CN104198639A - Quantitative analysis method for micromolecular organic acids in fluid extracted from oil field - Google Patents
Quantitative analysis method for micromolecular organic acids in fluid extracted from oil field Download PDFInfo
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- CN104198639A CN104198639A CN201410455315.5A CN201410455315A CN104198639A CN 104198639 A CN104198639 A CN 104198639A CN 201410455315 A CN201410455315 A CN 201410455315A CN 104198639 A CN104198639 A CN 104198639A
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Abstract
The invention discloses a quantitative analysis method for micromolecular organic acids in fluid extracted from an oil field. The method comprises the following steps: determining the natures of organic acid standard samples; quantifying a low-concentration organic acid standard sample; quantifying a high-concentration organic acid standard sample; analyzing an organic acid mixed sample with known concentration; carrying out preliminary treatment on the samples in the scene; preprocessing the samples in the scene; and carrying out chromatographic analysis on the preprocessed samples by virtue of a chromatographic instrument, so as to obtain a test result. The solution preprocessed by the method does not pollute a chromatographic column of the chromatographic instrument, so that the method has the characteristic of high detection accuracy, which is greater than 96%; therefore, the quantitative analysis method can be widely applied to the field of detection of micromolecular acids in the fluid extracted from the oil field.
Description
Technical field
The invention belongs to field of chemical detection, be specifically related to the quantitative analysis method of a kind of oil field mining liquid small molecular acid.
Background technology
Microorganism is improved recovery ratio and refers to a kind of oil exploitation technology of utilizing microorganism and metabolic product thereof to increase oil production rate.The small molecular organic acid that the oil extraction microbial metabolism of taking hydrocarbon as carbon source produces is mainly formic acid, acetic acid, propionic acid etc.Organic acid type, content and variation tendency research thereof, for analyze microorganism metabolic activity, understand Microbe Oil Recovery, instruct laboratory experiment, the carrying out of fermentation technology optimization and mining site application, and the popularization of Microbial Enhanced Oil Recovery has great significance.The bibliographical information that prior art produces organic acid analysis to microbial metabolism has the ancient beautiful quantitative determination of high-performance liquid oil extraction microbial of nguktrum, also has the Analysis of Metabolites of Microorganisms Used for Oil Recovery of Bao Mutai etc.But these method preprocessing process complexity, relate to reagent many, and the factor that affects accuracy is many, and amount of samples is large, and the test duration is long, in analytic process, easily causes damage.Due to the singularity of oily field produced water, contain the complicated ingredients such as a large amount of crude oil, chemical reagent, impurity in addition, if sample pretreatment is improper, chromatographic column is polluted, not only directly affect test result, and can damage chromatographic column.Special in the time that oilfield produced fluid small molecular acid content is lower, in the time of the linear regression of conventional gas chromatographic analysis and actual value deviation very large, impact analysis result.
Summary of the invention
The present invention is directed to the deficiencies in the prior art and provide the quantitative analysis method of a kind of oil field mining liquid small molecular organic acid, the method to have the advantages that accuracy in detection is high, cost is low, simple to operate and with strong points.
The quantitative analysis method of a kind of oil field mining liquid small molecular organic acid, is characterized in that, the method comprises the following steps:
(1) organic acid standard model is qualitative
Acetic acid, propionic acid, the butyric acid titer of compound concentration 50mg/L respectively, sample introduction successively, record retention time and peak area separately, repeat six times, determine the organic acid in sample according to retention time: acetic acid is 9.342min, propionic acid is 11.425min, and butyric acid is 12.615min.
(2) low-concentration organic acid standard model is quantitative
Get respectively acetic acid, propionic acid, butyric acid titer, be mixed with mass concentration and be 0mg/L, 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L series organic acid standard, sample introduction successively, record retention time and peak area separately, taking organic acid concentration as horizontal ordinate, peak area is ordinate mapping, sets up low strength range typical curve.
(3) high concentration organic acid standard model is quantitative
Get respectively acetic acid, propionic acid, butyric acid titer, be mixed with mass concentration and be 50mg/L, 100mg/L, 150mg/L, 200mg/L, 250mg/L series organic acid standard, repeat said process, set up high concentration range typical curve.
(4) concentration known organic acid biased sample is analyzed
Accurately compound concentration is respectively 50mg/L and 200mg/L acetic acid, propionic acid, butyric acid mixed liquor, analyze according to fixed every experiment parameter, by integral and calculating peak area, return to again typical curve contrast, draw various organic acid content and sample recovery rate and detection precision, average recovery rate is all in 100% ± 2%.
(5) pre-treatment of on-the-spot sample
By on-the-spot institute sample thief Buchner funnel suction filtration, collect filtrate, suction filtration 1～2 time, until filtrate is bright.
(6) pre-service of on-the-spot sample
After filter membrane by filtrate by 0.45 μ m, move in the little centrifuge tube of 1.5mL, then add volume ratio 1:1 sulfuric acid solution 1d, shake up, be prepared into pretreatment sample.
(7) with chromatograph, pretreated sample is carried out to stratographic analysis
Extract the pretreated sample of 1 μ L with microsyringe and carry out stratographic analysis, according to the peak area of component to be measured and relative correction factor, can obtain the percentage composition of tested component in sample, component below concentration range 50mg/L is calculated net result with low concentration typical curve, and concentration adopts high concentration typical curve to calculate net result higher than the component of 50mg/L.
Organic acid in described step (1), (2), (3) and (4) is chromatographically pure standard model.
The filter paper adopting in described step (5) is 4 layers of qualitative Medium speed filter paper.
In described step (7), chromatographic test condition is detecting device: flame ionization detector, and column temperature: 100 DEG C, vaporizer temperature: 250 DEG C, 10 DEG C/min of heating rate, 300 DEG C of detected temperatures, carrier gas: 180kPa, hydrogen: 60kPa, air: 200kPa, shunt volume: 45kPa.
Compared with prior art, the present invention has the following advantages:
(1) can not pollute chromatographic chromatographic column through pretreated solution.
(2) this method adopts the typical curve of low concentration, through the standard model checking of concentration known, can improve accuracy and the sensitivity of detection, and accuracy is greater than 96%.
Brief description of the drawings
Fig. 1 is low strength range typical curve;
Fig. 2 is high concentration range typical curve.
Embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail.
Embodiment 1:
Utilize method of the present invention to sample 1 small molecular acid test, concrete steps are as follows:
(1) organic acid standard model is qualitative: get acetic acid, propionic acid, the butyric acid titer of concentration 50mg/L, and sample introduction successively, record retention time and peak area separately, repeats six times, determines the organic acid retention time in sample according to retention time.
(2) low-concentration organic acid standard model is quantitative: get respectively acetic acid, propionic acid, butyric acid titer, be mixed with mass concentration and be 0mg/L, 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L series organic acid standard, sample introduction successively, record retention time and peak area separately, taking organic acid concentration as horizontal ordinate, peak area is ordinate mapping, set up low strength range typical curve, see Fig. 1.
(3) high concentration organic acid standard model is quantitative: get respectively acetic acid, propionic acid, butyric acid titer, be mixed with mass concentration and be 50mg/L, 100mg/L, 150mg/L, 200mg/L, 250mg/L series organic acid standard, repeat said process, set up high concentration range typical curve, see Fig. 2.
(4) concentration known organic acid biased sample is analyzed: accurately compound concentration is respectively 50mg/L and 200mg/L acetic acid, propionic acid, butyric acid mixed liquor, analyze according to fixed every experiment parameter, by integral and calculating peak area, return to again typical curve contrast, draw various organic acid content and sample recovery rate and detection precision.
(5) pre-treatment of on-the-spot sample
Get 4 layers of middling speed qualitative filter paper suction filtration for sample that known propionic acid concentration is 45mg/L, collect filtrate, filtrate is bright.
(6) pre-service of on-the-spot sample
With syringe taking-up 1mL filtrate, inject 1.5mL centrifuge tube by the filter membrane of 0.45 μ m, then add 1d volume ratio 1:1 sulfuric acid solution, after shaking up, be prepared into pretreatment fluid.
(7) with chromatograph, pretreated sample is carried out to stratographic analysis
Extract the pretreatment fluid of 1 μ L with microsyringe, injection gas chromatography carries out little molecule acid test, and test condition is as follows:
Adopting low concentration typical curve to calculate acquired results is that acetic acid concentration is 44.8mg/L successively, and propionic acid concentration is 44.9mg/L, and butyric acid density is 45mg/L; Accuracy is respectively 99.6%, 99.8% and 100%.
Embodiment 2
Utilize method of the present invention to sample 2 small molecular acid test, concrete steps are as follows:
(1) organic acid standard model is qualitative: get acetic acid, propionic acid, the butyric acid titer of concentration 50mg/L, and sample introduction successively, record retention time and peak area separately, repeats six times, determines the organic acid retention time in sample according to retention time.
(2) low-concentration organic acid standard model is quantitative: get respectively acetic acid, propionic acid, butyric acid titer, be mixed with mass concentration and be 0mg/L, 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L series organic acid standard, sample introduction successively, record retention time and peak area separately, taking organic acid concentration as horizontal ordinate, peak area is ordinate mapping, sets up low strength range typical curve.
(3) high concentration organic acid standard model is quantitative: get respectively acetic acid, propionic acid, butyric acid titer, be mixed with mass concentration and be 50mg/L, 100mg/L, 150mg/L, 200mg/L, 250mg/L series organic acid standard, repeat said process, set up high concentration range typical curve.
(4) the organic acid biased sample of concentration known is analyzed: accurately compound concentration is respectively 50mg/L and 200mg/L acetic acid, propionic acid, butyric acid mixed liquor, analyze according to fixed every experiment parameter, by integral and calculating peak area, return to again typical curve contrast, draw various organic acid content and sample recovery rate and detection precision.
(5) pre-treatment of on-the-spot sample
Getting known acetic acid concentration is 4 layers of middling speed qualitative filter paper suction filtration for sample of 240mg/L, collects filtrate W1, and filtrate is bright.
(6) pre-service of on-the-spot sample
With syringe taking-up 1mL filtrate, inject 1.5mL centrifuge tube by the filter membrane of 0.45 μ m, then add 1d volume ratio 1:1 sulfuric acid solution, after shaking up, be prepared into pretreatment fluid.
(7) with chromatograph, pretreated sample is carried out to stratographic analysis
The pretreatment fluid that extracts 1 μ L with microsyringe, injection gas chromatography is tested, and test condition is as follows:
Adopting high concentration typical curve to calculate acquired results is that acetic acid concentration is 237mg/L successively, and propionic acid concentration is 238mg/L, and butyric acid density is 239mg/L; Accuracy is respectively 98.8%, 99.2% and 99.6%.
Embodiment 3
Utilize method of the present invention to sample 3 small molecular acid test, concrete steps are as follows:
(1) organic acid standard model is qualitative: get acetic acid, propionic acid, the butyric acid titer of concentration 50mg/L, and sample introduction successively, record retention time and peak area separately, repeats six times, determines the organic acid retention time in sample according to retention time.
(2) low-concentration organic acid standard model is quantitative: get respectively acetic acid, propionic acid, butyric acid titer, be mixed with mass concentration and be 0mg/L, 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L series organic acid standard, sample introduction successively, record retention time and peak area separately, taking organic acid concentration as horizontal ordinate, peak area is ordinate mapping, sets up low strength range typical curve.
(3) high concentration organic acid standard model is quantitative: get respectively acetic acid, propionic acid, butyric acid titer, be mixed with mass concentration and be 50mg/L, 100mg/L, 150mg/L, 200mg/L, 250mg/L series organic acid standard, repeat said process, set up high concentration range typical curve.
(4) the organic acid biased sample of concentration known is analyzed: accurately compound concentration is respectively 50mg/L and 200mg/L acetic acid, propionic acid, butyric acid mixed liquor, analyze according to fixed every experiment parameter, by integral and calculating peak area, return to again typical curve contrast, draw various organic acid content and sample recovery rate and detection precision.
(5) pre-treatment of on-the-spot sample
Getting known acetic acid concentration is 4 layers of middling speed qualitative filter paper suction filtration for sample of 240mg/L, collects filtrate W1, and filtrate is bright.
(6) pre-service of on-the-spot sample
With syringe taking-up 1mL filtrate, inject 1.5mL centrifuge tube by the filter membrane of 0.45 μ m, then add 1d volume ratio 1:1 sulfuric acid solution, after shaking up, be prepared into pretreatment fluid.
(7) with chromatograph, pretreated sample is carried out to stratographic analysis
The pretreatment fluid that extracts 1 μ L with microsyringe, injection gas chromatography is tested, and test condition is as follows:
It is 147mg/L that test result adopts high concentration typical curve to calculate acetic acid result, and butyric acid result is 198mg/; Adopting low concentration typical curve to calculate propionic acid result is 29mg/L.The accuracy of acetic acid, propionic acid and butyric acid is respectively 98%, 97% and 99%.
Claims (4)
1. a quantitative analysis method for oil field mining liquid small molecular acid, is characterized in that, the method comprises the following steps:
(1) organic acid standard model is qualitative
Acetic acid, propionic acid, the butyric acid titer of compound concentration 50mg/L respectively, sample introduction successively, record retention time and peak area separately, repeat six times, determine the organic acid in sample according to retention time: acetic acid is 9.342min, propionic acid is 11.425min, and butyric acid is 12.615min;
(2) low-concentration organic acid standard model is quantitative
Get respectively acetic acid, propionic acid, butyric acid titer, be mixed with mass concentration and be 0mg/L, 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L series organic acid standard, sample introduction successively, record retention time and peak area separately, taking organic acid concentration as horizontal ordinate, peak area is ordinate mapping, sets up low strength range typical curve;
(3) high concentration organic acid standard model is quantitative
Get respectively acetic acid, propionic acid, butyric acid titer, be mixed with mass concentration and be 50mg/L, 100mg/L, 150mg/L, 200mg/L, 250mg/L series organic acid standard, repeat said process, set up high concentration range typical curve;
(4) the organic acid biased sample of concentration known is analyzed
Accurately compound concentration is respectively 50mg/L and 200mg/L acetic acid, propionic acid, butyric acid mixed liquor, analyze according to fixed every experiment parameter, by integral and calculating peak area, return to again typical curve contrast, draw various organic acid content and sample recovery rate and detection precision, average recovery rate is all in 100% ± 2%;
(5) pre-treatment of on-the-spot sample
By on-the-spot institute sample thief Buchner funnel suction filtration, collect filtrate, suction filtration 1～2 time, until filtrate is bright;
(6) pre-service of on-the-spot sample
After filter membrane by filtrate by 0.45 μ m, move in the little centrifuge tube of 1.5mL, then add volume ratio 1:1 sulfuric acid solution 1d, shake up, be prepared into pretreatment sample;
(7) with chromatograph, pretreated sample is carried out to stratographic analysis
Extract the pretreated sample of 1 μ L with microsyringe and carry out stratographic analysis, according to the peak area of component to be measured and relative correction factor, can obtain the percentage composition of tested component in sample, component below concentration range 50mg/L is calculated net result with low concentration typical curve, and concentration adopts high concentration typical curve to calculate net result higher than the component of 50mg/L.
2. the quantitative analysis method of oil field mining liquid small molecular according to claim 1 acid, is characterized in that described organic acid is chromatographically pure standard model.
3. the quantitative analysis method of oil field mining liquid small molecular according to claim 1 acid, is characterized in that described filter paper is 4 layers of qualitative Medium speed filter paper.
4. the quantitative analysis method of oil field mining liquid small molecular according to claim 1 acid, it is characterized in that described chromatographic test condition: detecting device is flame ionization detector, column temperature is 100 DEG C, vaporizer temperature is 250 DEG C, and heating rate is 10 DEG C/min, and detected temperatures is 300 DEG C, carrier gas is 180kpa, hydrogen is 60kPa, and air is 200kPa, and shunt volume is 45kPa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109991352A (en) * | 2019-04-09 | 2019-07-09 | 上海实朴检测技术服务有限公司 | The method for measuring adipic acid in soil |
| CN115112807A (en) * | 2022-08-18 | 2022-09-27 | 青岛排水有限公司 | Method for rapidly determining volatile fatty acid in sludge |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109991352A (en) * | 2019-04-09 | 2019-07-09 | 上海实朴检测技术服务有限公司 | The method for measuring adipic acid in soil |
| CN115112807A (en) * | 2022-08-18 | 2022-09-27 | 青岛排水有限公司 | Method for rapidly determining volatile fatty acid in sludge |
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Application publication date: 20141210 |