CN114563516A - Method for determining wax oil group composition - Google Patents
Method for determining wax oil group composition Download PDFInfo
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- CN114563516A CN114563516A CN202011357130.2A CN202011357130A CN114563516A CN 114563516 A CN114563516 A CN 114563516A CN 202011357130 A CN202011357130 A CN 202011357130A CN 114563516 A CN114563516 A CN 114563516A
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- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 150
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- 238000005481 NMR spectroscopy Methods 0.000 description 8
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- 238000001228 spectrum Methods 0.000 description 2
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- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/68—Flame ionisation detectors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Pathology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for measuring the composition of wax oil groups, which can divide wax oil into four parts of saturated hydrocarbon (alkane and cyclane), olefin, aromatic hydrocarbon and colloid through a 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 70-100 wt%; the stationary phase of the solid phase extraction column B is alumina loaded with silver ions, and the loading capacity of the silver ions is 1-15 wt%. The method can simultaneously separate and enrich saturated hydrocarbons (alkane + cyclane), olefin, aromatic hydrocarbon and colloid in the wax oil, and the separated components can be used for determining the composition of wax oil families and analyzing the molecular composition of the wax oil, and have the advantages of short processing time, low separation cross amount among the components, small solvent consumption and high recovery rate.
Description
Technical Field
The invention relates to a method for measuring the composition of a wax oil family, in particular to a method for separating a wax oil sample into saturated hydrocarbon (alkane and cyclane), olefin, aromatic hydrocarbon and colloid by adopting a solid phase extraction method to obtain the composition of the wax oil family.
Background
With the increasing demand for light oil products and chemical products and the increasingly obvious heavy crude oil resources, the utilization of heavy oil is more and more emphasized by people. The processability of the heavy oil is closely related to the composition of the heavy oil, and the group composition data is important basic data for predicting the product distribution in the process of developing the current process and has important guiding significance for formulating a heavy oil processing scheme. Group composition data of heavy oil, especially saturated hydrocarbon data, is closely related to olefin yield in the steam cracking process; olefins in saturated hydrocarbon are easy to condense on a catalyst to form coke, so that long-period operation of the catalyst is influenced, but long-chain olefins are important chemical raw materials and can be used for manufacturing high-added-value detergents, emulsifiers, high-performance lubricating oil and the like.
At present, the analysis methods of the heavy oil composition mainly comprise column chromatography (SH/T0509-. The method can generally divide the wax oil into three parts of saturated hydrocarbon, aromatic hydrocarbon and colloid according to the polarity, but has a plurality of problems in practical application, such as complicated procedures, large using amount of stationary phase, long analysis time, large amount of toxic solvent, serious environmental pollution and great damage to the body of an operator in column chromatography; although the high performance liquid chromatography achieves the purpose of rapidly separating each component of heavy oil, the response difference of different samples is very large by generally adopting a differential refraction detector and the like, and great difficulty is brought to accurate quantification.
The method for determining the hydrocarbons of the saturated hydrocarbon fraction in the petrochemical standard gas oil is SH/T0509, the saturated hydrocarbon and the aromatic hydrocarbon in the wax oil fraction are separated by a solid phase extraction method, the adopted pretreatment method has the characteristics of simple operation and no need of complex equipment, and the contents of the hydrocarbons such as paraffin, monocyclic naphthene, bicyclic naphthene, tricyclic naphthene, tetracyclic naphthene, pentacyclic naphthene, hexacyclic naphthene, monocyclic aromatic hydrocarbon and the like are finally obtained. However, the method is the same as the previous analysis method, and cannot separate the olefin component from the saturated hydrocarbon, mainly because the polarity of the high-carbon olefin is similar to that of the high-carbon alkane and the cycloalkane, and the high-carbon alkane and the cycloalkane are difficult to be completely separated by column chromatography, solid phase extraction and the like; the unsaturated double bonds of the naphthenic hydrocarbon and the olefin with the same molecular weight have the same number, the mass spectrograms of the naphthenic hydrocarbon and the olefin are similar, and the traditional method for determining the group composition by mass spectrometry cannot distinguish and develop the olefin and the naphthenic hydrocarbon, so that the content of the naphthenic hydrocarbon is higher, and the quantitative result is inaccurate.
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 n-alkanes, cyclanes and alkenes in wax oil have similar polarity, and it is difficult to separate the two groups of compounds well, and solid phase extraction is a feasible way to solve the problem. In addition, there is no report on the separation of olefin compounds from wax oil by solid phase extraction.
Disclosure of Invention
The invention aims to provide an analysis method for separating hydrocarbon components with different structures in wax oil by using a solid phase extraction method to determine the composition of wax oil families. On one hand, the wax oil sample is separated into four parts of saturated hydrocarbon (alkane + cyclane), olefin, aromatic hydrocarbon and colloid, so that the interference of the olefin on the qualitative and quantitative determination of the cyclane is eliminated, and accurate wax oil family composition data is obtained; on the other hand, the method can also be used for the pretreatment process of the wax oil, and provides samples for the subsequent study of the detailed molecular composition of the wax oil.
The invention provides a method for separating wax oil composition by a solid phase extraction method, which comprises the following steps:
the method comprises the following steps: diluting wax oil and a diluent according to a certain proportion to obtain a flowable wax oil sample;
step two: 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, wetting the solid phase extraction column A by using a first eluent, adding a diluted flowable wax oil sample from the upper layer 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 to obtain a saturated hydrocarbon component 1;
step three: 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 2; mixing the saturated hydrocarbon component 1 and the saturated hydrocarbon component 2 to obtain a saturated hydrocarbon component;
step four: replacing the collector, and washing the solid-phase extraction column B by using a second eluent to obtain an olefin component;
step five: replacing the collector, and washing the solid-phase extraction column A by using a third eluent to obtain an aromatic hydrocarbon component;
step six: replacing the collector, and washing the solid-phase extraction column A by using a fourth eluent to obtain colloid;
wherein the diluent is at least one selected from the group consisting of n-hexane, n-heptane, cyclohexane and methylcyclohexane;
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, butanone and acetonitrile.
The method of the invention is characterized in that a stationary phase is arranged in the solid phase extraction column A, the stationary phase is a mixture of silica gel and alumina, wherein the content of the alumina is 70-100 wt%.
The method comprises the step of loading a stationary phase in the solid-phase extraction column B, wherein the stationary phase is alumina loaded with silver ions, and the loading capacity of the silver ions is 1-15 wt%.
The method of the invention, wherein 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 of the invention, wherein the specific surface area of the alumina is 150-450m2Per g, pore volume of 0.05-0.4mL/g, average pore diameter of 1-3 nm.
The method of the invention comprises the step one, wherein the amount of the wax oil is 0.3-3g, and the mass ratio of the diluent to the wax oil is 0.45-0.9: 1.
The method of the invention, wherein the volume ratio of a to b in the second eluent is 0.25-1.25: 1.
The method of the invention, wherein the volume ratio of c to d in the third eluent is 0.6-4: 1.
The method of the invention, wherein in the second step, the dosage of the first eluent for wetting the solid phase extraction column A is 1-3 mL.
The method of the invention, wherein in the second step, the dosage of the first eluent for washing the solid-phase extraction column A and the solid-phase extraction column B is 5-10mL, and in the third step, the dosage of the first eluent for washing the solid-phase extraction column B is 3-6 mL.
The method of the present invention, wherein in step four, the amount of the second eluent used for washing the solid-phase extraction column B is 5-10 mL.
The method of the invention, wherein in the fifth step, the amount of the third eluent for washing the solid-phase extraction column A is 5-15 mL.
The method of the invention, wherein in the sixth step, the amount of the fourth eluent for washing the solid-phase extraction column A is 5-15 mL.
The method of the invention, wherein the wax oil is wax oil produced by petrochemical industry or coal chemical industry.
The method of the invention is characterized in that the wax oil is produced by catalytic cracking, delayed coking, visbreaking, steam cracking and other processes.
The method of the invention is characterized in that the wax oil is produced by a Fischer-Tropsch synthesis process.
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 saturated hydrocarbon (paraffin and cyclane), olefin, aromatic hydrocarbon and colloid in a wax oil sample by matching 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 70-100 wt%; the stationary phase of the solid phase extraction column B is alumina loaded with silver ions, wherein the loading amount of the silver ions is 1-15 wt%. The method can be used for enriching the olefin compounds in the wax oil sample, solves the interference of the olefin compounds on the qualitative and quantitative determination of the cycloalkane, provides a feasible pretreatment means for accurately determining the composition of the wax oil sample group by applying the petrochemical standard SH/T0659, and enlarges the application range of the standard.
The preparation method of the silica gel and 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; roasting neutral alumina at the temperature of 350-550 ℃ for 1-5 hours, and then putting the neutral alumina into a dryer for cooling to obtain activated neutral alumina; and uniformly mixing the activated silica gel and the neutral alumina according to a certain proportion to obtain the stationary phase required by the solid-phase extraction column A. And (3) soaking the alumina and the aqueous solution containing the silver ions in the same volume and in a dark place for 24h, roasting at 350-550 ℃ for 2-6 h, and then putting into a dryer for cooling to obtain activated alumina loaded with the silver ions, thus obtaining the stationary phase required by the 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 wax oil, and nitrogen purging is preferably selected for product concentration. Volatilizing and concentrating the solution to about 0.5mL, and performing related analysis by using a Gas Chromatography (GC), or directly performing chromatographic analysis without concentration under partial conditions; the content of each component can also be determined by a constant weight method. The content and the composition of each component are analyzed by an internal standard method by adopting a Gas Chromatography (GC) -Mass Spectrum (MS) -hydrogen Flame Ionization Detector (FID). The mass spectrum is one of main research tools for qualitative structure of the compounds, various compounds in the enriched substances can be qualitatively analyzed through means such as spectrogram retrieval, generally, the influence factors of the hydrogen flame ionization detector on the compounds are not greatly different, and therefore quantitative analysis is carried out through GC-FID to judge the separation cross amount. And (3) quantifying by an internal standard method, and selecting n-tetradecane as an internal standard compound. The chemical shifts of hydrogen atoms in different chemical environments on a nuclear magnetic resonance instrument spectrogram are different, and the separation cross amount of different components can be judged according to the content of the hydrogen atoms in different chemical shifts on the nuclear magnetic resonance instrument spectrogram.
The method adopts a solid phase extraction method to separate the wax oil into components with different compositions, separates a wax oil sample into four parts of saturated hydrocarbon (alkane and cyclane), olefin, aromatic hydrocarbon and colloid by adjusting the polarity and the dosage of an eluent, can be used for determining the composition of a wax oil family and analyzing the molecular composition of the wax oil, and has the advantages of short treatment time, low separation cross amount among the components, small solvent dosage and high recovery rate. . The method can solve the problem of qualitative and quantitative interference of olefin on the cycloparaffin, obtain accurate wax oil group composition data, and can also be used in the pretreatment process of wax oil samples to provide samples for the subsequent research of detailed molecular composition of the wax oil. 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 time for separating once is only 20-30min, so that the separation efficiency is greatly improved.
Drawings
FIG. 1 is a nuclear magnetic resonance image of a saturated hydrocarbon (alkane + cycloalkane) component obtained by the pretreatment method of example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance image of an olefin component obtained by the pretreatment method of example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance image of an aromatic hydrocarbon component obtained by the pretreatment method of example 1 of the present invention;
FIG. 4 is a GC-MS graph of the olefin component obtained by the pretreatment method of example 5 of the present invention.
Detailed Description
The present invention will be further specifically described below with reference to specific examples, but the present invention is not limited to the following examples. Any modification which does not depart from the spirit and scope of the invention is deemed to be within the scope of the invention.
The silica gel used in the examples is a silica gel for chromatography produced by national pharmaceutical group chemical reagents, Inc., the particle size is not less than 70.0%, and the specific surface area is 511.9m2Pore volume of 0.468 mL/g. The 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 150 ℃ for 5 hours to obtain activated silica gel; the neutral alumina was calcined at 500 ℃ for 4 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 (3) mixing the activated alumina and a silver nitrate solution in equal volume according to the loading capacity of silver ions being 1-15 wt%, standing for 24h in a dark place, drying at 150 ℃ for 5h, and cooling in a dryer to obtain the activated silver ion-loaded alumina, thus obtaining the stationary phase of the solid-phase extraction column B.
The GC-MS instrument model used for the analysis was 7890A GC-5975 MS with a FID detector. GC conditions were as follows: an empty capillary chromatography column, 30 mm x 0.25 mm; programming to raise the initial temperature to 120 deg.c, maintaining for 5min, raising the temperature at 20 deg.c/min rate to final temperature of 350 deg.c and maintaining for 8 min; the carrier gas is high-purity helium, the constant current operation is carried out, and the flow rate is 1.5 mL/min; the injection port temperature is 400 ℃, the split ratio is 20:1, and the injection amount is 1 mu L. MSD conditions: EI ionization source (70eV), ion source temperature 250 ℃, quadrupole rod temperature 150 ℃, full scanning mass range 45-600u, interface temperature 310 ℃ and solvent delay 2 min. FID conditions: the temperature of the detector is 400 ℃, the air flow is 300mL/min, the hydrogen flow is 30mL/min, and the tail gas blowing is 25 mL/min.
The NMR spectrometer used was model Bruker Avance Neo 600 MHz. The measurement conditions were: pulse sequence: 30 degree monopulse1H NMR; spectral width 9615Hz (16 ppm); excitation intermediate frequency is 6 ppm; time domain sampling points 65536; relaxation delay 40 s; the number of sampling times is 16; the test temperature was 300K. 0.5-1ppm is referred to as methyl hydrogen; 1-2ppm refers to methylene hydrogen/methine hydrogen; 2-4ppm refers to hydrogen/methine hydrogen considered to be alpha to the aromatic ring; 4-6ppm refer to olefinic hydrogen; 6-9ppm are referred to as aromatic hydrogen.
Example 1
4g of silica gel-alumina stationary phase having an alumina content of 70 wt% was packed in the solid phase extraction column A, 3g of silver-alumina stationary phase having a silver content of 1 wt% was packed in the solid phase extraction column B, and the solid phase extraction column A was wetted with 1mL of the first eluent (n-pentane).
0.3g of 1# wax oil produced in the catalytic cracking process of a certain company is taken, a diluent cyclohexane and the 1# wax oil are diluted according to the mass ratio of 0.45:1, and then the diluted wax oil sample is completely added to the upper part of a solid phase extraction column A and is completely adsorbed by a stationary phase. Washing the solid phase extraction column A + B with 5mL of the first eluent, separating the solid phase extraction column A from the solid phase extraction column B, and adding 3mL of the first eluent to the solid phase extraction column B to obtain saturated hydrocarbon, which is marked as component 1. The solid phase extraction column B was washed with 5mL of a second eluent (dichloromethane to ethanol volume ratio 0.25:1) and was labeled as component 2. The solid phase extraction column A was washed with 5mL of a third eluent (n-pentane to dichloromethane volume ratio 0.6:1) as component 3. The solid phase extraction column A was washed with 5mL of a fourth eluent (methanol) and was designated as fraction 4. The whole process takes 20 min.
The solvent in each component is removed by nitrogen purging, and then the constant weight is obtained. As a result, the mass of component 1 was 0.1217g, the mass of component 2 was 0.0243g, the mass of component 3 was 0.1403g, the mass of component 4 was 0.0208g, and the total recovery of the sample was 102.4%.
And analyzing the component 1, the component 2 and the component 3 by adopting nuclear magnetic resonance. The results show that the vast majority (98.5%) of the integrated area of the signals in the component 1 spectrum appears between 0.5 and 2ppm, and are attributed to the aliphatic methyl and aliphatic methylene/methine signals, indicating that component 1 is mainly saturated hydrocarbon; a 1-substituted olefin signal appears in a spectrum of the component 2 within the range of 4-6ppm, the integral area ratio is 4.182%, and almost no signal appears in an aromatic hydrocarbon region of 6-9 ppm; in the spectrogram of the component 3, stronger signals appear in the ranges of 2-4ppm and 6-9ppm, the signals are attributed to aromatic ring alpha-position hydrogen and aromatic hydrocarbon, the integral area accounts for 26.5 percent, a small amount of olefin signals appear in the range of 4-6ppm, and the integral area accounts for 0.1 percent.
Therefore, the analysis method provided by the invention can be used for separating the wax oil into four parts, namely saturated hydrocarbon (alkane and cyclane), olefin, aromatic hydrocarbon and colloid, so that qualitative and quantitative interference between the olefin and the cyclane is eliminated, the separation recovery rate is high, the cross quantity among the components is low, and the separation effect is good.
Example 2
4g of silica gel-alumina stationary phase having an alumina content of 80 wt% was packed in the solid phase extraction column A, 3g of silver-alumina stationary phase having a silver content of 5 wt% was packed in the solid phase extraction column B, and the solid phase extraction column A was wetted with 2mL of a first eluent (n-hexane).
0.8g of No. 2 wax oil produced in the delayed coking process of a certain company is taken, a diluent n-hexane and the No. 2 wax oil are diluted according to the mass ratio of 0.6:1, and then the diluted wax oil sample is completely added to the upper part of a solid phase extraction column A and is completely adsorbed by a stationary phase. The solid phase extraction column a + B was washed with 7mL of the first eluent, then the solid phase extraction column a and the solid phase extraction column B were separated, and 4mL of the first eluent was added to the solid phase extraction column B to obtain saturated hydrocarbon, which was designated as component 1. The solid phase extraction column B was washed with 7mL of a second eluent (chloroform to methanol volume ratio 0.4:1) and was identified as component 2. The solid phase extraction column A was washed with 8mL of a third eluent (n-hexane to chloroform volume ratio 1:1) and was recorded as fraction 3. The solid phase extraction column A was washed with 7mL of a fourth eluent (ethanol) and was designated as fraction 4. The whole process takes 23 min.
The solvent in each component is removed by nitrogen purging, and then the constant weight is obtained. As a result, the mass of component 1 was 0.2600g, the mass of component 2 was 0.0714g, the mass of component 3 was 0.4121g, the mass of component 4 was 0.0326g, and the total recovery of the sample was 97.0%.
Example 3
4g of a silica gel-alumina stationary phase having an alumina content of 90 wt% was packed in the solid phase extraction column A, 3g of a silver-alumina stationary phase having a silver content of 8 wt% was packed in the solid phase extraction column B, and the solid phase extraction column A was wetted with 3mL of a first eluent (n-heptane).
3g of 3# wax oil produced in the visbreaking process of a certain company is taken, a diluent n-heptane and the 3# wax oil are diluted according to the mass ratio of 0.7:1, and then the diluted wax oil sample is completely added to the upper part of a solid phase extraction column A and is completely adsorbed by a stationary phase. The solid phase extraction column a + B was washed with 10mL of the first eluent, then the solid phase extraction column a and the solid phase extraction column B were separated, and 6mL of the first eluent was added to the solid phase extraction column B to obtain saturated hydrocarbon, which was designated as component 1. The solid phase extraction column B was washed with 10mL of a second eluent (diethyl ether to isopropanol volume ratio 0.8:1) and was labeled as component 2. The solid phase extraction column A was washed with 15mL of a third eluent (n-heptane to ether volume ratio 4:1) and was labeled as fraction 3. The solid phase extraction column a was washed with 15mL of a fourth eluent (isopropanol) and was designated as component 4. The whole process takes 30 min.
After the solvent is evaporated to dryness, the components are subjected to constant weight. As a result, the mass of component 1 was 1.1429g, the mass of component 2 was 0.1568g, the mass of component 3 was 1.4279g, the mass of component 4 was 0.1226g, and the total recovery of the sample was 95.0%.
Example 4
4g of silica gel-alumina stationary phase having an alumina content of 90 wt% was packed in the solid phase extraction column A, 3g of silver-alumina stationary phase having a silver content of 10 wt% was packed in the solid phase extraction column B, and the solid phase extraction column A was wetted with 2mL of the first eluent (petroleum ether).
2g of No. 4 wax oil produced in the steam cracking process of a certain company is taken, a diluent methylcyclohexane and the No. 4 wax oil are diluted according to the mass ratio of 0.8:1, and then the diluted wax oil sample is completely added to the upper part of a solid phase extraction column A and is completely adsorbed by a stationary phase. Washing the solid phase extraction column A + B with 9mL of the first eluent, separating the solid phase extraction column A from the solid phase extraction column B, and adding 5mL of the first eluent to the solid phase extraction column B to obtain saturated hydrocarbon, which is marked as component 1. The solid phase extraction column B was washed with 9mL of a second eluent (benzene to acetone volume ratio 1.25:1) and was labeled as component 2. The solid phase extraction column A was washed with 13mL of a third eluent (3: 1 by volume petroleum ether to benzene) and was labeled as fraction 3. The solid phase extraction column A was washed with 12mL of a fourth eluent (acetone) and was designated as fraction 4. The whole process takes 27 min.
After the solvent is evaporated to dryness, the components are subjected to constant weight. As a result, the mass of component 1 was 0.3996g, the mass of component 2 was 0.1889g, the mass of component 3 was 1.1948g, the mass of component 4 was 0.2048g, and the total recovery of the sample was 99.4%.
Example 5
The solid phase extraction column A was packed with 4g of alumina for phasing, the solid phase extraction column B was packed with 3g of a silver-alumina stationary phase having a silver content of 15% by weight, and the solid phase extraction column A was wetted with 2mL of a first eluent (petroleum ether).
1g of No. 5 wax oil produced in the high-temperature Fischer-Tropsch synthesis process of a certain company is taken, a diluent methylcyclohexane and the No. 5 wax oil are diluted according to the mass ratio of 0.9:1, and then the diluted wax oil sample is completely added to the upper part of a solid-phase extraction column A and is completely adsorbed by a stationary phase. The solid phase extraction column a + B was washed with 8mL of the first eluent, then the solid phase extraction column a and the solid phase extraction column B were separated, and 4mL of the first eluent was added to the solid phase extraction column B to obtain saturated hydrocarbon, which was designated as component 1. The solid phase extraction column B was washed with 8mL of a second eluent (toluene to butanone volume ratio 1:1) and was labeled as component 2. The solid phase extraction column A was washed with 10mL of a third eluent (2: 1 by volume petroleum ether to toluene) and was labeled as fraction 3. The solid phase extraction column A was washed with 10mL of a fourth eluent (acetonitrile) and was designated as fraction 4. The whole process takes 25 min.
After the solvent is evaporated to dryness, the components are subjected to constant weight. As a result, the mass of component 1 was 0.4370g, the mass of component 2 was 0.3014g, the mass of component 3 was 0.0882g, the mass of component 4 was 0.1424g, and the total recovery of the sample was 96.9%.
Comparative example 1
The wax oil saturated component, the aromatic hydrocarbon and the colloid component are separated by adopting petrochemical standard SH/T0509-.
A little absorbent cotton is plugged at the lower end of the cleaned adsorption column, 40g of activated alumina is added from the upper end, meanwhile, a thin rod coated with rubber is used for lightly beating the column to ensure that the alumina is compact and uniform, and then 30mL of n-heptane is immediately added to rinse the chromatographic column. 0.3g of a No. 1 wax oil sample produced by a catalytic cracking process of a certain company is weighed by a beaker and dissolved by 10mL of n-heptane, and the dissolved wax oil sample is added immediately after all the n-heptane pre-wetting enters an alumina adsorption layer. The saturated hydrocarbon was flushed by adding 70mL of n-heptane, and the flow rate was adjusted using a two-ball joint to ensure that the flow rate was maintained at 2-3 mL/min. 80mL of toluene was added to rinse the aromatic component. Adding a toluene-ethanol mixed solution (the volume ratio is 1:1), and 40mL of toluene and ethanol respectively to rinse the colloid component. The whole process takes 160 min.
The weight of the saturated hydrocarbon, the aromatic hydrocarbon and the colloid is constant after the solvent is volatilized. As a result, the mass of the saturated hydrocarbon was 0.1438g, the mass of the aromatic hydrocarbon 2 was 0.1311g, the mass of the gum 3 was 0.0167g, and the total recovery rate of the sample was 97.2%.
Therefore, the reproducibility of the wax oil group composition result measured by the SH/T0509-2010 method and the result measured by the method meets the requirements of the method of SH/T0509-2010, and the analysis method provided by the invention has higher accuracy. However, the SH/T0509-2010 method does not provide olefin content, and therefore the present invention can give more detailed wax oil composition results.
Comparative example 2
4g of silica gel-alumina stationary phase having an alumina content of 80 wt% was packed in the solid phase extraction column A, 3g of silver-silica gel stationary phase having a silver content of 5 wt% was packed in the solid phase extraction column B, and the solid phase extraction column A was wetted with 2mL of a first eluent (n-hexane).
0.8g of No. 2 wax oil produced in the delayed coking process of a certain company is taken, a diluent n-hexane and the No. 2 wax oil are diluted according to the mass ratio of 0.6:1, and then the diluted wax oil sample is completely added to the upper part of a solid phase extraction column A and is completely adsorbed by a stationary phase. The solid phase extraction column a + B was washed with 7mL of the first eluent, then the solid phase extraction column a and the solid phase extraction column B were separated, and 4mL of the first eluent was added to the solid phase extraction column B to obtain saturated hydrocarbon, which was designated as component 1. The solid phase extraction column B was washed with 7mL of a second eluent (chloroform to methanol volume ratio 0.4:1) and was identified as component 2. The solid phase extraction column A was washed with 8mL of a third eluent (n-hexane to chloroform volume ratio 1:1) and was recorded as fraction 3. The solid phase extraction column A was washed with 7mL of a fourth eluent (ethanol) as component 4. The whole process takes 23 min.
The solvent in each component is removed by nitrogen purging, and then the constant weight is obtained. As a result, the mass of component 1 was 0.2934g, the mass of component 2 was 0.0287g, the mass of component 3 was 0.4034g, the mass of component 4 was 0.0212g, and the total recovery of the sample was 93.3%.
It can be seen that, compared to the solid phase extraction method using the silica gel-alumina stationary phase and the silver-alumina stationary phase provided in example 2 of the present invention, the separation method of comparative example 2 is employed to introduce part of the olefin compounds into the saturated hydrocarbons (paraffin + naphthene), and thus the olefins and the saturated hydrocarbons (paraffin + naphthene) cannot be separated effectively.
Comparative example 3
The solid phase extraction column a was packed with 3g of a silver-alumina stationary phase having a silver content of 8 wt%, and the solid phase extraction column a was wetted with 3mL of a first eluent (n-heptane).
3g of 3# wax oil produced in the visbreaking process of a certain company is taken, a diluent n-heptane and the 3# wax oil are diluted according to the mass ratio of 0.7:1, and then the diluted wax oil sample is completely added to the upper part of a solid phase extraction column A and is completely adsorbed by a stationary phase. The solid phase extraction column A was washed with 10mL of the first eluent to give a saturated hydrocarbon as fraction 1. The solid phase extraction column A was washed with 5mL of a second eluent (dichloromethane) to give the aromatic hydrocarbon as component 2. Wash column A with 5mL of a third eluent (dichloromethane to ethanol volume ratio 1:1) to give a gum as component 3.
After the solvent is evaporated, the components are subjected to constant weight. As a result, the mass of component 1 was 1.3687g, the mass of component 2 was 0.13673g, the mass of component 3 was 0.1459g, and the total recovery of the sample was 96.1%.
It can be seen that the process provided in comparative example 3 has consistent overall saturates, aromatics, gum yields and comparable recovery as the process provided in example 3, but the process provided in comparative example 3 does not separate the olefins from the paraffins + naphthenes.
Comparative example 4
And (3) separating and enriching a high-temperature Fischer-Tropsch synthesis 5# wax oil sample of a certain company according to a method described in petrochemical standard SH/T0659.
0.1g of a sample was weighed and placed in a 5mL glass beaker, and 1mL of 60 ℃ heated n-hexane was added and sufficiently dissolved. Adding 1mL of normal hexane into a special solid-phase extraction column for SH/T0659, and completely transferring the sample in the small beaker to a sieve plate in the solid-phase extraction column after the normal hexane is completely adsorbed by the stationary phase. Washing the stationary phase by using 4mL of normal hexane and 1mL of dichloromethane in sequence, and eluting the saturated hydrocarbon fraction adsorbed in the stationary phase; washing the stationary phase by using 5mL of dichloromethane, washing the solid phase extraction column by using 5mL of a mixed solvent of absolute ethyl alcohol and dichloromethane in a ratio of 1:1 when the dichloromethane just completely enters the stationary phase, observing that a colloid ring in the stationary phase gradually moves downwards, and continuing washing by using a mixed solvent of absolute ethyl alcohol and dichloromethane in a ratio of 1:1 until the colloid ring moves to the bottom of the solid phase extraction column to obtain an aromatic hydrocarbon component; the solid phase extraction column was washed with 5mL of a 1:1 mixture of absolute ethanol and dichloromethane to obtain a gum fraction.
Therefore, compared with the solid phase extraction method provided by the invention, the solid phase extraction method adopting the petrochemical standard SH/T0659 can only obtain saturated hydrocarbon, aromatic hydrocarbon and colloid components, and the nuclear magnetic resonance mass spectrometry is adopted to analyze the saturated hydrocarbon and aromatic hydrocarbon components, so that the olefin is mainly concentrated in the saturated hydrocarbon components, and the olefin causes a higher naphthenic hydrocarbon result in a determination result, and the accuracy of the determination result is influenced.
Claims (16)
1. A method for determining the composition of wax oil families, which is characterized by comprising the following steps:
the method comprises the following steps: diluting the wax oil by using a diluent to obtain a flowable wax oil sample;
step two: 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, wetting the solid phase extraction column A by using a first eluent, adding a flowable wax oil sample from the upper layer of the solid phase extraction column A, and washing the solid phase extraction column A and the solid phase extraction column B by using the first eluent to obtain a saturated hydrocarbon component 1;
step three: 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 the first eluent to obtain a saturated hydrocarbon component 2; mixing the saturated hydrocarbon component 1 and the saturated hydrocarbon component 2 to obtain a saturated hydrocarbon component;
step four: replacing the collector, and washing the solid-phase extraction column B by using a second eluent to obtain an olefin component;
step five: replacing the collector, and washing the solid-phase extraction column A by using a third eluent to obtain an aromatic hydrocarbon component;
step six: replacing the collector, and washing the solid-phase extraction column A by using a fourth eluent to obtain colloid;
wherein the diluent is at least one selected from the group consisting of n-hexane, n-heptane, cyclohexane and methylcyclohexane;
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, butanone and acetonitrile.
2. The method according to claim 1, wherein the solid phase extraction column A is filled with a stationary phase, the stationary phase is a mixture of silica gel and alumina, and the content of the alumina is 70-100 wt%.
3. The method as claimed in claim 2, wherein the silica gel has a specific surface area of 500-850m2Per g, pore volume of 0.1-0.6mL/g, average pore diameter of 1-4 nm.
4. The method according to claim 1, wherein the solid phase extraction column B is filled with a stationary phase, and the stationary phase is alumina loaded with silver ions, wherein the loading amount of the silver ions is 1-15 wt%.
5. The method as claimed in claim 2 or 4, wherein the specific surface area of the alumina is 150-450m2Per g, pore volume of 0.05-0.4mL/g, average pore diameter of 1-3 nm.
6. The method according to claim 1, wherein in step one, the amount of the wax oil is 0.3 to 3g, and the mass ratio of the diluent to the wax oil is 0.45 to 0.9: 1.
7. The method according to claim 1, wherein the volume ratio of a to b in the second eluent is 0.25-1.25: 1.
8. The method according to claim 1, wherein the volume ratio of c to d in the third eluent is 0.6-4: 1.
9. The method as claimed in claim 1, wherein in step two, the amount of the first eluent used for wetting the solid phase extraction column A is 1-3 mL.
10. The method as claimed in claim 1, wherein in step two, the amount of the first eluent used for washing the solid phase extraction column A and the solid phase extraction column B is 5-10mL, and in step three, the amount of the first eluent used for washing the solid phase extraction column B is 3-6 mL.
11. The method as claimed in claim 1, wherein in step four, the amount of the second eluent used for washing the solid phase extraction column B is 5-10 mL.
12. The method as claimed in claim 1, wherein in step five, the third eluent for washing the solid phase extraction column A is used in an amount of 5-15 mL.
13. The method as claimed in claim 1, wherein in step six, the amount of the fourth eluent used for washing the solid phase extraction column A is 5-15 mL.
14. The method according to claim 1, wherein the wax oil is a wax oil produced in petrochemical or coal chemical industry.
15. The method of claim 1, wherein the wax oil is produced by catalytic cracking, delayed coking, visbreaking, steam cracking, or the like.
16. The method of claim 1, wherein the wax oil is a Fischer-Tropsch process produced wax oil.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079987A (en) * | 2009-11-27 | 2011-06-01 | 中国石油化工股份有限公司 | Method for separating heavy oils by solid phase extraction |
| 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 |
| CN105251437A (en) * | 2014-07-16 | 2016-01-20 | 中国石油化工股份有限公司 | Stationary phase for solid phase extraction and separation of heavy oil hydrocarbons |
| CN105273742A (en) * | 2014-07-16 | 2016-01-27 | 中国石油化工股份有限公司 | Method for solid phase extraction separating of components in heavy oil |
| CN107703020A (en) * | 2017-10-18 | 2018-02-16 | 中石化炼化工程（集团）股份有限公司 | A kind of method for determining wax tailings solid content |
| 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 |
| CN109839449A (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 separation diesel oil |
| CN109839450A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | The method that Solid Phase Extraction separates nitrogenous compound and phenolic compound in diesel oil simultaneously |
-
2020
- 2020-11-27 CN CN202011357130.2A patent/CN114563516B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079987A (en) * | 2009-11-27 | 2011-06-01 | 中国石油化工股份有限公司 | Method for separating heavy oils by solid phase extraction |
| 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 |
| CN105251437A (en) * | 2014-07-16 | 2016-01-20 | 中国石油化工股份有限公司 | Stationary phase for solid phase extraction and separation of heavy oil hydrocarbons |
| CN105273742A (en) * | 2014-07-16 | 2016-01-27 | 中国石油化工股份有限公司 | Method for solid phase extraction separating of components in heavy oil |
| CN107703020A (en) * | 2017-10-18 | 2018-02-16 | 中石化炼化工程（集团）股份有限公司 | A kind of method for determining wax tailings solid content |
| 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 |
| CN109839449A (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 separation diesel oil |
| CN109839450A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | The method that Solid Phase Extraction separates nitrogenous compound and phenolic compound in diesel oil simultaneously |
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