CN114561228B - Method for separating oxygen-containing compound in coal-based wax oil - Google Patents

Method for separating oxygen-containing compound in coal-based wax oil Download PDF

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CN114561228B
CN114561228B CN202011357126.6A CN202011357126A CN114561228B CN 114561228 B CN114561228 B CN 114561228B CN 202011357126 A CN202011357126 A CN 202011357126A CN 114561228 B CN114561228 B CN 114561228B
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wax oil
coal
eluent
oxygen
extraction column
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CN114561228A (en
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史得军
陈菲
喻昊
舒颖琦
何京
周婧
薛慧峰
崔晨曦
任春晓
孙欣婵
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Petrochina Co Ltd
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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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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a method for separating oxygen-containing compounds in coal-based wax oil, which can divide a coal-based wax oil sample into two parts of oxygen-containing compound components and non-oxygen-containing compound components (saturated hydrocarbon, olefin and aromatic hydrocarbon). The invention adopts a solid-phase extraction method, the stationary phase of the extraction column is a mixture composed of silica gel, alumina and water, wherein the content of the alumina is 50-90wt% and the content of the water is 0-10wt%. The method adopts a two-step method to separate and enrich the oxygen-containing compound in the coal-based wax oil sample, firstly uses a first eluent to wash the solid-phase extraction column to obtain non-oxygen-containing compound components (saturated hydrocarbon, olefin and aromatic hydrocarbon) in the coal-based wax oil, and then uses a second eluent to wash the solid-phase extraction column 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, less solvent consumption, low impurity content of the oxygen-containing compound component and high recovery rate of the oxygen-containing compound.

Description

Method for separating oxygen-containing compound in coal-based wax oil
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 rapidly separating the oxygen-containing compounds from saturated hydrocarbon and aromatic hydrocarbon by a solid-phase extraction method for the subsequent determination of the oxygen-containing compound composition of the coal-based wax oil.
Background
The coal chemical industry comprises a technology for preparing olefin by coal, preparing oil by coal, and the technology for preparing oil by coal plays an important role in the efficient and clean utilization of coal in China. The coal-to-oil technology can be divided into a direct coal liquefaction technology and an indirect coal liquefaction technology, wherein the indirect coal liquefaction technology is an important development direction of the current C1 chemical industry, and the indirect coal liquefaction synthetic oil has the advantages of cleanness, environmental protection, excellent combustion performance and the like, can also be used for producing a large amount of byproducts of chemical products, prolongs a product chain, enhances market adaptability, and becomes a hot spot development direction [ Sun Qiwen, wu Jianmin, zhang Zongsen, and the like ] of the current clean coal technology: 1-12.].
In the face of the severe situation of high enterprise and low oil price in the current coal chemical industry, the development of high-grade chemicals which are clean and environment-friendly 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% per 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, the method relies on expensive natural oil raw materials, and the method is required to be imported from Malaysia, philippines and other countries. Therefore, the productivity and yield of higher alcohols are greatly limited. The method relies on the coal chemical technology, and the production of high-additional fine chemical products by taking coal as raw materials is an important attempt to improve the economic benefit of the coal chemical technology and the competitiveness of the coal chemical route, so that the Fischer-Tropsch synthesis industry chain can be expanded, and a solution is provided for the product structure upgrading of coal-to-oil enterprises.
The crude products of the synthetic high-carbon alcohols in the coal chemical industry contain a large amount of unsaturated compounds such as alkene, aldehyde, acid, ester and the like besides alcohols and alkanes, so that the crude products are required to be converted into corresponding alkanes and alcohols by a hydrofining method, so that the next-stage rectifying and separating treatment [ Ai Jun, li Li, golden ring years, research on the hydrofining of Fischer-Tropsch synthesis light oil [ J ]. Modern chemical industry, 2016,36 (4): 144-147 ]. The gas chromatography is used for measuring the oxygen-containing compound [ J ]. Modern chemical industry, 2016 (7): 197-200 ] ] in Fischer-Tropsch synthetic oil, and the main principle is to extract the oxygen-containing compound from the oil product by utilizing the strong solvent capacity of dimethyl sulfoxide to polar oxygen-containing compound. However, the related literature report about the enrichment of the oxygen-containing compounds of the coal-based wax oil is very few, because the oxygen-containing compounds in the coal-based wax oil have high carbon number and low polarity, and the oxygen-containing compound component obtained by enrichment through a liquid-liquid extraction method has 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 coal-based wax oil samples by utilizing a solid phase extraction method, which is used for a pretreatment method for subsequently analyzing the oxygen-containing compounds such as alcohols, ketones, aldehydes, esters, acids and the like in the coal-based wax oil. The invention solves the problems of low recovery rate and high impurity content of high carbon number oxygen-containing compounds in the enriched coal-based wax oil by a liquid-liquid extraction method, and ensures that the oxygen-containing compounds in the coal-based wax oil can be effectively separated and enriched.
In order to achieve the above object, the present invention provides a solid phase extraction column, wherein the solid phase extraction column is filled with a stationary phase prepared by mixing silica gel, alumina and water, the content of alumina in the stationary phase is 50-90wt%, and the content of water is 0-10wt%. The method can effectively enrich the oxygen-containing compound 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, less solvent consumption and small separation and crossing among components.
The invention can be further described as follows:
the invention provides a method for separating oxygen-containing compounds in coal-based wax oil, which comprises the following steps: adding coal-based wax oil into a solid phase extraction column, firstly flushing the solid phase extraction column by adopting a first eluent to obtain a non-oxygen compound component, and then flushing the solid phase extraction column by adopting a second eluent to obtain an oxygen compound component; the solid phase extraction column is internally provided with a stationary phase, and the stationary phase is a mixture of silica gel, alumina and water.
The method for separating the oxygen-containing compound in the coal-based wax oil of the invention, wherein the specific surface area of the silica gel in the stationary phase is 500-850m 2 Per gram, the pore volume is 0.1-0.6mL/g, and the average pore diameter is 1-4nm.
The method for separating the oxygen-containing compound in the coal-based wax oil of the invention, wherein the specific surface area of the alumina in the fixed phase is 200-450m 2 Per gram, the pore volume is 0.05-0.4mL/g, and the average pore diameter is 1-3nm.
The method for separating the oxygen-containing compound in the coal-based wax oil further comprises the following steps:
step one: diluting wax oil and a diluent according to a certain proportion to obtain a flowable wax oil sample;
step two: wetting the solid phase extraction column with a first eluent, and adding a diluted flowable wax oil sample from an upper layer of the solid phase extraction column;
step three: continuing to rinse the solid phase extraction column with the first eluent to obtain a non-oxygenate component;
step four: the collector is replaced, and the solid phase extraction column is flushed with a second eluent to obtain an oxygenate 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 0.5-4mL.
The method of the invention, wherein in the third step, the dosage of the first eluent for flushing the solid phase extraction column is 10-15mL; in the fourth step, the dosage of the second eluent for washing the solid phase extraction column is 7-12mL.
The method of the invention, wherein the coal-based wax oil is a direct coal liquefaction wax oil, an indirect coal liquefaction wax oil or a wax oil produced by other coal chemical processes.
The method of the invention, wherein the coal-based wax oil is a Fischer-Tropsch synthesis wax oil.
The invention can be further described as follows:
in order to achieve the above purpose, the invention provides a solid phase extraction method, wherein a solid phase extraction column is filled with a stationary phase, the stationary phase consists of silica gel, alumina and water, the content of the alumina in the stationary phase is 50-90wt%, and the content of the water in the stationary phase is 0-10wt%. 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 treatment capacity, simple treatment steps and small separation and crossing 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 alumina in the solid phase extraction column comprises the following steps: drying the silica gel at 100-160 ℃ for 3-6 hours to obtain activated silica gel; roasting the alumina at 450-6000 ℃ for 3-5 hours to obtain the activated alumina. Mixing activated silica gel and alumina uniformly according to the proportion, adding 0-10wt% 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 evaporation and concentration, and the solvent evaporation work is preferably carried out by rotary evaporation and nitrogen purging. And volatilizing and concentrating the solution to about 0.4mL to analyze the components by gas phase chromatography. The present invention preferably employs a gas chromatograph-mass spectrometer-hydrogen flame ionization detector (GC-MS-FID) to determine the concentrated oxygenate morphology. And (3) injecting the enriched oxygen-containing compound into a gas chromatograph, separating by a chromatographic column in the gas chromatograph according to the boiling point and the polarity of the oxygen-containing compound, and then respectively entering an MS and an FID for 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 standard substances.
The method is mainly used for separating and enriching the oxygen-containing compounds such as alcohols, aldehydes, ketones, esters, acids and the like in the coal-based wax oil sample, and separates the coal-based wax oil sample into a non-oxygen compound component and an oxygen-containing compound component by optimizing the composition of a solid-phase extraction column and adjusting the polarity and the dosage of an eluent. . 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 filling repeatability of the extraction column, low solvent consumption of the elution solvent under pressure, high recovery rate of the oxygen-containing compound and low impurity content. Compared with the traditional liquid-liquid extraction method, the method provided by the invention has the advantages that the time for separating and enriching the oxygen-containing compound in one coal-based wax oil sample is 25-45min, and the separation efficiency is greatly improved.
Drawings
FIG. 1 is a GC-MS diagram of a non-oxygen compound component obtained using the method of example 1 of the present invention.
FIG. 2 is an m/z 58 (ketone) extraction ion of an oxygenate component obtained by the method of example 1 of the present invention.
FIG. 3 shows an m/z 45 (alcohol compound) extraction ion of an oxygenate component obtained by the method of example 1 of the present invention.
Detailed Description
The present invention will be further specifically described with reference to the following 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 present invention is intended to be within the scope of the present invention.
Silica gel used in the examplesSilica gel for chromatography produced by national pharmaceutical group chemical reagent Co., ltd. With granularity not less than 70.0% and specific surface area of 511.9m 2 Per gram, pore volume was 0.468mL/g. The alumina is chromatographic alumina produced by national medicine group chemical reagent Co., ltd, the ignition weight loss is less than or equal to 8.0%, and the specific surface area is 236.1m 2 Per gram, pore volume was 0.255mL/g.
Drying the silica gel at 150 ℃ for 5 hours to obtain activated silica gel; the alumina was calcined at 600 c for 4 hours to obtain activated alumina.
The GC-MS instrument used for the analysis was model 7890A GC-5975MS with FID detector. GC conditions: HP-5MS capillary chromatographic column, 30m x 0.25mm x 0.25 μm; heating to 120 ℃ at the initial temperature of programming, keeping for 3min, heating at the speed of 4 ℃/min, and keeping for 10min at the final temperature of 320 ℃; the carrier gas is high purity helium, and the constant pressure operation is carried out at a pressure of 35.374psi; the temperature of the sample inlet is 350 ℃, the split ratio is 20:1, and the sample feeding amount is 1 mu L. MSD conditions: EI ionization source (70 eV), ion source temperature 250 ℃, quaternary rod temperature 150 ℃, full scan mass range 30-600u, interface temperature 310 ℃, solvent delay 3min. FID conditions: the detector temperature is 350 ℃, the air flow rate is 300mL/min, the hydrogen flow rate is 30mL/min, and the tail blowing air is 25mL/min.
Example 1
The solid phase extraction column was packed with 4g of a silica gel-alumina stationary phase having an alumina content of 50wt%, a water content of 10wt% and wetted with 2mL of a first eluent (volume ratio of n-pentane to dichloromethane 4:1).
Diluting a high-temperature Fischer-Tropsch synthesis No. 1 wax oil sample of a certain company with n-hexane according to a volume ratio of 1:0.5, taking 0.5mL of diluted coal-based wax oil sample by a liquid-transferring gun, adding the diluted coal-based wax oil sample into the upper part of a solid-phase extraction column, and completely adsorbing by a stationary phase. The solid phase extraction column was washed with 15mL of the first eluent to give a non-oxygenate component, designated component 1. The solid phase extraction column was rinsed with 7mL of a second eluent, ethanol, to give an oxygenate, designated as component 2. And (3) removing the solvent in the extraction fraction by adopting nitrogen purging, and adding a certain amount of benzyl alcohol as an internal standard to obtain a sample to be tested. The whole pretreatment process takes about 30min.
The GC-MS-FID is adopted to analyze the forms of the components 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 in the component 2 accounts for 29.3wt%, the ketone compound accounts for 41.8wt%, the ester compound accounts for 25.3wt% and the content of the non-oxygen compound accounts for 3.6wt%. The non-oxygen compounds in the component 2 are mainly polycyclic aromatic hydrocarbons, and do not influence the nature and the quantification of the oxygen-containing compounds.
The effect of enriching the oxygenated compounds in the wax oil fraction by a solid-phase extraction method is examined by using the standard recovery rate of the stearyl alcohol and the ethyl stearyl. Taking two high-temperature Fischer-Tropsch synthesis No. 1 wax oil samples of a certain company, wherein a certain amount of stearyl alcohol and ethyl stearate are added into one sample to serve as standard adding samples. Both samples were separated and enriched for oxygenate components according to the above solid phase extraction method. Each of the compounds was analyzed by GC-FID with a certain amount of benzyl alcohol as an internal standard. The ratio of the difference value of the content of the stearyl alcohol and the content of the ethyl stearyl ester in the marked sample minus the content of the stearyl alcohol and the content of the ethyl stearyl ester in the unmarked sample to the theoretical value of the added stearyl alcohol and the added ethyl stearyl ester is the marked recovery rate of the two compounds, and the values are 101.5 percent and 92.3 percent in sequence.
The results show that the method has small content of cross components in the separation components, high recovery rate of the oxygen-containing compounds and better enrichment effect.
Example 2
The solid phase extraction column was packed with 4g of a silica gel-alumina stationary phase having an alumina content of 60wt%, a water content of 8wt% and wetted with 2mL of a first eluent (volume ratio of n-hexane to diethyl ether: 3:1).
And adding a certain amount of stearyl 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-adding oil. The wax oil sample and the n-heptane are diluted according to the volume ratio of 1:0.8, 1mL of diluted wax oil sample is taken by a liquid-transfering gun, added into the upper part of the solid-phase extraction column and is completely adsorbed by the stationary phase. The solid phase extraction column was washed with 13mL of the first eluent to give a non-oxygenate component, designated component 1. The solid phase extraction column was rinsed with 7mL of a second eluent, methanol, to give an oxygenate, designated as component 2. And removing the solvent in the eluent by adopting nitrogen purging, and adding the internal standard benzyl alcohol to obtain a sample to be detected. The whole pretreatment process takes about 25min.
The method is used for separating and enriching the high-temperature Fischer-Tropsch synthesis No. 2 wax oil sample and the oxygenated compounds in the labeled oil prepared by the high-temperature Fischer-Tropsch synthesis No. 2 wax oil sample, and a certain amount of chlorobenzene is added as an internal standard. The enrichment of the two wax oil samples was analyzed by 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 an oxygen-containing compound, and the content of impurities such as aromatic hydrocarbon in the component 2 is 6.3wt%; the standard recovery rate of the stearyl 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
The solid phase extraction column was packed with 3g of a silica gel-alumina stationary phase having an alumina content of 80wt% and a water content of 5wt% and wetted with 2mL of a first eluent (petroleum ether to toluene volume ratio 2:1).
Diluting a low-temperature Fischer-Tropsch synthesis 3# wax oil sample produced by a certain company and cyclohexane according to the volume ratio of 1:0.9, taking 2mL of the diluted wax oil sample, adding the diluted wax oil sample into the upper part of a solid phase extraction column, and completely adsorbing by a stationary phase. The solid phase extraction column was washed with 12mL of the first eluent to give a non-oxygenate component, designated component 1. The solid phase extraction column was rinsed with 12mL of a second eluent, acetone, to give an oxygenate, designated as component 2. And removing the solvent in the eluent by adopting 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 takes about 40min.
The composition of the enriched oxygenate component was analyzed by GC-MS-FID, and the result showed that the polycyclic aromatic hydrocarbon content in the enriched oxygenate was 4.3wt%.
The recovery rate of the oxygenated compounds is 95.1% and 91.2% measured by the standard recovery rate of the stearyl alcohol and the ethyl stearate.
Example 4
The solid phase extraction column was packed with 3g of a silica gel-alumina stationary phase having an alumina content of 90wt%, a water content of 0wt% and wetted with 2mL of a first eluent (1:1 by volume of n-heptane to toluene).
Diluting a direct liquefied 4# wax oil sample produced by a certain company with methylcyclohexane according to a volume ratio of 1:1, and then taking 3mL of the diluted wax oil sample, adding the diluted wax oil sample into the upper part of a solid phase extraction column, and completely adsorbing by a stationary phase. The solid phase extraction column was washed with 10mL of the first eluent to give a non-oxygenate component, designated component 1. The solid phase extraction column was washed with 12mL of a second eluent (methanol to ethanol volume ratio of 1:1) to give an oxygenate, designated as component 2. And removing the solvent in the eluent by adopting nitrogen purging, and adding a certain amount of chlorobenzene to serve as an internal standard to obtain a sample to be detected. The whole pretreatment process takes about 35min.
The GC-MS-FID analysis of the enriched oxygenated compounds shows that the content of impurities such as aromatic hydrocarbon in the 4# wax oil sample is 2.4wt% in the direct liquefaction.
The recovery rate of the oxygenated compounds is 98.3% and 94.5% measured by the standard recovery rate of the stearyl alcohol and the ethyl stearate.
Comparative example 1
10mL of a high-temperature Fischer-Tropsch synthesis No. 1 wax oil sample of a certain company is taken and added into a separating funnel, then 10mL of dimethyl sulfoxide is added, mixed and vibrated for 5min, and the mixture is stood for layering. The extract at the lower layer of the separating funnel was collected. The above liquid-liquid extraction process was repeated twice, and the lower extract was collected and the three extracted extracts were collected together. Adding 30mL of deionized water into the mixed extract, fully mixing and oscillating, standing for layering, and removing the lower raffinate phase to obtain the upper enriched oxygen-containing compound. The whole process takes about 45min.
The effect of enriching the oxygenated compounds in the wax oil fraction by a liquid-liquid extraction method is examined by using the standard recovery rate of the stearyl alcohol and the ethyl stearyl. The standard recovery rate of the stearyl alcohol and the ethyl stearate is 69.3 percent and 55.6 percent in sequence. The oxygenated component in the non-added standard sample contains a large amount of olefin, aromatic hydrocarbon and other impurity components, and the impurity content is 36.2wt%.
Compared with the solid-phase extraction method for separating and enriching the high-temperature Fischer-Tropsch synthesis wax oil oxygen-containing compound, the liquid-liquid extraction method has slightly low standard recovery rate, but the enrichment liquid of the liquid-liquid extraction method has higher content of impurities such as aromatic hydrocarbon and the like, which causes interference to subsequent qualitative analysis.
Comparative example 2
The solid phase extraction column was packed with 4g of a silica gel-alumina stationary phase having an alumina content of 60wt%, a water content of 15wt% and wetted with 2mL of a first eluent (volume ratio of n-hexane to diethyl ether: 3:1).
And adding a certain amount of stearyl 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-adding oil. The wax oil sample and the n-heptane are diluted according to the volume ratio of 1:0.8, 1mL of diluted wax oil sample is taken by a liquid-transfering gun, added into the upper part of the solid-phase extraction column and is completely adsorbed by the stationary phase. The solid phase extraction column was washed with 13mL of the first eluent to give a non-oxygenate component, designated component 1. The solid phase extraction column was rinsed with 7mL of a second eluent, methanol, to give an oxygenate, designated as component 2. And removing the solvent in the eluent by adopting nitrogen purging, and adding the internal standard benzyl alcohol to obtain a sample to be detected. The whole pretreatment process takes about 25min.
The method is used for separating and enriching the high-temperature Fischer-Tropsch synthesis No. 2 wax oil sample and the oxygenated compounds in the labeled oil prepared by the high-temperature Fischer-Tropsch synthesis No. 2 wax oil sample, and a certain amount of chlorobenzene is added as an internal standard. The enrichment of the two wax oil samples was analyzed by 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 an oxygen-containing compound, and the content of impurities such as aromatic hydrocarbon in the component 2 is 10.4wt%; the standard recovery rate of the stearyl alcohol and the ethyl stearate is 90.6 percent and 88.3 percent.
Comparative example 3
The solid phase extraction column was packed with 3g of a silica gel-alumina stationary phase having an alumina content of 40wt% and a water content of 5wt% and wetted with 2mL of a first eluent (petroleum ether to toluene volume ratio 2:1).
Diluting a low-temperature Fischer-Tropsch synthesis 3# wax oil sample produced by a certain company and cyclohexane according to the volume ratio of 1:0.9, taking 2mL of the diluted wax oil sample, adding the diluted wax oil sample into the upper part of a solid phase extraction column, and completely adsorbing by a stationary phase. The solid phase extraction column was washed with 12mL of the first eluent to give a non-oxygenate component, designated component 1. The solid phase extraction column was rinsed with 12mL of a second eluent, acetone, to give an oxygenate, designated as component 2. And removing the solvent in the eluent by adopting 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 takes about 40min.
The recovery rate of the oxygen-containing compound is 82.1% and 71.3% measured by the standard recovery rate of the stearyl alcohol and the ethyl stearate.
Comparative example 4
The solid phase extraction column was packed with 3g of a silica gel-alumina stationary phase having an alumina content of 90wt%, a water content of 0wt% and wetted with 2mL of a first eluent (1:1 by volume of n-heptane to toluene).
1.5mL of a direct liquefied No. 4 wax oil sample produced by a certain company is added into the upper part of the solid phase extraction column and is completely adsorbed by the stationary phase. The solid phase extraction column was washed with 10mL of the first eluent to give a non-oxygenate component, designated component 1. The solid phase extraction column was washed with 12mL of a second eluent (methanol to ethanol volume ratio of 1:1) to give an oxygenate, designated as component 2. And removing the solvent in the eluent by adopting nitrogen purging, and adding a certain amount of chlorobenzene to serve as an internal standard to obtain a sample to be detected. The whole pretreatment process takes about 30min.
The GC-MS-FID analysis of the enriched oxygenated compounds shows that the content of saturated hydrocarbon, olefin, aromatic hydrocarbon and other impurities in the 4# wax oil sample is 21.1wt% in the direct liquefaction process.
The recovery rate of the oxygenated compounds is 78.3% and 69.5% measured by the standard recovery rate of the stearyl alcohol and the ethyl stearate.

Claims (10)

1. A method for separating oxygenates from a coal-based wax oil, comprising the steps of: adding coal-based wax oil into a solid phase extraction column, firstly flushing the solid phase extraction column by adopting a first eluent to obtain a non-oxygen compound component, and then flushing the solid phase extraction column by adopting a second eluent to obtain an oxygen compound component; the solid phase extraction column is internally provided with a stationary phase which is a mixture of silica gel, alumina and water, wherein the content of water in the stationary phase is 0-10 wt%;
wherein 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 dosage of the first eluent is 10-15mL;
the second eluent is at least one selected from the group consisting of methanol, ethanol, isopropanol, acetone, butanone and acetonitrile; the dosage of the second eluent is 7-12 mL;
the oxygen-containing compound component is at least one of alcohols, ketones, aldehydes, esters and acids.
2. The method according to claim 1, wherein the specific surface area of the silica gel in the stationary phase is 500-850m 2 Per gram, a pore volume of 0.1-0.6mL/g and an average pore diameter of 1-4nm.
3. The method according to claim 1, wherein the specific surface area of the alumina in the stationary phase is 200-450m 2 Per gram, a pore volume of 0.05-0.4mL/g and an average pore diameter of 1-3nm.
4. The method according to claim 1, wherein the solid phase extraction column is prepared by uniformly mixing silica gel with alumina, adding water, uniformly mixing and filling; wherein the content of the alumina is 50-90 wt%.
5. The method of claim 1, further comprising the step of:
step one: 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 by using a first eluent, and adding a flowable wax oil sample from the upper layer of the solid phase extraction column;
step three: continuing to rinse the solid phase extraction column with the first eluent to obtain a non-oxygenate component;
step four: changing the collector, and flushing 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.
6. The method of claim 5, wherein the volume ratio of the diluent to the coal-based wax oil is 0.5-1:1.
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 waxy oil sample is added in an amount of 0.5 to 4mL.
9. The method according to claim 1, wherein the coal-based wax oil is a direct coal liquefaction wax oil or a wax oil produced by indirect coal liquefaction wax oil.
10. The method of claim 1, wherein the coal-based wax oil is a fischer-tropsch wax oil.
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