CN105717202A - Method for representing component and isotope fractionation effect in natural gas adsorption and desorption process of shale - Google Patents
Method for representing component and isotope fractionation effect in natural gas adsorption and desorption process of shale Download PDFInfo
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Abstract
The invention relates to a method for representing the component and isotope fractionation effect in the natural gas adsorption and desorption process of shale and belongs to the technical field of instruments used for analyzing materials by aid of measuring physical properties of the materials. The problem that in the prior art, due to the fact that a large amount of gas is lost in the drilling and sampling process, the experiment result cannot completely reflect the desorption process of shale gas is solved. According to the method, a competitive adsorption experiment is carried out in the shale gas adsorption and desorption process under high temperature and high pressure conditions, qualitative analysis is conducted on component fractionation in the process, qualitative analysis is conducted on isotope fractionation, and meanwhile a Langmuir model and an adsorption model are adopted for conducting numerical simulation on the adsorption quantity and the isotope value. Thus, elaborate description of the competitive adsorption effect in the shale gas adsorption and desorption process is realized, and it is beneficial for guiding gas-driven exploitation of the shale gas. The method can be widely applied to mathematical simulation research, gas-driven exploitation of the shale gas and other occasions.
Description
Technical field
The present invention relates to the method for component and isotope fractionation effect in shale adsorption-desorption natural gas process that characterizes, belong to the Instrument technology field carrying out analysis of material by means of the physical property measuring material.
Background technology
Adsorption Phase is that shale gas composes one of important phase of depositing, and the exploration and development of shale gas is significant.Being concentrated mainly on influence factor and the corresponding quantitative simulation of shale gas adsorbance to the research of Adsorption Phase shale gas, the component and the isotope fractionation Effect study that cause competitive adsorption effect in shale adsorption-desorption process are also little in the past.The difference of Various Components In Natural Gas absorption property determines some gas sorption ability strong (weak), it is easy to (difficulty) is adsorbed, it is difficult to (easily) desorbing, for there is the fractionation of component in the adsorption-desorption process of this natural gas.The competitive adsorption research of gas is concentrated mainly on coal bed gas field by forefathers, and coal sample tank desorption experiment illustrates to equally exist between different isotope composition the difference of absorption property, is the extension of component fractionation.Shale gas competitive adsorption has been carried out exploratory study by some research worker, does under low temperature (26 DEG C and 80 DEG C), low pressure (1atm, 2atm, 3atm) condition clay mineral (kaolinite, montmorillonite) and oil shale (green river shale) to the hydrocarbon gas (C1-C6) selective absorption experiment, and shale tank desorption experiment.
There it can be seen that at present that the research of shale gas competitive adsorption effect is also very limited, and all carry out under low Temperature-pressure Conditions.It addition, tank desorption experiment and vacuum sphere mill desorption experiment specimen in use have substantial amounts of gas in well-sampling process and scatter and disappear, experimental result can not intactly reflect the desorption process of shale gas.For this reason, it is necessary to the competitive adsorption experiment carried out under High Temperature High Pressure in the attached desorption process of shale aspiration, and corresponding mathematical modelling research, the competitive adsorption effect in shale gas adsorption-desorption process is carried out fine description, in order to instruct shale gas gas drive to exploit.
Summary of the invention
It is an object of the invention to the drawbacks described above overcoming prior art to exist, propose and a kind of characterize the method for component and isotope fractionation effect in shale adsorption-desorption natural gas process, by the competitive adsorption experiment carried out under high-temperature and high-pressure conditions in the attached desorption process of shale aspiration, and the component fractionation in this process is carried out qualitative analysis, while isotope fractionation is carried out qualitative analysis, adopt Langmuir model and absorption potential model that adsorbance and isotope value are carried out numerical simulation, achieve the fine description of competitive adsorption effect in shale gas adsorption-desorption process, the gas drive contributing to instructing shale gas is exploited.
The present invention adopts following technical scheme to realize: step one: the competitive adsorption experiment carried out under high-temperature and high-pressure conditions in the attached desorption process of shale aspiration: extracting sample is carried out multi component adsorption desorption experiment, free gas sampling is carried out at each pressure balance point, analysis component forms, and component fractionation is carried out qualitative analysis；Extracting sample is carried out the adsorption and desorption experiment of one pack system difference carbon isotope composition, free gas sampling is carried out at each pressure balance point, analyze isotopics, isotope fractionation is carried out qualitative analysis, and adopts Langmuir model and absorption potential model that adsorbance and isotope value are carried out numerical simulation.
Step 2: the component fractionation during competitive adsorption is tested carries out qualitative analysis: by analyzing the mixed gas sorption desorption process each component percentages of Free Gas body with the change of pressure and adsorbance, determine the competitive adsorption ability of each component.
Step 3: the isotope fractionation during competitive adsorption is tested carries out qualitative analysis: by free phase in analysis list component gas adsorption-desorption process and Adsorption Phase isotopics with the change of pressure and adsorbance, determine each isotopic competitive adsorption ability.Wherein Adsorption Phase carbon isotope value is according to material balance principle, formula (1) obtain.
δ13Cadsorption=(ninjection·δ13Cinjection-nfree·δ13Cfree-ndischarged·δ13Cdischarged)/nadsorption(1)
Wherein, ninjection、nfree、nadsorption、ndischargedRespectively experiment is injected the amount of free gas in the amount of gas, system, the amount of adsorbed gas and system pressure release and is discharged the amount of gas, δ13Cinjection、δ13Cfree、δ13Cadsorption、δ13CdischargedRespectively corresponding carbon isotope value.
Step 4: the isotope fractionation during competitive adsorption is tested adopts Langmuir model, with absorption potential model, with isotope value, adsorbance is carried out numerical simulation: be different isotopic adsorption-desorption curve by single-component gas adsorption-desorption curve separating, it is separately optimized different isotopic adsorbance calculating parameter afterwards adsorption-desorption curve is fitted, it is thus achieved that different isotopic adsorbances calculate parameter just can calculate corresponding carbon isotope value (method 1).After obtaining different isotopic adsorption-desorption curve, can be first right12CH4Adsorption-desorption curve is fitted, afterwards by optimizing13CH4Adsorbance calculate parameter directly the carbon isotope value in adsorption-desorption process is fitted (method 2).It is respectively adopted Langmuir model and absorption potential model use above two method adsorbance and isotope value are simulated.
Wherein, Langmuir model:
Langmuir (Langmuir) isotherm adsorption model is current most widely used equilibrium state monolayer adsorption model, shown in the expression formula of this model such as formula (2).Wherein, ViFor the adsorbance of i-th experimental point, unit is cm3/ g；VLFor Lan Shi volume, the maximal absorptive capacity of representative sample, unit is m3/ t；PLFor Lan Shi pressure, pressure corresponding when being adsorbance equal to Lan Shi volume half, unit is MPa；PiFor the pressure of i-th experimental point, unit is MPa.Formula (2) can be deformed into formula (3), can draw with p/V for abscissa according to experimental data accordingly, and p is the scatterplot of vertical coordinate, and it is carried out linear fit, and straight line equation slope is VL, and the opposite number of intercept is pL。
pi=VL·pi/Vi-pL(3)
Can by CH when studying isotope fractionation4It is divided into12CH4、13CH4Two kinds of components, obtain Langmuir model expression (4).Wherein12CViWith13CViFor i-th experimental point12CH4 and13The adsorbance of CH4, unit is cm3/ g；12CVL、13CVLFor12CH4With13CH4Lan Shi volume, unit is m3/ t；12CpL、13CpLFor12CH4With13CH4Lan Shi pressure, unit is MPa；12CpiWith13CpiFor i-th experimental point12CH4With13CH4Dividing potential drop, unit is MPa.
Application Langmuir models fitting CH4Adsorption-desorption carbon isotope curve is actually optimization and obtains12CH4With13CH4Lan Shi volume and Lan Shi pressure.First method is matching respectively12CH4With13CH4P～p/V experimental point, it is thus achieved that12CH4、13CH4Lan Shi volume and Lan Shi pressure, corresponding isotope value can be calculated.
Second method is to be obtained by method 112CH4Lan Shi volume and Lan Shi pressure after, by matching Adsorption Phase methane isotope value obtain13CH4Lan Shi volume and Lan Shi pressure.I-th experimental point isotope value can be obtained by formula (4), as shown in formula (5), wherein RstFor the carbon isotope ratio of standard sample, namely 1123.72 × 10-5。
1. build object function, be δ by testing measured isotope value when being located at a certain experimental point i13Ci-exp, at identical conditions, it is assumed that13CVL、13CpLAfterwards, model (5) isotope value calculated is δ13Ci-cal.If there being a certain group13CVL、13CpLMake that all of experimental point is had δ13Ci-calEqual to δ13Ci-exp, then this group13CVL、13CpLRequired by being.But due to the aspect such as experimental error, model defect, this is practically impossible.Therefore, can only ask and make δ13Ci-calAnd δ13Ci-expDifference is tried one's best little13CVL、13CpL.For this, structure object function, as shown in formula (6).
Here n is the sampling number on absorption or desorption experiment curve.So,13CVL、13CpLDetermination just become seeking non-negative object function (6) minimal point problem, simultaneously need to meet13CVL、13CpLFor nonnegative number.
2. building penalty, the above-mentioned minimizing Solve problems containing Prescribed Properties is more complicated, because except making target function value be gradually reduced, it is also noted that the reasonability of solution, namely sees whether solution meets the constraints for nonnegative number.This adopts Means of Penalty Function Methods that Constrained extreme-value problem is turned to Unconstrained Optimization Problems.For arbitrary constraints, it is possible to construct a function, when the extreme point tried to achieve meets this condition, functional value is 0, is otherwise positive number.Right13CVLThis constraints more than zero, constructed fuction such as formula (7).
Namely
In like manner have:
Formula (8), formula (9) can merge as follows:
G(13CVL,13CpL)=G1+G2
=[min (0,13CVL)]2+[min(0,13CpL)]2(10)
Take a sufficiently large positive integer R, (6) and (10) formula can construct penalty:
F(13CVL,13CpL)=Q (13CVL,13CpL)+R·G(13CVL,13CpL)(11)
If calculated minimal point exceeds constraints, then it is gradually increased R, when R is sufficiently large, the minimal solution of (11) formula is the minimal solution of object function (6) formula, and Constrained extreme-value problem thus turns to the Unconstrained Optimization Problems relatively easily solved.To solving without binding occurrence problem, mathematically provide multiple optimized algorithm.This selects convergence rate very fast and is programmed calculating without the matrix of second derivatives of loaded down with trivial details calculating and the variable-metric method of inverse matrix thereof.
Application Langmuir model, by the adsorption isotherm experiment data at a certain temperature, can only show that this formula can not predict the adsorbance under other condition of different temperatures suitable in the adsorption isotherm under this temperature conditions.And in actual geological work, generally require the adsorbance prediction carried out under condition of different temperatures.If application Langmuir model reaches this purpose, it is necessary to carry out the adsorption isotherm experiment under different temperatures respectively, experimental work amount is big, and absorption potential model can solve this problem preferably.
Wherein, absorption potential model:
The adsorption that Adsorption Potential Theory is thought between gas and solid is mainly dispersion force, and when adsorbent and adsorbate are certain, the relation curve of absorption potential and Adsorption Phase volume is unique, does not change with temperature, and this curve claims adsorpting characteristic curve.Therefore, as long as the adsorption isotherm data at known a certain temperature, adsorpting characteristic curve is obtained, so that it may calculate the adsorpting data at arbitrary temperature.
The foundation of absorption potential model is it is crucial that by calculating absorption potential and Adsorption Phase volume, obtain adsorpting characteristic curve.According to Adsorption Potential Theory, absorption potential and pressure and temperature meet formula (12) relation.Be typically on the critical temperature of the gases such as methane due to formation temperature, the saturated vapour pressure under critical condition is absent from.For this, Amankwah (1995) establishes the virtual saturated vapour pressure P under super critical conditions(formula (13)).Bring formula (13) into formula (12) and corresponding absorption potential can be drawn.Ask for absorption potential, just can set up adsorpting characteristic curve in conjunction with Adsorption Phase volume computing formula (formula (14)).During GEOLOGICAL APPLICATION, first being determined absorption potential by Temperature-pressure Conditions, the adsorpting characteristic curve that recycling has been set up just can obtain corresponding adsorbance (Lietal., 2015).
Wherein, P is balance pressure (MPa)；ε is absorption potential (J/mol)；P0For gas saturated vapour pressure (MPa)；PiFor gas balance pressure (MPa) at a certain temperature；R is gas constant (8.314J.mol-1.K-1)；T is absolute temperature (K).
Ps=Pc(T/Tc)k(13)
Wherein, PcAnd TcRespectively critical pressure and temperature, k is constant, can optimum option, this research value be 2.
W=VadM/ρad(14)
Wherein, w is Adsorption Phase volume (cm3/ g)；VadFor actual measurement adsorbance (mol/g)；M is gas molar quality (g/mol)；ρadFor gas absorption phase density (g/cm3), it is 0.375g/cm that this research takes methane adsorption phase density3。
Step calculated below, with Langmuir model, applies absorption potential models fitting CH4In adsorption-desorption process, Adsorption Phase carbon isotope curve is actually optimization acquisition12CH4With13CH4Adsorpting characteristic curve.First method is matching respectively12CH4With13CH4Adsorption Phase volume and absorption potential relation in adsorption-desorption process, it is thus achieved that12CH4、13CH4Adsorpting characteristic curve, corresponding isotope value can be calculated.
Second method is to be obtained by method 112CH4Adsorpting characteristic curve after, by matching Adsorption Phase methane isotope value obtain13CH4Adsorpting characteristic curve.12CH4With13CH4In adsorption-desorption process, Adsorption Phase volume and absorption potential relation can carry out good matching by unitary cubic polynomial, thus set up shown in adsorpting characteristic curve equation such as formula (15).
Wherein,12Cwi、13CwiRespectively i-th experimental point12CH4With13CH4Adsorption Phase volume,12Cεi、13CεiRespectively i-th experimental point12CH4With13CH4Absorption potential, a, b, c, d and a', b', c', d' are constant.
I-th experimental point isotope value can be obtained, as shown in formula (16) by formula (15).Thus equally build shown in object function such as formula (17) with Langmuir model, optimize to ask for and make Q-value try one's best little a', b', c', d'.
Compared with prior art, the invention has the beneficial effects as follows: the method for component and isotope fractionation effect in sign shale adsorption-desorption natural gas process of the present invention, by the competitive adsorption experiment carried out under high-temperature and high-pressure conditions in the attached desorption process of shale aspiration, and the component fractionation in this process is carried out qualitative analysis, while isotope fractionation is carried out qualitative analysis, adopt Langmuir model and absorption potential model that adsorbance and isotope value are carried out numerical simulation.Achieve the fine description of competitive adsorption effect in shale gas adsorption-desorption process, contribute to instructing the gas drive of shale gas to exploit.
Accompanying drawing explanation
Fig. 1 is CH in mixed gas sorption desorption process Free Gas body4Percentage composition is with the variation diagram of pressure (a) (b) He adsorbance (c) (d).
Fig. 2 is CH4In adsorption-desorption process, free phase and Adsorption Phase carbon isotope composition are with the variation diagram of pressure (a) (b) He adsorbance (c).
Fig. 3 is Langmuir model and absorption potential model pair12CH4(a)、13CH4The fitted figure of adsorbance in (b) adsorption process.
Fig. 4 is Langmuir model and absorption potential model pair12CH4(a)、13CH4The fitted figure of adsorbance in (b) desorption process.
Fig. 5 is that Langmuir model and absorption potential model are to CH4The fitted figure of Adsorption Phase isotope value in absorption (a), desorbing (b) process.
Detailed description of the invention
In order to make the purpose of the present invention, research method and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.
Below in conjunction with drawings and the specific embodiments, the technical method of the present invention is further described.
This research have chosen the husky three times sub-section shale of China's Jiyang Depression, The Bohaiwan Basin river 172 well, and the degree of depth is 3336.79m, and organic matter type is II1Type.The original total content of organic carbon of sample is 2.98%, and pyrolysis parameters of rock is as follows: S1=2.15mg/g, S2=16.74mg/g, Tmax=443 DEG C；After extracting, total content of organic carbon is 2.75%, and pyrolysis parameters of rock is as follows: S1=0.14mg/g, S2=14.47mg/g, Tmax=441 DEG C.X-ray diffraction analysis shows, sample mineral composition is: clay 39%, quartz 22%, plagioclase 2%, calcite 29%, pyrite 5%, siderite 3%；Clay mineral relative amount is: kaolinite 4%, chlorite 2%, illite 19%, Iraq/Mongolia interbed 75%, and interbed ratio is 20%.
Extracting sample has been carried out CH by this4, 50%CH4+ 50%CO2, 50%CH4+ 50%N2Adsorption and desorption experiment, carries out free gas sampling at each pressure balance point, analyzes component and (or) isotopics.
Fig. 1 is CH in mixed gas sorption desorption process Free Gas body4Percentage composition is with the variation diagram of pressure and adsorbance.By Fig. 1 a it can be seen that 50%CH4+ 50%CO2CH in competitive adsorption process4Absorbability is weaker than CO2, CH in free phase mixing gas4Content is consistently greater than 50%, and along with the rising of pressure is gradually increased.From Fig. 1 b it can be seen that 50%CH4+ 50%N2CH in competitive adsorption process4Absorbability is weaker than N2, CH in free phase mixing gas4Content is consistently greater than 50% equally.But along with the rising Changing Pattern of pressure is inconspicuous, show faint inverted parabolic curve shape.By Fig. 1 a to Fig. 1 b it can be seen that 50%CH in desorption process4+ 50%CO2, 50%CH4+ 50%N2Two kinds of system CH4Percentage composition is all stable to be raised.Wherein, 50%CH4+ 50%CO2System elevation amplitude is 8.35%, and 50%CH4+ 50%N2System elevation amplitude is less, is 5.74%.Above-mentioned phenomenon illustrates, CO2、N2Relative CH4There is Preferential adsorption, the feature of Hysteretic desorption, the displacement being used equally to shale gas is exploited, but CO2Flooding Efficiency be better than N2, CO2While displacement methane, self well can be stored in shale.By Fig. 1 c to Fig. 1 d it can be seen that CH in free gas4Percentage composition curve absorption late period and the early changes of desorbing comparatively obvious, when in explanation system, gas flow is maximum, competitive adsorption effect is the most obvious.
Fig. 2 depicts CH4In adsorption-desorption process, free phase and Adsorption Phase carbon isotope composition are with the change of pressure and adsorbance, and wherein Adsorption Phase carbon isotope value is according to material balance principle, formula (1) obtain.By Fig. 2 a it can be seen that in methane adsorption-desorption experiment process13CH4Preferential adsorption, Hysteretic desorption, thus causing free state methane carbon isotope value in adsorption process to lighten gradually, desorption process becomes weight gradually.It addition, from CH4In adsorption-desorption process, Adsorption Phase carbon isotope composition can be seen that with the change (Fig. 2 c) of pressure (Fig. 2 b) and adsorbance, adsorption process late period and desorption process early stage have significantly stronger carbon isotope fractionation, and this point is similar to component fractionation.
To the numerical simulation of Gas carbon isotopes value be substantially to each isotope composition (as12CH4With13CH4) simulation of amount of substance, the carbon isotope fractionation in methane adsorption desorption process is simulated by this research.
Fig. 3, Fig. 4 depict Langmuir model and absorption potential model pair12CH4、13CH4The fit solution of adsorbance in Adsorption and desorption process, there it can be seen that different models and different modeling method all can reach good fitting effect generally.But, owing to method 1 is directly adsorbance to be fitted, method 2 is that isotope value is fitted, and it is right13CH4The simulation of adsorbance is indirectly.Therefore, method 1 is right13CH4The fitting precision of adsorbance is slightly above method 2, for the ratio respectively 0.80 and 0.71 of Langmuir model method 1 and method 2 error sum of squares (Q), for absorption potential model respectively 0.99 and 1.But method 2 to the fitting precision of isotope value apparently higher than method 1 (Fig. 5), for the ratio respectively 0.43 and 0.30 of Langmuir model method 2 and method 1 error sum of squares (Q), absorption potential model respectively 0.93 and 0.88.The fitting effect of method 2 is better than method 1 generally, because small13CH4The change of adsorbance just can cause the change of bigger Methane Carbon Isotope value, because the method 2 can be only small to the sacrifice of adsorbance matching when isotope value is fitted.Isotope value can not be carried out effective matching by Langmuir model, is applicable only to the matching of adsorbance, and adsorbance and isotope value all can be carried out good matching by absorption potential model, and absorption potential model pair12CH4、13CH4The fitting precision of adsorbance, also above Langmuir model, illustrates the matching matching of Adsorption Phase isotope value being difficult to adsorbance, and the capability of fitting of absorption potential model is higher than Langmuir model.
Embodiment described above is only that the preferred embodiment of the present invention is described, and not the spirit and scope of the present invention is defined.Under the premise without departing from design concept of the present invention; various modification that technical scheme is made by this area ordinary person and improvement; protection scope of the present invention all should be dropped into, the technology contents that the present invention is claimed, all record in detail in the claims.
Claims (10)
1. one kind characterizes the method for component and isotope fractionation effect in shale adsorption-desorption natural gas process, it is characterised in that: comprise the steps:
Step one: the competitive adsorption experiment carried out under high-temperature and high-pressure conditions in the attached desorption process of shale aspiration；
Step 2: the component fractionation during competitive adsorption is tested carries out qualitative analysis；
Step 3: the isotope fractionation during competitive adsorption is tested carries out qualitative analysis；
Step 4: the isotope fractionation during competitive adsorption is tested adopts Langmuir model and absorption potential model that adsorbance and isotope value are carried out numerical simulation.
2. the method for component and isotope fractionation effect in sign shale adsorption-desorption natural gas process according to claim 1, it is characterized in that: in step one, extracting sample is carried out multi component adsorption desorption experiment, free gas sampling is carried out at each pressure balance point, analysis component forms, and component fractionation is carried out qualitative analysis；Extracting sample is carried out the adsorption and desorption experiment of one pack system difference carbon isotope composition, free gas sampling is carried out at each pressure balance point, analyze isotopics, isotope fractionation is carried out qualitative analysis, and adopts Langmuir model and absorption potential model that adsorbance and isotope value are carried out numerical simulation.
3. the method for component and isotope fractionation effect in sign shale adsorption-desorption natural gas process according to claim 1, it is characterized in that: in step 2, by analyzing the mixed gas sorption desorption process each component percentages of Free Gas body with the change of pressure and adsorbance, determine the competitive adsorption ability of each component.
4. the method for component and isotope fractionation effect in sign shale adsorption-desorption natural gas process according to claim 1, it is characterized in that: in step 3, by free phase in analysis list component gas adsorption-desorption process and Adsorption Phase isotopics with the change of pressure and adsorbance, determine each isotopic competitive adsorption ability；
Wherein Adsorption Phase carbon isotope value is according to material balance principle, formula (1) obtain:
δ13Cadsorption=(ninjection·δ13Cinjection-nfree·δ13Cfree-ndischarged·δ13Cdischarged)/nadsorption(1)
Wherein, ninjection、nfree、nadsorption、ndischargedRespectively experiment is injected the amount of free gas in the amount of gas, system, the amount of adsorbed gas and system pressure release and is discharged the amount of gas, δ13Cinjection、δ13Cfree、δ13Cadsorption、δ13CdischargedRespectively corresponding carbon isotope value.
5. the method for component and isotope fractionation effect in sign shale adsorption-desorption natural gas process according to claim 1, it is characterized in that: in step 4, it is different isotopic adsorption-desorption curves by single-component gas adsorption-desorption curve separating, it is separately optimized different isotopic adsorbance calculating parameter afterwards adsorption-desorption curve is fitted, it is thus achieved that different isotopic adsorbances calculate parameter just can calculate corresponding carbon isotope value.
6. the method for component and isotope fractionation effect in sign shale adsorption-desorption natural gas process according to claim 5, it is characterised in that: adopt Langmuir model that adsorbance and isotope value are simulated, matching respectively12CH4With13CH4P～p/V experimental point, it is thus achieved that12CH4、13CH4Lan Shi volume and Lan Shi pressure, corresponding isotope value can be calculated.
7. the method for component and isotope fractionation effect in sign shale adsorption-desorption natural gas process according to claim 5, it is characterised in that: adopt absorption potential model that adsorbance and isotope value are simulated, matching respectively12CH4With13CH4Adsorption Phase volume and absorption potential relation in adsorption-desorption process, it is thus achieved that12CH4、13CH4Adsorpting characteristic curve, corresponding isotope value can be calculated.
8. the method for component and isotope fractionation effect in sign shale adsorption-desorption natural gas process according to claim 1, it is characterised in that: in step 4, after obtaining different isotopic adsorption-desorption curve, first right12CH4Adsorption-desorption curve is fitted, afterwards by optimizing13CH4Adsorbance calculate parameter directly the carbon isotope value in adsorption-desorption process is fitted.
9. the method for component and isotope fractionation effect in sign shale adsorption-desorption natural gas process according to claim 8, it is characterised in that: adopt Langmuir model that adsorbance and isotope value are simulated, obtaining12CH4Lan Shi volume and Lan Shi pressure after, by matching Adsorption Phase methane isotope value obtain13CH4Lan Shi volume and Lan Shi pressure.
10. the method for component and isotope fractionation effect in sign shale adsorption-desorption natural gas process according to claim 8, it is characterised in that: adopt absorption potential model that adsorbance and isotope value are simulated, obtaining12CH4Adsorpting characteristic curve after, by matching Adsorption Phase methane isotope value obtain13CH4Adsorpting characteristic curve.
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| CN111855481A (en) * | 2020-07-13 | 2020-10-30 | 中国石油大学(北京) | Method and device for measuring fractionation data of adsorbed gas isotope |
| CN112149306A (en) * | 2020-09-27 | 2020-12-29 | 中国科学院地质与地球物理研究所 | Carbon isotope fractionation calculation method in natural gas analysis process and application |
| CN112151124A (en) * | 2020-09-24 | 2020-12-29 | 中国石油大学(华东) | Shale in-situ gas-containing parameter determination method and system based on carbon isotope fractionation |
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| CN111007233B (en) * | 2019-12-25 | 2022-03-11 | 西南石油大学 | Method for analyzing movement behavior of methane-carbon dioxide in micro pores of shale |
| CN111855481A (en) * | 2020-07-13 | 2020-10-30 | 中国石油大学(北京) | Method and device for measuring fractionation data of adsorbed gas isotope |
| CN112151124A (en) * | 2020-09-24 | 2020-12-29 | 中国石油大学(华东) | Shale in-situ gas-containing parameter determination method and system based on carbon isotope fractionation |
| CN112151124B (en) * | 2020-09-24 | 2022-11-04 | 中国石油大学(华东) | Shale in-situ gas-containing parameter determination method and system based on carbon isotope fractionation |
| CN112149306A (en) * | 2020-09-27 | 2020-12-29 | 中国科学院地质与地球物理研究所 | Carbon isotope fractionation calculation method in natural gas analysis process and application |
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