CN111423900B - Method for derivatization and separation of sulfur-containing compound alkyl in petroleum component - Google Patents
Method for derivatization and separation of sulfur-containing compound alkyl in petroleum component Download PDFInfo
- Publication number
- CN111423900B CN111423900B CN202010263556.5A CN202010263556A CN111423900B CN 111423900 B CN111423900 B CN 111423900B CN 202010263556 A CN202010263556 A CN 202010263556A CN 111423900 B CN111423900 B CN 111423900B
- Authority
- CN
- China
- Prior art keywords
- petroleum
- sulfur
- petroleum component
- component
- hexane
- 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.)
- Active
Links
- 239000003208 petroleum Substances 0.000 title claims abstract description 51
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 39
- 239000011593 sulfur Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000001212 derivatisation Methods 0.000 title claims abstract description 21
- 238000000926 separation method Methods 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 150000003568 thioethers Chemical class 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 17
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 silver hexafluoroantimonate Chemical compound 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000002168 alkylating agent Substances 0.000 claims abstract description 7
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229930192474 thiophene Natural products 0.000 claims abstract description 7
- 150000003577 thiophenes Chemical class 0.000 claims abstract description 7
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 45
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- MVXVYAKCVDQRLW-UHFFFAOYSA-N 1h-pyrrolo[2,3-b]pyridine Chemical compound C1=CN=C2NC=CC2=C1 MVXVYAKCVDQRLW-UHFFFAOYSA-N 0.000 claims description 12
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 10
- 239000010779 crude oil Substances 0.000 claims description 9
- 238000010898 silica gel chromatography Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical group IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000003209 petroleum derivative Substances 0.000 claims description 2
- 230000002152 alkylating effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000017858 demethylation Effects 0.000 abstract description 2
- 238000010520 demethylation reaction Methods 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- 239000002283 diesel fuel Substances 0.000 description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000004252 FT/ICR mass spectrometry Methods 0.000 description 5
- 238000000132 electrospray ionisation Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229930182555 Penicillin Natural products 0.000 description 4
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 229940049954 penicillin Drugs 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical class S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000002035 hexane extract Substances 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/26—Halogenated hydrocarbons
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Pathology (AREA)
- Immunology (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention provides a method for alkyl derivatization and separation of sulfur-containing compounds in petroleum components. The method comprises the following steps: dissolving a petroleum component in an organic solvent; adding an alkylating agent and silver hexafluoroantimonate into the dissolved petroleum component, and carrying out alkylation reaction for 20min-6h at the temperature of 0-80 ℃ to complete alkyl derivatization of the sulfur-containing compound in the petroleum component. The resulting sulfonium salt can be used to analyze the molecular composition of sulfur-containing compounds in petroleum; high purity thioethers and thiophenes can be isolated by selective stepwise demethylation. The derivatization method of the sulfur-containing compound in the petroleum component provided by the invention has the advantages of high reaction speed and high conversion rate.
Description
Technical Field
The invention relates to a separation method of sulfur-containing compounds in petroleum components, belonging to the technical field of petroleum component separation.
Background
In oil exploration research, sulfur-containing compounds contain important geochemical information such as oil deposition environment, thermal maturity and the like; in the petroleum processing process, sulfide can bring equipment corrosion, and the sulfide can bring serious environmental problems after combustion, so the removal of sulfide is always an important task in petroleum processing. The method has important significance for exploration, development, processing and utilization of petroleum by representing the molecular composition of sulfide of petroleum.
The sulfur-containing compound has complex composition and huge content difference, and the analysis of the molecular composition of the sulfur-containing compound from a complex petroleum matrix is an important task of petroleum composition analysis. The gas chromatography combined with a sulfur selectivity detector can obtain the composition information of sulfur-containing compounds in petroleum components, but is limited to volatile sulfides, and the amount of identifiable compounds is very limited. The most effective method for analyzing the molecular composition of sulfur-containing compounds in heavy oil is high-resolution mass spectrometry. The sulfides that are the highest in petroleum are thiophenic and thioether sulfides, but these compounds are not ionizable in conventional electrospray ionization sources and therefore must be converted to the sulfonium methyl salt prior to analysis. The general method for realizing methylation adopts methyl iodide and silver tetrafluoroborate as methyl derivatization reagents, the method is successfully used for analyzing the molecular composition of sulfides in various petroleum components, but derivatization reaction generally needs 1-2 days, even multiple reactions are needed to achieve higher conversion rate, and the application of the method is influenced by overlong reaction time.
Disclosure of Invention
It is an object of the present invention to provide a method for rapidly derivatizing sulfur-containing compounds in petroleum components, which enables rapid alkyl derivatization of sulfide molecules in petroleum.
It is another object of the present invention to provide a method for analyzing sulfur-containing compounds in petroleum components by excessively rapid derivatization, which enables rapid analysis of the molecular composition of sulfides in petroleum.
In order to achieve the above object, the present invention provides a method for alkyl-derivatizing a sulfur-containing compound in a petroleum fraction, wherein the method comprises the steps of:
dissolving a petroleum component in an organic solvent;
adding an alkylating agent and silver hexafluoroantimonate into the dissolved petroleum component, and carrying out alkylation reaction for 20min-6h at the temperature of 0-80 ℃ to complete alkyl derivatization of the sulfur-containing compound in the petroleum component.
In one embodiment of the present invention, the organic solvent is used in an amount of 1 to 20 times the volume of the petroleum component.
In one embodiment of the present invention, the amount of alkylating agent used is 5 to 20 times the total molar amount of sulfur in the petroleum component.
In the inventive process, silver hexafluoroantimonate is used as catalyst. In one embodiment of the present invention, the amount of silver hexafluoroantimonate used is 5 to 20 times the total molar amount of sulfur in the petroleum component.
In one embodiment of the invention, the alkylating agent used is methyl iodide or ethyl bromide. When methyl iodide is used as the alkylating agent, a methyl sulfonium salt is obtained.
In a specific embodiment of the invention, the organic solvent used is one or a mixture of ethanol, dichloromethane or dichloroethane.
In one embodiment of the invention, the petroleum component employed comprises petroleum crude oil and/or petroleum products; preferably, the petroleum component is one or a combination of several of crude oil, diesel oil fraction and vacuum gas oil fraction. Wherein the total sulfur content of the petroleum component is 0.001wt% to 8.0 wt%.
The samples after methyl derivatization treatment can be directly subjected to electrospray mass spectrometry, and preferably, the mass spectrometer used is a high-resolution mass spectrometer. More preferably, the mass spectrometer employed is a fourier transform ion cyclotron resonance mass spectrometer or an electric field orbitrap mass spectrometer.
In order to achieve the above technical objects, the present invention also provides a method for separating sulfur-containing compounds from petroleum components, comprising the steps of:
according to the method, alkyl derivatization of sulfur-containing compounds in the petroleum component is completed to obtain sulfonium salt;
dissolving sulfonium salt in acetonitrile, adding 7-azaindole, stirring for 24h, extracting and separating by n-hexane, combining n-hexane phases and concentrating; purifying by silica gel column chromatography to obtain thiophene compounds;
adding 4-dimethylaminopyridine into the acetonitrile solution extracted by the normal hexane, reacting for 12 hours under heating reflux, and cooling to room temperature; adding dilute hydrochloric acid aqueous solution, extracting the obtained solution by using normal hexane, and separating liquid; and mixing the normal hexane phases, concentrating, and purifying by silica gel column chromatography to obtain the thioether compounds.
In one embodiment of the invention, the 7-azaindole has an equivalent weight of 5mol to 20mol (10 mol); the equivalent weight of 4-dimethylaminopyridine added is 5-20 mol (10 mol).
Specifically, the step of further separating the sulfur-containing compounds from the derivatized sulfonium salt comprises:
the method comprises the following steps: centrifuging and precipitating the reaction mixture, and removing the generated silver iodide precipitate;
step two: volatilizing to remove the solvent;
step three: n-hexane washes away the hydrocarbon substrate to give an insoluble sulfonium salt;
step four: the sulfonium salt was dissolved in acetonitrile, 5mol-20mol equivalents of 7-azaindole was added and stirred at room temperature for 24 h. After the reaction is finished, extracting by using normal hexane (3X 10mL) and separating liquid, combining normal hexane phases and concentrating; purification by silica gel column chromatography (10g silica gel, 200mL n-hexane as eluent) gave thiophenes.
Step five: adding 5-20 mol equivalent of 4-dimethylamino pyridine into acetonitrile solution extracted by n-hexane, heating the obtained solution to reflux for reaction for 12h, and cooling to room temperature. A dilute aqueous hydrochloric acid solution (2mol/L) was added thereto, and the resulting solution was extracted with n-hexane and separated. The combined n-hexane phases were concentrated by a rotary distillation apparatus and purified by silica gel column chromatography (10g of silica gel, 200mL of n-hexane as eluent) to obtain a thioether compound.
The method for derivatizing the sulfur-containing compound in the petroleum component can quickly convert the sulfur-containing compound in the petroleum into the sulfonium salt, thereby realizing the mass spectrum analysis of the molecular composition of the sulfur-containing compound or the selective separation of sulfide and thiophene sulfides (the conversion rate of the sulfide and thiophene compounds in distillate is more than 90 percent). Has good applicability to crude oil, diesel oil fraction, vacuum gas oil fraction and the like. The method has the advantages of short reaction time and strong stability, and simultaneously solves the problem of analysis of the composition of trace sulfide-containing molecules in the refined oil product.
Drawings
FIG. 1 is a carbon number and DBE distribution diagram of sulfides in diesel oil of VI of some country obtained by analyzing sulfides in diesel oil of VI of some country through a positive ion electrospray ionization source and a Fourier transform ion cyclotron resonance mass spectrum through a methyl derivatization reaction in example 1.
FIG. 2 is a carbon number and DBE distribution diagram of sulfides in Kowitt crude oil analyzed by a positive ion electrospray ionization source in combination with Fourier transform ion cyclotron resonance mass spectrometry through a methyl derivatization reaction in example 2.
FIG. 3 is a GC-MS total ion chromatogram and mass chromatogram of the thiophene component and the thioether component separated by methyl derivatization and demethylation of example 3.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a method for methyl derivatization and molecular composition analysis of sulfur-containing compounds in refined diesel oil, which comprises the following specific steps:
firstly, 0.1 g of national VI diesel oil with the total sulfur content of 10ppm and 1 ml of dichloromethane are added into a 2 ml penicillin bottle, then 0.1 g of silver hexafluoroantimonate is added, 0.2 ml of methyl iodide is added by a syringe, and the penicillin bottle with a stopper is stirred and reacted for 2 hours under the condition of keeping out of the sun.
And (2) dissolving 20 mu L of supernatant into a mixed solvent (volume ratio is 1:3) of toluene and methanol, and using the mixed solvent for positive ion electrospray ionization source combined with Fourier transform ion cyclotron resonance mass spectrometry, wherein the operating conditions of the analysis are conventional in the field, and the molecular composition of sulfide in the obtained national VI diesel oil is counted and calculated and is shown in figure 1. DBE is the number of equivalent double bonds, i.e., the number of rings and the total number of double bonds in the molecule. It can be seen from fig. 1 that the carbon number distribution range of the sulfides in diesel oil of country vi is 15 to 28, DBE is mainly focused on 3 to 9, wherein DBE 6 and DBE 9 are the main components, and correspond to benzothiophenes and dibenzothiophenes, respectively, indicating that the sulfides that are difficult to be removed in refined diesel oil are mainly dibenzothiophenes of C15 to C20.
Example 2
This example provides an example of the analysis of the composition of sulfur-containing compounds in kowitte crude oil based on the methyl derivatization method of the present invention, which comprises the following steps:
first, 10mg of crude kowitt oil having a total sulfur content of 3.5 wt% and 1 ml of methylene chloride were put into a 2 ml penicillin bottle, 50 mg of silver hexafluoroantimonate was added, 0.1 ml of methyl iodide was added by a syringe, and the stopper-covered penicillin bottle was stirred in the dark for 20 minutes.
20 μ L of the supernatant was dissolved in a mixed solvent of toluene and methanol (volume ratio: 1:3) and used for positive ion electrospray ionization source combined with fourier transform ion cyclotron resonance mass spectrometry under the operating conditions conventionally used in the art, and the molecular composition of sulfides in the obtained kowitt crude oil was statistically calculated and shown in fig. 2. It can be seen from fig. 2 that the carbon number distribution of sulfides in the kowitt crude oil ranges from 15 to 50, DBE is mainly concentrated in 1 to 15, wherein the sulfides of DBE ═ 1 to 5 are cycloalkyl sulfides or aromatic substituted sulfides with 1 to 5 rings. The most abundant sulfides have DBEs of 6 and 9, corresponding to benzothiophenes and dibenzothiophenes, respectively.
Example 3
This example provides an example of analyzing sulfur-containing compounds of sulfides and thiophenes in kowitte VGO based on the methyl derivatization method of the present invention, which comprises the following specific steps:
first, 200mg of kowitt VGO and 20 ml of dichloromethane were added to a 40 ml vial, followed by addition of 0.3g of silver hexafluoroantimonate, addition of 0.5 ml of methyl iodide by a syringe, and the vial with the stopper was stirred under protection from light for 0.5 hour.
After completion of the reaction, the reaction mixture was filtered to remove the silver iodide precipitate, and the dichloromethane in the filtrate was removed by a rotary distillation apparatus. To the remaining oil was added 10mL of n-hexane, vigorously shaken and then cooled to 0 ℃. The sulfonium salt would precipitate under these conditions and accumulate at the bottom of the bottle under centrifugal conditions. The polar sulfonium salt can be isolated by decanting to an unreacted oil phase dissolved in n-hexane. This step was repeated 5 times to ensure that the sulfonium salt was free of unreacted oil phase.
The isolated sulfonium salt was dissolved in 5mL acetonitrile and 0.3g of 7-azaindole was added. The reaction was stirred at room temperature for 48h, extracted with n-hexane (3X 10mL) and separated. The n-hexane extracts were combined, concentrated and purified by silica gel column chromatography (5g silica gel, eluent 100mL n-hexane) to obtain thiophenes.
To the remaining acetonitrile phase was added 0.3g of 4-dimethylaminopyridine, and the resulting solution was reacted under reflux for 12 hours and then cooled to room temperature. 5mL of a dilute aqueous hydrochloric acid solution (2mol/L) was added thereto, and the resulting solution was extracted with n-hexane (3X 10mL) and separated. The n-hexane phases were combined and concentrated by a rotary distillation apparatus, and the thioether contained therein was purified by silica gel column chromatography (5g of silica gel, eluent 100mL of n-hexane).
The obtained thioether and thiophene components have the mass of 8.0mg and 37.2mg respectively, the sulfur content is 10.12 wt% and 11.06 wt% respectively, the separated components are subjected to GC-MS analysis respectively, and a total ion current chromatogram and a mass chromatogram are shown in figure 3, which indicates that the separated sulfide component has very high purity.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010263556.5A CN111423900B (en) | 2020-04-07 | 2020-04-07 | Method for derivatization and separation of sulfur-containing compound alkyl in petroleum component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010263556.5A CN111423900B (en) | 2020-04-07 | 2020-04-07 | Method for derivatization and separation of sulfur-containing compound alkyl in petroleum component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111423900A CN111423900A (en) | 2020-07-17 |
| CN111423900B true CN111423900B (en) | 2021-03-30 |
Family
ID=71557548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010263556.5A Active CN111423900B (en) | 2020-04-07 | 2020-04-07 | Method for derivatization and separation of sulfur-containing compound alkyl in petroleum component |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111423900B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114878725B (en) * | 2021-06-22 | 2023-08-11 | 长春大学 | Method for detecting sulfur dioxide in food |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2840917A1 (en) * | 2002-06-17 | 2003-12-19 | Inst Francais Du Petrole | Process for elimination of sulfur and nitrogen compounds from fluid catalytic cracking petrol and middle distillate hydrocarbon cuts by alkylation and extraction with a non-aqueous polar ionic solvent |
| CN103756719A (en) * | 2014-01-26 | 2014-04-30 | 中国石油天然气集团公司 | Method for separating sulfo compound in petroleum component |
| CN104745227A (en) * | 2015-04-01 | 2015-07-01 | 中国石油天然气集团公司 | Method for separating and analyzing non-alkaline nitrogen compound in petroleum component |
| CN105510456A (en) * | 2015-11-27 | 2016-04-20 | 中国石油天然气股份有限公司 | Method for determining high-maturity condensate oil source |
| CN105510561A (en) * | 2015-12-01 | 2016-04-20 | 中国石油天然气股份有限公司 | Method for determining oil source by using sulfur isotope in crude oil monomer sulfur-containing compound |
| CN106349184A (en) * | 2016-08-08 | 2017-01-25 | 江西师范大学 | Preparation method of 2- (ortho-alkylaryl) benzothiazole series |
-
2020
- 2020-04-07 CN CN202010263556.5A patent/CN111423900B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2840917A1 (en) * | 2002-06-17 | 2003-12-19 | Inst Francais Du Petrole | Process for elimination of sulfur and nitrogen compounds from fluid catalytic cracking petrol and middle distillate hydrocarbon cuts by alkylation and extraction with a non-aqueous polar ionic solvent |
| CN103756719A (en) * | 2014-01-26 | 2014-04-30 | 中国石油天然气集团公司 | Method for separating sulfo compound in petroleum component |
| CN104745227A (en) * | 2015-04-01 | 2015-07-01 | 中国石油天然气集团公司 | Method for separating and analyzing non-alkaline nitrogen compound in petroleum component |
| CN105510456A (en) * | 2015-11-27 | 2016-04-20 | 中国石油天然气股份有限公司 | Method for determining high-maturity condensate oil source |
| CN105510561A (en) * | 2015-12-01 | 2016-04-20 | 中国石油天然气股份有限公司 | Method for determining oil source by using sulfur isotope in crude oil monomer sulfur-containing compound |
| CN106349184A (en) * | 2016-08-08 | 2017-01-25 | 江西师范大学 | Preparation method of 2- (ortho-alkylaryl) benzothiazole series |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111423900A (en) | 2020-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Approach for selective separation of thiophenic and sulfidic sulfur compounds from petroleum by methylation/demethylation | |
| Snyder et al. | Nitrogen and oxygen compound types in petroleum. A general separation scheme | |
| CN111423900B (en) | Method for derivatization and separation of sulfur-containing compound alkyl in petroleum component | |
| CN103756719B (en) | A kind of method being separated sulfocompound in petroleum component | |
| CN104745227B (en) | A kind of separation and the method for non basic nitrogen compound in analysis petroleum component | |
| Small et al. | Lithium-ammonia reduction of benzyl alcohols to aromatic hydrocarbons. Improved procedure | |
| de Freitas et al. | Isolation and characterization of sulfur-containing compounds by positive-ion electrospray ionization and online HPLC/Atmospheric pressure chemical ionization coupled to Orbitrap mass spectrometry | |
| CN104946303A (en) | Method for selectively separating phenol mixture from oil | |
| CN106831455A (en) | A kind of method of the neutral oil in removal eutectic solvent | |
| CN108211423B (en) | Method for adsorbing and separating phenolic compounds in oil by using biodegradable compound as adsorbent | |
| CN103073499B (en) | A kind of extraction process prepares the method for rhenium ionic liquid | |
| CN112240905B (en) | Analysis method for molecular composition of thioether compound in petroleum | |
| CN108864177B (en) | [2H3]Synthesis method of (E) -1-methylamino-2-phenyl propane | |
| CN104557449A (en) | Synthetic method of stable isotope deuterium-labeled DDT | |
| Wood et al. | Combination of chemical reduction and tandem mass spectrometry for the characterization of sulfur-containing fuel constituents | |
| CN105572248B (en) | Method for determining sulfide in gasoline additive methyl tert-butyl ether | |
| CN107670333A (en) | Method for separating alkylphenol in crude oil | |
| Li et al. | Speciation and molecular characterization of thiophenic and sulfide compounds in petroleum by sulfonation and methylation followed by electrospray mass spectrometry | |
| CN104119950A (en) | Method for separating aromatic hydrocarbon and sulfur-containing aromatic hydrocarbon from heavy aromatic hydrocarbon | |
| RU2224749C2 (en) | Method for treatment of isoquinoline | |
| CN110857392B (en) | Method for separating alkaline nitride from heavy oil | |
| CN1837051A (en) | A kind of preparation method of sodium perthiocarbonate | |
| Hart | Action of Alkali Metals and Metal Hydrides on Deuterated Alkylaromatics and the Mechanism of Side-chain Alkylation | |
| CN106008982A (en) | Preparation method of boric acid silica gel pretreatment material | |
| CN114088797B (en) | Sulfonation method and analysis method of aromatic hydrocarbon compounds in petroleum products |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |