CN103675157B - A kind of quick pretreatment method of crude oil sample - Google Patents
A kind of quick pretreatment method of crude oil sample Download PDFInfo
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- CN103675157B CN103675157B CN201310428037.XA CN201310428037A CN103675157B CN 103675157 B CN103675157 B CN 103675157B CN 201310428037 A CN201310428037 A CN 201310428037A CN 103675157 B CN103675157 B CN 103675157B
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Abstract
The invention provides a kind of quick pretreatment device of crude oil sample, it comprise syringe, the extraction solvent be contained in syringe, condenser, sealing gasket, glass wool, sample cell, nitrogen pipeline, heating arrangement.Syringe comprises cylindrical shell and injection needle.Glass wool is arranged on sample cell inside.Glass wool is used for load detected sample.Sealing gasket is used for sealed sample Chi Kou.Condenser is for cooling the extraction solvent in injector cartridge.Extraction solvent is instilled in the glass wool in sample cell by injection needle.Heating arrangement is used for heated sample pond.Nitrogen pipeline is used for nitrogen is jetted from bottom to top bottom glass wool, and by injection needle winding-up in injector cartridge, discharges via injector cartridge mouth.The present invention also provides a kind of quick pretreatment method of crude oil sample.The present invention has the features such as reagent dosage is few, extraction time is short, accumulation rate is high, easy to use, cost is low, is a kind of green, efficient, environmentally friendly crude oil sample pre-treating method.
Description
Technical field
The invention belongs to oil sample separate analytical technique field, particularly relate to a kind of quick pretreatment device and method of crude oil sample.
Background technology
In order to improve recovery ratio and the scientific guidance oil exploration and exploitation of crude oil, comprehensive and accurate anatomy being carried out to crude oil chemical composition and seems most important.Crude oil sample has complicated chemical composition, first the pre-treatment of sample will be carried out to the analysis of compound in crude oil, namely stable hydrocarbon, aromatic hydrocarbons, colloid, bituminous matter separately, then the target compound required for gas chromatograph-mass spectrometer (GCMS) mensuration is utilized, according to the relative quantity of different target compound or absolute magnitude for judging oil and gas property (type and degree of ripeness), carrying out OIL SOURCE CORRELATION, sentencing and know sedimentary environment, stratigraphic division etc., also the change of some compounds contents can be utilized to determine the direction of oil-gas migration, is oil-gas exploration service.But, crude oil is a kind of potpourri of extreme complexity, although By Gas Chromatography-mass Spectrometry has had very high resolution, still be difficult to carry out desired separated to the component in crude oil, the a series of eluting peak altogether of normal appearance on chromatogram, except there is chromatographic peak overlapping phenomenon, sometimes also show as continuous print baseline lifting (namely what is often called " bulge ").These " bulge " components flowed out altogether are called as difficult resolution of complex potpourri (Unresolved Complex Mixtures, UCMs), the compound numbers that UCMs comprises in Biodegraded Oil especially up to 250,000.The complicacy of crude oil composition and the existence of UCMs cause geochemical information useful in a large number to be lost, and therefore, are the hot issue of research both at home and abroad to the chemical composition analysis in crude oil always.
In order to improve the resolution to oil component, need to carry out necessary pre-treatment, to alleviate the burden of chromatographic resolution to sample.But the pre-treating method generally adopted at present exists following not enough: 1) method is loaded down with trivial details, consuming time very long; 2) need to use a large amount of extraction solvent, have harmful effect to people, environment; 3) require higher to operative skill, otherwise experimental result reappearance is just difficult satisfactory; 4) recovery of method to component to be measured in oil sample is on the low side, causes the loss of constituent part, thus changes the content ratio of compound in crude oil, finally obtains the geochemical information of distortion.Therefore, a kind of green, efficient, environmentally friendly crude oil sample pre-treating method is urgently developed.
Summary of the invention
Technical matters to be solved by this invention is: the quick pretreatment device and method providing a kind of efficient simple crude oil sample.
The present invention for solving the problems of the technologies described above taked technical scheme is:
A kind of quick pretreatment device of crude oil sample, it comprises syringe, be contained in the extraction solvent in syringe, condenser, sealing gasket, glass wool, sample cell, nitrogen pipeline, and heating arrangement, described syringe comprises cylindrical shell and injection needle, described glass wool is arranged on sample cell inside, described glass wool is used for load detected sample, described sealing gasket is used for sealed sample Chi Kou, described condenser is for cooling the extraction solvent in injector cartridge, described extraction solvent is instilled in the glass wool in sample cell by injection needle, described heating arrangement is used for heated sample pond, described nitrogen pipeline is used for nitrogen is jetted from bottom to top bottom glass wool, and by described injection needle winding-up in injector cartridge, discharge via injector cartridge mouth.
In such scheme, described pretreating device also comprises stainless steel wire, and described stainless steel wire is inserted in injector cartridge.
A quick pretreatment method for crude oil sample, it is characterized in that, it comprises the following steps:
1) lower end of two sample hoses led to is loaded glass wool, then 6.0-8.0mg detected sample is joined on the glass wool of sample hose;
2) enter preheating by heating arrangement to sample hose, preheat temperature is 20 DEG C, and preheating time is 15-30min;
3) after preheating terminates, injector cartridge is cooled to-4 DEG C ~-5 DEG C, and nitrogen is jetted from bottom to top bottom glass wool, and by described injection needle winding-up in injector cartridge, discharge via injector cartridge mouth, the flow velocity of described nitrogen is 1-2ml/min;
4) sample hose installing sample is placed in heating arrangement, heating-up temperature is 280-320 DEG C, and with sealing gasket sealed sample Chi Kou;
5) be inserted in sample cell by the injection needle of syringe, in the cylindrical shell of syringe, then add extraction solvent 10-60 μ L, start extraction, extraction time is 1-5min;
6), after extraction terminates, extract syringe rapidly, extraction solvent is advanced into constant volume test tube, use solvent wash syringe subsequently, cleaning solvent is mixed with extraction solvent and is settled to 0.5-1.5mL, then take out 1 ~ 2 μ L constant volume liquid and carry out gas chromatographic analysis.
In such scheme, in step 5), the injection needle of syringe is inserted into after in sample cell, also comprises the step inserting stainless steel wire in injector cartridge.
In such scheme, when extraction solvent is greater than 10 μ L, described stainless steel wire is rolled into screw type.
Beneficial effect of the present invention is: the present invention carries out fast the chemical composition in crude oil sample, extract completely and concentrate, the extraction completely of chemical composition in crude oil sample can be realized in 5 minutes, the features such as the method has reagent dosage few (micro updating), extraction time is short, accumulation rate is high, easy to use, cost of use is low, be a kind of green, efficient, environmentally friendly crude oil sample pre-treating method, can be applicable to the pre-treatment of various crude oil sample in petroleum exploration domain.
Accompanying drawing explanation
The structural representation of the quick pretreatment device of the crude oil sample that Fig. 1 provides for the embodiment of the present invention.
Fig. 2 is the gas chromatogram obtained after syringe microextraction method (A) in embodiment 1 and conventional post chromatography (B) process a typical crude oil sample.
Fig. 3 is the gas chromatogram obtained after syringe microextraction method (A) in embodiment 2 and conventional post chromatography (B) process a typical crude oil sample.
Fig. 4 is the gas chromatogram obtained after syringe microextraction method (A) in embodiment 3 and conventional post chromatography (B) process a typical crude oil sample.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described, and certain following embodiment should not be construed as limitation of the present invention.
Embodiment 1
As shown in Figure 1, the quick pretreatment device of its a kind of crude oil sample provided for the embodiment of the present invention, it comprises syringe, the extraction solvent 2 be contained in syringe, condenser 3, sealing gasket 6, glass wool 7, sample cell 10, nitrogen pipeline 9, heating arrangement 8 and stainless steel wire 4.Syringe comprises cylindrical shell 1 and injection needle 5.In the present embodiment, the core bar of syringe is removed.Glass wool 7 is for load crude oil sample to be detected.It is inner that glass wool 7 is arranged on sample cell 10.Sealing gasket 6 is for sealed sample Chi Kou.Condenser 3 is for cooling the extraction solvent 2 in injector cartridge 1.Extraction solvent 2 is instilled in the glass wool 7 in sample cell 10 by injection needle 5.Heating arrangement 8 is for heated sample pond 10.Stainless steel wire 4 is inserted in injector cartridge 1.Nitrogen pipeline 9 is jetted bottom glass wool 7 from bottom to top for making nitrogen, and jets in injector cartridge 1 by injection needle 5, by injector cartridge 1 mouthful discharge.Condenser 3 in the present embodiment is liquid nitrogen condensation device.
The present embodiment also provides a kind of quick pretreatment method of crude oil sample, and it comprises the following steps:
1) lower end of two sample hoses led to is loaded glass wool, then 6.0mg detected sample is joined on the glass wool of sample hose;
2) enter preheating by heating arrangement to sample hose, preheat temperature is 20 DEG C, and preheating time is 15min;
3) after preheating terminates, injector cartridge is cooled to-4 DEG C, and nitrogen is jetted from bottom to top bottom glass wool, and by described injection needle winding-up in injector cartridge, discharge via injector cartridge mouth, the flow velocity of described nitrogen is 2ml/min;
4) sample hose installing sample is placed in heating arrangement, heating-up temperature is 280 DEG C, and with sealing gasket sealed sample Chi Kou;
5) be inserted in sample cell by the injection needle of syringe, in the cylindrical shell of syringe, then add extraction solvent 10 μ L, start extraction, extraction time is 5min;
6), after extraction terminates, extract syringe rapidly, extraction solvent is advanced into constant volume test tube, use solvent wash syringe subsequently, cleaning solvent is mixed with extraction solvent and is settled to 1.5mL, then take out 1 μ L constant volume liquid and carry out gas chromatographic analysis.
Fig. 2 A is the gas chromatogram using the pre-treating method of the present embodiment to obtain.Fig. 2 B is the gas chromatogram adopting conventional post Image processing crude oil sample to obtain.Conventional post Image processing crude oil sample (from being sampled to sample introduction analysis) needs 2-3 days, and this method only needs about 30 minutes; Classic method needs a large amount of organic solvent (normal hexane, methylene chloride etc.), and this method only needs 10-60 μ L organic solvent.It can also be seen that from Fig. 2 A: this method can trap many high-volatile light hydrocarbon components, and classic method lighter hydrocarbons lose in a large number.This shows that this method is a kind of more efficient, sensitive crude oil sample pre-treating method, has good application prospect.
It should be noted that, in step 5), the injection needle of syringe is inserted into after in sample cell, also comprise the step inserting stainless steel wire in injector cartridge, the syringe in order to avoid extraction solvent is emerged.With methylene chloride equal solvent washing stainless steel wire before inserting stainless steel wire.In the present invention, because nitrogen is constantly jetted, the extraction solvent in injector cartridge can not be got off in slump.After heating, after instrument temperature reduces to 45 degree, take out sample hose.
Embodiment 2
The quick pretreatment device of the crude oil sample of the present embodiment is identical with embodiment 1, and difference is pre-treating method.
The quick pretreatment method of the crude oil sample of the present embodiment comprises the following steps:
1) lower end of two sample hoses led to is loaded glass wool, then 7.0mg detected sample is joined on the glass wool of sample hose;
2) enter preheating by heating arrangement to sample hose, preheat temperature is 20 DEG C, and preheating time is 20min;
3) after preheating terminates, injector cartridge is cooled to-5 DEG C, and nitrogen is jetted from bottom to top bottom glass wool, and by described injection needle winding-up in injector cartridge, discharge via injector cartridge mouth, the flow velocity of described nitrogen is 1ml/min;
4) sample hose installing sample is placed in heating arrangement, heating-up temperature is 300 DEG C, and with sealing gasket sealed sample Chi Kou;
5) be inserted in sample cell by the injection needle of syringe, in the cylindrical shell of syringe, then add extraction solvent 60 μ L, start extraction, extraction time is 3min;
6), after extraction terminates, extract syringe rapidly, extraction solvent is advanced into constant volume test tube, use solvent wash syringe subsequently, cleaning solvent is mixed with extraction solvent and is settled to 0.5mL, then take out 1 μ L constant volume liquid and carry out gas chromatographic analysis.
It should be noted that, in step 5), the injection needle of syringe is inserted into after in sample cell, also comprise the step inserting stainless steel wire in injector cartridge, the syringe in order to avoid extraction solvent is emerged.When extraction solvent is greater than 10 μ L, stainless steel wire is rolled into screw type.
Embodiment 3
The quick pretreatment device of the crude oil sample of the present embodiment is identical with embodiment 1, and difference is pre-treating method.The quick pretreatment method of the crude oil sample of the present embodiment comprises the following steps:
1) lower end of two sample hoses led to is loaded glass wool, then 8.0mg detected sample is joined on the glass wool of sample hose;
2) enter preheating by heating arrangement to sample hose, preheat temperature is 20 DEG C, and preheating time is 30min;
3) after preheating terminates, injector cartridge is cooled to-5 DEG C, and nitrogen is jetted from bottom to top bottom glass wool, and by described injection needle winding-up in injector cartridge, discharge via injector cartridge mouth, the flow velocity of described nitrogen is 1ml/min;
4) sample hose installing sample is placed in heating arrangement, heating-up temperature is 320 DEG C, and with sealing gasket sealed sample Chi Kou;
5) be inserted in sample cell by the injection needle of syringe, in the cylindrical shell of syringe, then add extraction solvent 30 μ L, start extraction, extraction time is 2min;
6), after extraction terminates, extract syringe rapidly, extraction solvent is advanced into constant volume test tube, use solvent wash syringe subsequently, cleaning solvent is mixed with extraction solvent and is settled to 1mL, then take out 1 μ L constant volume liquid and carry out gas chromatographic analysis.
It should be noted that, in step 5), the injection needle of syringe is inserted into after in sample cell, also comprise the step inserting stainless steel wire in injector cartridge, the syringe in order to avoid extraction solvent is emerged.When extraction solvent is greater than 10 μ L, stainless steel wire is rolled into screw type.
A kind of injector type micro-extraction device that the present invention adopts carries out quick pretreatment to crude oil sample, and treasury is got, purify, simmer down to one.The method have simple to operate, reagent dosage is few, extraction efficiency is high, do not discriminate against the features such as effect to different component in crude oil.Crude oil sample is used for gas chromatographic analysis with after this new method and classic method pre-treatment respectively, result shows: except in classic method being obtained well, high boiling component is accurately separated, this method can also isolate some low boiling components that some classic methods lose, and proves that the quick pretreatment method of this crude oil sample is more effectively reliable.
It should be noted that, those of ordinary skill in the art should be appreciated that and can modify to technical scheme of the present invention or equivalent replacement, and does not depart from aim and the scope of technical solution of the present invention, and it all should be encompassed in the middle of right of the present invention.
Claims (3)
1. a quick pretreatment method for crude oil sample, it is characterized in that, it comprises the following steps:
1) lower end of two sample hoses led to is loaded glass wool, then 6.0-8.0mg detected sample is joined on the glass wool of sample hose;
2) enter preheating by heating arrangement to sample hose, preheat temperature is 20 DEG C, and preheating time is 15-30min;
3) after preheating terminates, injector cartridge is cooled to-4 DEG C ~-5 DEG C, and nitrogen is jetted from bottom to top bottom glass wool, and by injection needle winding-up in injector cartridge, discharge via injector cartridge mouth, the flow velocity of described nitrogen is 1-2ml/min;
4) sample hose installing sample is placed in heating arrangement, heating-up temperature is 280-320 DEG C, and with sealing gasket sealed sample Chi Kou;
5) be inserted in sample cell by the injection needle of syringe, in the cylindrical shell of syringe, then add extraction solvent 10-60 μ L, start extraction, extraction time is 1-5min;
6), after extraction terminates, extract syringe rapidly, extraction solvent is advanced into constant volume test tube, use solvent wash syringe subsequently, cleaning solvent is mixed with extraction solvent and is settled to 0.5-1.5mL, then take out 1 ~ 2 μ L constant volume liquid and carry out gas chromatographic analysis.
2. pre-treating method as claimed in claim 1, is characterized in that, in step 5) in the injection needle of syringe is inserted into after in sample cell, also comprise the step inserting stainless steel wire in injector cartridge.
3. pre-treating method as claimed in claim 2, is characterized in that, when extraction solvent is greater than 10 μ L, described stainless steel wire is rolled into screw type.
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| JP2008249572A (en) * | 2007-03-30 | 2008-10-16 | Toppan Printing Co Ltd | Sample pretreatment device and gas chromatography analysis method |
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| WO2005057206A1 (en) * | 2003-12-09 | 2005-06-23 | Bgb Analytik Ag | Device for sample preparation |
| JP2008249572A (en) * | 2007-03-30 | 2008-10-16 | Toppan Printing Co Ltd | Sample pretreatment device and gas chromatography analysis method |
| CN101632876A (en) * | 2009-08-07 | 2010-01-27 | 延边大学 | Airflow type headspace liquid-phase microextraction method |
| CN201662565U (en) * | 2010-04-22 | 2010-12-01 | 延边大学 | New air flow type micro-injector liquid phase micro-extraction device |
| CN101871921A (en) * | 2010-07-02 | 2010-10-27 | 娄大伟 | Needle type extraction device suitable for gas chromatography and using method |
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