CN111099992B - Liquid-liquid extraction method of carboxylic acid compounds in petroleum - Google Patents
Liquid-liquid extraction method of carboxylic acid compounds in petroleum Download PDFInfo
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- CN111099992B CN111099992B CN202010004206.7A CN202010004206A CN111099992B CN 111099992 B CN111099992 B CN 111099992B CN 202010004206 A CN202010004206 A CN 202010004206A CN 111099992 B CN111099992 B CN 111099992B
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- crude oil
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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Abstract
The invention provides a liquid-liquid extraction method of carboxylic acid compounds in petroleum, which comprises the following steps: weighing a crude oil sample, putting the crude oil sample into a centrifugal tube, and adding a solvent to dissolve the crude oil sample to obtain a crude oil sample solution; adding an extracting agent into the crude oil sample solution, oscillating, transferring the carboxylic acid compound in the crude oil sample solution into the extracting agent, standing, layering the crude oil sample solution and the extracting agent, placing the crude oil sample solution separated from the carboxylic acid compound on the upper layer, placing the extracting agent containing the carboxylic acid compound on the lower layer, and sucking out the extracting agent on the lower layer by using an injector, so that the carboxylic acid compound is separated from the crude oil sample. The method provided by the invention has the advantages of small sample dosage, small solvent dosage, no need of back extraction, one-time transfer and concentration, direct machine test after extraction, effective simplification of extraction operation, shortened extraction time and improved extraction recovery rate.
Description
Technical Field
The invention relates to the technical field of petroleum extraction, in particular to a liquid-liquid extraction method of carboxylic acid compounds in petroleum.
Background
The carboxylic acid compound in petroleum has dual capacities of biogenic and ancient environment tracers and surfactants in the transportation, polymerization and storage processes of oil and gas. Due to the extremely complex matrix of petroleum samples, selective separation of carboxylic acid compounds in petroleum samples is required before analytical testing of the compounds. The separation of carboxylic acid compounds from petroleum is generally carried out by liquid-liquid extraction. The traditional liquid-liquid extraction separation of carboxylic acid compounds in crude oil is generally carried out by ionizing the carboxylic acid compounds in crude oil with a large amount of strongly alkaline aqueous solution, extracting the ionized carboxylic acid compounds from the organic phase to an aqueous phase, adjusting the pH of the aqueous phase with a strong acid to make the aqueous phase acidic, converting the carboxylic acid compounds from the ionic state to a neutral molecular state, and back-extracting the molecules of the carboxylic acid compounds in the aqueous phase with an organic solvent. The method comprises extraction and back extraction, the steps are complicated, the consumption of crude oil samples and reagents is large, and the concentration step of a large amount of extraction solvent usually causes the loss of light boiling point components.
Disclosure of Invention
In view of the above, the present invention provides a liquid-liquid extraction method for carboxylic acid compounds in petroleum, which has the advantages of simple steps, short extraction time and high extraction recovery rate.
The invention provides a liquid-liquid extraction method of carboxylic acid compounds in petroleum, which comprises the following steps:
s1, weighing a crude oil sample, putting the crude oil sample into a centrifugal tube, and adding a solvent to dissolve the crude oil sample to obtain a crude oil sample solution;
s2, adding an extracting agent into the crude oil sample solution, oscillating, transferring the carboxylic acid compound in the crude oil sample solution into the extracting agent, standing, layering the crude oil sample solution and the extracting agent, placing the crude oil sample solution separated from the carboxylic acid compound on the upper layer and the extracting agent containing the carboxylic acid compound on the lower layer, and sucking out the extracting agent on the lower layer by using an injector, namely separating the carboxylic acid compound from the crude oil sample.
Further, the centrifuging tube that uses is sharp bottom glass centrifuging tube, and the volume of centrifuging tube is 2mL, and the mouth of pipe area screw cap, and the centrifuging tube total length is 78mm, and the centrifuging tube includes centrifuging tube upper portion and centrifuging tube lower part, and centrifuging tube upper portion is the straight tube that the diameter is 11mm, and the centrifuging tube lower part is the toper, and the angle of centrifuging tube lower part is about 31, and separation extractant is selectively drawn after conical centrifuging tube lower part is convenient for save micro-extraction agent and the extraction.
Furthermore, the solvent is n-hexane.
Further, the extractant is a mixed solution of ammonia water and acetonitrile, and the volume ratio of the ammonia water to the acetonitrile is 5: 95-30: 70.
Further, the syringe is 100 μ L microsyringe.
The extracting agent used in the method is immiscible with the crude oil sample solution, the density of the extracting agent is greater than that of the crude oil sample solution, and the extracting agent is positioned at the lower layer after layering; the ammonia water in the extractant is used as weak base, can react with the carboxylic acid compound, and promotes the ionization polarization of the carboxylic acid compound to enhance the polarity of the carboxylic acid compound; in-CN of acetonitrile molecule, carbon atom and nitrogen atom are connected by triple bond, and have strong polarity; the two components of the extractant act together to promote the mass transfer of the carboxylic acid compound from the nonpolar crude oil sample solution to the polar organic solvent acetonitrile, thereby improving the extraction recovery rate.
The technical scheme provided by the invention has the beneficial effects that: according to the method provided by the invention, the pointed-bottom glass centrifuge tube is used as a liquid-liquid extraction container, a micro-extraction agent can be used for extraction experiments, the using amount of the extraction agent is reduced, a concentration step is not needed after extraction, and the micro-extraction agent is stored at the tube bottom of the centrifuge tube and is convenient to move; the extractant used in the method provided by the invention is a mixed solution of ammonia water/acetonitrile, does not contain metal salt, has an organic solvent as a main component, does not need a back extraction step, and can be directly used for subsequent instrument analysis and test; the method provided by the invention has the advantages of small sample dosage, small solvent dosage, no need of back extraction, one-time transfer and concentration, direct machine test after extraction, effective simplification of extraction operation, shortened extraction time and improved extraction recovery rate.
Drawings
FIG. 1 is a schematic flow diagram of a process for the liquid-liquid extraction of carboxylic acid compounds from petroleum according to the present invention.
FIG. 2 is a graph of the experimental procedure for extraction using the liquid-liquid extraction method of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the accompanying drawings.
In the following examples, ammonia water was used at a concentration of not less than 25% by weight, and acetonitrile was used at a concentration of not less than 99.9% by weight.
Example 1:
referring to fig. 1 and 2, example 1 of the present invention provides a method for liquid-liquid extraction of carboxylic acid compounds from petroleum, comprising the steps of:
weighing 100mg of crude oil sample into a pointed-bottom glass centrifuge tube, and adding 1mL of n-hexane to dissolve the crude oil sample to obtain a crude oil sample solution; then, adding 50 μ L of ammonia water/acetonitrile (the volume ratio of ammonia water to acetonitrile is 10: 90) mixed solution into the crude oil sample solution, layering the extractant and the crude oil sample solution, wherein the upper layer is the crude oil sample solution, and the lower layer is the extractant (shown in figure 2 a); after the cover of the pointed-bottom glass centrifuge tube is closed, the solution in the tube is fully vibrated, and the extractant is dispersed in the crude oil sample solution (as shown in fig. 2b, in order to clearly distinguish the extractant from the crude oil sample solution, a small drop is used for representing the extractant); shaking for 5min, transferring carboxylic acid compound in crude oil sample solution into the extractant, standing for 30s, separating crude oil sample solution from the extractant, sucking lower layer of extractant containing carboxylic acid compound with 100 μ L microinjector (as shown in FIG. 2 c), and analyzing and testing carboxylic acid compound in the extractant by using chromatography-mass spectrometer.
FIG. 2 is the experimental procedure of extraction carried out in example 1, wherein 1 in FIG. 2a represents a pointed-bottom glass centrifuge tube, the total length of the pointed-bottom glass centrifuge tube is 78mm, the pointed-bottom glass centrifuge tube comprises an upper part of the centrifuge tube and a lower part of the centrifuge tube, the upper part of the centrifuge tube is a straight tube with the diameter of 11mm, the lower part of the centrifuge tube is conical, the angle of the lower part of the centrifuge tube is about 31 degrees, 2 represents crude oil sample solution, and 3 represents an extractant; in FIG. 2b, 4 denotes a dispersed extractant; in FIG. 2c, 5 denotes a 100. mu.L micro syringe, and 6 denotes an extractant containing a carboxylic acid compound.
Example 2:
weighing 100mg of crude oil sample into a pointed-bottom glass centrifuge tube, and adding 1mL of n-hexane to dissolve the crude oil sample to obtain a crude oil sample solution; then, adding 50 mu L of mixed solution of ammonia water and acetonitrile (the volume ratio of the ammonia water to the acetonitrile is 20: 80) into the crude oil sample solution, layering an extracting agent and the crude oil sample solution, wherein the upper layer is the crude oil sample solution, and the lower layer is the extracting agent; after the pointed-bottom glass centrifugal tube is covered with a cover, fully oscillating the solution in the tube, and dispersing an extracting agent in a crude oil sample solution; shaking for 5min, transferring the carboxylic acid compound in the crude oil sample solution into an extracting agent, standing for 30s, layering the crude oil sample solution and the extracting agent, sucking the extracting agent containing the carboxylic acid compound at the lower layer by using a 100-mu-L micro-injector, and analyzing and testing the carboxylic acid compound in the extracting agent by adopting a chromatographic-mass spectrometer.
In this document, the terms front, back, upper and lower are used to define the components in the drawings and the positions of the components relative to each other, and are used for clarity and convenience of the technical solution. It is to be understood that the use of the directional terms should not be taken to limit the scope of the claims.
The features of the embodiments and embodiments described herein above may be combined with each other without conflict.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. A liquid-liquid extraction method of carboxylic acid compounds in petroleum is characterized by comprising the following steps:
s1, weighing a crude oil sample, putting the crude oil sample into a centrifugal tube, and adding a solvent to dissolve the crude oil sample to obtain a crude oil sample solution; the solvent is n-hexane;
s2, adding an extracting agent into the crude oil sample solution, oscillating, transferring the carboxylic acid compound in the crude oil sample solution into the extracting agent, standing, layering the crude oil sample solution and the extracting agent, enabling the crude oil sample solution separated from the carboxylic acid compound to be located at the upper layer and the extracting agent containing the carboxylic acid compound to be located at the lower layer, and sucking out the extracting agent at the lower layer by using an injector, namely separating the carboxylic acid compound from the crude oil sample; the extractant is a mixed solution of ammonia water and acetonitrile, and the volume ratio of the ammonia water to the acetonitrile is 5: 95-30: 70.
2. The method for liquid-liquid extraction of carboxylic acid compounds in petroleum according to claim 1, wherein the centrifuge tube used is a pointed glass centrifuge tube, the volume of the centrifuge tube is 2mL, the total length of the centrifuge tube is 78mm, the centrifuge tube comprises an upper part of the centrifuge tube and a lower part of the centrifuge tube, the upper part of the centrifuge tube is a straight tube with a diameter of 11mm, and the lower part of the centrifuge tube is conical.
3. The method according to claim 1, wherein the syringe is a 100 μ L micro syringe.
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| CN202010004206.7A CN111099992B (en) | 2020-01-03 | 2020-01-03 | Liquid-liquid extraction method of carboxylic acid compounds in petroleum |
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| US2795532A (en) * | 1954-10-04 | 1957-06-11 | Sun Oil Co | Refining heavy mineral oil fractions with an anhydrous mixture of sodium hydroxide and potassium hydroxide |
| US4199440A (en) * | 1977-05-05 | 1980-04-22 | Uop Inc. | Trace acid removal in the pretreatment of petroleum distillate |
| CN1123825A (en) * | 1995-09-05 | 1996-06-05 | 新疆石油管理局克拉玛依炼油厂 | Deacidifying process for petroleum cut fraction with amino-alcohol |
| CN101200652A (en) * | 2006-12-12 | 2008-06-18 | 中国石油天然气股份有限公司 | Method for removing petroleum acid in petroleum distillate oil by using membrane dispersion extraction equipment |
| CN104897456A (en) * | 2015-05-08 | 2015-09-09 | 河北工业大学 | Method for enriching phenol in water by utilizing [C4mim]PF6-TBP binary extractant |
| CN105675771A (en) * | 2016-03-22 | 2016-06-15 | 河北工业大学 | Method for gathering aromatic amine compounds from water |
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2020
- 2020-01-03 CN CN202010004206.7A patent/CN111099992B/en not_active Expired - Fee Related
Patent Citations (6)
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|---|---|---|---|---|
| US2795532A (en) * | 1954-10-04 | 1957-06-11 | Sun Oil Co | Refining heavy mineral oil fractions with an anhydrous mixture of sodium hydroxide and potassium hydroxide |
| US4199440A (en) * | 1977-05-05 | 1980-04-22 | Uop Inc. | Trace acid removal in the pretreatment of petroleum distillate |
| CN1123825A (en) * | 1995-09-05 | 1996-06-05 | 新疆石油管理局克拉玛依炼油厂 | Deacidifying process for petroleum cut fraction with amino-alcohol |
| CN101200652A (en) * | 2006-12-12 | 2008-06-18 | 中国石油天然气股份有限公司 | Method for removing petroleum acid in petroleum distillate oil by using membrane dispersion extraction equipment |
| CN104897456A (en) * | 2015-05-08 | 2015-09-09 | 河北工业大学 | Method for enriching phenol in water by utilizing [C4mim]PF6-TBP binary extractant |
| CN105675771A (en) * | 2016-03-22 | 2016-06-15 | 河北工业大学 | Method for gathering aromatic amine compounds from water |
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