CN117269334A - Method for separating saturated hydrocarbon and aromatic hydrocarbon from diesel oil containing polar agent and method for measuring content - Google Patents
Method for separating saturated hydrocarbon and aromatic hydrocarbon from diesel oil containing polar agent and method for measuring content Download PDFInfo
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- CN117269334A CN117269334A CN202210673117.0A CN202210673117A CN117269334A CN 117269334 A CN117269334 A CN 117269334A CN 202210673117 A CN202210673117 A CN 202210673117A CN 117269334 A CN117269334 A CN 117269334A
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- 239000002283 diesel fuel Substances 0.000 title claims abstract description 95
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 77
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 74
- 229930195734 saturated hydrocarbon Natural products 0.000 title claims abstract description 51
- 239000003480 eluent Substances 0.000 claims abstract description 108
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 35
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 20
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 9
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000011049 filling Methods 0.000 claims abstract description 6
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 31
- 238000000926 separation method Methods 0.000 claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical class [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Chemical class 0.000 claims description 16
- 239000001301 oxygen Chemical class 0.000 claims description 16
- 239000000741 silica gel Substances 0.000 claims description 16
- 229910002027 silica gel Inorganic materials 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000010828 elution Methods 0.000 claims description 8
- 239000005416 organic matter Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001819 mass spectrum Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010813 internal standard method Methods 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000004445 quantitative analysis Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005259 measurement Methods 0.000 abstract description 11
- 238000001514 detection method Methods 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 38
- 239000004215 Carbon black (E152) Substances 0.000 description 29
- 229930195733 hydrocarbon Natural products 0.000 description 29
- 239000000203 mixture Substances 0.000 description 23
- 239000002904 solvent Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000605 extraction Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- JXTPJDDICSTXJX-UHFFFAOYSA-N triacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 monocyclic aromatic hydrocarbons Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 125000004062 acenaphthenyl group Chemical class C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/42—Selective adsorption, e.g. chromatography characterised by the development mode, e.g. by displacement or by elution
- B01D15/424—Elution mode
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
-
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/68—Flame ionisation detectors
-
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7206—Mass spectrometers interfaced to gas chromatograph
-
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/78—Detectors specially adapted therefor using more than one detector
-
- 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
- G01N2030/042—Standards
- G01N2030/045—Standards internal
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- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present disclosure relates to a method for separating saturated hydrocarbons and aromatic hydrocarbons from diesel oil containing a polar agent and a method for determining the content thereof, the method comprising the steps of: (1) Filling a stationary phase in a solid phase extraction column, and adding a diesel oil sample containing a polar reagent to be detected into the stationary phase; (2) Washing the stationary phase by sequentially using a first eluent and a second eluent to obtain a first eluent containing saturated hydrocarbon; (3) Washing the stationary phase obtained in the step (2) by using a third eluent and a fourth eluent in sequence to obtain a second eluent containing aromatic hydrocarbon; wherein the polar agent comprises one or more of toluene, sulfolane, 3-methyl sulfolane, dimethyl sulfoxide and N, N-dimethyl amide. The method can effectively separate the saturated hydrocarbon and the aromatic hydrocarbon in the diesel oil containing the polar agent, avoid the interference of the polar agent, has high detection speed, adopts the gas chromatography-mass spectrometry to measure the content of the saturated hydrocarbon and the aromatic hydrocarbon, and can improve the measurement accuracy.
Description
Technical Field
The present disclosure relates to the field of petrochemical industry, and in particular, to a method for separating saturated hydrocarbons and aromatic hydrocarbons from diesel oil containing a polar agent, and a method for content determination.
Background
Aromatic hydrocarbons are important chemical raw materials, and the demand of the aromatic hydrocarbons is gradually increased along with continuous progress and development of social economy. In recent years, the aromatic hydrocarbon industry in China develops rapidly, and in 2019, the total yield of aromatic hydrocarbon reaches 5800 ten thousand t/a. Aromatic separation is an important step in aromatic production, and aromatic separation techniques include techniques such as rectification, azeotropic distillation, solvent extraction, extractive distillation, adsorption separation, percolation separation, crystallization separation, and complexation separation. A large amount of solvent is often used in the aromatic separation process. For example, the extraction of aromatic hydrocarbon with wider industrial application is to select a proper extractant to realize the liquid-liquid extraction process of aromatic hydrocarbon separation, and sulfolane, dimethyl sulfoxide, N-methylpyrrolidone and the like are solvents commonly used in the current aromatic hydrocarbon extraction; the adsorption separation technology is to utilize the difference of adsorption capacity of the adsorbent to the separation components to realize the adsorption and analysis of the target components under the action of the mobile phase, wherein the mobile phase comprises toluene, methylcyclohexane and the like.
The composition of hydrocarbon compounds in the diesel oil containing the reagent generated in the aromatic hydrocarbon separation process is an important basis for judging the aromatic hydrocarbon separation effect, solvent ratio, flow rate and other technological parameters, so that the establishment of a simple and rapid method for analyzing the composition of hydrocarbon in the diesel oil containing the polar reagent has important significance in aromatic hydrocarbon production activities.
At present, a sample direct distillation method is generally adopted in China to analyze the hydrocarbon content in sulfolane of an extraction solvent of an aromatic device so as to determine the extraction capacity of the extraction solvent and the regeneration effect of the solvent. However, the distillation method has the advantages of large sample consumption, long analysis time, poor accuracy of analysis results, easy environmental pollution, and higher boiling point of C9 and heavier aromatic hydrocarbon, and can not be completely distilled from the solvent, so that the distillation method is difficult to meet the analysis requirements in production.
Cheng Guangjian et al [ "screening study of aromatic separation extractant in catalytic diesel ]: 170-173, that the hydrocarbon content analyzer can only analyze the hydrocarbon composition of diesel oil, but can not analyze the diesel oil composition containing the extractant, so that the extractant is separated from the aromatic hydrocarbon by a liquid-liquid extraction method, and then the hydrocarbon composition in the aromatic hydrocarbon is measured. The process is similar to distillation: requiring a large number of samples, consuming time and effort, and resulting in poor accuracy.
Wen Lixin et al [ "determination of hydrocarbon content in sulfolane as aromatic extraction solvent by gas chromatography", "petrochemical", 2003, 32 (1): 62-64] the hydrocarbon content in sulfolane as aromatic hydrocarbon extraction solvent is determined by gas chromatography. The method is mainly used for carrying out qualitative and quantitative analysis on benzene, toluene, ethylbenzene and m-xylene in aromatic hydrocarbon, and has a small measurement range. In addition, when the solvent contains diesel oil, only the quantitative analysis of the diesel oil can be roughly performed, and the specific composition of the diesel oil hydrocarbon compound in the sample cannot be obtained.
Zhao Huiju et al [ "gas chromatography-mass spectrometry to determine hydrocarbon content in an aromatic extraction sulfolane lean agent", "mass spectrometry report, 2012, 33 (6): 363-369 establishes a method for analyzing the structure and content of each hydrocarbon component in the aromatic hydrocarbon extraction sulfolane lean agent by gas chromatography/mass spectrometry. The method has a small application range, and the determined hydrocarbon only comprises specific aromatic hydrocarbons such as benzene, toluene and the like aiming at the aromatic hydrocarbon extraction sulfolane lean agent, so that the overall composition of the hydrocarbon is incompletely known.
In general, the current methods for hydrocarbon composition in diesel containing polar agents have the advantages of small application range, large sample demand, long time, poor result accuracy and unfriendly environment and operators.
Disclosure of Invention
The purpose of the present disclosure is to provide a method for separating and measuring the content of saturated hydrocarbons and aromatic hydrocarbons in diesel oil containing a polar agent, which can quickly and simply separate and measure the content of saturated hydrocarbons and aromatic hydrocarbons in diesel oil containing a polar agent, and can avoid the interference of the polar agent.
To achieve the above object, a first aspect of the present disclosure provides a method for separating saturated hydrocarbons and aromatic hydrocarbons from diesel oil containing a polar agent, and a method for measuring the content thereof, the method comprising the steps of:
(1) Filling a stationary phase in a solid phase extraction column, and adding a diesel oil sample containing a polar reagent to be detected into the stationary phase;
(2) Washing the stationary phase by sequentially using a first eluent and a second eluent to obtain a first eluent containing saturated hydrocarbon;
(3) Washing the stationary phase obtained in the step (2) by using a third eluent and a fourth eluent in sequence to obtain a second eluent containing aromatic hydrocarbon;
wherein the polar agent comprises one or more of toluene, sulfolane, 3-methyl sulfolane, dimethyl sulfoxide and N, N-dimethyl amide;
the first eluent comprises normal alkane;
the second eluent and the third eluent respectively comprise normal alkane and chlorinated alkane;
the fourth eluent comprises chlorinated alkane and oxygen-containing organic matters;
the chloralkane comprises one or more of chloralkanes with the chlorine atom number of 2-4;
the n-alkane comprises one or more of n-alkanes with the carbon number of 5-7;
the oxygen-containing organic matter comprises one or more of oxygen-containing organic matters with the carbon number of 1-4.
Optionally, in the diesel oil sample containing the polar agent to be detected, the content of the polar agent is 5-95% by volume.
Optionally, in steps (2) and (3), the elution rate is 1-3mL/min.
Optionally, in the second eluent, the volume ratio of the chlorinated alkane to the normal alkane is 1: (1-10);
in the third eluent, the volume ratio of the chlorinated alkane to the normal alkane is 1: (1-10);
in the fourth eluent, the volume ratio of the chlorinated alkane to the oxygen-containing organic is (2-10): 1.
optionally, the n-alkane comprises one or more of n-pentane, n-hexane and n-heptane;
the chlorinated alkane comprises one or more of dichloromethane, trichloromethane and tetrachloromethane;
the oxygen-containing organic matter comprises one or more of alcohol with 1-4 carbon atoms and ester with 3-4 carbon atoms, preferably one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol and ethyl acetate.
Optionally, the weight ratio of the diesel oil sample containing the polar agent to be detected to the stationary phase is 1: (10-120);
the volume ratio of the diesel oil sample containing the polar agent to be detected to the first eluent is 1: (15-125);
the volume ratio of the diesel oil sample containing the polar agent to be detected to the second eluent is 1: (2-30);
the volume ratio of the diesel oil sample containing the polar agent to be detected to the third eluent is 1: (35-150);
the volume ratio of the diesel oil sample containing the polar agent to be detected to the fourth eluent is 1: (2-40).
Optionally, the stationary phase comprises silica gel and/or alumina;
optionally, the specific surface area of the silica gel is 400-750m 2 Per gram, particle size of 0.038-0.15mm, total pore volume of 0.35-0.90cm 3 /g；
Optionally, the specific surface area of the alumina is 80-250m 2 /g, particle size of 0.038-0.15mm.
Optionally, the method further comprises: before step (1), drying the silica gel, wherein the conditions of the drying treatment comprise: the temperature is 100-200 ℃ and the time is 3-8h;
the method further comprises, prior to step (1), subjecting the alumina to a calcination treatment, the conditions of the calcination treatment comprising: the time is 2-6h, and the temperature is 300-500 ℃.
A second aspect of the present disclosure provides a method of determining the content of saturated hydrocarbons and aromatic hydrocarbons in a polar agent-containing diesel fuel, the method comprising: separating a first eluent and a second eluent from the diesel oil sample containing the polar agent to be detected by adopting the separation method of the first aspect of the disclosure;
determining the content of saturated hydrocarbon in the first eluent and the content of aromatic hydrocarbon in the second eluent by adopting gas chromatography-mass spectrometry;
wherein the quantitative method of the gas chromatography-mass spectrometry is an internal standard method.
Optionally, the internal standard adopted by the internal standard method comprises one or more of n-alkanes with carbon atoms of 26-40.
Optionally, the test conditions of the gas chromatograph include: the temperature of the sample inlet is 200-300 ℃, the sample injection amount is 0.1-2.0 mu L, and the split ratio is (10-100): 1, the flow rate of carrier gas is 0.5-1.5mL/min;
the test conditions of the mass spectrum include: the ionization mode is electron ionization, the electron energy is 70eV, the ion source temperature is 200-250 ℃, the scanning mode is a full scanning mode, and the mass scanning range is 50-500amu.
Through the technical scheme, the saturated hydrocarbon and the aromatic hydrocarbon in the diesel oil containing the polar agent are separated by using the specific eluent, the interference of the polar agent is eliminated, the saturated hydrocarbon and the aromatic hydrocarbon in the diesel oil are rapidly and accurately quantitatively analyzed by adopting the gas chromatography-mass spectrometry, and the content can be effectively separated and measured when the content of the polar agent is relatively low.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:
fig. 1 is a FID chromatogram of a first eluent obtained by separating a diesel sample #1 containing a polar agent to be tested in example 1 of the present disclosure.
Fig. 2 is a FID chromatogram of a second eluent obtained by separating a diesel sample #1 containing a polar agent to be tested in example 1 of the present disclosure.
Fig. 3 is a total ion flow chromatogram of a first eluent obtained by separating a diesel sample #1 containing a polar agent to be tested in example 1 of the present disclosure.
Fig. 4 is a total ion flow chromatogram of a second eluent obtained by separating a diesel sample #1 containing a polar agent to be tested in example 1 of the present disclosure.
Fig. 5 is a mass spectrum of a first eluent obtained by separating a diesel sample #1 containing a polar agent to be tested in example 1 of the present disclosure.
Fig. 6 is a mass spectrum of a second eluent obtained by separating a diesel sample #1 containing a polar agent to be tested in example 1 of the present disclosure.
Fig. 7 is a FID chromatogram of a diesel sample #1 to be tested containing a polar agent of comparative example 1 of the present disclosure.
Fig. 8 is a FID chromatogram of a first eluent obtained by separating a diesel fuel sample containing a polar agent to be tested according to comparative example 2 of the present disclosure.
Fig. 9 is a FID chromatogram of a second eluent obtained by separating a diesel fuel sample containing a polar agent to be tested according to comparative example 2 of the present disclosure.
Detailed Description
Specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
A first aspect of the present disclosure provides a method for separating saturated hydrocarbons and aromatic hydrocarbons in a diesel fuel containing a polar agent, the method comprising the steps of:
(1) Filling a stationary phase in a solid phase extraction column, and adding a diesel oil sample containing a polar reagent to be detected into the stationary phase;
(2) Washing the stationary phase by sequentially using a first eluent and a second eluent to obtain a first eluent containing saturated hydrocarbon;
(3) Washing the stationary phase obtained in the step (2) by using a third eluent and a fourth eluent in sequence to obtain a second eluent containing aromatic hydrocarbon;
wherein the polar agent comprises one or more of toluene, sulfolane, 3-methyl sulfolane, dimethyl sulfoxide and N, N-dimethyl amide;
the first eluent comprises normal alkane;
the second eluent and the third eluent respectively comprise normal alkane and chlorinated alkane;
the fourth eluent comprises chlorinated alkane and oxygen-containing organic matters;
the chloralkane comprises one or more of chloralkanes with the chlorine atom number of 2-4;
the n-alkane comprises one or more of n-alkanes with the carbon number of 5-7;
the oxygen-containing organic matter comprises one or more of oxygen-containing organic matters with the carbon number of 1-4.
According to one embodiment of the present disclosure, the method of the present disclosure is applicable to the separation of saturated hydrocarbons and aromatic hydrocarbons of diesel fuels of different contents, different classes of polar agents; in the diesel oil sample containing the polar reagent to be detected, the content of the polar reagent is 5-95% by volume.
In order to ensure efficient separation of saturated hydrocarbons and aromatic hydrocarbons, in steps (2) and (3) the elution rate is 1-3mL/min, preferably 1.5-2mL/min, according to one embodiment of the present disclosure; elution rate refers to the rate of elution of the separated first and second eluents.
According to one embodiment of the disclosure, the first eluent and the second eluent are used for separating saturated hydrocarbon in the diesel oil containing the polar agent, the third eluent and the fourth eluent are used for separating aromatic hydrocarbon in the diesel oil containing the polar agent, and the polar agent in the eluent can not influence the elution and determination of the aromatic hydrocarbon; further, in the second eluent, the volume ratio of chlorinated alkane to normal alkane is 1: (1-10), preferably 1: (1-3); in the third eluent, the volume ratio of chlorinated alkane to normal alkane is 1: (1-10), preferably 1: (1-3); in the fourth eluent, the volume ratio of chloralkane to oxygen-containing organic matter is (2-10): 1, preferably (4-6): 1.
according to one embodiment of the present disclosure, the n-alkanes include one or more of n-pentane, n-hexane, and n-heptane; the chlorinated alkane may be a chlorinated alkane having 1 carbon atom, for example, including one or more of dichloromethane, chloroform and tetrachloromethane; the oxygen-containing organic matter may include alcohols and/or esters, for example, one or more of alcohols having 1 to 4 carbon atoms and esters having 3 to 4 carbon atoms, wherein the alcohols having 1 to 4 carbon atoms may include saturated monohydric alcohols having 1 to 4 carbon atoms and/or saturated dihydric alcohols having 1 to 4 carbon atoms, and the esters having 3 to 4 carbon atoms may be monoesters; further, the oxygen-containing organic matter preferably includes one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, and ethyl acetate, and more preferably includes methanol and/or ethanol.
According to one embodiment of the disclosure, the weight ratio of the diesel fuel sample containing the polar agent to be measured to the stationary phase is 1: (10-120), preferably 1: (30-60); the volume ratio of the diesel oil sample containing the polar agent to be detected to the first eluent is 1: (15-125), preferably 1: (30-50); the volume ratio of the diesel oil sample containing the polar agent to be detected to the second eluent is 1: (2-30), preferably 1: (4-10); the volume ratio of the diesel oil sample containing the polar agent to be detected to the third eluent is 1: (35-150), preferably 1: (40-50); the volume ratio of the diesel oil sample containing the polar agent to be detected to the fourth eluent is 1: (2-40), preferably 1: (4-10).
According to one embodiment of the present disclosure, the stationary phase includes silica gel and/or alumina, and when the stationary phase is silica gel and alumina, the silica gel and alumina may be mixed in any ratio. The silica gel and/or alumina is used as a stationary phase, so that saturated hydrocarbon and aromatic hydrocarbon can be effectively separated.
According to one embodiment of the present disclosure, the silica gel has a specific surface area of 400-750m 2 Preferably 500-650m 2 /g; particle size of 0.038-0.15mm, preferably 0.074-0.15mm; the total pore volume is 0.35-0.90cm 3 Preferably 0.35-0.50 cm/g 3 And/g. Alumina oxideHas a specific surface area of 80-250m 2 Preferably 90-200m 2 /g; the particle size is 0.038-0.15mm, preferably 0.074-0.15mm.
According to one embodiment of the present disclosure, the method of the present disclosure further comprises: before the step (1), drying the silica gel, wherein the drying conditions include: the temperature is 100-200deg.C, preferably 150-200deg.C; the time is 3-8 hours, preferably 5-8 hours.
According to one embodiment of the present disclosure, the method of the present disclosure further comprises: before step (1), roasting the alumina, wherein the roasting condition comprises a temperature of 300-500 ℃, preferably 350-450 ℃; the time is 2-6 hours, preferably 4-6 hours.
According to one embodiment of the disclosure, after filling the stationary phase, adding n-alkane with the carbon number of 5-7 into the solid phase extraction column, wetting the stationary phase, wherein the volume ratio of the sample to be tested to the n-alkane is 1: (5-20).
According to the present disclosure, the first and second eluents are continuously added, the third and fourth eluents are continuously added, i.e., the second eluent is continuously added to the stationary phase immediately after the first eluent has completely entered the stationary phase, and the third eluent is added to the stationary phase when no more eluent flows out; and (3) after the third eluent completely enters the stationary phase, continuing to add the fourth eluent to the stationary phase to obtain the second eluent.
A second aspect of the present disclosure provides a method of determining the content of saturated hydrocarbons and aromatic hydrocarbons in a polar agent-containing diesel fuel, the method comprising: separating a first eluent and a second eluent from the diesel oil sample containing the polar agent to be detected by adopting the separation method of the first aspect of the disclosure;
determining the content of saturated hydrocarbon in the first eluent and the content of aromatic hydrocarbon in the second eluent by adopting gas chromatography-mass spectrometry;
wherein the quantitative method of the gas chromatography-mass spectrometry is an internal standard method.
According to one embodiment of the present disclosure, the internal standard employed by the internal standard method comprises one or more of n-alkanes having 26 to 40 carbon atoms; preferably, n-alkanes having 28 to 32 carbon atoms are included to provide better separation of the internal standard from the sample and solvent peaks in the chromatogram. When in use, the internal standard is preferably dissolved in a solvent to prepare an internal standard solution; further preferably, the solvent comprises one or more of n-pentane, n-hexane and n-heptane; the content of the internal standard substance in the internal standard solution is 0.5 to 10.0 mass%, preferably 0.8 to 3.0 mass%. The volume ratio of the added internal standard solution to the sample is (10-40): 1, preferably (10-20): 1.
according to one embodiment of the present disclosure, conventional gas chromatography and mass spectrometry test conditions may be employed to test the content of saturated hydrocarbons and aromatic hydrocarbons in a diesel sample containing polar agents; in particular, the test conditions for gas chromatography may include: the temperature of the sample inlet is 200-300 ℃, preferably 280-300 ℃; the sample injection amount is 0.1-2.0 mu L, preferably 1.0-1.5 mu L; the split ratio is (10-100): 1, preferably (10-30): 1, a step of; the flow rate of the carrier gas is 0.5-1.5mL/min, preferably 0.8-1.5mL/min; the column box temperature program of the gas chromatograph may be set as: the initial temperature was 60℃for 2min, and the temperature was raised to 300℃at a heating rate of 40℃per min for 5min.
According to one embodiment of the present disclosure, the test conditions of the mass spectrum may include: the ionization mode is Electron Ionization (EI), the electron energy is selected to be 70eV, the ion source temperature is 200-250 ℃, and the preferable temperature is 220-230 ℃; the scanning mode is selected to be a full scanning mode, and the mass scanning range is 50-500amu, preferably 50-300amu.
The method for separating and measuring saturated hydrocarbons and aromatic hydrocarbons in the diesel fuel containing polar agent of the present application is described below by way of example, but not limited thereto.
The reagents used in the examples and comparative examples are commercially available without any particular explanation.
The diesel oils used in the examples and comparative examples were supplied from the institute of petrochemical industry, china petrochemical industry, inc., and the distillation range was in the range of 170-365 ℃.
The silica gel used in examples and comparative examples was silica gel produced by Qingdao ocean chemical plant division, and had a particle size of 0.074-0.15mm and a total pore volume of 0.36cm 3 Per gram, specific surface area 635m 2 /g。
The alumina used in examples and comparative examples was neutral alumina for column chromatography, produced by national medicine group chemical reagent Co., ltd. Particle size of 0.074-0.150mm and specific surface area of 152m 2 /g。
The model of the gas chromatograph-mass spectrometer is 7890GC/5975MS.
Gas chromatography conditions: the temperature of the sample inlet is 300 ℃, the sample feeding amount is 1.0 mu L, the split ratio is 10:1, the temperature of the column box is set to be 60 ℃ at the initial temperature, the temperature is kept for 2min, the temperature is raised to 300 ℃ at 40 ℃/min, the temperature is kept for 5min, and the carrier gas flow rate is 1.5mL/min.
The mass spectrum condition is ionization type EI, electron energy is selected to be 70eV, ion source temperature is 220 ℃, solvent delay is 2.5min, scanning mode is selected to be full scanning mode, and mass scanning range is 50-300amu.
In examples and comparative examples, in the gas chromatography-mass spectrometry total ion flow chromatogram and the FID chromatogram, the ordinate is the relative adsorption amount, and the abscissa is the retention time in min. In the mass spectrum, the ordinate is abundance, and the abscissa is mass-to-charge ratio (m/z).
Example 1
The silica gel was dried at 150℃for 5h to give an activated silica gel for use.
Preparing a diesel oil sample containing a polar reagent to be tested: sulfolane was added to diesel sample a to prepare sample #1 containing 10% by volume sulfolane.
The method comprises the following steps of separating and measuring saturated hydrocarbon and aromatic hydrocarbon in a diesel oil sample containing a polar agent to be measured:
(1) Filling 1.5g of silica gel as a stationary phase in a solid phase extraction column, wetting the solid phase extraction column with 0.5mL of n-hexane, taking 50 mu L of the sample #1, and adding the sample #1 into the solid phase extraction column;
(2) After the diesel oil sample is completely adsorbed by the stationary phase, the solid phase extraction column is washed by using 2mL of normal hexane as a first eluent, and after the normal hexane just completely enters the stationary phase, the volume ratio of 0.5mL is 1:1 as a second eluent, continuing to wash the stationary phase at an elution speed of 2mL/min to obtain a first eluent containing saturated hydrocarbon;
(3) The volume ratio of 2mL is 1:1 as a third eluent, 0.5mL volume ratio is 5:1 as a fourth eluent, washing the stationary phase obtained in the step (2) at an elution speed of about 2mL/min to obtain a second eluent containing aromatic hydrocarbon;
wherein, the weight ratio of the sample to be measured to the stationary phase is 1:30, the volume ratio of the sample to be tested to the first eluent is 1:40, the volume ratio of the sample to be tested to the second eluent is 1:10, the volume ratio of the sample to be tested to the third eluent is 1:40, the volume ratio of the sample to be tested to the fourth eluent is 1:10, in the step (1), the volume ratio of the sample to be detected to the normal alkane is 1:10;
(4) Respectively adding 1mL of internal standard solution into the first eluent and the second eluent for gas chromatography-mass spectrometry detection; the internal standard solution is prepared by dissolving n-triacontane in n-hexane, wherein the content of the n-triacontane is 1 mass percent, and the volume ratio of the internal standard solution to a sample is 20:1, a step of;
(5) Subjecting the obtained first and second eluents to chromatographic test, wherein FID chromatograms are shown in figures 1 and 2, and total ion flow chromatograms are shown in figures 3 and 4;
(6) The saturated hydrocarbon and aromatic hydrocarbon contents were calculated to be 79.4 mass% and 20.6 mass%, respectively, based on the SH/T0606 method and the obtained FID chromatogram;
(7) According to the total ion flow chromatograms, mass chromatograms of saturated hydrocarbon and aromatic hydrocarbon in diesel are obtained, as shown in fig. 5 and 6 respectively, and hydrocarbon content in a diesel sample containing polar agent is calculated according to the SH/T0606 method. The comparison result of the measurement result and the actual content of the sample is shown in Table 1.
TABLE 1
According to fig. 1 and 2, the first eluent and the second eluent do not contain sulfolane, which indicates that the method disclosed by the disclosure can effectively separate saturated hydrocarbon and aromatic hydrocarbon in diesel oil containing polar agent, is not affected by the polar agent, and avoids the interference of the polar agent in the sample on the determination of hydrocarbon components.
From the data in table 1, it can be seen that the method for separating and determining the saturated hydrocarbon and aromatic hydrocarbon content in the diesel oil sample containing the polar agent by using the method disclosed by the invention is very similar to the saturated hydrocarbon and aromatic hydrocarbon content in the diesel oil as it is, and the absolute error of the measured hydrocarbon composition content is between 0 and 0.4 mass%, which indicates that the method disclosed by the invention has good separation effect on the saturated hydrocarbon and aromatic hydrocarbon in the diesel oil sample containing the polar agent, and the accuracy of the content determination result is high and is not influenced by the polar agent.
The above results demonstrate that the methods of the present disclosure are applicable to the determination of hydrocarbon composition in diesel fuel containing polar agents. Meanwhile, the separation and measurement method provided by the disclosure is simple and rapid to operate, small in sample and reagent volumes for analysis and friendly to operators and environment.
Comparative example 1
Sample #1 was directly subjected to gas chromatography-mass spectrometry without separation, and the FID chromatogram is shown in fig. 7.
From fig. 7, it can be seen that the peak time of sulfolane coincides with the peak time of a portion of the hydrocarbon compounds in the diesel, indicating that sulfolane cannot be effectively separated from the hydrocarbon compounds in the diesel sample by the instrument alone. In addition, the peak area of sulfolane is much larger than that of hydrocarbon compounds, i.e. the sulfolane has a higher response in FID than hydrocarbon compounds, and thus the presence of trace amounts of sulfolane also interferes with the determination of hydrocarbon compounds in diesel samples. The method disclosed by the disclosure is suitable for separating and measuring the content of hydrocarbon compounds in diesel oil containing trace polar reagents.
Example 2
This example illustrates the good reproducibility of the measurement of saturated hydrocarbons and aromatic hydrocarbons in diesel fuel containing polar agents using the methods of the present disclosure.
Sample preparation: and respectively adding different polar reagents into the diesel oil sample B to prepare a diesel oil sample #2 containing 50% by volume of the polar reagent to be detected, wherein the polar reagent is toluene.
The hydrocarbon composition of the polar agent-containing diesel fuel samples was analyzed by the method of example 1, the samples were repeatedly separated 3 times, and the measurement results are shown in table 2.
TABLE 2
From the data in table 2, it can be seen that the saturated hydrocarbon and aromatic hydrocarbon contents in the polar agent-containing diesel oil samples measured by the method of the present disclosure have high reproducibility, the absolute error of the three repeated experiments from the original is 0 to 0.4 mass%, and the Relative Standard Deviation (RSD) is in the range of 0 to 5.41%.
The above results indicate that the methods of the present disclosure are particularly well reproducible and can be used for analysis of hydrocarbon composition in diesel samples containing polar agents.
Example 3
This example illustrates that saturated hydrocarbons and aromatic hydrocarbons in diesel fuel containing different types of polar agents can be separated and content determined using the methods of the present disclosure.
Sample preparation: and respectively adding different polar reagents into the diesel oil sample A to prepare diesel oil samples #3, #4, #5, #6 and #7 containing 10% by volume of polar reagents to be detected, wherein the polar reagents are toluene, sulfolane, 3-methyl sulfolane, dimethyl sulfoxide and N, N-dimethyl amide respectively.
The hydrocarbon composition of the diesel fuel samples containing different polarity reagents was analyzed by the method of example 1. The results of comparison of the measurement results with the actual content of the sample are shown in tables 3 and 4.
TABLE 3 Table 3
TABLE 4 Table 4
From the data in tables 3 and 4, it can be seen that the saturated hydrocarbon and aromatic hydrocarbon contents in the samples of the diesel oil containing the polar agent, which were measured by the method of the present disclosure, were very close to the saturated hydrocarbon and aromatic hydrocarbon contents in the diesel oil as it is, with an absolute error of 0 to 0.9 mass%, and the accuracy was high.
The results show that the method disclosed by the invention is applicable to diesel oil samples containing different types of polar agents, has wide applicability, and can meet the analysis of hydrocarbon compositions in diesel oil containing polar agents in different processes in actual production.
Example 4
This example illustrates that the methods of the present disclosure are useful for separating and determining saturated hydrocarbons and aromatic hydrocarbons in diesel fuels containing varying amounts of polar agents.
Sample preparation: different volumes of toluene were added to diesel sample a to prepare diesel samples #8, #9, #10, #11, #12, #13 containing 5%, 10%, 50%, 80%, 90% and 95% by volume of toluene, respectively.
The hydrocarbon composition of the above diesel fuel samples was analyzed as described in example 1. The results of comparison of the measurement results with the actual content of the sample are shown in tables 5 and 6.
TABLE 5
TABLE 6
The results show that the method disclosed by the invention is used for separating and measuring the content of saturated hydrocarbon and aromatic hydrocarbon in a diesel oil sample with the toluene content ranging from 5 to 95 percent by volume, and the results are not influenced. Meanwhile, as can be seen from the data of tables 5 and 6, the results of determining the hydrocarbon composition in the diesel oil sample containing the polar agent by the method of the present disclosure are close to the results of determining the hydrocarbon composition in the diesel oil as it is, and the accuracy is high.
The results show that the method disclosed by the invention is suitable for separating and measuring the content of saturated hydrocarbon and aromatic hydrocarbon in diesel oil containing different polar reagents, and has accurate measurement results and wide applicability.
Example 5
This example is intended to illustrate that the method provided by the present invention is applicable to different types of diesel fuel samples.
Sample preparation: to 900. Mu.L of diesel C, D, E and F, G having aromatic hydrocarbon contents of 8.6 mass%, 20.1 mass%, 42.5 mass%, 63.2 mass% and 86.8 mass%, respectively, 100. Mu.L of sulfolane was added to prepare diesel samples #14, #15, #16, #17 and #18 containing 10% by volume of sulfolane.
The hydrocarbon composition of the above diesel fuel samples was analyzed as in example 1. The results of comparison of the measurement results with the actual content of the sample are shown in tables 7 and 8.
TABLE 7
TABLE 8
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From the data in tables 7 and 8, it can be seen that the results of hydrocarbon composition in the different types of diesel fuel samples measured using the methods of the present disclosure are close to the as-received results of diesel fuel, with high accuracy, indicating that the methods of the present disclosure are applicable to analysis of hydrocarbon composition in different types of diesel fuel.
Example 6
This example is used to illustrate the applicability of the solid phase extraction column packing in the method provided by the invention.
The saturated hydrocarbons and aromatic hydrocarbons in the diesel oil sample #1 were separated and content-measured by the method of example 1, except that alumina was calcined at 400 c for 4 hours to obtain activated alumina, and the result of comparison of the measurement result with the actual content of the sample using alumina as a stationary phase is shown in table 9.
TABLE 9
| Sample name | A | #1 | - |
| Polar agent | Without any means for | Sulfolane (TMP) | - |
| - | - | - | Absolute error/mass% |
| Paraffin content/mass% | 45.2 | 45.3 | 0.1 |
| Content of cycloalkane/mass% | 19.4 | 19.4 | 0 |
| Content/mass% of bicycloalkane | 11.0 | 10.3 | 0.7 |
| Content/mass% of tricycloparaffins | 3.7 | 3.6 | 0.1 |
| Content of Total cycloalkane/mass% | 34.1 | 33.3 | 0.8 |
| Content of total saturated hydrocarbons/mass% | 79.3 | 78.6 | 0.7 |
| Content of alkylbenzene/mass% | 9.0 | 9.1 | 0.1 |
| Indane or tetrahydronaphthalene content/mass% | 6.9 | 7.2 | 0.3 |
| Indenes and/or C n H 2n-10 Content/mass% | 2.5 | 2.6 | 0.1 |
| Content/mass% of total monocyclic aromatic hydrocarbons | 18.4 | 18.9 | 0.5 |
| Naphthalene content/mass% | 0.2 | 0.2 | 0 |
| Naphthalene content/mass% | 0.7 | 0.8 | 0.1 |
| Acenaphthenes and/or C n H 2n-l4 Content/mass% | 0.5 | 0.6 | 0.1 |
| Fluorenes and/or C n H 2n-l6 Content/mass% | 0.7 | 0.7 | 0 |
| Content/mass of total bicyclic aromatic hydrocarbons％ | 2.1 | 2.3 | 0.2 |
| Content/mass% of tricyclic aromatic hydrocarbons | 0.2 | 0.2 | 0 |
| Content of total aromatic hydrocarbons/mass% | 20.7 | 21.4 | 0.7 |
As can be seen from the data in Table 9, the use of alumina as a solid phase extraction column packing is equally suitable for separating saturated hydrocarbons and aromatic hydrocarbons from a sample of diesel fuel containing a polar agent, the results of which are very close to the saturated hydrocarbons and aromatic hydrocarbons content of the diesel fuel as it is, with an absolute error of 0 to 0.8 mass%.
Comparative example 2
The diesel oil sample containing 3-methyl sulfolane was analyzed according to the diesel oil hydrocarbon composition determination method in SH/T0606 method, and FID chromatograms obtained are shown in FIGS. 8 and 9, respectively.
As a result, it was found that the peak position of 3-methyl sulfolane in FIG. 9 coincides with a part of aromatic hydrocarbon, indicating that a large amount of 3-methyl sulfolane is mixed in the separated aromatic hydrocarbon component, which interferes with the next calculation of hydrocarbon compounds. Therefore, the existing method for separating and measuring the content of saturated hydrocarbon and aromatic hydrocarbon in diesel oil without polar agent cannot be applied to the separation and measuring the content of saturated hydrocarbon and aromatic hydrocarbon in diesel oil with polar agent.
According to the embodiment and the comparative example, the method adopts a solid-phase extraction method-GC/MS method to analyze the hydrocarbon composition in the diesel oil containing the polar agent, can avoid the interference of the polar agent on the measurement of the hydrocarbon composition of the diesel oil, and has simple operation, accurate result and wide application range.
The preferred embodiments of the present disclosure have been described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations are not described further in this disclosure in order to avoid unnecessary repetition.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (11)
1. A method for separating saturated hydrocarbon and aromatic hydrocarbon in diesel oil containing polar agent, which is characterized by comprising the following steps:
(1) Filling a stationary phase in a solid phase extraction column, and adding a diesel oil sample containing a polar reagent to be detected into the stationary phase;
(2) Washing the stationary phase by sequentially using a first eluent and a second eluent to obtain a first eluent containing saturated hydrocarbon;
(3) Washing the stationary phase obtained in the step (2) by using a third eluent and a fourth eluent in sequence to obtain a second eluent containing aromatic hydrocarbon;
wherein the polar agent comprises one or more of toluene, sulfolane, 3-methyl sulfolane, dimethyl sulfoxide and N, N-dimethyl amide;
the first eluent comprises normal alkane;
the second eluent and the third eluent respectively comprise normal alkane and chlorinated alkane;
the fourth eluent comprises chlorinated alkane and oxygen-containing organic matters;
the chloralkane comprises one or more of chloralkanes with the chlorine atom number of 2-4;
the n-alkane comprises one or more of n-alkanes with the carbon number of 5-7;
the oxygen-containing organic matter comprises one or more of oxygen-containing organic matters with the carbon number of 1-4.
2. The separation method according to claim 1, wherein the content of the polar agent in the diesel fuel sample containing the polar agent to be measured is 5 to 95% by volume.
3. The separation method according to claim 1, wherein in the steps (2) and (3), the elution rate is 1 to 3mL/min.
4. The separation method according to claim 1, wherein in the second eluent, a volume ratio of the chlorinated alkane to the normal alkane is 1: (1-10);
in the third eluent, the volume ratio of the chlorinated alkane to the normal alkane is 1: (1-10);
in the fourth eluent, the volume ratio of the chlorinated alkane to the oxygen-containing organic is (2-10): 1.
5. the separation method according to claim 1, wherein the n-alkane comprises one or more of n-pentane, n-hexane and n-heptane;
the chlorinated alkane comprises one or more of dichloromethane, trichloromethane and tetrachloromethane;
the oxygen-containing organic matter comprises one or more of alcohol with 1-4 carbon atoms and ester with 3-4 carbon atoms, preferably one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol and ethyl acetate.
6. The separation method according to claim 1, wherein the weight ratio of the diesel fuel sample containing the polar agent to be measured to the stationary phase is 1: (10-120);
the volume ratio of the diesel oil sample containing the polar agent to be detected to the first eluent is 1: (15-125);
the volume ratio of the diesel oil sample containing the polar agent to be detected to the second eluent is 1: (2-30);
the volume ratio of the diesel oil sample containing the polar agent to be detected to the third eluent is 1: (35-150);
the volume ratio of the diesel oil sample containing the polar agent to be detected to the fourth eluent is 1: (2-40).
7. The separation method of claim 1, wherein the stationary phase comprises silica gel and/or alumina;
optionally, the specific surface area of the silica gel is 400-750m 2 Per gram, particle size of 0.038-0.15mm, total pore volume of 0.35-0.90cm 3 /g；
Optionally, the specific surface area of the alumina is 80-250m 2 /g, particle size of 0.038-0.15mm.
8. The separation method of claim 7, wherein the method further comprises: before step (1), drying the silica gel, wherein the conditions of the drying treatment comprise: the temperature is 100-200 ℃ and the time is 3-8h;
the method further comprises, prior to step (1), subjecting the alumina to a calcination treatment, the conditions of the calcination treatment comprising: the time is 2-6h, and the temperature is 300-500 ℃.
9. A method for determining the content of saturated hydrocarbons and aromatic hydrocarbons in a diesel fuel containing a polar agent, the method comprising: separating a first eluent and a second eluent from the diesel fuel sample containing the polar agent to be detected by adopting the separation method of any one of claims 1 to 8;
determining the content of saturated hydrocarbon in the first eluent and the content of aromatic hydrocarbon in the second eluent by adopting gas chromatography-mass spectrometry;
wherein the quantitative method of the gas chromatography-mass spectrometry is an internal standard method.
10. The method of claim 9, wherein the internal standard used in the internal standard method comprises one or more of n-alkanes having 26-40 carbon atoms.
11. The method of claim 9, wherein the test conditions of the gas chromatograph comprise: the temperature of the sample inlet is 200-300 ℃, the sample injection amount is 0.1-2.0 mu L, and the split ratio is (10-100): 1, the flow rate of carrier gas is 0.5-1.5mL/min;
the test conditions of the mass spectrum include: the ionization mode is electron ionization, the electron energy is 70eV, the ion source temperature is 200-250 ℃, the scanning mode is a full scanning mode, and the mass scanning range is 50-500amu.
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