CN114561228A - Method for separating oxygen-containing compounds in coal-based wax oil - Google Patents
Method for separating oxygen-containing compounds in coal-based wax oil Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 77
- 150000001875 compounds Chemical class 0.000 title claims abstract description 76
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000001301 oxygen Substances 0.000 title claims abstract description 61
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 61
- 239000003245 coal Substances 0.000 title claims abstract description 58
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 67
- 239000003480 eluent Substances 0.000 claims abstract description 50
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001868 water Inorganic materials 0.000 claims abstract description 17
- 239000000741 silica gel Substances 0.000 claims abstract description 13
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 13
- 150000002927 oxygen compounds Chemical class 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
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- 230000009969 flowable effect Effects 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 5
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N ortho-diethylbenzene Natural products CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 22
- 239000002904 solvent Substances 0.000 abstract description 16
- 239000012535 impurity Substances 0.000 abstract description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 10
- 150000001336 alkenes Chemical class 0.000 abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 7
- 229930195734 saturated hydrocarbon Natural products 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 abstract description 5
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 32
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 32
- 239000000126 substance Substances 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 14
- 238000000622 liquid--liquid extraction Methods 0.000 description 9
- 238000000638 solvent extraction Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000010926 purge Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 235000019445 benzyl alcohol Nutrition 0.000 description 5
- -1 ketone compound Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
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- 239000000243 solution Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000131505 Gloriosa Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001374 Invar Inorganic materials 0.000 description 1
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- 239000013064 chemical raw material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009342 intercropping Methods 0.000 description 1
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Classifications
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- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- 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
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for separating oxygen-containing compounds from coal-based wax oil, which can divide a coal-based wax oil sample into two parts of an oxygen-containing compound component and a non-oxygen compound component (saturated hydrocarbon, olefin and aromatic hydrocarbon). The invention adopts a solid phase extraction method, and the stationary phase of an extraction column is a mixture consisting of silica gel, alumina and water, wherein the content of the alumina is 50-90 wt%, and the content of the water is 0-10 wt%. According to the method, the oxygen-containing compounds in the enriched coal-based wax oil sample are separated by adopting a two-step method, the solid phase extraction column is washed by using a first eluent to obtain non-oxygen compound components (saturated hydrocarbon, olefin and aromatic hydrocarbon) in the coal-based wax oil, and then the solid phase extraction column is washed by using a second eluent to obtain the oxygen-containing compound components in the wax oil sample. The method is used for separating and enriching the oxygen-containing compound in the coal-based wax oil sample, and has the advantages of short treatment time, small solvent consumption, low impurity content of the oxygen-containing compound component and high recovery rate of the oxygen-containing compound.
Description
Technical Field
The invention relates to a method for separating and enriching oxygen-containing compounds in coal-based wax oil, in particular to a pretreatment method for quickly separating the oxygen-containing compounds from saturated hydrocarbons and aromatic hydrocarbons by utilizing a solid phase extraction method for the subsequent determination of the composition of the oxygen-containing compounds in the coal-based wax oil.
Background
The coal chemical industry comprises technologies of coal-to-olefin, coal-to-oil and the like, wherein the coal-to-oil technology plays an important role in efficient and clean utilization of coal in China. Coal-to-liquid technology can be divided into direct coal liquefaction and indirect coal liquefaction technologies, wherein the indirect coal liquefaction technology is an important development direction of the current C1 chemical industry, indirect coal liquefaction synthetic oil has the advantages of cleanness, environmental protection, excellent combustion performance and the like, and meanwhile, a large number of chemical products can be produced as byproducts, so that a product chain is prolonged, market adaptability is enhanced, and the indirect coal liquefaction technology becomes a hotspot development direction of the current clean coal technology [ Sunzenlighten, Wumin, Zhang Zongson, and the like. 1-12.].
In the face of the current severe situation of high cost and low oil price in the coal chemical industry, the development of clean and environment-friendly high-grade chemicals in the coal chemical industry is an important breakthrough direction. The high-carbon alcohol is an important chemical raw material, is widely applied to the synthesis of plasticizers, detergents and dispersants, increases the world demand by about 10 percent of acceleration every year, and is a fine chemical raw material with high added value. The existing high-carbon alcohol synthesis method in China is mainly a natural oil hydrogenation method, depends on expensive natural oil raw materials, and needs to be imported from Malaysia, Philippines and other countries. Therefore, the productivity and yield of higher alcohols are greatly limited. The method is an important attempt for improving the economic benefit of the coal chemical industry process and improving the competitiveness of the coal chemical industry route by relying on the coal chemical industry technology and taking coal as a raw material to produce high-additional fine chemical products, can expand the Fischer-Tropsch synthesis industrial chain, and provides a solution for upgrading the product structure of coal-to-liquid enterprises.
The crude product of high-carbon alcohol synthesized by coal chemical industry contains a large amount of unsaturated compounds such as olefin, aldehyde, acid and ester besides alcohol and alkane, so that the crude product needs to be converted into corresponding alkane and alcohol by a hydrofining method so as to facilitate the next-stage rectification separation treatment [ Aijun, Li, Jinhuanian, research on Fischer-Tropsch synthesis light oil hydrofining [ J ]. modern chemical industry, 2016,36(4):144-147 ]. The method comprises the steps of separating and enriching oxygen-containing compounds of coal-based diesel oil samples by a liquid-liquid extraction method (sanderian 29130, invar, gloriosa, and the like), measuring the oxygen-containing compounds [ J ] in Fischer-Tropsch synthetic oil by a gas chromatography method, and carrying out modern chemical engineering 2016(7):197 and 200.), wherein the oxygen-containing compounds are extracted from oil products by utilizing the strong solvent capacity of dimethyl sulfoxide to polar oxygen-containing compounds. However, the related documents about enriching the oxygenated compounds of the coal-based wax oil disclosed at present have few reports, because the oxygenated compounds in the coal-based wax oil have high carbon number and small polarity, and the oxygenated compounds obtained by enriching by adopting a liquid-liquid extraction method have low recovery rate and high impurity content.
Disclosure of Invention
The invention aims to provide a method for separating and enriching oxygen-containing compounds in a coal-based wax oil sample by using a solid-phase extraction method so as to be used as a pretreatment method for the subsequent analysis of the oxygen-containing compounds such as alcohols, ketones, aldehydes, esters, acids and the like in the coal-based wax oil. The method solves the problems of low recovery rate and high impurity content of high-carbon-number oxygen-containing compounds in the coal-based wax oil enriched by a liquid-liquid extraction method, and effectively separates and enriches the oxygen-containing compounds in the coal-based wax oil.
In order to achieve the above object, the present invention provides a solid phase extraction column, wherein the solid phase extraction column is internally provided with a stationary phase prepared by mixing silica gel, alumina and water, wherein the alumina content in the stationary phase is 50-90 wt%, and the water content is 0-10 wt%. The method can effectively enrich the oxygen-containing compounds in the coal-based wax oil, meets the requirements of subsequent analysis on the concentration and purity of the sample, and has the advantages of simple treatment steps, small solvent consumption and small intercropping of components.
The invention can also be detailed as follows:
the invention provides a method for separating oxygen-containing compounds from coal-based wax oil, which comprises the following steps: adding coal-based wax oil into a solid-phase extraction column, firstly washing the solid-phase extraction column by using a first eluent to obtain a non-oxygen compound component, and then washing the solid-phase extraction column by using a second eluent to obtain an oxygen-containing compound component; the solid-phase extraction column is internally provided with a stationary phase which is a mixture of silica gel, alumina and water.
The method for separating the oxygen-containing compounds in the coal-based wax oil has the specific surface area of 500-850m2Per g, pore volume of 0.1-0.6mL/g, average pore diameter of 1-4 nm.
The method for separating the oxygen-containing compounds in the coal-based wax oil, provided by the invention, has the specific surface area of alumina in the fixed phase of 200-450m2Per g, pore volume of 0.05-0.4mL/g, average pore diameter of 1-3 nm.
The method for separating the oxygen-containing compounds in the coal-based wax oil further comprises the following steps:
the method comprises the following steps: diluting wax oil and a diluent according to a certain proportion to obtain a flowable wax oil sample;
step two: wetting the solid phase extraction column with a first eluent, adding a diluted flowable wax oil sample from an upper layer of the solid phase extraction column;
step three: continuously washing the solid phase extraction column by using the first eluent to obtain a non-oxygen compound component;
step four: and replacing the collector, and washing the solid phase extraction column by using a second eluent to obtain the oxygen-containing compound component.
Wherein the diluent is at least one selected from the group consisting of n-hexane, n-heptane, petroleum ether, cyclohexane and methylcyclohexane;
the first eluent is a mixture of a and b, wherein a is at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, petroleum ether, cyclohexane and methylcyclohexane, and b is at least one selected from the group consisting of dichloromethane, chloroform, diethyl ether, benzene and toluene;
the second eluent is at least one selected from the group consisting of methanol, ethanol, isopropanol, acetone, butanone and acetonitrile.
The method of the invention, wherein the volume ratio of the diluent to the coal-based wax oil is 0.5-1: 1.
The method of the invention, wherein the volume ratio of a to b in the first eluent is 1-4: 1.
The method of the present invention, wherein the diluted flowable coal-based wax oil is added in an amount of 0.5-4 mL.
In the method of the invention, in the third step, the dosage of the first eluent for washing the solid phase extraction column is 10-15 mL; in step four, the amount of the second eluent used for washing the solid-phase extraction column is 7-12 mL.
The method of the invention, wherein the coal-based wax oil is the wax oil directly liquefied from coal, the wax oil indirectly liquefied from coal or the wax oil produced by other coal chemical industry processes.
The method of the invention, wherein the coal-based wax oil is Fischer-Tropsch wax oil.
The invention can also be detailed as follows:
in order to realize the aim, the invention provides a solid phase extraction method, wherein a solid phase extraction column is internally provided with a stationary phase, and the stationary phase consists of silica gel, alumina and water, wherein the content of the alumina in the stationary phase is 50-90 wt%, and the content of the water is 0-10 wt%. The method can effectively separate the oxygen-containing compounds from the saturated hydrocarbon, the aromatic hydrocarbon and the olefin in the coal-based wax oil, has the advantages of large sample processing capacity, simple processing steps and small separation cross among components, greatly improves the separation and enrichment efficiency, and is suitable for large-scale popularization and use.
The preparation method of the stationary phase silica gel and the alumina in the solid phase extraction column comprises the following steps: drying the silica gel at the temperature of 100-160 ℃ for 3-6 hours to obtain activated silica gel; the alumina is roasted at 6000 ℃ for 3-5 hours at 450 ℃ to obtain the activated alumina. And (3) uniformly mixing the activated silica gel and the alumina according to the proportion, adding 0-10 wt% of deionized water, mixing and oscillating for 10-60min to obtain the alumina-silica gel stationary phase.
The solution obtained by the solid phase extraction separation method can obtain a non-oxygen compound component and an oxygen-containing compound after solvent volatilization and concentration, and rotary evaporation and nitrogen purging are preferably selected for solvent volatilization. The solution is volatilized and concentrated to about 0.4mL, and then the components can be analyzed by gas chromatography. The present invention preferably employs a gas chromatography-mass spectrometry-hydrogen flame ionization detector (GC-MS-FID) to determine the concentrated oxygenate morphology. Injecting the enriched oxygen-containing compound into a gas chromatograph, separating the oxygen-containing compound by a chromatographic column in the gas chromatograph according to the boiling point and the polarity of the oxygen-containing compound, and then respectively performing MS and FID analysis to obtain the structure and content information of the oxygen-containing compound. The quantification can be carried out by adopting an internal standard method, and benzyl alcohol and chlorobenzene are selected as internal standards.
The method adopts a solid phase extraction method to enrich the oxygenated chemicals in the coal-based wax oil, is mainly used for separating and enriching the oxygenated chemicals such as alcohols, aldehydes, ketones, esters, acids and the like in the coal-based wax oil sample, separates the coal-based wax oil sample into a non-oxygenated chemical component and the oxygenated chemicals by optimizing the composition of a solid phase extraction column and adjusting the polarity and the dosage of an eluent, and has the advantages of short treatment time, small solvent dosage, low content of impurities in the oxygenated chemical component and high recovery rate of the oxygenated chemicals. . Compared with the traditional liquid-liquid extraction method, the solid-phase extraction method adopted by the invention has the advantages of high column efficiency, high repeatability of filling the extraction column, elution of solvent under pressure, small solvent dosage, high recovery rate of oxygen-containing compounds and low impurity content. Compared with the traditional liquid-liquid extraction method, the method has the advantages that the time for separating and enriching the oxygen-containing compounds in the coal-based wax oil sample is 25-45min, and the separation efficiency is greatly improved.
Drawings
FIG. 1 is a GC-MS diagram of the non-oxygen compound components obtained by the method of example 1 of the present invention.
FIG. 2 is an m/z 58 (ketone compound) extracted ion diagram of the oxygen-containing compound component obtained by the method of example 1 of the present invention.
FIG. 3 is an m/z 45 (alcohol compound) extracted ion diagram of the oxygen-containing compound component obtained by the method of example 1 of the present invention.
Detailed Description
The present invention will be further specifically described below with reference to specific examples, but the present invention is not limited to the following examples. Any modification which does not depart from the spirit and scope of the invention is deemed to be within the scope of the invention.
The silica gel used in the examples is a silica gel for chromatography produced by national pharmaceutical group chemical reagents, Inc., the particle size is not less than 70.0%, and the specific surface area is 511.9m2Pore volume of 0.468 mL/g. The alumina is produced by national drug group chemical reagent limited company for chromatography, the ignition weight loss is less than or equal to 8.0 percent, and the specific surface area is 236.1m2G, pore volume 0.255 mL/g.
Drying the silica gel at 150 ℃ for 5 hours to obtain activated silica gel; the alumina was calcined at 600 ℃ for 4 hours to obtain activated alumina.
The GC-MS instrument model used for the analysis was 7890A GC-5975MS with a FID detector. GC conditions were as follows: HP-5MS capillary chromatographic column, 30m × 0.25mm × 0.25 μm; programming to raise the initial temperature to 120 deg.c, maintaining for 3min, raising the temperature at 4 deg.c/min rate to final temperature of 320 deg.c and maintaining for 10 min; the carrier gas was high purity helium, operating at constant pressure, 35.374 psi; the injection port temperature is 350 ℃, the split ratio is 20:1, and the injection amount is 1 mu L. MSD conditions: EI ionization source (70eV), ion source temperature 250 ℃, quadrupole rod temperature 150 ℃, full scanning mass range 30-600u, interface temperature 310 ℃ and solvent delay 3 min. FID conditions: the temperature of the detector is 350 ℃, the air flow is 300mL/min, the hydrogen flow is 30mL/min, and the tail gas blowing is 25 mL/min.
Example 1
The solid phase extraction column was packed with 4g of a silica gel-alumina stationary phase having an alumina content of 50 wt%, a water content of 10 wt%, and wetted with 2mL of a first eluent (the volume ratio of n-pentane to dichloromethane was 4: 1).
A high-temperature Fischer-Tropsch synthesis 1# wax oil sample and normal hexane of a certain company are diluted according to the volume ratio of 1:0.5, and then 0.5mL of diluted coal-based wax oil sample is taken by a liquid transfer gun and added into the upper part of a solid-phase extraction column and is completely adsorbed by a stationary phase. The solid phase extraction column was washed with 15mL of the first eluent to give the non-oxygenated compound fraction, designated fraction 1. The solid phase extraction column was washed with 7mL of a second eluent, ethanol, to give the oxygenate, designated as component 2. And removing the solvent in the extraction fraction by nitrogen purging, and adding a certain amount of benzyl alcohol as an internal standard to obtain the sample to be detected. The whole pretreatment process takes about 30 min.
The GC-MS-FID is adopted to analyze the compound forms of each component in the compounds of the component 1 and the component 2, and the result shows that the component 1 is mainly saturated hydrocarbon, olefin and aromatic hydrocarbon, and the component 2 is mainly oxygen-containing compound, wherein the alcohol compound accounts for 29.3 wt% of the component 2, the ketone compound accounts for 41.8 wt%, the ester compound accounts for 25.3 wt%, and the non-oxygen compound accounts for 3.6 wt%. The non-oxygen compounds in the component 2 are mainly polycyclic aromatic hydrocarbons, and the qualitative and quantitative properties of the oxygen-containing compounds are not influenced.
And (4) inspecting the effect of the solid-phase extraction method on enriching the oxygen-containing compounds in the wax oil fraction by using the standard recovery rate of octadecyl alcohol and ethyl stearate. Taking two samples of No. 1 wax oil synthesized by high-temperature Fischer-Tropsch of a certain company, and adding a certain amount of stearyl alcohol and ethyl stearate into one of the two samples to serve as a standard sample. And separating and enriching oxygen-containing compound components of the two samples according to the solid phase extraction method. A certain amount of benzyl alcohol is added as an internal standard, and the content of each compound is analyzed by GC-FID respectively. Subtracting the octadecyl alcohol and ethyl stearate content of the non-added sample from the octadecyl alcohol and ethyl stearate content of the added sample, wherein the difference value is the ratio of the theoretical value of the added octadecyl alcohol and ethyl stearate to the theoretical value of the added octadecyl alcohol and ethyl stearate, namely the added sample recovery rates of the two compounds are 101.5 percent and 92.3 percent in sequence.
The results show that the method has the advantages of low content of cross components in the separated components, high recovery rate of the oxygen-containing compounds and better enrichment effect.
Example 2
4g of a silica gel-alumina stationary phase having an alumina content of 60% by weight, a water content of 8% by weight, are packed in a solid phase extraction column, wetted with 2mL of a first eluent (the volume ratio of n-hexane to diethyl ether is 3: 1).
Adding a certain amount of octadecyl alcohol and ethyl stearate into a high-temperature Fischer-Tropsch synthesis No. 2 wax oil sample produced by a certain company to prepare the standard oil. Diluting the wax oil sample and n-heptane according to the volume ratio of 1:0.8, taking 1mL of diluted wax oil sample by using a pipette, adding the diluted wax oil sample to the upper part of the solid phase extraction column, and completely adsorbing the diluted wax oil sample by the stationary phase. The solid phase extraction column was washed with 13mL of the first eluent to give the non-oxygenated compound fraction, designated fraction 1. The solid phase extraction column was washed with 7mL of a second eluent, methanol, to give the oxygenate, designated as component 2. And removing the solvent in the eluent by adopting nitrogen purging, and adding benzyl alcohol as an internal standard to obtain a sample to be detected. The whole pretreatment process takes about 25 min.
The method is adopted to separate and enrich the high-temperature Fischer-Tropsch synthesis 2# wax oil sample and the oxygenated chemicals in the standard oil prepared by the sample, and a certain amount of chlorobenzene is added as an internal standard substance. And analyzing the enrichment liquid of the two wax oil samples by adopting GC-MS-FID. The result shows that the component 1 of the high-temperature Fischer-Tropsch synthesis 2# wax oil sample does not contain oxygen-containing compounds, and the content of impurities such as aromatic hydrocarbon and the like in the component 2 is 6.3 wt%; the standard recovery rate of the octadecyl alcohol and the ethyl stearate is 96.3 percent and 92.3 percent.
Therefore, the solid phase extraction method can be used for efficiently separating the oxygen-containing compounds in the high-temperature Fischer-Tropsch synthesis wax oil sample, and the recovery rate of the oxygen-containing compounds is high.
Example 3
3g of a silica gel-alumina stationary phase having an alumina content of 80 wt%, a water content of 5 wt%, was packed in a solid phase extraction column, and wetted with 2mL of a first eluent (petroleum ether to toluene volume ratio of 2: 1).
Diluting a low-temperature Fischer-Tropsch synthesis 3# wax oil sample produced by a certain company with cyclohexane according to the volume ratio of 1:0.9, adding 2mL of the diluted wax oil sample into the upper part of a solid-phase extraction column, and completely adsorbing the diluted wax oil sample by a stationary phase. The solid phase extraction column was washed with 12mL of the first eluent to give the non-oxygenated compound fraction, designated fraction 1. The solid phase extraction column was washed with 12mL of a second eluent, acetone, to give the oxygenate, designated as component 2. And removing the solvent in the eluent by nitrogen purging, and adding a certain amount of chlorobenzene as an internal standard substance to obtain a sample to be detected. The whole pretreatment process took about 40 min.
The composition of the enriched oxygen-containing compound components was analyzed by GC-MS-FID, and the results showed that the polycyclic aromatic hydrocarbon content in the enriched oxygen-containing compound was 4.3 wt%.
The recovery rates of the oxygen-containing compounds were 95.1% and 91.2% as measured by the standard recovery rates of stearyl alcohol and ethyl stearate.
Example 4
3g of a silica gel-alumina stationary phase having an alumina content of 90% by weight, a water content of 0% by weight, are packed in a solid phase extraction column, wetted with 2mL of a first eluent (n-heptane to toluene in a volume ratio of 1: 1).
A direct liquefaction No. 4 wax oil sample produced by a certain company is diluted with methylcyclohexane according to the volume ratio of 1:1, and then 3mL of the diluted wax oil sample is added to the upper part of a solid phase extraction column and is completely adsorbed by a stationary phase. The solid phase extraction column was washed with 10mL of the first eluent to give the non-oxygenated compound fraction, designated fraction 1. The solid phase extraction column was washed with 12mL of a second eluent (methanol to ethanol volume ratio 1:1) to give the oxygenate, designated as component 2. And removing the solvent in the eluent by nitrogen purging, and adding a certain amount of chlorobenzene as an internal standard to obtain a sample to be detected. The whole pretreatment process took about 35 min.
The enriched oxygen-containing compounds are analyzed by GC-MS-FID, and the result shows that the content of impurities such as aromatic hydrocarbon and the like in the directly liquefied No. 4 wax oil sample is 2.4 wt%.
The recovery rates of the oxygen-containing compounds are determined to be 98.3 percent and 94.5 percent according to the standard addition recovery rates of the octadecyl alcohol and the ethyl stearate.
Comparative example 1
And (3) adding 10mL of a high-temperature Fischer-Tropsch synthesis 1# wax oil sample of a certain company into a separating funnel, then adding 10mL of dimethyl sulfoxide, mixing and shaking for 5min, and standing for layering. Collecting the extract liquor in the lower layer of the separating funnel. Repeating the liquid-liquid extraction process twice, collecting the lower layer of extract liquor and collecting the extract liquors of three times of extraction together. And adding 30mL of deionized water into the mixed extract, fully mixing and oscillating, standing for layering, and removing the lower extraction raffinate to obtain the upper enriched oxygen-containing compound. The whole process takes about 45 min.
And (4) inspecting the effect of the liquid-liquid extraction method on enriching the oxygen-containing compounds in the wax oil fraction by using the standard recovery rate of octadecyl alcohol and ethyl stearate. The standard addition recovery rate of the octadecyl alcohol and the ethyl stearate is 69.3 percent and 55.6 percent in sequence. The oxygen-containing compound component in the non-added standard sample contains a large amount of impurity components such as olefin, aromatic hydrocarbon and the like, and the content of the impurity is 36.2 wt%.
Therefore, compared with the solid phase extraction method for separating and enriching the high-temperature Fischer-Tropsch synthesis wax oil oxygen-containing compounds, the method has the advantages that the standard recovery rate of the liquid-liquid extraction method is slightly low, but the content of impurities such as aromatic hydrocarbon in the enriched liquid of the liquid-liquid extraction method is high, and the subsequent qualitative analysis is interfered.
Comparative example 2
4g of a silica gel-alumina stationary phase having an alumina content of 60% by weight, a water content of 15% by weight, are packed in a solid phase extraction column, wetted with 2mL of a first eluent (the volume ratio of n-hexane to diethyl ether is 3: 1).
Adding a certain amount of octadecyl alcohol and ethyl stearate into a high-temperature Fischer-Tropsch synthesis No. 2 wax oil sample produced by a certain company to prepare the standard oil. Diluting the wax oil sample and n-heptane according to the volume ratio of 1:0.8, taking 1mL of diluted wax oil sample by using a pipette, adding the diluted wax oil sample into the upper part of the solid phase extraction column, and completely adsorbing the diluted wax oil sample by the stationary phase. The solid phase extraction column was washed with 13mL of the first eluent to give the non-oxygenated compound fraction, designated fraction 1. The solid phase extraction column was washed with 7mL of a second eluent, methanol, to give the oxygenate, designated as component 2. And removing the solvent in the eluent by adopting nitrogen purging, and adding benzyl alcohol as an internal standard to obtain a sample to be detected. The whole pretreatment process took about 25 min.
The method is adopted to separate and enrich the high-temperature Fischer-Tropsch synthesis 2# wax oil sample and the oxygenated chemicals in the standard oil prepared by the sample, and a certain amount of chlorobenzene is added as an internal standard substance. And analyzing the enrichment liquid of the two wax oil samples by adopting GC-MS-FID. The result shows that the component 1 of the high-temperature Fischer-Tropsch synthesis No. 2 wax oil sample does not contain oxygen-containing compounds, and the content of impurities such as aromatic hydrocarbon and the like in the component 2 is 10.4 wt%; the standard recovery rate of the octadecyl alcohol and the ethyl stearate is 90.6 percent and 88.3 percent.
Comparative example 3
3g of a silica gel-alumina stationary phase having an alumina content of 40% by weight, a water content of 5% by weight, are packed in a solid phase extraction column and wetted with 2mL of a first eluent (petroleum ether to toluene volume ratio 2: 1).
A low-temperature Fischer-Tropsch synthesis 3# wax oil sample produced by a certain company is diluted with cyclohexane according to the volume ratio of 1:0.9, and 2mL of the diluted wax oil sample is added into the upper part of a solid-phase extraction column and is completely adsorbed by a stationary phase. The solid phase extraction column was washed with 12mL of the first eluent to give the non-oxygenated compound fraction, designated fraction 1. The solid phase extraction column was washed with 12mL of a second eluent, acetone, to give the oxygenate, designated as component 2. And removing the solvent in the eluent by nitrogen purging, and adding a certain amount of chlorobenzene as an internal standard substance to obtain a sample to be detected. The whole pretreatment process took about 40 min.
The recovery rates of the oxygen-containing compounds were 82.1% and 71.3% as measured by the standard recovery rates of stearyl alcohol and ethyl stearate.
Comparative example 4
3g of a silica gel-alumina stationary phase having an alumina content of 90% by weight, a water content of 0% by weight, are packed in a solid phase extraction column, wetted with 2mL of a first eluent (n-heptane to toluene in a volume ratio of 1: 1).
1.5mL of a direct liquefaction No. 4 wax oil sample produced by a certain company is added to the upper part of a solid phase extraction column and is completely adsorbed by a stationary phase. The solid phase extraction column was washed with 10mL of the first eluent to give the non-oxygenated compound fraction, designated fraction 1. The solid phase extraction column was washed with 12mL of a second eluent (methanol to ethanol volume ratio 1:1) to give the oxygenate, designated as component 2. And removing the solvent in the eluent by nitrogen purging, and adding a certain amount of chlorobenzene as an internal standard to obtain a sample to be detected. The whole pretreatment process took about 30 min.
The enriched oxygen-containing compounds are analyzed by GC-MS-FID, and the result shows that the content of impurities such as saturated hydrocarbon, olefin, aromatic hydrocarbon and the like in the directly liquefied No. 4 wax oil sample is 21.1 wt%.
The recovery rates of the oxygen-containing compounds were 78.3% and 69.5% as measured by the standard recovery rates of stearyl alcohol and ethyl stearate.
Claims (11)
1. A method for separating oxygen-containing compounds in coal-based wax oil is characterized by comprising the following steps: adding coal-based wax oil into a solid-phase extraction column, firstly washing the solid-phase extraction column by using a first eluent to obtain a non-oxygen compound component, and then washing the solid-phase extraction column by using a second eluent to obtain an oxygen-containing compound component; the solid-phase extraction column is internally provided with a stationary phase which is a mixture of silica gel, alumina and water.
2. The method as claimed in claim 1, wherein the silica gel in the stationary phase has a specific surface area of 500-850m2Per g, pore volume of 0.1-0.6mL/g, average pore diameter of 1-4 nm.
3. The method as claimed in claim 1, wherein the specific surface area of the alumina in the stationary phase is 200-450m2Per g, pore volume of 0.05-0.4mL/g, average pore diameter of 1-3 nm.
4. The method of claim 1, wherein the solid phase extraction column is prepared by uniformly mixing silica gel and alumina, adding water, uniformly mixing and packing; wherein the content of the alumina is 50-90 wt%, and the content of the water is 0-10 wt%.
5. The method of claim 1, further comprising the steps of:
the method comprises the following steps: diluting the coal-based wax oil by using a diluent to obtain a flowable wax oil sample;
step two: wetting the solid phase extraction column with a first eluent, and adding a flowable wax oil sample from the upper layer of the solid phase extraction column;
step three: continuously washing the solid phase extraction column by using the first eluent to obtain a non-oxygen compound component;
step four: replacing the collector, and washing the solid-phase extraction column by using a second eluent to obtain an oxygen-containing compound component;
wherein the diluent is at least one selected from the group consisting of n-hexane, n-heptane, petroleum ether, cyclohexane and methylcyclohexane;
the first eluent is a mixture of a and b, wherein a is at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, petroleum ether, cyclohexane and methylcyclohexane, and b is at least one selected from the group consisting of dichloromethane, chloroform, diethyl ether, benzene and toluene;
the second eluent is at least one selected from the group consisting of methanol, ethanol, isopropanol, acetone, butanone, and acetonitrile.
6. The method according to claim 5, wherein the volume ratio of the diluent to the coal-based wax oil is 0.5 to 1: 1.
7. The method of claim 5, wherein the volume ratio of a to b in the first eluent is 1-4: 1.
8. The method of claim 5, wherein the flowable wax oil sample is added in an amount of 0.5-4 mL.
9. The method as claimed in claim 5, wherein in step three, the amount of the first eluent for washing the solid phase extraction column is 10-15 mL; in step four, the amount of the second eluent used for washing the solid-phase extraction column is 7-12 mL.
10. The method of claim 1, wherein the coal-based wax oil is a wax oil produced by direct coal liquefaction or indirect coal liquefaction.
11. The method of claim 1, wherein the coal-based wax oil is a fischer-tropsch wax oil.
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| CN102757810A (en) * | 2012-06-28 | 2012-10-31 | 神华集团有限责任公司 | Method for separating component from direct-coal-liquefaction full distillate oil by utilizing solid-phase extraction method |
| CN109839449A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Method for separating phenolic compounds in diesel oil by solid phase extraction |
| CN111308005A (en) * | 2020-03-30 | 2020-06-19 | 上海兖矿能源科技研发有限公司 | Method for determining content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil |
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| CN102757810A (en) * | 2012-06-28 | 2012-10-31 | 神华集团有限责任公司 | Method for separating component from direct-coal-liquefaction full distillate oil by utilizing solid-phase extraction method |
| CN109839449A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Method for separating phenolic compounds in diesel oil by solid phase extraction |
| CN111308005A (en) * | 2020-03-30 | 2020-06-19 | 上海兖矿能源科技研发有限公司 | Method for determining content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil |
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