CN106318438B - Double-column solid phase extraction method for nitrogen-containing compounds in diesel oil - Google Patents
Double-column solid phase extraction method for nitrogen-containing compounds in diesel oil Download PDFInfo
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- CN106318438B CN106318438B CN201510337223.1A CN201510337223A CN106318438B CN 106318438 B CN106318438 B CN 106318438B CN 201510337223 A CN201510337223 A CN 201510337223A CN 106318438 B CN106318438 B CN 106318438B
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- 238000002414 normal-phase solid-phase extraction Methods 0.000 title claims abstract description 139
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title abstract description 26
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title abstract description 9
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 102
- 239000003480 eluent Substances 0.000 claims abstract description 84
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000741 silica gel Substances 0.000 claims abstract description 32
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 32
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 29
- 230000002378 acidificating effect Effects 0.000 claims abstract description 29
- 230000007935 neutral effect Effects 0.000 claims abstract description 28
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 25
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000009736 wetting Methods 0.000 claims abstract description 5
- 238000010828 elution Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 67
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 45
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 45
- 239000003513 alkali Substances 0.000 claims description 32
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- 230000004913 activation Effects 0.000 claims description 25
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 238000004523 catalytic cracking Methods 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 abstract 4
- 238000000926 separation method Methods 0.000 description 26
- 229960001866 silicon dioxide Drugs 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000011084 recovery Methods 0.000 description 17
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 239000004411 aluminium Substances 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000004451 qualitative analysis Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
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- 238000004440 column chromatography Methods 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
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- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A double-column solid phase extraction method for nitrogen-containing compounds in diesel oil comprises the following steps: (1) and preparing a solid phase extraction column: the stationary phase of the solid phase extraction column A is a mixture of silica gel and acidic alumina, and the stationary phase of the solid phase extraction column B is a mixture of silica gel and alkaline alumina; (2) and (3) elution: wetting the solid phase extraction column A by using a first eluent, adding a diesel oil sample from the upper layer, and washing the solid phase extraction column A by using the first eluent to obtain saturated hydrocarbon; washing the solid phase extraction column A with a second eluent to obtain aromatic hydrocarbon; washing the solid phase extraction column A with a third eluent to obtain a neutral nitrogen-containing compound; and (3) connecting the solid phase extraction column A and the solid phase extraction column B in series, wherein the column A is arranged above, and washing the solid phase extraction column A, B by using a fourth eluent to obtain the basic nitrogen-containing compound.
Description
Technical field
The present invention relates to petrochemical industry, is that one kind uses twin columns method Solid phase extraction separation, enrichment diesel oil specifically
The method of neutral nitrogen compounds and basic nitrogen compound in sample.
Background technology
Nitrogen-containing compound in diesel oil easily forms the nitrogen oxides such as nitrogen dioxide in combustion.Such material is being arranged
Easily vehicle exhaust gas systems are caused to be poisoned during putting；After being discharged into air, such material is the master to form acid rain, acid mist
Want one of pollutant；In addition, nitrogen oxides can form photochemical fog with hydrocarbon, and ozone layer can be damaged.
Therefore, the requirement that nitrogen-containing compound content in diesel oil is fuels cleaning is reduced.According to the need of diesel oil denitrification process technological development
Will, nitrogen-containing compound qualitative and quantitative analysis method in diesel oil distillate is established, can be catalyst research and development and related process exploitation
Basic data is provided, and key message is provided for catalytic mechanism research.
Because the content of nitrogen-containing compound in diesel oil is very low, before qualitative analysis is carried out to nitrogen-containing compound, often need
Diesel oil is separated, enrichment processing.Conventional separation, the method for being enriched with nitrogen-containing compound have acid extraction method, ion exchange color
Spectrometry, column chromatography chromatogram method etc., wherein column chromatography chromatogram method have reproducible, post high income, stationary phase cost is relatively low, does not deposit
It is more and more extensive in the separation of diesel oil nitrogen-containing compound, rich pooled applications the water pollution the advantages that.Zhang Yueqin [split by Zhang Yueqin catalysis
Change the distribution petroleum refinings of nitrogen-containing compound type and chemical industry [J], 2013,44 (5) in diesel oil:87~91.] neutral silica gel is used
Post separation, the nitrogen-containing compound being enriched in catalytic cracking diesel oil, and the modified silicagel column of acid is further used by nitrogenous chemical combination
Thing is separated into neutral nitrogen compounds and basic nitrogen compound.But this method exist stationary phase dosage and solvent load compared with
Greatly, the problem of processing time is long.In addition, nitrogen-containing compound and other compound amounts of intersection are larger in sample separation process, influence
The qualitative analysis of nitrogen-containing compound.
The content of the invention
Separated using solid phase extraction techniques it is an object of the invention to provide a kind of, be enriched with nitrogen-containing compound in diesel samples
Method, it is mainly used in the pretreatment process of diesel samples during nitrogen-containing compound qualitative analysis in diesel oil.The present invention can solve to pass
Separated in the column chromatography chromatogram method of uniting separation, enrichment diesel oil during nitrogen-containing compound between component intersection amount is big, solvent load is big, processing when
Between it is long the problem of.
The present invention provides a kind of twin columns solid phase extraction of nitrogen-containing compound in diesel oil, comprises the following steps：
(1), the preparation of solid-phase extraction column
Solid-phase extraction column A stationary phase is the mixture of silica gel and acidic alumina, and solid-phase extraction column B stationary phase is silicon
The mixture of glue and alkali alumina；
(2), elute
Using the described solid-phase extraction column A of the first eluant, eluent wetting, diesel samples are added from upper strata, are rushed with the first eluant, eluent
Solid-phase extraction column A is washed, obtains saturated hydrocarbons；
Solid-phase extraction column A is rinsed with the second eluant, eluent, obtains aromatic hydrocarbons；
Solid-phase extraction column A is rinsed with the 3rd eluant, eluent, obtains neutral nitrogen compounds；
Solid-phase extraction column A is connected with B, A posts rinse solid-phase extraction column A, B upper, with the 4th eluant, eluent, obtain alkalescence and contain
Nitrogen compound；
Wherein, first eluant, eluent is in the group being made up of pentane, n-hexane, normal heptane and petroleum ether
It is at least one；
Second eluant, eluent is a and b mixture：The a is selected from the group being made up of dichloromethane, chloroform, benzene and toluene
At least one of group；The b is selected from least one of group being made up of pentane, n-hexane and hexamethylene；
3rd eluant, eluent is selected from least one of group being made up of vinyl chloride, dichloromethane and ethyl acetate；
4th eluant, eluent is the mixture of c and dichloromethane：The c is selected from by ethanol, isopropanol, n-butanol and acetone institute
At least one of group of composition.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, the specific surface area of the silica gel
Preferably 300-600m2/ g, pore volume are preferably 0.2-5mL/g.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, the ratio of the acidic alumina
Surface area is preferably 100-300m2/ g, pore volume are preferably 0.1-0.5mL/g.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, the ratio of the alkali alumina
Surface area is preferably 120-250m2/ g, pore volume are preferably 0.1-0.4mL/g, and aperture is preferably 4-10nm, and pH value preferably exists
10-14。
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, acid oxygen in solid-phase extraction column A
The content for changing aluminium is preferably 10-40wt%, and the content of solid-phase extraction column B neutral and alkali aluminum oxide is preferably 20-60wt%.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, step (1) solid-phase extraction column
In preparation, it is preferred that
Silica gel is dried into 2-6 hours under the conditions of 80-160 DEG C, obtains the silica gel of activation；
Acidic alumina is calcined 3-7 hours under the conditions of 350-550 DEG C, the acidic alumina activated；
Alkali alumina is calcined 2-6 hours under the conditions of 350-450 DEG C, the alkali alumina activated；
The silica gel of activation is well mixed with the acidic alumina activated, produces solid-phase extraction column A；By the silica gel of activation with
The alkali alumina of activation is well mixed, and produces solid-phase extraction column B.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, a described in the second eluant, eluent with
B volume ratio 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, c described in the 4th eluant, eluent with
The volume ratio of dichloromethane is preferably 0.1-0.3:1.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, diesel samples quality and solid phase
Extraction column A mass ratio is preferably in 0.1-1.5:1, diesel samples quality and solid-phase extraction column B mass ratio are preferably 0.15-
2.0:1。
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, first eluant, eluent and bavin
The volume ratio of oil samples is preferably 0.8-10:1；
The volume ratio of second eluant, eluent and diesel samples is preferably 1.3-16:1；
The volume ratio of 3rd eluant, eluent and diesel samples is preferably 2-24:1；
The volume ratio of 4th eluant, eluent and diesel samples is preferably 6-22:1.
The twin columns solid phase extraction of nitrogen-containing compound in diesel oil of the present invention, wherein, described diesel oil is preferably straight
Evaporate diesel oil, catalytic cracking diesel oil, coker gas oil, be hydrocracked diesel oil, hydrofining diesel oil or finished diesel fuel.
The present invention provides a kind of SPE column preparation method for separating nitrogen-containing compound in diesel oil.Pass through solid-phase extraction column
A, B matching, can be in the case where reducing solvent load, in being by nitrogen-containing compound separation, the enrichment in diesel oil effectively
Property nitrogen-containing compound and basic nitrogen compound, meet the requirement of nitrogen-containing compound qualitative and quantitative analysis.
The present invention uses twin columns method, by adjusting eluant, eluent polarity and dosage, diesel samples are separated into saturated hydrocarbons, virtue
Hydrocarbon, neutral nitrogen compounds and basic nitrogen compound, stationary phase dosage and solvent load is few, intersection amount is separated between component compared with
It is small.Compared to traditional column chromatography chromatogram method, the present invention separates, the time of nitrogen-containing compound is only in one diesel samples of enrichment
50min, substantially increase operating efficiency.
Brief description of the drawings
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 figures 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 figures of component 4 after Solid phase extraction separation.
Embodiment
The technical scheme in embodiments of the invention will be described in detail below, but following examples be only to
Understand the present invention, and the present invention can not be limited, the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
The stationary phase of solid-phase extraction column A used in the present invention is the mixture of silica gel and acidic alumina, wherein acid oxygen
The content for changing aluminium is 10-40wt%.Solid-phase extraction column B stationary phase is the mixture of silica gel and alkali alumina, its neutral and alkali
The content of aluminum oxide is 20-60wt%.By the matching of two kinds of stationary phase polarity, saturated hydrocarbons in diesel oil, virtue can not only be ensured
Hydrocarbon and nitrogen-containing compound efficiently separate, moreover it is possible to improve the rate of recovery of nitrogen-containing compound.
Silica gel specific surface area used in the present invention is 300-600m2/ g, pore volume 0.2-5mL/g, acidic alumina
Specific surface area is 100-300m2/ g, pore volume 0.1-0.5mL/g, the specific surface area of alkali alumina is 120-250m2/ g, hole
Volume is 0.1-0.4mL/g.Above-mentioned silica gel, the preparation method of aluminum oxide stationary phase are：Silica gel is done under the conditions of 80-160 DEG C
Dry 2-6 hours, obtain activated silica gel；Satisfactory acidic alumina is calcined 3-7 hours under the conditions of 350-550 DEG C, obtained
The acidic alumina of activation；By satisfactory alkali alumina with being calcined 2-6 hours under the conditions of 350-450 DEG C, activated
Alkali alumina.The silica gel of activation is well mixed with acidic alumina, silica gel with alkali alumina in required ratio, produced
Solid-phase extraction column A, B.
The present invention is using the nitrogen-containing compound in twin columns method separation diesel samples.Before adding diesel samples, 2mL can be used
First eluant, eluent wetting solid-phase extraction column A.Diesel samples are added and adsorbed completely in stationary phase from solid-phase extraction column A tops
On, solid-phase extraction column A is rinsed with the first eluant, eluent, extracts the saturated hydrocarbons in diesel oil；SPE is rinsed with the second eluant, eluent
Post A, extracts aromatic compound；Solid-phase extraction column A is rinsed with the 3rd eluant, eluent, extracts neutral nitrogen compounds.With 2mL
Three eluant, eluents soak solid-phase extraction column B, solid-phase extraction column A and B are together in series, wherein B posts are under.Rushed using the 4th eluant, eluent
Solid-phase extraction column A, B are washed, extracts basic nitrogen compound.First eluant, eluent used is selected from pentane, n-hexane, positive heptan
At least one of alkane, petroleum ether, the second eluant, eluent are selected from least one of dichloromethane, chloroform, benzene, toluene and positive penta
The mixture of at least one of alkane, n-hexane, hexamethylene, the 3rd eluant, eluent is in vinyl chloride, dichloromethane, ethyl acetate
One kind, the 4th eluant, eluent is using the mixture of ethanol, isopropanol, n-butanol, at least one of acetone with dichloromethane.The
At least one of the preferred pentane of one eluant, eluent, the second eluant dichloromethane, chloroform, benzene, toluene and pentane, just oneself
The volume ratio of at least one of alkane, hexamethylene is 0.2-0.5:1, the 3rd eluant, eluent is selected from vinyl chloride, dichloromethane, acetic acid second
At least one of one kind in ester, preferably vinyl chloride, the 4th eluant, eluent ethanol, isopropanol, n-butanol, acetone and dichloromethane
Volume ratio be 0.1-0.3:1.
The amount of diesel oil used in SPE is 0.5-6mL, rinses the first elution used in saturated hydrocarbons on solid-phase extraction column A
The volume ratio of agent and diesel samples is 0.8-10:1；Rinse the second eluant, eluent and diesel oil sample on solid-phase extraction column A used in aromatic hydrocarbons
The volume ratio of product is 1.3-16:1；Rinse the 3rd eluant, eluent and diesel oil sample on solid-phase extraction column A used in neutral nitrogen compounds
The volume ratio of product is 2-24:1；Rinse the 4th eluant, eluent and diesel oil sample used in the upper basic nitrogen compound of solid-phase extraction column A, B
The volume ratio of product is 6-22:1.
The isolated saturated hydrocarbons of the above method, aromatic hydrocarbons, neutral nitrogen compounds and basic nitrogen compound solution, through molten
Corresponding component is can obtain after agent volatilization concentration, preferentially carries out solvent volatilization work from rotary evaporation, nitrogen purging.Will be molten
Liquid volatilization, which is concentrated into 0.4mL or so, can enter gas chromatography-mass spectrum (GC-MS) and gas-chromatography-nitrogen chemical luminescence detector
(GC-NCD) qualitative and quantitative analysis is carried out.Eluant, eluent toxicity used in the present invention is low, dosage is few, while avoids sample and separating
During diesel component loss.
Currently preferred measure concentration nitrogen-containing compound morphological method is gas chromatography-mass spectrum-hydrogen ion fire defector
Device method (GC-MS-FID).The nitrogen-containing compound of enrichment is taken to inject GC-MS-FID, gas-chromatography is according to the boiling point of nitrogen-containing compound
Separated with polarity, then obtain the monomer information of nitrogen-containing compound through level Four bar mass spectral analysis.FID is to allization in diesel oil
The response factor of compound is substantially suitable, therefore calculates other compounds in nitrogen-containing compound by the chromatogram of each component after separation
Content.Nitrogen chemical luminescence detector only has response to nitrogen-containing compound, therefore passes through gas-chromatography-nitrogen chemical luminescence detector
(GC-NCD) chromatogram is that whether there is nitrogen-containing compound in each component for can determine whether separation.Surveyed using GC-NCD combinations internal standard method
Determine the concentration information of nitrogen-containing compound, internal standard compound can use tri-n-butylamine, DMA.
The present invention be applied to straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, be hydrocracked diesel oil, hydrofining diesel oil,
The enrichment of nitrogen-containing compound in finished diesel fuel.
The silica gel for chromatography that silica gel used produces for Chemical Reagent Co., Ltd., Sinopharm Group in example, granularity >=
70.0%, dry vector≤6.0%, specific surface area 511.9m2/ g, pore volume 0.468mL/g.Acidic alumina is traditional Chinese medicines
The chromatography aluminum oxide of chemical reagent Co., Ltd of group production, granularity >=75.0%, calcination loss≤8.0%, compares surface
Product is 177.8m2/ g, pore volume 0.255mL/g.1g acidic aluminas mix with the acetum that 2mL concentration is 1mol/L
It is even, aluminum oxide is washed with deionized after standing 1 hour until pH value is 4.Alkali alumina is that Chinese medicines group chemical reagent has
The chromatography aluminum oxide of limit company production, granularity >=75.0%, calcination loss≤8.0%, specific surface area 146.5m2/ g,
Pore volume is 0.254mL/g, aperture 7.8nm.1g alkali aluminas mix with the NaOH solution that 2mL concentration is 1mol/L
It is even, alkali alumina is washed with deionized after standing 1.5 hours until pH value is 12.
Analysis GC-MS INSTRUMENT MODELs used are 7890A GC-5975 MS, band fid detector.Analyze the GC of component 1,2
Condition：HP-5MS capillary chromatographic columns, 30m × 0.25mm × 0.25 μm；60 DEG C of temperature programming initial temperature, keep 2min after with 10
DEG C/min rises to 300 DEG C, keep 3min；Carrier gas is high-pure helium, constant current operation 0.6mL/min；300 DEG C of injector temperature, shunting
Than 30:1, the μ L of sample size 1.Analyze the GC conditions of component 3,4：HP-PONA capillary chromatographic columns, 50m × 0.2mm × 0.5 μm；Journey
Sequence 120 DEG C of initial temperature of heating, 4 DEG C/min of heating rate, 270 DEG C of final temperature, keeps 10min；Carrier gas is high-pure helium, constant current operation
0.9mL/min；280 DEG C of injector temperature, split ratio 30:1, the μ L of sample size 1.MSD conditions：EI ionization sources (70eV), ion gun
230 DEG C of temperature, 130 DEG C of level Four bar temperature, full scan 30~500u of mass range, 300 DEG C of interface temperature, solvent delay 4min.
FID conditions：350 DEG C, air mass flow 300mL/min, hydrogen flowing quantity 30mL/min of detector temperature.
Analysis GC-NCD model 7890A GC-255 NCD used.GC conditions：HP-PONA capillary chromatographic columns, 50m
×0.2mm×0.5μm；120 DEG C of temperature programming initial temperature, 4 DEG C/min of heating rate, 270 DEG C of final temperature, keep 10min；Carrier gas is height
Pure helium, constant current operation 0.8mL/min；280 DEG C of injector temperature, split ratio 30:1, the μ L of sample size 1.NCD conditions：Burner temperature
930 DEG C of degree；Hydrogen flow rate 5mL/min；Oxygen gas flow rate 10mL/min.
Embodiment 1
Silica gel-acidic alumina stationary phase that 3.5g acidic oxidations aluminium content is 10wt% is loaded in solid-phase extraction column A,
Soaked with the eluant, eluents of 2mL first (pentane).The silicon that the alkaline oxygenated aluminium contents of 2.5g are 60wt% is loaded in solid-phase extraction column B
Glue-alkali alumina stationary phase.The activation temperature of silica gel is 80 DEG C, soak time 6 hours, and acidic alumina activation temperature is
350 DEG C, soak time is 7 hours, and 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 to add solid-phase extraction column A tops with liquid-transfering gun and inhaled completely by stationary phase
It is attached.Solid-phase extraction column is rinsed with the eluant, eluents of 6mL first (pentane), obtains saturated hydrocarbons (component 1).With the eluant, eluents of 10mL second
(volume ratio of dichloromethane and pentane is 0.25:1) solid-phase extraction column is rinsed, obtains aromatic hydrocarbons (component 2).Washed with 12mL the 3rd
Solid-phase extraction column is rinsed in de- agent (dichloromethane), obtains neutral nitrogen compounds (component 3).It is solid with the wetting of the eluant, eluents of 1mL the 3rd
Phase extraction column B, solid-phase extraction column A, B are together in series, and wherein B posts are under.With 10mL the 4th eluant, eluent (acetone and dichloromethane
Volume ratio be 0.1:1) solid-phase extraction column A, B are rinsed, obtains basic nitrogen compound (component 4).Using Rotary Evaporators and
Nitrogen purging removes the partial solvent in component 1, component 2, component 3, component 4.
It is distributed using nitrogen-containing compound in GC-NCD analyses component 1, component 2, component 3, component 4, each component GC-NCD colors
Spectrogram is shown in Fig. 1 a, Fig. 1 b, Fig. 1 c, Fig. 1 d.From Fig. 1 a, Fig. 1 b, Fig. 1 c, Fig. 1 d, there is no nitrogen-containing compound in component 1,2
Chromatographic peak occurs, and shows saturated hydrocarbons, is substantially not present nitrogen-containing compound in aromatic component；Component 3, the nitrogen-containing compound point of component 4
Cloth differs, and shows that nitrogen-containing compound type differs in two kinds of components.
Using GC-MS-FID analyses component 1, component 2, component 3, type of compounds and content in component 4, each component always from
Subflow chromatogram is shown in Fig. 2 a, Fig. 2 b, Fig. 2 c, Fig. 2 d.From Fig. 2 a, Fig. 2 b, Fig. 2 c, Fig. 2 d, component 1 is mainly saturated hydrocarbons,
Component 2 is mainly aromatic hydrocarbons, and component 3 is mainly neutral nitrogen compounds, and component 4 is mainly basic nitrogen compound, wherein component 4
Middle phenol compound content is 20.3wt%, and component intersects content in error allowed band, do not influence nitrogen-containing compound
Quantification and qualification.
With the rate of recovery of all types of nitrogen-containing compounds in the blank recovery of standard addition measure diesel oil distillate of ethylenediamine.To 4mL
Ethylenediamine/n-heptane solution that 100 μ L concentration are 1.5g/L is added in diesel samples, is configured to contain ethylenediamine as internal standard
The diesel oil solution of compound.Diesel samples after mark-on carry out Solid phase extraction separation according to the method described above, obtained nitrogen-containing compound
After component rotary evaporation, removing partial solvent, the positive tri-n-butylamine that 100 μ L concentration of addition are 500mg/L is as internal standard, using GC-
NCD analyzes to obtain the content of ethylenediamine.Obtained ethylenediamine quality is subtracted each other with theoretical addition, its difference and theoretical addition
The ratio between be ethylenediamine blank recovery of standard addition, its value is 97.5wt%.
The above results show that the content of intersection component is small in the inventive method separation component, and the nitrogen-containing compound rate of recovery is high,
With preferable concentration effect.
Comparative example 1
20g drying process silica gel is weighed to be loaded into chromatographic column.Silica gel activating condition is the same as embodiment 1.With 10mL pentanes
Rinse chromatographic column, 2mL Qingyang Effect of Catalysis In Petrochemistry cracked diesel oil samples is added to chromatographic column top so that diesel samples are all fixed
Mutually adsorb.Sequentially adding petroleum ether, 40mL benzene/petroleum ether that 30mL boiling ranges are 60-90 DEG C, (benzene and petroleum ether volume ratio are 1:
3), (benzene and ethanol volume ratio are 1 to 40mL benzene/ethanol:1), 20mL alcohol flushings, obtain in order corresponding eluent A1, A2,
A3、A4.Each component is standby after rotary evaporation, nitrogen purging concentration.
Nitrogen-containing compound in eluent A3 is separated into neutral nitrogen compounds using the modified silicagel column of acid and contained with alkalescence
Nitrogen compound.Chromatographic column filling 20g100-200 mesh acid modified silica-gels, soaked with 10mL petroleum ethers, add eluent A3, successively
With 40mL dichloromethane, 25mL alcohol flushing chromatographic columns, obtain corresponding eluent B1, B2 in order, then it is rotated evaporation,
GC-MS analyses are carried out after nitrogen purging drying concentration.About taken 10 hours using chromatographic column method separation nitrogen-containing compound.
Diesel samples after separation enter GC-MS-FID analysis each component composition information.As a result showing, A1 is mainly alkane,
A2 is mainly aromatic hydrocarbons, and B1 is mainly neutral nitrogen compounds, aromatic hydrocarbons and a small amount of basic nitrogen compound, and B2 is mainly that alkalescence is nitrogenous
Compound, phenol compound.Arene content is 10.2wt% in B1, and basic nitrogen compound content is 6.5wt%.Benzene in B2
Content of phenolic compounds accounts for 70.3wt%.Ethylenediamine blank recovery of standard addition 93.4wt%.As can be seen here, it is rich using chromatographic column method
Collect nitrogen-containing compound separation intersection amount and solvent load is big, the used time is longer, less efficient.
Comparative example 2
Saturated hydrocarbons, aromatic hydrocarbons, neutral nitrogen compounds and the basic nitrogen compound in diesel oil are separated by the method for example 1,
The difference is that solid-phase extraction column A uses untreated alkali alumina using untreated acidic alumina, solid-phase extraction column B.
It is distributed using nitrogen-containing compound in GC-NCD analyses component 1, component 2, component 3, component 4, the results showed that component 1,2
The interior chromatographic peak without nitrogen-containing compound occurs, and shows saturated hydrocarbons, is substantially not present nitrogen-containing compound in aromatic component；Component 3,
Coincidence part is distributed with the nitrogen-containing compound of component 4, shows separation crossover phenomenon in two kinds of components be present.
Using type of compounds and content in GC-MS-FID analyses component 1, component 2, component 3, component 4, the results showed that group
It is mainly aromatic hydrocarbons to divide 1 predominantly saturated hydrocarbons, component 2, and component 3 is mainly aromatic hydrocarbons, neutral nitrogen compounds, the nitrogenous chemical combination of alkalescence
Thing, component 4 are mainly basic nitrogen compound, phenol compound.Arene content is 5.1wt% in component 3, alkaline nitrogen
Compound content is 4.2wt%, and phenol compound content is 85.1wt% in component 4.Ethylenediamine blank recovery of standard addition
96.4wt%, show separation process neutral and alkali nitrogen-containing compound lose it is larger, and each component exist separation crossover phenomenon.
Embodiment 2
Silica gel-acidic alumina stationary phase that 3.5g acidic oxidations aluminium content is 30wt% is loaded in solid-phase extraction column A,
Soaked with the eluant, eluents of 2mL first (n-hexane).The silicon that the alkaline oxygenated aluminium contents of 2.5g are 40wt% is loaded in solid-phase extraction column B
Glue-alkali alumina stationary phase.The activation temperature of silica gel is 100 DEG C, soak time 4 hours, and acidic alumina activation temperature is
400 DEG C, soak time is 5 hours, and alkali alumina activation temperature is 400 DEG C, and soak time is 4 hours.
Take 1mL Kelamayis petrochemical industry coker gas oil to add solid-phase extraction column A tops with liquid-transfering gun and inhaled completely by stationary phase
It is attached.Solid-phase extraction column is rinsed with the eluant, eluents of 8mL first (n-hexane), obtains saturated hydrocarbons (component 1).With 9mL the second eluant, eluent (chlorine
Imitative and n-hexane volume ratio is 0.2:1) solid-phase extraction column is rinsed, obtains aromatic hydrocarbons (component 2).With the eluant, eluent (chlorine of 14mL the 3rd
Ethene) solid-phase extraction column is rinsed, obtain neutral nitrogen compounds (component 3).Solid-phase extraction column B is soaked with the eluant, eluents of 1mL the 3rd,
Solid-phase extraction column A, B are together in series, wherein B posts are under.With the eluant, eluents of 8mL the 4th, (volume ratio of ethanol and dichloromethane is
0.2:1) solid-phase extraction column A, B are rinsed, obtains basic nitrogen compound (component 4).Gone using Rotary Evaporators and nitrogen purging
Except the partial solvent in component 1, component 2, component 3, component 4.
It is distributed using nitrogen-containing compound in GC-NCD analyses component 1, component 2, component 3, component 4.As a result show, component 1,
The chromatographic peak for not having nitrogen-containing compound in 2 occurs；Component 3, the distribution of the nitrogen-containing compound of component 4 differ, and show in two kinds of components
Nitrogen-containing compound type differs.
Using type of compounds and content in GC-MS-FID analyses component 1, component 2, component 3, component 4, the results showed that,
Component 1 is mainly saturated hydrocarbons；Component 2 is mainly aromatic hydrocarbons；Component 3 is mainly neutral nitrogen compounds, aromatic compound, wherein virtue
Hydrocarbon content 4.4wt%；Component 4 is mainly basic nitrogen compound, and wherein phenol compound content is 1.5wt%.Component is handed over
Fork amount does not influence the quantification and qualification of nitrogen-containing compound in error allowed band.
Time of all types of nitrogen-containing compounds in the petrochemical industry coker gas oil of Kelamayi is determined with ethylenediamine blank recovery of standard addition
Yield, ethylenediamine blank recovery of standard addition 95.7wt%.
Embodiment 3
Silica gel-acidic alumina stationary phase that 3.5g acidic oxidations aluminium content is 40wt% is loaded in solid-phase extraction column A,
Soaked with the eluant, eluents of 2mL first (normal heptane).The silicon that the alkaline oxygenated aluminium contents of 2.5g are 20wt% is loaded in solid-phase extraction column B
Glue-alkali alumina stationary phase.The activation temperature of silica gel is 120 DEG C, soak time 3 hours, and acidic alumina activation temperature is
450 DEG C, soak time is 4 hours, and alkali alumina activation temperature is 450 DEG C, soak time 2 hours.
Take 5mL Daqing petrochemicals straight-run diesel oil to add solid-phase extraction column A tops with liquid-transfering gun and adsorbed completely by stationary phase.With
The eluant, eluents of 9mL first (normal heptane) rinse solid-phase extraction column, obtain saturated hydrocarbons (component 1).With the eluant, eluents of 7mL second (toluene with
The volume ratio of hexamethylene is 0.4:1) solid-phase extraction column is rinsed, obtains aromatic hydrocarbons (component 2).With eluant, eluent (the acetic acid second of 14mL the 3rd
Ester) solid-phase extraction column is rinsed, obtain neutral nitrogen compounds (component 3).Solid-phase extraction column B is soaked with the eluant, eluents of 1mL the 3rd, will
Solid-phase extraction column A, B are together in series, and wherein B posts are under.With the eluant, eluents of 7mL the 4th, (volume ratio of isopropanol and dichloromethane is
0.3:1) solid-phase extraction column A, B are rinsed, obtains basic nitrogen compound (component 4).Gone using Rotary Evaporators and nitrogen purging
Except the partial solvent in component 1, component 2, component 3, component 4.
It is distributed using nitrogen-containing compound in GC-NCD analyses component 1, component 2, component 3, component 4.As a result show, component 1,
The chromatographic peak for not having nitrogen-containing compound in 2 occurs；Component 3, the distribution of the nitrogen-containing compound of component 4 differ, and show in two kinds of components
Nitrogen-containing compound type differs.
Using type of compounds and content in GC-MS-FID analyses component 1, component 2, component 3, component 4, the results showed that,
Component 1 is mainly saturated hydrocarbons；Component 2 is mainly aromatic hydrocarbons, contains fractional saturation hydrocarbon；Component 3 is mainly neutral nitrogen compounds, virtue
Hydrocarbon compound, wherein arene content 4.4wt%；Component 4 is mainly basic nitrogen compound, and wherein phenol compound content is
1.5wt%.Component intersects content in error allowed band, does not influence the quantification and qualification of nitrogen-containing compound.
The rate of recovery of all types of nitrogen-containing compounds in Daqing petrochemical straight-run diesel oil is determined with ethylenediamine blank recovery of standard addition,
Ethylenediamine blank recovery of standard addition 94.3wt%.
Embodiment 4
Silica gel-acidic alumina stationary phase that 3.5g acidic oxidations aluminium content is 30wt% is loaded in solid-phase extraction column A,
Soaked with the eluant, eluents of 2mL first (petroleum ether).The silicon that the alkaline oxygenated aluminium contents of 2.5g are 20wt% is loaded in solid-phase extraction column B
Glue-alkali alumina stationary phase.The activation temperature of silica gel is 120 DEG C, soak time 3 hours, and acidic alumina activation temperature is
500 DEG C, soak time is 4 hours, and alkali alumina activation temperature is 450 DEG C, and soak time is 2 hours.
Take 6mL Daqing petrochemicals hydrofining diesel oil to add solid-phase extraction column A tops with liquid-transfering gun and inhaled completely by stationary phase
It is attached.Solid-phase extraction column is rinsed with the eluant, eluents of 9mL first (petroleum ether), obtains saturated hydrocarbons (component 1).With 8mL the second eluant, eluent (benzene
Volume ratio with pentane is 0.5:1) solid-phase extraction column is rinsed, obtains aromatic hydrocarbons (component 2).With the eluant, eluent (dichloros of 14mL the 3rd
Methane) solid-phase extraction column is rinsed, obtain neutral nitrogen compounds (component 3).Solid-phase extraction column B is soaked with the eluant, eluents of 1mL the 3rd,
Solid-phase extraction column A, B are together in series, wherein B posts are under.With the eluant, eluent (volume ratios of n-butanol and dichloromethane of 8mL the 4th
For 0.15:1) solid-phase extraction column A, B are rinsed, obtains basic nitrogen compound (component 4).Purged using Rotary Evaporators and nitrogen
Remove the partial solvent in component 1, component 2, component 3, component 4.
It is distributed using nitrogen-containing compound in GC-NCD analyses component 1, component 2, component 3, component 4.As a result show, component 1,
The chromatographic peak for not having nitrogen-containing compound in 2 occurs；Component 3, the distribution of the nitrogen-containing compound of component 4 differ, and show in two kinds of components
Nitrogen-containing compound type differs.
Using type of compounds and content in GC-MS-FID analyses component 1, component 2, component 3, component 4, the results showed that,
Component 1 is mainly saturated hydrocarbons；Component 2 is mainly aromatic hydrocarbons, contains fractional saturation hydrocarbon；Component 3 is mainly neutral nitrogen compounds, virtue
Hydrocarbon compound, wherein arene content 2.4wt%；Component 4 is substantially not present nitrogen-containing compound.Component is intersected content and allowed in error
In the range of, the quantification and qualification of nitrogen-containing compound is not influenceed.
Time of all types of nitrogen-containing compounds in Daqing petrochemical hydrofining diesel oil is determined with ethylenediamine blank recovery of standard addition
Yield, ethylenediamine blank recovery of standard addition 98.5wt%.
Embodiment 5
Silica gel-acidic alumina stationary phase that 3.5g acidic oxidations aluminium content is 25wt% is loaded in solid-phase extraction column A,
Soaked with the eluant, eluents of 2mL first (pentane).The silicon that the alkaline oxygenated aluminium contents of 2.5g are 20wt% is loaded in solid-phase extraction column B
Glue-alkali alumina stationary phase.The activation temperature of silica gel is 160 DEG C, soak time 2 hours, and acidic alumina activation temperature is
550 DEG C, soak time is 3 hours, and alkali alumina activation temperature is 450 DEG C, and soak time is 2 hours.
Take 4mL states IV0# finished diesel fuels to add solid-phase extraction column A tops with liquid-transfering gun and adsorbed completely by stationary phase.With
The eluant, eluents of 7mL first (pentane) rinse solid-phase extraction column, obtain saturated hydrocarbons (component 1).With 9mL the second eluant, eluent (dichloromethanes
The volume ratio of alkane and pentane is 0.2:1) solid-phase extraction column is rinsed, obtains aromatic hydrocarbons (component 2).With the eluant, eluent (chlorine of 10mL the 3rd
Ethene) solid-phase extraction column is rinsed, obtain neutral nitrogen compounds (component 3).Solid-phase extraction column B is soaked with the eluant, eluents of 1mL the 3rd,
Solid-phase extraction column A, B are together in series, wherein B posts are under.With the eluant, eluents of 9mL the 4th, (volume ratio of acetone and dichloromethane is
0.15:1) solid-phase extraction column A, B are rinsed, obtains basic nitrogen compound (component 4).Gone using Rotary Evaporators and nitrogen purging
Except the partial solvent in component 1, component 2, component 3, component 4.
It is distributed using nitrogen-containing compound in GC-NCD analyses component 1, component 2, component 3, component 4.As a result show, component 1,
The chromatographic peak for not having nitrogen-containing compound in 2 occurs；Component 3, the distribution of the nitrogen-containing compound of component 4 differ, and show in two kinds of components
Nitrogen-containing compound type differs.
Using type of compounds and content in GC-MS-FID analyses component 1, component 2, component 3, component 4, the results showed that,
Component 1 is mainly saturated hydrocarbons；Component 2 is mainly aromatic hydrocarbons, contains fractional saturation hydrocarbon；Component 3 is mainly neutral nitrogen compounds, virtue
Hydrocarbon compound, wherein arene content 4.8wt%；Component 4 is substantially not present nitrogen-containing compound.Component is intersected content and allowed in error
In the range of, the quantification and qualification of nitrogen-containing compound is not influenceed.
The rate of recovery of all types of nitrogen-containing compounds in state's IV 0# finished diesel fuels is determined with ethylenediamine blank recovery of standard addition,
Ethylenediamine blank recovery of standard addition 95.6wt%.
Claims (12)
1. the twin columns solid phase extraction of nitrogen-containing compound, comprises the following steps in a kind of diesel oil：
(1), the preparation of solid-phase extraction column
Solid-phase extraction column A stationary phase is the mixture of silica gel and acidic alumina, solid-phase extraction column B stationary phase for silica gel and
The mixture of alkali alumina；
(2), elute
Using the described solid-phase extraction column A of the first eluant, eluent wetting, diesel samples are added from upper strata, are rinsed with the first eluant, eluent solid
Phase extraction column A, obtains saturated hydrocarbons；
Solid-phase extraction column A is rinsed with the second eluant, eluent, obtains aromatic hydrocarbons；
Solid-phase extraction column A is rinsed with the 3rd eluant, eluent, obtains neutral nitrogen compounds；
Solid-phase extraction column A is connected with B, A posts rinse solid-phase extraction column A, B upper, with the 4th eluant, eluent, obtain alkaline nitrogen
Compound；
Wherein, first eluant, eluent in the group being made up of pentane, n-hexane, normal heptane and petroleum ether at least
It is a kind of；
Second eluant, eluent is a and b mixture：The a is in the group being made up of dichloromethane, chloroform, benzene and toluene
At least one；The b is selected from least one of group being made up of pentane, n-hexane and hexamethylene；
3rd eluant, eluent is selected from least one of group being made up of vinyl chloride, dichloromethane and ethyl acetate；
4th eluant, eluent is the mixture of c and dichloromethane：The c is selected from and is made up of ethanol, isopropanol, n-butanol and acetone
At least one of group.
2. the twin columns solid phase extraction of nitrogen-containing compound in diesel oil according to claim 1, it is characterised in that the silica gel
Specific surface area be 300-600m2/ g, pore volume 0.2-5mL/g.
3. the twin columns solid phase extraction of nitrogen-containing compound in diesel oil according to claim 1, it is characterised in that the acidity
The specific surface area of aluminum oxide is 100-300m2/ g, pore volume 0.1-0.5mL/g.
4. the twin columns solid phase extraction of nitrogen-containing compound in diesel oil according to claim 1, it is characterised in that the alkalescence
The specific surface area of aluminum oxide is 120-250m2/ g, pore volume 0.1-0.4mL/g, aperture 4-10nm, pH value is in 10-14.
5. the twin columns solid phase extraction of nitrogen-containing compound in diesel oil according to claim 1, it is characterised in that SPE
The content of acidic alumina is 10-40wt% in post A, and the content of solid-phase extraction column B neutral and alkali aluminum oxide is 20-60wt%.
6. the twin columns solid phase extraction of nitrogen-containing compound in diesel oil according to claim 1, it is characterised in that step (1)
In the preparation of solid-phase extraction column,
Silica gel is dried into 2-6 hours under the conditions of 80-160 DEG C, obtains the silica gel of activation；
Acidic alumina is calcined 3-7 hours under the conditions of 350-550 DEG C, the acidic alumina activated；
Alkali alumina is calcined 2-6 hours under the conditions of 350-450 DEG C, the alkali alumina activated；
The silica gel of activation is well mixed with the acidic alumina activated, produces solid-phase extraction column A；By the silica gel of activation and activation
Alkali alumina be well mixed, produce solid-phase extraction column B.
7. the twin columns solid phase extraction of nitrogen-containing compound in diesel oil according to claim 1, it is characterised in that the second elution
A described in agent and b volume ratio is 0.2-0.5:1.
8. the twin columns solid phase extraction of nitrogen-containing compound in diesel oil according to claim 1, it is characterised in that the 4th elution
The volume ratio of c described in agent and dichloromethane is 0.1-0.3:1.
9. the twin columns solid phase extraction of nitrogen-containing compound in diesel oil according to claim 1, it is characterised in that diesel samples
Quality and solid-phase extraction column A mass ratio are in 0.1-1.5:1, diesel samples quality and solid-phase extraction column B mass ratio are 0.15-
2.0:1。
10. the twin columns solid phase extraction of nitrogen-containing compound in diesel oil according to claim 1, it is characterised in that described
The volume ratio of one eluant, eluent and diesel samples is 0.8-10:1；
The volume ratio of second eluant, eluent and diesel samples is 1.3-16:1；
The volume ratio of 3rd eluant, eluent and diesel samples is 2-24:1；
The volume ratio of 4th eluant, eluent and diesel samples is 6-22:1.
11. the twin columns solid phase extraction of nitrogen-containing compound in diesel oil according to claim 1, it is characterised in that described
Diesel oil is finished diesel fuel.
12. the twin columns solid phase extraction of nitrogen-containing compound in diesel oil according to claim 11, it is characterised in that described
Finished diesel fuel is straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, is hydrocracked diesel oil or hydrofining diesel oil.
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| CN112946089B (en) * | 2019-11-26 | 2023-05-05 | 中国石油化工股份有限公司 | Method for determining content and/or molecular structure of nitride in diesel oil |
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| CN114075448B (en) * | 2020-08-14 | 2023-04-25 | 中国石油天然气股份有限公司 | Solid phase extraction method for separating nitrogen-containing compound and sulfur-containing compound in diesel oil |
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| CN112903872B (en) * | 2021-01-15 | 2022-06-28 | 中国石油大学(北京) | Separation method and application of carbazole nitride in petroleum component |
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| US6541273B1 (en) * | 1999-11-12 | 2003-04-01 | Aventis Cropscience, S.A. | Multiple sorbent cartridges for solid phase extraction |
| CN1632063A (en) * | 2004-11-17 | 2005-06-29 | 南京工业大学 | Method for removing basic nitrogen compounds in diesel oil and gasoline by solid phase coordination extraction |
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| US6541273B1 (en) * | 1999-11-12 | 2003-04-01 | Aventis Cropscience, S.A. | Multiple sorbent cartridges for solid phase extraction |
| CN1632063A (en) * | 2004-11-17 | 2005-06-29 | 南京工业大学 | Method for removing basic nitrogen compounds in diesel oil and gasoline by solid phase coordination extraction |
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