CN112229940A - Method for detecting alkyl alcohol polyoxyethylene ether sulfate in crude oil by adopting liquid chromatography analysis - Google Patents

Method for detecting alkyl alcohol polyoxyethylene ether sulfate in crude oil by adopting liquid chromatography analysis Download PDF

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CN112229940A
CN112229940A CN202011362654.0A CN202011362654A CN112229940A CN 112229940 A CN112229940 A CN 112229940A CN 202011362654 A CN202011362654 A CN 202011362654A CN 112229940 A CN112229940 A CN 112229940A
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polyoxyethylene ether
crude oil
ether sulfate
alkyl alcohol
alcohol polyoxyethylene
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王立成
王旭生
郭勇
梁晓静
王帅
王磊
卢晓峰
李亦婧
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N2030/022—Column chromatography characterised by the kind of separation mechanism
    • G01N2030/027—Liquid chromatography
    • 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
    • G01N2030/8859—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 inorganic compounds

Abstract

The invention discloses a method for analyzing and detecting alkyl alcohol polyoxyethylene ether sulfate in crude oil by adopting liquid chromatography, which comprises the following chromatographic conditions: the chromatographic column is a 5 cm weak anion exchange column; the mobile phase A is n-hexane, and the mobile phase B is methanol and 0.02 mol/L NH4Ac aqueous solution mixed liquor (volume ratio 3/2), gradient elution, 0-2 min: 100% A, 2-8 min: 100% B, 8.01 min: 100% A, flow rate 1.0 mL/min; detecting by adopting a mass spectrum detector, an ESI source and a negative mode; diluting a crude oil sample to be detected by 10 times with n-hexane, removing impurities by an organic filter membrane, and carrying out sample injection by 20 mu L. And (4) measuring the chromatographic peak area of the alkyl alcohol polyoxyethylene ether sulfate, and quantifying by an external standard method. The method for detecting the alkyl alcohol polyoxyethylene ether sulfate in the crude oil has the characteristics of simplicity, accuracy, rapidness, sensitivity and the like, and provides technical support for the research of the migration rule of the oil displacement agent in the oil reservoir environment.

Description

Method for detecting alkyl alcohol polyoxyethylene ether sulfate in crude oil by adopting liquid chromatography analysis
Technical Field
The invention relates to a method for determining alkyl alcohol polyoxyethylene ether sulfate anionic surfactant in crude oil, in particular to a method for determining alkyl alcohol polyoxyethylene ether sulfate in crude oil by adopting a high performance liquid chromatography, and belongs to the technical field of analytical chemistry.
Background
As an important tertiary oil recovery technology, the action mechanism of air foam flooding is that foam is generated by using a surfactant foaming agent to effectively plug a stratum, so that the crude oil recovery rate is improved, and the method has the advantages of low cost, environmental friendliness, high oil displacement efficiency and the like. The alkyl alcohol polyoxyethylene ether sulfate is a common surfactant for foam flooding, and the structure of the surfactant is composed of alkyl alcohol polyoxyethylene ether nonionic and sulfate anion. After entering an oil reservoir, the foaming agent alkyl alcohol polyoxyethylene ether sulfate does not simply stay in a water phase, and a part of the foaming agent alkyl alcohol polyoxyethylene ether sulfate enters an oil phase, so that the foam flooding crude oil contains a certain amount of alkyl alcohol polyoxyethylene ether sulfate. The detection of the alkyl alcohol polyoxyethylene ether sulfate in the crude oil is carried out, which is favorable for the detection of the distribution rule and the migration rule of the surfactant in an oil displacement system.
At present, the detection method of the alkyl alcohol polyoxyethylene ether sulfate mainly comprises a titration method, a colorimetric method and the like, and the methods have the disadvantages of complicated operation steps, low sensitivity, poor reproducibility and difficulty in detection of the alkyl alcohol polyoxyethylene ether sulfate in crude oil. Therefore, it is necessary to develop an accurate, rapid and sensitive method for analyzing and detecting alkyl alcohol polyoxyethylene ether sulfate in crude oil.
Disclosure of Invention
The invention aims to provide a method for detecting alkyl alcohol polyoxyethylene ether sulfate in crude oil by adopting liquid chromatography analysis.
The invention discloses a method for detecting alkyl alcohol polyoxyethylene ether sulfate in crude oil by adopting liquid chromatography analysis, which comprises the following steps:
(1) chromatographic conditions
A chromatographic column: 5 cm weak anion exchange column;
mobile phase: the mobile phase A isN-hexane, the mobile phase B is methanol and 0.02 mol/LNH4Ac aqueous solution mixed liquor (volume ratio 3/2), gradient elution, 0-2 min: 100% A, 2-8 min: 100% B, 8.01 min: 100% A, flow rate 1.0 mL/min;
a detector: mass spectrum detector, ESI source, negative mode detection;
(2) standard Curve sample preparation
Crude oil solution diluted by 10 times of normal hexane is taken as a matrix solvent, and alkyl alcohol polyoxyethylene ether sulfate crude oil solutions with different concentrations of 1, 2, 5, 10, 20, 50, 100 mg/L and the like are respectively prepared, wherein the concentrations of alkyl alcohol polyoxyethylene ether sulfate in the corresponding crude oil are respectively 10, 20, 50, 100, 200, 500 and 1000 mg/L.
And (3) carrying out sample injection under the chromatographic condition of 20 mu L, measuring the chromatographic peak area of the alkyl alcohol polyoxyethylene ether sulfate, and carrying out linear regression treatment by taking the peak area integral value as a vertical coordinate and the concentration of the alkyl alcohol polyoxyethylene ether sulfate in the crude oil as a horizontal coordinate to obtain a standard curve (shown in figure 1).
The result shows that within the range of 100-1000 mg/L, the concentration of the alkyl alcohol polyoxyethylene ether sulfate in the crude oil and the chromatographic peak area have a good linear relation, and the specific linear equation is as follows:
y = 1172830 + 8013.691X, linear correlation coefficient R = 0.99784
Wherein, the concentration of the X-alkyl alcohol polyoxyethylene ether sulfate is unit mg/L
Y-area of mass spectrum chromatogram peak, unit: intens.
(3) Quantification by external standard method
Diluting a crude oil sample to be detected by 10 times of normal hexane, and removing impurities by an organic filter membrane; injecting samples under the chromatographic condition, wherein the sample injection amount is 20 muL; and (3) measuring the peak area of the alkyl alcohol polyoxyethylene ether sulfate in the sample, and calculating the concentration of the alkyl alcohol polyoxyethylene ether sulfate in the crude oil sample according to the linear relation.
(4) Detection limit determination
Under the chromatographic conditions, the concentration of the alkyl alcohol polyoxyethylene ether sulfate is continuously diluted, the mass spectrum chromatographic peak response intensity is measured, the detection limit of the method can be determined to be as low as 20 mg/L, and the sensitivity of the method is verified.
(5) Repeatability test
Under the chromatographic conditions, samples with the concentration of the alkyl alcohol polyoxyethylene ether sulfate being 200 mg/L in the crude oil are injected in the first day, the third day and the fifth day respectively, the mass spectrum chromatographic peak area is measured, the detection concentration is calculated, and the repeatability of the data is inspected. The detection concentrations are 223.6, 207.5 and 190.8 respectively through measurement, and the relative standard deviation is 7.91 percent through calculation, so that the relative standard deviation is small, and the repeatability of the data is good.
(6) Oil well produced liquid standard-adding recovery rate experiment
Adding 200 ppm alkyl alcohol polyoxyethylene ether sulfate into three groups of crude oil including willow 76-61, willow 74-63 and apricot 73-31, measuring peak area, deducting background, and calculating the concentration according to linear relation. The measured concentration is compared with 200 ppm, and the standard recovery rate of the alkyl alcohol polyoxyethylene ether sulfate in different crude oils is obtained, which is shown in table 1:
Figure DEST_PATH_IMAGE001
as can be seen from Table 1, the standardized recovery rates of the alkyl alcohol polyoxyethylene ether sulfate in the three groups of crude oil samples are all 82.76-96.77%, and the reliability of the provided liquid chromatography analysis and detection method for the alkyl alcohol polyoxyethylene ether sulfate in the crude oil is proved.
In conclusion, the method for detecting the alkyl alcohol polyoxyethylene ether sulfate in the crude oil has the characteristics of simplicity, accuracy, rapidness, sensitivity and the like.
Drawings
FIG. 1 is a linear relationship between the concentration of alkyl alcohol polyoxyethylene ether sulfate in crude oil and the chromatographic peak area.
FIG. 2 is a mass spectrum chromatogram of 200 mg/L alkyl alcohol polyoxyethylene ether sulfate in crude oil.
Detailed Description
The following will further describe the liquid chromatography analysis and detection method of alkyl alcohol polyoxyethylene ether sulfate in crude oil by using specific examples.
Example one
1. Preparing a sample to be tested: respectively diluting crude oil of crude oil willow 76-61 and crude oil willow 74-63 with 10 times volume of n-hexane, and removing impurities through an organic filter membrane.
2. Detection of
Figure 307842DEST_PATH_IMAGE002
Chromatographic conditions
A chromatographic column: 5 cm weak anion exchange column; mobile phase: the mobile phase A is n-hexane, and the mobile phase B is methanol and 0.02 mol/LNH4Ac aqueous solution mixed liquor (volume ratio 3/2), gradient elution, 0-2 min: 100% A, 2-8 min: 100% B, 8.01 min: 100% A, flow rate 1.0 mL/min; a detector: mass spectrum detector, ESI source, negative mode detection;
Figure DEST_PATH_IMAGE003
under the chromatographic conditions, 20 mu L of sample is injected, and no alkyl alcohol polyoxyethylene ether sulfate chromatographic peak exists in 5.5-7.0 min, which proves that no alkyl alcohol polyoxyethylene ether sulfate exists in 2 kinds of crude oil.
Example two
1. Sample preparation
Respectively diluting crude oil of Salix 76-61, crude oil of Salix 74-63, and crude oil of Prunus 73-31 with n-hexane for 10 times, adding 20 mg/L of alkyl alcohol polyoxyethylene ether sulfate into the dilution, respectively, corresponding to crude oil samples containing 200 mg/L of alkyl alcohol polyoxyethylene ether sulfate.
2. Detection of
Figure 208671DEST_PATH_IMAGE002
Chromatographic conditions
A chromatographic column: 5 cm weak anion exchange column; mobile phase: the mobile phase A is n-hexane, and the mobile phase B is methanol and 0.02 mol/LNH4Ac aqueous solution mixed liquor (volume ratio 3/2), gradient elution, 0-2 min: 100% A, 2-8 min: 100% B, 8.01 min: 100% A, flow rate 1.0 mL/min; a detector: mass spectrum detector, ESI source, negative mode detection;
Figure 129354DEST_PATH_IMAGE003
under the chromatographic conditions, 20 mu L of the standard sample solution is injected, the alkyl alcohol polyoxyethylene ether sulfate peaks within 5.5-7.0 min (see figure 2), and the chromatographic peak areas of the alkyl alcohol polyoxyethylene ether sulfate in different crude oils are measured.
3. Quantification by external standard method
According to a linear relationship: y = 1172830 + 8013.691X, the concentrations of the alkyl alcohol polyoxyethylene ether sulfate in different crude oil samples such as the willow 76-61 crude oil, the willow 74-63 crude oil, the apricot 73-31 crude oil and the like are calculated to be 165.52 mg/L, 186.84 mg/L and 193.54 mg/L respectively, and are equivalent to 200 mg/L, and the reliability of the detection method is proved.

Claims (2)

1. The method for detecting the alkyl alcohol polyoxyethylene ether sulfate in the crude oil by adopting liquid chromatography analysis comprises the following steps:
(1) chromatographic conditions
A chromatographic column: 5 cm weak anion exchange column;
mobile phase: the mobile phase A is n-hexane, and the mobile phase B is methanol and 0.02 mol/LNH4Ac aqueous solution is mixed, and the methanol in the mobile phase B is mixed with 0.02 mol/LNH4The volume ratio of the Ac aqueous solution is 3/2; gradient elution, 0-2 min: 100% A, 2-8 min: 100% B, 8.01 min: 100% A, flow rate 1.0 mL/min;
a detector: mass spectrum detector, ESI source, negative mode detection;
(2) crude oil sample pretreatment: diluting a crude oil sample to be detected by 10 times of normal hexane, and removing impurities through an organic filter membrane to obtain a sample to be detected;
(3) quantifying by an external standard method: injecting samples under the chromatographic condition, wherein the sample injection amount is 20 muL; and (3) determining the peak area of the alkyl alcohol polyoxyethylene ether sulfate in the sample to be detected, and calculating the concentration of the alkyl alcohol polyoxyethylene ether sulfate in the crude oil sample according to the linear relation.
2. The method for detecting alkyl alcohol polyoxyethylene ether sulfate in crude oil by liquid chromatography as claimed in claim 1, wherein: within the range of 100-1000 mg/L, the concentration of the alkyl alcohol polyoxyethylene ether sulfate in the crude oil and the chromatographic peak area have a good linear relation, and the specific linear equation is as follows:
y = 1172830 + 8013.691X, linear correlation coefficient R = 0.99784
Wherein, the concentration of X-alkyl alcohol polyoxyethylene ether sulfate is unit mg/L
Y-area of mass spectrum chromatogram peak, unit: intens.
CN202011362654.0A 2020-11-27 2020-11-27 Method for detecting alkyl alcohol polyoxyethylene ether sulfate in crude oil by adopting liquid chromatography analysis Pending CN112229940A (en)

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