CN104749298B - A kind of solid-phase extraction column and application process that separates different hydrocarbon components in diesel oil - Google Patents
A kind of solid-phase extraction column and application process that separates different hydrocarbon components in diesel oil Download PDFInfo
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Abstract
The solid-phase extraction column of different hydrocarbon components in a kind of Solid phase extraction separation diesel oil, formed by upper and lower two solid-phase extraction columns that communicate, the fixing of upper strata solid-phase extraction column is the mixture of silica gel and aluminium oxide mutually, wherein alumina content is 1～40 quality %, the fixing of lower floor's solid-phase extraction column is the silica gel that adds the load silver ion of water treatment mutually, the fixing silver content taking silica gel as benchmark is 1～12 quality %, and water content is 4～15 quality %. This post is for the separation of diesel oil olefin component, can solve from diesel oil the separation of olefins length consuming time, problem that olefin recovery is low.
Description
Technical field
The present invention is solid-phase extraction column and the application side of dissimilar hydrocarbon component in a kind of separating hydrocarbons compoundMethod specifically, is a kind ofly separate the solid-phase extraction column of dissimilar hydrocarbon component in diesel oil and apply this post and divideFrom the method for dissimilar hydrocarbon component in diesel oil, and isolated olefin component is carried out to the side of composition analysisMethod.
Background technology
Alkene is one of product in diesel oil process, and diesel quality is had to considerable influence. Therefore, to bavinOil fully characterizes, understand olefin(e) centent, type and monomer composition wherein to optimize diesel oil processing scheme,Control product quality has great significance.
Diesel oil structure composition is complicated, and contained alkene is identical with the molecular mass of cycloalkane, only relies on instrumentDevice cannot obtain monomer information accurately, and it is high and intersect little pre-of component that this just need to carry out separative efficiency to itProcessing procedure, obtains different components, and the quality of alkene and cycloalkane is overlapping when eliminating mass spectral analysis, thenAnalyse in depth for each component. Liu Zelong etc. [" analysis of Olefins in Secondary Processsing Diesel Oil " [J]. analyzeChemistry, 1996,24(5): 530-534] report that employing silicagel column is by the pre-separation of secondary processing diesel oil sampleBecome non-aromatics, aromatic hydrocarbons and colloid three parts, then in conjunction with the type in bromine addition/FI mass spectroscopy non-aromaticsAnd content. The method complex operation, analysis time is long.
Solid phase extraction techniques is widely used in the preprocessing process of oil product in recent years. Utilize two bond energys of alkeneWith Ag+There is mating reaction and form complex, and saturated hydrocarbons and Ag+Almost without any effect principle,Can be by saturated hydrocarbons and separation of olefins. Xu Yanqin etc. [" measure by organophosphorous pesticides-flight time mass spectrumThe carbon number distribution of alkene in diesel oil " [J]. petroleum journal, 2010,24(3): 431-436] by Ag+Load onOn silica, make Ag-SiO2Solid-phase extraction column, flushes out saturated point in diesel samples with pentane,Divide with the mixing that benzene flushes out aromatic hydrocarbon and alkene again. The mixing obtaining by pre-separation divide enter gas-chromatography/FI-flight time mass spectrum (GC-FI/TOFMS) analysis obtains type and the carbon number distribution information of alkene.Although the quality of alkene and cycloalkane is overlapping when the method can be eliminated mass spectral analysis, do not obtain yet pureOlefin component, exists and disturbs the discriminating of olefinic monomer molecule. In addition, use benzene as eluant, eluent, to realityThe person's of testing health is unfavorable.
Bai Xue etc. [alkene type and the sign [J] that distributes in catalytic cracking diesel oil and coker gas oil. petroleum refining and changeWork, 2011,42(11): 76-79] proposition twin columns solid phase extraction separation catalytic cracking diesel oil and coker gas oil,Upper prop filling gel, lower column filling Ag-SiO2But the method olefin recovery is low, adopt traditional oneDimension gas chromatography-mass spectrography is to olefin component analysis, and it is serious, qualitative, quantitatively accurate that overlap of peaks flows out phenomenon altogetherReally property is not good enough.
Summary of the invention
The object of this invention is to provide and a kind ofly separate the solid-phase extraction column of different hydrocarbon components in diesel oil and use this postThe method that separates different hydrocarbon components in diesel oil, can solve the separation of olefins length consuming time, olefin recovery from diesel oilLow problem.
Another object of the present invention is to provide the full two-dimensional gas of a kind of olefin component that above-mentioned separation is obtainedPhase chromatographic isolation, then use the method for flying time mass spectrum analysis olefin component monomer composition.
The solid-phase extraction column of different hydrocarbon components in Solid phase extraction separation diesel oil provided by the invention, by upper and lower twoThe solid-phase extraction column composition communicating, the fixing of upper strata solid-phase extraction column is the mixture of silica gel and aluminium oxide mutually,Wherein alumina content is 1～40 quality %, and the fixing of lower floor's solid-phase extraction column is the load that adds water treatment mutuallyThe silica gel of silver ion, the fixing silver content taking silica gel as benchmark is 1～12 quality %, water content is4～15 quality %.
The present invention adopts twin columns solid phase extraction to separate aromatic hydrocarbons, saturated hydrocarbons and the alkene in diesel oil, SPEIt is fixing phase that post upper strata adopts the mixture of silica gel and aluminium oxide, and lower floor's extraction column adopts the load that adds water treatmentThe silica gel of silver ion, for fixing phase, can effectively separate the olefin component in diesel oil, improves separative efficiency and alkeneThe rate of recovery. Isolated comprehensive two dimensional gas chromatography for olefin component-flight time mass spectrum detects, and can improve alkeneThe recall rate of the contained monomer of component, the alkadienes in Accurate Determining alkene and cycloolefin content.
Brief description of the drawings
Fig. 1 is the TIC of catalytic cracking diesel oil olefin component in the inventive method.
Fig. 2 is the proton nmr spectra spectrogram of catalytic cracking diesel oil saturated hydrocarbon component in the inventive method.
Fig. 3 is the TIC of coker gas oil olefin component in the inventive method.
Fig. 4 is the proton nmr spectra spectrogram of coker gas oil saturated hydrocarbon component in the inventive method.
Fig. 5 is the comprehensive two dimensional gas chromatography figure of coker gas oil olefin component in the inventive method.
Detailed description of the invention
Fixing that solid-phase extraction column of the present invention upper strata extraction column is filled is SiO mutually2-Al2O3, lower floor's extractionGetting fixing of filling in post is the Ag-SiO through adding water treatment mutually2. The combination of two kinds of fixing phases, can not onlyEnough ensure separating of aromatic hydrocarbons and alkene in diesel oil, can also improve the rate of recovery of alkene. Use above-mentioned extraction to fixPhase, adopts suitable extractant to rinse the fixing phase in upper strata of absorption aromatic hydrocarbons and the lower floor of adsorbs olefins and saturated hydrocarbonsFixing phase, can effectively separate aromatic hydrocarbons, alkene and saturated hydrocarbons in diesel oil, and eluant, eluent toxicity used is low, consumptionFew, be convenient to post-processed, avoided a large amount of losses of sample simultaneously. The full two-dimensional gas of the olefin component of gainedPhase chromatogram-flight time mass spectrum carries out monomer component mensuration, can improve the resolution ratio of olefinic monomer component, obtainsQualitative, the quantitative result of olefinic monomer more accurately.
SPE provided by the invention is made up of upper and lower two solid-phase extraction columns that communicate, preferably middle employingAdapter is communicated with, and described adapter is the joint that is communicated with two extraction columns.
The mass ratio of the described contained fixing phase of upper strata/lower floor solid-phase extraction column be 0.5～1.5:1, preferably 0.8～1.2：1。
The present invention prepares fixing silica gel mutually used and is preferred for the Kiselgel A of chromatography, and aperture is too little,Macromolecular substances is trapped in duct, causes sample loss, the rate of recovery low, and aperture is separating effect too greatlyVariation. The specific area of described silica gel is 400～750m2/ g, preferred 500～650m2/ g, pore volume is0.35～0.90mL/g, preferred 0.35～0.5mL/g, the hole of bore dia 20～35nm account for 40 of pore volume～65%. The specific area of described aluminium oxide is 80～250m2/ g, preferred 90～200m2/g。
The upper strata of solid-phase extraction column of the present invention is that the fixing of upper prop filling is SiO mutually2-Al2O3, wherein aluminium oxideContent is 3～20 quality % preferably. The lower floor of solid-phase extraction column is the fixing mutually for adding water treatment of lower prop fillingAg-SiO2, its silver content taking silica gel as benchmark is 1.5～8 quality % preferably, water content preferably 5～10Quality %.
Above-mentioned SiO2-Al2O3The preparation method of fixing phase is: silica gel is dry 3～8 little in 100～200 DEG CTime, obtain activated silica gel, by aluminium oxide in 300～500 DEG C, preferably 350～450 DEG C of roastings 2～6 hoursTo the aluminium oxide of activation. In required ratio, the silica gel of activation and aluminium oxide are mixed and obtain SiO2-Al2O3Fixing phase.
Add the Ag-SiO of water treatment2Preparation method be: silver salt solution is added in silica gel, after stirringLeave standstill 1～24 hour, preferably 3～10 hours, make silver ion evenly be adsorbed on Silica Surface, 100～200 DEG CDry 1～10 hour, obtain Ag-SiO2Fixing phase. The preferred silver nitrate of described silver salt. Get appropriate Ag-SiO2Fixing phase, adds water to mix, and leaves standstill 12～24 hours, must add the Ag-SiO of water treatment2。
The method of different hydrocarbon components in Solid phase extraction separation diesel oil provided by the invention, comprises and uses the first eluant, eluentThe fixing phase of wetting solid-phase extraction column of the present invention, adds diesel samples from upper strata, with the first eluant, eluent punchingWash solid-phase extraction column, saturated hydrocarbons and alkene are flushed to after lower prop, separately twin columns, with the second eluant, eluent flushingUpper prop extracts aromatic hydrocarbons, with first eluant, eluent rinse lower prop first extract saturated hydrocarbons, then with the 3rd eluant, eluent rushWash lower prop and extract alkene.
In said method, test adds diesel samples and the ratio of fixing phase gross mass are 1:20～70, preferably 1:40～70。
Add before diesel samples, wetting solid-phase extraction column the first eluant, eluent used with the mass ratio of fixing phase is0.5～3:1, then adds diesel samples, and the component in diesel oil is fixed and adsorbs mutually, with the first eluant, eluent punchingWash solid-phase extraction column, saturated hydrocarbons and alkene are flushed to lower prop the first eluant, eluent used and the body of diesel samplesLong-pending ratio is 30～90:1, preferred 40～80:1. Column extracting aromatic hydrocarbons the second eluant, eluent used and diesel oil in flushingThe volume ratio of sample is 30～100:1, preferred 30～70:1, rinses lower column extracting saturated hydrocarbons used first and washesDe-agent and the volume ratio of diesel samples are 20～90:1, preferred 30～60:1, rinse time column extracting alkene instituteWith the volume ratio of the 3rd eluant, eluent and diesel samples be 60～180:1, preferred 80～160:1.
The first described eluant, eluent is selected from least one in pentane, n-hexane, normal heptane and benzinum,The second eluant, eluent is selected from least one in carrene, chloroform, benzene, ethanol, isopropyl alcohol and ethyl acetate,The 3rd eluant, eluent is selected from the mixture of carrene or benzene and ethanol or isopropyl alcohol.
The mixed liquor that the described preferred carrene of the second eluant, eluent and ethanol mass ratio are 6～9:1, the 3rdThe mixed liquor that the preferred carrene of eluant, eluent and ethanol mass ratio are 2～5:1.
In the inventive method, rinse lower column extracting alkene and preferably carry out in two steps, first use dichloromethane rinse,The volume ratio of carrene used and diesel samples is 60～130:1, preferred 70～120:1, then uses qualityThan be 2～5:1 dichloromethane-ethanol solution rinse, dichloromethane-ethanol solution used and diesel oil sampleThe volume ratio of product is 20～50:1, preferred 20～40:1.
Said method separates the aromatic hydrocarbons, saturated hydrocarbons and the olefin solution that obtain, will after solvent evaporates, obtain each component,Preferably make solvent evaporates with water-bath or infrared radiation, then get test specimens add 1mL carrene dissolve, use1HNMR and GC-MS analyze component, (separated to determine the intersection component containing in each componentComponent) content, judge separating effect. Measure gained aromatic component with gas chromatography-mass spectrum (GC-MS)Saturated hydrocarbon content, the aromatic hydrocarbons in olefin component and paraffinicity, use1HNMR detects in saturated hydrocarbon componentWhether there is alkene.
The present invention preferably measures the method for alkene in diesel oil, comprises with the alkene in the inventive method separation diesel oilHydrocarbon, gets diesel samples and injects comprehensive two dimensional gas chromatography-time of-flight mass spectrometer, uses comprehensive two dimensional gas chromatography basisThe boiling point of alkene enters flying time mass spectrum analysis after carrying out orthogonal separation with polarity, obtains olefin componentMonomer composition.
The applicable diesel oil of the inventive method is the diesel oil containing alkene, as catalytic cracking diesel oil, coker gas oil or subtractSticky cracked diesel oil.
Further describe the present invention below by example, but the present invention is not limited to this.
In example, silica gel used is the Kiselgel A that subsidiary factory of Haiyang Chemical Plant, Qingdao produces, granularity is 0.150～0.074 millimeter, pore volume 0.36mL/g, specific area 635m2/ g, the Kong Zhankong of bore dia 20～35nm56% of volume.
Aluminium oxide is column chromatography neutral alumina, and Chemical Reagent Co., Ltd., Sinopharm Group produces. Granularity is0.150～0.074 millimeter, specific area 152m2/ g, igloss weightlessness≤8.0%.
Analyzing instrument is level Four bar gas chromatograph-mass spectrometer (GC-MS), and model is 7890GC/5975MS,Band fid detector. Gas-chromatography (GC) condition of work: sample size 1uL, Splitless injecting samples, chromatographic columnFor DM-5MS capillary column, 300 DEG C of injector temperatures, column temperature rise program is 60 DEG C of initial temperatures, protectsHold after 2min, then rise to 300 DEG C with the heating rate of 5 DEG C/min, keep 6min. Mass spectrum (MS) workMake condition: EI ionizes mode, bombarding voltage 70eV, sweep limits, 220 DEG C of ion source temperatures.
Comprehensive two dimensional gas chromatography-flight time mass spectrum used, model is Pegasus4D, data are by LECOChromaTOF software is processed, and frequency acquisition is 100Hz.
Example 1
Prepare silica gel solid phasing and the fixing phase of silica gel-aluminium oxide of load silver ion of the present invention.
Kiselgel A, in 150 DEG C of dry 5h, is obtained to activated silica gel (SG), be put in drier for subsequent use.Neutral alumina, in 400 DEG C of roasting 4h, is obtained to activated alumina (SAL). Take in proportion SG andSAL, mixes, and is made into the fixing phase of silica gel-aluminium oxide of certain mass mark. Put into drier for subsequent use.
Get 3g silver nitrate and be dissolved in wiring solution-forming in 50g water, get 50g silica gel, silica gel is added while stirringIn liquor argenti nitratis ophthalmicus, after stirring, leave standstill 5 hours, 150 DEG C are dried 5 hours, obtain silver content and areThe Ag-SiO of 3.8 quality %2Fixing phase (ASG). Take out a part and accurately weigh quality, add certain weightThe distilled water of amount, concussion shakes up, and obtains the Ag-SiO through adding water treatment2Fixing phase.
Example 2
With aromatic hydrocarbons, alkene and saturated hydrocarbons in SPE method separation catalytic cracking diesel oil of the present invention.
Silica gel-the aluminium oxide that loads 1.5g alumina content and be 15 quality % in the upper prop of solid-phase extraction column is solidPhasing, loads the Ag-SiO of the moisture 8 quality % of 1.5g in lower prop2Fixing phase (ASG-1). Use respectively 1.5mLPentane wetting.
The catalytic cracking diesel oil of getting 180～350 DEG C of 60 μ L boiling ranges adds upper prop. With 3mL pentane by saturatedHydrocarbon and olefin component are rinsed to lower prop, separately twin columns. The dichloromethane that upper prop is 5:1 by 4mL volume ratioAlkane-ethanolic solution rinses, and obtains aromatic hydrocarbons solution. Lower prop rinses with 2mL pentane, obtains saturated hydrocarbon solution,The dichloromethane-ethanol solution that is 9:1 by 7mL carrene and 2mL volume ratio successively again rinses,To olefin solution.
Adopt heating water bath to steam except the solvent in saturated hydrocarbons, alkene, aromatic component. Adopt GC/MS to analyze,The TIC of olefin component is shown in Fig. 1, and in olefin component, arene content is 2.2 quality %, alkaneContent is 1.33 quality %, and in aromatic component, saturated hydrocarbon content is 1.3 quality %, shows and separates in major constituentThe intersection constituent content being separated is all lower than 5 quality %, within error allowed band.
The proton nmr spectra of gained saturated hydrocarbon component as shown in Figure 2, at chemical shift 4～6 places without alkene spyLevy peak, show in saturated hydrocarbons substantially not containing alkene.
Measure the rate of recovery of alkene in diesel oil distillate with the recovery of standard addition of n-hexadecene. Get two parts of identical bavinsOil samples, it is standard substance that a copy of it adds a certain amount of n-hexadecene, two duplicate samples are all as stated aboveCarry out Solid phase extraction separation, the olefin component obtaining steams after solvent, carries out GC/MS analysis and obtains positive tenThe content of six alkene. The n-hexadecene content of mark-on portion deducts the not n-hexadecene content of mark-on portion, and it is poorValue is olefin recovery with the ratio of the theoretical value that adds n-hexadecene standard specimen, and its value is 97.42 quality %.
The above results shows, intersection component (separated component) content in the inventive method separation component is little,Olefin recovery is high, has good separating effect.
Example 3
Silica gel-the aluminium oxide that loads 1.5g alumina content and be 15 quality % in the upper prop of solid-phase extraction column is solidPhasing, loads the Ag-SiO that 1.5g water content is 15 quality % in lower prop2Fixing phase (ASG-2), respectivelyWetting with the pentane of 1.5mL.
The catalytic cracking diesel oil of getting 180～350 DEG C of 60 μ L boiling ranges adds upper prop. With 3mL pentane by saturatedHydrocarbon and olefin component are rinsed to lower prop, separately twin columns. The dichloromethane that upper prop is 5:1 by 4mL volume ratioAlkane-ethanolic solution rinses and obtains aromatic hydrocarbons solution. Lower prop rinses and obtains saturated hydrocarbon solution with 2mL pentane, thenThe dichloromethane-ethanol solution that is 9:1 by 7mL carrene and 2mL volume ratio successively rinses and obtains alkeneHydrocarbon solution.
Adopt heating water bath to steam except the solvent in saturated hydrocarbons, alkene, aromatic component. Adopt GC/MS to analyzeIn olefin component, arene content is 2.5 quality %, and paraffinicity is 3.83 quality %, and aromatic component is embezzledWith hydrocarbon content be 0.8 quality %, intersect constituent content all lower than 5 quality %.
Saturated hydrocarbon component proton nmr spectra is presented at chemical shift 4～6 places without alkene characteristic peak, shows saturatedIn hydrocarbon, substantially do not contain alkene.
The olefin recovery of measuring taking the recovery of standard addition of n-hexadecene is as 95.17 quality %.
Example 4
Silica gel-the aluminium oxide that loads 1.5g alumina content and be 15 quality % in the upper prop of solid-phase extraction column is solidPhasing, loads the Ag-SiO that 1.5g water content is 5 quality % in lower prop2Fixing phase (ASG-3), respectivelyWetting with the pentane of 1.5mL.
Getting 60 μ L boiling ranges is that 180～350 DEG C of catalytic cracking diesel oils add upper prop. With 3mL pentane by saturatedHydrocarbon and olefin component are rinsed to lower prop, separately twin columns. The dichloromethane that upper prop is 5:1 by 4mL volume ratioAlkane-ethanolic solution rinses and obtains aromatic hydrocarbons solution. Lower prop rinses and obtains saturated hydrocarbon solution with 2mL pentane, thenThe dichloromethane-ethanol solution that is 9:1 by 7mL carrene and 2mL volume ratio successively rinses and obtains alkeneHydrocarbon solution.
Adopt heating water bath to steam except the solvent in saturated hydrocarbons, alkene, aromatic component. Adopt GC/MS to analyzeArene content in olefin component is 1.7 quality %, and paraffinicity is 1.26 quality %, in aromatic componentSaturated hydrocarbon content is 2.1 quality %, intersects constituent content all lower than 5 quality %.
Saturated hydrocarbon component proton nmr spectra is presented at chemical shift 4～6 places without alkene characteristic peak, shows saturatedIn hydrocarbon, substantially do not contain alkene.
The olefin recovery of measuring taking the recovery of standard addition of n-hexadecene is as 96.53 quality %.
Example 5
In the upper prop of solid-phase extraction column, loading 1.5g alumina content and be silica gel-aluminium oxide of 5 quality % fixesPhase, loads the Ag-SiO that 1.5g water content is 8 quality % in lower prop2Fixing phase (ASG-1), uses respectively1.5mL pentane is wetting.
The catalytic cracking diesel oil of getting 60 μ L boiling ranges and be 180～350 DEG C adds upper prop. To satisfy with 3mL pentaneRinse to lower prop with hydrocarbon and olefin component, separately twin columns. The dichloro that upper prop is 5:1 by 4mL volume ratioMethane-ethanolic solution rinses and obtains aromatic hydrocarbons solution. Lower prop rinses and obtains saturated hydrocarbon solution with 2mL pentane,The dichloromethane-ethanol solution that is 9:1 by 7mL carrene and 2mL volume ratio successively again rinses and obtainsOlefin solution.
Adopt heating water bath to steam except the solvent in saturated hydrocarbons, alkene, aromatic component. Adopt GC/MS to analyze,In olefin component, arene content is 4.7 quality %, and paraffinicity is 2.22 quality %, and aromatic component is embezzledWith hydrocarbon content be 1.1 quality %, intersect constituent content all lower than 5 quality %.
Saturated hydrocarbon component proton nmr spectra is presented at chemical shift 4～6 places without alkene characteristic peak, shows saturatedIn hydrocarbon, substantially do not contain alkene.
The olefin recovery of measuring taking the recovery of standard addition of n-hexadecene is as 96.89 quality %.
Example 6
In SPE upper prop, loading 1.5g alumina content is the fixing phase of silica gel-aluminium oxide of 30 quality %,In lower prop, load the Ag-SiO that 1.5g water content is 8 quality %2Fixing phase (ASG-1), uses respectively 1.5mLPentane is wetting.
The catalytic cracking diesel oil of getting 60 μ L boiling ranges and be 180～350 DEG C adds upper prop. To satisfy with 3mL pentaneRinse to lower prop with hydrocarbon and olefin component, separately twin columns. The dichloro that upper prop is 5:1 by 4mL volume ratioMethane-ethanolic solution rinses and obtains aromatic hydrocarbons solution. Lower prop rinses and obtains saturated hydrocarbon solution with 2mL pentane,The dichloromethane-ethanol solution that is 9:1 by 7mL carrene and 2mL volume ratio successively again rinses and obtainsOlefin component.
Adopt heating water bath to steam except the solvent in saturated hydrocarbons, alkene, aromatic component. Adopt GC/MS to analyzeArene content in olefin component is 0.9 quality %, and paraffinicity is 2.22 quality %, in aromatic componentSaturated hydrocarbon content is 3.8 quality %, intersects constituent content all lower than 5 quality %.
Saturated hydrocarbon component proton nmr spectra is presented at chemical shift 4～6 places without alkene characteristic peak, shows saturatedIn hydrocarbon, substantially do not contain alkene.
The olefin recovery of measuring taking the recovery of standard addition of n-hexadecene is as 95.07 quality %.
Example 7
This example separates aromatic hydrocarbons, alkene and the saturated hydrocarbons in coker gas oil by SPE method of the present invention.
Silica gel-the aluminium oxide that loads 1.5g alumina content and be 15 quality % in the upper prop of solid-phase extraction column is solidPhasing, loads the Ag-SiO that 1.5g water content is 8 quality % in lower prop2Fixing phase (ASG-1), respectivelyWetting with 1.5mL pentane.
The coker gas oil of getting 50 μ L boiling ranges and be 180～350 DEG C adds upper prop. With 4mL pentane by saturated hydrocarbonsRinse to lower prop with olefin component, separately twin columns. Carrene that upper prop is 5:1 by 3mL volume ratio-Ethanolic solution rinses and obtains aromatic hydrocarbons solution. Lower prop rinses and obtains saturated hydrocarbon solution with 3mL pentane, more successivelyThe dichloromethane-ethanol solution that is 9:1 by 6mL carrene and 2mL volume ratio rinses and obtains alkene groupPoint.
Adopt heating water bath to steam except the solvent in saturated hydrocarbons, alkene, aromatic component. Adopt GC/MS to analyze,The TIC of olefin component is shown in Fig. 3. Arene content in olefin component is 3.1 quality %, alkaneHydrocarbon content is 1.22 quality %, and in aromatic component, saturated hydrocarbon content is 1.8 quality %, and the constituent content that intersects is equalLower than 5 quality %.
Saturated hydrocarbon component proton nmr spectra is shown in Fig. 4, is presented at chemical shift 4～6 places without alkene characteristic peak,Show in saturated hydrocarbons substantially not containing alkene.
The olefin recovery of measuring taking the recovery of standard addition of n-hexadecene is as 96.82 quality %.
Comparative example 1
With the Ag-SiO that does not add water treatment2The fixing separation of carrying out mutually diesel component.
The method of pressing example 2 separates aromatic hydrocarbons, alkene and the saturated hydrocarbons in diesel oil, and different is consolidating in lower propPhasing is the Ag-SiO that 1.5g does not add water2Fixing phase (ASG). Adopt GC/MS to analyze, saturated hydrocarbons groupIn point, arene content is 0%, and in olefin component, arene content is 2.7 quality %, the content of saturated hydrocarbons in aromatic hydrocarbonsBe 1.9 quality %, all lower than 5 quality %, within error allowed band, but return with the mark-on of n-hexadeceneThe olefin recovery that yield records is 83.64 quality %, shows part alkene and fixedly combines not by wash-out,Alkene loss is larger.
Comparative example 2
Adopting upper prop is that silica gel solid phasing, lower prop are the Ag-SiO that does not add water treatment2Fixedly be separated in diesel oilEach component.
The method of pressing example 2 separates aromatic hydrocarbons, alkene and the saturated hydrocarbons in diesel oil, and different is consolidating in upper propPhasing is the silica gel (SG) of 1.5g, the fixing Ag-SiO not adding water for 1.5g mutually in lower prop2Fixing phase(ASG). Adopt GC/MS to analyze, in saturated hydrocarbon component, arene content is 2.8 quality %, olefin componentMiddle arene content is 6.7 quality %, and in aromatic hydrocarbons, saturated hydrocarbon content 2.2 quality %, return with the mark-on of n-hexadeceneThe olefin recovery that yield records is 84.71 quality %. Result shows that part aromatic hydrocarbons can not be effectively by upper propSilica gel solid phasing absorption, be easy to saturated hydrocarbon component, together by low polar solvent wash-out, to cause handing between componentFork is serious. In addition, part alkene with fixedly combine not by wash-out, alkene loss is larger.
Example 8
The feelings of this example for illustrating that employing comprehensive two dimensional gas chromatography-flight time mass spectrum is analyzed olefin componentCondition.
Adopt example 7 to separate the olefin component obtaining, it is carried out to comprehensive two dimensional gas chromatography-flight time mass spectrumAnalyze, the comprehensive two dimensional gas chromatography figure obtaining is shown in Fig. 5, and in Fig. 5, each point represents a kind of olefinic monomer, recordsThe type of different carbon number monomer alkene distributes in table 1.
Above-mentioned analysis result shows, separates through two-dimentional chromatographic column, and qualification obtains more than 1000 olefin component altogetherPeak, than adopting more than 100 peak height that GC/MS obtains to go out an order of magnitude in example 7, flows out phenomenon altogetherObviously reduce, can analyze cycloolefin and alkadienes, qualitative, the quantitative accuracy of olefinic monomer obviously improves.
Table 1
Claims (10)
1. a solid-phase extraction column for different hydrocarbon components in Solid phase extraction separation diesel oil, communicates by upper and lower twoSolid-phase extraction column composition, the fixing of upper strata solid-phase extraction column is the mixture of silica gel and aluminium oxide mutually, whereinAlumina content is 1～40 quality %, lower floor's solid-phase extraction column fixing mutually for the load silver that adds water treatment fromThe silica gel of son, the fixing silver content taking silica gel as benchmark is 1～12 quality %, water content is 4～15Quality %.
2. according to solid-phase extraction column claimed in claim 1, it is characterized in that described upper strata/lower floor solid phaseThe mass ratio of the contained fixing phase of extraction column is 0.5～1.5:1.
3. according to solid-phase extraction column claimed in claim 1, it is characterized in that the specific surface of described silica gelAmassing is 400～750m2/ g, pore volume is 0.35～0.90mL/g, the specific area of described aluminium oxide is80～250m2/g。
4. a method for different hydrocarbon components in Solid phase extraction separation diesel oil, comprises with the first eluant, eluent wettingSolid-phase extraction column claimed in claim 1 is fixed phase, adds diesel samples from upper strata, with the first eluant, eluent punchingWash solid-phase extraction column, saturated hydrocarbons and alkene are flushed to after lower prop, separately twin columns, with the second eluant, eluent flushingUpper prop extracts aromatic hydrocarbons, with first eluant, eluent rinse lower prop first extract saturated hydrocarbons, then with the 3rd eluant, eluent rushWash lower prop and extract alkene; The first described eluant, eluent is selected from pentane, n-hexane, normal heptane and benzinumIn at least one, the second eluant, eluent is selected from carrene, chloroform, benzene, ethanol, isopropyl alcohol and acetic acid secondAt least one in ester, the 3rd eluant, eluent is selected from the mixture of carrene and/or carrene and alcohol, described inAlcohol be ethanol or isopropyl alcohol.
5. in accordance with the method for claim 4, it is characterized in that diesel samples and fixing phase gross massThan being 1:20～70.
6. in accordance with the method for claim 4, it is characterized in that adding after diesel samples wetting solid phaseExtraction column the first eluant, eluent used is 0.5～3:1 with the mass ratio of fixing phase, and saturated hydrocarbons and alkene are flushed toThe first eluant, eluent that lower prop is used and the volume ratio of diesel samples are 30～90:1, column extracting aromatic hydrocarbons institute in flushingWith the volume ratio of the second eluant, eluent and diesel samples be 30～100:1, rinse lower column extracting saturated hydrocarbons used theThe volume ratio of one eluant, eluent and diesel samples is 20～90:1, rinses lower column extracting alkene the 3rd eluant, eluent usedWith the volume ratio of diesel samples be 60～180:1.
7. in accordance with the method for claim 4, it is characterized in that the second described eluant, eluent is dichloromethaneThe mixed liquor that alkane and ethanol mass ratio are 6～9:1, the 3rd eluant, eluent is that carrene and ethanol mass ratio areThe mixed liquor of 2～5:1.
8. in accordance with the method for claim 6, it is characterized in that rinsing lower column extracting alkene enters in two stepsOK, first use dichloromethane rinse, the volume ratio of carrene used and diesel samples is 60～130:1, thenThe dichloromethane-ethanol solution that is 2～5:1 with mass ratio rinses, dichloromethane-ethanol solution used and bavinThe volume ratio of oil samples is 20～50:1.
9. in accordance with the method for claim 4, it is characterized in that described diesel oil be catalytic cracking diesel oil,Coker gas oil or visbreaking diesel oil.
10. measure a method for alkene in diesel oil, comprise and use the method for claim 4 to separate in diesel oilOlefin component, gets diesel samples and injects comprehensive two dimensional gas chromatography-time of-flight mass spectrometer, with complete two-dimentional gas phase lookAfter spectrum is carried out orthogonal separation according to the boiling point of alkene with polarity difference, enter flight time mass spectrum analysis,Obtain the monomer composition of olefin component.
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