CN111308005A - Method for determining content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil - Google Patents
Method for determining content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil Download PDFInfo
- Publication number
- CN111308005A CN111308005A CN202010234821.7A CN202010234821A CN111308005A CN 111308005 A CN111308005 A CN 111308005A CN 202010234821 A CN202010234821 A CN 202010234821A CN 111308005 A CN111308005 A CN 111308005A
- Authority
- CN
- China
- Prior art keywords
- oxygen
- fischer
- hydrocarbon
- eluent
- hydrocarbons
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
-
- 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
-
- 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
- G01N30/12—Preparation by evaporation
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
-
- 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
- G01N2030/062—Preparation extracting sample from raw material
-
- 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
- G01N30/12—Preparation by evaporation
- G01N2030/126—Preparation by evaporation evaporating sample
-
- 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
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
-
- 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
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
- G01N2030/8854—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds involving hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to a method for determining the content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil, which comprises the steps of separating Fischer-Tropsch synthetic oil by a solid phase extraction method to obtain a hydrocarbon mixed component and an oxygen-containing compound mixed component, respectively carrying out gas chromatography-mass spectrometry combined analysis, determining a reference component in an obtained spectrogram, calculating the retention index of each peak, determining the hydrocarbons or the oxygen-containing compounds corresponding to each peak according to the retention index and a compound qualitative database, and obtaining the content of each hydrocarbon or the oxygen-containing compounds according to the peak area. Compared with the prior art, the method realizes the rapid separation of the hydrocarbons and the oxygen-containing compounds in the Fischer-Tropsch synthetic oil through the solid phase extraction method, effectively eliminates the mutual interference of the hydrocarbons and the oxygen-containing compounds in the Fischer-Tropsch synthetic oil in the retention time through the GC-MS, and realizes the rapid qualitative and quantitative analysis of each component by combining the qualitative advantages of the GC-MS and a simple data processing algorithm.
Description
Technical Field
The invention belongs to the technical field of analysis and detection, relates to a method for determining the content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil, and particularly relates to a method for determining the content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil, which is simple and rapid to operate and has less interference.
Background
The research of Fischer-Tropsch synthesis has been in the history of nearly one hundred years, and in recent years, Fischer-Tropsch synthesis has become one of the research hotspots in the field of energy substitution at home and abroad due to the exploration of coal and natural gas for increasing reserves, adjustment of energy industrial structures of various countries and the like. The Fischer-Tropsch synthesis oil is one of main products of a Fischer-Tropsch synthesis process, and comprises main components of alkane, alkene, cyclane, aromatic hydrocarbon and oxygen-containing compounds, wherein the oxygen-containing compounds mainly comprise alcohol and ketone. The content of various hydrocarbons and oxygen-containing compounds in the Fischer-Tropsch synthetic oil is accurately analyzed, and the deep processing research of the Fischer-Tropsch synthetic oil is very necessary.
Common analytical methods for the oil component content are Gas Chromatography (GC) analysis, including one-dimensional chromatography and multidimensional chromatography. The one-dimensional chromatography is to separate each component in the oil by using a high performance capillary chromatographic column and then carry out quantification by using peak area normalization, but because the composition of the Fischer-Tropsch synthetic oil is very complicated, the peaks of hydrocarbons and oxygen-containing compounds are overlapped greatly, and the separation effect of the common gas chromatography is not good. The multidimensional chromatography method is characterized in that two or more chromatographic columns are connected through valves, so that a better separation effect can be obtained, but the method is usually only suitable for accurate quantification of a certain part of compounds, and for example, an SH/T0663 method has higher accuracy only on part of oxygen-containing compounds of C6 and below in test gasoline; SH/T0741 has good effect only on hydrocarbon substances below C12 in test gasoline, and the problem of mutual interference of partial oxygen-containing compounds and aromatic compounds cannot be solved, and the test requirements on the content of the hydrocarbon and the oxygen-containing compounds in Fischer-Tropsch synthetic oil cannot be met.
CN102079987A, CN104749298B and CN106947515B disclose methods for separating different types of compounds from crude oil or heavy oil by solid phase extraction, respectively, to separate oil into various hydrocarbons such as alkane and arene and colloid fractions, but all focus mainly on analyzing the hydrocarbon substances in the oil, and do not analyze the oxygen-containing compounds in the colloid further, and these analysis methods are not suitable for fischer-tropsch synthetic oils with greatly different compositions.
CN103257186B discloses a method for determining the content of oxygen-containing compounds in Fischer-Tropsch synthetic oil by using a gas chromatography/oxygen selective ionization detector (GC/O-FID), wherein the special detector only responds to the oxygen-containing compounds and can effectively eliminate the interference of hydrocarbon substances. However, the oxygen selective ionization detector has no qualitative function, and cannot distinguish the carbon number and the type of the oxygen-containing compound at all, and all compounds need to be qualified by a standard sample. Moreover, when the amount of the oxygen-containing compound is large, it is impossible to judge whether or not a single chromatographic peak represents a pure substance. In these respects, its performance is far inferior to that of a mass spectrometer. In addition, the oxygen selective ionization detector comprises a high-temperature cracking device, the price is high, the requirement on carrier gas is high, the failure rate is very high, and the later maintenance and repair cost are high. The usage of this type of detector is still low today. In contrast, if the oxygen-containing compound can be separated out by a simple means and then subjected to chromatographic analysis, the maintenance cost of the instrument can be greatly reduced, and the purchase of a standard oxygen-containing compound with a low price on a large scale can be avoided.
In order to improve the accuracy of the analysis without greatly increasing the cost, it is necessary to develop a new and simple method for determining the contents of hydrocarbons and oxygen-containing compounds in the Fischer-Tropsch synthesis oil.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for measuring the contents of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil, which is used for realizing the rapid and convenient measurement of the contents of the hydrocarbons and the oxygen-containing compounds in the Fischer-Tropsch synthetic oil.
The purpose of the invention can be realized by the following technical scheme:
a method for determining the content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil comprises the following steps: firstly, separating a Fischer-Tropsch synthetic oil sample to be detected by a solid phase extraction method to obtain a hydrocarbon mixed component and an oxygen-containing compound mixed component, respectively carrying out gas chromatography-mass spectrometry analysis on the two mixed components, determining a reference component in an obtained spectrogram, calculating a retention index of each peak, determining the hydrocarbon or the oxygen-containing compound corresponding to each peak according to the retention index and a pre-established compound qualitative database, and obtaining the content of each hydrocarbon or the oxygen-containing compound according to the peak area.
Wherein, the qualitative analysis and the quantitative analysis of the hydrocarbons and the oxygen-containing compounds are specifically as follows: the retention time of a reference component is found out by utilizing a mass spectrum library, the retention time of other peaks and the retention time of the corresponding reference component are substituted into the formula (1), a retention index is obtained by calculation, and the retention index is compared with a pre-established compound qualitative database, so that the peaks in a chromatogram can be rapidly determined; and then deducting the content of the solvent for analysis in the chromatogram, and converting according to the mass of the corresponding eluent collected in the solid phase extraction method to obtain the absolute content of each hydrocarbon and oxygen-containing compound in the Fischer-Tropsch synthetic oil.
Wherein, IxRetention index for desired defined peak, z is carbon number of reference component peak preceding desired defined peak, tR(x)Determination of the retention time of the peaks, t, for the purposes of the desiredR(z)Retention time, t, of the previous reference component peak to the desired identified peakR(z+1)The retention time of the next reference component peak to the desired identified peak.
As a preferred technical scheme, the Fischer-Tropsch synthetic oil to be detected is subjected to fraction cutting to obtain a plurality of fractions, the fractions are respectively used as Fischer-Tropsch synthetic oil samples to be detected, a hydrocarbon mixed component and an oxygen-containing compound mixed component are obtained through separation by a solid phase extraction method, gas chromatography-mass spectrometry analysis is respectively carried out on the two mixed components of each fraction, a reference component is determined in an obtained spectrogram according to retention time, the retention index of each peak is calculated, the hydrocarbon or the oxygen-containing compound corresponding to each peak is determined according to the retention index and a pre-established compound qualitative database, the content of each hydrocarbon or the oxygen-containing compound is obtained according to the peak area, and then the content of each hydrocarbon or the oxygen-containing compound in each fraction and the Fischer-Tropsch synthetic oil is obtained.
As a further preferable technical scheme, the Fischer-Tropsch synthetic oil to be tested is subjected to fraction segmentation to obtain light oil and heavy oil, wherein the carbon number of the light oil is C3-C20, the light oil is mainly concentrated at C5-C14, and the distillation range is distributed at 30-250 ℃; the carbon number of the heavy oil is C6-C40, the heavy oil is mainly concentrated in C10-C28, and the distillation range is distributed at 200-500 ℃.
Further, the solid phase extraction method specifically comprises the steps of loading a Fischer-Tropsch synthesis oil sample to be detected into a solid phase extraction column, then eluting with a first eluent and a second eluent in sequence, concentrating the obtained first eluent to obtain a hydrocarbon mixed component, and concentrating the obtained second eluent to obtain an oxygen-containing compound mixed component.
Furthermore, in the solid phase extraction column, the stationary phase comprises silica gel and neutral alumina;
the specific surface area of the stationary phase is 200-500m2(ii) a pore volume of 0.5 to 1.5 mL/g.
As a preferred technical scheme, the specific surface area of the stationary phase is 300-450m2(ii) a pore volume of 0.7 to 1.2 mL/g.
Further, the stationary phase in the solid phase extraction column is pretreated before being filled, and the pretreatment condition is constant temperature at 130-160 ℃ for 3-7 h.
The filling height of the stationary phase in the solid phase extraction column is 35-45mm/2g of Fischer-Tropsch synthetic oil sample to be detected.
As a preferable technical scheme, the pretreatment condition is constant temperature at 145-150 ℃ for 4-5 h.
As a preferred technical scheme, the filling height of the stationary phase is 38-40mm/2g of Fischer-Tropsch synthetic oil sample to be detected.
As a preferred technical scheme, after the stationary phase is filled, a first eluent is added to wet the stationary phase, then a Fischer-Tropsch synthetic oil sample to be detected is added, and the first eluent is used for washing again to enable the sample to be detected.
Further, the first eluent is saturated hydrocarbon of C5-C7.
Preferably, the first eluent is at least one of n-pentane, n-hexane and n-heptane.
As a further preferable technical scheme, the first eluent is n-hexane.
Further, the second eluent is a mixture of halogenated alkane and alcohol compounds;
the halogenated alkane comprises dichloromethane, trichloromethane and 1, 2-dichloroethane;
the alcohol compounds comprise methanol and ethanol;
the volume ratio of the halogenated alkane to the alcohol compound is (8-12) to 1.
According to a preferable technical scheme, the halogenated alkane is dichloromethane, the alcohol compound is ethanol, and the volume ratio of the halogenated alkane to the alcohol compound is 9: 1.
Further, the dosage of the first eluent is 30-45mL/2g of Fischer-Tropsch synthetic oil; the dosage of the second eluent is 20-35mL/2g of Fischer-Tropsch synthetic oil;
the elution speed of the first eluent and the second eluent is 2.0-6.0 mL/min.
As a preferred technical scheme, the dosage of the first eluent is 32-36mL/2g of Fischer-Tropsch synthesis oil; the dosage of the second eluent is 24-26mL/2g of Fischer-Tropsch synthetic oil;
the elution and washing speeds of the first eluent and the second eluent are both 3.0-4.0 mL/min.
Further, the concentration process is completed by a nitrogen blowing instrument.
Further, in the gas chromatography-mass spectrometry combined analysis process, the working conditions of the gas chromatography comprise that the sample injection amount is 0.1-0.5 muL, split-flow sample injection is carried out, the chromatographic column is one of HP-1, DB-1, HP-PONA and DB-Petro capillary columns, the sample injection port temperature is 250-300 ℃, and the temperature raising program of the column box is as follows: the initial temperature is 30-40 ℃, the heating rate is 2-5 ℃/min, and the end temperature is 250-;
the working conditions of the mass spectrum comprise an EI ionization mode, the bombardment voltage is 50-70eV, the scanning range is 15-500amu, and the ion source temperature is 200-250 ℃.
As a preferred technical scheme, in the working conditions of the gas chromatography, the sample injection amount is 0.2 mu L, the chromatographic column is an HP-PONA capillary column, the sample injection port temperature is 300 ℃, the initial temperature of a column box temperature-rising program is 35 ℃, the temperature-rising rate is 2 ℃/min, and the end point temperature is 300 ℃.
As a preferred technical scheme, in the working conditions of the mass spectrum, the bombardment voltage is 70eV, the scanning range is 20-300amu, and the ion source temperature is 230 ℃.
Further, the method for establishing the compound qualitative database comprises the following steps:
1) respectively carrying out gas chromatography-mass spectrometry combined analysis on a hydrocarbon component standard substance and an oxygen-containing compound standard substance to determine the retention time of each standard substance, wherein the standard substances are pure substances of hydrocarbons or oxygen-containing compounds;
2) selecting a plurality of common Fischer-Tropsch synthetic oil samples, respectively separating by a solid phase extraction method to obtain a hydrocarbon standard mixed component and an oxygen-containing compound standard mixed component, then respectively carrying out gas chromatography-mass spectrometry, and determining the hydrocarbon or the oxygen-containing compound corresponding to each retention time by using mass spectrometry; the common samples of the Fischer-Tropsch synthetic oil are Fischer-Tropsch synthetic oil containing different components obtained by different process conditions;
3) and calculating the retention index of each hydrocarbon or oxygen-containing compound according to the selected reference component and the retention time, and then corresponding the retention index to each hydrocarbon or oxygen-containing compound to obtain the compound qualitative database.
Wherein, for the hydrocarbon mixed component, the reference component is normal alkane; for the oxygenate blend component, the reference component is 2-normal ketone.
According to the invention, by combining the solid phase extraction and the gas chromatography-mass spectrometry, hydrocarbons and oxygen-containing compounds can be rapidly separated from Fischer-Tropsch synthetic oil, mutual interference of hydrocarbon components and the oxygen-containing compounds in the Fischer-Tropsch synthetic oil on retention time is effectively eliminated by adopting chromatographic analysis, and rapid qualitative and quantitative analysis of each component is realized by combining the advantages of the gas chromatography-mass spectrometry in the qualitative aspect and a simple data processing algorithm.
Compared with the prior art, the invention has the following characteristics:
1) the solid phase extraction column has low cost, easily obtained raw materials, convenient preparation and good separation effect, can quickly separate hydrocarbon components and oxygen-containing compounds from the Fischer-Tropsch synthetic oil, and simultaneously removes pollutants in the Fischer-Tropsch synthetic oil through the strong adsorption action of the stationary phase, thereby improving the accuracy of test results, prolonging the service life of the chromatographic column and reducing the maintenance frequency of a chromatograph;
2) by a fraction cutting method, the Fischer-Tropsch synthetic oil is divided into light oil and heavy oil, so that the distillation range of each analysis of the oil sample can be shortened, the component amount of each analysis of the oil sample can be reduced, the components of the middle fraction section of the Fischer-Tropsch synthetic oil can be split and simplified, and the mutual interference between compounds with relatively high boiling points and compounds with relatively low boiling points in the middle fraction section can be reduced; meanwhile, the components of different fractions are further split according to polarity by combining a solid phase extraction method, so that the analysis interference between the hydrocarbon components and the oxygen-containing compounds is avoided; the method for combining the fraction cutting with the solid-phase extraction can pre-separate the Fischer-Tropsch synthetic oil according to the boiling point and the polarity before the chromatographic analysis, can effectively simplify the raw oil, reduce the matrix effect of a sample, effectively improve the quantitative accuracy of the gas chromatography-mass spectrometry combined analysis, and meet the measurement requirements of hydrocarbon components and oxygen-containing compounds in the Fischer-Tropsch synthetic oil;
3) the analysis method of gas chromatography-mass spectrometry can quickly locate the normal alkane and 2-normal ketone with relatively high content in the hydrocarbon mixed component and the oxygen-containing compound mixed component, and the normal alkane and 2-normal ketone are used as reference peaks to calculate the retention index of each other peak, thereby completing the qualitative analysis of each component; meanwhile, the qualitative analysis method is carried out by retaining indexes, so that the interference caused by instability of an instrument, carrier gas fluctuation or mass spectrum library identification deviation can be effectively eliminated, the compound can be rapidly determined with high accuracy, and the rapid batch analysis and treatment of the same type of samples can be realized;
4) the method is simple and convenient to operate, easy to realize, quick and efficient in analysis and data processing processes, and suitable for Fischer-Tropsch synthetic oil obtained by different Fischer-Tropsch synthetic processes.
Drawings
FIG. 1 is a total ion flow chromatogram of hydrocarbons in Fischer-Tropsch synthesis light oil in example 2;
FIG. 2 is a total ion flow chromatogram of oxygenates in Fischer-Tropsch synthesized light oil of example 2;
FIG. 3 is a chromatogram of the total ion flow of hydrocarbons in the Fischer-Tropsch synthesized heavy oil in example 3;
FIG. 4 is a total ion flow chromatogram of oxygenates in Fischer-Tropsch synthesized heavy oil of example 3.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
A method for determining the content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil comprises the following steps:
a1, separating a Fischer-Tropsch synthesis oil sample to be detected by a solid phase extraction method to obtain a hydrocarbon mixed component and an oxygen-containing compound mixed component;
a2, carrying out gas chromatography-mass spectrometry combined analysis on the hydrocarbon mixed component to obtain a total ion current chromatogram of the hydrocarbon compound, then taking normal paraffin as a hydrocarbon reference component, finding out the retention time of the hydrocarbon reference component by using a mass spectrum library, converting the retention time of each other peak into a retention index by taking normal paraffin as a reference, and comparing the retention index with a hydrocarbon compound qualitative database to determine the compound attribution of each peak; then deducting the content of the solvent for chromatographic analysis from the analysis result, and calculating by combining the eluent and the total mass of the sample to be tested of the Fischer-Tropsch synthetic oil to obtain the absolute content of each hydrocarbon component;
a3, carrying out gas chromatography-mass spectrometry combined analysis on the oxygen-containing compound mixed component to obtain an oxygen-containing compound total ion chromatogram, then taking 2-orthoketone as an oxygen-containing compound reference component, finding out the retention time of the oxygen-containing compound reference component by using a mass spectrum library, converting the retention time of each other peak into a retention index by taking 2-orthoketone as a reference, and comparing the retention index with an oxygen-containing compound qualitative database to determine the compound attribution of each peak; and then deducting the content of the solvent for chromatographic analysis from the analysis result, and calculating by combining the eluent and the total mass of the to-be-detected sample of the Fischer-Tropsch synthetic oil to obtain the absolute content of each oxygen-containing compound component.
The calculation method of the retention index comprises the following steps:
in the formula IxRetention index for desired defined peak, z is carbon number of reference component peak preceding desired defined peak, tR(x)Determination of the retention time of the peaks, t, for the purposes of the desiredR(z)Retention time, t, of the previous reference component peak to the desired identified peakR(z+1)The retention time of the next reference component peak to the desired identified peak.
The establishment method of the hydrocarbon compound qualitative database and the oxygen-containing compound qualitative database comprises the following steps:
b1, analyzing the hydrocarbon and the oxygen-containing compound standard substance, namely the hydrocarbon and the oxygen-containing compound pure substance by gas chromatography-mass spectrometry to determine the retention time of the hydrocarbon and the oxygen-containing compound standard substance;
b2, selecting a plurality of common Fischer-Tropsch synthetic oil samples, splitting the common Fischer-Tropsch synthetic oil samples into a hydrocarbon part and an oxygen-containing compound part through a solid phase extraction method, respectively carrying out gas chromatography-mass spectrometry combined analysis, and determining compounds corresponding to each retention time through mass spectrometry;
and B3, for hydrocarbon and oxygen-containing compound parts, respectively taking normal alkane and 2-normal ketone as reference components, calculating retention indexes of the compounds, and corresponding the retention indexes to the compounds one by one to obtain a hydrocarbon compound qualitative database and an oxygen-containing compound qualitative database.
The solid phase extraction method specifically comprises the following steps:
c1, calcining the silica gel or the neutral alumina at the constant temperature of 130-160 ℃ (preferably 145-150 ℃) for 3-7h (preferably 4-5h) to obtain the activated silica gel or the neutral alumina, wherein the specific surface area of the silica gel and the neutral alumina is 200-500 m-2(preferably 300 ℃ C.)/g (preferably 450 ℃ C.), a pore volume of 0.5 to 1.5mL/g (preferably 0.7 to 1.2 mL/g);
c2, filling the activated silica gel and neutral alumina into a solid phase extraction column to obtain a stationary phase, wherein the filling height is 35-45mm (preferably 38-40mm), and adding n-pentane, n-hexane and n-heptane to wet the stationary phase;
c3, transferring 2g of Fischer-Tropsch synthesis oil to a solid phase extraction column, adding n-pentane, n-hexane and n-heptane to adsorb a Fischer-Tropsch synthesis oil sample to a stationary phase, washing the stationary phase with 30-45mL of a first eluent (preferably 32-36mL) and 20-35mL of a second eluent (preferably 24-26mL), respectively, collecting the first eluent and the second eluent in two 50mL conical bottles, respectively, wherein the first eluent is one of n-pentane, n-hexane and n-heptane, the second eluent is a mixture of halogenated alkane and alcohol compound with a volume ratio of (8-12):1, wherein the halogenated alkane is one of dichloromethane, trichloromethane and 1, 2-dichloroethane, the alcohol compound is methanol or ethanol (the second eluent is preferably a mixture of dichloromethane and ethanol with a volume ratio of 9:1), the elution speed of the first eluent and the second eluent is 2.0-6.0mL/min (preferably 3.0-4.0 mL/min);
c4, respectively concentrating the first eluent and the second eluent to 1mL by using a nitrogen blowing instrument, and weighing to respectively obtain a hydrocarbon mixed component and an oxygen-containing compound mixed component;
wherein, in the gas chromatography-mass spectrometry combined analysis process, the working conditions of the gas chromatography comprise that the sample volume is 0.1-0.5 muL (preferably 0.2 muL), the split-flow sample injection is carried out, the chromatographic column is one of HP-1, DB-1, HP-PONA and DB-Petro capillary columns (preferably HP-PONA), the temperature of the sample injection port is 250-300 ℃ (preferably 300 ℃), and the temperature raising program of the column box is as follows: the initial temperature is 30-40 deg.C (preferably 35 deg.C), the heating rate is 2-5 deg.C/min (preferably 2 deg.C/min), and the final temperature is 250-300 deg.C (preferably 300 deg.C);
the working conditions of the mass spectrum include EI ionization mode, bombardment voltage of 50-70eV (preferably 70eV), scanning range of 15-500amu (preferably 20-300amu), ion source temperature of 200-250 deg.C (preferably 230 deg.C).
Example 1:
establishing a compound qualitative database:
1) carrying out gas chromatography-mass spectrometry analysis on the hydrocarbon and oxygen-containing compound standard substance to determine the retention time of the hydrocarbon and oxygen-containing compound standard substance;
2) selecting a plurality of common Fischer-Tropsch synthetic oil samples, splitting the common Fischer-Tropsch synthetic oil samples into a hydrocarbon part and an oxygen-containing compound part through a solid phase extraction method, respectively carrying out gas chromatography-mass spectrometry, and determining a compound corresponding to each retention time through mass spectrometry;
3) for hydrocarbon and oxygen-containing compound parts, respectively taking n-alkane and 2-n-ketone as reference components, calculating retention indexes of the compounds, and corresponding the retention indexes to the compounds one by one to obtain a hydrocarbon compound qualitative database and an oxygen-containing compound qualitative database, wherein partial results are shown in tables 1 and 2.
TABLE 1 qualitative database partial results for hydrocarbon compounds
TABLE 2 qualitative database partial results for oxygenates
Wherein, the solid phase extraction method in the step 2) comprises the following steps:
2-1) activating the silica gel at a constant temperature of 150 ℃ for 5h, taking out, filling the silica gel in a solid phase extraction column to obtain a stationary phase with the filling height of 40mm, and then adding n-hexane to wet the silica gel;
2-2) accurately weighing 2g of common Fischer-Tropsch synthetic oil sample, transferring the common Fischer-Tropsch synthetic oil sample to a solid phase extraction column, adding 1mL of n-hexane for washing to enable the sample to be adsorbed on a stationary phase, and then respectively washing the stationary phase by using 35mL of n-hexane and 20mL of dichloromethane-ethanol mixed solution (the volume ratio is 9:1) to ensure that the washing speed is 3.0 mL/min; collecting the obtained eluent in two 50mL conical bottles respectively;
2-3) respectively concentrating the first eluent and the second eluent to 1mL by using a nitrogen blowing instrument, and weighing to respectively obtain a hydrocarbon part and an oxygen-containing compound part.
In this example, the silica gel used was purchased from Qingdao ocean chemical plant and had a specific surface area of 355m2(ii)/g, pore volume of 1.15mL/g, average pore diameter of 13.0 nm; the gas chromatography-mass spectrometer is purchased from Agilent technologies, Inc., and has a model number of 7890B/5977A; the working conditions of the gas chromatography are as follows: the sample introduction amount is 0.2 mu L, split sample introduction is carried out, a chromatographic column is an HP-PONA capillary column, the sample introduction port temperature is 300 ℃, the temperature raising program of a column box is 35 ℃ of initial temperature, and the temperature raising speed is raised to 300 ℃ at the speed of 2 ℃/min; the working conditions of the mass spectrum are as follows: EI ionization mode, bombardment voltage 70eV, scanning range 20-300amu, ion source temperature 230 ℃;
example 2:
determining the content of hydrocarbons and oxygen-containing compounds in the Fischer-Tropsch synthesis light oil:
1) collecting Fischer-Tropsch synthesis oil obtained from a Fischer-Tropsch synthesis device, performing fraction cutting on the Fischer-Tropsch synthesis oil through an actual boiling point device, and collecting light oil with the boiling point of less than 250 ℃;
2) activating silica gel at a constant temperature of 150 ℃ for 5h, taking out, filling the silica gel into a solid phase extraction column to obtain a stationary phase with the filling height of 40mm, and wetting the silica gel with n-hexane;
3) accurately weighing 2g of light oil, transferring the light oil to a solid phase extraction column, adding 1mL of n-hexane for washing to enable the light oil to be adsorbed on a stationary phase, and then respectively washing the stationary phase by 35mL of n-hexane and 20mL of dichloromethane-ethanol mixed solution (the volume ratio is 9:1) to ensure that the washing speed is basically controlled at 3.0 mL/min; sequentially and respectively collecting a first eluent and a second eluent which are eluted by using n-hexane and a dichloromethane-ethanol mixed solution by using 250 mL conical flasks below the solid-phase extraction column, and respectively concentrating the volume of the 2 eluents to 1mL by using a nitrogen blowing instrument to respectively obtain a hydrocarbon mixed component and an oxygen-containing compound mixed component;
4) carrying out gas chromatography-mass spectrometry combined analysis on the hydrocarbon mixed component in the step 3), wherein the obtained total ion flow chromatogram of the hydrocarbon compound is shown in figure 1; then, taking normal alkane as a hydrocarbon reference component, searching the retention time of the hydrocarbon reference component by using a mass spectrum library, converting the retention time of each other peak into a retention index by taking normal alkane as a reference, comparing the retention index with the qualitative database of the hydrocarbon compound obtained in the example 1, and determining the compound attribution of each peak; then, the content of the solvent for chromatographic analysis is deducted from the analysis result, and the absolute content of each hydrocarbon component is calculated by combining the total mass of the eluant n-hexane, dichloromethane-ethanol mixed solution and light oil, wherein the content of the hydrocarbon component with the carbon number of 8 is shown in table 3;
5) carrying out gas chromatography-mass spectrometry analysis on the oxygen-containing compound mixed component in the step 3), wherein the obtained total ion current chromatogram of the oxygen-containing compound is shown in figure 2; then, 2-normal ketone is used as an oxygen-containing compound reference component, a mass spectrum library is used for searching the retention time of the oxygen-containing compound reference component, the retention time of other peaks is converted into a retention index by using the 2-normal ketone as a reference, the retention index is compared with the oxygen-containing compound qualitative database obtained in the example 1, and the compound attribution of each peak is determined; then, the content of the solvent for chromatography was subtracted from the analysis results, and the absolute content of each oxygen-containing compound component was calculated by combining the total mass of the eluent n-hexane, dichloromethane-ethanol mixed solution and light oil, wherein the content of a part of the oxygen-containing compound components is shown in table 4.
The working conditions of the silica gel, the gas chromatography and the mass spectrometer used therein were the same as in example 1.
TABLE 3 content of partial hydrocarbon components in Fischer-Tropsch light oil
TABLE 4 content of part of the oxygenate component in the Fischer-Tropsch light oil
| Name of Compound | Retention index | Content (wt%) |
| Carbon heptaisomeric ketone | 668.9 | 0.05 |
| 2-heptanone | 700.0 | 0.40 |
| Carbon heptaisomeric alcohol | 715.8 | 0.08 |
| Carbon heptaisomeric alcohol | 748.0 | 0.28 |
| Carbon heptaisomeric alcohol | 759.5 | 0.08 |
| Carbooctaisomeric ketones | 774.7 | 0.06 |
| 1-heptanol | 783.2 | 0.88 |
| 2-octanones | 800.0 | 0.33 |
| 1-octanal | 811.5 | 0.09 |
| Alcohols with octa carbon isomers | 843.4 | 0.02 |
| Alcohols with octa carbon isomers | 845.8 | 0.13 |
| Alcohols with octa carbon isomers | 849.5 | 0.22 |
| Alcohols with octa carbon isomers | 856.3 | 0.04 |
| 3-methylphenol | 876.5 | 0.09 |
| 1-octanol | 882.1 | 0.70 |
Example 3:
determining the content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthesis heavy oil:
1) collecting Fischer-Tropsch synthesis oil obtained from a Fischer-Tropsch synthesis device, performing fraction cutting on the Fischer-Tropsch synthesis oil through an actual boiling point device, and collecting heavy oil with the boiling point of more than 250 ℃;
2) activating silica gel at a constant temperature of 150 ℃ for 5h, taking out, filling the silica gel into a solid phase extraction column to obtain a stationary phase with the filling height of 40mm, and wetting the silica gel with n-hexane;
3) accurately weighing 2g of heavy oil, transferring the heavy oil to a solid-phase extraction column, adding 1mL of n-hexane for washing to enable the light oil to be adsorbed on a stationary phase, and then respectively washing the stationary phase by 35mL of n-hexane and 20mL of dichloromethane-ethanol mixed solution (the volume ratio is 9:1) to ensure that the washing speed is basically controlled at 3.0 mL/min; sequentially and respectively collecting a first eluent and a second eluent which are eluted by using n-hexane and a dichloromethane-ethanol mixed solution by using 250 mL conical flasks below the solid-phase extraction column, and respectively concentrating the volume of the 2 eluents to 1mL by using a nitrogen blowing instrument to respectively obtain a hydrocarbon mixed component and an oxygen-containing compound mixed component;
4) carrying out gas chromatography-mass spectrometry combined analysis on the hydrocarbon mixed component in the step 3), wherein the obtained total ion flow chromatogram of the hydrocarbon compound is shown in figure 3; then, taking normal alkane as a hydrocarbon reference component, searching the retention time of the hydrocarbon reference component by using a mass spectrum library, converting the retention time of each other peak into a retention index by taking normal alkane as a reference, comparing the retention index with the qualitative database of the hydrocarbon compound obtained in the example 1, and determining the compound attribution of each peak; then, the content of the solvent for chromatographic analysis is deducted from the analysis result, and the absolute content of each hydrocarbon component is calculated by combining the total mass of the eluant n-hexane, dichloromethane-ethanol mixed solution and heavy oil, wherein the content of the part of the hydrocarbon components with the carbon number of 16 is shown in table 5;
5) carrying out gas chromatography-mass spectrometry analysis on the oxygen-containing compound mixed component in the step 3), wherein the obtained total ion current chromatogram of the oxygen-containing compound is shown in figure 4; then, 2-normal ketone is used as an oxygen-containing compound reference component, a mass spectrum library is used for searching the retention time of the oxygen-containing compound reference component, the retention time of other peaks is converted into a retention index by using the 2-normal ketone as a reference, the retention index is compared with the oxygen-containing compound qualitative database obtained in the example 1, and the compound attribution of each peak is determined; then, the content of the solvent for chromatography was subtracted from the analysis results, and the absolute content of each oxygen-containing compound component was calculated by combining the total mass of the eluent n-hexane, dichloromethane-ethanol mixed solution and heavy oil, wherein the content of a part of the oxygen-containing compound components is shown in table 6.
The working conditions of the silica gel, the gas chromatography and the mass spectrometer used therein were the same as in example 1.
TABLE 5 content of some hydrocarbon components in Fischer-Tropsch heavy oil
TABLE 6 content of part of the oxygenate component in Fischer-Tropsch heavy oil
| Name of Compound | Retention index | Content (wt%) |
| 2-nonanones | 900.0 | 0.05 |
| Isomeric nonanols | 945.6 | 0.02 |
| N-nonanol | 981.5 | 0.09 |
| 2-maldone | 1000.0 | 0.09 |
| 1-capric aldehyde | 1013.5 | 0.01 |
| Propylphenol | 1023.1 | 0.01 |
| Isomeric pelargonic alcohols | 1043.8 | 0.04 |
| N-nonanoic acid | 1067.8 | 0.01 |
| Corylvanillyl alcohol | 1080.9 | 0.14 |
| Butyl phenol | 1119.2 | 0.01 |
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method for determining the content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil is characterized by comprising the following steps: firstly, separating a Fischer-Tropsch synthetic oil sample to be detected by a solid phase extraction method to obtain a hydrocarbon mixed component and an oxygen-containing compound mixed component, respectively carrying out gas chromatography-mass spectrometry analysis on the two mixed components, determining a reference component in an obtained spectrogram, calculating a retention index of each peak, determining the hydrocarbon or the oxygen-containing compound corresponding to each peak according to the retention index and a pre-established compound qualitative database, and obtaining the content of each hydrocarbon or the oxygen-containing compound according to the peak area.
2. The method for determining the content of the hydrocarbons and the oxygen-containing compounds in the Fischer-Tropsch synthesis oil according to claim 1, wherein the solid phase extraction method specifically comprises the steps of loading a sample to be tested of the Fischer-Tropsch synthesis oil into a solid phase extraction column, then sequentially eluting with a first eluent and a second eluent, concentrating the obtained first eluent to obtain the hydrocarbon mixed component, and concentrating the obtained second eluent to obtain the oxygen-containing compound mixed component.
3. The method of claim 2, wherein the solid phase extraction column comprises a stationary phase comprising silica gel and neutral alumina;
the specific surface area of the stationary phase is 200-500m2(ii) a pore volume of 0.5 to 1.5 mL/g.
4. The method as claimed in claim 3, wherein the stationary phase in the solid phase extraction column is pretreated before being packed, and the pretreatment condition is constant temperature at 130-160 ℃ for 3-7 h.
5. The method for determining the content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthesis oil according to claim 2, wherein the first eluent is a saturated hydrocarbon of C5-C7.
6. The method for determining the content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthesis oil according to claim 2, wherein the second eluent is a mixture of halogenated alkanes and alcohol compounds;
the halogenated alkane comprises dichloromethane, trichloromethane and 1, 2-dichloroethane;
the alcohol compounds comprise methanol and ethanol;
the volume ratio of the halogenated alkane to the alcohol compound is (8-12) to 1.
7. The method for determining the content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthesis oil according to claim 2, wherein the amount of the first eluent is 30-45mL/2g of Fischer-Tropsch synthesis oil; the dosage of the second eluent is 20-35mL/2g of Fischer-Tropsch synthetic oil;
the elution speed of the first eluent and the second eluent is 2.0-6.0 mL/min.
8. The method for determining the content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthesis oil according to claim 2, wherein the concentration process is performed by a nitrogen blower.
9. The method as claimed in claim 2, wherein the operating conditions of the gas chromatography include a sample amount of 0.1-0.5 μ L, split injection, one of HP-1, DB-1, HP-PONA and DB-Petro capillary columns, an injection port temperature of 250-: the initial temperature is 30-40 ℃, the heating rate is 2-5 ℃/min, and the end temperature is 250-;
the working conditions of the mass spectrum comprise an EI ionization mode, the bombardment voltage is 50-70eV, the scanning range is 15-500amu, and the ion source temperature is 200-250 ℃.
10. The method for determining the contents of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthesis oil according to claim 1, wherein the method for establishing the qualitative compound database comprises the following steps:
1) respectively carrying out gas chromatography-mass spectrometry combined analysis on the hydrocarbon component standard substance and the oxygen-containing compound standard substance to determine the retention time of each standard substance;
2) selecting a plurality of common Fischer-Tropsch synthetic oil samples, respectively separating by a solid phase extraction method to obtain a hydrocarbon standard mixed component and an oxygen-containing compound standard mixed component, then respectively carrying out gas chromatography-mass spectrometry, and determining the hydrocarbon or the oxygen-containing compound corresponding to each retention time by using mass spectrometry;
3) calculating the retention index of each hydrocarbon or oxygen-containing compound according to the selected reference component and the retention time, and then corresponding the retention index to each hydrocarbon or oxygen-containing compound to obtain a compound qualitative database;
wherein, for the hydrocarbon mixed component, the reference component is normal alkane; for the oxygenate blend component, the reference component is 2-normal ketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010234821.7A CN111308005A (en) | 2020-03-30 | 2020-03-30 | Method for determining content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010234821.7A CN111308005A (en) | 2020-03-30 | 2020-03-30 | Method for determining content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111308005A true CN111308005A (en) | 2020-06-19 |
Family
ID=71145904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010234821.7A Pending CN111308005A (en) | 2020-03-30 | 2020-03-30 | Method for determining content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111308005A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112229926A (en) * | 2020-09-29 | 2021-01-15 | 上海兖矿能源科技研发有限公司 | Method for determining composition and content of aromatic hydrocarbon in high-temperature Fischer-Tropsch synthetic oil |
| CN112285225A (en) * | 2020-10-15 | 2021-01-29 | 广东石油化工学院 | Detection method for rapidly determining content of isononyl alcohol |
| CN114075447A (en) * | 2020-08-14 | 2022-02-22 | 中国石油天然气股份有限公司 | Method for separating oxygen-containing compounds in coal-based diesel oil |
| CN114075446A (en) * | 2020-08-14 | 2022-02-22 | 中国石油天然气股份有限公司 | Method for separating oxygen-containing compound in gasoline |
| CN114432740A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Double-layer solid phase extraction column for separating Fischer-Tropsch synthetic oil middle fraction and application thereof |
| CN114561228A (en) * | 2020-11-27 | 2022-05-31 | 中国石油天然气股份有限公司 | Method for separating oxygen-containing compounds in coal-based wax oil |
| CN114965792A (en) * | 2022-06-14 | 2022-08-30 | 宁夏滨泽新能源科技有限公司 | Analysis method for rapidly detecting content of C4-C22 alkane |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040087824A1 (en) * | 2002-10-30 | 2004-05-06 | O'rear Dennis J. | Novel process to upgrade fischer-tropsch products and form light olefins |
| CN103257186A (en) * | 2012-02-16 | 2013-08-21 | 中国石油化工股份有限公司 | Method of determining content of oxygen-containing compounds in F-T synthetic oil by GC/O-FID |
| CN106645533A (en) * | 2015-10-29 | 2017-05-10 | 中国石油化工股份有限公司 | Extraction separation method and determination method for organic nitrogen-containing and/or oxygen-containing additive in gasoline |
| CN107525706A (en) * | 2016-06-21 | 2017-12-29 | 中国石油化工股份有限公司 | A kind of method of n-alkane in SPE removing oil product |
| CN108469471A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | The solid-phase extraction column and application process of different Group Components in separating synthetic gas olefine reaction oil-phase product |
| US20190004019A1 (en) * | 2015-12-29 | 2019-01-03 | Total Raffinage Chimie | Method for Detecting and Quantifying Oxygen in Oxidizable Compounds |
| CN109839448A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Solid phase extraction column and method for separating phenolic compounds in diesel oil by solid phase extraction |
| CN109839450A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Method for simultaneously separating nitrogen-containing compounds and phenolic compounds in diesel oil by solid phase extraction |
-
2020
- 2020-03-30 CN CN202010234821.7A patent/CN111308005A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040087824A1 (en) * | 2002-10-30 | 2004-05-06 | O'rear Dennis J. | Novel process to upgrade fischer-tropsch products and form light olefins |
| CN103257186A (en) * | 2012-02-16 | 2013-08-21 | 中国石油化工股份有限公司 | Method of determining content of oxygen-containing compounds in F-T synthetic oil by GC/O-FID |
| CN106645533A (en) * | 2015-10-29 | 2017-05-10 | 中国石油化工股份有限公司 | Extraction separation method and determination method for organic nitrogen-containing and/or oxygen-containing additive in gasoline |
| US20190004019A1 (en) * | 2015-12-29 | 2019-01-03 | Total Raffinage Chimie | Method for Detecting and Quantifying Oxygen in Oxidizable Compounds |
| CN107525706A (en) * | 2016-06-21 | 2017-12-29 | 中国石油化工股份有限公司 | A kind of method of n-alkane in SPE removing oil product |
| CN108469471A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | The solid-phase extraction column and application process of different Group Components in separating synthetic gas olefine reaction oil-phase product |
| CN109839448A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Solid phase extraction column and method for separating phenolic compounds in diesel oil by solid phase extraction |
| CN109839450A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Method for simultaneously separating nitrogen-containing compounds and phenolic compounds in diesel oil by solid phase extraction |
Non-Patent Citations (3)
| Title |
|---|
| 刘俊彦: "固相萃取-气相色谱法测定合成气制烯烃产物中的含氧化合物", 《色谱》, vol. 32, no. 11, 30 November 2014 (2014-11-30), pages 1280 - 1285 * |
| 田文卿等: "固相萃取-气相色谱法测定甲醇制烯烃副产汽油及甲醇制汽油产物中的含氧化合物", 《色谱》, vol. 35, no. 11, 8 November 2017 (2017-11-08), pages 1204 - 1209 * |
| 顾晟燊: "萃取/气相色谱法对费托合成油的全组成分析", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》, 15 August 2016 (2016-08-15), pages 25 - 32 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075447A (en) * | 2020-08-14 | 2022-02-22 | 中国石油天然气股份有限公司 | Method for separating oxygen-containing compounds in coal-based diesel oil |
| CN114075446A (en) * | 2020-08-14 | 2022-02-22 | 中国石油天然气股份有限公司 | Method for separating oxygen-containing compound in gasoline |
| CN114075446B (en) * | 2020-08-14 | 2024-01-30 | 中国石油天然气股份有限公司 | Method for separating oxygen-containing compound in gasoline |
| CN112229926A (en) * | 2020-09-29 | 2021-01-15 | 上海兖矿能源科技研发有限公司 | Method for determining composition and content of aromatic hydrocarbon in high-temperature Fischer-Tropsch synthetic oil |
| WO2022068174A1 (en) * | 2020-09-29 | 2022-04-07 | 上海兖矿能源科技研发有限公司 | Method for determining composition and content of aromatic hydrocarbons in high-temperature fischer-tropsch synthetic oil |
| CN112285225A (en) * | 2020-10-15 | 2021-01-29 | 广东石油化工学院 | Detection method for rapidly determining content of isononyl alcohol |
| CN114432740A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Double-layer solid phase extraction column for separating Fischer-Tropsch synthetic oil middle fraction and application thereof |
| CN114432740B (en) * | 2020-10-30 | 2024-01-09 | 中国石油化工股份有限公司 | Double-layer solid phase extraction column for separating middle distillate of Fischer-Tropsch synthetic oil and application thereof |
| CN114561228A (en) * | 2020-11-27 | 2022-05-31 | 中国石油天然气股份有限公司 | Method for separating oxygen-containing compounds in coal-based wax oil |
| CN114965792A (en) * | 2022-06-14 | 2022-08-30 | 宁夏滨泽新能源科技有限公司 | Analysis method for rapidly detecting content of C4-C22 alkane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111308005A (en) | Method for determining content of hydrocarbons and oxygen-containing compounds in Fischer-Tropsch synthetic oil | |
| Hertz et al. | Determination of individual organic compounds in shale oil | |
| CN112229926B (en) | Method for determining composition and content of aromatic hydrocarbon in high-temperature Fischer-Tropsch synthetic oil | |
| CN103913534B (en) | A kind of series hydrocarbon compound carbon isotope analysis method in natural gas | |
| CN110870985B (en) | Separation and characterization method of heavy oil aromatic hydrocarbon component, two-dimensional liquid chromatography and device | |
| CN110672764A (en) | Quantitative analysis method for judging petroleum degradation grade | |
| CN218099031U (en) | VOCs online and offline rapid monitoring device in environmental atmosphere | |
| Willis | Column switching in gas chromatography | |
| O'Connor et al. | Molecular sieve adsorption. Application to hydrocarbon type analysis | |
| CN1292252C (en) | Process for determining hydrocarbon composition of vacuum gas oil by combination of solid phase extraction and mass spectrum | |
| CN103792297A (en) | Chromatography-mass spectrometry method for determining oxygen-containing compounds in complex olefin matrix | |
| Packham et al. | Column switching for the high-performance liquid chromatographic analysis of polynuclear aromatic hydrocarbons in petroleum products | |
| CN114075446B (en) | Method for separating oxygen-containing compound in gasoline | |
| CN1428605A (en) | Analysis method of hydrocarbon composition in asphalt, heavy oil and tar | |
| CN103995061B (en) | The analytical approach of diesel oil distillate and heavy oil fraction hydrocarbon system composition in micro-anti-fluid product | |
| CN114076808B (en) | Pretreatment method for determining composition of coal-based diesel oil family | |
| Sanzo | Chromatographic analyses of fuels | |
| CN116381098A (en) | Method for measuring content of trace main oxygen-containing compound in high-temperature Fischer-Tropsch synthetic oil | |
| CN113533606A (en) | Method for determining hydrocarbon composition in crude oil | |
| CN114075450B (en) | Method for separating diesel oil group composition by solid phase extraction | |
| CN111579654A (en) | Method for separating, purifying and simultaneously measuring antioxidant and anti-icing agent in aviation kerosene | |
| CN117214333B (en) | Adamantane compound analysis and determination method | |
| CN114563516B (en) | Method for determining wax oil group composition | |
| CN114563506B (en) | Pretreatment method for determining content and composition of olefin compounds in wax oil | |
| CN1831531A (en) | Instrument for quantitative analysing micro-alkyne in C5 fraction and its analysing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |