CN110542733A - Method for determining concentration of petroleum sulfonate in oil well produced liquid through liquid chromatography analysis - Google Patents
Method for determining concentration of petroleum sulfonate in oil well produced liquid through liquid chromatography analysis Download PDFInfo
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- CN110542733A CN110542733A CN201910855356.6A CN201910855356A CN110542733A CN 110542733 A CN110542733 A CN 110542733A CN 201910855356 A CN201910855356 A CN 201910855356A CN 110542733 A CN110542733 A CN 110542733A
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- 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
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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
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Abstract
The invention discloses a method for determining the concentration of petroleum sulfonate in oil well produced liquid by utilizing liquid chromatography analysis, which comprises the following chromatographic conditions: the chromatographic column is a 10 cm SAX strong anion exchange column; the mobile phase is a mixed solution of methanol and 0.02 mol/LNH4Ac aqueous solution, the volume ratio is 3/2, the flow rate is 1.0 mL/min, and isocratic elution is carried out; detecting by adopting an ultraviolet detector, wherein the detection wavelength is 225 nm; and (3) carrying out sample injection by 20 muL, measuring the ultraviolet chromatographic peak area of the petroleum sulfonate, and quantifying by an external standard method. Within 5-500 mg/L, the linear relation between the concentration of the petroleum sulfonate and the chromatographic peak area is as follows: y = -93.358+ 12.126X, linear correlation coefficient R = 0.99965. The method for detecting the petroleum sulfonate in the oil well produced water has the characteristics of simplicity, accuracy, rapidness, sensitivity, low detection limit, good repeatability and the like.
Description
Technical Field
the invention relates to a method for measuring the concentration of petroleum sulfonate in an oil well produced liquid, in particular to a method for measuring the concentration of petroleum sulfonate in the oil well produced liquid by adopting a high performance liquid chromatography, belonging to the technical field of oil field chemical analysis.
Background
The surfactant plays an important role in binary compound flooding oil recovery and ternary compound flooding oil recovery, and the action mechanism of the surfactant is to effectively reduce the oil-water interfacial tension, enhance the emulsification performance of a system and further improve the crude oil recovery rate. As a kind of commonly used surfactant, petroleum sulfonate is widely applied to the field of tertiary oil recovery, and the structure of the petroleum sulfonate is an anionic surfactant consisting of an alkylaryl hydrophobic group and a sulfonate anionic group. In order to develop the quantity-effect relationship between the detected quantity and the oil displacement efficiency of the petroleum sulfonate oil well produced liquid and research on the migration rule, adsorption loss and the like of the petroleum sulfonate in an oil reservoir environment, the concentration of the petroleum sulfonate in the oil well produced liquid needs to be accurately detected, and the method for detecting the concentration of the petroleum sulfonate in the oil well produced liquid needs to be established.
the concentration detection method of the petroleum sulfonate comprises a titration method, a colorimetric method and the like, but the methods are complex to operate, low in sensitivity and poor in repeatability, and aiming at a complex matrix environment of oil well produced liquid, the anti-interference capability is low, and the accurate detection of the petroleum sulfonate is difficult to realize. In addition, aiming at the concentration detection of petroleum sulfonate, a high performance liquid chromatography analysis and detection method for gradient elution is established by Lanzhou chemical and physical research institute of Chinese academy of sciences, wherein a 5 cm SAX strong anion exchange column is used as a chromatographic column, methanol/water and methanol/0.25 mol/L NaH2PO4 aqueous solution are respectively used as mobile phases, and the method has the characteristics of accuracy, rapidness and sensitivity, but has the defect that a large amount of NaH2PO4 inorganic salt is contained in the mobile phases, so that the chromatographic flow path is blocked due to precipitation of the inorganic salt, troubles are brought to the analysis work, and meanwhile, the gradient elution is not beneficial to the grasp of ordinary oilfield analysis and test personnel. Therefore, it is necessary to develop a simpler detection method for petroleum sulfonate by high performance liquid chromatography.
Disclosure of Invention
the invention aims to provide a method for measuring the concentration of petroleum sulfonate in oil well produced liquid by liquid chromatography.
The invention relates to a method for quantitatively detecting petroleum sulfonate in oil well produced liquid by liquid chromatography, which comprises the following steps:
A chromatographic column: 10 cm SAX strong anion exchange column;
Mobile phase: mixing methanol and 0.02 mol/L NH4Ac aqueous solution in a volume ratio of 3/2; the flow rate is 1.0 mL/min, and the elution is carried out in equal gradient;
an ultraviolet detector: the detection wavelength is 225 nm;
preparation of a sample: preparing series petroleum sulfonate standard solutions (5, 10, 20, 50, 100, 200, 500 and 1000 mg/L) with different concentrations by using oilfield injection water respectively;
injecting sample under the chromatographic condition, and injecting 20 mu L of sample; and (3) measuring the chromatographic peak area of the petroleum sulfonate, and quantifying the concentration of the petroleum sulfonate by an external standard method. The peak area integral value was used as the ordinate, the control concentration was used as the abscissa, and a standard curve was obtained by linear regression (see fig. 1).
the result shows that within the range of 20-500 mg/L, the concentration of the petroleum sulfonate and the chromatographic peak area have a good linear relation, and the specific linear equation is as follows:
y = -93.358+ 12.126X, linear correlation coefficient R =0.99965
Wherein, the concentration of X-petroleum sulfonate is unit mg/L
y-chromatographic peak area, units: intens.
Detection limit measurement: the chromatographic conditions are the same as the above, the concentration of the petroleum sulfonate is continuously diluted, the response intensity of the chromatographic peak is measured, and the detection limit of the method can be determined to be as low as 2 mg/L.
And (3) repeatability test: and (4) introducing 50 mg/L petroleum sulfonate respectively on the first day, the third day and the fifth day under the same chromatographic conditions, measuring the peak area of the chromatogram, and inspecting the repeatability of the data. The measured chromatographic peak areas are 466.2, 484.7 and 492.3 respectively, and the calculated relative standard deviation is 2.79 percent, which is small, and shows that the repeatability of the data is good.
oil well produced liquid standard adding recovery rate experiment: adding 50 ppm petroleum sulfonate into three groups of oil well produced fluids of propane 5A237, propane 6A235 and 7A237, feeding 20 mu L of sample, measuring peak area, deducting background peak area, calculating measured concentration according to a linear relation, comparing the measured concentration with 50 ppm, and obtaining the standard addition recovery rate in the oil well produced fluids, wherein the table 1 is shown in the specification:
As can be seen from Table 1, the normalized recovery rates of the petroleum sulfonate in the three oil well produced fluids are all between 95.84% and 102.26%, and the reliability of the method for quantitatively detecting the petroleum sulfonate in the oil well produced fluid by using the high performance liquid chromatography is proved.
In conclusion, the high performance liquid chromatography method for detecting petroleum sulfonate in oil well produced fluid has the characteristics of simplicity, accuracy, rapidness, sensitivity, low detection limit, good repeatability and the like.
drawings
FIG. 1 is a linear relationship between the concentration of petroleum sulfonate and the chromatographic peak area.
FIG. 2 is a chromatogram of 200 mg/L petroleum sulfonate.
Detailed Description
the method for analyzing and detecting the concentration of petroleum sulfonate in the produced fluid of an oil well by high performance liquid chromatography according to the present invention is further described by the following specific examples.
example 1
1. Preparing a sample to be tested: 6AT216 oil well produced water and 6A237 oil well produced water;
2. Detection of
Chromatographic conditions are as follows: 10 cm SAX strong anion exchange column is chromatographic column; the mixed solution (volume ratio 3/2) of methanol and 0.02 mol/L NH4Ac aqueous solution is used as a mobile phase, the flow rate is 1.0 mL/min, and the elution is carried out in equal gradient; an ultraviolet detector for detecting the wavelength at 225 nm;
Under the chromatographic conditions, 20 mu L of the produced water of the sample injection oil well has no petroleum sulfonate chromatographic peak within 5.07 min, and the 2 kinds of oil well produced water are proved to contain no petroleum sulfonate.
example 2
1. Sample preparation: respectively preparing petroleum sulfonate solution with the concentration of 50 mg/L by using distilled water, oil well simulated brine, 6AT216 oil well produced water and 6A237 oil well produced water;
2. Detection of
chromatographic conditions are as follows: 10 cm SAX strong anion exchange column is chromatographic column; the mixed solution (volume ratio 3/2) of methanol and 0.02 mol/L NH4Ac aqueous solution is used as a mobile phase, the flow rate is 1.0 mL/min, and the elution is carried out in equal gradient; an ultraviolet detector for detecting the wavelength at 225 nm;
Under the chromatographic condition, 20 mu L of the standard solution is injected, the petroleum sulfonate generates peaks at 5.07 min (shown in figure 2), and the chromatographic peak areas of the petroleum sulfonate in different aqueous solutions are measured;
According to a linear relationship: y = -93.358+ 12.126X, the concentrations of petroleum sulfonate in different aqueous solutions such as distilled water, oil well simulated brine, 6AT216 oil well produced water, 6A237 oil well produced water and the like are calculated to be 47.62 mg/L, 48.26 mg/L, 53.73 mg/L and 52.26 mg/L respectively, and are equivalent to 50 mg/L, and the reliability of the detection method is proved.
Claims (2)
1. The method for determining the concentration of petroleum sulfonate in the produced liquid of the oil well by liquid chromatography analysis comprises the following steps:
a chromatographic column: 10 cm SAX strong anion exchange column;
Mobile phase: mixing methanol and 0.02 mol/L NH4Ac aqueous solution at a volume ratio of 3/2, a flow rate of 1.0 mL/min, and performing equal gradient elution;
An ultraviolet detector: the detection wavelength is 225 nm;
Injecting sample of 20 muL under the chromatographic condition, measuring the chromatographic peak area of petroleum sulfonate, and quantifying the concentration of the petroleum sulfonate by an external standard method; within a certain range, the concentration of the petroleum sulfonate has a good linear relation with the chromatographic peak area.
2. The method for determining the concentration of petroleum sulfonate in an oil well production fluid by liquid chromatography as claimed in claim 1, wherein: in the range of 5-500 mg/L, the concentration of the petroleum sulfonate and the chromatographic peak area have the following linear relationship:
y = -93.358+ 12.126X, linear correlation coefficient R =0.99965
X-concentration of Petroleum sulfonate in mg/L
Y-chromatographic peak area, units: intens.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112229940A (en) * | 2020-11-27 | 2021-01-15 | 中国科学院兰州化学物理研究所 | Method for detecting alkyl alcohol polyoxyethylene ether sulfate in crude oil by adopting liquid chromatography analysis |
| CN112697892A (en) * | 2020-11-19 | 2021-04-23 | 中国石油天然气股份有限公司 | Method for quantitatively detecting naphthenic base sulfonate component and residual oil sulfonate component in petroleum produced liquid |
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| CN1790015A (en) * | 2004-12-17 | 2006-06-21 | 中国科学院兰州化学物理研究所 | Analysis method for single and double petroleum sulphonate in crude oil |
| CN109799300A (en) * | 2019-03-18 | 2019-05-24 | 中国科学院兰州化学物理研究所 | A kind of method of mahogany acid salt content in analysis detection oil sample |
| CN109884233A (en) * | 2019-03-05 | 2019-06-14 | 中国科学院兰州化学物理研究所 | The liquid-phase chromatographic analysis detection method of alkyl alcohol ethoxylates sulphates content in a kind of measurement oil well produced liquid |
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- 2019-09-11 CN CN201910855356.6A patent/CN110542733A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1790015A (en) * | 2004-12-17 | 2006-06-21 | 中国科学院兰州化学物理研究所 | Analysis method for single and double petroleum sulphonate in crude oil |
| CN109884233A (en) * | 2019-03-05 | 2019-06-14 | 中国科学院兰州化学物理研究所 | The liquid-phase chromatographic analysis detection method of alkyl alcohol ethoxylates sulphates content in a kind of measurement oil well produced liquid |
| CN109799300A (en) * | 2019-03-18 | 2019-05-24 | 中国科学院兰州化学物理研究所 | A kind of method of mahogany acid salt content in analysis detection oil sample |
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| GUNTHER SOCHER 等: "Analysis of sulfonated compounds by ion-exchange high-performance liquid chromatography–mass spectrometry", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| NING PAN 等: "Separation of anionic surfactants on anion exchangers", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| RUDOLPH H. STEHL: "Separation and Determination of Aromatic Sulfonates by Ion Exchange Column Chromatography", 《ANALYTICAL CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112697892A (en) * | 2020-11-19 | 2021-04-23 | 中国石油天然气股份有限公司 | Method for quantitatively detecting naphthenic base sulfonate component and residual oil sulfonate component in petroleum produced liquid |
| CN112229940A (en) * | 2020-11-27 | 2021-01-15 | 中国科学院兰州化学物理研究所 | Method for detecting alkyl alcohol polyoxyethylene ether sulfate in crude oil by adopting liquid chromatography analysis |
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