CN114076808A - Pretreatment method for determining composition of coal-based diesel group - Google Patents
Pretreatment method for determining composition of coal-based diesel group Download PDFInfo
- Publication number
- CN114076808A CN114076808A CN202010816899.XA CN202010816899A CN114076808A CN 114076808 A CN114076808 A CN 114076808A CN 202010816899 A CN202010816899 A CN 202010816899A CN 114076808 A CN114076808 A CN 114076808A
- Authority
- CN
- China
- Prior art keywords
- solid phase
- phase extraction
- extraction column
- eluent
- coal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003245 coal Substances 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 238000002203 pretreatment Methods 0.000 title claims abstract description 35
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 110
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 52
- 239000002283 diesel fuel Substances 0.000 claims abstract description 49
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 44
- 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 43
- 238000000034 method Methods 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 32
- 239000000741 silica gel Substances 0.000 claims abstract description 16
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 16
- -1 heteroatom compound Chemical class 0.000 claims abstract description 11
- 239000003480 eluent Substances 0.000 claims description 66
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000003208 petroleum Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000009736 wetting Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N ortho-diethylbenzene Natural products CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims 4
- 239000002904 solvent Substances 0.000 abstract description 15
- 238000000926 separation method Methods 0.000 abstract description 13
- 125000005842 heteroatom Chemical group 0.000 abstract description 12
- 238000011084 recovery Methods 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 description 23
- 239000012535 impurity Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 18
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- QHMGJGNTMQDRQA-UHFFFAOYSA-N dotriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC QHMGJGNTMQDRQA-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel 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
- 239000013067 intermediate product Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000010117 shenhua Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
Landscapes
- 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
A pretreatment method for determining the composition of coal-based diesel oil is to divide the diesel oil into three parts of saturated hydrocarbon, aromatic hydrocarbon and heteroatom compound by a solid phase extraction column. The solid phase extraction column used in the invention consists of two solid phase extraction columns, the stationary phase of the solid phase extraction column is a mixture consisting of silica gel and alumina, wherein the content of the alumina in the solid phase extraction column A is 20-50 wt%, and the content of the alumina in the solid phase extraction column B is 80-100 wt%. The method can obtain the content of saturated hydrocarbon, aromatic hydrocarbon and heteroatom compounds in the coal-based diesel oil, and has the advantages of short treatment time, low separation cross amount among components, small solvent consumption and high recovery rate.
Description
Technical Field
The invention relates to a pretreatment method for determining the composition of a coal-based diesel group, in particular to a pretreatment method for rapidly providing an experimental sample for the subsequent determination of the composition of the group and separating the coal-based diesel sample into saturated hydrocarbon, aromatic hydrocarbon and heteroatom compounds by using a solid phase extraction method.
Background
The energy resource of China is characterized by rich coal, poor oil and less gas. With the demand of economic development of China on energy, the development of coal chemical industry is an important measure for adjusting the energy structure of China and also an important measure for ensuring the energy safety of China. The modern coal chemical industry can be divided into five contents, namely coal-to-liquid and coal-to-olefin, and the like, not only meets the requirements of industrial development on clean energy, but also meets the requirements of industrial development on chemical raw materials, and is beneficial to improving clean utilization and high-efficiency conversion of coal [ Li Zhi Jian, development and focus of the modern coal chemical industry [ J ]. chemical industry, 2013,31(6):9-14 ].
Compared with petroleum-based oil products, the oil products produced by coal chemical industry have no essential difference in distillation range, hydrocarbon compound type or other physical properties. However, because the sulfur, nitrogen, oxygen and other contents of the coal are high, the sulfur, nitrogen, oxygen, metal contents and the like of the intermediate products of the coal chemical industry process are obviously higher than those of petroleum-based oil products, so that the group composition data of the oil products obtained by the coal chemical industry process and the petroleum-based oil products are greatly different. The method for analyzing the composition of the oil product family in the coal chemical industry at present basically adopts a determination method of the composition of the petroleum-based oil product family [ Sun wisdom, Li Sten, Marianxia, et al.
The coal-based diesel oil is mainly derived from direct coal liquefaction, indirect coal liquefaction technology and the like, has high contents of oxygenated compounds such as alcohol, ketone, aldehyde and the like, and is not seen in petroleum-based diesel oil. Therefore, the method is commonly used for measuring the composition of petroleum-based diesel oil families, such as chromatographic column chromatography, mass spectrometry, infrared spectrometry and the like [ Gouyixian, Zhang Jian Feng, in hong Wei, and the like. Analysis and characterization of direct liquefaction cycle oil of Shenhua coal [ J ] fuel chemistry report, 2007,35(1): 104-. The method adopts column chromatography, has the defects of long analysis time, high consumption of solvent and stationary phase and the like, is not suitable for pretreatment of a large amount of samples, and limits the application of the method.
Disclosure of Invention
The invention aims to provide a pretreatment method for separating coal-based diesel into saturated hydrocarbon, aromatic hydrocarbon and heteroatom compounds by utilizing a solid phase extraction technology, which can be used for the determination process of coal-based diesel group composition and the molecular composition analysis of the saturated hydrocarbon, aromatic hydrocarbon and heteroatom compounds, eliminates the mutual interference between the qualitative and quantitative properties of hydrocarbon compounds and non-hydrocarbon compounds, and improves the accuracy of analysis results. The invention can solve the problems of long separation time, large using amount of solvent and stationary phase, large separation cross among components and the like of the traditional column chromatography, and can quickly and accurately provide an experimental sample for the subsequent determination of group composition.
The invention provides a pretreatment method for determining the composition of a coal-based diesel group, which adopts a solid phase extraction column to separate a coal-based diesel sample into three parts of saturated hydrocarbon, aromatic hydrocarbon and heteroatom compounds, and comprises the following steps:
the method comprises the following steps: 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 above, wetting the solid phase extraction column A by using a first eluent, adding a diesel oil sample from the upper layer of the solid phase extraction column A, and then washing the solid phase extraction column by using the first eluent to obtain a saturated hydrocarbon component 1;
step two: separating the solid phase extraction column A from the solid phase extraction column B, and continuously washing the solid phase extraction column B by using a first eluent to obtain a saturated hydrocarbon component 2;
mixing the saturated hydrocarbon components 1 and 2 to obtain saturated hydrocarbon components;
step three: washing the solid phase extraction column B with a second eluent to obtain an aromatic hydrocarbon component 1;
step four: washing the solid phase extraction column A with a second eluent to obtain an aromatic hydrocarbon component 2;
combining the aromatic hydrocarbon components 1 and 2 to obtain an aromatic hydrocarbon component;
step five: washing the solid phase extraction column A with a third eluent to obtain a heteroatom compound;
wherein the first eluent is at least one of 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 n-pentane, n-hexane, n-heptane and petroleum ether, and b is at least one selected from the group consisting of dichloromethane, chloroform, diethyl ether, benzene and toluene;
the third eluent is at least one of the group consisting of methanol, ethanol, isopropanol, acetone and butanone.
The pretreatment method for determining the composition of the coal-based diesel family is characterized in that a 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 20-50 wt%.
The pretreatment method for determining the composition of the coal-based diesel family is characterized in that a stationary phase is arranged in the solid phase extraction column B, and the stationary phase is a mixture of silica gel and alumina, wherein the content of the alumina is 80-100 wt%.
The pretreatment method for determining the composition of the coal-based diesel is characterized in that the specific surface area of the silica gel is 500-850m2Per g, pore volume of 0.1-0.6mL/g, average pore diameter of 1-4 nm.
The invention relates to the determination of coal-based diesel groupThe pretreatment method is characterized in that the specific surface area of the alumina is 200-450m2Per g, pore volume of 0.05-0.4mL/g, average pore diameter of 1-3 nm.
The pretreatment method for determining the composition of the coal-based diesel oil family is characterized in that the volume ratio of a to b in the second eluent is 2-5: 1.
The pretreatment method for determining the composition of the coal-based diesel is characterized in that the mass ratio of the added diesel sample to the solid phase extraction column A is 0.13-1:1, and the mass ratio of the added diesel sample to the solid phase extraction column B is 0.1-1: 1.
The pretreatment method for determining the composition of the coal-based diesel oil family is characterized in that in the first step, the volume usage amount of the first eluent for wetting the solid-phase extraction column A is 2mL, the solid-phase extraction columns A and B are washed, the volume usage amount of the first eluent for washing the solid-phase extraction columns A and B is 4-8mL, and the volume usage amount of the first eluent in the second step is 2-4 mL.
The pretreatment method for determining the composition of the coal-based diesel oil family is characterized in that the volume consumption of the second eluent in the third step is 3-8mL, and the volume consumption of the second eluent in the fourth step is 4-9 mL.
The pretreatment method for determining the composition of the coal-based diesel oil family is characterized in that the volume dosage of the third eluent in the fifth step is 3-9 mL.
The pretreatment method for determining the composition of the coal-based diesel family is characterized in that the diesel sample is produced by coal chemical industry.
The pretreatment method for determining the composition of the coal-based diesel family is characterized in that the diesel sample is diesel produced by a Fischer-Tropsch synthesis process.
Solid phase extraction is to separate substances into components with different polarities by adjusting the polarity of an eluent by utilizing the difference of adsorption capacities of different compounds on a stationary phase. Therefore, the choice of eluent for solid phase extraction is very important, but even mixing the same solvent in different ratios will result in eluents of different polarity and different solvent selectivity, resulting in a great difference in the final separation results. Because the aromatic hydrocarbon and the ether compound in the coal-based diesel oil have similar polarities, the aromatic hydrocarbon and the ether compound are difficult to separate well. In addition, no relevant report on the separation of aromatic hydrocarbons and heteroatom compounds in coal-based diesel oil by using solid phase extraction exists at present.
The invention can also be detailed as follows:
in order to achieve the purpose, the invention provides two solid phase extraction columns, and the separation of different components of the coal-based diesel oil is realized through the combination of the solid phase extraction columns. The solid phase extraction column A is a mixture of silica gel and alumina, wherein the content of the alumina is 20-50 wt%, and the solid phase extraction column B is a mixture of silica gel and alumina, wherein the content of the alumina is 80-100 wt%. The method can effectively enrich saturated hydrocarbon, aromatic hydrocarbon and heteroatom compounds in the coal-based diesel oil, has the advantages of large sample processing capacity, simple processing steps and small separation cross among components, greatly improves the separation and enrichment efficiency, and is suitable for large-scale popularization and use.
The preparation method of the silica gel and neutral alumina stationary phase comprises the following steps: drying the silica gel at 80-160 ℃ for 2-6 hours, and then putting the silica gel into a dryer for cooling to obtain activated silica gel; the neutral alumina is roasted for 1 to 5 hours at the temperature of 350-550 ℃, and then is put into a dryer for cooling, so as to obtain the activated neutral alumina. The activated silica gel and the neutral alumina are mixed evenly according to a certain proportion to obtain the required stationary phase.
The solution obtained by solid phase extraction and separation of the invention can be subjected to solvent volatilization and concentration to obtain three parts of saturated hydrocarbon, aromatic hydrocarbon and heteroatom compound, and rotary evaporation and nitrogen purging are selected for product concentration. The solution is volatilized and concentrated to about 0.5mL, and then the relevant analysis can be carried out by Gas Chromatography (GC). Saturated hydrocarbons, aromatic hydrocarbons, and heteroatom compounds were analyzed by Gas Chromatography (GC) -Mass Spectrometry (MS) -hydrogen Flame Ionization Detector (FID). The mass spectrum is one of main research tools for the structure qualitative of the compounds, and various compounds in the enriched material can be qualitatively analyzed by means of spectrogram retrieval and the like to judge whether the separated components are crossed or not. Since the influence factors of the hydrogen flame ionization detector on the compounds are not greatly different, quantitative analysis by GC-FID is considered to determine the level of the separation cross amount.
The method for determining the contents of the respective components obtained by the pretreatment method of the present invention is a GC-FID method. And (3) injecting the enriched liquid into a gas chromatography, separating the enriched liquid by a chromatographic column in the gas chromatography according to the boiling point and the polarity of the compound, and then entering a detector to obtain the monomer content information of the compound. The invention utilizes an internal standard method for quantification, and selects deuterated terphenyl and chlorobenzene as internal standards.
The coal-based diesel oil is separated into three parts of saturated hydrocarbon, aromatic hydrocarbon and heteroatom compounds by adopting a solid phase extraction method, and the separation cross among the components is small. Compared with the traditional column chromatography, the solid phase extraction method adopted by the invention has high column efficiency, high repeatability of the filling of the extraction column, elution solvent under pressure and small solvent dosage, so that the method has high repeatability and high speed. The method is suitable for being used as a pretreatment method for determining the group composition of the coal-based diesel oil sample, and can effectively solve the problems of long separation time and low analysis efficiency of the traditional column chromatography. The time for separating the coal-based diesel oil sample at one time is only 30min, so that the separation efficiency of the coal-based diesel oil is greatly improved, and an experimental sample can be rapidly provided for subsequent determination of group composition.
Drawings
FIG. 1 is a GC-MS diagram of a saturated hydrocarbon component obtained by applying the pretreatment method of example 1 of the present invention.
FIG. 2 is a GC-MS diagram of an aromatic hydrocarbon component obtained by applying the pretreatment method of example 1 of the present invention.
FIG. 3 is a GC-MS diagram of the heteroatom compound component obtained by applying the pretreatment method of example 1 of the present invention.
Detailed Description
The following provides a detailed description of embodiments of the invention. The present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The silica gel used in the examples is a chemical reagent of the national drug groupThe produced silica gel for chromatography has granularity of more than or equal to 70.0 percent and specific surface area of 511.9m2Pore volume of 0.468 mL/g. The alumina is produced by national drug group chemical reagent limited company for chromatography, the ignition weight loss is less than or equal to 8.0 percent, and the specific surface area is 177.8m2Pore volume was 0.255 mL/g.
Drying the silica gel at 135 ℃ for 5 hours to obtain activated silica gel; the alumina was calcined at 550 ℃ for 3 hours to obtain activated alumina.
The GC-MS instrument model used for the analysis was 7890A GC-5975MS with a FID detector. GC conditions were as follows: HP-PONA capillary chromatographic column, 50m × 0.2mm × 0.5 μm; programming to raise the initial temperature to 80 deg.c, maintaining for 5min, raising the temperature at 40 deg.c/min rate to final temperature of 300 deg.c and maintaining for 9 min; the carrier gas was high purity helium, operating at constant pressure, 35.374 psi; the injection port temperature is 320 ℃, the split ratio is 20:1, and the injection amount is 1 mu L. MSD conditions: EI ionization source (70eV), ion source temperature 230 ℃, quadrupole rod temperature 130 ℃, total scanning mass range 30-500u, interface temperature 310 ℃ and solvent delay 5 min. FID conditions: the temperature of the detector is 350 ℃, the air flow is 300mL/min, the hydrogen flow is 30mL/min, and the tail gas blowing is 25 mL/min.
Example 1
3g of silica gel-alumina stationary phase having an alumina content of 40 wt% was packed in the solid phase extraction column A, 4g of silica gel-alumina stationary phase having an alumina content of 90 wt% was packed in the solid phase extraction column B, and the solid phase extraction column A was wetted with 2mL of the first eluent (n-pentane).
2g of a high-temperature Fischer-Tropsch synthesis 1# diesel oil sample of a certain company is taken by a liquid transfer gun, added into the upper part of a solid phase extraction column A and completely adsorbed by a stationary phase. The solid phase extraction column A + B was washed with 6mL 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 to give a saturated hydrocarbon as fraction 1. The solid phase extraction column B was washed with 5mL of a second eluent (the volume ratio of n-pentane to dichloromethane was 70:30) and then with 7mL of a second eluent to obtain aromatic hydrocarbons, which were designated as component 2. The solid phase extraction column a was washed with 6mL of a third eluent, methanol, to give the heteroatom compound, designated as component 3. The solvent in each component was removed by nitrogen purge. The whole process takes 28 min.
The GC-MS-FID is adopted to analyze the component 1, the component 2, the component 3 and the component 4, and the result shows that the component 1 is mainly saturated hydrocarbon and accounts for 12.3 wt% of the diesel oil sample, wherein the content of the impurity olefin component is 0.3 wt%; component 2 is predominantly olefin and represents 58.4 wt% of the diesel sample, with the impurity saturated hydrocarbons containing 0.1 wt% and essentially no aromatics; the component 3 is mainly aromatic hydrocarbon and accounts for 13.2 wt% of the diesel oil sample, 0.5 wt% of impurity olefin and 0.2 wt% of oxygen-containing compound; the component 4 is mainly an oxygen-containing compound and accounts for 14.9 wt% of the diesel oil sample, and the content of impurity aromatic hydrocarbon is 0.1 wt%.
The effect of separating each component of the diesel oil by the solid phase extraction method is examined by the standard recovery rate of naphthalene and n-octanol. Taking two samples of 1# diesel oil synthesized by low-temperature Fischer-Tropsch of a certain company, and adding a certain amount of naphthalene and n-octanol into one of the two samples to serve as a standard sample. The two samples are separated into three parts according to the solid phase extraction method, a certain amount of deuterated terphenyl is added as an internal standard, and the content of each compound is analyzed by GC-FID respectively. The difference value of the naphthalene content and the n-octanol content of the non-labeled sample subtracted from the naphthalene content and the n-octanol content of the labeled sample is the ratio of the theoretical value of the naphthalene content and the theoretical value of the n-octanol content to the standard recovery rate of the two compounds, and the values are 97.4 percent and 98.9 percent in sequence.
The results show that the method has high recovery rate of each component in the separated components, low cross quantity among the components and better enrichment effect.
Example 2
3g of a silica gel-alumina stationary phase having an alumina content of 50 wt% was packed in the solid phase extraction column A, 4g of an alumina stationary phase was packed in the solid phase extraction column B, and the solid phase extraction column A was wetted with 2mL of a first eluent (n-pentane).
4g of a high-temperature Fischer-Tropsch synthesis No. 2 diesel oil sample of a certain company is taken by a liquid transfer gun, added into the upper part of a solid phase extraction column A and completely adsorbed 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 3mL of the first eluent was added to B to give a saturated hydrocarbon as fraction 1. The solid phase extraction column B was washed with 8mL of a second eluent (the volume ratio of n-pentane to dichloromethane was 70:30) and then the solid phase extraction column A was washed with 9mL of a second eluent to obtain aromatic hydrocarbons, which were designated as component 2. The solid phase extraction column a was washed with 9mL of a third eluent, methanol, to give the heteroatom compound, designated as component 3. The solvent in each component was removed by nitrogen purge. The whole process takes 25 min.
The GC-MS-FID analysis of the component 1, the component 2 and the component 3 shows that the component 1 is mainly saturated hydrocarbon with the impurity aromatic hydrocarbon component content of 3.5 wt%, the component 2 is mainly aromatic hydrocarbon with the impurity saturated hydrocarbon content of 4.3 wt% and does not contain heteroatom compounds, and the component 3 is mainly oxygen-containing compound with the impurity aromatic hydrocarbon content of 4.2 wt%.
The effect of separating each component of the diesel oil by the solid phase extraction method is examined by the standard recovery rate of naphthalene and n-octanol, and the standard recovery rates of the two compounds are 96.4 percent and 97.8 percent in sequence.
Example 3
3g of silica gel-alumina stationary phase having an alumina content of 30 wt% was packed in the solid phase extraction column A, 4g of silica gel-alumina stationary phase having an alumina content of 90 wt% was packed in the solid phase extraction column B, and the solid phase extraction column A was wetted with 2mL of the first eluent (petroleum ether).
1g of a company direct liquefied 3# diesel sample is taken by a liquid transfer gun, added to the upper part of a solid phase extraction column A and completely adsorbed 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 4mL of the first eluent was added to B to give a saturated hydrocarbon as fraction 1. The solid phase extraction column B was washed with 4mL of a second eluent (75: 25 by volume of petroleum ether to chloroform) and then the solid phase extraction column A was washed with 6mL of a second eluent to obtain aromatic hydrocarbons, which were designated as component 2. The solid phase extraction column a was washed with 4mL of a third eluent ethanol to give the heteroatom compound, designated as component 3. The solvent in each component was removed by nitrogen purge. The whole process takes 30 min.
The GC-MS-FID analysis of the component 1, the component 2 and the component 3 shows that the component 1 is mainly saturated hydrocarbon with the impurity aromatic hydrocarbon component content of 2.6 wt%, the component 2 is mainly aromatic hydrocarbon with the impurity saturated hydrocarbon content of 5.3 wt% and does not contain heteroatom compounds, and the component 3 is mainly sulfur-containing, nitrogen-containing and oxygen-containing compounds with the impurity aromatic hydrocarbon content of 2.7 wt%.
The effect of separating each component of the diesel oil by the solid phase extraction method is examined by the standard recovery rate of naphthalene and n-octanol, and the standard recovery rates of the two compounds are 98.6 percent and 99.5 percent in sequence.
Example 4
3g of a silica gel-alumina stationary phase having an alumina content of 20 wt% was packed in the solid phase extraction column A, 4g of a silica gel-alumina stationary phase having an alumina content of 80 wt% was packed in the solid phase extraction column B, and the solid phase extraction column A was wetted with 2mL of a first eluent (petroleum ether).
0.4g of a low-temperature Fischer-Tropsch synthesis No. 4 diesel oil sample of a certain company is taken by a liquid transfer gun, added into the upper part of a solid phase extraction column A and completely adsorbed by a stationary phase. The solid phase extraction column A + B was washed with 4mL of the first eluent, then the solid phase extraction columns A and B were separated, and 2mL of the first eluent was added to B to give a saturated hydrocarbon as fraction 1. The solid phase extraction column B was washed with 3mL of a second eluent (the volume ratio of n-pentane to dichloromethane was 70:30) and then with 4mL of a second eluent to obtain aromatic hydrocarbons, which were designated as component 2. The solid phase extraction column a was washed with 3mL of a third eluent methanol to give an oxygenate, designated as component 3. The solvent in each component was removed by nitrogen purge. The whole process takes 28 min.
The GC-MS-FID analysis of the component 1, the component 2 and the component 3 shows that the component 1 is mainly saturated hydrocarbon with the impurity aromatic hydrocarbon component content of 2.1 wt%, the component 2 is mainly aromatic hydrocarbon with the impurity saturated hydrocarbon content of 4.8 wt% and does not contain oxygen-containing compounds, and the component 3 is mainly oxygen-containing compounds with the impurity aromatic hydrocarbon content of 2.1 wt%.
The effect of separating each component of the diesel oil by the solid phase extraction method is examined by the standard recovery rate of naphthalene and n-octanol, and the standard recovery rates of the two compounds are 95.4 percent and 96.1 percent in sequence.
Example 5
3g of silica gel-alumina stationary phase having an alumina content of 25 wt.% was packed in the solid phase extraction column A, 4g of silica gel-alumina stationary phase having an alumina content of 75 wt.% was packed in the solid phase extraction column B, and the solid phase extraction column A was wetted with 2mL of the first eluent (petroleum ether).
0.6g of a low-temperature Fischer-Tropsch synthesis No. 4 diesel oil sample of a certain company is taken by a liquid transfer gun, added into the upper part of a solid phase extraction column A and completely adsorbed 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 to give a saturated hydrocarbon as fraction 1. The solid phase extraction column B was washed with 4mL of a second eluent (the volume ratio of n-pentane to dichloromethane was 70:30) and then the solid phase extraction column A was washed with 5mL of a second eluent to obtain aromatic hydrocarbons, which were designated as component 2. The solid phase extraction column a was washed with 4mL of a third eluent methanol to give the oxygenate, designated as component 3. The solvent in each component was removed by nitrogen purge. The whole process takes 25 min.
The GC-MS-FID analysis of the component 1, the component 2 and the component 3 shows that the component 1 is mainly saturated hydrocarbon with the impurity aromatic hydrocarbon component content of 3.2 wt%, the component 2 is mainly aromatic hydrocarbon with the impurity saturated hydrocarbon content of 5.3 wt% and does not contain oxygen-containing compounds, and the component 3 is mainly oxygen-containing compounds with the impurity aromatic hydrocarbon content of 3.3 wt%.
The effect of separating each component of the diesel oil by the solid phase extraction method is examined by the standard recovery rate of naphthalene and n-octanol, and the standard recovery rates of the two compounds are 94.8 percent and 97.1 percent in sequence.
Comparative example 1
The column was packed with 20g of silica gel.
10mL of n-pentane was added to activate the column. When the liquid level of the n-pentane is lower than the upper part of the chromatographic column, 2g of high-temperature Fischer-Tropsch synthesis No. 1 diesel oil from a certain company is transferred by a liquid transfer gun and added into the upper part of the chromatographic column. 2g of quartz sand was added to fix the diesel sample. Adding 35mL of n-pentane to elute saturated hydrocarbon components, adding 60mL of toluene to elute aromatic hydrocarbon, adding 50mL of methanol to elute heteroatom compounds, and adjusting the flow of an eluent to be 1.5mL/min by using a double-chain ball. The solvent in each component was removed by nitrogen purge. The whole process takes 160 min.
The GC-MS-FID analysis of the component 1, the component 2 and the component 3 shows that the component 1 is mainly saturated hydrocarbon with the impurity aromatic hydrocarbon component content of 8.9 wt%, the component 2 is mainly aromatic hydrocarbon with the impurity saturated hydrocarbon content of 10.5 wt%, the heteroatom compound content of 8.5 wt%, and the component 3 is mainly oxygen-containing compound with the impurity aromatic hydrocarbon content of 12.5 wt%.
Therefore, the method for separating the coal-based diesel oil sample by adopting the column chromatography has long time consumption, large solvent dosage and large stationary phase dosage, and is not suitable for pretreatment for determining the composition of the coal-based diesel oil group.
Comparative example 2
And separating and enriching a high-temperature Fischer-Tropsch synthesis 1# diesel oil sample of a certain company according to the method described in petrochemical standard SH/T0606 appendix B.
0.1mL of sample is dropped into the upper part of a solid phase extraction column special for petrochemical standard SH/T0606 and is completely adsorbed. The stationary phase was washed with 2mL of n-pentane and 0.5mL of dichloromethane in that order and extracted to obtain saturated hydrocarbons. The stationary phase was washed with 2mL of dichloromethane to obtain aromatic hydrocarbons. Adding a certain amount of n-dotriacontane as an internal standard, and performing GC-MS-FID analysis on the group composition, wherein the result shows that the content of saturated hydrocarbon components accounts for 70.5 wt% of the total amount of the diesel oil sample, and the content of impurity aromatic hydrocarbon is 2.4 wt%; the content of aromatic hydrocarbon components is 22.6 wt%, and the content of impurity saturated hydrocarbon is 4.5 wt%.
Therefore, compared with the solid phase extraction method provided by the invention, the solid phase extraction method adopting the petrochemical standard SH/T0606 can only obtain saturated hydrocarbon and aromatic hydrocarbon components, wherein olefin can influence the quantitative determination of the saturated hydrocarbon, and oxygen-containing compounds can influence the quantitative determination of the aromatic hydrocarbon components, so that the content results of the saturated hydrocarbon and the aromatic hydrocarbon in the determination result are higher, and the accuracy of the determination result is influenced.
Claims (12)
1. A pretreatment method for determining the composition of a coal-based diesel group is characterized by comprising the following steps:
the method comprises the following steps: 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 above, wetting the solid phase extraction column A by using a first eluent, adding a diesel oil sample from the upper layer of the solid phase extraction column A, and then washing 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 two: separating the solid phase extraction column A from the solid phase extraction column B, and continuously washing the solid phase extraction column B by using a first eluent to obtain a saturated hydrocarbon component 2; mixing the saturated hydrocarbon component 1 and the saturated hydrocarbon component 2 to obtain a saturated hydrocarbon component;
step three: washing the solid phase extraction column B with a second eluent to obtain an aromatic hydrocarbon component 1;
step four: washing the solid phase extraction column A with a second eluent to obtain an aromatic hydrocarbon component 2; combining the aromatic hydrocarbon component 1 and the aromatic hydrocarbon component 2 to obtain an aromatic hydrocarbon component;
step five: washing the solid phase extraction column A with a third eluent to obtain a heteroatom compound;
wherein 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 n-pentane, n-hexane, n-heptane and petroleum ether, and b is at least one selected from the group consisting of dichloromethane, chloroform, diethyl ether, benzene and toluene;
the third eluent is at least one selected from the group consisting of methanol, ethanol, isopropanol, acetone, and butanone.
2. The pretreatment method for determining the composition of kerosene diesel fuel as claimed in claim 1, wherein said solid phase extraction column A contains a stationary phase, said stationary phase is a mixture of silica gel and alumina, and the content of alumina is 20-50 wt%.
3. The pretreatment method for determining the composition of kerosene diesel fuel as claimed in claim 1, wherein said solid phase extraction column B contains a stationary phase, said stationary phase is a mixture of silica gel and alumina, and the content of alumina is 80-100 wt%.
4. The pretreatment method for determining the composition of kerosene diesel fuel as claimed in claim 2 or 3, wherein said silica gel has a specific surface area of 500-850m2Per g, pore volume of 0.1-0.6mL/g, average pore diameter of 1-4 nm.
5. The pretreatment method for determining the composition of kerosene diesel fuel as claimed in claim 2 or 3, wherein said alumina has a specific surface area of 200-450m2Per g, pore volume of 0.05-0.4mL/g, average pore diameter of 1-3 nm.
6. The pretreatment method for determining the composition of the coal-based diesel family according to claim 1, wherein the volume ratio of a to b in the second eluent is 2-5: 1.
7. The pretreatment method for determining the composition of coal-based diesel fuel family as claimed in claim 1, wherein in the first step, the mass ratio of the diesel fuel sample to the solid phase extraction column A is 0.13-1:1, and the mass ratio of the diesel fuel sample to the solid phase extraction column B is 0.1-1: 1.
8. The pretreatment method for determining the composition of the coal-based diesel fuel family as claimed in claim 1, wherein in the first step, the volume usage amount of the first eluent for wetting the solid phase extraction column A is 2mL, and the volume usage amount of the first eluent for washing the solid phase extraction columns A and B is 4-8 mL; in the second step, the volume dosage of the first eluent for washing the solid-phase extraction column B is 2-4 mL.
9. The pretreatment method for determining the composition of the coal-based diesel family according to claim 1, wherein in the third step, the volume of the second eluent is 3-8 mL; in the fourth step, the volume dosage of the second eluent is 4-9 mL.
10. The pretreatment method for determining the coal-based diesel family composition determination of claim 1, wherein in the fifth step, the volume dosage of the third eluent is 3-9 mL.
11. The pretreatment method for determining the composition of a coal-based diesel fuel family according to claim 1, wherein the diesel fuel sample is diesel fuel produced by coal chemical industry.
12. The pretreatment method for determining the composition of the coal-based diesel family according to claim 1, wherein the diesel sample is a diesel produced by a Fischer-Tropsch synthesis process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010816899.XA CN114076808A (en) | 2020-08-14 | 2020-08-14 | Pretreatment method for determining composition of coal-based diesel group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010816899.XA CN114076808A (en) | 2020-08-14 | 2020-08-14 | Pretreatment method for determining composition of coal-based diesel group |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114076808A true CN114076808A (en) | 2022-02-22 |
Family
ID=80280577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010816899.XA Pending CN114076808A (en) | 2020-08-14 | 2020-08-14 | Pretreatment method for determining composition of coal-based diesel group |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114076808A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110198291A1 (en) * | 2008-12-25 | 2011-08-18 | Katsuhisa Honda | Purifying agent for oily liquid containing polychlorinated biphenyls |
| CN105548421A (en) * | 2015-12-07 | 2016-05-04 | 中国石油天然气集团公司 | Analysis method of polycyclic aromatic hydrocarbon content and application thereof |
| CN106318438A (en) * | 2015-06-17 | 2017-01-11 | 中国石油天然气股份有限公司 | Double-column solid phase extraction method of nitrogen-containing compounds in diesel oil |
-
2020
- 2020-08-14 CN CN202010816899.XA patent/CN114076808A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110198291A1 (en) * | 2008-12-25 | 2011-08-18 | Katsuhisa Honda | Purifying agent for oily liquid containing polychlorinated biphenyls |
| CN106318438A (en) * | 2015-06-17 | 2017-01-11 | 中国石油天然气股份有限公司 | Double-column solid phase extraction method of nitrogen-containing compounds in diesel oil |
| CN105548421A (en) * | 2015-12-07 | 2016-05-04 | 中国石油天然气集团公司 | Analysis method of polycyclic aromatic hydrocarbon content and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| 余卫娟 等: "原油族组分的分离及检测方法", 石油化工, vol. 39, pages 209 - 214 * |
| 王欢业;刘卫国;张普;: "地质样品正构烷烃组分分离纯化的部分问题探究", 岩矿测试, vol. 30, no. 01, pages 1 - 6 * |
| 黄宁选 等: "环境中石油烃污染物组分的气相色谱分析", 陕西科技大学学报, vol. 21, pages 25 - 29 * |
| 黄瀛华 等编: "煤化学及工艺学实验", 30 September 1988, pages: 147 - 149 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Separation and purification of chlorogenic acid by molecularly imprinted polymer monolithic stationary phase | |
| CN109839448B (en) | Solid phase extraction column and method for separating phenolic compounds in diesel oil by solid phase extraction | |
| CN109839450B (en) | Method for simultaneously separating nitrogen-containing compounds and phenolic compounds in diesel oil by solid phase extraction | |
| WO2022068174A1 (en) | Method for determining composition and content of aromatic hydrocarbons in high-temperature fischer-tropsch synthetic oil | |
| CN111308005A (en) | Method for determining content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil | |
| CN102253136A (en) | Method for analyzing carbon isotopes of micro single hydrocarbons in natural gas | |
| CN109839449B (en) | Method for separating phenolic compounds in diesel oil by solid phase extraction | |
| CN106478379A (en) | A kind of coal tar oil ingredient continuous separation technology and device | |
| O'Connor et al. | Molecular sieve adsorption. Application to hydrocarbon type analysis | |
| CN104845651A (en) | Method of separating components of coal tar | |
| CN114076808A (en) | Pretreatment method for determining composition of coal-based diesel group | |
| CN114075450B (en) | Method for separating diesel oil group composition by solid phase extraction | |
| CN103869027B (en) | A kind of method being separated n-alkane in oil geology sample | |
| EP4206169A1 (en) | Composite adsorbent for separating ethylbenzene by adsorptive rectification and use thereof | |
| CN105572248B (en) | The assay method of sulfide in a kind of methyl tertiary-butyl ether | |
| CN114075447B (en) | Method for separating oxygen-containing compound in coal-based diesel oil | |
| CN114561228B (en) | Method for separating oxygen-containing compound in coal-based wax oil | |
| CN110066232B (en) | Separation method of active components in petroleum sulfonate | |
| CN106124660A (en) | The separation method of benzene compound in a kind of oil | |
| CN112986455A (en) | Separation method of coal liquefied oil component | |
| CN111579654A (en) | Method for separating, purifying and simultaneously measuring antioxidant and anti-icing agent in aviation kerosene | |
| CN106542974B (en) | A kind of method of sulfide in enrichment methyl tertiary-butyl ether | |
| CN114563516B (en) | Method for determining wax oil group composition | |
| Černý et al. | Separation and identification of nitrogen compounds in coal-tar pitch | |
| CN114563506B (en) | Pretreatment method for determining content and composition of olefin compounds in wax oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |