CN1591004A - Method of analyzing diesel oil hydrocarbon composition using solid phase extraction and mass chromatogrophy - Google Patents
Method of analyzing diesel oil hydrocarbon composition using solid phase extraction and mass chromatogrophy Download PDFInfo
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- CN1591004A CN1591004A CN 03155996 CN03155996A CN1591004A CN 1591004 A CN1591004 A CN 1591004A CN 03155996 CN03155996 CN 03155996 CN 03155996 A CN03155996 A CN 03155996A CN 1591004 A CN1591004 A CN 1591004A
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 43
- 238000002414 normal-phase solid-phase extraction Methods 0.000 title claims abstract description 35
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 102
- 229930195733 hydrocarbon Natural products 0.000 title claims description 102
- 238000004817 gas chromatography Methods 0.000 claims abstract description 11
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 10
- 238000004949 mass spectrometry Methods 0.000 claims abstract description 7
- 238000004364 calculation method Methods 0.000 claims abstract description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 79
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 28
- 230000005526 G1 to G0 transition Effects 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 23
- 238000000605 extraction Methods 0.000 claims description 21
- 239000000284 extract Substances 0.000 claims description 16
- 238000002798 spectrophotometry method Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 210000004907 gland Anatomy 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000004587 chromatography analysis Methods 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 238000009834 vaporization Methods 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 12
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 14
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 13
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000010813 internal standard method Methods 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- -1 alkane Chemical class 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 238000004523 catalytic cracking Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QHMGJGNTMQDRQA-UHFFFAOYSA-N dotriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC QHMGJGNTMQDRQA-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 125000004062 acenaphthenyl group Chemical class C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 2
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 150000002469 indenes Chemical class 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
一种利用固相萃取和质谱分析柴油烃族组成的方法，包括用固相萃取方法将柴油样品中的饱和烃和芳烃分离，将萃取得到的饱和烃和芳烃溶液全部收集后，分别加入等量内标物，再分别取样进行气相色谱和质谱分析；通过芳烃和饱和烃的气相色谱图计算二者的相对含量，由质谱图得出芳烃和饱和烃的烃族组成；再根据饱和烃和芳烃的相对含量，由归一计算法得到柴油的烃族组成。该方法适用于柴油样品中烃族组成的快速分析。A method for analyzing the hydrocarbon group composition of diesel oil by solid phase extraction and mass spectrometry, comprising separating saturated hydrocarbons and aromatics in a diesel sample by solid phase extraction, collecting all the extracted saturated hydrocarbons and aromatics solutions, adding an equal amount of internal standard, and then sampled for gas chromatography and mass spectrometry analysis; the relative content of the two was calculated through the gas chromatogram of aromatics and saturated hydrocarbons, and the hydrocarbon group composition of aromatics and saturated hydrocarbons was obtained from the mass spectrogram; The relative content of the diesel oil is obtained by the normalized calculation method. This method is suitable for rapid analysis of hydrocarbon group composition in diesel oil samples.
Description
Technical field
The present invention is a kind of method by the group composition of mass spectrophotometry diesel hydrocarbon, specifically, is a kind of method of utilizing Solid-Phase Extraction and the group composition of mass spectrophotometry diesel hydrocarbon.
Background technology
Strengthening gradually and the requirement of clean fuel for vehicle improved constantly along with people's environmental protection consciousness.In new " the world fuel fuel oil meter model " announced, gasoline and diesel oil have been stipulated three different quality classifications, wherein the total aromatic hydrocarbons of derv fuel oil and the content of palycyclic aromatic have been carried out strict restriction.In the light diesel fuel quality national standard of the new revision of China, also to further limit the content of aromatic hydrocarbons and palycyclic aromatic (more than two rings).
The content of accurately measuring aromatic hydrocarbons and palycyclic aromatic is an urgent demand of Oil Production, but in the production run of oil product, the variation of raw material and process conditions will directly influence the composition of petrol and diesel oil with fluctuation.The refinery need grasp the variation that oil product is formed as early as possible, in time adjusts operating conditions and just can produce qualified product.Therefore the analysis efficiency that improves oil product is extremely important in current oil refining production run.
At present, the newest standards method of measuring the diesel oil composition is ASTM D2425, the industry standard that the corresponding therewith mensuration diesel oil of China is formed is SH/T0606-94, be applicable to that the boiling range scope is the middle distillate of 204～343 ℃ (5～95v% recovered temperatures), can determine wherein stable hydrocarbon such as alkane, naphthenic hydrocarbon and the content of monocycle, dicyclo and thrcylic aromatic hydrocarbon.
ASTM D2425 and SH/T0606-94 all adopt the hydrocarbon system of mass spectroscopy diesel oil to form, but need before measuring the aromatic hydrocarbons in the diesel oil is separated with stable hydrocarbon, measure its relative content, carry out the percentage composition that mass spectrophotometry records each hydrocarbon system's component more respectively.According to the relative content of aromatic hydrocarbons and stable hydrocarbon, the hydrocarbon system that is calculated diesel oil by normalization method forms.
In the above-mentioned standard method, ASTM D2425 uses the method for ASTM D 2549, and SH/T0606-94 uses the method for appendix A to determine the relative content of aromatic hydrocarbons and stable hydrocarbon.Two kinds of methods all adopt column chromatography aromatics separation and stable hydrocarbon, adopt weight method to determine its relative content.The concrete operations step is: in separating column, loads porous solid adsorbent earlier, and then uses n-pentane and dichloromethane rinse adsorbent respectively, and flushing stable hydrocarbon and aromatic hydrocarbons wherein, the solvent of removing in the washing fluid by evaporation also reclaims.Treat the complete evaporate to dryness of solvent, weighing aromatic hydrocarbons and saturated hydrocarbon component are to constant weight, thus the relative percentage composition of definite aromatic hydrocarbons and stable hydrocarbon.Wherein the adsorbent of ASTM D2549 use is the bauxite of activation, and SH/T0606-94 is the silica gel of activation.
In the said method, be the accurately quality of weighing aromatic hydrocarbons and stable hydrocarbon, thereby accurately measure its relative content, need isolate more aromatic hydrocarbons and stable hydrocarbon, reach certain precision when guaranteeing to weigh with column chromatography.The difference as a result that general weighing precision requires to repeat twice weighing is not more than 20 milligrams.Therefore, the diesel samples consumption that is used for the column chromatography separation is generally 2～10 grams, and Dui Ying adsorbent consumption is about 70 grams with it.890 millimeters of the chromatogram adsorptive separation post length overalls of using, 10 millimeters of diameters.Separating an oil sample washes with 350 milliliters of n-pentanes and methylene chloride approximately.Operating process is time-consuming many, and about 8 hours of extraction separation process removes and desolvates and about 8 hours of constant weight weighing, so, can't satisfy the needs that express-analysis oil product in refinery's is formed.In addition, the used solvent toxicity of said method is bigger, has not only increased running cost, also can cause certain harm to human body.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing Solid-Phase Extraction and look-matter coupling to analyze diesel samples hydrocarbon system composition, this method analytic sample consumption is few, quick and accurate.
The method of analysis diesel hydrocarbon provided by the invention group composition, comprise with the Solid-Phase Extraction method stable hydrocarbon in the diesel samples is separated with aromatic hydrocarbons, stable hydrocarbon that extraction is obtained and aromatic hydrocarbons solution add the equivalent internal standard compound respectively after all collecting, and gas chromatography and mass spectrophotometry are carried out in sampling respectively again; Calculate the two relative content by the gas chromatogram of aromatic hydrocarbons and stable hydrocarbon, the hydrocarbon system that is drawn aromatic hydrocarbons and stable hydrocarbon by mass spectrogram forms; According to the relative content of stable hydrocarbon and aromatic hydrocarbons, the hydrocarbon system that is obtained diesel oil by the normalizing computing method forms again.
The present invention passes through to add the equivalent internal standard compound in aromatic hydrocarbons that Solid-Phase Extraction is separated and stable hydrocarbon, need not remove the solvent in aromatic hydrocarbons and the stable hydrocarbon extract, and adopt the gas chromatography (GC) of band flame ionic detector (FID) to measure the relative content of aromatic hydrocarbons and stable hydrocarbon in the diesel samples.Therefore, can significantly reduce the consumption of diesel samples, improve the speed that aromatic hydrocarbons and stable hydrocarbon relative content are separated and measured to Solid-Phase Extraction, shorten analysis time, also reduce the consumption of adsorbent and extract methylene chloride and n-pentane simultaneously.Compare with ASTM D2425, the time of assay determination diesel hydrocarbon of the present invention group composition only is about 30 minutes.
Description of drawings
Fig. 1 is the used solid-phase extraction column structural representation of the inventive method.
Fig. 2 is the chromatogram that separates and add the diesel oil saturated hydrocarbon fraction of internal standard compound with the inventive method.
Fig. 3 is the chromatogram that separates and add the arylhydrocarbon in diesel oil cut of internal standard compound with the inventive method.
Embodiment
It is diesel samples is splashed into the stationary phase in the solid-phase extraction column and to be adsorbed fully that the Solid-Phase Extraction that the present invention adopts is separated in the diesel samples method of stable hydrocarbon and aromatic hydrocarbons, extract the wherein stable hydrocarbon of absorption with n-pentane flushing stationary phase then, extract the wherein aromatic hydrocarbons of absorption with the dichloromethane rinse stationary phase again.So the saturated hydrocarbon solution that extraction obtains is the n-pentane solution of stable hydrocarbon, aromatic hydrocarbons solution is the dichloromethane solution of aromatic hydrocarbons.
The diesel samples amount that described Solid-Phase Extraction method needs is the 0.1-0.2 gram, and the 10-25 that the consumption that is used to extract the n-pentane of stable hydrocarbon and aromatic hydrocarbons and methylene chloride is respectively the diesel samples quality doubly.Extract with n-pentane and methylene chloride preferred 0.5-2.0 of time minute.
Described Solid-Phase Extraction is carried out in solid-phase extraction column, and the Solid-Phase Extraction rod structure of employing as shown in Figure 1.As shown in Figure 1, solid-phase extraction column is made up of gland 2 and extraction column 3, gland and extraction column are tightly connected, overflow to prevent component, gland is provided with sample inlet 1, and the extraction column bottom is provided with sample export 6, and stationary phase 5 is housed in the extraction column, stationary phase 5 is equipped with sieve plate 4 up and down, so that sample or extract can be uniformly distributed in the stationary phase.
The post height of solid-phase extraction column of the present invention is the 40-70 millimeter, and column internal diameter is the 4-9 millimeter, and the amount of filling stationary phase is the 1.0-2.0 gram.
The preferred silicon dioxide of described stationary phase, its specific surface area are 450-750 rice
2/ gram, pore volume is 0.35-0.55 milliliter/gram, the aperture is the 50-70% that the hole of 290-350 nanometer accounts for total pore volume.
The use solid-phase extraction column carries out method of extraction and is: earlier diesel samples is splashed in the sample inlet 1 of solid-phase extraction column, sample infiltrates in the stationary phase by the upper strata sieve plate and is adsorbed fully.Then n-pentane is fed solid-phase extraction column and make its outflow, promptly feeding n-pentane from sample inlet 1 makes it pass through to flow out from sample export 6 behind the stationary phase again, when n-pentane passes through stationary phase, stable hydrocarbon in the diesel samples is dissolved in wherein, flow out solid-phase extraction column with n-pentane, thereby extract the stable hydrocarbon that adsorbs in the stationary phase.Afterwards methylene chloride is fed solid-phase extraction column and it is flowed out, methylene chloride is dissolved in the aromatic hydrocarbons of stationary phase absorption wherein, thereby extracts the aromatic hydrocarbons that adsorbs in the stationary phase.
After stable hydrocarbon in the diesel oil and the aromatic hydrocarbons process said method difference extract and separate, obtain the n-pentane solution of stable hydrocarbon and the dichloromethane solution of aromatic hydrocarbons, respectively to the internal standard compound that wherein adds equivalent, get stable hydrocarbon and aromatic hydrocarbons solution example behind an amount of adding internal standard compound again, carry out gas chromatography and Mass Spectrometer Method respectively.By the relative content of stable hydrocarbon and aromatic hydrocarbons in the chromatogram calculation sample, calculate the hydrocarbon composition of diesel samples by mass spectrogram, form by the hydrocarbon system that the relative content of stable hydrocarbon and aromatic hydrocarbons calculates diesel oil by the normalizing computing method again.
In the inventive method, the gas chromatographic analysis of stable hydrocarbon and aromatic hydrocarbons solution, can use gas chromatography (GC-FID) analyser of independent band flame ionic detector, also can adopt gas chromatography-mass spectrum (GC-MS) analyser with the mass spectrometer coupling, be called for short look-matter combined instrument, preferably with quadrupole rod look-matter combined instrument of FID.
During analysis, stable hydrocarbon and aromatic hydrocarbons solution are fed gas chromatography and mass spectrometric injection port successively respectively.Can feed the solution of stable hydrocarbon earlier, feed the solution of aromatic hydrocarbons again, also can feed the solution of aromatic hydrocarbons earlier, feed the solution of stable hydrocarbon again.The amount of stable hydrocarbon and aromatic hydrocarbons solution example should satisfy the needs of analysis, and general consumption is 0.2-2.0 μ L.
When using look-matter combined instrument to carry out the diesel samples analysis, stable hydrocarbon that Solid-Phase Extraction can be obtained and aromatic hydrocarbons solution feed the injection port of chromatographic analysis systems respectively and the injection port of mass spectrometry system is analyzed, preferable methods is that sample is fed look-matter combined instrument that an injection port is arranged, after sample enters the injection port vaporization, be divided into two parts by diverting valve, a part enters chromatographic analysis systems, detect by flame ionic detector, another part enters mass spectrometry system, is detected by mass detector.
Solvent in the described Solid-Phase Extraction liquid, promptly n-pentane and methylene chloride do not need to separate with stable hydrocarbon or aromatic hydrocarbons before analyzing gas chromatographic analysis, only need to add the relative content that internal standard compound can be obtained stable hydrocarbon and aromatic hydrocarbons by the chromatogram analysis.The C that described internal standard compound is selected from
26-C
40N-alkane so that internal standard compound separates with solvent peak well with sample in the spectrogram.Preferred internal standard compound is C
28-C
32N-alkane, more preferably positive structure dotriacontane.Need before internal standard compound uses it is dissolved in n-pentane or the normal hexane, making concentration is 0.5-10.0 quality %, the solution of preferred 0.8-3.0 quality %.
The stable hydrocarbon that obtains behind the adding internal standard compound and the gas chromatogram of aromatic hydrocarbons solution are respectively as shown in Figures 2 and 3.As seen from the figure, the peak wide apart that solvent, measured object, internal standard compound went out in the sample illustrates that they all can separate well, and internal standard compound and solvent all can not influence the test result of stable hydrocarbon or aromatic hydrocarbons.
The present invention is calculated the relative content of stable hydrocarbon and aromatic hydrocarbons according to adding the stable hydrocarbon behind the internal standard compound and the gas chromatogram of aromatic fraction by following method:
If the internal standard compound quality that adds is w, the total peak area of stable hydrocarbon is A in the chromatogram shown in Figure 2
s, interior mark peak area is A
Ns, the total area at aromatic hydrocarbons peak shown in Figure 3 is A
a, interior mark peak area is A
Na, then
Saturated hydrocarbon content %=(A
s* w/A
Ns)/[(A
s* w/A
Ns)+(A
a* w/A
Na)]
＝(A
s/A
ns)/[(A
s/A
ns)+(A
a/A
na)]
Arene content %=(A
a* w/A
Na)/[(A
s* w/A
Ns)+(A
a* w/A
Na)]
＝(A
a/A
na)/[(A
s/A
ns)+(A
a/A
na)]
As can be seen from the above equation, because the internal standard compound that is added in stable hydrocarbon and the aromatic hydrocarbons solution is identical in quality, when calculating relative content, the peak area that only needs to calculate internal standard compound and tested component gets final product.Therefore, interior mark liquid concentration reaches in put procedure because the concentration change that solvent evaporates caused does not have influence to analysis result.
Adopting isolated stable hydrocarbon of Solid-Phase Extraction and aromatic hydrocarbons solution will carry out the hydrocarbon system that mass spectrophotometry just can record separately forms.During operation, press the method control mass spectrophotometry condition of ASTM D2425 or SH/T0606-94, the stable hydrocarbon that records is similar with Fig. 3 to Fig. 2 with the total ions chromatogram of aromatic fraction, internal standard compound, solvent effectively separate with the mass spectrum peak energy of measured object, and promptly internal standard compound and solvent all do not influence the hydrocarbon composition calculating of sample.After the stable hydrocarbon that mass spectrum is recorded and the mass spectrogram of aromatic hydrocarbons sample add up, calculate the mass percent of stable hydrocarbon such as alkane, naphthenic hydrocarbon and monocycle, dicyclo and thrcylic aromatic hydrocarbon respectively by the method for ASTM D2425 or SH/T0606-94.This percentage be multiply by with the stable hydrocarbon of internal standard method GC-FID mensuration and the relative content of aromatic hydrocarbons, and normalizing calculates the hydrocarbon system that promptly draws diesel samples and forms.
The suitable diesel oil of measuring with the inventive method has straight-run diesel oil, hydrogenated diesel oil, catalytic cracking diesel oil and commercial Dissel oil.
Below by example in detail the present invention, but the present invention is not limited to this.
The used instrument of example is the quadrupole rod gas chromatograph-mass spectrometer (GCMS), and model is HP6890GC/5973MS, the band fid detector.Operating conditions is: sample size 0.5 μ L, split ratio 20: 1, chromatographic column HP-5MS capillary column 30m * 0.25mm * 0.1 μ m, 300 ℃ of GC injector temperatures, 280 ℃ of GC/MS interface temperature, GC post oven temperature, degree keeps 3min for 80 ℃, rise to 300 ℃ with 40 ℃/min again, keep 5min.
Example 1
Investigate the applicability that internal standard method GC-FID of the present invention measures stable hydrocarbon and aromatic hydrocarbons relative content in the diesel samples.
The activation silicon dioxide of filling 1.6 grams in the solid-phase extraction column that, internal diameter high 60 millimeters at post is 7.0 millimeters, its specific surface area is 600 meters
2/ gram, pore volume are that 0.45 milliliter/gram, aperture are that the hole of 290-330 nanometer accounts for 60% of total pore volume.
Press the method for ASTM D2549 and separate the stable hydrocarbon and the aromatic hydrocarbons of diesel samples, separately after the constant weight weighing, be mixed with the sample of 4 different stable hydrocarbon and arene content, the preparation sample of getting 0.12 gram splashes in the solid-phase extraction column, and the sample aerosil that promptly is fixed adsorbs fully.In solid-phase extraction column, add 2.0 milliliters of n-pentanes then, flushing stationary phase extraction stable hydrocarbon wherein, the time is 0.5 minute, collects the n-pentane extract.Go out the aromatic hydrocarbons of stationary phase absorption again with 2.0 milliliters of dichloromethane extractions, the extraction time is 0.5 minute, collects dichloromethane extraction liquid.
The concentration that adds 1.0 milliliters in n-pentane extract that collection obtains and dichloromethane extraction liquid respectively is the n-pentane solution of the positive structure dotriacontane of 1.0 quality %, get n-pentane extract and each 0.5 μ L of dichloromethane extraction liquid of adding behind the internal standard compound then, feed the injection port of GC-MS combined instrument successively, pass through diverting valve, a part of sample is sent into the GC-FID detection system, carry out stratographic analysis; Another sample is sent into the Mass Spectrometer Method system, measures hydrocarbon system and forms.By the calculated by peak area stable hydrocarbon of chromatogram and the relative content of aromatic hydrocarbons.
The present invention uses the stable hydrocarbon of the preparation sample that internal standard method GC-FID measures and the comparing result of aromatic hydrocarbons relative content and sample actual content to see Table 1, and employing internal standard method GC-FID replication the results are shown in Table 2.
As shown in Table 1, adopt the actual content of the stable hydrocarbon of stable hydrocarbon that internal standard method GC-FID measures and arene content and the sample of preparation in advance and aromatic hydrocarbons very approaching, illustrate that the accuracy of mensuration is higher.Method of testing of the present invention as known from Table 2 has better repeatability.
Example 2
Method by example 1 is analyzed different diesel samples, the different diesel samples that splash in extraction column when being Solid-Phase Extraction.Aromatic hydrocarbons and saturated hydrocarbon content that internal standard method GC-FID measures see Table 3, and hydrocarbon system's composition of mass spectroscopy sees Table 4, and wherein hydrocarbon system's composition is pressed the calculating of ASTM D2425 method.To form complete analysis time be 30 minutes to each sample to providing hydrocarbon system from extract and separate.
In the table 3, the used internal standard method GC-FID of the present invention measures the stable hydrocarbon of diesel oil and compares with ASTM D2549 method with the aromatic hydrocarbons relative content, and in 8 diesel samples analyzing, difference is 1.2% to the maximum, satisfies the repeatability requirement of ASTM D2549 fully.
As shown in Table 4, the inventive method is compared with ASTM D2425, and total aromatic hydrocarbons difference is all less than 1%, and palycyclic aromatic differs 2.5% except that catalytic cracking diesel oil, and straight-run diesel oil and hydrogenated diesel oil differ all less than 0.6%, satisfy the repeatability requirement of ASTM D2425 substantially.But the indane or the tetralin of some samples exceed standard, hydrogenated diesel oil particularly, because the raw material of hydrogenated diesel oil is a catalytic cracking diesel oil, its double ring arene content is very high, and after hydrotreating, an aromatic ring is saturated by hydrogenation, causes indane or tetralin class content very high.Indane or tetralin class content is when 2-5% in the ASTMD2425 method, and repeatability is less than 0.5%, and the content of the indane of some hydrogenated diesel oil and tetralin class is considerably beyond 5%, and this is the main cause that indane and tetralin class repeatability exceed standard.
Table 1
The content that internal standard method GC-FID measures, quality % actual content, quality %
The preparation sample
Stable hydrocarbon aromatic hydrocarbons stable hydrocarbon aromatic hydrocarbons
1 49.5 50.5 49.5 50.5
2 62.2 37.8 61.6 38.4
3 77.6 22.4 77.4 22.6
4 85.2 14.8 85.0 15.0
Table 2
Multiplicity 123456 mean values
Stable hydrocarbon 49.2 49.3 49.9 49.7 49.6 49.3 49.5
Aromatic hydrocarbons 50.8 50.7 50.1 50.3 50.4 50.7 50.5
Table 3
The interior mark GC-FID that the D2549 method is measured measures
Diesel samples content, the content of quality %, quality % difference, %
Stable hydrocarbon aromatic hydrocarbons stable hydrocarbon aromatic hydrocarbons
Straight-run diesel oil 87.8 12.2 87.5 12.5 0.3
Hydrogenated diesel oil 1 84.9 15.1 85.0 15.0 0.1
Hydrogenated diesel oil 2 76.0 24.0 76.7 23.3 0.7
Hydrogenated diesel oil 3 65.9 34.1 66.0 34.0 0.1
Hydrogenated diesel oil 4 62.6 37.4 61.7 38.3 0.9
Hydrogenated diesel oil 5 59.7 40.3 59.9 40.1 0.2
Hydrogenated diesel oil 6 51.0 49.0 52.2 47.8 1.2
Catalytic cracking diesel oil 68.2 31.8 68.9 31.1 0.7
Table 4
Sample straight-run diesel oil hydrogenated diesel oil 1 hydrogenated diesel oil 2 hydrogenated diesel oils 3
This
Analytical approach D2425 D2425 of the present invention D2425 of the present invention D2425 of the present invention
Bright
Hydrocarbon composition, quality %
Alkane 56.0 53.2 45.9 45.9 37.5 40.0 38.9 40.6
One ring cycloalkanes 20.7 21.6 14.8 15.8 9.5 9.5 13.5 10.6
Bicyclic ring alkane 8.6 10.1 16.7 16.2 16.2 15.1 8.4 9.4
Tricyclic naphthenes 2.2 2.3 6.8 6.0 12.5 11.5 4.5 4.8
Total naphthenic hydrocarbon 31.2 34.0 38.0 38.0 38.2 36.1 26.4 24.8
Total stable hydrocarbon 87.5 87.2 84.2 83.9 75.7 76.1 65.3 65.4
Alkyl benzene 3.6 3.8 6.6 7.5 5.5 5.2 7.5 8.4
Indane or
2.5 2.5 4.8 4.3 10.1 8.7 14.6 13.7
The tetralin class
Indenes class 1.0 0.9 2.0 2.0 5.9 6.6 6.7 6.7
Total mononuclear aromatics 7.1 7.2 13.4 13.8 21.5 20.5 28.8 28.8
Naphthalene class 3.0 3.1 1.1 1.1 1.7 2.0 2.9 2.8
Acenaphthene class 0.9 0.8 0.7 0.6 0.4 0.5 1.4 1.5
Acenaphthylene class 0.8 0.9 0.4 0.4 0.5 0.7 1.3 1.2
Total double ring arene 4.7 4.8 2.2 2.1 2.6 3.2 5.6 5.5
Thrcylic aromatic hydrocarbon 0.7 0.8 0.2 0.2 0.2 0.2 0.3 0.3
Total aromatic hydrocarbons 12.5 12.8 15.8 16.1 24.3 23.9 34.7 34.6
Continuous table 4
Sample hydrogenated diesel oil 4 hydrogenated diesel oils 5 hydrogenated diesel oils 6 catalytic cracking diesel oil *
Ben Fabenfabenfabenfa
Analytical approach D2425 D2425 D2425 D2425
Obviously
Hydrocarbon composition, quality %
Alkane 41.0 39.7 39.7 38.8 37.6 39.9 39.6 39.6
One ring cycloalkanes 6.8 10.6 9.9 9.3 10.2 8.0 6.9 11.6
Bicyclic ring alkane 10.1 8.8 7.3 8.5 2.4 3.1 15.8 11.8
Tricyclic naphthenes 4.0 3.1 2.4 2.9 0.6 1.0 5.9 5.9
Total naphthenic hydrocarbon 20.9 22.5 19.6 20.7 13.2 12.1 28.6 29.3
Total stable hydrocarbon 61.9 62.2 59.3 59.5 50.8 52.0 68.2 68.9
Alkyl benzene 9.6 10.1 10.7 11.5 12.7 12.5 9.5 10.4
Indane or
16.1 15.1 17.4 16.0 20.3 18.2 5.0 4.8
The tetralin class
Indenes class 5.3 5.6 4.9 5.5 4.3 5.1 1.8 2.9
Total mononuclear aromatics 31.0 30.8 33.0 33.0 37.3 35.8 16.3 18.1
Naphthalene class 2.9 3.0 3.1 3.1 4.5 4.8 7.9 6.3
Acenaphthene class 2.0 1.7 1.8 1.8 3.7 3.3 3.4 2.7
Acenaphthylene class 1.6 1.6 2.0 1.8 2.3 2.6 2.2 2.2
Total double ring arene 6.5 6.3 6.9 6.7 10.5 10.7 13.5 11.2
Thrcylic aromatic hydrocarbon 0.6 0.7 0.8 0.8 1.4 1.5 2.0 1.8
Total aromatic hydrocarbons 38.1 37.8 40.7 40.5 49.2 48.0 31.8 31.1
*Classical way is isolated 0.9% colloid.
Claims (11)
1, a kind of method of utilizing Solid-Phase Extraction and the group composition of mass spectrophotometry diesel hydrocarbon, comprise with the Solid-Phase Extraction method stable hydrocarbon in the diesel samples is separated with aromatic hydrocarbons, after stable hydrocarbon that extraction is obtained and aromatic hydrocarbons solution are all collected, add the equivalent internal standard compound respectively, gas chromatography and mass spectrophotometry are carried out in sampling respectively again; Calculate the two relative content by the gas chromatogram of aromatic hydrocarbons and stable hydrocarbon, the hydrocarbon system that is drawn aromatic hydrocarbons and stable hydrocarbon by mass spectrogram forms; According to the relative content of stable hydrocarbon and aromatic hydrocarbons, the hydrocarbon system that is obtained diesel oil by the normalizing computing method forms again.
2, in accordance with the method for claim 1, it is characterized in that described Solid-Phase Extraction method is diesel samples is splashed into the stationary phase in the solid-phase extraction column and to be adsorbed fully, extract the wherein stable hydrocarbon of absorption with n-pentane flushing stationary phase then, extract the wherein aromatic hydrocarbons of absorption with the dichloromethane rinse stationary phase again.
3, in accordance with the method for claim 1, it is characterized in that extracting the n-pentane solution that the saturated hydrocarbon solution that obtains is a stable hydrocarbon, aromatic hydrocarbons solution is the dichloromethane solution of aromatic hydrocarbons.
4, in accordance with the method for claim 2, it is characterized in that used diesel samples is the 0.1-0.2 gram, the amount that extracts used n-pentane and methylene chloride is respectively 10-25 times of diesel samples quality.
5, in accordance with the method for claim 2, it is characterized in that described solid-phase extraction column is made up of gland (2) and extraction column (3), gland and extraction column are tightly connected, gland is provided with sample inlet (1), the extraction column bottom is provided with sample export (6), stationary phase (5) is housed in the extraction column, and stationary phase (5) is equipped with sieve plate (4) up and down.
6, in accordance with the method for claim 5, it is characterized in that the post height of described extraction column is the 40-70 millimeter, column internal diameter is the 4-9 millimeter, and the stationary phase of filling is the 1.0-2.0 gram.
7, according to described any one method of claim 2-6, it is characterized in that described stationary phase is a silicon dioxide, its specific surface area is a 450-750 rice
2/ gram, pore volume is 0.35-0.55 milliliter/gram, the aperture is the 50-70% that the hole of 290-350 nanometer accounts for total pore volume.
8, in accordance with the method for claim 1, it is characterized in that described internal standard compound is C
26-C
40N-alkane, need before using it is dissolved in n-pentane or the normal hexane, make the solution that concentration is 0.5-10.0 quality %.
9, in accordance with the method for claim 1, it is characterized in that adopting the look-matter combined instrument that has flame ionic detector that stable hydrocarbon and aromatic hydrocarbons solution are carried out gas chromatography and mass spectrophotometry.
10, in accordance with the method for claim 9, it is characterized in that described look-matter combined instrument is quadrupole rod look-matter combined instrument.
11, according to claim 9 or 10 described methods, it is characterized in that described look-matter combined instrument has an injection port, after sample enters the injection port vaporization, be divided into two parts by diverting valve, a part enters chromatographic analysis systems, detected by flame ionic detector, another part enters mass spectrometry system, is detected by mass detector.
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