CN101526489B - Method for detecting contents of paraffin and asphaltene in oil - Google Patents
Method for detecting contents of paraffin and asphaltene in oil Download PDFInfo
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- CN101526489B CN101526489B CN2008100809985A CN200810080998A CN101526489B CN 101526489 B CN101526489 B CN 101526489B CN 2008100809985 A CN2008100809985 A CN 2008100809985A CN 200810080998 A CN200810080998 A CN 200810080998A CN 101526489 B CN101526489 B CN 101526489B
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Abstract
The invention relates to a method for measuring concentrations of paraffin and asphaltene in oil. The method comprises: extracting three crude oil samples; dissolving two extracted samples in a solvent, and then removing the solvent and light oil; simultaneously, removing the asphaltene from one sample subjected to solvent treatment; measuring free induction falling curves of the three samples by using a nuclear magnetic resonance method; determining the ratio of a solid hydrogen-containing part to a liquid hydrogen-containing part suspended in the oil; through the content of the solid hydrogen-containing part in the sample subjected to asphaltene removal and solvent treatment, judging the concentration of the paraffin; through the content of the solid hydrogen-containing part in another sample subjected to solvent treatment and the consideration of the determined concentration of the paraffin, judging the concentration of the asphaltene; and based on the determined ratio of the paraffin to the asphaltene in the solid hydrogen-containing part, determining the concentrations of the paraffin and the asphaltene in the crude oil.
Description
Technical field
The present invention relates to geology, geochemistry, oil refining and petrochemistry, that is, relate to the paraffin in the oil and the mensuration of asphalt content, this mensuration can have special practicality in analyzing heavy oil and pitch.
Background technology
Form about oil, particularly the data about heavy (solid) concentration partly make the optimization of oil exploitation and oil refining process obviously become simple.Yet because be used to measure the complicacy, uncertain and expensive of method of the state of the art of the concentration of some oil ingredients, this information may not be always available.Although can separate the light oil part with rectificating method by simply distill, simply method does not allow us to measure the concentration of heavy oil part (paraffin and bituminous matter).
It is respectively standardized according to GOST11851 and GOST 11858 being used for the paraffin of oil and the method formerly of asphaltene concentration detection.
On May 21st, 1985 by the standard GOST 11851-85 of USSR Gosstandart approval " oil. the paraffin assay method " (" Oil.Paraffin Wax Determination Method ") established two kinds of methods (A and B) that are used for measuring the paraffin weight ratio of oil.Method A requires the preliminary deasphalting-resinoid that removes from oil, extract and pitch-resinoid that absorption is removed, and serviceability temperature is-20 ℃ an acetone/toluene mixture separating paraffin subsequently.Vacuum distillation method preliminary deasphalting-resinoid that removes from oil that method B require to use adopts the cut 250-550 ℃ of temperature to extract, and be-20 ℃ cooperation solvent, i.e. alcohol+ether mixture separating paraffin with temperature.
The immediate analog of proposed invention is the fresh approach of the weight concentration of the bituminous matter, resin and the paraffin that are used for measuring oil, this method is to be developed by OOO " PermNIPIneft " according to GOST 8.563-96, and by Russian Gosstandart ' s Perm Center forStandardization, Metrology and Certification (M 01-12-81) authentication.The Federal Register of Measurement Systems registration (accession designation number FR.1.31.2004.00985) that this method comes into force under country's tolerance monitoring and supervision.
According to described method, the mensuration of three kinds of macromolecule oil ingredients is implemented based on the combination of following three kinds of methods:
1) the bituminous matter sedimentation of use sherwood oil or hexane;
2) use coordination method and complex decomposition subsequently and the resin extraction of adopting titanium tetrachloride, resin compound is separated with the oil residue of deasphalting;
3) make paraffin from deasphalting with go to freeze out the oil residue of resin.
It is quite complicated being used for measuring the paraffin of oil and the known method of asphaltene concentration, and reason is to operate in a large number, and they are very consuming time.
Summary of the invention
The engineering result who realizes by embodiment of the present invention obtains a kind of simple but effective method that is used for measuring the paraffin and the asphaltene concentration of oil, and this method can be used in well at laboratory condition or with real-time mode.
Above-mentioned engineering result obtains by following method: extract three crude oil samples out, wherein two are dissolved in the solvent; Afterwards, remove solvent, and from a sample, remove bituminous matter by this solvent processing with light oil part.To all three samples use magnetic nuclear resonance methods with measure free induction decline curve and mensuration be suspended in the oil solid hydrogen-containing partly with the ratio of the hydrogeneous part of liquid.Judge paraffin concentration by the content partly of the solid hydrogen-containing in the sample of removing bitum solvent processing.By the solid hydrogen-containing in the sample of another solvent processing partly content and consider that definite paraffin concentration judges asphaltene concentration.Based on determined solid hydrogen-containing partly in paraffin and paraffin and the bitum concentration of bitum ratio detection in original oil.
Description of drawings
By description of drawings the present invention.Fig. 1 and Fig. 2 have shown the free induction decline curve at the oil of existing field produces.
Embodiment
The known time from solid hydrogen-containing NMR signal relaxation partly is far fewer than the time from the NMR signal relaxation of the hydrogeneous part of liquid; Definite solid of this permission and liquid component are to the contribution of the accumulation free induction decline curve of oil samples.Therefore, the free induction decline curve of analyzing oil samples allow to be determined at wherein the solid hydrogen-containing component and the ratio of the hydrogeneous component of liquid.
In fact the solid particle of all suspensions that comprise in oil is formed all presents (present) by paraffin and bituminous matter.If resin is separated with oil, resin can exist with solid-state form under normal operation, yet, in the time of in being dissolved in other oily liquid component, opposite with paraffin and bituminous matter, they become the part of liquid phase, and NMR signal is produced distinctive contribution.
Do not contain
1The H atom, but therefore the solid nonhydrocarbon particle that may be present in other suspension in the oil can be got rid of in further considering the not contribution of free induction decline curve.
In order to determine paraffin and the bitum concentration in the oil, must measure three free induction decline curves of following three samples: first sample is the primary sample that will measure paraffin and bitum concentration; Other two is the sample that carries out special processing, and can be known as " deasphalting " and " reference " sample.The sample that uses following method preparation to handle:
The sample of deasphalting:
1) is dissolved in (for example, in heptane/pentane/sherwood oil etc.) in the solvent;
2) remove bituminous matter;
3) solvent is partly removed (allowing to increase the proportion of solid constituent and the optional stage of reducing the volume of sample) with light oil.
The reference sample:
1) is dissolved in (for example, in hexane/pentane/sherwood oil etc.) in the solvent;
2) prevent sediment sedimentation from bituminous matter (for example, passing through biased sample);
3) solvent is partly removed (allowing to increase the proportion of solid constituent and the optional stage of reducing the volume of sample) with light oil.
Nuclear magnetic resonance spectroscopy can obtain the free induction decline curve of all three samples.
Each bar free induction decline curve can be divided into following two parts: 1) from the solid hydrogen-containing signal partly that is suspended in the oil; 2) from the hydrogeneous oil of liquid signal partly.In fact, can calculate the hydrogeneous part of solid/liquid of all three samples.
Use the solid hydrogen-containing ratio partly in the following method working sample.Let us supposes that normalized free induction value equals 1 (or 100%), and let us observe it how to descend in time (Fig. 1).The free induction decline curve comprises two parts.At initial part, liquid and solid oil component are all contributed the free induction value.In case through tens microseconds, the contribution of solid constituent no longer is sufficient.At this time point (for different samples, the exact position difference of this time point), it is obvious that the sudden change of free induction decline curve becomes.In second portion, after the curve sudden change, all remaining free inductions all can be owing to liquid component.Therefore, the function that is fit to of the second portion of approximate by utilizing (approximating) curve, and crossing by this function is extended to axis of ordinates, promptly can estimate solid and liquid part share in the oil.
Straight line is the simplest example of approximate function.For example, (curve 2 Fig. 1) contains 0.09 (9%) solid particle and 0.91 (91%) liquid by the oil samples of the deasphalting materialization (de-asphaltenized) of first field produces.(exponentially vanishing) approximate function that can also use index to go to zero.
Solid all signals partly from the oil samples of deasphalting materialization have been explained in the existence of paraffin.The reference sample has the composition identical with the sample of deasphalting materialization, adds also to producing the bituminous matter of their contribution from solid signal partly.Therefore, the data of " deasphalting materialization " sample and " reference " sample relatively produce about the solid of the oil that the is studied bituminous matter in partly and the information of the ratio of paraffin.
For example, corresponding with curve 3 (with reference to figure 1.a) the reference oil sample from oil field 1 contains 0.16 (16%) solid part and 0.84 (84%) liquid part.Because the 9%th, the solid paraffin ratio is 0.07 (7%) so can estimate asphaltene concentration, and paraffin and asphaltene concentration ratio in the solid part account for 0.56 and 0.44 respectively.
Behind the hydrogeneous component of liquid in knowing " original " sample and the ratio of solid hydrogen-containing component and the paraffin and bitum ratio (share) in the solid part, can calculate paraffin and bitum concentration in original oil.
For example, as (curve 1, analysis Fig. 1) find out that the content of solid and liquid component accounts for 0.08 (8%) and 0.92 (92%) respectively from the free induction decline curve from the oil in oil field 1.Know paraffin and bitum ratio in the solid part, can estimate paraffin and bitum concentration in primary sample, they account for 4.5% and 3.5% respectively.
" deasphalting materialization " and " reference " sample of handling are obtained by following method from crude oil: it is dissolved in the heptane, and heptane is partly evaporated from original oil with lightweight.Because the evaporation of light part, the solid in the sample of handling is compared with primary rate with liquid ratio partly; Yet the data of these samples make can be determined from paraffin in the resultant signal of oily solid constituent and bitum ratio.Then, know the total concentration of the solid hydrogen-containing component in the primary sample that in its nuclear magnetic resonance spectroscopy process, obtains, calculate therein paraffin and bitum concentration easily.
Fig. 2 is the other example from the oil of another field produces.The method that we propose is provided at paraffin and the bitum concentration in the reference sample, and they equal 4% and 3.5% respectively.Therefore, account for 1.6% and 1.4% respectively in paraffin and bitum concentration from the primary sample of the oil of second field produces.
Should be noted that the solid NMR signal partly from " deasphalting materialization " sample only is attributable simply to paraffin.The resin that exists in sample does not produce contribution, because they exist in solution with liquid form.
The method that detects paraffin and bitum concentration can use or be implemented and be used for online underground survey at laboratory condition being used for of being proposed.
Claims (2)
1. be used for measuring the paraffin of oil and the method for bitum concentration, described method comprises:
Use solvent to make the bituminous matter sedimentation, wherein extract three oil samples out;
A sample is a primary sample;
The sample dissolution of two extractions in solvent, and is removed bituminous matter from the sample of a solvent processing, the solvent processing of another sample is comprised the step of biased sample, wherein said solvent is heptane, pentane or sherwood oil;
Use magnetic nuclear resonance method to measure the free induction decline curve of all three samples;
Determine to be suspended in the oil solid hydrogen-containing partly with the ratio of the hydrogeneous part of liquid;
Based on the content partly of the solid hydrogen-containing in the sample of removing bitum described solvent processing, can judge the content of described paraffin;
By the content of the part of the solid hydrogen-containing in the sample of another solvent processing and the concentration of considering determined paraffin, judge asphaltene concentration;
Behind the ratio of hydrogeneous component of the liquid in knowing described primary sample and solid hydrogen-containing component and the paraffin and bitum ratio in the solid part, calculate paraffin and bitum concentration in original oil.
According to claim 1 be used for measuring the paraffin of oil and the method for bitum concentration, wherein with two sample dissolution in solvent, and described solvent partly removed with light oil.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101975788B (en) * | 2010-09-01 | 2012-02-15 | 苏州纽迈电子科技有限公司 | Method for identifying quality of edible oil with low-field NMR (Nuclear Magnetic Resonance) |
| WO2013098854A2 (en) * | 2011-12-26 | 2013-07-04 | Emcure Pharmaceuticals Limited | Synthesis of raltegravir |
| US9176251B2 (en) * | 2012-11-09 | 2015-11-03 | Schlumberger Technology Corporation | Asphaltene evaluation based on NMR measurements and temperature / pressure cycling |
| US9074460B2 (en) * | 2013-01-18 | 2015-07-07 | Schlumberger Technology Corporation | Method of analyzing a petroleum reservoir |
| CN104614278A (en) * | 2015-01-30 | 2015-05-13 | 西安热工研究院有限公司 | Detection method for oil sludge in oil used in electric power industry |
| CN105136836B (en) * | 2015-09-28 | 2017-10-10 | 中国石油大学(北京) | Low-field nuclear magnetic resonance determines the method and device of asphalt content |
| CN106124552B (en) * | 2016-09-12 | 2017-12-19 | 沧州市市政工程股份有限公司 | A kind of foamed asphalt moisture method of testing |
| CN106837318B (en) * | 2016-12-23 | 2020-01-07 | 中国石油天然气股份有限公司 | Method and device for obtaining rock stratum thick oil content |
| CN106769627B (en) * | 2016-12-27 | 2019-09-27 | 陕西延长石油（集团）有限责任公司 | A kind of detection method of high solids content liquefied coal coil asphalt content |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1370317A (en) * | 1970-12-30 | 1974-10-16 | Texaco Development Corp | Means and method for on-line determination of the aromatic naphthene and paraffin contents of charge oil |
| CN1629632A (en) * | 2004-10-18 | 2005-06-22 | 中国科学院山西煤炭化学研究所 | Group composition analysis method for hydrocarbon series of residual oil and bitumen |
| CA2675045A1 (en) * | 2006-12-28 | 2008-07-10 | Kazan State University | Method for determining paraffin and asphalthene content in oil |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1370317A (en) * | 1970-12-30 | 1974-10-16 | Texaco Development Corp | Means and method for on-line determination of the aromatic naphthene and paraffin contents of charge oil |
| CN1629632A (en) * | 2004-10-18 | 2005-06-22 | 中国科学院山西煤炭化学研究所 | Group composition analysis method for hydrocarbon series of residual oil and bitumen |
| CA2675045A1 (en) * | 2006-12-28 | 2008-07-10 | Kazan State University | Method for determining paraffin and asphalthene content in oil |
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