CN110066232B

CN110066232B - Separation method of active components in petroleum sulfonate

Info

Publication number: CN110066232B
Application number: CN201910443534.4A
Authority: CN
Inventors: 王帅; 郭勇; 梁晓静; 王立成; 王磊
Original assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Current assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Priority date: 2019-05-27
Filing date: 2019-05-27
Publication date: 2021-08-24
Anticipated expiration: 2039-05-27
Also published as: CN110066232A

Abstract

The invention discloses a method for separating active components in petroleum sulfonate, which comprises the steps of adopting a chromatographic technique, carrying out segmentation cutting on a petroleum sulfonate sample according to time intervals in a gradient elution mode, dividing the petroleum sulfonate sample into 24 components, combining the components with similar structural compositions according to a mass spectrometry analysis result, and finally obtaining 14 components with different structures. The components are respectively subjected to interface activity and emulsification performance tests, and the components with better interface activity and emulsification performance in the petroleum sulfonate sample are screened and accurately separated, so that accurate raw material selection guidance is provided for producing and preparing the petroleum sulfonate sample with excellent performance.

Description

Separation method of active components in petroleum sulfonate

Technical Field

The invention relates to a method for separating active components in petroleum sulfonate, in particular to a method for separating components with optimal interfacial activity and emulsifying property in a petroleum sulfonate sample, and belongs to the technical field of surfactant analysis and evaluation in the technical field of oilfield chemical flooding for improving recovery efficiency.

Background

Petroleum sulfonate is an anionic surfactant which is most widely applied in chemical flooding of oil fields. The petroleum sulfonate has complex structure composition, and large difference exists between reaction raw materials and reaction processes, so that large physical and chemical properties and performance difference exists among petroleum sulfonate samples produced by different sources and different manufacturers, wherein the physical and chemical properties include average molecular weight, molecular weight distribution range, structure type, interface activity, emulsifying property and the like. In practice, the petroleum sulfonate sample is treated as a whole, however, not all components have superior interfacial activity or emulsifying properties. The performance of the petroleum sulfonate sample directly influences the oil displacement efficiency and the exploitation cost of an oil field, and if the active components playing a role in the petroleum sulfonate sample can be accurately tracked and identified, the method is not only beneficial to understanding the interaction relation between the structure and the performance of the petroleum sulfonate on the theoretical basis, but also has very important guidance direction and value for producing and preparing the petroleum sulfonate sample with excellent quality.

The petroleum sulfonate has a very complex composition structure, and research works show that a petroleum sulfonate sample contains hundreds of compounds, mostly homologues and isomers, and the separation and characterization difficulty is very high. At present, no analysis method and research literature exists for rapidly and comprehensively separating and characterizing petroleum sulfonate quality and structural information, active components with excellent performance in petroleum sulfonate samples are screened and separated, and related research reports are not found. Therefore, the development of a method capable of accurately separating the active components in the petroleum sulfonate sample has a wide application prospect and is a technical problem and research work to be solved.

Disclosure of Invention

The invention aims to provide a method for separating active components in petroleum sulfonate, aiming at the technical blank existing in the identification and separation of components with better interface activity and emulsifying property in petroleum sulfonate samples.

The method for separating the active component in the petroleum sulfonate comprises the following steps:

(1) preparing a chromatographic column: filling chromatographic column by wet method, wherein the filler is hydrophobic reversed phase chromatographic filler, such as C₁₈Or C₈Bonding porous silica gel; the specification of the chromatographic column is that the inner diameter is 2.54 cm and the length is 30 cm;

(2) and (3) chromatographic separation: taking methanol and water as mobile phases, performing gradient elution for 0-20 min, and performing 50% methanol elution; 20-30 min, 70% methanol; 30-40 min, 90% methanol; 40-52 min, 100% methanol; the flow rate is 10 mL/min; the sample injection amount is 10 mL; the concentration of the sample solution is 20 mg/mL;

(3) collecting components: collecting the effluent solution from the chromatographic column from 4 min, wherein the collection time is 2 min each time, and collecting 24 solutions in total;

(4) according to the mass spectrometry result, the solutions with similar structural compositions are combined, and finally 14 components with different structures are obtained. Specifically, the obtained solutions are sorted into

solutions

1, 2 and 3 … 24 according to the collection order, wherein the solution 1 is the component 1, the solution 2 is the component 2, the combined solutions 3 and 4 are the component 3, the combined solutions 5 and 6 are the component 4, the combined solutions 7 to 10 are the component 5, the combined solutions 11 and 12 are the component 6, the solution 13 is the component 7, the solution 14 is the component 8, the combined solutions 15 to 17 are the component 9, the solution 18 is the component 10, the solution 19 is the component 11, the solution 20 is the component 12, the combined solutions 21 and 22 are the component 13, and the combined solutions 23 and 24 are the component 14.

The results of the interfacial tension tests on the components obtained above show that the component 10 has the optimal interfacial activity among 14 components obtained by separation, can achieve the ultralow interfacial tension, and is far superior to the original petroleum sulfonate sample and other component samples.

The emulsifying property test of each component shows that the component 10 has the optimal emulsifying property among 14 components obtained by separation, the oil emulsifying rate can reach 60 percent, is superior to 44 percent of the original petroleum sulfonate sample, and has better emulsifying property than other components.

Combining the results of the interfacial activity and emulsification performance tests, it can be determined that component 10 has both the optimal interfacial activity and the optimal emulsification performance, and thus, can be determined to be the active component in the petroleum sulfonate sample.

In conclusion, the petroleum sulfonate sample is segmented and cut according to time periods by adopting a chromatographic technology and a gradient elution mode, and is divided into 24 components; then according to the mass spectrometry result, combining the components with similar structural composition to finally obtain 14 components with different structures; the components are respectively subjected to interface activity and emulsification performance tests, and the components with better interface activity and emulsification performance in the petroleum sulfonate sample are screened and accurately separated, so that accurate raw material selection guidance is provided for producing and preparing the petroleum sulfonate sample with excellent performance.

Drawings

FIG. 1 is the results of interfacial tension testing of the separated components of the present invention.

FIG. 2 shows the results of the emulsion performance test of the separated components of the present invention.

FIG. 3 is a mass spectrum of the isolated active ingredient 10 of the present invention.

Detailed Description

The method of the present invention for separating active components from petroleum sulfonate is illustrated by the following specific examples.

The apparatus used was: mass spectrometer, agilent 1100 MSD, usa; interfacial tensiometer, Beijing Shengweiji science and technology Co., Ltd. TX-500, China.

Reagent: methanol, pure chromatography, beijing mai ruida technologies ltd; sodium chloride, analytical grade, Tianjin Baishi chemical Co., Ltd; petroleum sulfonate sample, crude oil for experiment, zone seven in Xinjiang oil field.

(1) Preparing a chromatographic column: filling the chromatographic column by a wet method, wherein the filler is C₁₈Bonding porous silica gel; the specification of the chromatographic column is that the inner diameter is 2.54 cm and the length is 30 cm;

(2) and (3) chromatographic separation: gradient eluting with methanol and water as mobile phase for 0-20 min, 50% methanol, 20-30 min, 70% methanol, 30-40 min, 90% methanol, 40-52 min, and 100% methanol; the flow rate is 10 mL/min; the sample injection amount is 10 mL; the concentration of the sample solution is 20 mg/mL;

(3) collecting components: collecting the effluent solution of the chromatographic column from the 4 th min, wherein the collection time is 2 min, collecting 24 solutions in total, and sequencing the obtained solutions into

solutions

1, 2 and 3 … 24 according to the collection sequence, wherein the solution 1 is the component 1, the solution 2 is the component 2, the combined solutions 3 and 4 are the component 3, the combined solutions 5 and 6 are the component 4, the combined solutions 7 to 10 are the component 5, the combined solutions 11 and 12 are the component 6, the solution 13 is the component 7, the solution 14 is the component 8, the combined solutions 15 to 17 are the component 9, the solution 18 is the component 10, the solution 19 is the component 11, the solution 20 is the component 12, the combined solutions 21 and 22 are the component 13, and the combined solutions 23 and 24 are the component 14. Repeating the operation for 10 times, respectively combining the obtained different components, and respectively placing the different components in a drying oven at 100 ℃ for drying to obtain solid samples of the different components. The content of each component is shown in table 1. As can be seen from Table 1, the component 10 accounts for the highest content, which is 20.34%, and the rest accounts for 79.66%;

(4) and (3) interfacial tension test: the interfacial tension test was carried out by preparing solutions of each of the different components each having a concentration of 3 mg/mL with saline (sodium chloride) having a degree of mineralization of 5 mg/mL. And (3) testing conditions are as follows: the rotating speed is 6000 r/min, the temperature is 40 ℃, the oil phase is crude oil in the seven middle areas of the Xinjiang oil field, and the testing time is 120 min. The test results are shown in FIG. 1. As can be seen from FIG. 1, of the 14 separated components, the component 10 has the optimal interfacial activity, and can achieve the ultra-low interfacial tension, which is far superior to that of the crude petroleum sulfonate sample and other component samples.

(5) And (3) testing the emulsifying property: 5 mL of sample solution and 5 mL of experimental crude oil are put in a test tube, sufficiently shaken and placed in an oven at 40 ℃ for standing for 3 hours, the volume of the oil phase is observed, the emulsification rate of the oil phase is calculated, and the test results are shown in figure 2 and table 2. According to the experimental results of fig. 2 and table 2, it can be seen that the component 10 of the 14 components obtained by separation has the optimal emulsifying property, and the emulsifying oil rate can reach 60%, which is better than the 44% emulsifying oil rate of the crude petroleum sulfonate sample, and is better than the emulsifying property of other components.

(6) Mass spectrometry test: the analysis conditions are that the flow rate of the atomizing gas (nitrogen) is 15L/min, the flow rate of the drying gas (helium) is 8L/min, the temperature is 350 ℃, and the detection is carried out in an anion mode. Mass spectrometry was performed on the active ingredient 10 solution and the results are shown in FIG. 3. As can be seen from FIG. 3, the molecular weight distribution range of the active ingredient 10 is 390-470, and the average molecular weight is 432.5; wherein the molecular weight distribution range of the components with higher content is 405-445, and the distribution range is very narrow and is about 40.

Claims

1. A method for separating active components in petroleum sulfonate comprises the following steps:

(1) preparing a chromatographic column: filling a chromatographic column by adopting a wet method, wherein the filler is hydrophobic reversed-phase chromatographic filler; the specification of the chromatographic column is that the inner diameter is 2.54 cm and the length is 30 cm; the hydrophobic reversed-phase chromatographic packing is C₁₈Or C₈Bonding porous silica gel;

(2) and (3) chromatographic separation: taking methanol and water as mobile phases, performing gradient elution for 0-20 min, and performing 50% methanol elution; 20-30 min, 70% methanol; 30-40 min, 90% methanol; 40-52 min, 100% methanol; the flow rate is 10 mL/min; the sample injection amount is 10 mL; the concentration of the petroleum sulfonate sample solution is 10-20 mg/mL;

(3) collecting components: collecting the effluent solution from the chromatographic column from 4 min, wherein the collection time is 2 min each time, and collecting 24 solutions in total; sequencing the obtained solutions into solutions 1-24 according to the collection sequence;

(4) according to the mass spectrometry result, combining the solutions with similar structural compositions to obtain components with different structures; wherein the solution 1 is a component 1, the solution 2 is a component 2, the combined solutions 3 and 4 are components 3, the combined solutions 5 and 6 are components 4, the combined solutions 7-10 are components 5, the combined solutions 11 and 12 are components 6, the solution 13 is a component 7, the solution 14 is a component 8, the combined solutions 15-17 are components 9, the solution 18 is a component 10, the solution 19 is a component 11, the solution 20 is a component 12, the combined solutions 21 and 22 are components 13, and the combined solutions 23 and 24 are components 14; drying each component to obtain solid samples of different components;

(5) by testing the interfacial tension and the emulsifying property of each component, the component 10 with the optimal interfacial activity and the optimal emulsifying property is determined to be the active component in the petroleum sulfonate sample.