is the quality for being passed through normal butane, iso-butane and propane gas, obtains the concentration of normal butane, iso-butane and propane in oil and is respectively
X1=1000(m1- m0)/ m1、X2=1000(m2- m0)/ m2And X2=1000(m3- m0)/ m3
In formula：
X1Concentration of the-- normal butane in oil, unit is every gram of milligram（mg/g）；
X2Concentration of the-- iso-butane in oil, unit is every gram of milligram（mg/g）；
X3Concentration of the-- propane in oil, unit is every gram of milligram（mg/g）；
m0--without liquefied petroleum gas components product oil quality, unit for gram（g）；
m1--be passed through normal butane it is stable after oily quality, unit for gram（g）；
m2--be passed through iso-butane it is stable after oily quality, unit for gram（g）.
m3--be passed through propane it is stable after oily quality, unit for gram（g）.
（2）The preparation of series standard solution：Quality is pipetted respectively for m1′、m2' and m3' the step of（1）In three kinds of stable storing solutions into the dry tool plug ml headspace bottle of cleaning, then it is m to add the product oil without liquid gas fraction to the quality of oil into respective bottle, and close plug obtains a series of normal butanes, iso-butane and propane titer so as to prepare, and its concentration is respectively（m1′×X1）/m、（m2′×X2）/ m and（m3′×X3）/m
In formula：
m1'-- pipettes the amount of normal butane standard reserving solution, unit for gram（g）；
m2'-- pipettes the amount of iso-butane standard reserving solution, unit for gram（g）；
m3'-- pipettes the amount of propane standard reserving solution, unit for gram（g）；
M-- be used for gas chromatographic detection oil sample amount, unit for gram（g）.
（3）Head space gas chromatography：By step（2）In it is identical in quality（m）Different normal butanes, the series standard Solutions Solution of iso-butane and propane concentration, respectively with 500 rpm 10~60 min of rotating speed stirring balance in 40~70 DEG C of thermostat water baths, it is immediately inserted into microsyringe or syringe pipettes the μ L of gasification bottle top tank air 100, carry out head space gas chromatography, write down peak area, using peak area as ordinate, the concentration of normal butane, iso-butane and propane is abscissa, draws standard curve；Wherein GC conditions are：Preferred column HP-PLOT Al2O3-S（15m*0.53 mm*15.00 μm）, flame ionization ditector（FID）, 40~100 DEG C of column temperature, 150~250 DEG C of the temperature of vaporizer and detector, carrier gas（N2）7.2 mL/min, the mL/min of hydrogen 50, the mL/min of air 500；Pipette identical in quality（m）Testing sample deposit 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, the peak area of each component measurement is write down, contrast standard curve, calculates normal butane in testing sample, iso-butane and propane content respectively（mg/g）, finally carry out identity transformation（mg/kg）：X=1000X′
In formula：
The content of normal butane, iso-butane and propane in X '-- testing sample, unit is every gram of milligram（mg/g）；
The content of normal butane, iso-butane and propane in X-- testing sample, unit for milligrams per kilogram（mg/kg）.
（4）The evaluation of method accuracy：To testing sample（The product of commercially available liquefied petroleum gas extraction）By step（3）Head space equilibrium condition and GC conditions carry out 6 parallel replications, dissolvent residual in sample is calculated according to standard curve, and calculate respective relative standard deviation（RSD）<5%；The sample is subjected to recovery of standard addition experiment again, the hybrid standard product (high, medium and low concentration) of three levels are added, average recovery of standard addition is that 98 ~ 120%, RSD is 1 ~ 5%.
Product oil of the present invention without liquefied petroleum gas refers to same oil plant or natural products using No. 6 solvents, petroleum ether, supercritical COs2Or the grease that the extraction such as milling process is obtained, or the product oil that liquefied petroleum gas is extracted carries out 100 DEG C of 12~24 h of heating, drains butane therein and propane.
Advantages of the present invention：
（1）The inflationtime that the present invention gives abundance to the product oil without liquefied petroleum gas components is weighed with appropriate stable standing time and accurately, product oil is absorbed normal butane, iso-butane and propane calibrating gas well and dissolve each other and reach certain balance, calibrating gas is overcome to be injected directly into grease, the deficiency of its dissolubility and stability difference, improves the degree of accuracy of liquefied petroleum gas residue detection；
（2）The present invention is used with oily identical oil to be measured as matrix oil, normal butane, iso-butane, propane are identical with the Interaction Force of the oily and to be measured oil of matrix, there is identical adsorption-desorption dynamic equilibrium, therefore in headspace gas chromatography sample introduction, the final equilibrium system of standard oil solution does not change, and the experimental data measured is accurate；
（3）The present invention is using liquefied petroleum gas in HS GC detection grease（Main component normal butane, iso-butane and propane）Content have the advantages that low cost, easy to operate, specificity are strong and pollute small to instrument system.
Brief description of the drawings
Soybean germ oil standard mixed solution gas chromatogram in Fig. 1 embodiments 1；Wherein No. 1 peak propane, No. 2 peak iso-butanes and No. 3 peak normal butanes, concentration are respectively 0.0010 mg/g, 0.0359 mg/g, 0.0206 mg/g；The soybean embryo fat/oil product gas chromatogram of liquefied petroleum gas extraction to be measured in Fig. 2 embodiments 1；Propane standard curve made from Fig. 3 embodiments 1；Iso-butane standard curve made from Fig. 4 embodiments 1；Normal butane standard curve made from Fig. 5 examples 1.
Embodiment
The present invention is further elaborated with reference to embodiment.
Embodiment 1
Three parts of commercially available No. 6 solvent-extracted g of soybean embryo fat/oil 50.0000 are taken, load the 150ml ventilation bottles of homemade clean dried constant weight（Including plastic bottle with cover, air inlet pipe and blast pipe）In.Normal butane, iso-butane and propane calibrating gas are stored in steel cylinder, there is the valve of control flow above steel cylinder, communicated with rubber tube with the external world, separately one section of rubber tube is taken to be communicated by emulsion tube with the rubber tube of steel cylinder, the g of gross mass 110.3620 of oil and air-breather, open cylinder valve, by normal butane, iso-butane and propane calibrating gas are slowly passed through in product oil, valve is closed after 0.5 h, the gross mass for weighing oil solution and air-breather is respectively 111.3423 g, 111.3453 g and 111.3323 g, 72 h of static placement are distinguished at room temperature, the gross mass of product oil and air-breather is weighed again, its quality is stablized 110.3661 respectively, 110.3692 g and 110.3624（Do not change in 1h）, increased quality is the quality of fat absorption normal butane, iso-butane and propane before and after comparing ventilation, so as to obtain the Standard Stock solutions that concentration is 0.0824mg/g, 0.1435mg/g and 0.0080mg/g；Take three kinds of Standard Stock solutions of certain mass quantitative to 10.00 g with the soybean embryo fat/oil mixed diluting without liquefied petroleum gas components respectively,Normal butane concentration of standard solution is made and is followed successively by 0.0412 mg/g,0.0309 mg/g,0.0206 mg/g ,0.0165 mg/g, 0.0082 mg/g,0.0041 mg/g,0.0033 mg/g ,0.0016 mg/g, 0.0008 mg/g,0.0004 mg/g,Iso-butane concentration of standard solution is followed successively by 0.0718 mg/g, 0.0538 mg/g,0.0359mg/g ,0.0287 mg/g,0.0144 mg/g, 0.0072 mg/g,0.0057 mg/g ,0.0029 mg/g,0.0014 mg/g,0.0007 mg/g,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 in 135 mL ml headspace bottles close plug,Respectively with 500 rpm 15 min of rotating speed stirring balance in 50 DEG C of thermostat water baths,Extract 100 μ L top tank airs from ml headspace bottle with microsyringe immediately,Pass through gas chromatographic analysis,Write down component and measure peak area,With peak area to normal butane,Iso-butane and propane concentration carry out linear regression,It is respectively normal butane y=498265x-233.939 to obtain regression equation（Correlation coefficient r=0.9995, the range of linearity is 0.0004~0.0412 mg/g）, iso-butane y=508887x -349.456（Correlation coefficient r=0.9996, the range of linearity is 0.0007~0.0718 mg/g）, (correlation coefficient r=0.9991, the range of linearity is 0.0002~0.0041 mg/g to propane y=565377x-57.101）.The soybean germ oil product for taking 10.00 g liquefied petroleum gas to extract（Laboratory is made）The close plug in 135 mL ml headspace bottles, the min of water bath with thermostatic control 15 at 50 DEG C, extract 100 μ L top tank airs from bottle with micro syringe immediately and carry out head space gas chromatography, write down the peak area that each component is measured, each standard curve is compared, the residual quantity for calculating normal butane, iso-butane and propane in the soybean embryo fat/oil of liquefied petroleum gas extraction is respectively 0.55 mg/kg, 0. 82mg/kg and 0.22mg/kg, the content for being finally converted to liquefied petroleum gas in testing sample is 1.59 mg/kg.
Wherein gas-chromatography reference conditions：
Chromatographic column：HP-PLOT Al2O3-S(15m*0.53mm*15.00μm)
Detector：FID
Column temperature：70℃
Temperature of vaporization chamber：180℃
Detector temperature：210℃
Carrier gas（N2）：7.2 mL/min
Hydrogen：50 mL/min
Air：500 mL/min
Take three parts of supercritical COs2The g of wheat-germ oil 100.0000 of extraction, is fitted into the 150ml of homemade clean dried constant weight ventilation bottles.Normal butane, iso-butane and propane calibrating gas are stored in steel cylinder, there is the valve of control flow above steel cylinder, communicated with rubber tube with the external world, separately one section of rubber tube is taken to be communicated by emulsion tube with the rubber tube of steel cylinder, the g of gross mass 160.3453 of oil and air-breather, open cylinder valve, by normal butane, iso-butane and propane calibrating gas are slowly passed through in product oil, valve is closed after 1 h, the gross mass for weighing oil and air-breather is respectively 161.9256 g, 161.9266 g and 161.9173 g, 84 h of static placement are distinguished at room temperature, the gross mass of product oil and air-breather is weighed again, its quality is stablized 160.4661 respectively, 160.3642 g and 160.3467（Do not change in 1h）, increased quality is the quality of fat absorption normal butane, iso-butane and propane before and after comparing ventilation, so as to obtain the Standard Stock solutions that concentration is 0.1120mg/g, 0.2259 mg/g and 0.0140mg/g；Take three kinds of Standard Stock solutions of certain mass quantitative to 10.00 g with the wheat-germ oil mixed diluting without liquefied petroleum gas components respectively,Normal butane concentration of standard solution is made and is followed successively by 0.0560 mg/g,0.0420 mg/g,0.0280 mg/g,0.0224 mg/g,0.0112 mg/g,0.0056 mg/g,0.0022 mg/g,0.0011 mg/g,0.0006mg/g,Iso-butane concentration of standard solution is followed successively by 0.0847 mg/g,0.0565 mg/g,0.0452 mg/g,0.0226 mg/g,0.0113 mg/g, 0.0045 mg/g,0.0023 mg/g,0.0011 mg/g,0.0006 mg/g,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 in 135 mL ml headspace bottles close plug,Respectively with 500 rpm 15 min of rotating speed stirring balance in 50 DEG C of thermostat water baths,Extract 100 μ L top tank airs from ml headspace bottle with microsyringe immediately,Pass through gas chromatographic analysis,Write down peak area,With peak area to normal butane,Iso-butane and propane concentration carry out linear regression,It is respectively normal butane y=500495x-170.179 to obtain regression equation（Correlation coefficient r=0.9994, the range of linearity is 0.0006~0.0560 mg/g）, iso-butane y=509214x -46.595（Correlation coefficient r=0.9996, the range of linearity is 0.0006~0.0847 mg/g）, (correlation coefficient r=0.9997, the range of linearity is 0.0001~0.0070 mg/g to propane y=507627x-36.541）.The wheat embryo oil product for taking 10.00 g liquefied petroleum gas to extract（Commercially available, company is avenged in Anyang all over the sky）The close plug in 135 mL ml headspace bottles, in 50 DEG C of min of water bath with thermostatic control 15, extract 100 μ L top tank airs from bottle with micro syringe immediately and carry out head space gas chromatography, write down the peak area that each component is measured, above-mentioned each standard curve is compared, solvent residual amount in the wheat-germ oil of liquefied petroleum gas extraction is calculated and does not detect.
Wherein gas-chromatography reference conditions：
Chromatographic column：HP-PLOT Al2O3-S(15m*0.53mm*15.00μm)
Detector：FID
Column temperature：40℃
Temperature of vaporization chamber：150℃
Detector temperature：250℃
Carrier gas（N2）：7.2 mL/min
Hydrogen：50 mL/min
Air：500 mL/min
Embodiment 3
Three parts of commercially available No. 6 solvent-extracted g of rice bran oil 50.0000 are taken, load the 150ml ventilation bottles of homemade clean dried constant weight（Including plastic bottle with cover, air inlet pipe and blast pipe）In.Normal butane, iso-butane and propane calibrating gas are stored in steel cylinder, there is the valve of control flow above steel cylinder, communicated with rubber tube with the external world, separately one section of rubber tube is taken to be communicated by emulsion tube with the rubber tube of steel cylinder, the g of gross mass 110.3620 of oil and air-breather, open cylinder valve, by normal butane, iso-butane and propane calibrating gas are slowly passed through in product oil, valve is closed after 0.5 h, the gross mass for weighing oil solution and air-breather is respectively 111.3425 g, 111.3449 g and 111.3329 g, 72 h of static placement are distinguished at room temperature, the gross mass of product oil and air-breather is weighed again, its quality is stablized 110.3656 respectively, 110.3676 g and 110.3625（Do not change in 1h）, increased quality is the quality of fat absorption normal butane, iso-butane and propane before and after comparing ventilation, so as to obtain the Standard Stock solutions that concentration is 0.0714mg/g, 0.1135mg/g and 0.0100mg/g；Take three kinds of Standard Stock solutions of certain mass quantitative to 10.00 g with the rice bran oil mixed diluting without liquefied petroleum gas components respectively,Normal butane concentration of standard solution is made and is followed successively by 0.0357 mg/g,0.0268 mg/g,0.0179 mg/g ,0.0143 mg/g, 0.0071 mg/g,0.0036 mg/g,0.0014 mg/g ,0.0007 mg/g, 0.0004 mg/g,Iso-butane concentration of standard solution is followed successively by 0.0718 mg/g, 0.0568mg/g,0.0426mg/g ,0.0284mg/g,0.0227 mg/g, 0.0114 mg/g,0.0023 mg/g ,0.0011 mg/g,0.0006 mg/g,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 in 135 mL ml headspace bottles close plug,Respectively with 500 rpm 15 min of rotating speed stirring balance in 50 DEG C of thermostat water baths,Extract 100 μ L top tank airs from ml headspace bottle with microsyringe immediately,Pass through gas chromatographic analysis,Write down component and measure peak area,With peak area to normal butane,Iso-butane and propane concentration carry out linear regression,It is respectively normal butane y=499265x-245.843 to obtain regression equation（Correlation coefficient r=0.9992, the range of linearity is 0.0004~0.0357 mg/g）, iso-butane y=508787x -349.322（Correlation coefficient r=0.9996, the range of linearity is 0.0006~0.0718 mg/g）, (correlation coefficient r=0.9991, the range of linearity is 0.0003~0.0050 mg/g to propane y=565468x-168.261）.The rice bran oil product for taking 10.00 g liquefied petroleum gas to extract（Laboratory is made）The close plug in 135 mL ml headspace bottles, the min of water bath with thermostatic control 15 at 50 DEG C, extract 100 μ L top tank airs from bottle with micro syringe immediately and carry out head space gas chromatography, write down the peak area that each component is measured, above-mentioned each standard curve is compared, solvent residual amount in the rice bran oil of liquefied petroleum gas extraction is calculated and does not detect.
Wherein gas-chromatography reference conditions：
Chromatographic column：HP-PLOT Al2O3-S(15m*0.53mm*15.00μm)
Detector：FID
Column temperature：70℃
Temperature of vaporization chamber：180℃
Detector temperature：210℃
Carrier gas（N2）：7.2 mL/min
Hydrogen：50 mL/min
Air：500 mL/min.
Claims (2)
1. the detection method of dissolvent residual in liquefied petroleum gas extracted products, it is characterised in that carry out as steps described below：
（1）The preparation of standard reserving solution：It is m to weigh three parts of finished product oil qualities without liquefied petroleum gas components0, normal butane, iso-butane and propane gas are each led into three parts of oil and stop being passed through three kinds of gases after 10~60 min, the quality for then weighing oil after the h of ambient-temp-stable 12~96 respectively again is m1、m2And m3, increased weight is the quality for being passed through normal butane, iso-butane and propane gas, obtains the concentration of normal butane, iso-butane and propane in oil and is respectively
X1=1000(m1- m0)/ m1、X2=1000(m2- m0)/ m2And X2=1000(m3- m0)/ m3
In formula：
X1Concentration of the-- normal butane in oil, unit is every gram of milligram；
X2Concentration of the-- iso-butane in oil, unit is every gram of milligram；
X3Concentration of the-- propane in oil, unit is every gram of milligram；
m0--without liquefied petroleum gas components product oil quality, unit for gram；
m1--be passed through normal butane it is stable after oily quality, unit for gram；
m2--be passed through iso-butane it is stable after oily quality, unit for gram；
m3--be passed through propane it is stable after oily quality, unit for gram；
（2）The preparation of series standard solution：Quality is pipetted respectively for m1′、m2' and m3' the step of（1）In three kinds of stable storing solutions into the dry tool plug ml headspace bottle of cleaning, then it is m to add the product oil without liquid gas fraction to the quality of oil into respective bottle, and close plug obtains a series of normal butanes, iso-butane and propane titer so as to prepare, and its concentration is respectively（m1′×X1）/m、（m2′×X2）/ m and（m3′×X3）/m
In formula：
m1'-- pipettes the amount of normal butane standard reserving solution, unit for gram；
m2'-- pipettes the amount of iso-butane standard reserving solution, unit for gram；
m3'-- pipettes the amount of propane standard reserving solution, unit for gram；
M-- be used for gas chromatographic detection oil sample amount, unit for gram；
（3）Head space gas chromatography：By step（2）In m identical in quality different normal butanes, iso-butane and propane concentration series standard Solutions Solution, respectively with 500 rpm 10~60 min of rotating speed stirring balance in 40~70 DEG C of thermostat water baths, it is immediately inserted into microsyringe or syringe pipettes the μ L of gasification bottle top tank air 100, carry out head space gas chromatography, write down peak area, using peak area as ordinate, the concentration of normal butane, iso-butane and propane is abscissa, draws standard curve；The testing sample for 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, carry out head space gas chromatography, write down the peak area of each component measurement, contrast standard curve, calculates normal butane in testing sample, iso-butane and propane content mg/g respectively, finally carries out identity transformation mg/kg：X=1000X′
In formula：
The content of normal butane, iso-butane and propane in X '-- testing sample, unit is every gram of milligram；
The content of normal butane, iso-butane and propane in X-- testing sample, unit for milligrams per kilogram；
（4）The evaluation of method accuracy：The product of liquefied petroleum gas extraction commercially available to testing sample presses step（3）Head space equilibrium condition and GC conditions carry out 6 parallel replications, dissolvent residual in sample is calculated according to standard curve, and calculate respective relative standard deviation RSD<5%；The sample is subjected to recovery of standard addition experiment again, the hybrid standard product of high, medium and low three levels of concentration are added, average recovery of standard addition is that 98 ~ 120%, RSD is 1 ~ 5%.
2. the detection method of dissolvent residual in liquefied petroleum gas extracted products according to claim 1, it is characterised in that
Wherein GC conditions are：Chromatographic column HP-PLOT Al2O3- S, specification is 15m*0.53 mm*15.00 μm, flame ionization ditector FID, 40~100 DEG C of column temperature, 150~250 DEG C of the temperature of vaporizer and detector, carrier gas N27.2 mL/min, the mL/min of hydrogen 50, the mL/min of air 500.
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