CN108827995A - A kind of construction method of kerogen average molecular structure model - Google Patents
A kind of construction method of kerogen average molecular structure model Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
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- G01N23/2273—Measuring photoelectron spectrum, e.g. electron spectroscopy for chemical analysis [ESCA] or X-ray photoelectron spectroscopy [XPS]
Abstract
The present invention provides a kind of construction methods of kerogen average molecular structure model comprising following steps：Calculate the hydrogen index (HI) HI of each sample and the kerogen average molecular structure parameter of the block shale；It extracts the kerogen sample in slate flour sample and carries out xps energy spectrum analysis and FTIR spectrum analysis, judge element composition in kerogen sample, carbon atom and heteroatomic atom when heteroatomic existing forms；Calculated by peak area kerogen microstructure parameter is fitted according to the characteristic peak of group each in FTIR spectrum；The total carbon number for determining kerogen average molecular structure constructs initial kerogen average molecular structure；Main carbon backbone structure and heteroatom functional is kept to roll into a ball constant, each aliphatic chain carbon number and heteroatom functional cumularsharolith constantly adjusted in initial kerogen average molecular structure is set, until model structure parameter adjusted and XPS and FTIR experimental result are more consistent, the kerogen average molecular structure model of region shale is obtained.
Description
Technical field
The invention belongs to petrochemistry fields, are related to a kind of construction method of kerogen average molecular structure model.
Background technique
Shale gas is resourceful, and commercialization exploitation can greatly alleviate world energy sources pressure, restructures the use of energy.Page
Rock gas is with ADSORPTION STATE, free state and solubilised state preservation in the nanoscale hole of reservoir.Wherein adsorbed gas is in shale gas reserves
In the highest flight, 60-85% of the content up to gas gross.Kerogen root is specific surface area and adsorption capacity in shale gas
Significant contributor.Studying shale kerogen has weight to shale gas Reserves Evaluation and shale gas exploitation to the characterization of adsorption of gas
The directive significance wanted.
Research kerogen mainly has adsorption isotherm experiment method and molecule simulation method to the absorption of gas at present.Due to reality
The limitation of experiment device, adsorption isotherm experiment method can not simulate kerogen adsorbed gas under practical shale reservoir high-temperature and high-pressure conditions
The behavior of body can not also probe into the microcosmic mechanism of kerogen adsorbed gas.Molecule simulation method can effectively make up isothermal adsorption reality
The limitation of proved recipe method.It but is the reasonable kerogen of building with the premise of molecule simulation method research kerogen absorption property
Average molecular structure model.
It is well known that kerogen is a kind of three-dimensional macromolecular mixture without fixed chemical structure, it can not be obtained really
Fixed molecular structure, at present mainly using average molecular structure come its chemical structure of approximate simulation.Kerogen average molecular structure
Refer to the atom set body obtained after carrying out the fragrant cluster in structure averagely, usually as a kind of molecular model, and borrows
This reflects kerogenic typical physical and chemical property.To establish kerogenic average molecular structure, need to take structural characterization
Experiment is to obtain its important structural parameters.Currently used structure characterization methods include oxidation plus hydrogen, halogenation, depolymerization, heat
Solution, alkylation and functional group analysis etc., such method is mainly characterized by needing to destroy kerogenic chemical structure to be had
Representative information fragmentation, and kerogenic original macromolecular structure is gone out according to the structure prediction of the information fragmentation.For example, 2012
Year, Ru X, Cheng Z, Song L et al. is in paper " Experimental and computational studies on
The average molecular structure of Chinese Huadian oil shale kerogen ",
(Journal of Molecular Structure,2012,1030:It 10-18.) has disclosed a kind of using pyrolysis-gas phase color
Spectrum-mass spectrometry method characterizes the kerogenic structural framework of Huadian Oil Shales, and binding molecule analogy method constructs
The method for testing the three-dimensional separation flow of kerogen sample, this approach includes the following steps：(1) at the acidification of Huadian Oil Shale sample
Reason, asphalt extraction obtain kerogen sample；(2) Huadian kerogen C, H, O, N, S elemental analysis；(3) Huadian kerogen pyrolysis-
Gas chromatography-mass spectrum test, analyzes the composition of thermal decomposition product, counter to push away kerogen structure segment；(4) company between structure fragment is determined
Order member and connection site, construct initial kerogen molecular structure；(5) the 13C NMR spectra of cheese analogue root, with experiment
The spectrogram of test compares, and adjustment kerogen molecular structure coincide until the spectrogram approximation simulated and tested；(6) molecular simulation is used
Means optimize kerogen molecular structure, obtain Huadian kerogen molecular model.But the kerogen construction method exists
Following disadvantage：Pyrolysis in structural characterization experiment needs to destroy kerogenic chemical structure, and it is some important that this will lead to loss
Structural information；And kerogenic structure is pushed away come indirectly counter using the construction debris that pyrolysis obtains, have biggish not true
It is qualitative；The indirect arrangements information obtained for single laboratory sample cannot reflect such kerogenic average molecular structure.
Therefore, a kind of construction method that can quick and precisely determine kerogen average molecular structure model is established, to shale
Gas exploitation has important directive significance.
Summary of the invention
The shortcomings that in view of the above-mentioned prior art, the purpose of the present invention is to provide a kind of kerogen average molecular structure models
Construction method.This method can quickly determine the reasonable average molecular structure parameter of same type kerogen sample, and combine
Direct characterization method constructs representative shale kerogen average molecular structure model.
In order to reach goal of the invention above-mentioned, the present invention provides a kind of building side of kerogen average molecular structure model
Method comprising following steps：
Step 1：The total organic carbon amount TOC and pyrolysis hydrocarbon content S2 for obtaining the same area muti-piece slate flour sample, calculate
The hydrogen index (HI) HI of each sample, and calculate by hydrogen index (HI) HI the kerogen average molecular structure parameter of the block shale；
Step 2：It extracts the kerogen sample at least one slate flour sample and carries out xps energy spectrum analysis and FTIR light
Spectrum analysis, when heteroatomic there are shapes for element composition, carbon atom and the heteroatomic atom for judging in the kerogen sample
State；
And the cheese is calculated based on the characteristic peak of group each in FTIR spectrum fitting peak area according to the following formula
The kerogen microstructure parameter of root sample：
Wherein, SPkFor k-th of kerogen microstructure parameter；PAiFor the fitting area at A class group ith feature peak；
PBjFor the fitting area of B class j-th of characteristic peak of group；N and M is respectively the characteristic peak number of A class group and B class group；It is described
A class group and B class group are to determine SPkRelated group；
Step 3：The total carbon number for determining the kerogen average molecular structure constructs initial kerogen average molecular structure；
Step 4：It keeps main carbon backbone structure and heteroatom functional group type constant, constantly adjusts the initial kerogen
Each fat chain structure and heteroatom functional cumularsharolith in average molecular structure are set, until model structure parameter adjusted and XPS
With FTIR experimental result and the calculated result relative error based on hydrogen index (HI) HI is to obtain the region shale within 5%
Kerogen average molecular structure model；
Wherein, the hetero atom is the atom in addition to hydrocarbon.
In the construction method of above-mentioned kerogen average molecular structure model, xps energy spectrum refers to x-ray photoelectron spectroscopy, packet
Include XPS compose entirely and XPS finely compose；FTIR spectrum refers to FTIR spectrum, and element composition can generally be composed entirely according to XPS to be divided
Analysis obtains, and determines after comprehensive analysis can also being carried out in conjunction with conventional elemental analysis method；Similarly, carbon atom and heteroatomic original
Son, can also be in conjunction with conventional elemental analysis side than the calculated by peak area after each element swarming fitting in being composed entirely by XPS
Method determines after carrying out comprehensive analysis；In step 2, heteroatomic existing forms, which can finely compose swarming by the XPS of corresponding element, to be intended
Conjunction judges its that may be present and carbon atom or other heteroatomic bonding structure, then deduces hetero atom in kerogen sample
In possible existing forms hetero atom can be determined dry in conjunction with the kerogen microstructure parameter that FTIR spectrum analysis obtains
Existing forms in junket root sample.The hetero atom includes but is not limited to O, N and S.Wherein, the existing forms of N atom can be straight
The peak position in finely being composed by XPS after the fitting of N1s swarming is connect to determine.And the existing forms of O atom are complex, generally require knot
It closes FTIR spectrum ability qualitative analysis and goes out various oxygen-containing groups, then further according to each oxygen-containing group in kerogen microstructure parameter
Accounting percentage, quantitatively determine existing forms of the O atom in kerogen sample.According to the absorption of group each in FTIR spectrum
It includes but is not limited to aliphatic chain that peak peak position fitting calculated by peak area, which obtains the kerogen microstructure parameter of the kerogen sample,
Length CL, aromatic carbon rate AR, fragrant cluster agglomerate degree DOC, carbonyl score Oca, alcohol radical score OalWith ether score OetIn at least
One kind also determining the content of each chemical structure while determining kerogen sample chemical structure (group, functional group), letter
The step process of the initial kerogen average molecular structure of building is changed.In the initial kerogen mean molecule knot of step 4 adjusting and optimizing
When structure, main carbon backbone structure and heteroatom functional is kept to roll into a ball constant, the kerogenic fundamental property of basic guarantee, and adjust initial
Each aliphatic chain carbon number and heteroatom functional cumularsharolith in kerogen average molecular structure are set, by a relatively simple, but also adjustment
Model structure parameter afterwards is relatively easy to be fitted with XPS and FTIR experimental result.Wherein, main carbon backbone structure includes but is not limited to
Fragrant cluster, formulaIn, the A class group and B class group are to determine SPkRelated group, for example,
Fatty chain length (CL) is by CH2The fitting peak area and CH of group characteristic peak3The ratio of the fitting peak area of group characteristic peak is true
It is fixed, it can specifically refer to the following table 1.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the cheese of the kerogen sample
Root microstructure parameter includes fatty chain length CL, aromatic carbon rate AR, fragrant cluster cohesion degree DOC, carbonyl score Oca, alcohol radical score
OalWith ether score OetAt least one of.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the cheese of the kerogen sample
Root microstructure parameter is calculated by the physical definition in table 1：
Table 1
In table 1, absorption peak bit allocation can be inquired according to the following table 1-1, and table 1-1 is the assignments of infrared absorption peak.
Table 1-1
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the hetero atom includes O, N and S
At least one.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the existing forms of the N atom by
N1s swarming quantitative analysis determination after being fitted on the xps energy spectrum.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the existing forms packet of the N atom
Include at least one of pyrroles, pyridine and quaternary nitrogen
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the existing forms of the O atom by
The accounting percentage quantitative analysis of each oxygen-containing group determines in the kerogen microstructure parameter.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the oxygen-containing group include carbonyl,
At least one of alcohol radical and ether.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the existing forms of the S atom by
Fragrant sulphur content number f in the kerogen average molecular structure parameter in organic sulfursIt is determined with fatty sulphur content number.It is highly preferred that
The fragrance methylthio group is thiophene, and the fat methylthio group is thioether.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the kerogen mean molecule knot
Structure parameter includes H/C atomic ratio Hc, aromatic carbon content fa, aliphatic chain carbon number Cn, fragrant sulphur content number f in organic sulfursWith fragrant cluster
In fragrant carbon number Ca.With aliphatic chain carbon number CnDifference, kerogen microstructure parameter fatty chain length CL are based on FTIR spectrogram
It is calculated, is used for qualitative evaluation fatty chain length, and CnWhat is reflected is then the carbon number in aliphatic chain, for quantitative assessment fat
Chain length.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the H/C atomic ratio HcPass through public affairs
Formula (1) calculates：
Hc=0.1426HI+49.143 (1)；
After carry out organic carbon (TOC) test and Pyrolysis Experiment test to the same area muti-piece slate flour sample,
Organic carbon amounts TOC and pyrolysis hydrocarbon content S2 are obtained, the hydrogen index (HI) HI of each sample is then calculated by the following formula out：
HI=S2 × 100/TOC.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the aromatic carbon content faPass through
Formula (2) calculates：
Hc=-1.5183fa+179.32 (2)。
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the aliphatic chain carbon number CnPass through
Formula (3) calculates：
fa=-24.07ln (Cn)+85.556 (3)。
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the fragrant sulphur in the organic sulfur
Score fsIt is calculated by formula (4)：
fs=0.7112fa+20.89 (4)。
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the aromatic carbon in the fragrance cluster
Number CaIt is calculated by formula (5)：
Ca=0.225fa+1.55 (5)。
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the initial kerogen average mark
Minor structure is constructed by following steps：
According to the total carbon number and aromatic carbon content f of the kerogen average molecular structure parametera, it is flat to calculate initial kerogen
Total fragrant carbon number in equal molecular structure, and according to the fragrant carbon number C in total fragrant carbon number and the fragrant clusteraIt calculates just
Fragrant number of clusters amount in beginning kerogen average molecular structure；
According to total carbon number of the kerogen average molecular structure parameter, carbon atom and heteroatomic atomic ratio, calculate just
Heteroatomic number in beginning kerogen average molecular structure, and each heteroatomic official is determined according to the heteroatomic existing forms
Type and quantity can be rolled into a ball；
By the aliphatic chain carbon number CnObtain amount of carbon atom between fragrant cluster in aliphatic chain and collateral aromatic carbon quantity
Ratio, and determine the average length of connection unit between fragrant cluster；
The fragrant cluster, heteroatom functional group are connected, and adjusts the structural parameters of aliphatic chain between fragrant cluster, is constructed initial
Kerogen average molecular structure；The structural parameters of the aliphatic chain include at least one of bond distance, bond angle and dihedral angle.It is preferred that
Ground, connection unit are that carbon number is CnAliphatic chain.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the kerogen mean molecule knot
Total carbon number of structure parameter is 150-250.Total carbon number of kerogen average molecular structure determines kerogen average molecular structure
Size, kerogen average molecular structure has minimum dimension limitation, undersized rationally to reflect kerogenic structure
Composition and physicochemical properties.Kerogen average molecular structure size is bigger, and analog in nature is more accurate, but the corresponding calculating time
It is longer.Comprehensively consider minimum dimension effect and simulation calculates economy principle, the kerogen mean molecule knot that this specification determines
Total carbon number range of structure is 150-250, and when practical application can randomly choose in this range.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the construction method further includes using
Molecular Simulation Technique optimizes the step of kerogen average molecular structure model.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the Molecular Simulation Technique includes
At least one of geometry optimization, annealing optimization and molecular dynamics relaxation.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the construction method further includes building
The step of kerogen three-dimensional separation flow；
Specially：It is required and is simulated to calculate economy principle according to the minimum dimension of kerogen three-dimensional separation flow, really
Determine the quantity of kerogen average molecular structure model in three-dimensional simulation box, and establishes initial kerogen three in low density condition
Tie up molecular model；Geometry optimization is carried out to the initial kerogen three-dimensional separation flow, to obtain the minimum structure of local energy
Then type carries out annealing optimization, to obtain the minimum configuration of global energy；At the target pressure in order, the global energy is minimum
Configuration from high temperature (1000K) to target temperature, molecular dynamics relaxation is gradually carried out using NPT assemblage, is obtained final dry
Junket root three-dimensional separation flow.
Wherein, minimum dimension requires to refer to atomic quantity≤1300, and model side length≤2.5nm, low density condition refers to close
Degree≤0.10.1g/cm3, the high temperature of molecular dynamics relaxation is 1000K.Goal pressure and target temperature can be according to shale institutes
It is determined in geological environment.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the construction method further includes to institute
State the step of kerogen three-dimensional separation flow carries out reasonability and representative test.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the method for inspection is to described dry
Junket root three-dimensional separation flow carries out thermodynamic property and the simulation of hole property, and compares with experimental result.
In the construction method of above-mentioned kerogen average molecular structure model, it is preferable that the thermodynamic property includes
Phsyical density and isothermal compressibility, the hole property includes porosity.
This specification also provides a kind of kerogen average molecular structure model, by above-mentioned kerogen average molecular structure mould
The construction method of type constructs.
This specification also provides a kind of kerogen three-dimensional separation flow, is based on above-mentioned kerogen average molecular structure mould
The three-dimensional kerogen average molecular structure model of type building.The minimum dimension for being typically based on molecular model requires and the meter of simulation
Economy principle is calculated, 10 or so kerogen average molecular structure model foundation said three-dimensional body phase kerogen mean molecule knots are chosen
Structure model.
The construction method for the kerogen average molecular structure model that this specification provides, there are following beneficial effects：
The construction method for the kerogen average molecular structure model that this specification provides, it is only necessary to the hydrogen index (HI) number of shale samples
According to can quickly obtain the kerogen average molecular parameters of same type muti-piece shale samples.Based on advanced structural characterization hand
Section, can accurately obtain the element existing forms of single kerogen sample.And the structure before kerogen sample broke is remained as far as possible
Information.
Secondly, the construction method of the kerogen average molecular structure model proposes a set of new structural parameters definition, knot
The fitting areal calculation for closing FTIR chromatogram characteristic peak obtains kerogenic structural parameters, according to the carbonyl score of definition, alcohol radical point
Several and ether score calculation method quantitative analysis has gone out the amount of the existing forms of oxygen and each form oxygen-containing group in kerogen.And its
Fatty chain length, aromatic carbon rate and fragrant cluster cohesion degree in middle kerogen structure parameter can the kerogenic chemistry knots of qualitative analysis
Structure, and the average molecular parameters obtained with empirical equation (1)-(5) are mutually authenticated, and make the kerogen average molecular structure pair of building
True shale kerogen has good representativeness.
Furthermore the kerogen average molecular structure constructed by above-mentioned construction method is same type kerogen sample
Reasonable average molecular structure can be used for subsequent from the storage of micro-scale research shale gas, transmitting and the mechanism for improving recovery ratio.
In addition, the construction method economy for the kerogen average molecular structure model that this specification provides, simplicity, the quick structure of energy
It builds, and transplantation type is strong, quickly, at low cost can determine that representative kerogen molecular model provides theory for specific Shale Region block
Guidance.
Detailed description of the invention
Fig. 1 is 1 shale kerogen average molecular structure model construction process of embodiment；
Fig. 2 is the kerogenic FTIR spectrogram of embodiment 1N201-2 Longma small stream group shale and functional group's distribution；
Fig. 3 is the fitting of embodiment 1N201-2 Longma small stream group shale kerogen FTIR spectrogram swarming；
Fig. 4 is the Longma small stream group shale kerogen average molecular structure model that embodiment 1 constructs；
Fig. 5 is the Longma small stream group shale three-dimensional kerogen molecular structure model that embodiment 1 constructs.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out following detailed description, but should not be understood as the restriction to enforceable range of the present invention.
Embodiment 1
A kind of construction method of kerogen average molecular structure model is present embodiments provided, with Sichuan Basin Longma small stream
Group shale samples are as research object, and the process of specific construction method is as shown in Figure 1, include the following steps：
(1) 10 pieces of Sichuan Basin Longma small stream group shale samples are taken, by sample comminution to size less than 100 mesh, by 1-2g powder
Last sample is heated to 540 DEG C in LECO CS230 carbon/sulphur content analyzer, the TOC content of test sample, by 100mg powder sample
600 DEG C are heated to from 90 DEG C in Evaluation of Oil And Gas (OGE) work station, the pyrolysis hydrocarbon content (S2) of sample is obtained, according to formula HI
The hydrogen index (HI) (HI) of sample is calculated in=S2 × 100/TOC.Table 2 is the hydrogen index (HI) that sample is pyrolyzed test result and calculating
(HI)。
Table 2
(2) based on shale kerogen structure parameter calculation formula (1)-(5) in table 3, the hydrogen index (HI) obtained in conjunction with table 2 (HI)
Calculate the kerogenic average molecular parameters of Longma small stream group shale, including H/C atomic ratio (Hc), aromatic carbon content (fa), aliphatic chain carbon
Number (Cn), the fragrant sulphur content number (f in organic sulfurs), the fragrant carbon number (C in fragrant clustera).Calculated result is as shown in table 4.
Table 3
| Numbering of equation | Calculation formula | The degree of correlation/R2 |
| 1 | Hc=0.1426HI+49.143 | 0.9525 |
| 2 | Hc=-1.5183fa+179.32 | 0.9188 |
| 3 | fa=-24.07ln (Cn)+85.556 | 0.941 |
| 4 | fs=0.7112fa+20.89 | 0.8906 |
| 5 | Ca=0.225fa+1.55 | 0.8404 |
Table 4
| Sample number into spectrum | H/C (%) | fa(%) | Cn | fs(%) | Ca |
| N201-1 | 49.46 | 85.53 | 1.00 | 81.72 | 20.79 |
| N201-2 | 49.47 | 85.53 | 1.00 | 81.72 | 20.79 |
| N201-3 | 49.28 | 85.65 | 1.00 | 81.80 | 20.82 |
| N201-4 | 49.35 | 85.61 | 1.00 | 81.77 | 20.81 |
| N201-5 | 49.33 | 85.61 | 1.00 | 81.78 | 20.81 |
| N201-6 | 49.29 | 85.64 | 1.00 | 81.80 | 20.82 |
| CQ-1 | 49.31 | 85.63 | 1.00 | 81.79 | 20.82 |
| CQ-2 | 49.37 | 85.59 | 1.00 | 81.76 | 20.81 |
| CQ-3 | 49.24 | 85.67 | 1.00 | 81.82 | 20.83 |
| CQ-4 | 49.45 | 85.54 | 1.00 | 81.72 | 20.80 |
| Average value | 49.36 | 85.60 | 1.00 | 81.77 | 20.81 |
As shown in Table 4, the kerogen structure parameter differences of 10 pieces of shale samples of Longma small stream group are smaller, this is conducive to building one
A average Longma small stream group shale kerogen molecular structure.The kerogen structure parameter of 10 pieces of shale samples is averaged, is obtained
The molecular structural parameter average to Longma small stream group rock kerogen, the wherein fragrant sulphur content number (f in organic sulfurs) it is up to 81.77%,
Therefore, Main Morphology existing for sulphur in fragrant 10 pieces of shale samples of sulphur Longma small stream group.
(3) N201-2 slate flour sample is taken at random, extracts removal pitch group in Soxhlet extractor first with chloroform
Point, then using the inorganic mineral in the method removing shale samples of pickling step by step, obtain N201-2 shale kerogen sample.
In acid cleaning process, uses concentration to remove the carbonate mineral in sample for the HCl solution of 20wt% first, sample is taken out
Filter, washing, drying；Then use concentration for the HNO of 20wt%3Solution removes the pyrite in sample, sample is filtered,
Washing, drying；Finally use the mixed acid solution (volume ratio 1 of HCl (20wt%) and HF (40wt%):1) it removes in sample
Silicate mineral filters sample, is washed, is dried, and N201-2 shale kerogen sample is obtained.Wherein HCL processing is used for
Remove the carbonate mineral in shale, HNO3Processing is for removing pyrite, and HCL/HF processing is for removing silicate mineral.
(4) C, H, O, N, S elemental analysis are carried out to N201-2 shale kerogen sample, it here can be in conjunction in step 5
Then xps energy spectrum analysis method calculates separately the atomic ratio of H/C, O/C, N/C and S/C.Calculated result is as shown in table 5.
Table 5
| Atomic ratio | H/C | O/C | N/C | S/C |
| N201-2 | 0.494 | 0.047 | 0.02 | 0.035 |
(5) XPS test is carried out to N201-2 shale kerogen sample, and to the N 1s signal (397- on xps energy spectrum
Swarming fitting 404ev) is carried out, determine nitrogen in kerogen is primarily present form.Table 6 is the N201-2 shale cheese being calculated
The existing forms of nitrogen in root.
Table 6
| Nitrogen form | Pyrroles | Pyridine | Quaternary nitrogen |
| Molar fraction (%) | 62 | 15 | 23 |
As shown in Table 6, the nitrogen in N201-2 shale kerogen mainly exists in the form of pyrroles.
(6) FTIR spectrum test is carried out to N201-2 shale kerogen sample, obtains its FTIR spectrogram, as shown in Fig. 2, its
In (1) section spectrogram indicate water in hydroxyl；(2) section spectrogram indicates fragrance CHx；(3) section spectrogram indicates fat CHx；(4) section spectrogram table
Show carbonyl；(5) section spectrogram indicates aromatic carbon；(6) section spectrogram indicates fat CHx plane inner bending；(7) section spectrogram indicates alcoholic extract hydroxyl group
And ether；(8) section spectrogram indicates fragrance CHx surface deformation.To 3000-2800cm in FTIR spectrogram-1Between peak carry out swarming
Fitting, as shown in figure 3, and the fitting area of each characteristic peak is calculated, the structural parameters in conjunction with table 1 based on FTIR spectrum are fixed
Justice calculates the fatty chain length (CL) of N201-2 shale kerogen sample, using same method, believes aromatic carbon signal, carbonyl
Number, the characteristic peak of alcohol radical signal, the common group signal of ether signal hetero atom carries out swarming fitting, and calculates each characteristic peak peak face
Product is defined then in conjunction with table 1 based on the structural parameters of FTIR spectrum, calculate aromatic carbon rate (AR), fragrant cluster cohesion degree (DOC),
Carbonyl score Oca, alcohol radical score OalWith ether score OetEqual N201-2 shale kerogen sample kerogen microstructure parameter, meter
The results are shown in Table 7 for calculation.
Table 7
| Sample number into spectrum | CL | AR (%) | DOC | Oca(%) | Oet(%) | Oal(%) |
| N201-2 | 1.65 | 83.45 | 0.95 | 0.00 | 100.00 | 0.00 |
As shown in Table 7, fatty chain length CL (for 1.65) is smaller in N201-2 shale kerogen, show aliphatic chain mainly with
Short chain form exists, and aromatic carbon rate AR has reached 83.45%, and therefore, aromatic carbon is in N201-2 shale kerogen sample structure
Most important carbon type, fragrant cluster cohesion degree DOC (for 0.95) then show fragrant in N201-2 shale kerogen sample structure
Cluster size is larger.Table 7 is passed through based on formula (1)-(5) by the N201-2 shale kerogen structure information and table 4 that FTIR is obtained
Obtained average molecular parameters are compared, as a result more consistent, this further demonstrates the strong applicability of 1 formula of table.Table 7
In oxygen-containing functional group the result shows that, for the N201-2 shale kerogen of post-mature degree, ether is unique oxygen-containing functional group.
(7) according to table 4 obtain Longma small stream group shale kerogen average molecular parameters, table 5 kerogen Elements Atom ratio,
Table 6, table 7 and O, N and S are primarily present form, construct kerogenic initial average molecular structure.
Kerogen structure construction step is：
The total carbon number for determining Longma small stream group kerogen average molecular structure is 194, by aromatic carbon content (fa) determine structure
In aromatic carbon quantity be 166；
According to kerogen Elements Atom ratio as a result, determining that H, O, N and S atom number are respectively 96,9,4 and 7 in structure；
It is primarily present form based on hetero atom, determines type functional group and the quantity of O, N and S atom, in kerogen structure
There are 9 ethers, 3 pyrroles, 1 pyridine, 6 fragrant sulphur, 1 fatty sulphur；
By the fragrant carbon number (C in total fragrant carbon number and fragrant clustera), determine that the fragrant number of clusters mesh in structure is 8；
By aliphatic chain carbon number (Cn), determine that the connection unit type between fragrance cluster is mainly the short chain of fat of 2 carbon atoms；
Fragrant cluster is connected, and adjusts the parameters such as bond distance, bond angle, dihedral angle, the initial kerogen average mark constructed
Minor structure, as shown in Figure 4.
(8) it is based on the initial average molecular structure of kerogen, keeps fragrant clustering architecture constant, constantly adjusts the fat in structure
Thus carbon atom and heteroatom functional group obtain most until the experimental result of the structural parameters and table 4- table 7 of model is more consistent
Whole Longma small stream group shale kerogen average molecular structure model.Table 8 is final Longma small stream group shale kerogen mean molecule
The comparison of structural model structural parameters and experimental result.
Table 8
As shown in Table 8, the structural parameters of the Longma small stream group shale kerogen average molecular structure model of building and experiment are tied
Fruit more coincide, and shows that the Longma small stream group shale kerogen average molecular structure model of building has stronger representativeness.
(9) using molecular simulations means such as geometry optimization, annealing optimization and molecular dynamics relaxation to Longma small stream group page
Rock kerogen average molecular structure model carries out configuration optimization, and the minimum dimension based on molecular model requires and the calculating of simulation
Economy principle chooses 10 kerogenic average molecular structures and constructs Longma small stream group shale said three-dimensional body phase kerogen molecular structure
Model, as shown in Figure 5.Then to the phsyical density of the Longma small stream group shale said three-dimensional body phase kerogen molecular structure model, isothermal
The holes property such as the thermodynamic properties such as the compressed coefficient and porosity is simulated, and is compared with experimental result to examine mould
The reasonability and representativeness of type.Table 9 is the thermodynamic property of simulation and the comparison of hole property and experimental result.
Table 9
| Property | Density (g/cm3) | Isothermal compressibility (Pa-1) | Porosity |
| Analog result | 1.226-1.261 | 3.8×10-10 | 17.25 |
| Experimental result | 1.21-1.28 | 2-7.2×10-10 | 4.45-22.50 |
As shown in Table 9, it is using the Longma small stream group shale kerogen average molecular structure model that the present embodiment method constructs
The physical property and experimental result of the kerogenic said three-dimensional body phase molecule model constructed based on this model are almost the same, this shows this
The method of embodiment can be used in constructing representative kerogen average molecular structure model.
In conclusion the construction method for the kerogen average molecular structure model that this specification provides, it is only necessary to shale samples
Hydrogen index (HI) data, can quickly obtain the kerogen average molecular parameters of same type muti-piece shale samples.Based on advanced
Structural characterization means can accurately obtain the element existing forms of single kerogen sample.And it is broken to remain kerogen sample as far as possible
Structural information before bad.It is fixed that a set of new structural parameters are proposed according to the construction method of the kerogen average molecular structure model
Kerogenic microstructure parameter can be calculated in conjunction with the fitting area at FTIR chromatogram characteristic peak, according to the carbonyl of definition in justice
It is oxygen-containing that base score, alcohol radical score and ether score calculation method quantitative analysis have gone out the existing forms of oxygen and each form in kerogen
The amount of group.And wherein the fatty chain length in kerogen structure parameter, aromatic carbon rate and fragrant cluster cohesion degree can qualitative analyses
Kerogenic chemical structure, and the average molecular parameters obtained with empirical equation (1)-(5) are mutually authenticated, and make the kerogen of building
Average molecular structure has good representativeness to true shale kerogen.The kerogen constructed by above-mentioned construction method is average
Molecular structure is the reasonable average molecular structure of same type kerogen sample, be can be used for subsequent from micro-scale research shale
Gas storage, transmitting and the mechanism for improving recovery ratio.
In addition, the construction method economy for the kerogen average molecular structure model that this specification provides, simplicity, the quick structure of energy
It builds, and transplantation type is strong, quickly, at low cost can determine that representative kerogen molecular model provides theory for specific Shale Region block
Guidance.There is considerable application prospect in fields such as oil exploitations.
To keep the above objects, features, and advantages of this specification more obvious and easy to understand, above in conjunction with attached drawing to this theory
The specific embodiment of bright book is described in detail.Elaborate many details in the above description in order to fully understand
This specification.But this specification can be implemented with being much different from other way described above, those skilled in the art
Similar improvement can be done without prejudice to this specification intension, therefore this specification is not by specific implementation disclosed above
The limitation of example.Also, each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not right
The all possible combination of each technical characteristic in above-described embodiment is all described, as long as however, the group of these technical characteristics
It closes and contradiction is not present, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
The limitation to this specification the scope of the patents therefore cannot be interpreted as.It should be pointed out that for the ordinary skill people of this field
For member, under the premise of not departing from this specification design, various modifications and improvements can be made, these belong to this explanation
The protection scope of book.Therefore, the scope of protection shall be subject to the appended claims for this specification patent.
Claims (10)
1. a kind of construction method of kerogen average molecular structure model comprising following steps：
Step 1：The total organic carbon amount TOC and pyrolysis hydrocarbon content S2 for obtaining the same area muti-piece slate flour sample, calculate various kinds
The hydrogen index (HI) HI of product, and calculate by hydrogen index (HI) HI the kerogen average molecular structure parameter of the block shale；
Step 2：It extracts the kerogen sample at least one slate flour sample and carries out xps energy spectrum analysis and FTIR spectrum point
Analysis judges element composition in the kerogen sample, carbon atom and heteroatomic atom when heteroatomic existing forms；
And the kerogen sample is calculated based on the characteristic peak of group each in FTIR spectrum fitting peak area according to the following formula
The kerogen microstructure parameter of product：
Wherein, SPkFor k-th of kerogen microstructure parameter；PAiFor the fitting area at A class group ith feature peak；PBjFor B
The fitting area of j-th of characteristic peak of class group；N and M is respectively the characteristic peak number of A class group and B class group；The A class base
Group and B class group are to determine SPkRelated group；
Step 3：The total carbon number for determining the kerogen average molecular structure constructs initial kerogen average molecular structure；
Step 4：It keeps main carbon backbone structure and heteroatom functional group type constant, it is average constantly to adjust the initial kerogen
Each fat chain structure and heteroatom functional cumularsharolith in molecular structure are set, until model structure parameter adjusted and XPS and
FTIR experimental result and calculated result relative error based on hydrogen index (HI) HI are to obtain the dry of the region shale within 5%
Junket root average molecular structure model；
Wherein, the hetero atom is the atom in addition to hydrocarbon.
2. the construction method of kerogen average molecular structure model according to claim 1, it is characterised in that：The cheese
The kerogen microstructure parameter of root sample includes fatty chain length CL, and aromatic carbon rate AR, fragrant cluster agglomerates degree DOC, carbonyl point
Number Oca, alcohol radical score OalWith ether score OetAt least one of；
Preferably, the kerogen microstructure parameter of the kerogen sample is calculated by the physical definition of table 1：
Table 1
3. the construction method of kerogen average molecular structure model according to claim 1 or 2, it is characterised in that：
The hetero atom includes at least one of O, N and S；
Preferably, by the N1s swarming on the xps energy spectrum, the quantitative analysis after being fitted determines the existing forms of the N atom；
Preferably, the existing forms of the N atom include at least one of pyrroles, pyridine and quaternary nitrogen；
Preferably, the existing forms of the O atom by each oxygen-containing group in the kerogen microstructure parameter accounting percentage
Number quantitative analysis determines；
Preferably, the oxygen-containing group includes at least one of carbonyl, alcohol radical and ether；
Preferably, the existing forms of the S atom are by the fragrant sulphur in organic sulfur in the kerogen average molecular structure parameter
Score fsIt is determined with fatty sulphur content number；
Preferably, the fragrant methylthio group is thiophene, and the fat methylthio group is thioether.
4. the construction method of kerogen average molecular structure model according to claim 1, it is characterised in that：The cheese
Root average molecular structure parameter includes H/C atomic ratio Hc, aromatic carbon content fa, aliphatic chain carbon number Cn, fragrant sulphur content in organic sulfur
Number fsWith the fragrant carbon number C in fragrant clustera；
Preferably, the H/C atomic ratio HcIt is calculated by formula (1)：
Hc=0.1426HI+49.143 (1)；
Preferably, the aromatic carbon content faIt is calculated by formula (2)：
Hc=-1.5183fa+179.32 (2)；
Preferably, the aliphatic chain carbon number CnIt is calculated by formula (3)：
fa=-24.07ln (Cn)+85.556 (3)；
Preferably, the fragrant sulphur content number f in the organic sulfursIt is calculated by formula (4)：
fs=0.7112fa+20.89 (4)；
Preferably, the fragrant carbon number C in the fragrant clusteraIt is calculated by formula (5)：
Ca=0.225fa+1.55 (5)。
5. the construction method of kerogen average molecular structure model according to claim 4, it is characterised in that：It is described initial
Kerogen average molecular structure is constructed by following steps：
According to the total carbon number and aromatic carbon content f of the kerogen average molecular structure parametera, calculate initial kerogen average mark
Total fragrant carbon number in minor structure, and according to the fragrant carbon number C in total fragrant carbon number and the fragrant clusteraIt calculates initial dry
Fragrant number of clusters amount in junket root average molecular structure；
According to total carbon number of the kerogen average molecular structure parameter, carbon atom and heteroatomic atomic ratio, calculate initial dry
Heteroatomic number in junket root average molecular structure, and each heteroatomic functional group is determined according to the heteroatomic existing forms
Type and quantity；
By the aliphatic chain carbon number CnThe ratio of the amount of carbon atom and collateral aromatic carbon quantity between fragrant cluster in aliphatic chain is obtained,
And determine the average length of connection unit between fragrant cluster；
The fragrant cluster, heteroatom functional group are connected, and adjusts the structural parameters of aliphatic chain between fragrant cluster, constructs initial cheese
Root average molecular structure；The structural parameters of the aliphatic chain include at least one of bond distance, bond angle and dihedral angle.
6. the construction method of kerogen average molecular structure model according to claim 1, it is characterised in that：The cheese
Total carbon number of root average molecular structure parameter is 150-250.
7. the construction method of kerogen average molecular structure model according to claim 1, it is characterised in that：The building side
Method further includes the steps that optimizing the kerogen average molecular structure model using Molecular Simulation Technique；
Preferably, the Molecular Simulation Technique includes at least one of geometry optimization, annealing optimization and molecular dynamics relaxation.
8. the construction method of kerogen average molecular structure model according to claim 1, it is characterised in that：The building side
Method further includes the steps that constructing kerogen three-dimensional separation flow：
Specially：It is required and is simulated to calculate economy principle according to the minimum dimension of kerogen three-dimensional separation flow, determine three
The quantity of kerogen average molecular structure model in dimension simulation box, and initial kerogen three-dimensional point is established in low density condition
Submodel；
Geometry optimization is carried out to the initial kerogen three-dimensional separation flow, to obtain the minimum configuration of local energy, then
Carry out annealing optimization, to obtain the minimum configuration of global energy；
At the target pressure in order, by the minimum configuration of the global energy from high temperature (1000K) to target temperature, NPT is gradually used
Assemblage carries out molecular dynamics relaxation, obtains final kerogen three-dimensional separation flow；
Preferably, which further includes the step that reasonability and representative test are carried out to the kerogen three-dimensional separation flow
Suddenly；
Preferably, which is to carry out thermodynamic property and hole property mould to the kerogen three-dimensional separation flow
It is quasi-, and compared with experimental result；
Preferably, the thermodynamic property includes phsyical density and isothermal compressibility, and the hole property includes porosity.
9. a kind of kerogen average molecular structure model, by any one of the claim 1-8 kerogen average molecular structure
The construction method of model constructs.
10. a kind of kerogen three-dimensional separation flow is based on kerogen average molecular structure model structure as claimed in claim 9
The three-dimensional kerogen average molecular structure model built.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110211144A (en) * | 2019-06-10 | 2019-09-06 | 中国石油大学(华东) | A kind of mud shale scanning electron microscopic picture hole extracting method and system |
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| CN111912960B (en) * | 2020-08-24 | 2022-11-08 | 东北石油大学 | Quantitative evaluation method and system for kerogen free oil in shale |
| CN112014345A (en) * | 2020-08-31 | 2020-12-01 | 重庆科技学院 | Kerogen type division method based on FTIR analysis |
| CN113903230A (en) * | 2021-11-19 | 2022-01-07 | 中国矿业大学 | Method for constructing coal macromolecule 2D structure model |
| CN113903230B (en) * | 2021-11-19 | 2024-01-30 | 中国矿业大学 | Method for constructing coal macromolecule 2D structure model |
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