CN106318438A - Double-column solid phase extraction method of nitrogen-containing compounds in diesel oil - Google Patents
Double-column solid phase extraction method of nitrogen-containing compounds in diesel oil Download PDFInfo
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Abstract
A double-column solid phase extraction method of nitrogen-containing compounds in diesel oil comprises the following steps: 1, producing solid phase extraction columns, wherein the stationary phase of the solid phase extraction column A is a silica gel and acidic alumina mixture, and the stationary phase of the solid phase extraction column B is a silica gel and alkaline alumina mixture; and 2, eluting: wetting the solid phase extraction column A by a first eluent, adding a diesel oil sample from an upper layer, flushing the solid phase extraction column A with the first eluent to obtain saturated hydrocarbons, flushing the solid phase extraction column A with a second eluent to obtain aromatic hydrocarbons, flushing the solid phase extraction column A with a third eluent to obtain neutral nitrogen-containing compounds, serially connecting the solid phase extraction column A with the solid phase extraction column B, and flushing the solid phase extraction columns A and B with a fourth eluent to obtain alkaline nitrogen-containing compounds, wherein the column A is arranged above the column B.
Description
Technical field
The present invention relates to petrochemical industry, specifically, be a kind of use twin columns method Solid phase extraction separation,
Neutral nitrogen compounds in enrichment diesel samples and the method for basic nitrogen compound.
Background technology
Nitrogen-containing compound in diesel oil the most easily forms the nitrogen oxides such as nitrogen dioxide.Such thing
Matter easily causes vehicle exhaust gas systems to be poisoned in discharge process；After being discharged into air, such material is
Form one of major pollutants of acid rain, acid mist；Additionally, nitrogen oxides can be formed photochemical with Hydrocarbon
Learn smog, and ozone layer can be damaged.Therefore, reducing nitrogen-containing compound content in diesel oil is that fuel is clear
The requirement of clean.According to the needs of diesel oil denitrification process technological development, set up nitrogen-containing compound in diesel oil distillate
Qualitative and quantitative analysis method, can be catalyst research and development and related process exploitation offer basic data, and be
Catalytic mechanism research provides key message.
Owing in diesel oil, the content of nitrogen-containing compound is the lowest, before nitrogen-containing compound is carried out qualitative analysis,
Often need to separate diesel oil, enrichment processes.Conventional separation, the method for enrichment nitrogen-containing compound have acid
Extraction, ion exchange chromatography, column chromatography chromatogram method etc., wherein column chromatography chromatogram method have reproducible,
Post yield is high, fixing, and phase cost is relatively low, there is not the advantages such as water pollution, separate at diesel oil nitrogen-containing compound,
Rich pooled applications is more and more extensive.Zhang Yueqin [Zhang Yueqin. nitrogen-containing compound type distribution in catalytic cracking diesel oil.
Petroleum refining and chemical industry [J], 2013,44 (5): 87～91.] use neutral silica gel post to separate, be enriched catalysis and split
Change the nitrogen-containing compound in diesel oil, and during nitrogen-containing compound is separated into by the silicagel column using acid modified further
Property nitrogen-containing compound and basic nitrogen compound.But the fixing phase consumption of the method existence and solvent load are relatively
Greatly, the problem processing time length.Additionally, nitrogen-containing compound intersects with other compound in sample separation process
Amount is relatively big, have impact on the qualitative analysis of nitrogen-containing compound.
Summary of the invention
It is an object of the invention to provide one to utilize solid phase extraction techniques to separate, be enriched with nitrogen in diesel samples
The method of compound, is mainly used in the pretreatment process of diesel samples during nitrogen-containing compound qualitative analysis in diesel oil.
Separate between component when the present invention can solve nitrogen-containing compound in the separation of conventional post thin layer chromatography method, enrichment diesel oil
The problem that intersection amount is big, solvent load big, process time length.
The present invention provides the twin columns solid phase extraction of nitrogen-containing compound in a kind of diesel oil, comprises the steps:
(1), the preparation of solid-phase extraction column
Solid-phase extraction column A fixing is the mixture of silica gel and acidic alumina mutually, solid-phase extraction column B's
Fixing is the mixture of silica gel and alkali alumina mutually；
(2), eluting
Use the solid-phase extraction column A described in the first eluant moistening, add diesel samples from upper strata, with first
Eluant rinses solid-phase extraction column A, obtains saturated hydrocarbons；
Rinse solid-phase extraction column A with the second eluant, obtain aromatic hydrocarbons；
Rinse solid-phase extraction column A with the 3rd eluant, obtain neutral nitrogen compounds；
Solid-phase extraction column A with B is connected, A post upper, with the 4th eluant rinse solid-phase extraction column A,
B, obtains basic nitrogen compound；
Wherein, described first eluant selects free pentane, normal hexane, normal heptane and petroleum ether to be constituted
At least one in group；
Second eluant is the mixture of a and b: described a selects free dichloromethane, chloroform, benzene and toluene
At least one in the group constituted；Described b selects free pentane, normal hexane and hexamethylene to be constituted
At least one in group；
3rd eluant selects at least in the group that free vinyl chloride, dichloromethane and ethyl acetate are constituted
Kind；
4th eluant is the mixture of c and dichloromethane: described c selects free ethanol, isopropanol, positive fourth
At least one in the group that alcohol and acetone are constituted.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, the ratio of described silica gel
Surface area is preferably 300-600m2/ g, pore volume is preferably 0.2-5mL/g.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, described acidic oxidation
The specific surface area of aluminum is preferably 100-300m2/ g, pore volume is preferably 0.1-0.5mL/g.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, described alkaline oxygenated
The specific surface area of aluminum is preferably 120-250m2/ g, pore volume is preferably 0.1-0.4mL/g, and aperture is preferably
4-10nm, pH value is preferably at 10-14.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, solid-phase extraction column A
The content of middle acidic alumina is preferably 10-40wt%, and the content of solid-phase extraction column B neutral and alkali aluminium oxide is excellent
Elect 20-60wt% as.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, step (1) is solid
In the preparation of phase extraction column, it is preferred that
Silica gel is dried 2-6 hour under the conditions of 80-160 DEG C, obtains the silica gel of activation；
By acidic alumina roasting 3-7 hour under the conditions of 350-550 DEG C, obtain the acidic alumina of activation；
By alkali alumina roasting 2-6 hour under the conditions of 350-450 DEG C, obtain the alkali alumina of activation；
The silica gel of activation is mixed homogeneously with the acidic alumina of activation, obtains solid-phase extraction column A；Will activation
Silica gel mix homogeneously with the alkali alumina of activation, obtain solid-phase extraction column B.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, in the second eluant
The volume ratio of described a Yu b is preferably 0.2-0.5:1.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, in the 4th eluant
Described c is preferably 0.1-0.3:1 with the volume ratio of dichloromethane.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, diesel samples quality
With the mass ratio of solid-phase extraction column A preferably at 0.1-1.5:1, diesel samples quality is with solid-phase extraction column B's
Mass ratio is preferably 0.15-2.0:1.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, described first eluting
Agent is preferably 0.8-10:1 with the volume ratio of diesel samples；
Described second eluant is preferably 1.3-16:1 with the volume ratio of diesel samples；
Described 3rd eluant is preferably 2-24:1 with the volume ratio of diesel samples；
Described 4th eluant is preferably 6-22:1 with the volume ratio of diesel samples.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, described diesel oil is excellent
Elect straight-run diesel oil, catalytic cracking diesel oil, coker gas oil as, be hydrocracked diesel oil, hydrofining diesel oil or one-tenth
Product diesel oil.
The present invention provides a kind of Solid-Phase Extraction column preparation method separating nitrogen-containing compound in diesel oil.Pass through solid phase
The coupling of extraction column A, B, can reduce in the case of solvent load, effectively nitrogenous by diesel oil
Compound separates, enrichment for neutral nitrogen compounds and basic nitrogen compound, meet nitrogen-containing compound qualitative,
The requirement of quantitative analysis.
The present invention uses twin columns method, by adjusting eluant polarity and consumption, diesel samples is separated into saturated
Hydrocarbon, aromatic hydrocarbons, neutral nitrogen compounds and basic nitrogen compound, fix phase consumption and solvent load be few, group
Intersection amount is separated less between Fen.Compared to conventional post thin layer chromatography method, the present invention separates, one diesel oil of enrichment
In sample, the time of nitrogen-containing compound is only 50min, substantially increases work efficiency.
Accompanying drawing explanation
Fig. 1 a: after Solid phase extraction separation component 1 GC-NCD figure,
Fig. 1 b: after Solid phase extraction separation component 2 GC-NCD figure,
Fig. 1 c: after Solid phase extraction separation component 3 GC-NCD figure,
Fig. 1 d: the GC-NCD figure of component 4 after Solid phase extraction separation；
Fig. 2 a: after Solid phase extraction separation component 1 GC-MS figure,
Fig. 2 b: after Solid phase extraction separation component 2 GC-MS figure,
Fig. 2 c: after Solid phase extraction separation component 3 GC-MS figure,
Fig. 2 d: the GC-MS figure of component 4 after Solid phase extraction separation.
Detailed description of the invention
Technical scheme in embodiments of the invention will be described in detail below, but below embodiment is only
Being to understand the present invention, and can not limit the present invention, the present invention can be defined by the claims and cover
Multitude of different ways is implemented.
Solid-phase extraction column A used by the present invention fixing is the mixture of silica gel and acidic alumina mutually, its
The content of middle acidic alumina is 10-40wt%.The fixing of solid-phase extraction column B is that silica gel is with alkaline oxygenated mutually
The mixture of aluminum, wherein the content of alkali alumina is 20-60wt%.By two kinds of fixing phase polarity
Join, efficiently separating of saturated hydrocarbons in diesel oil, aromatic hydrocarbons and nitrogen-containing compound can not only be ensured, moreover it is possible to improve and contain
The response rate of nitrogen compound.
Silica gel specific surface area used by the present invention is 300-600m2/ g, pore volume is 0.2-5mL/g, acid
The specific surface area of aluminium oxide is 100-300m2/ g, pore volume is 0.1-0.5mL/g, the ratio of alkali alumina
Surface area is 120-250m2/ g, pore volume is 0.1-0.4mL/g.Above-mentioned silica gel, aluminium oxide fix phase
Preparation method is: is dried 2-6 hour under the conditions of 80-160 DEG C by silica gel, obtains activated silica gel；To meet
Acidic alumina roasting 3-7 hour under the conditions of 350-550 DEG C required, obtains the acidic alumina of activation；
By roasting under the conditions of satisfactory alkali alumina and 350-450 DEG C 2-6 hour, obtain the alkalescence of activation
Aluminium oxide.In required ratio, the silica gel of activation is mixed homogeneously with alkali alumina with acidic alumina, silica gel,
Obtain solid-phase extraction column A, B.
The present invention uses the nitrogen-containing compound in twin columns method separation diesel samples.Before adding diesel samples, permissible
Use 2mL the first eluant moistening solid-phase extraction column A.Diesel samples is added from solid-phase extraction column A top
Enter and adsorbed completely and go up mutually fixing, rinse solid-phase extraction column A with the first eluant, extract in diesel oil
Saturated hydrocarbons；Rinse solid-phase extraction column A with the second eluant, extract aromatic compound；With the 3rd eluting
Solid-phase extraction column A is rinsed in agent, extracts neutral nitrogen compounds.By 2mL the 3rd eluant moistening solid phase
Extraction column B, is together in series solid-phase extraction column A with B, wherein B post under.Use the 4th eluant
Rinse solid-phase extraction column A, B, extract basic nitrogen compound.First eluant used is selected from positive penta
At least one in alkane, normal hexane, normal heptane, petroleum ether, the second eluant selected from dichloromethane, chloroform,
At least one in benzene, toluene and the mixture of at least one in pentane, normal hexane, hexamethylene, the
Three eluant one in vinyl chloride, dichloromethane, ethyl acetate, the 4th eluant employing ethanol,
At least one in isopropanol, n-butyl alcohol, acetone and the mixture of dichloromethane.First eluant is the most just
Pentane, at least one in the second eluant dichloromethane, chloroform, benzene, toluene and pentane, normal hexane,
The volume ratio of at least one in hexamethylene is 0.2-0.5:1, the 3rd eluant selected from vinyl chloride, dichloromethane,
One in ethyl acetate, preferably vinyl chloride, in the 4th eluant ethanol, isopropanol, n-butyl alcohol, acetone
At least one volume ratio with dichloromethane be 0.1-0.3:1.
The amount of the diesel oil used by Solid-Phase Extraction is 0.5-6mL, on flushing solid-phase extraction column A used by saturated hydrocarbons
The volume ratio of the first eluant and diesel samples be 0.8-10:1；On flushing solid-phase extraction column A used by aromatic hydrocarbons
The volume ratio of the second eluant and diesel samples be 1.3-16:1；Rinse on solid-phase extraction column A neutral nitrogenous
The 3rd eluant used by compound is 2-24:1 with the volume ratio of diesel samples；Flushing solid-phase extraction column A,
The 4th eluant used by the upper basic nitrogen compound of B is 6-22:1 with the volume ratio of diesel samples.
The saturated hydrocarbons of said method isolated, aromatic hydrocarbons, neutral nitrogen compounds and basic nitrogen compound are molten
Liquid, i.e. can get corresponding component after solvent volatilization concentrates, preferentially selects rotary evaporation, nitrogen to be purged into
Row solvent volatilization work.Solution evaporation is concentrated into about 0.4mL and can enter gas chromatography-mass spectrum
And gas chromatogram-nitrogen chemical luminescence detector (GC-NCD) carries out qualitative and quantitative analysis (GC-MS).
Used by the present invention, eluant toxicity is low, consumption is few, avoids sample diesel component in separation process simultaneously
Loss.
The currently preferred concentration nitrogen-containing compound morphological method that measures is gas chromatography-mass spectrum-hydrion fire
Flame detector method (GC-MS-FID).The nitrogen-containing compound taking enrichment injects GC-MS-FID, gas phase color
Spectrum separates according to boiling point and the polarity of nitrogen-containing compound, then obtains nitrogen through level Four bar mass spectral analysis
The monomer information of compound.FID is substantially suitable to the response factor of compounds all in diesel oil, therefore by dividing
The content of other compound in the chromatogram calculation nitrogen-containing compound of rear each component.Nitrogen chemical luminescence detector
Only nitrogen-containing compound there is response, therefore by gas chromatogram-nitrogen chemical luminescence detector (GC-NCD)
Chromatogram i.e. can determine whether whether there is nitrogen-containing compound in each component separated.In using GC-NCD to combine
Mark method measures the concentration information of nitrogen-containing compound, and internal standard substance can use tri-n-butylamine, DMA.
The present invention is applicable to straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, is hydrocracked diesel oil, hydrogenation
The enrichment of nitrogen-containing compound in refined diesel oil, finished diesel fuel.
Silica gel used in example is the silica gel for chromatography that Chemical Reagent Co., Ltd., Sinopharm Group produces, granule
Degree >=70.0%, is dried vector≤6.0%, and specific surface area is 511.9m2/ g, pore volume is 0.468mL/g.
Acidic alumina is the chromatography aluminium oxide that Chemical Reagent Co., Ltd., Sinopharm Group produces, granularity >=
75.0%, calcination loss≤8.0%, specific surface area is 177.8m2/ g, pore volume is 0.255mL/g.1g
Acidic alumina is mixed homogeneously with the acetum that 2mL concentration is 1mol/L, spends after standing 1 hour
Ionized water washing aluminium oxide is until pH value is 4.Alkali alumina is Chemical Reagent Co., Ltd., Sinopharm Group
The chromatography aluminium oxide produced, granularity >=75.0%, calcination loss≤8.0%, specific surface area is 146.5
m2/ g, pore volume is 0.254mL/g, and aperture is 7.8nm.1g alkali alumina and 2mL concentration are 1
The NaOH solution mix homogeneously of mol/L, is washed with deionized alkali alumina after standing 1.5 hours straight
It is 12 to pH value.
GC-MS INSTRUMENT MODEL used by analysis is 7890A GC-5975 MS, band fid detector.Point
The GC condition of analysis component 1,2: HP-5MS capillary chromatographic column, 30m × 0.25mm × 0.25 μm；
Temperature programming initial temperature 60 DEG C, rises to 300 DEG C with 10 DEG C/min after keeping 2min, keeps 3min；
Carrier gas is high-pure helium, constant current operation 0.6mL/min；Injector temperature 300 DEG C, split ratio 30:1, enter
Sample amount 1 μ L.The GC condition of analysis component 3,4: HP-PONA capillary chromatographic column, 50m × 0.2
mm×0.5μm；Temperature programming initial temperature 120 DEG C, 4 DEG C/min of heating rate, final temperature 270 DEG C, protect
Hold 10min；Carrier gas is high-pure helium, constant current operation 0.9mL/min；Injector temperature 280 DEG C, shunting
Ratio 30:1, sample size 1 μ L.MSD condition: EI ionization source (70eV), ion source temperature 230 DEG C,
Level Four bar temperature 130 DEG C, full scan mass range 30～500u, interface temperature 300 DEG C, solvent delay
4min.FID condition: detector temperature 350 DEG C, air mass flow is 300mL/min, and hydrogen flowing quantity is
30mL/min。
GC-NCD model used by analysis is 7890A GC-255 NCD.GC condition: HP-PONA
Capillary chromatographic column, 50m × 0.2mm × 0.5 μm；Temperature programming initial temperature 120 DEG C, heating rate 4 DEG C
/ min, final temperature 270 DEG C, keep 10min；Carrier gas is high-pure helium, constant current operation 0.8mL/min；Sample introduction
Mouth temperature 280 DEG C, split ratio 30:1, sample size 1 μ L.NCD condition: burner temperature 930 DEG C；
Hydrogen flow rate 5mL/min；Oxygen gas flow rate 10mL/min.
Embodiment 1
Silica gel-acidic oxidation that 3.5g acidic alumina content is 10wt% is loaded in solid-phase extraction column A
Aluminum fixes phase, with 2mL the first eluant (pentane) moistening.2.5g is loaded in solid-phase extraction column B
Alkali alumina content is that the silica gel-alkali alumina of 60wt% fixes phase.The activation temperature of silica gel is 80
DEG C, soak time 6 hours, acidic alumina activation temperature is 350 DEG C, and soak time is 7 hours,
Alkali alumina activation temperature is 350 DEG C, and soak time is 6 hours.
Take 2mL Qingyang Effect of Catalysis In Petrochemistry cracked diesel oil with liquid-transfering gun add solid-phase extraction column A top and fixed
Adsorb the most completely.Rinse solid-phase extraction column with 6mL the first eluant (pentane), obtain saturated hydrocarbons (group
Divide 1).Rinse solid with 10mL the second eluant (dichloromethane is 0.25:1 with the volume ratio of pentane)
Phase extraction column, obtains aromatic hydrocarbons (component 2).Solid phase is rinsed with 12mL the 3rd eluant (dichloromethane)
Extraction column, obtains neutral nitrogen compounds (component 3).By 1mL the 3rd eluant moistening Solid-Phase Extraction
Post B, is together in series solid-phase extraction column A, B, wherein B post under.With 10mL the 4th eluant (third
Ketone is 0.1:1 with the volume ratio of dichloromethane) rinse solid-phase extraction column A, B, obtain basic nitrogen compound
(component 4).Rotary Evaporators and nitrogen purging is used to remove component 1, component 2, component 3, component 4
In partial solvent.
GC-NCD is used to analyze nitrogen-containing compound distribution in component 1, component 2, component 3, component 4,
Each component GC-NCD chromatogram is shown in Fig. 1 a, Fig. 1 b, Fig. 1 c, Fig. 1 d.By Fig. 1 a, Fig. 1 b, Fig. 1 c,
Fig. 1 d is visible, does not has the chromatographic peak of nitrogen-containing compound to occur, show saturated hydrocarbons, aromatic hydrocarbons group in component 1,2
Nitrogen-containing compound it is substantially not present in Fen；The distribution of component 3, component 4 nitrogen-containing compound differs, and shows two
In planting component, nitrogen-containing compound type differs.
GC-MS-FID is used to analyze in component 1, component 2, component 3, component 4 type of compounds and contain
Amount, each component total ions chromatogram is shown in Fig. 2 a, Fig. 2 b, Fig. 2 c, Fig. 2 d.By Fig. 2 a, Fig. 2 b,
Fig. 2 c, Fig. 2 d are visible, component 1 predominantly saturated hydrocarbons, and component 2 predominantly aromatic hydrocarbons, component 3 is predominantly
Neutral nitrogen compounds, component 4 predominantly basic nitrogen compound, wherein phenol compound in component 4
Content is 20.3wt%, and component intersection content, in error allowed band, does not affect the qualitative of nitrogen-containing compound
With quantitative analysis.
The response rate of all types of nitrogen-containing compounds in diesel oil distillate is measured with the blank recovery of standard addition of ethylenediamine.
Ethylenediamine/n-heptane solution that 100 μ L concentration are 1.5g/L is added, configuration in 4mL diesel samples
Become to contain the ethylenediamine diesel oil solution as internal standard compound.Diesel samples after mark-on is entered according to the method described above
Row Solid phase extraction separation, after the nitrogen-containing compound component rotary evaporation obtained, removing partial solvent, adds
100 μ L concentration are that the positive tri-n-butylamine of 500mg/L is analyzed obtain second two as internal standard, employing GC-NCD
The content of amine.The ethylenediamine quality obtained is subtracted each other with theoretical addition, the ratio of its difference and theoretical addition
Being the blank recovery of standard addition of ethylenediamine, its value is 97.5wt%.
The above results shows, the content of component of intersecting in the inventive method separation component is little, and nitrogen-containing compound returns
Yield is high, has preferable concentration effect.
Comparative example 1
Weigh 20g dried silica gel to be loaded in chromatographic column.Silica gel activating condition is with embodiment 1.With
10mL pentane rinse chromatographic column, adds 2mL Qingyang Effect of Catalysis In Petrochemistry cracked diesel oil sample to chromatographic column
Portion so that diesel samples is all fixed adsorbs mutually.It is sequentially added into the stone that 30mL boiling range is 60-90 DEG C
Oil ether, 40mL benzene/petroleum ether (benzene and petroleum ether volume ratio are 1:3), 40mL benzene/ethanol (benzene and second
Alcohol volume ratio is 1:1), 20mL alcohol flushing, obtain in order corresponding eluent A1, A2, A3,
A4.Each component is standby after rotary evaporation, nitrogen purging concentrate.
The silicagel column that nitrogen-containing compound in eluent A3 uses acid modified be separated into neutral nitrogen compounds with
Basic nitrogen compound.Chromatographic column filling 20g100-200 mesh acid modified silica-gel, moistens with 10mL petroleum ether
Wet, add eluent A3, successively with 40mL dichloromethane, 25mL alcohol flushing chromatographic column, by suitable
Sequence obtains corresponding eluent B1, B2, and the most rotated evaporation, nitrogen are carried out after drying up concentration
GC-MS analyzes.Chromatographic column method separation nitrogen-containing compound is used about to take 10 hours.
Diesel samples after separation is entered GC-MS-FID and is analyzed each component composition information.Result shows, A1
Predominantly alkane, A2 is mainly aromatic hydrocarbons, and B1 is mainly neutral nitrogen compounds, aromatic hydrocarbons and a small amount of alkalescence and contains
Nitrogen compound, B2 is mainly basic nitrogen compound, phenol compound.In B1, arene content is 10.2
Wt%, basic nitrogen compound content is 6.5wt%.In B2, phenol compound content accounts for 70.3wt%.
Ethylenediamine blank recovery of standard addition 93.4wt%.As can be seen here, chromatographic column method enrichment nitrogen-containing compound is used to divide
Big from intersection amount and solvent load, the used time is longer, inefficient.
Comparative example 2
Nitrogenous by saturated hydrocarbons, aromatic hydrocarbons, neutral nitrogen compounds and the alkalescence in the method separation diesel oil of example 1
Compound, except for the difference that solid-phase extraction column A uses untreated acidic alumina, solid-phase extraction column B to use
Untreated alkali alumina.
GC-NCD is used to analyze nitrogen-containing compound distribution in component 1, component 2, component 3, component 4,
Result does not has the chromatographic peak of nitrogen-containing compound to occur in showing component 1,2, show saturated hydrocarbons, aromatic component
Inside it is substantially not present nitrogen-containing compound；In place of component 3, component 4 nitrogen-containing compound are distributed coincidence, show
Exist in two kinds of components and separate crossover phenomenon.
GC-MS-FID is used to analyze in component 1, component 2, component 3, component 4 type of compounds and contain
Amount, result shows component 1 predominantly saturated hydrocarbons, component 2 predominantly aromatic hydrocarbons, component 3 predominantly aromatic hydrocarbons,
Neutral nitrogen compounds, basic nitrogen compound, component 4 predominantly basic nitrogen compound, phenol
Compound.In component 3, arene content is 5.1wt%, and basic nitrogen compound content is 4.2wt%, component 4
Middle phenol compound content is 85.1wt%.Ethylenediamine blank recovery of standard addition 96.4wt%, shows dividing
During from, basic nitrogen compound loss is relatively big, and each component exists separation crossover phenomenon.
Embodiment 2
Silica gel-acidic oxidation that 3.5g acidic alumina content is 30wt% is loaded in solid-phase extraction column A
Aluminum fixes phase, with 2mL the first eluant (normal hexane) moistening.2.5g is loaded in solid-phase extraction column B
Alkali alumina content is that the silica gel-alkali alumina of 40wt% fixes phase.The activation temperature of silica gel is 100
DEG C, soak time 4 hours, acidic alumina activation temperature is 400 DEG C, and soak time is 5 hours,
Alkali alumina activation temperature is 400 DEG C, and soak time is 4 hours.
Take 1mL Kelamayi petrochemical industry coker gas oil with liquid-transfering gun add solid-phase extraction column A top and fixed
Adsorb the most completely.Rinse solid-phase extraction column with 8mL the first eluant (normal hexane), obtain saturated hydrocarbons (group
Divide 1).Solid-Phase Extraction is rinsed with 9mL the second eluant (chloroform is 0.2:1 with the volume ratio of normal hexane)
Post, obtains aromatic hydrocarbons (component 2).Solid-phase extraction column is rinsed with 14mL the 3rd eluant (vinyl chloride),
Obtain neutral nitrogen compounds (component 3).With 1mL the 3rd eluant moistening solid-phase extraction column B, incite somebody to action
Solid-phase extraction column A, B are together in series, wherein B post under.With 8mL the 4th eluant (ethanol and two
The volume ratio of chloromethanes is 0.2:1) rinse solid-phase extraction column A, B, obtain basic nitrogen compound (component
4).Rotary Evaporators and nitrogen purging is used to remove the portion in component 1, component 2, component 3, component 4
Divide solvent.
GC-NCD is used to analyze nitrogen-containing compound distribution in component 1, component 2, component 3, component 4.
Result shows, does not has the chromatographic peak of nitrogen-containing compound to occur in component 1,2；Component 3, component 4 are nitrogenous
Compound distribution differs, and in showing two kinds of components, nitrogen-containing compound type differs.
GC-MS-FID is used to analyze in component 1, component 2, component 3, component 4 type of compounds and contain
Amount, result shows, component 1 predominantly saturated hydrocarbons；Component 2 predominantly aromatic hydrocarbons；Component 3 predominantly neutrality
Nitrogen-containing compound, aromatic compound, wherein arene content 4.4wt%；Component 4 predominantly alkalescence nitrogen
Compound, wherein phenol compound content is 1.5wt%.Component intersection amount is in error allowed band, no
Affect the quantification and qualification of nitrogen-containing compound.
All types of nitrogenous chemical combination in the petrochemical industry coker gas oil of Kelamayi are measured with ethylenediamine blank recovery of standard addition
The response rate of thing, ethylenediamine blank recovery of standard addition 95.7wt%.
Embodiment 3
Silica gel-acidic oxidation that 3.5g acidic alumina content is 40wt% is loaded in solid-phase extraction column A
Aluminum fixes phase, with 2mL the first eluant (normal heptane) moistening.2.5g is loaded in solid-phase extraction column B
Alkali alumina content is that the silica gel-alkali alumina of 20wt% fixes phase.The activation temperature of silica gel is 120
DEG C, soak time 3 hours, acidic alumina activation temperature is 450 DEG C, and soak time is 4 hours,
Alkali alumina activation temperature is 450 DEG C, soak time 2 hours.
Take 5mL Daqing petrochemical straight-run diesel oil with liquid-transfering gun and add solid-phase extraction column A top mutually complete by fixing
Full absorption.Rinse solid-phase extraction column with 9mL the first eluant (normal heptane), obtain saturated hydrocarbons (component
1).Solid-phase extraction column is rinsed with 7mL the second eluant (toluene is 0.4:1 with the volume ratio of hexamethylene),
Obtain aromatic hydrocarbons (component 2).Solid-phase extraction column is rinsed with 14mL the 3rd eluant (ethyl acetate),
To neutral nitrogen compounds (component 3).With 1mL the 3rd eluant moistening solid-phase extraction column B, by solid
Phase extraction column A, B are together in series, wherein B post under.With 7mL the 4th eluant (isopropanol and two
The volume ratio of chloromethanes is 0.3:1) rinse solid-phase extraction column A, B, obtain basic nitrogen compound (component
4).Rotary Evaporators and nitrogen purging is used to remove the portion in component 1, component 2, component 3, component 4
Divide solvent.
GC-NCD is used to analyze nitrogen-containing compound distribution in component 1, component 2, component 3, component 4.
Result shows, does not has the chromatographic peak of nitrogen-containing compound to occur in component 1,2；Component 3, component 4 are nitrogenous
Compound distribution differs, and in showing two kinds of components, nitrogen-containing compound type differs.
GC-MS-FID is used to analyze in component 1, component 2, component 3, component 4 type of compounds and contain
Amount, result shows, component 1 predominantly saturated hydrocarbons；Component 2 predominantly aromatic hydrocarbons, containing fractional saturation hydrocarbon；
Component 3 predominantly neutral nitrogen compounds, aromatic compound, wherein arene content 4.4wt%；Component 4
Predominantly basic nitrogen compound, wherein phenol compound content is 1.5wt%.Component intersection content exists
In error allowed band, do not affect the quantification and qualification of nitrogen-containing compound.
All types of nitrogen-containing compounds in Daqing petrochemical straight-run diesel oil are measured with ethylenediamine blank recovery of standard addition
The response rate, ethylenediamine blank recovery of standard addition 94.3wt%.
Embodiment 4
Silica gel-acidic oxidation that 3.5g acidic alumina content is 30wt% is loaded in solid-phase extraction column A
Aluminum fixes phase, with 2mL the first eluant (petroleum ether) moistening.2.5g is loaded in solid-phase extraction column B
Alkali alumina content is that the silica gel-alkali alumina of 20wt% fixes phase.The activation temperature of silica gel is 120
DEG C, soak time 3 hours, acidic alumina activation temperature is 500 DEG C, and soak time is 4 hours,
Alkali alumina activation temperature is 450 DEG C, and soak time is 2 hours.
Take 6mL Daqing petrochemical hydrofining diesel oil with liquid-transfering gun add solid-phase extraction column A top and fixed
Adsorb the most completely.Rinse solid-phase extraction column with 9mL the first eluant (petroleum ether), obtain saturated hydrocarbons (group
Divide 1).Solid-phase extraction column is rinsed with 8mL the second eluant (benzene is 0.5:1 with the volume ratio of pentane),
Obtain aromatic hydrocarbons (component 2).Solid-phase extraction column is rinsed with 14mL the 3rd eluant (dichloromethane),
To neutral nitrogen compounds (component 3).With 1mL the 3rd eluant moistening solid-phase extraction column B, by solid
Phase extraction column A, B are together in series, wherein B post under.With 8mL the 4th eluant (n-butyl alcohol and two
The volume ratio of chloromethanes is 0.15:1) rinse solid-phase extraction column A, B, obtain basic nitrogen compound (group
Divide 4).Rotary Evaporators and nitrogen purging is used to remove in component 1, component 2, component 3, component 4
Partial solvent.
GC-NCD is used to analyze nitrogen-containing compound distribution in component 1, component 2, component 3, component 4.
Result shows, does not has the chromatographic peak of nitrogen-containing compound to occur in component 1,2；Component 3, component 4 are nitrogenous
Compound distribution differs, and in showing two kinds of components, nitrogen-containing compound type differs.
GC-MS-FID is used to analyze in component 1, component 2, component 3, component 4 type of compounds and contain
Amount, result shows, component 1 predominantly saturated hydrocarbons；Component 2 predominantly aromatic hydrocarbons, containing fractional saturation hydrocarbon；
Component 3 predominantly neutral nitrogen compounds, aromatic compound, wherein arene content 2.4wt%；Component 4
It is substantially not present nitrogen-containing compound.Component intersection content, in error allowed band, does not affect nitrogen-containing compound
Quantification and qualification.
All types of nitrogenous chemical combination in Daqing petrochemical hydrofining diesel oil are measured with ethylenediamine blank recovery of standard addition
The response rate of thing, ethylenediamine blank recovery of standard addition 98.5wt%.
Embodiment 5
Silica gel-acidic oxidation that 3.5g acidic alumina content is 25wt% is loaded in solid-phase extraction column A
Aluminum fixes phase, with 2mL the first eluant (pentane) moistening.2.5g is loaded in solid-phase extraction column B
Alkali alumina content is that the silica gel-alkali alumina of 20wt% fixes phase.The activation temperature of silica gel is 160
DEG C, soak time 2 hours, acidic alumina activation temperature is 550 DEG C, and soak time is 3 hours,
Alkali alumina activation temperature is 450 DEG C, and soak time is 2 hours.
Take 4mL state IV0# finished diesel fuel with liquid-transfering gun and add solid-phase extraction column A top mutually complete by fixing
Full absorption.Rinse solid-phase extraction column with 7mL the first eluant (pentane), obtain saturated hydrocarbons (component
1).Solid phase extraction is rinsed with 9mL the second eluant (dichloromethane is 0.2:1 with the volume ratio of pentane)
Take post, obtain aromatic hydrocarbons (component 2).Solid-phase extraction column is rinsed with 10mL the 3rd eluant (vinyl chloride),
Obtain neutral nitrogen compounds (component 3).With 1mL the 3rd eluant moistening solid-phase extraction column B, incite somebody to action
Solid-phase extraction column A, B are together in series, wherein B post under.With 9mL the 4th eluant (acetone and two
The volume ratio of chloromethanes is 0.15:1) rinse solid-phase extraction column A, B, obtain basic nitrogen compound (group
Divide 4).Rotary Evaporators and nitrogen purging is used to remove in component 1, component 2, component 3, component 4
Partial solvent.
GC-NCD is used to analyze nitrogen-containing compound distribution in component 1, component 2, component 3, component 4.
Result shows, does not has the chromatographic peak of nitrogen-containing compound to occur in component 1,2；Component 3, component 4 are nitrogenous
Compound distribution differs, and in showing two kinds of components, nitrogen-containing compound type differs.
GC-MS-FID is used to analyze in component 1, component 2, component 3, component 4 type of compounds and contain
Amount, result shows, component 1 predominantly saturated hydrocarbons；Component 2 predominantly aromatic hydrocarbons, containing fractional saturation hydrocarbon；
Component 3 predominantly neutral nitrogen compounds, aromatic compound, wherein arene content 4.8wt%；Component 4
It is substantially not present nitrogen-containing compound.Component intersection content, in error allowed band, does not affect nitrogen-containing compound
Quantification and qualification.
Returning of all types of nitrogen-containing compounds in state IV 0# finished diesel fuel is measured with ethylenediamine blank recovery of standard addition
Yield, ethylenediamine blank recovery of standard addition 95.6wt%.
Claims (11)
1. a twin columns solid phase extraction for nitrogen-containing compound in diesel oil, comprises the steps:
(1), the preparation of solid-phase extraction column
Solid-phase extraction column A fixing is the mixture of silica gel and acidic alumina mutually, solid-phase extraction column B's
Fixing is the mixture of silica gel and alkali alumina mutually；
(2), eluting
Use the solid-phase extraction column A described in the first eluant moistening, add diesel samples from upper strata, with first
Eluant rinses solid-phase extraction column A, obtains saturated hydrocarbons；
Rinse solid-phase extraction column A with the second eluant, obtain aromatic hydrocarbons；
Rinse solid-phase extraction column A with the 3rd eluant, obtain neutral nitrogen compounds；
Solid-phase extraction column A with B is connected, A post upper, with the 4th eluant rinse solid-phase extraction column A,
B, obtains basic nitrogen compound；
Wherein, described first eluant selects free pentane, normal hexane, normal heptane and petroleum ether to be constituted
At least one in group；
Second eluant is the mixture of a and b: described a selects free dichloromethane, chloroform, benzene and toluene
At least one in the group constituted；Described b selects free pentane, normal hexane and hexamethylene to be constituted
At least one in group；
3rd eluant selects at least in the group that free vinyl chloride, dichloromethane and ethyl acetate are constituted
Kind；
4th eluant is the mixture of c and dichloromethane: described c selects free ethanol, isopropanol, positive fourth
At least one in the group that alcohol and acetone are constituted.
The twin columns solid phase extraction of nitrogen-containing compound, its feature in diesel oil the most according to claim 1
Being, the specific surface area of described silica gel is 300-600m2/ g, pore volume is 0.2-5mL/g.
The twin columns solid phase extraction of nitrogen-containing compound, its feature in diesel oil the most according to claim 1
Being, the specific surface area of described acidic alumina is 100-300m2/ g, pore volume is 0.1-0.5mL/g.
The twin columns solid phase extraction of nitrogen-containing compound, its feature in diesel oil the most according to claim 1
Being, the specific surface area of described alkali alumina is 120-250m2/ g, pore volume is 0.1-0.4mL/g,
Aperture is 4-10nm, and pH value is at 10-14.
The twin columns solid phase extraction of nitrogen-containing compound, its feature in diesel oil the most according to claim 1
Being, in solid-phase extraction column A, the content of acidic alumina is 10-40wt%, solid-phase extraction column B neutral and alkali
The content of aluminium oxide is 20-60wt%.
The twin columns solid phase extraction of nitrogen-containing compound, its feature in diesel oil the most according to claim 1
It is, in the preparation of step (1) solid-phase extraction column,
Silica gel is dried 2-6 hour under the conditions of 80-160 DEG C, obtains the silica gel of activation；
By acidic alumina roasting 3-7 hour under the conditions of 350-550 DEG C, obtain the acidic alumina of activation；
By alkali alumina roasting 2-6 hour under the conditions of 350-450 DEG C, obtain the alkali alumina of activation；
The silica gel of activation is mixed homogeneously with the acidic alumina of activation, obtains solid-phase extraction column A；Will activation
Silica gel mix homogeneously with the alkali alumina of activation, obtain solid-phase extraction column B.
The twin columns solid phase extraction of nitrogen-containing compound, its feature in diesel oil the most according to claim 1
Being, the volume ratio of a Yu b described in the second eluant is 0.2-0.5:1.
The twin columns solid phase extraction of nitrogen-containing compound, its feature in diesel oil the most according to claim 1
Being, c described in the 4th eluant is 0.1-0.3:1 with the volume ratio of dichloromethane.
The twin columns solid phase extraction of nitrogen-containing compound, its feature in diesel oil the most according to claim 1
Being, the mass ratio of diesel samples quality and solid-phase extraction column A is at 0.1-1.5:1, and diesel samples quality is with solid
The mass ratio of phase extraction column B is 0.15-2.0:1.
The twin columns solid phase extraction of nitrogen-containing compound, its feature in diesel oil the most according to claim 1
Being, described first eluant is 0.8-10:1 with the volume ratio of diesel samples；
Described second eluant is 1.3-16:1 with the volume ratio of diesel samples；
Described 3rd eluant is 2-24:1 with the volume ratio of diesel samples；
Described 4th eluant is 6-22:1 with the volume ratio of diesel samples.
The twin columns solid phase extraction of nitrogen-containing compound, its feature in 11. diesel oil according to claim 1
Being, described diesel oil is straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, is hydrocracked diesel oil, adds
Hydrogen refined diesel oil or finished diesel fuel.
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