CN109324012A - A method of for light hydrocarbon component quantitative analysis in crude oil - Google Patents
A method of for light hydrocarbon component quantitative analysis in crude oil Download PDFInfo
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- CN109324012A CN109324012A CN201811079735.2A CN201811079735A CN109324012A CN 109324012 A CN109324012 A CN 109324012A CN 201811079735 A CN201811079735 A CN 201811079735A CN 109324012 A CN109324012 A CN 109324012A
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 58
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 40
- 239000010779 crude oil Substances 0.000 title claims abstract description 28
- 238000004445 quantitative analysis Methods 0.000 title claims abstract description 16
- 238000002329 infrared spectrum Methods 0.000 claims abstract description 20
- 238000012360 testing method Methods 0.000 claims description 15
- 238000001228 spectrum Methods 0.000 claims description 13
- 238000012549 training Methods 0.000 claims description 11
- 238000010238 partial least squares regression Methods 0.000 claims description 8
- 238000004611 spectroscopical analysis Methods 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- 230000003595 spectral effect Effects 0.000 claims description 5
- 238000004422 calculation algorithm Methods 0.000 claims description 3
- 239000003921 oil Substances 0.000 abstract description 19
- 238000005259 measurement Methods 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 2
- 238000011156 evaluation Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 36
- 238000002156 mixing Methods 0.000 description 14
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000003384 imaging method Methods 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 239000001294 propane Substances 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000001273 butane Substances 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004497 NIR spectroscopy Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
This application discloses a kind of methods for light hydrocarbon component real-time quantitative analysis in crude oil, comprising: prepares calibration set sample, prepares the crude oil sample comprising known content light hydrocarbon component；The measurement of calibration set sample, acquires the near infrared spectrum of each calibration set sample, and record its corresponding light hydrocarbon component content；Calibration model is established, and establishes the relational model between the near infrared spectrum and the light hydrocarbon component content of the calibration set sample with modeling method；Model application carries out near infrared ray to sample to be tested, and is substituted into the calibration model, predicts the light hydrocarbon component content of the sample to be tested, and provide prediction error.The present processes, for light hydrocarbon component real-time, in quantitative detection downhole crude, Fast Evaluation exploration of oil and gas field.
Description
Technical field
This application involves oil fields, are espespecially related to a kind of method for light hydrocarbon component quantitative analysis in crude oil.
Background technique
Economic fast development increases the demand for fossil energy, and it is important that lighter hydrocarbons are that oil-gas reservoir stores in the medium
The quantitative analysis of form, lighter hydrocarbons can be efficiently applied in exploration of oil and gas field resource assessment.By analyzing lighter hydrocarbons, Ke Yifa
Feature on the composition and content of existing free hydrocarbon, characterizes the property and feature of some region of oil-gas reservoir.So in order to
Oil-gas reservoir in region is surveyed, the variation of the composition and content that can use free lighter hydrocarbons comes to the oil on horizontal section
Position, property of gas reservoir etc. are predicted and are judged.Therefore, by the way that measure lighter hydrocarbons and analyze can intuitively reaction oil gas reservoir
Property and location information, analyzed by the composition to a certain layer lighter hydrocarbons with content, grasp with can be convenient stratum and under
Lie prostrate the oil-bearing information of layer.
Light hydrocarbon component quantitative analysis is carried out at present, chromatography is carried out using high-resolution capillary column, obtain the lighter hydrocarbons of C1-C6
Substance information, then quantitative analysis is carried out to light hydrocarbon component with chromatography internal standard method.But the method exist cannot be used for on-line analysis,
The limitations such as loss can be generated to crude oil sample, can not be used in the measurement of downhole crude property.
Apply for content
In order to solve the above-mentioned technical problem, this application provides a kind of sides of light hydrocarbon component real-time quantitative analysis in crude oil
Method, for light hydrocarbon component real-time, in quantitative detection downhole crude, Fast Evaluation exploration of oil and gas field.The application is by preparing packet
The crude oil of the light hydrocarbon component containing known content, measures its near infrared spectrum, establishes between near infrared spectrum and light hydrocarbon component content and closes
The calibration model of system.For the crude oil sample of unknown light hydrocarbon component content, its near infrared spectrum is acquired, and substitute into calibration model,
Each component content can be calculated.
In this application, light hydrocarbon component refers to the straight chain with 1-5 carbon atom or branch alkane, has 2-5
The straight chain of a carbon atom or branch alkene, straight chain with 2-5 carbon atom or branch alkynes, there is 3-5 carbon
The straight chain of atom or branch cycloalkane.The present processes can be used for the reality of the light hydrocarbon component of 5 carbon atoms or more
When quantitative analysis.
In order to reach the application purpose, this application provides a kind of sides for light hydrocarbon component real-time quantitative analysis in crude oil
Method, comprising:
(1) calibration set sample is prepared, the crude oil sample comprising known content light hydrocarbon component is prepared.According to each in China Seas
The big data analysis of oil field block obtains the range intervals of each light hydrocarbon component content, is mixed when configuration by different proportion
It closes, reaches and be evenly distributed；Every kind of lighter hydrocarbons have range, such as mass fraction, C1 in 0-10%, C2 in 0-5%,
C3 in 0-5%, C4 in 0-5%, C5 in 0-5%, C6+ is in 70-100%.By taking C3 content is in 0-5% as an example, by etc.
Difference series modeling, such as propane content choose 1%, 2%, 3%, 4%, 5% 5 according to 1% equal difference in the region 0%-5%
Group data modeling, is uniformly distributed with realizing.In this application, the acquisition spectral region of near infrared spectroscopy instrument is in 1100-
2100nm.In this application, modeling when using the region 1600-1850nm spectral information；
(2) calibration set sample measures, and acquires the near infrared spectrum of each calibration set sample, and it is corresponding described to record its
Light hydrocarbon component content；
(3) calibration model establish, with modeling method establish the calibration set sample near infrared spectrum and the lighter hydrocarbons group
Divide the relational model between content.Each a certain proportion of lighter hydrocarbons mixing sample has one and is unique spectroscopic data,
If wherein some component ratio changes, the spectroscopic data of sample can change；100-200 sample is taken when modeling
Product, light hydrocarbon component content is prepared in these samples, acquires their corresponding spectroscopic datas, forms matching one by one,
Reach modeling to complete.
(4) model application carries out near infrared ray to sample to be tested, and is substituted into the calibration model, predicts
The light hydrocarbon component content of the sample to be tested, and provide prediction error.By preparing sample, (each component content of preparation is controlled
System), substitute into model and calculate each component content, check calculated constituent content and each component content prepared in advance it
Between error whether meet the requirements, error≤5% meets the requirements.
It,, can be by lighter hydrocarbons when preparing the crude oil containing light hydrocarbon component in step (1) in the present processes
Sample liquefies in 6MP pressure above.It pressurizes to sample, so that ethane, propane, butane liquefy, methane moiety dissolution.
In the present processes, in step (2), 3-5 acquisition near infrared spectrum can be carried out to the same sample,
The near infrared spectrum of acquisition is averaged, as standard spectrum.
In the present processes, in step (3), the correcting sample can be divided into training set and test set,
The training set is used for the performance of test model for establishing model, the test set.The result relative error of calculating is less than 5%
I.e. by testing, that is, the relative error between the known content of the content and actual disposition predicted is less than 5%.
In the present processes, sample segment can be carried out using CADEX and DUPLEX method.
It can also include spectrum before establishing model or before sample substitutes into model in the present processes
Pretreatment, to eliminate baseline drift and noise.Down-hole ambient temperature is high, and near-infrared is easy to be affected by temperature, and leads to base
Line drift can be eliminated with Gap-segment derivative；It might have bubble in crude oil, spectrum caused noise, Ke Yiyong occur
Savitzky-Golay method is eliminated.
In the present processes, in step (3), Partial Least Squares Regression (PLSR) and SVM can be used
The method for establishing model for returning (SVR), wherein the Partial Least Squares Regression is suitable for establishing linear model, and it is described support to
The recurrence of amount machine is suitable for establishing nonlinear model.
In the present processes, in step (3), quantitative computational algorithm can be made into dynamic link library, for extra large oil
Petroleum Imaging Logging System (National Copyright Administration of the People's Republic of China registration number 2014SR107551) is called.Extra large oilstone oil Imaging Logging System is integrated with
A large amount of logging tool and method.In the application, the near-infrared spectrum analysis used is in extra large oilstone oil Imaging Logging System
Spectrum analysis subsystem.The near infrared spectrum of extra large oilstone oil Imaging Logging System acquisition downhole crude, in order to predict underground in real time
Spectrum need to be substituted into established model by light hydrocarbons constituent content, extra large oilstone oil Imaging Logging System.The work of dynamic link library
With being to provide the interface for spectrum being substituted into model to extra large oilstone oil Imaging Logging System, then by dynamic link library (according to thing
First established model) light hydrocarbons constituent content is calculated, and return to extra large oilstone oil Imaging Logging System and carry out subsequent processing.
The algorithm of model, is all realized, be used in combination again with C Plus Plus according to the interface requirement of extra large oilstone oil Imaging Logging System
The dynamic link library is generated after 2008 compiling link of Microsoft Visual Studio.
It can only complete in laboratory environments compared with the prior art, laboratory can not simulate the severe of underground high temperature and pressure
Environment can not carry out on-line analysis to downhole crude sample, and the prior art uses traditional chemical analysis method, and original can be lost
Oil samples, the present processes nondestructively can carry out quantitative analysis to light hydrocarbon component in crude oil, it is light to can be realized downhole crude
The on-line checking of the hydrocarbon component.
Other features and advantage will illustrate in the following description, also, partly become from specification
It obtains it is clear that being understood and implementing the application.The purpose of the application and other advantages can be by specifications, right
Specifically noted structure is achieved and obtained in claim and attached drawing.
Detailed description of the invention
Attached drawing is used to provide to further understand technical scheme, and constitutes part of specification, with this
The embodiment of application is used to explain the technical solution of the application together, does not constitute the limitation to technical scheme.
Fig. 1 is the building-block of logic of the light hydrocarbon component quantitative analysis method of the application.
Fig. 2 is the flow chart of the light hydrocarbon component quantitative analysis method of the application.
Specific embodiment
For the purposes, technical schemes and advantages of the application are more clearly understood, below in conjunction with attached drawing to the application
Embodiment be described in detail.It should be noted that in the absence of conflict, in the embodiment and embodiment in the application
Feature can mutual any combination.
The application provides a kind of method for light hydrocarbon component real-time quantitative analysis in crude oil.Initially set up correcting sample
Collection prepares the crude oil of known light hydrocarbon component content, measures the near infrared spectrum of each crude oil sample.Then, using CADEX and
It is training set and test set that DUPLEX method, which carries out sample segment to the correcting sample,.Spectrum is carried out to training set and test set
Pretreatment is to eliminate baseline drift and noise.Establish model using the training set of Pretreated spectra, that is, establish near infrared spectrum and
The corresponding relationship of light hydrocarbon component content.It is tested using the test the set pair analysis model of Pretreated spectra, the result of calculating is opposite accidentally
Difference passes through test less than 5%.The near infrared spectrum of sample to be tested is acquired, Pretreated spectra is carried out, by the sample of Pretreated spectra
Product substitute into model, obtain the content analysis of light hydrocarbon component.
The instrument used includes that pressure blending tank (pressure-bearing range 0-40Mp, have magnetic agitation), spectral scan probe (are held
Press range 0-50Mp, measurement range 1100-2100nm), digital calculation balance: Shuan Jie test equipment factory of Changshu City TC20K, manual pressure
Pump: Jiangsu Huaan Science Research Instrument Co., Ltd JB-3.
Embodiment 1
Sample is prepared, wherein methane (1.014%, 0.882472g), ethane (2.103%, 1.830028g), propane
(2.949%, 2.56148g), butane (3.38%, 2.940612g), pentane (3.665%, 3.188951g), crude oil
(86.89%, 75.6g), all ratios are mass ratio.
The crude oil that 90ml will be first poured into pressure blending tank, then seals the tank.The injection port for opening blending tank, will be different
Gas enter in pressure blending tank so that pentane 5ml, butane 5ml, propane 5ml, ethane 5ml, methane 20ml, utilize hand
Dynamic force (forcing) pump gives blending tank pressurization 6MP, so that gas liquefaction, then opens the outlet of blending tank, so that sample enters light
It composes in scanning head, measures the spectroscopic data for mixing sample at this time.
The correcting sample is divided by training set and test set, 100 samples of training set using CADEX and DUPLEX method
Product, 20 samples of test set.Nonlinear model is established using PLSR method.
Using extra large oilstone oil Imaging Logging System, the near infrared spectrum for acquiring downhole crude obtains near-infrared absorption spectrum
Numerical value, the data of 256 channels, 512 bytes, substitute into the model of foundation altogether, calculate lighter hydrocarbons group in crude oil by dynamic link library
The content divided, the content that C1-C5 is calculated is respectively 0.9886%, 3.325%, 2.271%, 2.592%, 2.785%, absolutely
It is respectively 0.025%, 1.222%, 0.678%, 0.788%, 0.88% to error.
Embodiment 2
Sample is prepared, wherein methane (1.5727%, 1.544326g), ethane (3.727%, 3.6601g), propane
(5.227%, 5.1323g), butane (5.989%, 5.88124g), pentane (6.495%, 6.3779g), crude oil (76.989%,
75.6g)。
The crude oil that 90ml will be first poured into pressure blending tank, then seals the tank.The injection port for opening blending tank, will be different
Gas enter in pressure blending tank so that pentane 10ml, butane 10ml, propane 10ml, ethane 10ml, methane 30ml, benefit
Blending tank pressurization 6MP is given with Manual pressurization pump, so that gas liquefaction, then opens the outlet of blending tank, so that sample enters
Into spectral scan probe, the spectroscopic data for mixing sample at this time is measured.
The correcting sample is divided by training set and test set, 100 samples of training set using CADEX and DUPLEX method
Product, 20 samples of test set.Nonlinear model is established using PLSR method.
Using extra large oilstone oil Imaging Logging System, the near infrared spectrum for acquiring downhole crude obtains near-infrared absorption spectrum
Numerical value, the data of 256 channels, 512 bytes, substitute into the model of foundation altogether, calculate lighter hydrocarbons group in crude oil by dynamic link library
The content divided, the content that C1-C5 is calculated is respectively 1.544%, 5.489%, 5.131%, 5.880%, 6.376%, absolutely
It is respectively 0.029%, 1.762%, 0.096%, 0.109%, 0.119% to error.
Although embodiment disclosed by the application is as above, the content only for ease of understanding the application and use
Embodiment is not limited to the application.Technical staff in any the application fields, is taken off not departing from the application
Under the premise of the spirit and scope of dew, any modification and variation, but the application can be carried out in the form and details of implementation
Scope of patent protection, still should be subject to the scope of the claims as defined in the appended claims.
Claims (11)
1. a kind of method for light hydrocarbon component real-time quantitative analysis in crude oil, comprising:
(1) calibration set sample is prepared, the crude oil sample comprising known content light hydrocarbon component is prepared；
(2) calibration set sample measures, and acquires the near infrared spectrum of each calibration set sample, and record its corresponding lighter hydrocarbons
Constituent content；
(3) calibration model is established, and establishes the near infrared spectrum of the calibration set sample with modeling method and the light hydrocarbon component contains
Relational model between amount；
(4) model application carries out near infrared ray to sample to be tested, and is substituted into the calibration model, described in prediction
The light hydrocarbon component content of sample to be tested, and provide prediction error.
2. according to the method described in claim 1, wherein, in step (1), when preparing the crude oil containing light hydrocarbon component,
The lighter hydrocarbons sample is liquefied in 6MP pressure above.
3. according to the method described in claim 1, wherein, in step (2), it is close red to carry out 3-5 acquisition to the same sample
External spectrum averages the near infrared spectrum of acquisition, the spectral value as the sample.
4. according to the method described in claim 1, wherein, in step (2), acquiring the light within the scope of 1100nm-2100nm
Spectrum.
5. according to the method described in claim 4, wherein, in step (2), acquiring the light within the scope of 1600nm-1850nm
Spectrum.
6. according to the method described in claim 1, wherein, in step (3), the correcting sample is divided into training set and survey
Examination collection, the training set are used for the performance of test model for establishing model, the test set.
7. the method stated according to claim 6, wherein carry out sample segment using CADEX and DUPLEX method.
8. according to the method described in claim 1, wherein, before establishing model, the spectroscopic data of sample is pre-processed,
To eliminate baseline drift and noise.
9. according to the method described in claim 8, wherein, eliminating baseline drift using Gap-segment derivative, using
Savitzky-Golay method eliminates noise.
10. according to the method described in claim 1, wherein, in step (3), using Partial Least Squares Regression (PLSR) and propping up
The method for establishing model that vector machine returns (SVR) is supportted, wherein the Partial Least Squares Regression is suitable for establishing linear model, and institute
Support Vector Regression is stated to be suitable for establishing nonlinear model.
11. according to the method described in claim 1, wherein, according to the interface requirement of logging system, the algorithm of the model is given birth to
At dynamic link library, after the near infrared spectrum of logging system acquisition crude oil, according to the model of foundation, by the dynamic
Chained library calculates light hydrocarbons constituent content, carrys out real-time quantitative analysis and shows light hydrocarbon component in crude oil.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112326594A (en) * | 2020-10-27 | 2021-02-05 | 安徽同心新材料科技有限公司 | Method for establishing quantitative model for rapidly detecting sulfur content in C5 oil product |
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Application publication date: 20190212 |