CN114563506B - Pretreatment method for determining content and composition of olefin compounds in wax oil - Google Patents
Pretreatment method for determining content and composition of olefin compounds in wax oil Download PDFInfo
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 79
- -1 olefin compounds Chemical class 0.000 title claims abstract description 37
- 238000002203 pretreatment Methods 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 133
- 150000001336 alkenes Chemical class 0.000 claims abstract description 64
- 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 53
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 52
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004332 silver Substances 0.000 claims abstract description 16
- 229910052709 silver Inorganic materials 0.000 claims abstract description 16
- 239000000741 silica gel Substances 0.000 claims abstract description 14
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 14
- 239000003480 eluent Substances 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 51
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 239000003085 diluting agent Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 6
- 238000004939 coking Methods 0.000 claims description 6
- 230000003111 delayed effect Effects 0.000 claims description 6
- 230000009969 flowable effect Effects 0.000 claims description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004523 catalytic cracking Methods 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000004230 steam cracking Methods 0.000 claims description 4
- 238000009736 wetting Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N ortho-diethylbenzene Natural products CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 18
- 238000011084 recovery Methods 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 10
- 150000001924 cycloalkanes Chemical class 0.000 abstract description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004445 quantitative analysis Methods 0.000 abstract description 3
- 238000004451 qualitative analysis Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 72
- 238000004458 analytical method Methods 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 15
- 230000000694 effects Effects 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000010926 purge Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- OBDUMNZXAIUUTH-HWKANZROSA-N (e)-tetradec-2-ene Chemical compound CCCCCCCCCCC\C=C\C OBDUMNZXAIUUTH-HWKANZROSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 239000003269 fluorescent indicator Substances 0.000 description 1
- 238000001457 gas chromatography time-of-flight mass spectrometry Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WMZHDICSCDKPFS-UHFFFAOYSA-N triacontene Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCC=C WMZHDICSCDKPFS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a pretreatment method for determining the content and composition of olefin compounds in wax oil, which separates olefin in wax oil from saturated hydrocarbon (alkane+cycloalkane) through a solid phase extraction column. The solid phase extraction column used in the invention consists of a solid phase extraction column A and a solid phase extraction column B, wherein the stationary phase of the solid phase extraction column A is a mixture of silica gel and alumina, the content of the alumina is 70-100wt%, and the stationary phase of the solid phase extraction column B is alumina loaded with silver ions. The invention can separate and enrich olefin compounds in wax oil from saturated hydrocarbon (alkane and naphthene), has the advantages of short treatment time, low separation and crossing amount among components, less solvent consumption and high recovery rate, and eliminates the interference of naphthene on qualitative and quantitative analysis of olefin compounds.
Description
Technical Field
The invention relates to a pretreatment method for determining the content and the composition of olefin compounds in wax oil, in particular to a pretreatment method for separating olefin compounds from saturated hydrocarbons (naphthenes and olefins) in a wax oil sample by utilizing a solid phase extraction method so as to quickly provide an experimental sample for the subsequent determination of the content and the composition of the olefin compounds.
Background
Olefin is an important chemical raw material, and olefin products with high added value can be produced in petrochemical and coal chemical processes which take crude oil and coal as raw materials. In addition to small molecular olefins such as ethylene, propylene, butadiene, etc., delayed coking processes [ Fu Jiansong, zhu Zelin, hao Rongkun, etc. ] separation of linear alpha-olefin rich wax oil from coker diesel [ J ]. Petroleum refining and chemical, 1997 (09): 36-40.], fischer-Tropsch synthesis processes [ Ma Lili, zhang Zhixiang, zhang Yongjun, etc. ], fischer-Tropsch synthesis product high value-added utilization studies [ J ]. Fine petrochemical progress, 2018,19 (05): 59-61.] produced high carbon number alpha-olefins are important raw materials for modern fine chemical production processes, and high value-added detergents, emulsifiers, high performance lubricating oils, etc. produced thereby are important profitable points for chemical enterprises.
Olefin is one of byproducts of petrochemical industry and coal chemical industry, and various hazards can be generated in the oil product processing and using processes. For example, the olefin is active in nature and is easy to be adsorbed on the surface of the catalyst, so that the catalyst is poisoned and carbon is deposited, and the service life of the catalyst is reduced; olefin is one of components of high-octane gasoline, which is beneficial to reducing emission of particulate matters and improving combustion efficiency of gasoline, but is easy to form sediment on a carburetor and an air inlet valve so as to worsen emission of an engine; olefins volatilized into the atmosphere are important initiators for forming photochemical pollution, and are extremely harmful to the environment; the olefin is one of main impurities of the coal-based high-carbon alcohol crude product, side reactions are easy to occur, the product yield is reduced, the product quality is influenced, and hydrogenation removal is needed.
With the development of the high-temperature Fischer-Tropsch synthesis process and the high-end lubricating oil base oil production process, the demand for understanding the composition of wax oil fraction segmented olefins is urgent, but no mature analysis method has been reported at present. The analysis of olefins is currently focused mainly on the segmentation of gasoline and diesel fractions, and the analysis methods include bromine valence method, fluorescent indicator method, nuclear magnetic resonance method, gas chromatography and the like [ Niu Luna, liu Zelong, zhou Jian, and the like ]. Full two-dimensional gas chromatography-time-of-flight mass spectrometry is used for identifying olefin compounds in diesel fractions [ J ]. Petroleum Instructions (Petroleum processing), 2014,30 (5): 851-860]. However, these several methods are not suitable for analysis of olefin compound composition in wax oil fraction fractions, mainly due to the following aspects: (1) The polarity of the high-carbon olefin is similar to that of the high-carbon alkane and the naphthene, and the traditional column chromatography and chromatographic method are difficult to separate the olefin from the saturated hydrocarbon completely; (2) The number of unsaturated double bonds of naphthenes and olefins is identical, mass spectra of the naphthenes and the olefins are similar, and the traditional group composition measurement method can only classify the content of the olefins into the total amount of the naphthenes, so that the measurement result of the content of the olefins is inaccurate; (3) The high-carbon olefin compound has low polarity and the traditional analysis methods such as fluorescence analysis and the like have low accuracy. Therefore, accurate information of olefin compounds in wax oil samples cannot be obtained only by means of an instrument, and a pretreatment process with high separation efficiency and small cross components is needed for the wax oil samples.
In recent years, the solid phase extraction technology is widely applied to the pretreatment process of oil products. The solid phase extraction is to separate the substances into components with different polarities by adjusting the polarity of the eluent by utilizing the difference of the adsorption capacity of different compounds on the stationary phase. Therefore, the choice of eluent for solid-phase extraction is very important, but even if the same solvent is mixed in different proportions, eluents of different polarity and different solvent selectivity are obtained, resulting in a great difference in the final separation result. Because the olefin and cycloparaffin in wax oil samples have similar polarity and identical carbon number compound molecular composition, the traditional column chromatography, chromatography and mass spectrometry are difficult to separate well, and the solid phase extraction method is a feasible way for solving the problem. In addition, few reports are currently associated with the use of solid phase extraction to separate olefin compounds from wax oil samples.
Disclosure of Invention
The invention aims to provide a pretreatment method for separating olefin compounds from wax oil by utilizing a solid phase extraction method so as to be used for measuring the content and the composition of the olefin compounds in the wax oil. The invention can solve the problem that the traditional column chromatography, chromatography and the like can not separate olefin in wax oil from saturated hydrocarbon (alkane+cycloalkane), eliminate the interference of cycloalkane on olefin compound qualitative and quantitative, and improve the accuracy of analysis results.
The invention provides a pretreatment method for determining the content and composition of olefin compounds in wax oil, which adopts a solid phase extraction column to separate olefin and saturated hydrocarbon (alkane+cycloalkane) in the wax oil, and comprises the following steps:
step one: diluting wax oil and a diluent according to a certain proportion to obtain a flowable wax oil sample;
step two: connecting a solid phase extraction column A and a solid phase extraction column B in series, wherein the solid phase extraction column A is arranged on the solid phase extraction column A, wetting the solid phase extraction column A by using a first eluent, adding a diluted flowable wax oil sample from the upper layer of the solid phase extraction column A, and then flushing the solid phase extraction column A and the solid phase extraction column B by using the first eluent to obtain a saturated hydrocarbon component 1;
step three: separating the solid phase extraction column A from the solid phase extraction column B, continuing to wash the solid phase extraction column B by using a first eluent to obtain a saturated hydrocarbon component 2, and combining the saturated hydrocarbon component 1 and the saturated hydrocarbon component 2 to obtain a saturated hydrocarbon component;
step four: the collector is replaced, and the solid phase extraction column B is washed by using a second eluent to obtain an olefin component.
Wherein the diluent is at least one selected from the group consisting of n-hexane, n-heptane, cyclohexane and methylcyclohexane;
the first eluent is at least one selected from the group consisting of n-pentane, n-hexane, n-heptane and petroleum ether;
the second eluent is a mixture of a and b, wherein a is at least one selected from the group consisting of dichloromethane, chloroform, diethyl ether, benzene and toluene, and b is at least one selected from the group consisting of methanol, ethanol, isopropanol, acetone and butanone.
The pretreatment method provided by the invention is characterized in that a stationary phase is filled in the solid phase extraction column A, wherein the stationary phase is a mixture of silica gel and alumina, and the content of the alumina is 70-100wt%.
The pretreatment method of the invention, wherein the solid phase extraction column B is internally provided with a stationary phase, the stationary phase is alumina loaded with silver ions, and the silver content is 1-15wt%.
The pretreatment method of the invention, wherein the specific surface area of the silica gel is 500-850m 2 Per gram, the pore volume is 0.1-0.6mL/g, and the average pore diameter is 1-4nm.
The pretreatment method of the invention, wherein the specific surface area of the solid phase extraction column A and the alumina of the solid phase extraction column A is 150-450m 2 Per gram, the pore volume is 0.05-0.4mL/g, and the average pore diameter is 1-3nm.
The pretreatment method of the invention, wherein the volume ratio of a to b in the second eluent is 0.25-1.25:1.
In the pretreatment method, in the first step, the volume ratio of the diluent to the wax oil is 0.5-1:1.
In the pretreatment method, in the second step, the addition amount of the diluted flowable wax oil sample is 1-5mL.
In the pretreatment method, in the second step, the volume of the first eluent used for wetting the solid-phase extraction column A is 1-3mL, the volume of the first eluent used for flushing the solid-phase extraction column A and the solid-phase extraction column B is 5-10mL, and in the third step, the volume of the first eluent used for flushing the solid-phase extraction column B is 3-6mL.
In the pretreatment method of the present invention, in the fourth step, the volume of the second eluent used for washing the solid phase extraction column B is 5-10mL.
The pretreatment method of the invention, wherein the wax oil is produced by petrochemical industry or coal chemical industry.
The pretreatment method of the invention, wherein the wax oil is produced by catalytic cracking, delayed coking, visbreaking, steam cracking and other processes.
The pretreatment method provided by the invention, wherein the wax oil is wax oil produced by a Fischer-Tropsch synthesis process.
In order to achieve the above object, the present invention provides two solid phase extraction columns, wherein the separation of olefin compounds from saturated hydrocarbons (alkane+cycloalkane) in wax oil is achieved by the combination of a solid phase extraction column A and a solid phase extraction column B. The stationary phase of the solid phase extraction column A is a mixture of silica gel and alumina, wherein the content of the alumina is 70-100wt%, and the stationary phase of the solid phase extraction column B is alumina loaded with silver ions, wherein the content of the silver ions is 1-15wt%. The method can effectively enrich olefin compounds in wax oil, has the advantages of large sample treatment capacity, simple treatment steps and small separation and cross among components, greatly improves the separation and enrichment efficiency, eliminates the qualitative and quantitative interference of naphthenes on olefin compounds, and is suitable for large-scale popularization and use. The preparation method of the silica gel and alumina stationary phase comprises the following steps: drying silica gel at 80-160deg.C for 2-6 hr, and cooling in a dryer to obtain activated silica gel; roasting neutral alumina at 350-550 deg.c for 1-5 hr, and cooling in drier to obtain activated alumina; and uniformly mixing the activated silica gel and the alumina according to a certain proportion to obtain the stationary phase required by the solid phase extraction column A. Soaking alumina and silver-containing water solution in equal volume in dark for 24 hr, roasting at 350-550 deg.c for 2-6 hr, and cooling in drier to obtain activated silver-loaded alumina, i.e. the stationary phase required by the solid phase extraction column B.
The solution obtained by solid phase extraction and separation is subjected to solvent evaporation and concentration to obtain saturated hydrocarbon (alkane+cycloalkane) and olefin, and the solvent is volatilized by adopting methods such as rotary evaporation, nitrogen purging and the like for analysis. And volatilizing and concentrating the solution to about 0.5mL to perform Gas Chromatography (GC) and Nuclear Magnetic Resonance (NMR) related analysis. Saturated hydrocarbons and olefins were analyzed by Gas Chromatography (GC) -Mass Spectrometry (MS) -hydrogen Flame Ionization Detector (FID). Mass spectrometry is one of main research tools for qualitatively analyzing the structure of a compound, and various compounds in an enriched substance can be qualitatively analyzed through means such as spectrogram retrieval, and the influence factors of a hydrogen flame ionization detector on the compound are not greatly different, so that quantitative analysis is carried out through GC-FID, and the separation crossing amount is judged. And quantifying by an internal standard method, and selecting n-tetradecane as an internal standard compound. The chemical shift of hydrogen atoms in different chemical environments on a nuclear magnetic resonance spectrometer spectrogram is different, and the size of the separation cross quantity among different components can be judged according to the content of the hydrogen atoms with different chemical shifts on the nuclear magnetic resonance spectrometer hydrogen spectrum.
The invention adopts a solid-phase extraction method to separate olefin components from saturated hydrocarbon (alkane and naphthene), aromatic hydrocarbon and the like in wax oil, has the advantages of short treatment time, high recovery rate of the separated olefin components, low separation cross quantity, less solvent consumption, high recovery rate, good enrichment effect and the like, and eliminates the interference of naphthene on qualitative and quantitative analysis of olefin compounds. Compared with the traditional column chromatography, the solid-phase extraction method adopted by the invention has high column efficiency, high extraction column filling repeatability, low solvent consumption and high speed, and the solvent is eluted under pressure. The method is suitable for being used as a pretreatment method for determining the olefin composition in wax oil, and can effectively solve the problems that the traditional column chromatography has long separation time and low analysis efficiency, and can not separate olefin and saturated hydrocarbon (alkane and naphthene). The time for separating olefin samples in the once wax oil is only 30-40min, so that the separation efficiency of wax oil olefin is greatly improved, and experimental samples can be provided for subsequent determination of group composition.
Drawings
FIG. 1 shows a saturated hydrocarbon (alkane + cycloalkane) component obtained by the pretreatment method of example 1 of the present invention 1 H-NMR chart.
FIG. 2 is a 1H-NMR chart of an olefin component obtained by the pretreatment method of example 1 of the invention.
FIG. 3 is a GC-MS diagram of a saturated hydrocarbon (alkane + cycloalkane) component obtained by the pretreatment method of example 5 of the present invention.
FIG. 4 is a graph of the total ion flow chromatogram of the olefin component obtained using the pretreatment method of example 5 of the present invention.
Detailed Description
The present invention will be further described in detail by way of examples, but the present invention is not limited thereto.
The silica gel used in the examples is silica gel for chromatography produced by national pharmaceutical systems and chemical reagents, inc., with a particle size of 70.0% or more and a specific surface area of 511.9m 2 Per gram, pore volume was 0.468mL/g. The alumina is chromatographic alumina produced by national medicine group chemical reagent company, and has firing weight loss less than or equal to 8.0% and specific surface area of 177.8m 2 Per gram, pore volume was 0.255mL/g.
Drying the silica gel at 150 ℃ for 5 hours to obtain activated silica gel; the neutral alumina was calcined at 500 c for 4 hours to obtain activated neutral alumina. And uniformly mixing the activated silica gel and the neutral alumina according to the proportion to obtain the neutral alumina-silica gel stationary phase used by the solid phase extraction column A. Mixing the activated alumina with the silver nitrate solution in equal volume according to the silver loading amount of 1-15wt%, standing for 24 hours in a dark place, drying at 150 ℃ for 5 hours, and cooling in a dryer to obtain activated silver-loaded alumina, thus obtaining the stationary phase of the solid phase extraction column B.
The GC-MS instrument used for the analysis was model 7890A GC-5975MS with FID detector. GC conditions: DB-1HT capillary chromatographic column, 30m x 0.25mm x 0.1 μm; heating to 120 ℃ at the initial temperature of programming, keeping for 3min, heating at the speed of 10 ℃/min, and keeping for 10min at the final temperature of 350 ℃; the carrier gas is high-purity helium, the constant-flow operation is carried out, and the flow is 1mL/min; the temperature of the sample inlet is 400 ℃, the split ratio is 20:1, and the sample feeding amount is 1 mu L. MSD conditions: EI ionization source (70 eV), ion source temperature 250 ℃, quaternary rod temperature 150 ℃, full scan mass range 45-600u, interface temperature 310 ℃, solvent delay 5min. FID conditions: the temperature of the detector is 400 ℃, the air flow rate is 300mL/min, the hydrogen flow rate is 30mL/min, and the tail blowing air is 25mL/min.
The type Bruker Avance Neo MHz of the nuclear magnetic resonance spectrometer used. The measurement conditions are as follows: pulse sequence: 30 degree sheetPulse 1 H NMR; spectral width 9615Hz (16 ppm); exciting the intermediate frequency to be 6ppm; time domain sampling points 65536; relaxation delay 40s; sampling times 16; the test temperature was 300K.0.5-1ppm refers to methyl hydrogen; 1-2ppm refers to methylene hydrogen/methine hydrogen; 2-4ppm refers to hydrogen/methine hydrogen considered alpha to the aromatic ring; 4-6ppm refers to hydrogen as an olefin; 6-9ppm refers to aromatic hydrocarbon hydrogen.
Example 1
The solid phase extraction column A was packed with 4g of a silica gel-alumina stationary phase having an alumina content of 70wt%, the solid phase extraction column B was packed with 3g of a silver-alumina stationary phase having a silver content of 1wt%, and the solid phase extraction column A was wetted with 1mL of a first eluent (n-pentane).
Diluting cyclohexane serving as a diluent with No. 1 wax oil produced in a catalytic cracking process of a certain company according to a volume ratio of 0.5:1, and then taking 1mL of diluted wax oil sample by a liquid-transfering gun, adding the diluted wax oil sample into the upper part of a solid-phase extraction column A, and completely adsorbing by a stationary phase. The solid phase extraction column A+B was washed with 5mL of the first eluent, then the solid phase extraction columns A and B were separated, and 3mL of the first eluent was added to B continuously to obtain saturated hydrocarbons, designated as component 1. The solid phase extraction column B was washed with 5mL of a second eluent (0.25:1 volume ratio of dichloromethane to ethanol) and designated as component 2. An amount of n-tetradecane was added as an internal standard. The solvent in each component was removed by nitrogen purging. The whole process takes 30min.
Analysis of component 1, component 2 by GC-MS-FID, indicated that component 1 was predominantly saturated hydrocarbons (paraffins+naphthenes) with 3.5wt% of the impurity olefin component; component 2 is predominantly olefin, with an impurity saturated hydrocarbon content of 4.2wt% and is substantially free of aromatic hydrocarbons.
The nuclear magnetic resonance analysis of the component 1 and the component 2 shows that the vast majority (98.5%) of the signal integration area in the spectrogram of the component 1 is between 0.5 and 2ppm and is classified into aliphatic methyl and aliphatic methylene/methine signals, which indicates that the component 1 is mainly saturated hydrocarbon; in the spectrum of component 2, a 1-substituted olefin signal appears in the range of 4-6ppm, the integral area ratio is 4.182%, and the aromatic hydrocarbon region of 6-9ppm has almost no signal.
The effect of separating wax oil olefin components by a solid phase extraction method is examined by the standard recovery rate of the normal thirty olefins. Taking two 1# wax oil samples generated in the catalytic cracking process of a certain company, wherein a certain amount of normal triacontene is added into one sample as a standard adding sample. The two samples are separated into olefin components according to the solid-phase extraction method, a certain amount of n-tetradecene is added as an internal standard, and the GC-FID analysis is carried out on the content of each compound. The ratio of the difference value of the normal thirty-olefin content in the marked sample minus the normal thirty-olefin content in the unmarked sample to the theoretical value of the normal thirty-olefin is the marked recovery rate of the normal thirty-olefin, and the values are 96.3 percent in sequence.
The results show that the method provided by the invention has the advantages of high recovery rate in separating wax oil olefin components, low crossing amount among components and good enrichment effect.
Example 2
The solid phase extraction column A was packed with 4g of a silica gel-alumina stationary phase having an alumina content of 80wt%, the solid phase extraction column B was packed with 3g of a silver-alumina stationary phase having a silver content of 5wt%, and the solid phase extraction column A was wetted with 2mL of a first eluent (n-hexane).
Diluting n-hexane serving as a diluent with 2# wax oil produced in a delayed coking process of a certain company according to a volume ratio of 0.6:1, and then taking 2mL of diluted wax oil sample by a liquid-transfering gun, adding the diluted wax oil sample into the upper part of a solid-phase extraction column A, and completely adsorbing by a stationary phase. The solid phase extraction column A+B was rinsed with 7mL of the first eluent, then the solid phase extraction columns A and B were separated, and 4mL of the first eluent was added to B to give saturated hydrocarbons, designated as component 1. The solid phase extraction column B was washed with 6mL of a second eluent (chloroform to methanol volume ratio of 0.4:1) and designated as component 2. An amount of n-tetradecane was added as an internal standard. The solvent in each component was removed by nitrogen purging. The whole process takes 35min.
The GC-MS-FID analysis of the components 1 and 2 shows that the component 1 is mainly saturated hydrocarbon, wherein the content of olefin components is 5.9wt%, the component 2 is mainly olefin, the content of impurity saturated hydrocarbon is 4.3wt%, and the content of aromatic hydrocarbon compound is 6.1wt%.
The effect of separating wax oil olefin components by a solid phase extraction method is examined by using the standard recovery rate of the normal thirty olefins, the values of the effect are 95.8 percent in sequence, and the result shows that the recovery rate of the solid phase extraction and separation of the delayed coking wax oil olefin components is higher.
Example 3
The solid phase extraction column A was packed with 4g of a silica gel-alumina stationary phase having an alumina content of 90wt%, the solid phase extraction column B was packed with 3g of a silver-alumina stationary phase having a silver content of 8wt%, and the solid phase extraction column A was wetted with 3mL of a first eluent (n-heptane).
Diluting n-heptane serving as a diluent with 3# wax oil produced in a certain visbreaking process according to a volume ratio of 0.7:1, and then taking 5mL of diluted wax oil sample by a liquid-transferring gun, adding the diluted wax oil sample into the upper part of the solid-phase extraction column A, and completely adsorbing by a stationary phase. The solid phase extraction column A+B was washed with 10mL of the first eluent, then the solid phase extraction columns A and B were separated, and 6mL of the first eluent was added to B to obtain saturated hydrocarbons, designated as component 1. The solid phase extraction column B was rinsed with 10mL of a second eluent (0.8:1 diethyl ether to isopropyl alcohol by volume), designated as component 2. An amount of n-tetradecane was added as an internal standard. The solvent in each component was removed by nitrogen purging. The whole process takes 40min.
The GC-MS-FID analysis of the components 1 and 2 shows that the component 1 is mainly saturated hydrocarbon, wherein the content of olefin components is 2.1 weight percent, the component 2 is mainly olefin, the content of impurity saturated hydrocarbon is 9.3 weight percent, and the content of aromatic hydrocarbon compound is 3.1 weight percent.
The effect of separating wax oil olefin components by a solid phase extraction method is examined by using the standard recovery rate of the normal thirty olefins, the values of the effect are 99.1 percent in sequence, and the result shows that the recovery rate of separating visbreaking wax oil olefin components by solid phase extraction is higher.
Example 4
The solid phase extraction column A was packed with 4g of a silica gel-alumina stationary phase having an alumina content of 90wt%, the solid phase extraction column B was packed with 3g of a silver-alumina stationary phase having a silver content of 10wt%, and the solid phase extraction column A was wetted with 2mL of a first eluent (petroleum ether).
Diluting the diluent methylcyclohexane with the No. 4 wax oil produced in the steam cracking process of a certain company according to the volume ratio of 0.8:1, and then taking 4mL of diluted wax oil sample by a pipette, adding the diluted wax oil sample into the upper part of the solid phase extraction column A, and completely adsorbing by a stationary phase. The solid phase extraction column A+B was washed with 8mL of the first eluent, then the solid phase extraction columns A and B were separated, and 5mL of the first eluent was added to B to obtain saturated hydrocarbons, designated as component 1. The solid phase extraction column B was rinsed with 7mL of a second eluent (benzene to acetone volume ratio 1:1), designated as component 2. An amount of n-tetradecane was added as an internal standard. The solvent in each component was removed by nitrogen purging. The whole process took 37min.
The GC-MS-FID analysis of the components 1 and 2 shows that the component 1 is mainly saturated hydrocarbon, wherein the content of olefin components is 4.9wt%, the component 2 is mainly olefin, the content of impurity saturated hydrocarbon is 3.7wt%, and the content of aromatic compound is 2.1wt%.
The effect of separating wax oil olefin components by a solid phase extraction method is examined by using the standard recovery rate of the normal thirty olefins, the values of the effect are 101.8 percent in sequence, and the result shows that the recovery rate of separating the steam cracking wax oil olefin components by the solid phase extraction method is higher.
Example 5
The solid phase extraction column A was packed with 4g of alumina stationary phase, the solid phase extraction column B was packed with 3g of silver-alumina stationary phase having a silver content of 15wt%, and the solid phase extraction column A was wetted with 2mL of the first eluent (n-hexane).
Diluting the diluent n-hexane and 5# wax oil produced by high-temperature Fischer-Tropsch synthesis of a certain company according to the volume ratio of 1:1, and then taking 2mL of diluted wax oil sample by a liquid-transferring gun, adding the diluted wax oil sample into the upper part of the solid-phase extraction column A, and completely adsorbing by a stationary phase. The solid phase extraction column A+B was rinsed with 7mL of the first eluent, then the solid phase extraction columns A and B were separated, and 5mL of the first eluent was added to B to obtain saturated hydrocarbons, designated as component 1. The solid phase extraction column B was rinsed with 6mL of a second eluent (toluene to butanone volume ratio of 1.25:1), designated as component 2. An amount of n-tetradecane was added as an internal standard. The solvent in each component was removed by nitrogen purging. The whole process takes 35min.
The GC-MS-FID analysis of the components 1 and 2 shows that the component 1 is mainly saturated hydrocarbon, wherein the content of olefin components is 4.7wt%, the component 2 is mainly olefin, the content of impurity saturated hydrocarbon is 5.5wt%, and the content of aromatic hydrocarbon compound is 1.1 wt%.
The effect of separating wax oil olefin components by a solid phase extraction method is examined by using the standard recovery rate of normal thirty olefins, the values of the effect are 96.4 percent in sequence, and the result shows that the recovery rate of separating high-temperature Fischer-Tropsch synthesized wax oil olefin components by the solid phase extraction method is higher.
Comparative example 1
And separating wax oil saturated fraction and aromatic hydrocarbon component by adopting petrochemical standard SH/T0509-2010.
A small amount of absorbent cotton is plugged into the lower end of the cleaned adsorption column, 40g of activated alumina is added from the upper end, the column is gently beaten by a fine rod coated with rubber, so that the alumina is compact and uniform, and then 30mL of n-heptane is immediately added to rinse the chromatographic column. 0.5g of a No. 1 wax oil sample produced by a catalytic cracking process of a company is weighed by a beaker, dissolved by 10mL of n-heptane, and immediately added to the dissolved wax oil sample after the pre-wetted n-heptane completely enters the alumina adsorption layer. 70mL of n-heptane is added to flush the saturated hydrocarbon component 1, and a double ball can be used to adjust the flow rate, so that the flow rate is maintained at 2-3mL/min. 80mL of toluene was added to rinse aromatic hydrocarbon component 2. The whole process takes 100min. Volatilizing the solvent from the saturated hydrocarbon component 1 and the aromatic hydrocarbon component 2, and then putting the solvent into a vacuum oven for drying to obtain constant weight.
Analysis of component 1, component 2 by GC-MS-FID, indicated that component 1 was predominantly saturated hydrocarbon, with olefin compounds enriched predominantly in the saturated hydrocarbon component, wherein the olefin compound content was 9.1wt%; component 2 was mainly aromatic hydrocarbon, in which the impurity saturated hydrocarbon content was 7.2wt% and the olefin compound content was 1.3wt%.
Therefore, the column chromatography is long in time consumption, large in solvent consumption and large in stationary phase consumption when separating the wax oil sample, and cannot be used for separating olefin compounds in the wax oil sample.
Comparative example 2
The solid phase extraction column A was packed with 4g of a silica gel-alumina stationary phase having an alumina content of 80wt%, the solid phase extraction column B was packed with 3g of a silver-silica gel stationary phase having a silver content of 5wt%, and the solid phase extraction column A was wetted with 2mL of a first eluent (n-hexane).
Diluting n-hexane serving as a diluent with 2# wax oil produced in a delayed coking process of a certain company according to a volume ratio of 0.6:1, and then taking 2mL of diluted wax oil sample by a liquid-transfering gun, adding the diluted wax oil sample into the upper part of a solid-phase extraction column A, and completely adsorbing by a stationary phase. The solid phase extraction column A+B was rinsed with 7mL of the first eluent, then the solid phase extraction columns A and B were separated, and 4mL of the first eluent was added to B to give saturated hydrocarbons, designated as component 1. The solid phase extraction column B was washed with 6mL of a second eluent (chloroform to methanol volume ratio of 0.4:1) and designated as component 2. An amount of n-tetradecane was added as an internal standard. The solvent in each component was removed by nitrogen purging. The whole process takes 35min.
The GC-MS-FID analysis of the components 1 and 2 shows that the component 1 is mainly saturated hydrocarbon, wherein the content of olefin components is 37.1 weight percent, the component 2 is mainly olefin, the content of impurity saturated hydrocarbon is 32.1 weight percent, and the content of aromatic hydrocarbon compound is 11.3 weight percent.
Therefore, compared with the solid phase extraction method using silica gel-alumina stationary phase and silver-alumina stationary phase provided in the embodiment 2 of the invention, the olefin compounds in the wax oil fraction cannot be effectively enriched by using the silica gel-alumina stationary phase and the silver-silica gel stationary phase.
Comparative example 3
The solid phase extraction column A was packed with 3g of a silver-alumina stationary phase having a silver content of 8wt% and wetted with 3mL of a first eluent (n-heptane).
Diluting n-heptane serving as a diluent with 3# wax oil produced in a certain visbreaking process according to a volume ratio of 0.7:1, and then taking 5mL of diluted wax oil sample by a liquid-transferring gun, adding the diluted wax oil sample into the upper part of the solid-phase extraction column A, and completely adsorbing by a stationary phase. The solid phase extraction column A was washed with 10mL of the first eluent to give saturated hydrocarbons, designated as component 1. The solid phase extraction column A was washed with 10mL of a second eluent (0.8:1 diethyl ether to isopropyl alcohol by volume) and designated as component 2. An amount of n-tetradecane was added as an internal standard. The solvent in each component was removed by nitrogen purging. The whole process takes 40min.
The GC-MS-FID analysis of the components 1 and 2 shows that the component 1 is mainly saturated hydrocarbon, wherein the content of olefin components is 24.8 weight percent, the component 2 is mainly olefin, the content of impurity saturated hydrocarbon is 39.6 weight percent, and the content of aromatic hydrocarbon compound is 9.7 weight percent.
Therefore, compared with the solid phase extraction method using silica gel-alumina stationary phase and silver-alumina stationary phase provided in example 3 of the present invention, the olefin compounds in the wax oil fraction cannot be effectively enriched only by using the silver-alumina stationary phase.
Comparative example 4
And (3) separating and enriching a high-temperature Fischer-Tropsch synthesis No. 5 wax oil sample of a certain company according to a method described by petrochemical standard SH/T0659.
0.1g of the sample was weighed into a 5mL glass beaker, and 1mL of 60℃heated n-hexane was added to dissolve thoroughly. 1mL of n-hexane is added into a solid phase extraction column special for SH/T0659, and after the n-hexane is completely adsorbed by a stationary phase, the sample in a small beaker is completely transferred to a sieve plate in the solid phase extraction column. Washing the stationary phase with 4mL of n-hexane and 1mL of dichloromethane in sequence, eluting the adsorbed saturated hydrocarbon fraction; washing the stationary phase with 5mL of dichloromethane, and washing the solid phase extraction column with a mixed solvent of 5mL of absolute ethyl alcohol and dichloromethane with the ratio of 1:1 when the dichloromethane just completely enters the stationary phase, wherein the gum ring in the stationary phase can be seen to gradually move downwards, and continuing washing with a mixed solvent of absolute ethyl alcohol and dichloromethane with the ratio of 1:1 until the gum ring moves to the bottom of the solid phase extraction column, so as to obtain an aromatic hydrocarbon component; the solid phase extraction column is washed by 5mL of mixed solvent of absolute ethyl alcohol and dichloromethane with the ratio of 1:1, and gum components are obtained.
Therefore, compared with the solid-phase extraction method provided by the invention, the solid-phase extraction method adopting petrochemical standard SH/T0659 can only obtain saturated hydrocarbon, aromatic hydrocarbon and colloid components, and cannot separate olefin compounds.
Claims (10)
1. A pretreatment method for determining the content and composition of olefin compounds in wax oil, comprising the steps of:
step one: diluting the wax oil by using a diluent to obtain a flowable wax oil sample;
step two: connecting a solid phase extraction column A and a solid phase extraction column B in series, wherein the solid phase extraction column A is arranged on the solid phase extraction column A, wetting the solid phase extraction column A by using a first eluent, adding a flowable wax oil sample from the upper layer of the solid phase extraction column A, and flushing the solid phase extraction column A and the solid phase extraction column B by using the first eluent to obtain a saturated hydrocarbon component 1;
step three: separating the solid phase extraction column A from the solid phase extraction column B, continuing to wash the solid phase extraction column B by using a first eluent to obtain a saturated hydrocarbon component 2, and combining the saturated hydrocarbon component 1 and the saturated hydrocarbon component 2 to obtain a saturated hydrocarbon component;
step four: changing the collector, and flushing the solid-phase extraction column B by using a second eluent to obtain an olefin component;
wherein the diluent is at least one selected from the group consisting of n-hexane, n-heptane, cyclohexane and methylcyclohexane;
the first eluent is at least one selected from the group consisting of n-pentane, n-hexane, n-heptane and petroleum ether;
the second eluent is a mixture of a and b, wherein a is at least one selected from the group consisting of dichloromethane, chloroform, diethyl ether, benzene and toluene, and b is at least one selected from the group consisting of methanol, acetone and butanone; the volume ratio of a to b in the second eluent is 0.25-1.25:1;
the solid phase extraction column A is internally provided with a stationary phase, the stationary phase is a mixture of silica gel and alumina, and the content of the alumina is 70-100 wt%;
the solid phase extraction column B is internally provided with a stationary phase, the stationary phase is alumina loaded with silver ions, and the content of the silver ions is 1-15wt%.
2. The pretreatment method according to claim 1, wherein the silica gel has a specific surface area of 500 to 850m 2 Per gram, a pore volume of 0.1-0.6mL/g and an average pore diameter of 1-4nm.
3. The pretreatment method according to claim 1, wherein the specific surface area of the alumina in the solid phase extraction column a or the solid phase extraction column B is 150 to 450m 2 Per gram, a pore volume of 0.05-0.4mL/g and an average pore diameter of 1-3nm.
4. The pretreatment method according to claim 1, wherein in the first step, the volume ratio of the diluent to the wax oil is 0.5-1:1.
5. The pretreatment method according to claim 1, wherein in the second step, the flowable wax oil sample is added in an amount of 1 to 5mL.
6. The pretreatment method according to claim 1, wherein in the second step, the volume of the first eluent used for wetting the solid phase extraction column a is 1 to 3mL, the volume of the first eluent used for washing the solid phase extraction column a and the solid phase extraction column B is 5 to 10mL, and in the third step, the volume of the first eluent used for washing the solid phase extraction column B is 3 to 6mL.
7. The pretreatment method according to claim 1, wherein in the fourth step, the second eluent for washing the solid phase extraction column B is used in an amount of 5 to 10% mL by volume.
8. The pretreatment method according to claim 1, wherein the wax oil is a wax oil produced in petrochemical or coal chemical industry.
9. The pretreatment method according to claim 1, wherein the wax oil is produced by catalytic cracking, delayed coking, visbreaking, steam cracking.
10. The pretreatment method according to claim 1, wherein the wax oil is a wax oil produced by a fischer-tropsch synthesis process.
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