CN114425183B - Separation method of chromatographic column and crude oil group component and application - Google Patents
Separation method of chromatographic column and crude oil group component and application Download PDFInfo
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- CN114425183B CN114425183B CN202011016542.XA CN202011016542A CN114425183B CN 114425183 B CN114425183 B CN 114425183B CN 202011016542 A CN202011016542 A CN 202011016542A CN 114425183 B CN114425183 B CN 114425183B
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- 239000010779 crude oil Substances 0.000 title claims abstract description 71
- 238000000926 separation method Methods 0.000 title claims abstract description 45
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 59
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 50
- 239000003921 oil Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- 238000005070 sampling Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000004587 chromatography analysis Methods 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 11
- 235000012239 silicon dioxide Nutrition 0.000 description 11
- 230000005526 G1 to G0 transition Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002026 chloroform extract Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001457 gas chromatography time-of-flight mass spectrometry Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/22—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
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- 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
- B01D15/426—Specific type of solvent
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/34—Arrangements for separating materials produced by the well
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder
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Abstract
The invention discloses a chromatographic column and a separation method and application of crude oil group components. The chromatographic column comprises a first cylinder, a second cylinder, a third cylinder and a cone which are sequentially communicated from top to bottom, wherein a material flow inlet is formed in the top end of the first cylinder, and a material flow outlet is formed in the bottom of the cone. The separation method comprises the following steps: step 1, according to the difference of adsorption capacities of fixed relative different components, saturated hydrocarbon and aromatic hydrocarbon in crude oil are sequentially displaced by a solvent and separated and flow out, and are collected according to the sequence; and step 2, determining the hydrocarbon composition characteristics of the effluent fractions in different time periods according to the refractive index of the hydrocarbons and the fluorescence characteristics of the aromatic compounds under ultraviolet irradiation. The chromatographic column and the separation method separate condensate oil or light oil in the crude oil, and have the advantages of short separation time, capability of reducing volatilization of light components in the crude oil and relatively and completely retaining component information in the crude oil.
Description
Technical Field
The invention relates to a chromatographic column for separating crude oil components and application thereof, and a separation method and application of crude oil components.
Background
Along with the exploration and development of deep and sea-phase high-evolution oil gas in China, more and more light crude oil is discovered. Light crude oil is an important component of crude oil and generally refers to a relative density of less than 0.87g/cm 3 Can be further subdivided into light oils (0.81-0.87 g/cm 3 ) Volatile oil (0.70-0.81 g/cm) 3 ) And condensate oil<0.71g/cm 3 ). API Gravity (american petroleum institute Gravity) is another index for distinguishing heavy crude oil from light crude oil, and is greater than 31.1, belonging to light crude oil; the light crude oil has less 'impurities', and the exploitation and oil refining process flow and technology are relatively simple. In the oil refining process, crude oil with the same volume and light crude oil can be refined to produce more high-value products (such as petroleum gas, aviation gasoline, diesel oil, kerosene and the like). Therefore, light crude oil is a high-quality resource in crude oil, is more popular with people, and has higher international market price.
When the geochemical property of crude oil is analyzed in the geological exploration field, the crude oil is often divided into four types of saturated hydrocarbon, aromatic hydrocarbon, non-hydrocarbon and asphaltene. Saturated hydrocarbons and aromatic hydrocarbons are the main researches of organic geochemistry, and the deposition environment, maturity, sources and the like of crude oil can be judged by judging the composition, properties, parameter ratio and the like of compounds in the saturated hydrocarbons and the aromatic hydrocarbons. However, due to the low boiling point and volatile property of the saturated hydrocarbon and the aromatic hydrocarbon of the light crude oil, the conventional separation method is easy to cause the loss of the light components in the saturated hydrocarbon and the aromatic hydrocarbon, and the judgment of the property of the crude oil is seriously influenced.
Bie Daozhe (1999) the rotary thin layer chromatography is used for analyzing the chloroform extract of the rock and the crude oil components, and the method has the characteristics of small sample size, high recovery rate and wide application range; however, the method can not solve the defect of strong volatility of the light crude oil, and can cause larger loss of light components.
The analysis of the group components of light crude oils has been studied exclusively by the use of the column chromatography method for separating the group components. The sample is added into the chromatographic column, and each component is sequentially ejected out of the chromatographic column by using a displacing agent which has stronger adsorption or dissolution capacity to the stationary phase than all the sample components. The application range of the method can be popularized to the analysis of the light part of heavy crude oil. However, the adsorption column used in the method is overlong, small in inner diameter, inconvenient to operate, longer in experimental time and unfavorable for large-scale popularization and application.
CN110579543a uses full two-dimensional gas chromatography-time-of-flight mass spectrometry to analyze samples, which is accurate in quantification, but can only be directly analyzed by chromatography-mass spectrometry, cannot be used for component preparation, and cannot be used for isotope or other analysis of light crude oil components.
CN106390520a proposes a chromatographic column analysis method for analyzing crude oil group components, in which the chromatographic column is complex, formed by connecting several glass columns, is complex to install, is easy to form leakage points, has long separation time, and cannot avoid loss of light components.
Disclosure of Invention
Aiming at the volatilization problems of condensate oil, light oil and the like in crude oil, the prior art has the problems of long measurement time, incapability of solving the volatilization problem, light component loss, incapability of fully utilizing saturated hydrocarbon and aromatic hydrocarbon and incapability of performing isotope research on oil components, the invention provides a novel chromatographic column for separating crude oil components.
The invention provides a chromatographic column for separating crude oil group components, which comprises a first cylinder, a second cylinder, a third cylinder and a cone, wherein the first cylinder, the second cylinder, the third cylinder and the cone are sequentially communicated from top to bottom, a material flow inlet is arranged at the top end of the first cylinder, and a material flow outlet is arranged at the bottom of the cone; wherein the inner diameter ratio of the first cylinder, the second cylinder and the third cylinder is 3-5:1-2:1.
According to some embodiments of the chromatography column of the invention, the ratio of the inner diameter of the third cylinder to the inscribed circle diameter of the cone base is 4-8:1.
According to some embodiments of the chromatography column of the invention, the height ratio of the first cylinder, the second cylinder, the third cylinder and the cone is 6-10:25-35:20-30:1.
According to some embodiments of the chromatography column of the invention, the first cylinder and the second cylinder, the second cylinder and the third cylinder, and the third cylinder and the cone may be connected by a tapered cone tube, such as shown in fig. 1.
According to some embodiments of the chromatography column of the present invention, the material of the chromatography column may be, but is not limited to, glass or the like.
According to some embodiments of the chromatography column of the invention, the chromatography column of the invention is suitable for the separation of crude oil family components, in particular for the separation of light oil or condensate family components.
In a second aspect, the present invention provides a method for separating crude oil family components, comprising the steps of:
step 1, according to the difference of adsorption capacities of fixed relative different components, saturated hydrocarbon and aromatic hydrocarbon in crude oil are sequentially displaced by a solvent and separated and flow out, and are collected according to the sequence;
and step 2, determining the hydrocarbon composition characteristics of the effluent fractions in different time periods according to the refractive index of the hydrocarbons and the fluorescence characteristics of the aromatic compounds under ultraviolet irradiation.
According to some embodiments of the separation method of the present invention, prior to step 1, the method further comprises determining the refractive index of the crude oil at room temperature and converting to a standard refractive index of 20 ℃ and determining the sample size;
preferably, the refractive index is less than or equal to 1.43, and the sampling amount is 10-12mL;1.45 The refractive index is more than or equal to 1.43, and the sampling amount is 7-9mL; the refractive index is more than or equal to 1.45, and the sampling amount is 4-6mL. The invention has the advantages of high efficiency, short time and good separation effect in the sampling amount range. When the sampling amount is larger than the range defined in the present invention, i.e., the sampling amount is large, there is a possibility that the problem of poor separation effect may not be solved due to the limited carrying capacity of the column.
According to some embodiments of the separation method of the present invention, the method of step 2 comprises the steps of:
step 2.1, the amount of the received fraction is 20-80% of the sampling amount, each 0.2-0.3mL of the received fraction is connected with one fraction, each fraction is checked by using a 254nm ultraviolet fluorescent lamp to determine whether fluorescence is generated, and if no fluorescence is generated, a saturated hydrocarbon fraction is obtained, and the saturated hydrocarbon fraction is collected and weighed;
2.2, when fraction fluorescence is carried out, obtaining saturated hydrocarbon and aromatic hydrocarbon mixed fractions, carrying out one fraction every 0.1-0.2mL, converting to obtain the refractive index of each fraction at 20 ℃, until the refractive index value of the highest refractive index fraction at 20 ℃ and the refractive index value of the previous fraction at 20 ℃ are larger than 0.01, and collecting to obtain saturated hydrocarbon and aromatic hydrocarbon mixed fractions;
2.3, obtaining mixed fraction of aromatic hydrocarbon and solvent, wherein the refractive index value of the highest refractive index fraction at 20 ℃ and the refractive index value of the previous fraction at 20 ℃ are more than 0.01; after all solvents flow into the liquid-solid chromatographic column, eluting the residual polar component in the fixed phase by using an eluting agent to obtain mixed fractions of aromatic hydrocarbon and the eluting agent, and collecting the mixed fractions;
and 2.4, mixing the mixed fraction of saturated hydrocarbon and aromatic hydrocarbon, the mixed fraction of aromatic hydrocarbon and solvent and the mixed fraction of aromatic hydrocarbon and eluent to obtain a middle fraction, and performing solvent volatilizing treatment and weighing.
According to some embodiments of the separation method of the present invention, the process of the solvent swing treatment of step 2.4 comprises: evaporating to middle distillate of 4-6mL at 50-60deg.C, and volatilizing to dryness at room temperature under negative pressure in a fume hood.
According to some embodiments of the separation process according to the invention, the content of the group components is obtained according to formulae I to IV;
wherein: x is X S 、X A 、X N And X B Respectively representing mass fractions of saturated hydrocarbon, aromatic hydrocarbon, colloid and asphaltene; x is X ZS 、X ZA 、X ZN And X ZB Respectively representing the mass fractions of saturated hydrocarbon, aromatic hydrocarbon, colloid and asphaltene in the middle distillate; g Z G represents the mass of the middle distillate; g Si G represents the mass of the ith saturated hydrocarbon fraction; g Ai G represents the mass of the ith aromatic fraction; m represents the mass of the sample, g.
According to some embodiments of the separation method of the present invention, the conversion formula that yields a refractive index of 20 ℃ is formula V:
n D 20 ＝n D ' +0.0004 (t-20) (formula V)
Wherein: n is n D 20 Refractive index at 20 ℃; n is n D ' is the refractive index measured at t, t being the actual test temperature.
According to some embodiments of the separation methods of the present invention, the solvent has a wide range of choices, such as, but not limited to, ethanol and the like.
According to some embodiments of the separation method of the present invention, the eluting agent has a wide selection range, and may be selected from at least one of chloroform, ethanol and chloroform, for example.
According to some embodiments of the separation method of the present invention, the stationary phase has a wide selection range, and may be, for example, silicic acid and/or alumina, preferably silicic acid, more preferably 80-120 mesh silicic acid.
According to some embodiments of the separation process of the present invention, the process of the present invention is suitable for the separation of crude oil family components, in particular for the separation of light oil or condensate family components.
According to some embodiments of the separation methods of the present invention, the separation method of crude oil family components comprises the steps of:
(1) The refractive index of the sample in the greenhouse was measured and converted to a standard refractive index of 20℃and the amount of the sample was determined based on the refractive index. Refractive index is less than or equal to 1.43, and sampling amount is 10mL;1.45 The refractive index is more than or equal to 1.43, and the sampling amount is 7mL; the refractive index is more than or equal to 1.45, and the sampling amount is 5mL. The properly submitted sample was accurately removed with a quantitative pipette, weighed on a balance to an accuracy of 0.01g, and its mass was recorded.
The standard refractive index conversion formula at 20 ℃ is as follows:
n D 20 ＝n D ' +0.0004 (t-20) (formula V)
Wherein: n is n D 20 Refractive index at 20 ℃; n is n D ' is the refractive index measured at t, t being the actual test temperature.
(2) Filling a small amount of absorbent cotton at the bottom of the chromatographic column, filling about 10g of activated 100-mesh silicic acid, and lightly beating to tightly and uniformly fill the silicic acid. And accurately transferring the same amount of sample by using a quantitative pipette, injecting the sample into a chromatographic column, and adding a silicic acid layer with the thickness of about 1cm and about 15mL of ethanol after the sample is completely infiltrated into the silicic acid.
(3) As the sample moves downward within the column, the displaced fraction is received in a centrifuge tube of constant weight. The first fraction is 20-80 wt% of the sample, 0.2-0.3mL of each fraction is changed into one fraction, each fraction is checked by 254nm ultraviolet fluorescent lamp to check whether fluorescence is generated, and then the fraction is weighed, and the non-fluorescent fraction is saturated hydrocarbon.
(4) And (3) receiving fluorescence of the fractions to obtain saturated hydrocarbon and aromatic hydrocarbon mixed fractions, receiving one fraction every 0.1-0.2mL, converting to obtain the refractive index of each fraction at 20 ℃, until the refractive index value of the highest refractive index fraction at 20 ℃ and the refractive index value of the previous fraction at 20 ℃ are larger than 0.01, and collecting to obtain the saturated hydrocarbon and aromatic hydrocarbon mixed fractions.
(5) The refractive index value of the highest refractive index fraction at 20 ℃ and the refractive index value of the previous fraction at 20 ℃ is more than 0.01, so as to obtain a mixed fraction of aromatic hydrocarbon and ethanol; when the refractive index of the components is close to or equal to 1.3615, the whole ethanol flows into the chromatographic column, and the experiment is stopped. After all ethanol flows into the liquid-solid chromatographic column, the residual polar component in the stationary phase is leached by chloroform to obtain the mixed fraction of aromatic hydrocarbon and leaching agent and collected.
(6) Transferring the saturated hydrocarbon and aromatic hydrocarbon mixed fraction obtained in the step (4) into a collection container obtained in the step (5) by using chloroform or chloroform, combining the saturated hydrocarbon and aromatic hydrocarbon mixed fraction, aromatic hydrocarbon and solvent mixed fraction and aromatic hydrocarbon and eluting agent mixed fraction into middle fraction (the middle fraction is obtained by mixing the saturated hydrocarbon and aromatic hydrocarbon mixed fraction, aromatic hydrocarbon and eluting agent mixed fraction), evaporating the middle fraction to 4-6mL at 50-60 ℃, and volatilizing the middle fraction to dryness at room temperature under negative pressure. Preferably, the negative pressure in the fume hood is evaporated to dryness at room temperature, after which the weight is constant. The constant weight middle distillate was measured for its group component content according to the specifications of chapter four SY/T5119-2016,
the mass fraction of each group of components in the sample is calculated according to the formulas I to IV.
Wherein: x is X S 、X A 、X N And X B Respectively representing mass fractions of saturated hydrocarbon, aromatic hydrocarbon, colloid and asphaltene; x is X ZS 、X ZA 、X ZN And X ZB Respectively representing the mass fractions of saturated hydrocarbon, aromatic hydrocarbon, colloid and asphaltene in the middle distillate; g Z G represents the mass of the middle distillate; g Si Represents the ith saturated hydrocarbonThe mass of the fraction, g; g Ai G represents the mass of the ith aromatic fraction; m represents the mass of the sample, g.
The invention has the beneficial effects that:
(1) The chromatographic column for separating crude oil group components can slow down the flow rate of crude oil, thereby improving the separation effect.
(2) The method for separating the crude oil group components can accurately analyze the group components of the crude oil with smaller density such as light crude oil (including light oil, volatile oil and condensate oil), can reduce volatilization of the light components in the crude oil, can completely retain the component information in the crude oil, and is simple to operate.
(3) The separation method can obtain saturated hydrocarbon and aromatic hydrocarbon, and can research the composition, the isotope and the like of the oil component according to the needs, thereby realizing the full utilization of the saturated hydrocarbon and the aromatic hydrocarbon.
Drawings
FIG. 1 is a schematic diagram of a chromatographic column for separation of crude oil family components provided in example 1 of the present invention;
FIG. 2 is a schematic diagram of a conventional column of comparative example 1.
Description of the reference numerals
1. A first cylinder 2, a second cylinder 3, and a third cylinder
4. Cone cone
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
[ example 1 ]
The chromatographic column for separating crude oil group components comprises a first cylinder, a second cylinder, a third cylinder and a cone which are sequentially communicated from top to bottom, wherein a material flow inlet is arranged at the top end of the first cylinder, and a material flow outlet is arranged at the bottom of the cone; wherein the inner diameter of the first cylinder is 2.5cm, and the height is 8cm; the inner diameter of the second cylinder is 0.9cm, and the height is 30cm; the inner diameter of the third cylinder is 0.6cm, and the height of the third cylinder is 25cm; the bottom is a cone, the inner diameter of the bottom circle of the cone is 0.1cm, and the height is about 1cm. The chromatographic column is made of glass.
[ example 2 ]
The separation of Y10 crude oil group components of the eastern sea field was performed using the chromatographic column for crude oil group component separation of example 1, comprising the steps of:
(1) The refractive index of the sample in the greenhouse was measured and converted to a standard refractive index of 20℃and the amount of the sample was determined based on the refractive index. Refractive index is less than or equal to 1.43, and sampling amount is 10mL;1.45 The refractive index is more than or equal to 1.43, and the sampling amount is 7mL; the refractive index is more than or equal to 1.45, and the sampling amount is 5mL. The properly submitted sample was accurately removed with a quantitative pipette, weighed on a balance to an accuracy of 0.01g, and its mass was recorded.
The standard refractive index conversion formula at 20 ℃ is as follows:
n D 20 ＝n D ’+0.0004(t-20)
wherein: n is n D 20 Refractive index at 20 ℃; n is n D ' is the refractive index measured at t, t being the actual test temperature.
(2) Filling a small amount of absorbent cotton at the bottom of the chromatographic column, filling about 10g of activated 100-mesh silicic acid, and lightly beating to tightly and uniformly fill the silicic acid. And accurately transferring the same amount of sample by using a quantitative pipette, injecting the sample into a chromatographic column, and adding a silicic acid layer with the thickness of about 1cm and about 15mL of ethanol after the sample is completely infiltrated into the silicic acid.
(3) As the sample moves downward within the column, the displaced fraction is received in a centrifuge tube of constant weight. The amount of the first fraction was 50% by weight of the sampled amount, followed by 0.3mL of each fraction per flow, and each fraction was checked for fluorescence by a 254nm UV fluorescent lamp, and then weighed, and the non-fluorescent fraction was saturated.
(4) When the fraction emits fluorescence, the saturated hydrocarbon aromatic hydrocarbon mixed fraction is replaced by carrying one fraction every 0.2mL, the volume is recorded, the refractive index at room temperature is measured, and the refractive index of the non-fluorescent saturated hydrocarbon component before the first fluorescent intermediate component is complemented. And (3) taking the fraction with the refractive index difference smaller than 0.01 between every two adjacent fractions before and after the highest refractive index fraction (the fraction with the highest refractive index) as aromatic hydrocarbon fraction, and collecting to obtain saturated hydrocarbon and aromatic hydrocarbon mixed fraction.
(5) The refractive index value of the highest refractive index fraction at 20 ℃ and the refractive index value of the previous fraction at 20 ℃ are larger than 0.01, the mixed fraction of aromatic hydrocarbon and ethanol is obtained, each 0.5mL of the mixed fraction is connected with one component, the volume of the mixed fraction is recorded, and the refractive index of the mixed fraction is measured. When the refractive index of the components is close to or equal to 1.3615, the experiment is stopped after all ethanol flows into the chromatographic column. After all ethanol flows into the liquid-solid chromatographic column, the residual polar component in the stationary phase is leached by 15mL of chloroform to obtain a mixed fraction of aromatic hydrocarbon and leaching agent and collected.
(6) Transferring the saturated hydrocarbon aromatic hydrocarbon mixed fraction in the step (4) into a collecting container in the step (5) by using chloroform or chloroform, combining the saturated hydrocarbon aromatic hydrocarbon mixed fraction, the aromatic hydrocarbon mixed fraction and the mixed fraction of the eluent into a middle fraction (the middle fraction is obtained by mixing the saturated hydrocarbon aromatic hydrocarbon mixed fraction, the aromatic hydrocarbon mixed fraction and the mixed fraction of the eluent), evaporating the mixture at the temperature of 60 ℃ under reduced pressure until the middle fraction is 5mL, and volatilizing the mixture at the temperature of room temperature in a fume hood under reduced pressure until the mixture is dried, thereby obtaining constant weight. The constant weight middle distillate was measured for its group component content according to SY/T5119-2016 chapter IV.
The mass fraction of each group of components in the sample is calculated according to the formulas I to IV, and the obtained result retains two decimal places.
Wherein: x is X S 、X A 、X N And X B Respectively representing mass fractions of saturated hydrocarbon, aromatic hydrocarbon, colloid and asphaltene; x is X ZS 、X ZA 、X ZN And X ZB Respectively representing the mass fractions of saturated hydrocarbon, aromatic hydrocarbon, colloid and asphaltene in the middle distillate; g Z G represents the mass of the middle distillate; g Si G represents the mass of the ith saturated hydrocarbon fraction; g Ai G represents the mass of the ith aromatic fraction; m represents the mass of the sample, g.
The volume of the separated aromatic hydrocarbon, the volume of the saturated hydrocarbon, the content of the calculated aromatic hydrocarbon and the content of the saturated hydrocarbon, and the recovery rate are shown in Table 1.
[ examples 3 to 7 ]
The chromatographic column for crude oil group component separation of example 1 was employed, and the separation method of example 2 was followed, except that the group components were separated for Y16 crude oil, Y03 crude oil, Y12 crude oil, Y13 crude oil, Y15 crude oil, respectively, in the eastern sea oil field, and the respective recovery rates were calculated.
The volume of the separated aromatic hydrocarbon, the volume of the saturated hydrocarbon, the content of the calculated aromatic hydrocarbon and the content of the saturated hydrocarbon, and the recovery rate are shown in Table 1.
TABLE 1
Examples 8 to 11
The column for separation of crude oil group components of example 1 was used, and the separation method of example 2 was followed, except that the separation of group components was performed on Y07 crude oil, Y11 crude oil, Y09 crude oil, and Y10 crude oil, respectively, and the respective aromatic hydrocarbon content, saturated hydrocarbon content, non-hydrocarbon content, saturation aromatic ratio, and relative error were calculated, and the results are shown in table 2.
Comparative examples 1 to 4
The group components of the Y07 crude oil, the Y11 crude oil, the Y09 crude oil and the Y10 crude oil of examples 8 to 11 were separated by using a common column (inner diameter: 8mm, length: 40 cm) shown in FIG. 2, and the aromatic hydrocarbon content, the saturated hydrocarbon content, the non-hydrocarbon content, the saturation aromatic ratio and the relative error were calculated, respectively, and the results are shown in Table 2.
TABLE 2
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent modifications and improvements will occur to those skilled in the art, and are intended to be within the scope of the present invention, as a matter of common general knowledge in the art, in light of the technical teaching provided by the present invention.
Claims (12)
1. The chromatographic column for separating the crude oil group components is characterized by comprising a first cylinder, a second cylinder, a third cylinder and a cone which are sequentially communicated from top to bottom, wherein a material flow inlet is formed at the top end of the first cylinder, and a material flow outlet is formed at the bottom of the cone; wherein the inner diameter ratio of the first cylinder, the second cylinder and the third cylinder is 3-5:1-2:1.
2. The chromatography column of claim 1, wherein the ratio of the inner diameter of the third cylinder to the inscribed circle diameter of the cone base is 4-8:1.
3. The chromatography column of claim 1 or 2, wherein the height ratio of the first cylinder, the second cylinder, the third cylinder and the cone is 6-10:25-35:20-30:1.
4. A method for separating crude oil group components using the column according to any one of claims 1 to 3, comprising the steps of:
step 1, according to the difference of adsorption capacities of fixed relative different components, saturated hydrocarbon and aromatic hydrocarbon in crude oil are sequentially displaced by a solvent and separated and flow out, and are collected according to the sequence;
and step 2, determining the hydrocarbon composition characteristics of the effluent fractions in different time periods according to the refractive index of the hydrocarbons and the fluorescence characteristics of the aromatic compounds under ultraviolet irradiation.
5. The separation method according to claim 4, wherein the method further comprises, before the step 1, measuring the refractive index of crude oil at room temperature and converting the refractive index to a standard refractive index of 20 ℃ and determining the sampling amount.
6. The separation method according to claim 5, wherein the refractive index is 1.43 or less and the sampling amount is 10 to 12mL;1.45 The refractive index is more than or equal to 1.43, and the sampling amount is 7-9mL; the refractive index is more than or equal to 1.45, and the sampling amount is 4-6mL.
7. The separation method according to any one of claims 4 to 6, wherein the method of step 2 comprises the steps of:
step 2.1, the amount of the received fraction is 20-80% of the sampling amount, each 0.2-0.3mL of the received fraction is connected with one fraction, each fraction is checked by using a 254nm ultraviolet fluorescent lamp to determine whether fluorescence is generated, and if no fluorescence is generated, a saturated hydrocarbon fraction is obtained, and the saturated hydrocarbon fraction is collected and weighed;
2.2, when fraction fluorescence is carried out, obtaining saturated hydrocarbon and aromatic hydrocarbon mixed fractions, carrying out one fraction every 0.1-0.2mL, converting to obtain the refractive index of each fraction at 20 ℃, until the refractive index value of the highest refractive index fraction at 20 ℃ and the refractive index value of the previous fraction at 20 ℃ are larger than 0.01, and collecting to obtain saturated hydrocarbon and aromatic hydrocarbon mixed fractions;
2.3, obtaining mixed fraction of aromatic hydrocarbon and solvent, wherein the refractive index value of the highest refractive index fraction at 20 ℃ and the refractive index value of the previous fraction at 20 ℃ are more than 0.01; after all solvents flow into the liquid-solid chromatographic column, eluting the residual polar component in the fixed phase by using an eluting agent to obtain mixed fractions of aromatic hydrocarbon and the eluting agent, and collecting the mixed fractions;
and 2.4, mixing the mixed fraction of saturated hydrocarbon and aromatic hydrocarbon, the mixed fraction of aromatic hydrocarbon and solvent and the mixed fraction of aromatic hydrocarbon and eluent to obtain a middle fraction, and performing solvent volatilizing treatment and weighing.
8. The separation method of claim 7, wherein the process of the solvent swing treatment of step 2.4 comprises: evaporating to middle distillate at 50-60deg.C and at room temperature under negative pressure until the middle distillate is dried.
9. The separation process according to claim 7, wherein the content of each group component is obtained according to formulae I to IV;
(formula I);
(formula II);
(formula III);
(formula IV);
wherein: x is X S 、X A 、X N And X B Respectively representing mass fractions of saturated hydrocarbon, aromatic hydrocarbon, colloid and asphaltene; x is X ZS 、X ZA 、X ZN And X ZB Respectively representing the mass fractions of saturated hydrocarbon, aromatic hydrocarbon, colloid and asphaltene in the middle distillate; g Z G represents the mass of the middle distillate; g Si G represents the mass of the ith saturated hydrocarbon fraction; g Ai G represents the mass of the ith aromatic fraction; m represents the mass of the sample, g.
10. The separation method according to claim 7, wherein the conversion formula for converting the refractive index at 20 ℃ is formula V:
n D 20 =n D ' +0.0004 (t-20) (formula V)
Wherein: n is n D 20 Refractive index at 20 ℃; n is n D ' is the refractive index measured at t, t being the actual test temperature.
11. The separation method according to claim 7, wherein the solvent is ethanol; and/or the number of the groups of groups,
the leaching agent is at least one selected from ethanol and chloroform.
12. Use of a chromatographic column for the separation of crude oil family components as claimed in any of claims 1 to 3 or of a separation process as claimed in any of claims 4 to 11 in oil and gas exploration.
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