CN1690704A - Process for determining hydrocarbon composition of vacuum gas oil by combination of solid phase extraction and mass spectrum - Google Patents
Process for determining hydrocarbon composition of vacuum gas oil by combination of solid phase extraction and mass spectrum Download PDFInfo
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- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 109
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- 238000000034 method Methods 0.000 title claims abstract description 63
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- 238000010606 normalization Methods 0.000 claims abstract description 4
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Abstract
A composition measurement method for hydrocarbon of vacuum gas oil by solid phase extraction combination mass spectrum comprises that separate the oil to three parts of saturated hydrocarbon, arene and gum by solid phase extraction, analyze their corresponding content by weighing or gas chromatography; detect makeup of saturated hydrocarbon and arene by mass spectrum; use normalization method to compute hydrocarbon composition of vacuum gas oil according to corresponding content of saturated hydrocarbon and arene; stationary phase of aforementioned solid phase extraction is silicon dioxide with specific surface is 450~750m<SUP>2<SUP>g, pore volume is 0.35~0.55ml/g, and pore with aperture 290~350nm takes up 50~70% of total pore volume. The method need less oil sample, and is quick and accurate.
Description
Technical field
The present invention is a kind of method of forming by mass spectroscopy vacuum gas oil hydrocarbon system, specifically, is that a kind of Solid-Phase Extraction and mass spectrometry method of utilizing measured the method that vacuum gas oil hydrocarbon system forms.
Background technology
The hydrocarbon composition of vacuum gas oil (VGO) distributes directly influences catalytic cracking and lube base oil properties of product, also is simultaneously the important evidence of selecting reasonable processing scheme, therefore, need set up VGO sample hydrocarbon group composition analysis method fast and accurately.
At present, the method for analysis VGO hydrocarbon composition mainly contains classical liquid phase chromatography, high performance liquid chromatography, supercritical fluid chromatography, thin-layer chromatography-flame ion detection method (TLC-FID) and ultraviolet spectroscopy etc.These methods have solved VGO to a certain extent and have produced and scientific research requirements, but also have some problems.
Mass spectrometry (MS) has highly sensitive, flexible operation, can provide the hydrocarbon composition of complicated hydrocarbon mixture in the oil product and the advantages such as detailed data of homolog carbon number distribution, therefore is the important means that oil and petroleum products hydrocarbon composition are analyzed always.
ASTM D2786 and D3239 method set up respectively use lowly differentiate, method that macroion voltage mass spectrum is measured heavy oil fraction stable hydrocarbon and aromatic hydrocarbon cut hydrocarbon composition, this two methods are to measure mink cell focus hydrocarbon system to form comparatively ripe standard method at present.But these two methods need be carried out the pre-service separation to working sample, separate wherein stable hydrocarbon and aromatic hydrocarbon, to obtain their relative content.Method shown in the separation employing ASTM D2549 is utilized stable hydrocarbon, aromatic hydrocarbon and the colloid in the solid phase extraction sample separation.The chromatographic column that this method Solid-Phase Extraction is used is the bulb tube of top dribbling shape interface, and what be connected with the bulb tube bottom is a long and narrow column jecket, and column length is 760～1150 millimeters.The top of long and narrow post and bulb tube joint filling stationary phase, the bottom of stationary phase is a glass fibre, and the middle level is a silicon dioxide, and the upper strata is a bauxite.For guaranteeing the accuracy of test, the consumption of sample is 2～10 grams.Elder generation's weighing example weight during extracting operation, add n-pentane again with sample dissolution, be poured in the bulb tube of chromatographic column top, make it flow into stationary phase and be adsorbed, use n-pentane, diethyl ether, methenyl choloride, ethanol extraction stable hydrocarbon, aromatic hydrocarbon, colloid then respectively, obtain the extract of each component, dry then extract, remove solvent wherein, and determine with the method for weighing whether solvent volatilizees fully, and the stable hydrocarbon that obtains of calculating separation and the relative content of aromatic hydrocarbon.Though this method is accurate, many with the sample amount, the detachment process step is many, and the extraction solvent consumption is big, velocity of separation is slow, and weighing determines that the time of stable hydrocarbon and aromatic hydrocarbon content is long.Therefore, be unsuitable for analyzing in batches, apace the needs of VGO sample.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing Solid-Phase Extraction and mass spectrophotometry vacuum gas oil hydrocarbon system to form, the used sample size of this method is few, analyzes fast, accurately.
Solid-Phase Extraction provided by the invention and mass spectrometry are measured the method that vacuum gas oil hydrocarbon system forms, comprise vacuum gas oil is divided into stable hydrocarbon, aromatic hydrocarbon and three components of colloid by Solid-Phase Extraction, by weighing or the relative content of three kinds of components is measured in gas chromatographic analysis, with the stable hydrocarbon of mass spectroscopy gained and the hydrocarbon composition of aromatic component, form with the hydrocarbon system that normalization method calculates vacuum gas oil according to the relative content of stable hydrocarbon and aromatic hydrocarbon again, the used stationary phase of described Solid-Phase Extraction is a silicon dioxide, and 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.
The present invention adopts aromatic hydrocarbons, stable hydrocarbon and the colloid in the solid phase extraction separation vacuum gas oil, the used stationary phase silicon dioxide of Solid-Phase Extraction has suitable surface area and pore volume distribution, can be under the few situation of amount of samples, effectively separate each component in the vacuum gas oil, satisfy the requirement of follow-up analysis.Thereby can shorten analysis time, reduce the consumption of stationary phase and the used extract of extraction simultaneously.Compare with the ASTMD3239 method with ASTM D2786, the time that assay determination VGO of the present invention hydrocarbon system forms is about 0.5～1.0 hour.
Description of drawings
Fig. 1 is the used solid-phase extraction column structural representation of the inventive method.
Fig. 2 is the chromatogram of the saturated hydrocarbon fraction of the vacuum gas oil of adding internal standard compound in the inventive method.
Fig. 3 is the chromatogram of the aromatic hydrocarbon cut of the vacuum gas oil of adding internal standard compound in the inventive method.
Fig. 4 is the chromatogram of the colloid cut of the vacuum gas oil of adding internal standard compound in the inventive method.
Embodiment
The inventive method adopts stable hydrocarbon, aromatic hydrocarbon and the glial component in the solid phase extraction separation vacuum gas oil, and then adopt weight method or gas chromatography to determine their relative content, hydrocarbon system by mass spectrophotometry stable hydrocarbon, aromatic hydrocarbon forms, and determines that with normalization method the hydrocarbon system of vacuum gas oil forms according to the two relative content in vacuum gas oil again.
Described Solid-Phase Extraction is the vacuum gas oil sample 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 or normal hexane flushing stationary phase then, extract the wherein aromatic hydrocarbon of absorption with the dichloromethane rinse stationary phase again, the mixed liquor flushing stationary phase with benzene-ethanol extracts the wherein colloid of absorption afterwards.The volume ratio of benzene and ethanol is 1 in the mixed liquor of described benzene-ethanol: 0.5-5.0, preferred 1: 1.0-2.0.
The amount of the used vacuum gas oil of Solid-Phase Extraction is the 0.1-0.3 gram, the consumption that is used to extract the n-pentane of stable hydrocarbon or normal hexane be vacuum gas oil 10-30 doubly, the methylene chloride consumption of extraction aromatic hydrocarbon is 10-25 a times of vacuum gas oil, and the benzene-ethanol consumption of extraction colloid is 10-15 a times of vacuum gas oil.The time that extracts described stable hydrocarbon, aromatic hydrocarbon and colloid was respectively 0.5-2.0 minute, preferred 0.5-1.0 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 described extraction column is the 40-70 millimeter, and column internal diameter is the 4-9 millimeter, and the stationary phase of filling is the 1.0-2.0 gram.
The use solid-phase extraction column carries out method of extraction and is: earlier the vacuum gas oil sample 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 sample is dissolved in wherein, flow out solid-phase extraction column with n-pentane, thereby extract the stable hydrocarbon that adsorbs in the stationary phase.The also available normal hexane of described n-pentane replaces.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 treating that methylene chloride all flows out,, obtain containing the benzene-ethanolic solution of colloid from the colloid that sample inlet 1 feeds benzene-ethanol extraction sample.
Solid-Phase Extraction is separated the stable hydrocarbon, aromatic hydrocarbon and the colloidal solution that obtain can pass through weight method or each components contents of gas chromatography determination.The method of weighing is saturated hydrocarbon solution dry evaporation in 50-60 ℃ of water-bath that extraction is obtained, remove desolvate n-pentane or normal hexane, the room temperature weighing can obtain the content of stable hydrocarbon to constant weight, same in 50-60 ℃ of water-bath the extract of dry aromatic hydrocarbon, methylene chloride is wherein evaporated, the room temperature weighing can record the content of aromatic hydrocarbon to constant weight.With colloidal solution dry evaporation in 80-90 ℃ of water-bath that extraction obtains, remove solvent benzol-ethanol, the room temperature weighing can obtain the content of colloid to constant weight.
Method with three component concentrations in the gas chromatography determination sample is: in the stable hydrocarbon that after extraction, obtains, aromatic hydrocarbon and the glial component successively by 1: 1: the amount of 0.2-0.8 adds internal standard compound, and described internal standard compound is selected from C
14-C
18N-alkane, get each component that adds behind the internal standard compound then and feed gas chromatograph successively, carry out gas Chromatographic Determination respectively, by the relative content of stable hydrocarbon, aromatic hydrocarbons and colloid in the chromatogram calculation sample.Solvent in each extract, promptly n-pentane, methylene chloride or benzene-ethanol do not need to separate with stable hydrocarbon, aromatic hydrocarbons or colloid before carrying out gas chromatographic analysis.
Before adding internal standard compound, internal standard compound is dissolved in makes the solution that concentration is 0.3～5.0 quality %, preferred 0.2-2.0 quality % in n-pentane or the normal hexane earlier.
The gas chromatogram that adds the stable hydrocarbon, aromatic hydrocarbons and the colloidal solution that obtain behind the internal standard compound is respectively shown in Fig. 2,3,4.As seen from the figure, the peak wide apart that 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 their test result.
According to the gas chromatogram of stable hydrocarbon, aromatic hydrocarbons and colloid cut behind the adding internal standard compound, by the relative content between the following formula calculating three.
The stable hydrocarbon relative content:
S％＝(A
s×w
1/A
nS)/[(A
s×w
1/A
nS)+(A
A×w
2/A
nA)+(A
R×w
3/A
nR)]????(1)
The aromatic hydrocarbon relative content:
A％＝(A
A×w
2/A
nA)/[(A
s×w
1/A
nS)+(A
A×w
2/A
nA)+(A
R×w
3/A
nR)]????(2)
The colloid relative content:
R％＝(A
R×w
3/A
nR)/[(A
s×w
1/A
nS)+(A
A×w
2/A
nA)+(A
R×w
3/A
nR)]????(3)
In formula (1)～(3), A-peak area, a-aromatic hydrocarbons, s-stable hydrocarbon, r-colloid, n-internal standard compound;
A
NS, A
NA, A
NRBe respectively on the stable hydrocarbon that adds internal standard compound, aromatic hydrocarbon, the colloid chromatogram peak area of internal standard compound;
w
1, w
2, w
3Be respectively the weight that adds internal standard compound in stable hydrocarbon, aromatic hydrocarbon, the colloidal solution.
As shown from the above formula: when the interior scalar that adds in stable hydrocarbon, aromatic hydrocarbons and the colloidal solution was proportional, interior scalar was not participated in calculating when asking each component relative content.Therefore, interior mark liquid concentration reaches in put procedure because the concentration change that solvent evaporates caused does not have influence to analysis result.
Adopt isolated stable hydrocarbon of Solid-Phase Extraction and aromatic component will carry out mass spectrophotometry and could measure separately hydrocarbon system's composition.During operation, press the method control mass spectrophotometry condition of ASTM D2425 or SH/T0606-94, the total ions chromatogram of stable hydrocarbon that records and aromatic hydrocarbon cut is similar with Fig. 3 to Fig. 2, internal standard compound effectively separates 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 hydrocarbon 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 the relative content of stable hydrocarbon and aromatic hydrocarbon after the influence of the removal gum level of measuring with chromatography or weight method, be about to extract the stable hydrocarbon and the aromatic hydrocarbon content that obtain and be considered as 100% the two relative content of calculating, by the stable hydrocarbon of removing the colloid influence and the relative content of aromatic hydrocarbon, the hydrocarbon system that normalizing calculates vacuum gas oil forms again.
In the inventive method, the gas chromatographic analysis of stable hydrocarbon, aromatic hydrocarbon and colloidal 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, the amount of stable hydrocarbon, aromatic hydrocarbon and colloidal solution sample should satisfy the needs of analysis, and general consumption is 0.2-2.0 μ L.
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, detect the relative content of stable hydrocarbon, aromatic hydrocarbon and colloid by flame ionic detector, stable hydrocarbon and aromatic component in another part enter mass spectrometry system, are detected the group composition of stable hydrocarbon and aromatic hydrocarbon by mass detector.
The sample that is suitable for the inventive method mensuration is the straight run vacuum gas 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.
Gas chromatography (GC) condition of work: sample size 0.5uL, split ratio 20: 1, chromatographic column are empty capillary column 30m * 0.25mm, 330 ℃ of injector temperatures, post oven temperature, degree kept 1 minute at 90 ℃, was warming up to 330 ℃ with 30 ℃ of/minute speed then, kept 5 minutes.
Mass spectrum (MS) condition of work: EI ionization mode, bombarding voltage 70eV, sweep limit 50～700amu, 250 ℃ of ion source temperatures, 300 ℃ of GC/MS interface temperature.
Example 1
Investigate the applicability that internal standard method GC-FID of the present invention measures stable hydrocarbon and aromatic hydrocarbon relative content in the VGO sample.
The activation silicon dioxide of filling 1.8 grams in the solid-phase extraction column that, internal diameter high 60 millimeters at as shown in Figure 1 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, get 2 gram VGO samples, separate wherein stable hydrocarbon, aromatic hydrocarbons and colloid, separately after the constant weight weighing, be mixed with 4 samples with different stable hydrocarbon and arene content, the preparation sample of getting 0.10 gram splashes in the solid-phase extraction column, and the sample aerosil that promptly is fixed adsorbs fully.In solid-phase extraction column, add 2.5 milliliters of n-pentanes then, flushing stationary phase extraction stable hydrocarbon wherein, the time is 1 minute, collects the n-pentane extract.Go out the aromatic hydrocarbons of stationary phase absorption again with 2.5 milliliters of dichloromethane extractions, the extraction time is 1 minute, collects dichloromethane extraction liquid.Use the benzene-ethanolic solution of 1.5 milliliters of preparations in 1: 1 by volume to extract the colloid that stationary phase adsorbs again, the extraction time is 0.5 minute, collects benzene-alcohol extraction liquid.
The inner mark solution that adds 1.0,1.0,0.2 milliliters in n-pentane extract, dichloromethane extraction liquid and the benzene-alcohol extraction liquid that collection obtains respectively, inner mark solution is the n-pentane solution of the normal cetane of concentration 0.5 quality %.Get each the 0.5 μ L of n-pentane extract, dichloromethane extraction liquid and benzene-alcohol extraction liquid that adds behind the internal standard compound, feed the injection port of GC-MS combined instrument successively,, a part of sample is sent into the GC-FID detection system, carry out stratographic analysis by diverting valve; Another sample is sent into the Mass Spectrometer Method system, measures hydrocarbon system and forms.Relative content by calculated by peak area stable hydrocarbon, aromatic hydrocarbons and the colloid of chromatogram.
The present invention uses internal standard method GC-FID to measure stable hydrocarbon, aromatic hydrocarbon and the colloid relative content of preparation sample and the comparing result of sample actual content sees Table 1, adopts internal standard method GC-FID replication to the results are shown in Table 2.
As shown in Table 1, the result who adopts internal standard method GC-FID to measure is very approaching with the actual content of stable hydrocarbon, aromatic hydrocarbon and the colloid of the sample of preparing in advance, illustrates that the accuracy of measuring 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 the VGO sample, and different is to splash into the VGO sample in solid-phase extraction column, extracts wherein stable hydrocarbon, aromatic hydrocarbon and colloid.With the extract of the stable hydrocarbon of gained, aromatic hydrocarbon in 50～60 ℃ of water-baths dry 30 minutes respectively, weigh under the room temperature, and then under this temperature dry 10 minutes, weigh again, repeat dry and the step of weighing, solvent all volatilizees in extract, and twice weighing result numerical difference between is no more than 10 milligrams, promptly is considered as constant weight.The stable hydrocarbon that obtains after the record weighing constant weight and the quality of aromatic hydrocarbon, the colloidal solution that in the same way extraction is obtained is dry in 80～90 ℃ of water-baths then, is weighed into solvent and all volatilizees, the colloid quality that obtains after the record weighing constant weight.The overall recovery of measuring 6 VGO sample Solid-Phase Extraction/weight methods sees Table 3.Table 3 is the result show, the Solid-Phase Extraction overall recovery illustrates that all more than 98% the measurement result of the used weight method of the present invention is reliable.According to the result of weighing measurement, calculate stable hydrocarbon and the relative content of aromatic hydrocarbon in the two total amount.
Get stable hydrocarbon, each 0.5 μ L of aromatic hydrocarbon sample after weighing, carry out mass spectrophotometry, press the method for ASTM D2425 and calculate hydrocarbon system's composition, multiply by the relative content of stable hydrocarbon, aromatic hydrocarbon more respectively, hydrocarbon system's composition of the VGO sample that obtains sees Table 4.
Example 3
Method by example 1 is analyzed the VGO sample, and different is to splash into the VGO sample in solid-phase extraction column, extracts wherein stable hydrocarbon, aromatic hydrocarbon and colloid.Get each the 0.5 μ L of each component extracting liquid that adds internal standard compound, feed the injection port of GC-MS combined instrument,, a part of sample is sent into the GC-FID detection system, carry out stratographic analysis by diverting valve; Another sample is sent into the Mass Spectrometer Method system, measures hydrocarbon system and forms.Relative content by calculated by peak area stable hydrocarbon, aromatic hydrocarbon and the colloid of gas chromatogram, press the method for ASTM D2425 and calculate hydrocarbon system's composition, the stable hydrocarbon that the GC-FID spectrogram is calculated, the relative content of aromatic hydrocarbon in the two total content then, promptly remove in the sample colloid to the influence of the relative content of stable hydrocarbon, aromatic hydrocarbon, the hydrocarbon system of multiply by the stable hydrocarbon of mass spectroscopy and aromatic hydrocarbon respectively with its relative content forms and carries out normalizing and calculate again, obtains hydrocarbon system in the VGO sample and forms and see Table 4.
As known from Table 4, it is basic identical that the VGO hydrocarbon system that Solid-Phase Extraction of the present invention/weigh/MS method and Solid-Phase Extraction/FID/MS method records forms the data of measuring with ASTM D2549/MS method, and the absolute error of hydrocarbon composition data generally all is controlled at below 0.5% in detail.Illustrate that the inventive method has higher accuracy.
Table 1
| Sample number | Actual value, quality % | Internal standard method GC-FID measured value, quality % | ||||
| Stable hydrocarbon | Aromatic hydrocarbon | Colloid | Stable hydrocarbon | Aromatic hydrocarbon | Colloid | |
| ??1 ??2 ??3 ??4 | ??75.0 ??60.8 ??51.7 ??39.5 | ??23.7 ??37.9 ??44.1 ??55.9 | ??1.3 ??1.3 ??4.2 ??4.6 | ??75.5 ??61.5 ??53.7 ??40.2 | ??22.5 ??37.5 ??43.1 ??55.1 | ??2.0 ??1.0 ??3.2 ??4.7 |
Table 2
Table 3
| Sample number into spectrum | ??1 | ??2 | ??3 | ??4 | ??5 | ??6 |
| Overall recovery | ??99.2 | ??98.6 | ??99.3 | ??98.0 | ??98.1 | ??99.6 |
Table 4
| Sample number into spectrum | ?????????????1 | ???????????????2 | ???????????????3 | ||||||
| Assay method | ??EC * | ??SFC ** | ??FID *** | ??EC | ??SFC | ??FID | ??EC | ??SFC | ??FID |
| Hydrocarbon composition; The total thrcylic aromatic hydrocarbon pyrene of the total double ring arene of the total mononuclear aromatics naphthalene of the total cycloalkane alkylbenzene of quality % alkane one cycloalkane bicyclic alkane, the three cycloalkane Fourth Ring alkane five rings alkane six cycloalkane cycloalkyl benzene bicyclic alkyl benzene class acenaphthene class+dibenzo furan fluorenes class luxuriant and rich with fragrance class of luxuriant and rich with fragrance class cycloalkanes class is bent the total Fourth Ring of the class total thiophene of aromatic hydrocarbons north class dibenzanthracene total five rings aromatic hydrocarbons benzothiophene dibenzothiophenes naphthalene benzothiophene and is not identified the total aromatic hydrocarbons colloid of aromatic hydrocarbons gross weight, quality % | ? ??50 ??12. ??6.4 ??3.5 ??2.9 ??2 ??0 ??27. ??5.5 ??2.6 ??2.5 ??10. ??2 ??2 ??2 ??6 ??1.4 ??0.6 ??2 ??0.6 ??0.3 ??0.9 ??0.2 ??0 ??0.2 ??0.1 ??0.1 ??0.1 ??0.3 ??1.3 ??21. ??1.5 ??100 | ? ??50.8 ??12.5 ??6.5 ??3.5 ??2.9 ??2 ??0 ??27.4 ??5.4 ??2.5 ??2.9 ??10.8 ??1.9 ??1.9 ??2 ??5.8 ??1.3 ??0.6 ??1.9 ??0.5 ??0.1 ??0.6 ??0.2 ??0 ??0.2 ??0.1 ??0.1 ??0.1 ??0.3 ??1.1 ??20.7 ??1.1 ??100 | ? ??50.8 ??12.5 ??6.5 ??3.5 ??2.9 ??2 ??0 ??27.4 ??5.3 ??2.5 ??2.5 ??10.3 ??2 ??2 ??2 ??6 ??1.3 ??0.6 ??1.9 ??0.6 ??0.3 ??0.9 ??0.2 ??0 ??0.2 ??0.1 ??0.1 ??0.1 ??0.3 ??1.3 ??20.9 ??0.9 ??100 | ? ??5.9 ??6.3 ??12.9 ??14.1 ??10.2 ??4.3 ??0 ??47.8 ??5 ??6 ??6.1 ??17.1 ??3.2 ??3.5 ??4.4 ??11.1 ??3.2 ??2.1 ??5.3 ??1.9 ??0.9 ??2.8 ??0.6 ??0 ??0.6 ??0.7 ??0.3 ??0.1 ??1.1 ??2.6 ??40.6 ??5.7 ??100 | ? ??5.6 ??5.8 ??12.6 ??15.1 ??11.2 ??4.5 ??0 ??49.2 ??4.2 ??5.4 ??5.8 ??15.4 ??2.9 ??3.5 ??4.3 ??10.7 ??3 ??2.4 ??5.4 ??2.3 ??1.1 ??3.4 ??0.6 ??0.1 ??0.7 ??0.7 ??0.4 ??0.3 ??1.4 ??2 ??39.7 ??5.5 ??100 | ? ??6 ??6.3 ??13 ??14.1 ??10.3 ??4.3 ??0 ??48 ??4.8 ??6 ??6 ??16.8 ??3.2 ??3.4 ??4.4 ??11 ??3.2 ??2.1 ??5.3 ??1.9 ??0.8 ??2.7 ??0.6 ??0 ??0.6 ??0.7 ??0.3 ??0.1 ??1.1 ??2.5 ??40 ??6 ??100 | ? ??27.6 ??13.9 ??13.5 ??8.2 ??5.1 ??3 ??0 ??43.7 ??5.1 ??3.4 ??3.6 ??12.1 ??2.3 ??2 ??2.2 ??6.5 ??1.3 ??0.6 ??1.9 ??0.6 ??0.3 ??0.9 ??0.2 ??0 ??0.2 ??0.6 ??0.4 ??0.2 ??1.2 ??1.1 ??23.9 ??4.2 ??100 | ? ??27.9 ??13.7 ??13.1 ??8.7 ??6 ??3.3 ??0 ??44.8 ??4.9 ??3.3 ??3.6 ??11.8 ??2.2 ??2 ??2.4 ??6.6 ??1.5 ??0.7 ??2.2 ??0.7 ??0.3 ??1 ??0.2 ??0 ??0.2 ??0.7 ??0.4 ??0.1 ??1.2 ??0.9 ??23.9 ??3.4 ??100 | ? ??28.5 ??13.8 ??13.2 ??8.8 ??6 ??3.3 ??0 ??45.1 ??5 ??3.3 ??3.5 ??11.8 ??2.1 ??2 ??2.4 ??6.5 ??1.5 ??0.7 ??2.2 ??0.7 ??0.3 ??1 ??0.2 ??0 ??0.2 ??0.7 ??0.4 ??0.1 ??1.2 ??0.9 ??23.8 ??2.6 ??100 |
Continuous table 4
| Sample number into spectrum | ???????????????4 | ????????????????5 | ???????????????6 | ||||||
| Assay method | ??EC | ??SFC | ??FID | ??EC | ??SFC | ??FID | ??EC | ??SFC | ??FID |
| Hydrocarbon composition; The total thrcylic aromatic hydrocarbon pyrene of the total double ring arene of the total mononuclear aromatics naphthalene of the total cycloalkane alkylbenzene of quality % alkane one cycloalkane bicyclic alkane, the three cycloalkane Fourth Ring alkane five rings alkane six cycloalkane cycloalkyl benzene bicyclic alkyl benzene class acenaphthene class+dibenzofurans fluorenes class luxuriant and rich with fragrance class of luxuriant and rich with fragrance class cycloalkanes class is bent the total Fourth Ring of the class total thiophene of aromatic hydrocarbons north class dibenzanthracene total five rings aromatic hydrocarbons benzothiophene dibenzothiophenes naphthalene benzothiophene and is not identified the total aromatic hydrocarbons colloid of aromatic hydrocarbons gross weight, quality % | ? ??14.2 ??9.8 ??12.2 ??8.7 ??6.5 ??5.9 ??0 ??43.1 ??4.8 ??5.2 ??6.2 ??16.2 ??2.6 ??3.5 ??4.4 ??10.5 ??2.8 ??1.6 ??4.4 ??1.5 ??0.7 ??2.2 ??0.6 ??0.2 ??0.8 ??1.4 ??0.9 ??0.5 ??2.8 ??4 ??40.9 ??1.8 ??100 | ? ??13.7 ??9.6 ??11.8 ??8 ??6.6 ??5.8 ??0 ??41.8 ??5.6 ??4.9 ??5.6 ??18.1 ??2.5 ??3.4 ??4.2 ??10.1 ??2 ??1.5 ??3.5 ??1.3 ??0.7 ??2 ??0.6 ??0.2 ??0.8 ??1.3 ??1.4 ??0.9 ??3.6 ??4.2 ??42.3 ??2.2 ??100 | ? ??14.3 ??9.9 ??12.3 ??8.3 ??6.9 ??6 ??0 ??43.4 ??5.4 ??5.5 ??6 ??16.9 ??2.4 ??3.5 ??4.2 ??10 ??2.6 ??1.5 ??4.1 ??1.4 ??0.7 ??2.1 ??0.6 ??0.2 ??0.8 ??1.2 ??1.3 ??0.9 ??3.4 ??4 ??40.3 ??2.5 ??100 | ? ??21.4 ??14.7 ??14.4 ??8.5 ??5 ??2.9 ??0 ??45.5 ??5.4 ??4.6 ??4.9 ??14.9 ??2.1 ??2.5 ??2.6 ??7.2 ??1.5 ??0.9 ??2.4 ??0.9 ??0.4 ??1.3 ??0.3 ??0.1 ??0.4 ??1.5 ??1 ??0.4 ??2.9 ??1.8 ??30.9 ??2.2 ??100 | ? ??21.2 ??14.5 ??13.8 ??8.5 ??5.4 ??2.9 ??0 ??45.1 ??5.3 ??4.1 ??4.9 ??14.3 ??1.7 ??2.6 ??3.1 ??7.4 ??1.9 ??1 ??2.9 ??1.2 ??0.4 ??1.6 ??0.3 ??0.1 ??0.4 ??1.6 ??1.2 ??0.3 ??3.1 ??1.8 ??31.5 ??2.2 ??100 | ? ??21.2 ??14.5 ??14.1 ??8.4 ??5 ??2.8 ??0 ??44.8 ??5.7 ??4.7 ??5.1 ??15.5 ??2.1 ??2.6 ??2.7 ??7.4 ??1.6 ??0.9 ??2.5 ??0.9 ??0.4 ??1.3 ??0.3 ??0.1 ??0.4 ??1.6 ??1 ??0.4 ??3 ??1.8 ??31.9 ??2.1 ??100 | ? ??11.9 ??9.1 ??10.6 ??7.4 ??4.7 ??2.4 ??0 ??34.2 ??6.6 ??6.9 ??7.8 ??21.3 ??3.1 ??4.4 ??4.9 ??12.4 ??2.5 ??2.3 ??4.8 ??1.9 ??0.8 ??2.7 ??0.5 ??0.1 ??0.6 ??3.3 ??1.7 ??0.9 ??5.9 ??2.7 ??50.4 ??3.5 ??100 | ? ??11.6 ??8.8 ??10.1 ??8 ??5.4 ??2.5 ??0 ??34.8 ??7.3 ??6.7 ??7.9 ??21.9 ??2.6 ??4.6 ??5.2 ??12.4 ??2.9 ??2.2 ??5.1 ??2 ??0.9 ??2.9 ??0.5 ??0.1 ??0.6 ??3 ??2 ??0.8 ??5.8 ??2.9 ??51.6 ??2.6 ??100 | ? ??11.8 ??9.0 ??10.6 ??7.4 ??4.9 ??2.4 ??0 ??34.2 ??6.9 ??6.8 ??7.8 ??21.2 ??3.0 ??4.4 ??5.1 ??12.5 ??2.6 ??2.3 ??4.8 ??2 ??0.8 ??2.8 ??0.5 ??0.1 ??0.6 ??3.2 ??1.8 ??0.8 ??5.8 ??2.7 ??50.7 ??2.8 ??100 |
*ASTM D2594/MS method;
*Solid-Phase Extraction/weigh/MS method;
* *Solid-Phase Extraction/FID/MS method
Claims (11)
1, a kind of Solid-Phase Extraction and mass spectrometry are measured the method that vacuum gas oil hydrocarbon system forms, comprise vacuum gas oil is divided into stable hydrocarbon, aromatic hydrocarbon and three components of colloid by Solid-Phase Extraction, by weighing or the relative content of three kinds of components is measured in gas chromatographic analysis, with the stable hydrocarbon of mass spectroscopy gained and the hydrocarbon composition of aromatic component, form with the hydrocarbon system that normalization method calculates vacuum gas oil according to the relative content of stable hydrocarbon and aromatic hydrocarbon again, the used stationary phase of described Solid-Phase Extraction is a silicon dioxide, and 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.
2, in accordance with the method for claim 1, it is characterized in that described Solid-Phase Extraction is the vacuum gas oil sample 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 or normal hexane flushing stationary phase then, extract the wherein aromatic hydrocarbon of absorption with the dichloromethane rinse stationary phase again, the mixed liquor flushing stationary phase with benzene-ethanol extracts the wherein colloid of absorption afterwards.
3, in accordance with the method for claim 2, it is characterized in that benzene in the mixed liquor of described benzene-ethanol: the volume ratio of ethanol is 1: 0.5-5.0.
4, 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.
5, in accordance with the method for claim 4, 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.
6, in accordance with the method for claim 1, the amount that it is characterized in that used vacuum gas oil is the 0.1-0.3 gram.
7, in accordance with the method for claim 1, in stable hydrocarbon, aromatic hydrocarbon and the glial component that it is characterized in that after extraction, obtaining successively by 1: 1: the amount of 0.2-0.8 adds internal standard compound, and described internal standard compound is selected from C
14-C
18N-alkane, get each component that adds behind the internal standard compound then and feed gas chromatograph successively, measure the relative content of each component.
8, in accordance with the method for claim 7, it is characterized in that before adding internal standard compound, internal standard compound is dissolved in makes the solution that concentration is 0.3～5.0 quality % in n-pentane or the normal hexane earlier.
9, in accordance with the method for claim 1, it is characterized in that the hydrocarbon system that adopts look-matter combined instrument to analyze vacuum gas oil forms.
10,, it is characterized in that adopting the gas chromatograph of being with flame ionic detector to analyze the relative content of stable hydrocarbon, aromatic hydrocarbon and colloid according to claim 1 or 9 described methods.
11, in accordance with the method for claim 9, it is characterized in that 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, by the relative content of flame ionic detector detection stable hydrocarbon, aromatic hydrocarbon and colloid, stable hydrocarbon and aromatic component in another part enter mass spectrometry system, are detected the group composition of stable hydrocarbon and aromatic hydrocarbon by mass detector.
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