CN114075450A - Method for solid phase extraction separation of diesel oil family composition - Google Patents

Method for solid phase extraction separation of diesel oil family composition Download PDF

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CN114075450A
CN114075450A CN202010822713.1A CN202010822713A CN114075450A CN 114075450 A CN114075450 A CN 114075450A CN 202010822713 A CN202010822713 A CN 202010822713A CN 114075450 A CN114075450 A CN 114075450A
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phase extraction
solid phase
extraction column
eluent
diesel oil
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CN114075450B (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

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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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

A solid-phase extraction method for separating diesel oil from its components features that the diesel oil is separated into four parts, namely saturated hydrocarbon (paraffin and cyclane), olefin, aromatic hydrocarbon and heteroatom compound, by solid-phase extraction column. The solid phase extraction column used in the invention consists of a solid phase extraction column A and a solid phase extraction column 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 80-90 wt%; the stationary phase of the solid phase extraction column B is silica gel loaded with silver, and the loading amount of the silver is 5-15 wt%. The method can simultaneously separate and enrich saturated hydrocarbon, olefin, aromatic hydrocarbon and heteroatom compounds in the diesel oil, and the separated components can be used for determining the composition of diesel oil families, and have the advantages of short processing time, low separation cross amount among the components, small solvent consumption and high recovery rate.

Description

Method for solid phase extraction separation of diesel oil family composition
Technical Field
The invention relates to the field of coal chemical industry, in particular to a method for separating a coal-based diesel oil sample into saturated hydrocarbon (alkane and cyclane), olefin, aromatic hydrocarbon and heteroatom compounds by adopting a solid phase extraction method so as to provide an experimental sample for the subsequent determination of diesel oil family composition.
Background
In 2019, the external dependence of crude oil in China reaches over 70 percent, so that the energy safety in China has a large risk, and the stable and continuous development of economy in China is threatened, so that the crude oil exploitation strength in China is increased, and a feasible crude oil replacement strategy is provided. The energy resources in China have the characteristics of rich coal, poor oil and less gas, the modern coal chemical industry is developed completely, the coal-to-oil and coal-to-chemical product process route based on coal is developed vigorously, clean energy products such as clean oil products and natural gas required by industrial production are produced, and petroleum substitute products such as olefin, aromatic hydrocarbon and glycol are developed in an extending way, so that the method is an important safety measure for guaranteeing the energy safety in China [ Guzongzhilin, China modern coal chemical industry progress [ J ] coal processing and comprehensive utilization, 2016,199(04):6-10 ].
Although there is no essential difference in the kind of compounds between the coal-based oil product and the petroleum-based oil product, there is a large difference in the physical properties such as octane number and cetane number and the composition of the compounds due to the difference in the process route [ Gong Lai, Wu Xiu Chao, Luweimin, etc.. coal-based high temperature Fischer-Tropsch synthesis technology progress [ J ] chemical engineering progress 2016,35(S1): 122-. In order to better use coal-based oil products as clean fuels, the family composition and the molecular composition of the coal-based oil products need to be researched, and then a processing technology is developed in a targeted manner to adjust the molecular composition of the oil products and produce the clean oil products with qualified quality.
At present, a method for analyzing the characterization of the coal-based oil group composition basically refers to a method for determining the petroleum-based oil group composition, and the difference of the molecular compositions of the coal-based oil group composition and the petroleum-based oil group composition is not considered, so that the determination result cannot completely reflect the actual composition of the coal-based oil, and the difficulties are caused for the research of the reaction principle and the optimization of the process conditions. For example, the family composition of coal-based diesel oil is usually determined by using a standard SH/T0606 established on the basis of petroleum-based diesel oil, but the standard SH/T0606 requires that the content of non-hydrocarbon compounds in a diesel oil sample is not higher than 0.2 wt%, and otherwise, the reliability of the content of aromatic compounds in a determination result is poor; the olefin content of the diesel sample was not higher than 5 wt%, which would result in a higher naphthene content. Therefore, the standard SH/T0606 is not suitable for being directly used in the 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 hydrocarbons (alkane and cyclane), olefins, aromatic hydrocarbons and heteroatom compounds by utilizing a solid phase extraction technology, which can be used for enriching and purifying the olefins and the 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 a pretreatment method for the composition of the coal-based diesel oil sample group does not exist, provides a feasible pretreatment means for accurately measuring the composition of the coal-based diesel oil sample group by applying petrochemical standard SH/T0606, and enlarges 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:
the method comprises the following steps: connecting a solid phase extraction column A and a solid phase extraction column B in series, wherein the solid phase extraction column A is arranged above the solid phase extraction column A, wetting the solid phase extraction column A by using a first eluent, adding a diesel oil sample from the upper part of the solid phase extraction column A, and then washing 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 continuously washing the solid phase extraction column B by using a first eluent to obtain a saturated hydrocarbon component;
step three: washing the solid phase extraction column B with a second eluent to obtain an olefin component;
step four: washing the solid phase extraction column A with a third eluent to obtain an aromatic hydrocarbon component;
step five: washing the solid phase extraction column A with 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 components of the diesel oil family by solid phase extraction is characterized in that a solid phase is arranged in a solid phase extraction column A, and the solid phase is a mixture of silica gel and alumina, wherein the content of the alumina is 80-100 wt%.
The method for separating the components of the diesel oil family by solid-phase extraction is characterized in that a solid phase is arranged in a solid-phase extraction column B, the solid phase is silica gel loaded with silver, and the loading amount of the silver is 5-15 wt%.
The method for separating the components of the diesel oil family by solid phase extraction is characterized in that the specific surface area of the silica gel is 500-850m2Per g, pore volume of 0.1-0.6mL/g, average pore diameter of 1-4 nm.
The method for separating the components of the diesel oil family by solid phase extraction is characterized in that the specific surface area of the alumina is 200-450m2Per g, pore volume of 0.05-0.4mL/g, average pore diameter of 1-3 nm.
The method for separating diesel oil group components 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 diesel oil group components 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 components by solid phase extraction is characterized in that the mass ratio of the addition amount of a diesel oil sample to a solid phase extraction column A is 0.07-0.7:1, and the mass ratio of the addition amount of the diesel oil sample to a solid phase extraction column B is 0.07-0.7: 1.
The method for separating diesel oil group components by solid phase extraction is characterized in that in the step one, the volume consumption of the first eluent for wetting the solid phase extraction column A is 0.5mL, the volume consumption of the first eluent for washing the solid phase extraction columns A and B is 1.5-5mL, and in the step two, the volume consumption of the first eluent for washing the solid phase extraction column B is 2-4 mL.
The method for separating the diesel oil composition by solid phase extraction is characterized in that in the third step, the volume dosage of the second eluent is 2-6 mL.
The method for separating the diesel oil composition by solid phase extraction is characterized in that in the fourth step, the volume dosage of the third eluent is 2-6 mL.
The method for separating the diesel oil group components by solid phase extraction is characterized in that in the fifth step, the volume usage amount of the fourth eluent is 2-6 mL.
The method for separating the components of the diesel oil family by solid phase extraction is characterized in that the diesel oil sample is the diesel oil of a coal chemical process.
The method for separating the components of the coal-based diesel group by solid phase extraction is characterized in that the diesel sample is coal direct liquefied diesel and coal indirect liquefied diesel.
Solid phase extraction is to separate substances into components with different polarities by adjusting the polarity of an eluent by utilizing the difference of adsorption capacities of different compounds on a stationary phase. Therefore, the choice of eluent for solid phase extraction is very important, but even mixing the same solvent in different ratios will result in eluents of different polarity and different solvent selectivity, resulting in a great difference in the final separation results. The polarity of naphthenic hydrocarbon and olefin, aromatic hydrocarbon and ether compounds in the coal-based diesel oil is similar, so that the two groups of compounds are difficult to be well separated. In addition, no relevant report on the separation of aromatic hydrocarbons and heteroatom compounds in coal-based diesel oil by using solid phase extraction exists at present.
The invention can also be detailed as follows:
in order to achieve the purpose, the invention provides a solid phase extraction method, which realizes the separation of different components in a diesel oil sample by the cooperation of a solid phase extraction column A and a solid phase extraction column 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 80-100 wt%; the stationary phase of the solid phase extraction column B is silica gel loaded with silver, wherein the silver loading is 5-15 wt%. The invention can be used for enriching olefin and heteroatom compounds in coal-based diesel oil samples, solves the interference of other hydrocarbon compounds on two qualitative and quantitative methods, also can solve the problem that a pretreatment method for separating the composition of coal-based diesel oil samples is not available, provides a feasible pretreatment means for accurately quantifying the composition of the coal-based diesel oil samples by applying petrochemical standard SH/T0606, and enlarges the application range of the standard.
The preparation method of the silica gel and neutral alumina stationary phase comprises the following steps: drying the silica gel at 80-160 ℃ for 2-6 hours, and then putting the silica gel into a dryer for cooling to obtain activated silica gel; the neutral alumina is roasted for 1 to 5 hours at the temperature of 350-550 ℃, and then is put into a dryer for cooling, so as to obtain the activated neutral alumina. And mixing the activated silica gel with silver nitrate solution in equal volume according to the silver loading of 5-15 wt%, standing for 24h, drying at 80-160 ℃ for 2-6 h, and cooling in a dryer to obtain the activated silver-loaded silica gel. Mixing silica gel and alumina according to a certain proportion to obtain a stationary phase of a solid-phase extraction column A, and mixing silver-loaded silica gel and alumina according to a certain proportion to obtain a stationary phase of a solid-phase extraction column B.
The solution obtained by solid phase extraction and separation can be subjected to solvent volatilization and concentration to obtain each component of the diesel oil, and nitrogen purging is preferably selected for product concentration. The solution is volatilized and concentrated to about 0.5mL, and then the related analysis can be carried out by Gas Chromatography (GC), and the analysis can also be carried out by directly carrying out the chromatography without concentration under partial conditions. Preferably, the analysis is performed by Gas Chromatography (GC) -Mass Spectrometry (MS) -hydrogen Flame Ionization Detector (FID). The mass spectrum is one of main research tools for the structure qualitative of the compounds, and various compounds in the enriched substances can be qualitatively analyzed by means of spectrogram retrieval and the like. Since the influence factors of the hydrogen flame ionization detector on the compounds are considered to be not very different, the components can be quantitatively analyzed by a GC-FID chromatogram to judge the level of the separation cross amount. And (3) injecting the enriched liquid into a gas chromatography, separating the enriched liquid by a chromatographic column in the gas chromatography 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 quantification can be performed by an internal standard method, and the internal standard substance is preferably deuterated terphenyl or chlorobenzene.
The invention adopts a solid phase extraction method to separate coal-based diesel into components with different compositions, and separates a diesel sample into four parts of saturated hydrocarbon (alkane and cyclane), olefin, aromatic hydrocarbon and heteroatom compounds by adjusting the polarity and the dosage of an eluent, so that the separation cross among the components is small. The method can solve the problem that olefin and heteroatom compounds interfere with the quantification of olefin and aromatic hydrocarbon when the coal-based diesel oil is analyzed by adopting petrochemical standard 0606. Compared with the traditional column chromatography, the solid phase extraction method adopted by the invention has high column efficiency, high repeatability of the filling of the extraction column, elution solvent under pressure and small solvent dosage, so that the method has high repeatability and high speed. The method can simultaneously separate and enrich the olefin and the heteroatom compounds in the diesel oil sample at one time, and the time for one-time separation is only 30min, thereby greatly improving the separation efficiency.
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 component 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 the heteroatom compound component obtained by applying the pretreatment method of example 1 of the present invention.
Detailed Description
The following provides a detailed description of embodiments of the invention. The present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
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 neutral alumina is chromatographic neutral alumina produced by national drug group chemical reagent limited company, the ignition weight loss is less than or equal to 8.0 percent, and the specific surface area is 177.8m2Pore volume was 0.255 mL/g.
Drying the silica gel at 140 ℃ for 5 hours to obtain activated silica gel; the neutral alumina is calcined at 500 ℃ 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. And mixing the activated silica gel with silver nitrate solution in equal volume according to the silver loading of 5-15 wt%, standing for 24h, drying at 140 ℃ for 5 h, and cooling in a dryer to obtain the activated silver-loaded silica gel. Mixing the silver-carrying silica gel and alumina according to a certain proportion to obtain the stationary phase of the solid-phase extraction column B.
The GC-MS instrument used for the analysis was 7890AGC-5975MS with FID detector. GC conditions were as follows: HP-PONA capillary chromatographic column, 50m × 0.2mm × 0.5 μm; programming to raise the initial temperature to 80 deg.c, maintaining for 5min, raising the temperature at 40 deg.c/min rate to final temperature of 300 deg.c and maintaining for 9 min; the carrier gas was high purity helium, operating at constant pressure, 35.374 psi; the injection port temperature is 320 ℃, the split ratio is 20:1, and the injection amount is 1 mu L. MSD conditions: EI ionization source (70eV), ion source temperature 230 ℃, quadrupole rod temperature 130 ℃, total scanning mass range 30-500u, interface temperature 310 ℃ and solvent delay 5 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 A was packed with 1.2g of alumina stationary phase, the solid phase extraction column B was packed with 1.2g of silver-loaded silica gel stationary phase having a silver content of 5 wt%, and the solid phase extraction column A was wetted with 0.5mL of the first eluent (n-pentane).
0.08g of a high-temperature Fischer-Tropsch synthesis 1# diesel oil sample of a certain company is taken by a liquid transfer gun, added into the upper part of a solid phase extraction column A and completely adsorbed by a 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 added to the solid phase extraction column B to give a saturated hydrocarbon, as component 1. The solid phase extraction column B was washed with 6mL of a second eluent (dichloromethane to ethanol volume ratio 90:10) to give the olefin component, designated as component 2. The solid phase extraction column A was washed with 4mL of a third eluent (n-pentane to dichloromethane volume ratio 90:10) to give the aromatic hydrocarbons as component 3. The solid phase extraction column A was washed with 6mL of a fourth eluent, methanol, to give the heteroatom compound, designated as component 4. Adding a certain amount of deuterated terphenyl into each component as an internal standard, and removing the solvent in each component by nitrogen purging.
The GC-MS-FID is adopted to analyze the component 1, the component 2, the component 3 and the component 4, and the result shows that the component 1 is mainly saturated hydrocarbon and accounts for 12.3 wt% of the diesel oil sample, wherein the content of the impurity olefin component is 0.3 wt%; component 2 is predominantly olefin and represents 58.4 wt% of the diesel sample, with the impurity saturated hydrocarbons containing 0.1 wt% and essentially no aromatics; the component 3 is mainly aromatic hydrocarbon and accounts for 13.2 wt% of the diesel oil sample, 0.5 wt% of impurity olefin and 0.2 wt% of oxygen-containing compound; the component 4 is mainly an oxygen-containing compound and accounts for 14.9 wt% of the diesel oil sample, and the content of impurity aromatic hydrocarbon is 0.1 wt%.
And (3) inspecting the effect of separating each component of the diesel oil by the solid phase extraction method by using the standard recovery rate of decene-1 and n-octanol. Taking two samples of 1# diesel oil synthesized by a certain company through low-temperature Fischer-Tropsch synthesis, wherein a certain amount of decene-1 and n-octanol are added into one sample to serve as a standard sample. The two samples are 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 respectively. The difference value of the content of decene-1 and the content of n-octanol in the labeled sample minus the content of decene-1 and the content of n-octanol in the unlabeled sample is the ratio of the theoretical value of the content of decene-1 and the theoretical value of n-octanol, namely the labeled recovery rate of the two compounds, and the values are 96.7 percent and 97.8 percent in sequence.
The results show that the method has high recovery rate of each component in the separated components, low cross quantity among the components and better enrichment effect.
Example 2
The solid phase extraction column A was packed with 1.2g of alumina stationary phase, the solid phase extraction column B was packed with 1.2g of silver-loaded silica gel stationary phase having a silver content of 8 wt%, and the solid phase extraction column A was wetted with 0.5mL of a first eluent (n-hexane).
0.24g of a No. 2 diesel oil sample produced by high-temperature Fischer-Tropsch synthesis of a certain company is taken by a liquid-transferring gun, added into the upper part of a solid-phase extraction column A and completely adsorbed by a 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 added to the solid phase extraction column B to obtain a saturated hydrocarbon, as component 1. The solid phase extraction column B was washed with 6mL of a second eluent (dichloromethane to ethanol volume ratio 85:15) to give the olefin component, designated as component 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 obtain aromatic hydrocarbons, which were designated as component 3. The solid phase extraction column A was washed with 6mL of a fourth eluent, methanol, to give the heteroatom compound, designated as component 4. Adding a certain amount of deuterated terphenyl into each component as an internal standard, and removing the solvent in each component by nitrogen purging.
And (3) observing the separation effect of the high-temperature Fischer-Tropsch synthetic diesel oil pretreated by the solid-phase extraction method by using the standard recovery rates of decene-1 and n-octanol, wherein the standard recovery rates of the decene-1 and the n-octanol are 94.5% and 95.2% in sequence.
Example 3
The solid phase extraction column A was filled with 1.2g of a silica-alumina stationary phase having an alumina content of 90 wt%, the solid phase extraction column B was filled with 1.2g of a silver-loaded silica stationary phase having a silver content of 10 wt%, and the solid phase extraction column A was wetted with 0.5mL of a first eluent (n-hexane).
0.56g of a company direct liquefaction 3# diesel oil sample is taken by a liquid transfer gun, added to the upper part of a solid phase extraction column A and completely adsorbed by a 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 added to the solid phase extraction column B to obtain a saturated hydrocarbon, noted as component 1. The solid phase extraction column B was washed with 2mL of a second eluent (dichloromethane to ethanol volume ratio 70:30) to give the olefin component, designated as component 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 obtain aromatic hydrocarbons, which were designated as component 3. The solid phase extraction column A was washed with 4mL of a fourth eluent, methanol, to give the heteroatom compound, designated as component 4. Adding a certain amount of deuterated terphenyl into each component as an internal standard, and removing the solvent in each component by nitrogen purging.
The GC-MS-FID is adopted to analyze the component 1, the component 2, the component 3 and the component 4, and the result shows that the component 1 is mainly saturated hydrocarbon and accounts for 55.1 wt% of the diesel oil sample, wherein the content of the impurity olefin component is 0.1 wt%; the component 2 is mainly olefin and accounts for 8.7 wt% of the diesel oil sample, wherein the content of impurity saturated hydrocarbon is 0.1 wt%, and the content of aromatic hydrocarbon is 0.0 wt%; the component 3 is mainly aromatic hydrocarbon and accounts for 20.7 wt% of the diesel oil sample, wherein the content of impurity olefin is 0.2 wt%, and the content of heteroatom compounds is 1.1 wt%; the component 4 is a nitrogen-containing and oxygen-containing compound and accounts for 13.7 wt% of the diesel sample, wherein the content of impurity aromatic hydrocarbon is 0.3 wt%.
The separation effect of the direct liquefied diesel oil pretreated by the solid phase extraction method is examined by using the standard recovery rates of decene-1 and n-octanol, and the standard recovery rates of the decene-1 and the n-octanol are 97.9% and 98.1% in sequence.
Example 4
The solid phase extraction column A was filled with 1.2g of a silica-alumina stationary phase having an alumina content of 80 wt%, the solid phase extraction column B was filled with 1.2g of a silver-loaded silica stationary phase having a silver content of 15 wt%, and the solid phase extraction column A was wetted with 0.5mL of a first eluent (n-hexane).
0.80g of a low-temperature Fischer-Tropsch synthesis No. 4 diesel sample of a certain company is taken by a liquid transfer gun, added into the upper part of a 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 added to the solid phase extraction column B to give a saturated hydrocarbon, as component 1. The solid phase extraction column B was washed with 4mL of a second eluent (dichloromethane to ethanol volume ratio 60:40) to give the olefin component, designated as component 2. The solid phase extraction column A was washed with 2mL of a third eluent (volume ratio of n-hexane to dichloromethane 60:40) to obtain aromatic hydrocarbons, which were designated as component 3. The solid phase extraction column A was washed with 2mL of a fourth eluent, methanol, to give the heteroatom compound, designated as component 4. Adding a certain amount of deuterated terphenyl into each component as an internal standard, and removing the solvent in each component by nitrogen purging.
The GC-MS-FID analysis is adopted for the components 1, 2, 3 and 4, and the result shows that the component 1 is mainly saturated hydrocarbon and accounts for 75.7 wt% of the diesel oil sample, wherein the content of the impurity olefin component is 0.0 wt%; component 2 is predominantly olefin and comprises 15.4 wt% of the diesel sample, wherein the impurity saturated hydrocarbons comprise 0.5 wt% and are substantially free of aromatic hydrocarbons; the component 3 is mainly aromatic hydrocarbon and accounts for 5.6 wt% of the diesel oil sample, 0.0 wt% of impurity olefin and 0.1 wt% of oxygen-containing compound; the component 4 is mainly an oxygen-containing compound and accounts for 2.6 wt% of the diesel oil sample, and the content of impurity aromatic hydrocarbon is 0.1 wt%.
And (3) inspecting the separation effect of the low-temperature Fischer-Tropsch synthetic diesel oil pretreated by the solid-phase extraction method by using the standard recovery rates of decene-1 and n-octanol, wherein the standard recovery rates of the decene-1 and the n-octanol are 99.1% and 96.5% in sequence.
Comparative example 1
And separating and enriching a high-temperature Fischer-Tropsch synthesis 1# diesel oil sample of a certain company according to the method described in petrochemical standard SH/T0606 appendix B.
0.1mL of sample is dropped into the upper part of a solid phase extraction column special for petrochemical standard SH/T0606 and is completely adsorbed. The stationary phase was washed with 2mL of n-pentane and 0.5mL of dichloromethane in that order and extracted to obtain saturated hydrocarbons. The stationary phase was washed with 2mL of dichloromethane to obtain aromatic hydrocarbons. Adding a certain amount of n-dotriacontane as an internal standard, and performing GC-MS-FID analysis on the group composition, wherein the result shows that the content of saturated hydrocarbon components accounts for 70.5 wt% of the total amount of the diesel oil sample, and the content of impurity aromatic hydrocarbon is 2.4 wt%; the content of aromatic hydrocarbon components is 22.6 wt%, and the content of impurity saturated hydrocarbon is 4.5 wt%.
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 quantitative determination of the saturated hydrocarbon, and oxygen-containing compounds can influence the quantitative determination of the aromatic hydrocarbon components, so that the content results of the saturated hydrocarbon and the aromatic hydrocarbon in the determination result are higher, and the accuracy of the determination 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 the n-pentane is lower than the upper part of the chromatographic column, 2g of high-temperature Fischer-Tropsch synthesis No. 1 diesel oil from a certain company is transferred by a liquid transfer gun and added into the upper part of the chromatographic column. 2g of quartz sand was added to fix the diesel sample. Adding 35mL of n-pentane to elute saturated hydrocarbon components, adding 60mL of toluene to elute aromatic hydrocarbon, adding 50mL of methanol to elute heteroatom compounds, and adjusting the flow of an eluent to be 1.5mL/min by using a double-chain ball. The solvent in each component was removed by nitrogen purge. The whole process takes 160 min.
The GC-MS-FID analysis of the component 1, the component 2 and the component 3 shows that the component 1 is mainly saturated hydrocarbon with the impurity aromatic hydrocarbon component content of 8.9 wt%, the component 2 is mainly aromatic hydrocarbon with the impurity saturated hydrocarbon content of 10.5 wt%, the heteroatom compound content of 8.5 wt%, and the component 3 is mainly oxygen-containing compound with the impurity aromatic hydrocarbon content of 12.5 wt%.
Therefore, the method for separating the coal-based diesel oil sample by adopting the column chromatography has long time consumption, large solvent dosage and large stationary phase dosage, cannot separate paraffin and olefin, and is not suitable for pretreatment for determining the composition of the coal-based diesel oil group.

Claims (14)

1. A method for separating diesel oil group components by solid phase extraction is characterized by comprising the following steps:
the method comprises the following steps: connecting a solid phase extraction column A and a solid phase extraction column B in series, wherein the solid phase extraction column A is arranged above the solid phase extraction column A, wetting the solid phase extraction column A by using a first eluent, adding a diesel oil sample from the upper part of the solid phase extraction column A, and then washing 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 continuously washing the solid phase extraction column B by using a first eluent to obtain a saturated hydrocarbon component;
step three: washing the solid phase extraction column B with a second eluent to obtain an olefin component;
step four: washing the solid phase extraction column A with a third eluent to obtain an aromatic hydrocarbon component;
step five: washing the solid phase extraction column A with 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.
2. The method according to claim 1, wherein the solid phase extraction column A is filled with a stationary phase, and the stationary phase is a mixture of silica gel and alumina, wherein the content of the alumina is 80-100 wt%.
3. The method according to claim 1, wherein the solid phase extraction column B is filled with a stationary phase, and the stationary phase is silica gel loaded with silver, wherein the loading amount of silver is 5-15 wt%.
4. The method of claim 2, whichIs characterized in that the specific surface area of the silica gel is 500-850m2Per g, pore volume of 0.1-0.6mL/g, average pore diameter of 1-4 nm.
5. The method as claimed in claim 2, wherein the specific surface area of the alumina is 200-450m2Per g, pore volume of 0.05-0.4mL/g, average pore diameter of 1-3 nm.
6. The method according to claim 1, wherein the volume ratio of a to b in the second eluent is 1.5-19: 1.
7. The method according to 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 added diesel sample to the solid phase extraction column A is 0.07-0.7:1, and the mass ratio of the added diesel sample to the solid phase extraction column B is 0.07-0.7: 1.
9. The method as claimed in claim 1, wherein in the first step, the volume of the first eluent for wetting the solid-phase extraction column A is 0.5mL, and the volume of the first eluent for washing the solid-phase extraction columns A and B is 1.5-5 mL; in the second step, the volume dosage of the first eluent for washing the solid-phase extraction column B is 2-4 mL.
10. The method as claimed in claim 1, wherein the volume of the second eluent in the third step is 2-6 mL.
11. The method as claimed in claim 1, wherein in the fourth step, the volume of the third eluent is 2-6 mL.
12. The method as claimed in claim 1, wherein in the fifth step, the volume of the fourth eluent is 2-6 mL.
13. The method of claim 1, wherein the diesel sample is diesel from a coal chemical process.
14. The method of claim 1, wherein the diesel sample is coal direct liquefied diesel or coal indirect liquefied diesel.
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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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