CN114075450B - Method for separating diesel oil group composition by solid phase extraction - Google Patents

Method for separating diesel oil group composition by solid phase extraction Download PDF

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CN114075450B
CN114075450B CN202010822713.1A CN202010822713A CN114075450B CN 114075450 B CN114075450 B CN 114075450B CN 202010822713 A CN202010822713 A CN 202010822713A CN 114075450 B CN114075450 B CN 114075450B
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phase extraction
solid phase
extraction column
eluent
diesel oil
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CN114075450A (en
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史得军
陈菲
王春燕
何京
薛慧峰
霍明辰
赫丽娜
王艳斌
田畅
师为炬
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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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • 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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Abstract

A solid-phase extraction method for separating diesel oil group components includes that diesel oil components can be divided into four parts of saturated hydrocarbon (alkane+cycloalkane), olefin, aromatic hydrocarbon and heteroatom compounds through a solid-phase extraction column. The solid phase extraction column used in the invention consists of solid phase extraction columns A and B, wherein the stationary phase of the solid phase extraction column A is a mixture of silica gel and alumina, and the content of the alumina is 80-90wt%; the stationary phase of the solid phase extraction column B is silica gel loaded with silver, and the loading amount of silver is 5-15wt%. The invention can separate and enrich saturated hydrocarbon, olefin, aromatic hydrocarbon and heteroatom compound in diesel oil at the same time, the component after separation can be used for the composition measurement of diesel oil family, have the advantage of short treatment time, low cross quantity of separation among components, little solvent consumption, high recovery rate.

Description

Method for separating diesel oil group composition by solid phase extraction
Technical Field
The invention relates to the field of coal chemical industry, in particular to a method for separating coal-based diesel oil samples into saturated hydrocarbon (alkane and naphthene), olefin, aromatic hydrocarbon and heteroatom compounds by adopting a solid-phase extraction method so as to provide experimental samples for subsequent measurement of diesel oil group compositions.
Background
In 2019, the external dependence of crude oil in China reaches over 70 percent, so that the energy safety of China is at great risk, and the stable and sustainable development of the economy of China is threatened, so that the crude oil exploitation strength is increased in China, and a feasible crude oil substitution strategy is provided. The energy resources of China have the characteristics of rich coal, lean oil and less gas, the modern coal chemical industry is developed fully, the process route of coal-based coal-to-oil and coal-to-chemical products is developed greatly, clean energy products such as clean oil products, natural gas and the like required by industrial production are produced, petroleum substitute products such as olefin, aromatic hydrocarbon and ethylene glycol are developed and extended, and the energy resources of China are important safety measures [ Gu Zongqin ] for guaranteeing the energy safety of China.
Although there is no essential difference in the types of compounds between coal-based oils and petroleum-based oils, there is a large difference in physical properties such as octane number and cetane number between them, and the composition of the compounds, due to the difference in the process routes [ public epitaxy, wu Xiuzhang, lu Weimin, etc. coal-based high temperature Fischer-Tropsch synthesis technology advances [ J ]. Chemical industry advances, 2016,35 (S1): 122-129 ]. In order to better use the coal-based oil product as the clean fuel, the group composition and the molecular composition of the coal-based oil product need to be researched firstly, then the processing technology is developed in a targeted way, and the molecular composition of the oil product is adjusted to produce the clean oil product with qualified quality.
The existing analysis coal-based oil group composition characterization method basically refers to a petroleum-based oil group composition determination method, and the difference of molecular compositions of the two is not considered, so that the determination result can not completely reflect the actual composition of the coal-based oil, and difficulties are caused to the research of reaction principles and the optimization of process conditions. For example, coal-based diesel fuel is often tested for its family composition using standard SH/T0606 formulated based on petroleum-based diesel fuel, but standard SH/T0606 requires that the non-hydrocarbon compound content of the diesel fuel sample is not higher than 0.2wt%, which may cause deterioration in reliability of the aromatic compound content in the test result; the olefin content of the diesel oil sample is not higher than 5wt%, otherwise the measured result is higher in naphthene content. Standard SH/T0606 is therefore not suitable for direct use in a coal-based diesel family composition analysis process.
Disclosure of Invention
The invention aims to provide a pretreatment method for simultaneously separating a coal-based diesel oil sample into saturated hydrocarbon (alkane and naphthene), olefin, aromatic hydrocarbon and heteroatom compounds by utilizing a solid-phase extraction technology, which can be used for enriching and purifying olefin and heteroatom compounds in the coal-based diesel oil sample and eliminating the interference of other hydrocarbon compounds on qualitative and quantitative analysis. The invention can also solve the problem that no pretreatment method for the composition of the coal-based diesel oil sample group exists, provides a feasible pretreatment means for accurately measuring the composition of the coal-based diesel oil sample group by using petrochemical standard SH/T0606, and expands the application range of the standard.
The invention provides a method for separating diesel oil group components by solid phase extraction, which comprises the following steps:
step one: connecting the solid phase extraction column A and the solid phase extraction column B in series, wherein the solid phase extraction column A is arranged on the solid phase extraction column A, wetting the solid phase extraction column A by adopting a first eluent, adding a diesel oil sample from the upper part of the solid phase extraction column A, and then flushing the solid phase extraction column by using the first eluent;
step two: separating the solid phase extraction column A from the solid phase extraction column B, and continuing to rinse the solid phase extraction column B with a first eluent to obtain a saturated hydrocarbon component;
step three: flushing the solid phase extraction column B with a second eluent to obtain an olefin component;
step four: flushing the solid phase extraction column A with a third eluent to obtain an aromatic hydrocarbon component;
step five: flushing the solid phase extraction column A by a fourth eluent to obtain a heteroatom compound;
wherein the first eluent is at least one selected from the group consisting of n-pentane, n-hexane, n-heptane and petroleum ether;
the second eluent is a mixture of a and b, wherein a is at least one selected from the group consisting of dichloromethane, chloroform, diethyl ether, benzene and toluene, and b is at least one selected from the group consisting of methanol, ethanol, isopropanol, acetone and butanone;
the third eluent is a mixture of c and d, wherein c is at least one selected from the group consisting of n-pentane, n-hexane, n-heptane and petroleum ether, and d is at least one selected from the group consisting of dichloromethane, chloroform, diethyl ether, benzene and toluene;
the fourth eluent is at least one selected from the group consisting of methanol, ethanol, isopropanol, acetone and butanone.
The method for separating the diesel oil group composition by solid phase extraction is characterized in that a stationary phase is filled in a solid phase extraction column A, wherein the stationary phase is alumina or a mixture of silica gel and alumina, and the content of the alumina is 80-100wt%.
The method for separating the diesel oil group composition by solid phase extraction is characterized in that a stationary phase is filled in a solid phase extraction column B, the stationary phase is silica gel loaded with silver, and the loading amount of the silver is 5-15wt%.
The method for separating the diesel oil group composition by solid phase extraction is characterized in that the specific surface area of the silica gel 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 diesel oil group composition by solid phase extraction is characterized in that the specific surface area of the alumina 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 diesel oil group composition by solid phase extraction is characterized in that the volume ratio of a to b in the second eluent is 1.5-19:1.
The method for separating the diesel oil group composition by solid phase extraction is characterized in that the volume ratio of c to d in the third eluent is 1.5-9:1.
The method for separating the diesel oil group composition by solid phase extraction is characterized by comprising the following steps of 0.07-0.7:1 of the mass ratio of the addition amount of a diesel oil sample to the solid phase extraction column A and 0.07-0.7:1 of the mass ratio of the addition amount of the diesel oil sample to the solid phase extraction column B.
The method for separating the diesel oil group composition by solid phase extraction is characterized in that in the first step, the volume usage of a first eluent for wetting a solid phase extraction column A is 0.5mL, the volume usage of a first eluent for flushing the solid phase extraction columns A and B is 1.5-5mL, and in the second step, the volume usage of a first eluent for flushing the solid phase extraction column B is 2-4mL.
The method for separating the diesel oil group components by solid phase extraction is characterized in that in the third step, the volume usage of the second eluent is 2-6mL.
The method for separating the diesel oil group components by solid phase extraction is characterized in that in the fourth step, the volume usage amount of the third eluent is 2-6mL.
The method for separating the diesel oil group components by solid phase extraction is characterized in that in the fifth step, the volume dosage of the fourth eluent is 2-6mL.
The method for separating the diesel oil group components by solid phase extraction is characterized in that the diesel oil sample is diesel oil of a coal chemical process.
The method for separating the coal-based diesel oil group composition by solid phase extraction is characterized in that the diesel oil sample is coal direct liquefied diesel oil and coal indirect liquefied diesel oil.
The solid phase extraction is to separate the substances into components with different polarities by adjusting the polarity of the eluent by utilizing the difference of the adsorption capacity of different compounds on the stationary phase. Therefore, the choice of eluent for solid-phase extraction is very important, but even if the same solvent is mixed in different proportions, eluents of different polarity and different solvent selectivity are obtained, resulting in a great difference in the final separation result. The polarity of the naphthene and the olefine, and the aromatic hydrocarbon and the ether compound in the coal-based diesel is similar, and the two groups of compounds are difficult to separate well. In addition, there is no report on separation of aromatic hydrocarbons and heteroatom compounds in coal-based diesel by solid phase extraction.
The invention can be further described as follows:
in order to achieve the above purpose, the invention provides a solid phase extraction method, which realizes the separation of different components in a diesel oil sample through the cooperation of solid phase extraction columns A and B. The stationary phase of the solid phase extraction column A is a mixture of silica gel and alumina, wherein the content of the alumina is 80-100wt%; the stationary phase of the solid phase extraction column B is silica gel loaded with silver, wherein the loading amount of the silver is 5-15wt%. The invention can be used for enriching olefin and heteroatom compounds in coal-based diesel oil samples, solves the problem that other hydrocarbon compounds interfere two qualitative and quantitative methods, and can also solve the problem that no pretreatment method for separating coal-based diesel oil sample group components is available, thereby providing a feasible pretreatment means for accurately quantifying coal-based diesel oil sample group components by using petrochemical standard SH/T0606 and expanding the application range of the standard.
The preparation method of the silica gel and neutral alumina stationary phase comprises the following steps: drying silica gel at 80-160deg.C for 2-6 hr, and cooling in a dryer to obtain activated silica gel; roasting neutral alumina at 350-550 deg.c for 1-5 hr, and cooling in drier to obtain activated neutral alumina. Mixing the activated silica gel with the silver nitrate solution in equal volume according to the silver loading amount of 5-15wt%, standing for 24 hours, drying at 80-160 ℃ for 2-6 hours, and then putting into a dryer for cooling to obtain the activated silver-loaded silica gel. Mixing silica gel and alumina according to a certain proportion to obtain a stationary phase of the solid phase extraction column A, and mixing silver-carrying silica gel and alumina according to a certain proportion to obtain a stationary phase of the solid phase extraction column B.
The solution obtained by solid phase extraction and separation is subjected to solvent volatilization and concentration to obtain each component of diesel oil, and nitrogen is preferably selected for blowing to carry out product concentration. The solution is volatilized and concentrated to about 0.5mL to carry out relevant analysis by Gas Chromatography (GC), and the analysis can be carried out by directly carrying out chromatography without concentration under partial conditions. The analysis is preferably carried out using a Gas Chromatograph (GC) -Mass Spectrometer (MS) -hydrogen Flame Ionization Detector (FID). Mass spectrometry is one of main research tools for qualitative structure of compounds, and various compounds in the enriched materials can be qualitatively analyzed through means of spectrogram retrieval and the like. It is considered that the hydrogen flame ionization detector has little difference in the influencing factors of the compounds, so that the components can be quantitatively analyzed through a GC-FID chromatogram to judge the degree of separation crossing amount. And (3) injecting the enriched liquid into a gas chromatograph, separating by a chromatographic column in the gas chromatograph according to the boiling point and the polarity of the compound, and then entering a detector to obtain the monomer content information of the compound. The quantitative method can adopt an internal standard method, and the internal standard is preferably deuterated terphenyl or chlorobenzene.
The invention adopts a solid-phase extraction method to separate the coal-based diesel into components with different compositions, and the diesel sample is separated into four parts of saturated hydrocarbon (alkane+cycloalkane), olefin, aromatic hydrocarbon and heteroatom compound by adjusting the polarity and the dosage of the eluent, so that the separation and the intersection between the components are smaller. The invention can solve the problem of quantitative interference of olefin and heteroatom compounds on olefin and arene when coal-based diesel oil is analyzed by petrochemical standard 0606. Compared with the traditional column chromatography, the solid-phase extraction method adopted by the invention has high column efficiency, high extraction column filling repeatability, low solvent consumption and high speed, and the solvent is eluted under pressure. According to the invention, the olefin and the heteroatom compound in the enriched diesel oil sample can be separated and enriched at one time, the time for one-time separation is only 30min, and the separation efficiency is greatly improved.
Drawings
FIG. 1 is a GC-MS diagram of a saturated hydrocarbon (alkane+cycloalkane) component obtained by applying the pretreatment method of example 1 of the present invention;
FIG. 2 is a GC-MS diagram of an olefin composition obtained by applying the pretreatment method of example 1 of the present invention;
FIG. 3 is a GC-MS diagram of an aromatic hydrocarbon component obtained by applying the pretreatment method of example 1 of the present invention;
FIG. 4 is a GC-MS diagram of a heteroatom compound component obtained by applying the pretreatment method of example 1 of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. The present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
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.
The silica gel used in the examples is silica gel for chromatography produced by national pharmaceutical systems and chemical reagents, inc., with a particle size of 70.0% or more and a specific surface area of 511.9m 2 Per gram, pore volume was 0.468mL/g. The neutral alumina is chromatographic neutral alumina produced by national pharmaceutical chemicals, inc., has a loss on ignition of less than or equal to 8.0% and a specific surface area of 177.8m 2 Per gram, pore volume was 0.255mL/g.
Drying the silica gel at 140 ℃ for 5 hours to obtain activated silica gel; the neutral alumina was calcined at 500 c for 3 hours to obtain activated neutral alumina. And uniformly mixing the activated silica gel and the neutral alumina according to the proportion to obtain the neutral alumina-silica gel stationary phase used by the solid phase extraction column A. Mixing the activated silica gel with the silver nitrate solution in equal volume according to the silver loading of 5-15wt%, standing for 24h, drying at 140 ℃ for 5 hours, and cooling in a dryer to obtain the activated silver-loaded silica gel. And mixing the silver-carrying silica gel with alumina according to a certain proportion to obtain a stationary phase of the solid phase extraction column B.
The GC-MS instrument used for the analysis was model 7890A GC-5975MS with FID detector. GC conditions: HP-PONA capillary chromatographic column, 50m x 0.2mm x 0.5 μm; heating to 80deg.C, maintaining for 5min, heating at 40deg.C/min, and maintaining at 300 deg.C for 9min; 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 320 ℃, 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 230 ℃, quaternary rod temperature 130 ℃, full scan mass range 30-500u, interface temperature 310 ℃, solvent delay 5min. 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
1.2g of alumina stationary phase is filled in a solid phase extraction column A, 1.2g of silver-loaded silica gel stationary phase with a silver content of 5wt% is filled in a solid phase extraction column B, and the solid phase extraction column A is wetted with 0.5mL of a first eluent (n-pentane).
A sample of 0.08g of high-temperature Fischer-Tropsch synthesis No. 1 diesel oil from a certain company is taken by a liquid-transfering gun, added into the upper part of the solid-phase extraction column A and completely adsorbed by the stationary phase. The solid phase extraction column A+B was washed with 1.5mL of the first eluent, then the solid phase extraction columns A and B were separated, and 2mL of the first eluent was continuously added to the solid phase extraction column B to obtain saturated hydrocarbons, which were designated as component 1. The solid phase extraction column B was washed with 6mL of a second eluent (volume ratio of dichloromethane to ethanol 90:10) to give an olefin fraction designated as fraction 2. The solid phase extraction column A was washed with 4mL of a third eluent (90:10 volume ratio of n-pentane to dichloromethane) to afford the aromatic hydrocarbon, designated as component 3. The solid phase extraction column A was rinsed with 6mL of a fourth eluent, methanol, to afford the heteroatom compound designated as component 4. Adding a certain amount of deuterated terphenyl as an internal standard into each component, and removing the solvent in each component by adopting nitrogen purging.
The GC-MS-FID analysis of the components 1, 2, 3 and 4 shows that the component 1 is mainly saturated hydrocarbon and accounts for 12.3wt% of the diesel oil sample, wherein the content of the impurity olefin component is 0.3wt%; component 2 is mainly olefin and accounts for 58.4wt% of the diesel oil sample, wherein the impurity saturated hydrocarbon content is 0.1wt% and the diesel oil sample is basically free of aromatic hydrocarbon; component 3 is mainly aromatic hydrocarbon and accounts for 13.2wt% of the diesel oil sample, the content of impurity olefin is 0.5wt% and the content of oxygen-containing compound is 0.2wt%; component 4 is mainly an oxygen-containing compound accounting for 14.9wt% of the diesel oil sample, and the content of impurity aromatic hydrocarbon is 0.1wt%.
The effect of separating each component of diesel oil by a solid-phase extraction method is examined by using the marked recovery rate of decene-1 and n-octanol. Two low-temperature Fischer-Tropsch synthesis 1# diesel oil samples of a certain company are taken, and a certain amount of decene-1 and n-octanol are added into one sample to serve as standard adding samples. The two samples are respectively separated into four parts according to the solid-phase extraction method, a certain amount of deuterated terphenyl is added as an internal standard, and the content of each compound is analyzed by GC-FID. The ratio of the difference of the content of decen-1 and n-octanol in the marked sample minus the content of decen-1 and n-octanol in the unmarked sample to the theoretical value of decen-1 and n-octanol added is the marked recovery rate of the two compounds, and the values are 96.7% and 97.8% in sequence.
The results show that the method has high recovery rate of each component in the separated components, low crossing quantity among the components and good enrichment effect.
Example 2
1.2g of alumina stationary phase is filled in a solid phase extraction column A, 1.2g of silver-loaded silica gel stationary phase with 8wt% silver content is filled in a solid phase extraction column B, and the solid phase extraction column A is wetted with 0.5mL of a first eluent (n-hexane).
A liquid-transfering gun is used to take 0.24g of 2# diesel oil sample produced by high temperature Fischer-Tropsch synthesis of a company, and the sample is added into the upper part of the solid phase extraction column A and is completely adsorbed by the stationary phase. The solid phase extraction column A+B was washed with 4mL of the first eluent, then the solid phase extraction columns A and B were separated, and 3mL of the first eluent was continuously added to the solid phase extraction column B to obtain saturated hydrocarbons, which were designated as component 1. The solid phase extraction column B was washed with 6mL of a second eluent (volume ratio of dichloromethane to ethanol: 85:15) to give an olefin fraction designated as fraction 2. The solid phase extraction column A was washed with 6mL of a third eluent (volume ratio of n-hexane to dichloromethane 90:10) to give aromatic hydrocarbon, designated as component 3. The solid phase extraction column A was rinsed with 6mL of a fourth eluent, methanol, to afford the heteroatom compound designated as component 4. Adding a certain amount of deuterated terphenyl as an internal standard into each component, and removing the solvent in each component by adopting nitrogen purging.
The separation effect of the high-temperature Fischer-Tropsch synthesis diesel oil pretreated by a solid-phase extraction method is examined by using the standard recovery rate of decene-1 and n-octanol, and the standard recovery rates of the decene-1 and n-octanol are 94.5% and 95.2% in sequence.
Example 3
1.2g of silica gel-alumina stationary phase with 90wt% alumina content is filled in the solid phase extraction column A, 1.2g of silver-loaded silica gel stationary phase with 10wt% silver content is filled in the solid phase extraction column B, and the solid phase extraction column A is wetted with 0.5mL of a first eluent (n-hexane).
0.56g of a 3# diesel oil sample directly liquefied by a certain company is taken by a liquid-transferring gun, added into the upper part of the solid-phase extraction column A and completely adsorbed by the stationary phase. The solid phase extraction column A+B was washed with 4mL of the first eluent, then the solid phase extraction columns A and B were separated, and 2mL of the first eluent was continuously added to the solid phase extraction column B to obtain saturated hydrocarbons, which were designated as component 1. The solid phase extraction column B was washed with 2mL of a second eluent (volume ratio of dichloromethane to ethanol: 70:30) to give an olefin fraction, designated fraction 2. The solid phase extraction column A was washed with 3mL of a third eluent (volume ratio of n-hexane to dichloromethane: 75:25) to give aromatic hydrocarbon, designated as component 3. The solid phase extraction column A was rinsed with 4mL of a fourth eluent, methanol, to afford the heteroatom compound designated as component 4. Adding a certain amount of deuterated terphenyl as an internal standard into each component, and removing the solvent in each component by adopting nitrogen purging.
The GC-MS-FID analysis of the components 1, 2, 3 and 4 shows that the component 1 is mainly saturated hydrocarbon and accounts for 55.1wt% of the diesel oil sample, wherein the content of the impurity olefin component is 0.1wt%; the component 2 is mainly olefin and accounts for 8.7wt% of the diesel oil sample, wherein the impurity saturated hydrocarbon content is 0.1wt% and the aromatic hydrocarbon content is 0.0wt%; component 3 is mainly aromatic hydrocarbon and accounts for 20.7wt% of the diesel oil sample, wherein the content of impurity olefin is 0.2wt% and the content of heteroatom compound is 1.1wt%; component 4 is a nitrogen-containing and oxygen-containing compound accounting for 13.7wt% of the diesel oil sample, wherein the content of impurity aromatic hydrocarbon is 0.3wt%.
The separation effect of the direct liquefied diesel oil pretreated by the solid-phase extraction method is examined by using the standard recovery rate of decen-1 and n-octanol, and the standard recovery rates of the decen-1 and n-octanol are 97.9% and 98.1% in sequence.
Example 4
1.2g of silica gel-alumina stationary phase with 80wt% alumina content is filled in the solid phase extraction column A, 1.2g of silver-loaded silica gel stationary phase with 15wt% silver content is filled in the solid phase extraction column B, and the solid phase extraction column A is wetted with 0.5mL of a first eluent (n-hexane).
A sample of 0.80g of low-temperature Fischer-Tropsch synthesis No. 4 diesel oil from a certain company is taken by a liquid-transferring gun, added into the upper part of the solid-phase extraction column A and completely adsorbed by a stationary phase. The solid phase extraction column A+B was washed with 5mL of the first eluent, then the solid phase extraction columns A and B were separated, and 4mL of the first eluent was continuously added to the solid phase extraction column B to obtain saturated hydrocarbons, which were designated as component 1. The solid phase extraction column B was washed with 4mL of a second eluent (volume ratio of dichloromethane to ethanol: 60:40) to give an olefin fraction designated as fraction 2. The solid phase extraction column A was washed with 2mL of a third eluent (60:40 volume ratio of n-hexane to dichloromethane) to afford the aromatic hydrocarbon, designated as component 3. The solid phase extraction column A was rinsed with 2mL of a fourth eluent, methanol, to afford the heteroatom compound designated as component 4. Adding a certain amount of deuterated terphenyl as an internal standard into each component, and removing the solvent in each component by adopting nitrogen purging.
The GC-MS-FID analysis of the components 1, 2, 3 and 4 shows that the component 1 is mainly saturated hydrocarbon and accounts for 75.7wt% of the diesel oil sample, wherein the content of the impurity olefin component is 0.0wt%; component 2 is mainly olefin and accounts for 15.4wt% of the diesel oil sample, wherein the impurity saturated hydrocarbon content is 0.5wt% and the diesel oil sample is basically free of aromatic hydrocarbon; component 3 is mainly aromatic hydrocarbon, accounting for 5.6wt% of the diesel oil sample, the content of impurity olefin is 0.0wt% and the content of oxygen-containing compound is 0.1wt%; component 4 is mainly an oxygen-containing compound accounting for 2.6wt% of the diesel oil sample, and the content of impurity aromatic hydrocarbon is 0.1wt%.
The separation effect of the low-temperature Fischer-Tropsch synthesis diesel oil pretreated by a solid-phase extraction method is examined by using the standard recovery rate of decene-1 and n-octanol, and the standard recovery rates of the decene-1 and n-octanol are 99.1% and 96.5% in sequence.
Comparative example 1
And (3) separating and enriching a high-temperature Fischer-Tropsch synthesis No. 1 diesel oil sample of a certain company according to a method described in a petrochemical standard SH/T0606 annex B.
0.1mL of sample is dripped into the upper part of a special solid phase extraction column for petrochemical standard SH/T0606 and is completely adsorbed. The stationary phase was washed successively with 2mL of n-pentane and 0.5mL of methylene chloride, and saturated hydrocarbons were obtained by extraction. The stationary phase was then rinsed with 2mL of dichloromethane to give the aromatic hydrocarbon. Adding a certain amount of normal triacontane as an internal standard, and entering a GC-MS-FID analysis group to form, wherein the result shows that the content of saturated hydrocarbon components accounts for 70.5wt% of the total amount of the diesel oil sample, and the content of impurity aromatic hydrocarbon is 2.4wt%; the content of aromatic hydrocarbon component was 22.6wt% and the content of impurity saturated hydrocarbon was 4.5wt%.
Therefore, compared with the solid-phase extraction method provided by the invention, the solid-phase extraction method adopting the petrochemical standard SH/T0606 can only obtain saturated hydrocarbon and aromatic hydrocarbon components, wherein olefin can influence the quantification of saturated hydrocarbon, and an oxygen-containing compound can influence the quantification of aromatic hydrocarbon components, so that the results of the content of saturated hydrocarbon and aromatic hydrocarbon in the measurement result are higher, and the accuracy of the measurement result is influenced.
Comparative example 2
The column was packed with 20g of silica gel.
10mL of n-pentane was added to activate the column. When the liquid level of n-pentane is lower than the upper part of the chromatographic column, 2g of high-temperature Fischer-Tropsch synthesis No. 1 diesel oil of a certain company is removed by a liquid-transferring gun and added into the upper part of the chromatographic column. 2g of quartz sand was added to fix the diesel sample. 35mL of n-pentane was added to elute the saturated hydrocarbon component, 60mL of toluene was added to elute the aromatic hydrocarbon, 50mL of methanol was added to elute the heteroatom compound, and the flow rate of the eluent was adjusted to 1.5mL/min with double-stranded spheres. The solvent in each component was removed by nitrogen purging. The whole process takes 160min.
The GC-MS-FID analysis of the components 1, 2 and 3 shows that the component 1 is mainly saturated hydrocarbon, the impurity aromatic hydrocarbon component content is 8.9wt%, the component 2 is mainly aromatic hydrocarbon, the impurity saturated hydrocarbon content is 10.5wt%, the heteroatom compound content is 8.5wt%, and the component 3 is mainly oxygen-containing compound, wherein the impurity aromatic hydrocarbon content is 12.5wt%.
Therefore, when the column chromatography is adopted to separate the coal-based diesel oil sample, the time consumption is long, the solvent consumption is large, the stationary phase consumption is large, the paraffin and the olefin cannot be separated, and the method is not suitable for pretreatment for measuring the composition of the coal-based diesel oil.

Claims (14)

1. The method for separating the coal-based diesel oil group composition by solid phase extraction is characterized by comprising the following steps:
step one: connecting the solid phase extraction column A and the solid phase extraction column B in series, wherein the solid phase extraction column A is arranged on the solid phase extraction column A, wetting the solid phase extraction column A by using a first eluent, adding a coal-based diesel oil sample from the upper part of the solid phase extraction column A, and then flushing the solid phase extraction column A and the solid phase extraction column B by using the first eluent;
step two: separating the solid phase extraction column A from the solid phase extraction column B, and continuing to rinse the solid phase extraction column B with a first eluent to obtain a saturated hydrocarbon component;
step three: flushing the solid phase extraction column B with a second eluent to obtain an olefin component;
step four: flushing the solid phase extraction column A with a third eluent to obtain an aromatic hydrocarbon component;
step five: flushing the solid phase extraction column A by a fourth eluent to obtain a heteroatom compound;
wherein the first eluent is at least one selected from the group consisting of n-pentane, n-hexane, n-heptane and petroleum ether;
the second eluent is a mixture of a and b, wherein a is at least one selected from the group consisting of dichloromethane, chloroform, diethyl ether, benzene and toluene, and b is at least one selected from the group consisting of methanol, ethanol, isopropanol, acetone and butanone;
the third eluent is a mixture of c and d, wherein c is at least one selected from the group consisting of n-pentane, n-hexane, n-heptane and petroleum ether, and d is at least one selected from the group consisting of dichloromethane, chloroform, diethyl ether, benzene and toluene;
the fourth eluent is at least one selected from the group consisting of methanol, ethanol, isopropanol, acetone and butanone;
the heteroatom compound comprises at least one of an oxygen-containing compound and a nitrogen-containing compound.
2. The method according to claim 1, wherein the solid phase extraction column a is filled with a stationary phase, which is alumina, or a mixture of silica gel and alumina, wherein the content of alumina is 80-100wt%.
3. The method according to claim 1, wherein the solid phase extraction column B is filled with a stationary phase which is silver-loaded silica gel, wherein the silver loading is 5-15wt%.
4. The method according to claim 2, wherein the specific surface area of the silica gel is 500-850m 2 Per gram, the pore volume is 0.1-0.6mL/g, and the average pore diameter is 1-4nm.
5. The method according to claim 2, wherein the specific surface area of the alumina is 200-450m 2 Per gram, the pore volume is 0.05-0.4mL/g, and the average pore diameter is 1-3nm.
6. The method of claim 1, wherein the volume ratio of a to b in the second eluent is 1.5-19:1.
7. The method of claim 1, wherein the volume ratio of c to d in the third eluent is 1.5-9:1.
8. The method according to claim 1, wherein in the first step, the mass ratio of the addition amount of the coal-based diesel oil sample to the solid phase extraction column a is 0.07-0.7:1, and the mass ratio of the addition amount of the coal-based diesel oil sample to the solid phase extraction column B is 0.07-0.7:1.
9. The method according to claim 1, wherein in the first step, the volume of the first eluent used for wetting the solid phase extraction column a is 0.5mL, and the volume of the first eluent used for washing the solid phase extraction columns a and B is 1.5-5mL; in the second step, the volume dosage of the first eluent for flushing the solid-phase extraction column B is 2-4mL.
10. The method of claim 1, wherein in step three, the volume of the second eluent is used in an amount of 2-6mL.
11. The method of claim 1, wherein in step four, the volume of the third eluent is 2-6mL.
12. The method of claim 1, wherein in step five, the fourth eluent is used in a volume amount of 2-6mL.
13. The method of claim 1, wherein the coal-based diesel fuel sample is diesel fuel of a coal chemical process.
14. The method of claim 1, wherein the coal-based diesel sample is a direct coal liquefaction diesel or an indirect coal liquefaction diesel.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104749298A (en) * 2013-12-30 2015-07-01 中国石油化工股份有限公司 Solid phase extraction column for separating different hydrocarbon components in diesel oil and application method
CN106318438A (en) * 2015-06-17 2017-01-11 中国石油天然气股份有限公司 Double-column solid phase extraction method of nitrogen-containing compounds in diesel oil
CN109839448A (en) * 2017-11-28 2019-06-04 中国石油天然气股份有限公司 The method of phenolic compound in solid-phase extraction column and Solid phase extraction separation diesel oil

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104749298A (en) * 2013-12-30 2015-07-01 中国石油化工股份有限公司 Solid phase extraction column for separating different hydrocarbon components in diesel oil and application method
CN106318438A (en) * 2015-06-17 2017-01-11 中国石油天然气股份有限公司 Double-column solid phase extraction method of nitrogen-containing compounds in diesel oil
CN109839448A (en) * 2017-11-28 2019-06-04 中国石油天然气股份有限公司 The method of phenolic compound in solid-phase extraction column and Solid phase extraction separation diesel oil

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