CN106248521A - The hot authentication method of Organic Matter In Sediments early diagenesis evolution grade - Google Patents
The hot authentication method of Organic Matter In Sediments early diagenesis evolution grade Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
Abstract
The present invention relates to the authentication method of Organic Matter In Sediments diagenesis evolution degree, specifically disclose the hot authentication method of a kind of Organic Matter In Sediments early diagenesis evolution grade.The method includes: the pretreatment of sediment sample；Sediment sample thermogravimetric analysis；Sediment sample differential calorimetric scan；TGA collection of illustrative plates interprets, and obtains heating index；DSC collection of illustrative plates interprets, and obtains heating index；And organic matter is combined the quantitative analysis at peak with mineral.The method is by detecting the energy variation of Organic Matter In Sediments difference pyrolysis phase, the problem of thermal transition behavior adjoint in quantitative analysis Organic Matter In Sediments pyrolytic process, and analyze the stability that Organic Matter In Sediments is combined with mineral, thus set up the method using hot analysis and characterization Organic Matter In Sediments early diagenesis evolution grade.
Description
Technical field
The present invention relates to the authentication method of Organic Matter In Sediments diagenesis evolution degree, be specifically related to a kind of Organic Matter In Sediments
The hot authentication method of early diagenesis evolution grade.
Background technology
The organic thermal evolution of continental sedimentary basin is that it forms the important mechanism of oil under geology-ground effect.Right
The understanding of Effects of Organic Matter in Sediments thermal evolution characteristic is the important foundation analyzing oil formation mechenism.At present to petroleum gas
The report of formation mechenism is broadly divided into two kinds of theories: one is, kerogen thermal degradation in late period hydrocarbon theory mode, by extensively
General being applied to explains conventional oil, the formation of natural gas, evolution and the regularity of distribution.Two are, low-mature oil thermal evolution hydrocarbon pattern,
It is primarily upon the organic contribution to oil-gas formation of diagenesis-hypogenesis commitment.DSC and TGA etc. are senior, and heat is analyzed
The means experimental result to continental sedimentary basin Effects of Organic Matter in Sediments, can be the second mechanism " Organic Material Thermal Evolution " process
New information is provided.
Rock pyrolysis technology is currently the important technology of gentle high temperature pyrolysis in research Organic Matter In Sediments, and this technology is initial
It is used for studying sedimentary rock and kerogen, has been generalized to characterize in the organic Quality Research of modern ground thing.Brucellosis
The principle solved is in special pyrolysis furnace, carries out temperature programming to analyzing sample, makes the hydro carbons in sample and kerogen not
Synthermal lower volatilization and cracking, then by the purging of carrier gas, make hydrocarbon gas and the sample residue volatilizing in sample and cracking
Realize physical separation qualitatively.Its first characteristic peak (S1, less than 300 DEG C) correspond to the amount of free hydro carbons, second feature
(S2, between 300 to 600 DEG C) then represents the hydro carbons from kerogen cracking at peak.The structure in each stage of rock pyrolysis analysis turns
Become, pyrolysis peak temperature, the volatility organic components of release all studies have reported that, but rock pyrolysis cannot obtain in pyrolytic process
Thermodynamics information, it is impossible to detect that the heat absorption of each pyrolytic process, heat release are dynamic, Organic Matter In Sediments therefore can not be detected
The thermal transition behavior being not accompanied by weightlessness of the generation in pyrolytic process, it is impossible to analytical thermodynamics information and the pass of thermal decomposition process
System.
Summary of the invention
It is an object of the invention to for problems of the prior art, it is provided that a kind of by detecting Organic Matter In Sediments not
With the energy variation of pyrolysis phase, the problem of thermal transition behavior adjoint in quantitative analysis Organic Matter In Sediments pyrolytic process, with
And analyze the stability that Organic Matter In Sediments is combined with mineral, thus set up the hot analysis and characterization Organic Matter In Sediments of use in early days
The method of diagenesis evolution degree.
For achieving the above object, the solution of the present invention is: in continental sedimentary basin, Organic Matter In Sediments early diagenesis develops
The hot authentication method of degree, comprises the following steps:
Step one, the pretreatment of sediment sample
The column core of sediments collected is separated respectively, is respectively charged into expendable sealing bag；Weigh after lyophilization,
Grinding, freezing is sealed up for safekeeping standby；
Step 2, sediment sample thermogravimetric analysis (TGA)
Sediment sample through pretreatment is placed among platinum pallet, thermogravimetric analyzer (TGA) carries out heat analysis
Obtain TGA curve；
Step 3, sediment sample differential calorimetric scan (DSC)
Sediment sample through pretreatment is placed among standard aluminum dish, differential calorimetric scan instrument (DSC) carries out heat
Analyze and obtain DSC collection of illustrative plates；
Step 4, TGA collection of illustrative plates interpret, and obtain heating index
The TGA curve that step 2 obtains, obtains DTG curve by derivative analysis, analyzes the main heat of acquisition by onset and loses
The weight starting point at peak, terminal and peak temperature, then obtain the weight loss at main thermal weight loss peak by line integral analysis；
Step 5, DSC collection of illustrative plates interpret, and obtain heating index
The DSC collection of illustrative plates that step 4 obtains, analyzed by onset obtain principal endothermic peak and the starting point of exothermic peak, terminal and
Peak temperature, then obtains the energy variation of main thermal process by line integral analysis；
Step 6, the organic quantitative analysis being combined peak with mineral
DSC has two main endothermic peaks that the weightless peak main with DTG two is relative, and main in the two
Before endothermic peak occurs, there are two secondary endothermic peaks, be not accompanied by the most weightless process；
The main endothermic peak of said two represents the pyrolysis situation of organic matter, and the endothermic peak that said two is secondary has represent
Machine matter and the combination situation of clay mineral, they exist only in the sediment sample that deeper the sedimentary age is more long, enter it
Row quantitative analysis, is used for evaluating Organic Matter In Sediments early diagenesis evolution grade.
Described column core of sediments is separated with 1-3cm.
In described step one, polished sediment sample, cross 80-100 mesh sieve.
The amount of the deposit of the pretreatment in described step 2 and step 3 is 9.5-10.5mg, preferably 9.8-
10.2mg.In TGA and DSC test process, the precision of TGA curve and DSC collection of illustrative plates is affected relatively big by the amount of deposit, and it is suitable to select
Sediment yield be conducive to the accuracy of authentication method.
Described step 4 uses Universal Analysis 2000 software that TGA curve is carried out Treatment Analysis.
Described step 5 uses Universal Analysis 2000 software that DSC collection of illustrative plates is carried out Treatment Analysis.
Described thermogravimetric analysis, scans sample in a nitrogen atmosphere, each specimen disc from room temperature with 10-20 DEG C of min-1Speed
Rate is warming up to 110-130 DEG C, and keeps 30-60min, is cooled to room temperature, to remove the physical absorption water in sample；Thermogravimetric is divided
Analysis program is with 10-15 DEG C of min-1Speed from room temperature to 600-1000 DEG C.
Described differential scanning calorimetry, is carried out under nitrogen atmosphere encloses, and the powder sample through pretreatment is put into mark
In quasi-aluminum dish, the weight of specimen disc and comparing disk all through and being weighed, to improve DSC precision, it is ensured that its of poor quality 0.1mg it
In；Each specimen disc from room temperature with 10-20 DEG C of min-1Ramp to 110-130 DEG C, and keep 30-60min, then cool down
To room temperature, to remove the physical absorption water in sample；The sample analysis program of DSC is with 10-15 DEG C of min-1Speed from room temperature liter
To 600-1000 DEG C.
In described thermogravimetric analysis and differential scanning calorimetry, specimen disc programming rate rate, warming temperature and point
The heating rate correspondence of analysis program is identical.
Preferably, in described thermogravimetric analysis, the flow of nitrogen is 80-100ml min-1, improve the accuracy of result.
Preferably, described differential scanning calorimetry, in DSC experimentation, aluminum dish is not added a cover, and uses bigger nitrogen
Throughput 80-100ml min-1, bring the most true of result with sample generation secondary response reducing gaseous products in experimentation
Qualitative.
Preferably, described method also includes that the total organic carbon to deposit (TOC) measures, and utilizes XRD detection deposition
Thing CLAY MINERALS AND THEIR SIGNIFICANCE component.TOC and main thermal weight loss do correlation analysis, determine the behavior that thermal weight loss is the most organic；XRD examines
Survey major clay minerals component, get rid of the impact of Mineral pairs thermal map spectrum signature.
The analytical plan of sediment sample is improved by the present invention by senior heat analysis method, by DSC energy variation
In peak, energy variation process and the correspondence caloritropic energy variation process of corresponding thermal weight loss are analyzed respectively, are applied to terrestrial facies
In the column core of sediments of sedimentary basin.The organic information with clay mineral bond strength can be extracted after improvement, and analyze
Go out combining information and gradually increase along with the sedimentary age, thus realize detecting the effect of Organic Matter In Sediments early diagenesis evolution grade
Really.
Accompanying drawing explanation
Fig. 1 sediment portion sample XRD figure is composed；
Fig. 2 G1+2With TOC correlation analysis；
Fig. 3 deposit thermal parameter buries the differentiation of the time limit along with deposit；
Typical DSC and the DTG thermal analysis curve of Fig. 4 tetra-kinds；
Fig. 5 F2With G2Linear relationship；
Wherein, in Fig. 1,1-quartz, 2-calcite, 3-aragonite, 4-plagioclase.
Detailed description of the invention
Term of the present invention and technology abbreviation:
TOC, total organic carbon, total organic carbon；
TGA, thermal gravity analysis, thermogravimetric analysis；
DSC, differential scanning calorimetry, differential calorimetric scan.
Embodiment 1
The hot authentication method of Organic Matter In Sediments early diagenesis evolution grade in continental sedimentary basin, comprises the following steps:
Step one, the pretreatment of sediment sample
Utilize portable gravity type sediment sampler, acquire the post core deposit of 60cm at Bosten, choose 20
Sheet, scene separates deposit with 3cm respectively, is respectively charged into expendable sealing bag, air in venting bag, transports laboratory back, deposition
Weighing after thing sample lyophilization, ground 80 mesh sieves, freezing is sealed up for safekeeping standby.
Step 2, sediment sample thermogravimetric analysis (TGA)
10.0mg is placed among platinum pallet through the sediment sample of pretreatment, thermogravimetric analyzer (TGA) carries out
Heat is analyzed and is obtained TGA curve；
Step 3, sediment sample differential calorimetric scan (DSC)
10.0mg is placed among standard aluminum dish through the sediment sample of pretreatment, by differential calorimetric scan instrument (DSC)
Carry out heat and analyze acquisition DSC collection of illustrative plates；
Step 4, TGA collection of illustrative plates interpret, and obtain heating index
Use Universal Analysis 2000 software to open TGA destination file, obtain DTG by derivative analysis bent
Line, is analyzed starting point, terminal and the peak temperature obtaining main thermal weight loss peak, is then obtained by line integral analysis by onset
The weight loss at main thermal weight loss peak；
Step 5, DSC collection of illustrative plates interpret, and obtain heating index
Use Universal Analysis 2000 software to open DSC destination file, analyzed by onset and obtain mainly
Endothermic peak and the starting point of exothermic peak, terminal and peak temperature, then obtain the energy quantitative change of main thermal process by line integral analysis
Change；
Step 6, the organic quantitative analysis being combined peak with mineral
DSC has two main endothermic peaks that the weightless peak main with DTG two is relative, and main in the two
Before endothermic peak occurs, there are two secondary endothermic peaks, be not accompanied by the most weightless process；
The main endothermic peak of said two represents the pyrolysis situation of organic matter, and the endothermic peak that said two is secondary has represent
Machine matter and the combination situation of clay mineral, they exist only in the sediment sample that deeper the sedimentary age is more long, enter it
Row quantitative analysis, is used for evaluating Organic Matter In Sediments early diagenesis evolution grade.
The method of the present embodiment also includes that the total organic carbon to deposit (TOC) measures, and utilizes XRD to detect deposit
CLAY MINERALS AND THEIR SIGNIFICANCE component, as the reference information analyzed.TOC measure utilize total organic carbon analyzer (TOC-VCPH type,
Shimadzu (Shimadzu) company).
Wherein, thermogravimetric analysis is to use TGA (the TGA Q50 thermogravimetric analyzer of TA instrument company) to assess sample thermal weight loss
Process and the method for physical absorption water content.
Thermogravimetric analysis is at 80ml min-1Nitrogen atmosphere under scan sample, each specimen disc from room temperature with 10 DEG C of min-1
Ramp to 110 DEG C, and keep 30min, be cooled to room temperature, remove the physical absorption water in sample；Thermogravimetric analysis journey
Sequence is with 10 DEG C of min-1Speed from room temperature to 800 DEG C.
Differential scanning calorimetry DSC (the DSC Q20 differential calorimetric scan instrument of TA instrument company) is carried out.
Differential scanning calorimetry is at 80ml min-1Nitrogen atmosphere enclose under carry out, by the powder sample through pretreatment
Put into standard aluminum dish (Lot no.900786.901；TA instrument company) in, the weight of specimen disc and comparing disk is all passed through and is weighed,
To improve DSC precision, it is ensured that it is of poor quality within 0.1mg；Each specimen disc from room temperature with 10 DEG C of min-1Ramp extremely
110 DEG C, and keep 30min, it is cooled to room temperature, to remove the physical absorption water in sample；The sample analysis program of DSC is with 10
℃ min-1Speed rise to 600 DEG C from room temperature.
In DSC experimentation, aluminum dish is not added a cover, to reduce gaseous products and sample generation secondary response band in experimentation
Carry out the uncertainty of result.
Interpretation of result:
1, post core Ages of Sediments is analyzed
The age of deposit uses137Cs meter year method determines,137Cs is the artificial radloactive nucleus that blast is scattered in earth surface
Element, the half-life is 30.2, is widely used in Recent Lakes meter year.137The topmost feature of Cs is rising of air nuclear test
Nineteen fifty-two in age beginning, peak year 1963 generations and 1986 the Chernobyl nuclear leakage event of nuclear test produce137Cs is scattered
Peak.Report according to Liao Haiqing: in this post core deposit,137The Changing Pattern of Cs clearly, shows not exist in lake
Extensive disturbance, depositional environment is stable.Having obvious peak Distribution at the 60cm of post core, the global atmosphere representing 1964 is scattered
Fall to settling peak value.Thus calculate: post core sedimentation rate be 1.40mm/a, 60cm sedimentary column represent about 430 years deposition and
Early diagenesis evolutionary process.Sediment sample is according to 3cm mono-section layering, and therefore every layer of deposition process needing 21.5, each
The age of sediment sample is 21.5 numberings (table 1) being multiplied by layer.
2、XRD
Fig. 1 illustrates the XRD main clay mineral testing result of sample segment, calcite and quartz essential mineral group
Point, there is a small amount of aragonite and plagioclase simultaneously.In the sediment sample that age is more long, quartz accounts for greater proportion, and the age is near
In deposit, essential mineral gradually becomes calcite.
3、TGA
The present embodiment has carried out the thermogravimetric analysis of 20 sediment samples altogether.Organic pyrolytic process substantially occurs in
In 220-530 DEG C of this temperature range.The thermal weight loss process of sediment sample is broadly divided into 3 stages: first weightless process
G1Temperature range be that corresponding DTG peak temperature is 287 ± 14 (272.87,300.93) DEG C；Second weightless process G2's
Temperature range is 489 ± 14-516 ± 12 DEG C, and corresponding DTG peak temperature is 496 ± 17 (478.67,512.39) DEG C.Such as table 1
Shown in, G1And G2In temperature range, mass loss is respectively 3.10 ± 2.20% and 0.55 ± 0.40%.
Table 1 illustrates the thermogravimetric parameter of different depth sample.As it is shown in figure 1, G1And G2Summation G1,2Have well with TOC
Linear relationship (with r2=0.946, p < 0.001), illustrate that the pyrolysis of predominantly organic carbon is at G1And G2The two endothermic decomposition mistake
Journey is carried out.G1Peak can be with the pyrolysis behavior explanation of thermally labile carbon, and this part carbon is mainly fat present in organic matter
Race and carboxyl functional group.And G2The thermal decomposition containing aromatic structure molecule of the peak then main representative.
Its W as it is shown on figure 3, age deposit more remote is cut into slicesG2Proportion significantly greater than age shorter deposit cut
Sheet.Illustrate that the ratio relatively stablizing organic matter fraction gradually rises along with the increase of the degree of depth.
4、DSC
The differential thermal analysis of 20 sediment samples that this enforcement is carried out, DSC scanning result shows that the pyrolysis of organic matter is main
Occur in 220-540 DEG C of this temperature range.DSC curve can record the dissimilar spy of the thermal degradation heat absorption in each stage
Levy, and DTG record is thermal weight loss feature.
The DSC curve of sediment sample shows 4 characteristic peaks altogether: as shown in Fig. 5 and Biao 1, F1Peak temperature is 237.2
± 42.98 (194.22,280.18) DEG C, F1The temperature range at peak is 180-400 DEG C, and corresponding DTG peak is G1Peak, peak temperature
It it is 286.90 ± 14.03 DEG C；F2The temperature range of peak value is 456.56 ± 3.80；F3Peak temperature is 498.35 ± 30.09
(468.26,528.44), F3Temperature range be 456.72 ± 40.49 (416.23,497.2)-521.76 ± 14.15
(507.61,535.9) DEG C, corresponding DTG peak is G2Peak, peak temperature is 495.53 ± 16.86 (478.67,512.39) DEG C；F4
Peak temperature be 575.36 ± 0.50 (574.86,575.86).Wherein, F1、F3And F4It it is the main suction that has of each sample
Thermal spike, F2It it is the endothermic peak that only sample segment shows.F4It it is the alpha-quartz that the correspond to 573 DEG C endothermic peak to β-quartz inversion.
The pyrolysis of Stable Carbon gradually changes along with the increase of the sedimentary age, shows F1The change of peak feature, the most unstable
The evolution determining carbon shows as F2And F3The change of peak feature.F according to DSC1Labile carbon in pyrolysis peak, namely deposit
Feature, can by deposit section be divided into 3 main Types.As it is shown on figure 3, F1Along with the pillar degree of depth increases variation tendency
For, pillar epimere is the peak type (F of right side projection1bType), peak temperature is about 280 DEG C, such as 1#；Pillar stage casing is center protrusion
Peak type, peak temperature is about 250 DEG C, such as 7#；Pillar hypomere predominantly left side projection peak type (F1aType), peak temperature is 180
About DEG C, such as 14# and 17#.
F1It is by F1aAnd F1bTwo endothermic peak compositions, various years deposit F1aAnd F1bProportion difference create F1Go out
Existing flood wave type, F1Peak value occurs in the phenomenon in different temperatures.The contrast of DSC and DTG simultaneous is found, F1bCorrespond to G1Point
Xie Feng, therefore F1bIt is owing to the endothermic process that organic matter pyrolysis is adjoint produces；And F1aThere is no corresponding DTG peak, the most not
Owing to endothermic decomposition causes, and should be the precursor step of organic pyrolysis.
Calcite and quartz are the essential mineral components of this sediment sample, the thermal map spectrum of its DSC curve and deposit
Carry out relative analysis.Calcite and the DSC curve of quartz, outside quartz has an endothermic peak in addition to 575 DEG C, at 30-600 DEG C
In the range of there is no significant characteristic peak, thus without DSC characteristic peak being produced directly impact.
5, heat stability vertical distribution
F according to DSC2And F3The feature of Stable Carbon in peak, namely deposit, can be divided into 3 mainly by deposit section
Type.1-10# section only shows F3Peak (as a example by sample 1 and 7, such as Fig. 4), occurs for the first time from the section of 11# deposit sample
460.37 DEG C endothermic peak F2, and along with degree of depth increase is gradually increased.From the beginning of 14#, F2Increase to F3In the range of merge therewith
(as a example by sample 17, such as Fig. 4).From the beginning of 18#, F2And F3A peak F is shown as after fusion2,3.At the epimere of sedimentary column, F2To F3
Before peak produces impact, G2Thermogravimetric peak and F3The dependency (as shown in Figure 5) that endothermic peak has had, r2=0.923, p < 0.001, n=
13；But for whole sedimentary column, at F2To F3After peak produces impact, G2Weightless peak and F3The dependency of endothermic peak is the most very
Difference (as shown in Figure 5), r2=0.080, p=0.225, n=20.By the DSC-DTG relative analysis of each sample it is found that F3With
G2It is positioned at identical temperature scope, F2The most corresponding DTG peak.Therefore the F of DSC curve3Peak and the G of DTG curve2Peak generation
Table is same endothermic decomposition process, i.e. the Stable Carbon slow pyrolytic process of component anaerobism in the soil organism.And F2Should be
The endothermic processes such as phase in version, for F3Endothermic decomposition process accumulation energy, and F3Corresponding pyrolytic process is endothermic decomposition process.
The F of DSC1And F3There are significant change, F in peak along with the increase of the sedimentary column degree of depth1aAnd F2Proportion is all significantly increased.Explanation
Organic mineralization degree and heat stability are all being gradually increasing.
Along with the increase of sedimentary column sedimentation time, the heat stability of lake sediment organic carbon gradually steps up.Deep layer is organic
Carbon stability is higher, is because that deep layer deposit organic carbon is more to be bound by clay mineral, and this is deposit organic carbon and viscous
Chemical or that physical chemistry combines result between soil mineral.Organic stabilisation is the merit that mineral constituent chemical characteristic produces
Can, organic component can be adsorbed in the existence of polyvalent cation and the surface of mineral constituent.Mineral constituent is to organic absorption master
The intense beam binding force in multi-cellular structure, micropore is occurred to represent impossible adsorption process, because desorption speed is very
Low.This mechanism significantly reduces the bioavailability of organic matter.
By the method for the present embodiment, detection obtains two the pyrolysis rank identical with rock cracking process at the uniform velocity Study on Pyrolysis
Section, and DSC provides more detailed enthalpy change information the heat deflection process before pyrolysis being detected, and the heat of Organic Matter In Sediments is described
Stability was gradually increased along with the age, and the organic combination with mineral is also being gradually increased.
Embodiment 2
The hot authentication method of Organic Matter In Sediments early diagenesis evolution grade in continental sedimentary basin, comprises the following steps:
Step one, the pretreatment of sediment sample
The column core of sediments collected is separated with 1cm respectively, is respectively charged into expendable sealing bag；After lyophilization
Weighing, ground 80-100 mesh sieve, freezing is sealed up for safekeeping standby；
Step 2, sediment sample thermogravimetric analysis (TGA)
9.8mg is placed among platinum pallet through the sediment sample of pretreatment, thermogravimetric analyzer (TGA) carries out heat
Analyze and obtain TGA curve；
Step 3, sediment sample differential calorimetric scan (DSC)
9.8mg is placed among standard aluminum dish through the sediment sample of pretreatment, differential calorimetric scan instrument (DSC) enters
Row heat is analyzed and is obtained DSC collection of illustrative plates；
Step 4, TGA collection of illustrative plates interpret, and obtain heating index
Use Universal Analysis 2000 software to open TGA destination file, obtain DTG by derivative analysis bent
Line, is analyzed starting point, terminal and the peak temperature obtaining main thermal weight loss peak, is then obtained by line integral analysis by onset
The weight loss at main thermal weight loss peak；
Step 5, DSC collection of illustrative plates interpret, and obtain heating index
Use Universal Analysis 2000 software to open DSC destination file, analyzed by onset and obtain mainly
Endothermic peak and the starting point of exothermic peak, terminal and peak temperature, then obtain the energy quantitative change of main thermal process by line integral analysis
Change；
Step 6, the organic quantitative analysis being combined peak with mineral
DSC has two main endothermic peaks that the weightless peak main with DTG two is relative, and main in the two
Before endothermic peak occurs, there are two secondary endothermic peaks, be not accompanied by the most weightless process；
The main endothermic peak of said two represents the pyrolysis situation of organic matter, and the endothermic peak that said two is secondary has represent
Machine matter and the combination situation of clay mineral, they exist only in the sediment sample that deeper the sedimentary age is more long, enter it
Row quantitative analysis, is used for evaluating Organic Matter In Sediments early diagenesis evolution grade.
The method of the present embodiment also includes that the total organic carbon to deposit (TOC) measures, and utilizes XRD to detect deposit
CLAY MINERALS AND THEIR SIGNIFICANCE component, as the reference information analyzed.TOC measure utilize total organic carbon analyzer (TOC-VCPH type,
Shimadzu (Shimadzu) company).
Wherein, thermogravimetric analysis is to use TGA (the TGA Q50 thermogravimetric analyzer of TA instrument company) to assess sample thermal weight loss
Process and the method for physical absorption water content.
Thermogravimetric analysis is at 90ml min-1Nitrogen atmosphere under scan sample, each specimen disc from room temperature with 15 DEG C of min-1
Ramp to 120 DEG C, and keep 45min, be cooled to room temperature, remove the physical absorption water in sample；Thermogravimetric analysis journey
Sequence is with 12 DEG C of min-1Speed from room temperature to 600 DEG C.
Differential scanning calorimetry DSC (the DSC Q20 differential calorimetric scan instrument of TA instrument company) is carried out.
Differential scanning calorimetry is at 90ml min-1Nitrogen atmosphere enclose under carry out, by the powder sample through pretreatment
Put into standard aluminum dish (Lot no.900786.901；TA instrument company) in, the weight of specimen disc and comparing disk is all passed through and is weighed,
To improve DSC precision, it is ensured that it is of poor quality within 0.1mg；Each specimen disc from room temperature with 15 DEG C of min-1Ramp extremely
120 DEG C, and keep 45min, it is cooled to room temperature, to remove the physical absorption water in sample；The sample analysis program of DSC is with 12
℃ min-1Speed rise to 800 DEG C from room temperature.
In DSC experimentation, aluminum dish is not added a cover, to reduce gaseous products and sample generation secondary response band in experimentation
Carry out the uncertainty of result.
Embodiment 3
The hot authentication method of Organic Matter In Sediments early diagenesis evolution grade in continental sedimentary basin, comprises the following steps:
Step one, the pretreatment of sediment sample
The column core of sediments collected is separated with 2cm respectively, is respectively charged into expendable sealing bag；After lyophilization
Weighing, ground 80-100 mesh sieve, freezing is sealed up for safekeeping standby；
Step 2, sediment sample thermogravimetric analysis (TGA)
10.2mg is placed among platinum pallet through the sediment sample of pretreatment, thermogravimetric analyzer (TGA) carries out
Heat is analyzed and is obtained TGA curve；
Step 3, sediment sample differential calorimetric scan (DSC)
10.2mg is placed among standard aluminum dish through the sediment sample of pretreatment, by differential calorimetric scan instrument (DSC)
Carry out heat and analyze acquisition DSC collection of illustrative plates；
Step 4, TGA collection of illustrative plates interpret, and obtain heating index
Use Universal Analysis 2000 software to open TGA destination file, obtain DTG by derivative analysis bent
Line, is analyzed starting point, terminal and the peak temperature obtaining main thermal weight loss peak, is then obtained by line integral analysis by onset
The weight loss at main thermal weight loss peak；
Step 5, DSC collection of illustrative plates interpret, and obtain heating index
Use Universal Analysis 2000 software to open DSC destination file, analyzed by onset and obtain mainly
Endothermic peak and the starting point of exothermic peak, terminal and peak temperature, then obtain the energy quantitative change of main thermal process by line integral analysis
Change；
Step 6, the organic quantitative analysis being combined peak with mineral
DSC has two main endothermic peaks that the weightless peak main with DTG two is relative, and main in the two
Before endothermic peak occurs, there are two secondary endothermic peaks, be not accompanied by the most weightless process；
The main endothermic peak of said two represents the pyrolysis situation of organic matter, and the endothermic peak that said two is secondary has represent
Machine matter and the combination situation of clay mineral, they exist only in the sediment sample that deeper the sedimentary age is more long, enter it
Row quantitative analysis, is used for evaluating Organic Matter In Sediments early diagenesis evolution grade.
The method of the present embodiment also includes that the total organic carbon to deposit (TOC) measures, and utilizes XRD to detect deposit
CLAY MINERALS AND THEIR SIGNIFICANCE component, as the reference information analyzed.TOC measure utilize total organic carbon analyzer (TOC-VCPH type,
Shimadzu (Shimadzu) company).
Wherein, thermogravimetric analysis is to use TGA (the TGA Q50 thermogravimetric analyzer of TA instrument company) to assess sample thermal weight loss
Process and the method for physical absorption water content.
Thermogravimetric analysis is at 100ml min-1Nitrogen atmosphere under scan sample, each specimen disc from room temperature with 20 DEG C of min-1
Ramp to 130 DEG C, and keep 60min, be cooled to room temperature, remove the physical absorption water in sample；Thermogravimetric analysis journey
Sequence is with 15 DEG C of min-1Speed from room temperature to 1000 DEG C.
Differential scanning calorimetry DSC (the DSC Q20 differential calorimetric scan instrument of TA instrument company) is carried out.
Differential scanning calorimetry is at 100ml min-1Nitrogen atmosphere enclose under carry out, by the powder sample through pretreatment
Put into standard aluminum dish (Lot no.900786.901；TA instrument company) in, the weight of specimen disc and comparing disk is all passed through and is weighed,
To improve DSC precision, it is ensured that it is of poor quality within 0.1mg；Each specimen disc from room temperature with 20 DEG C of min-1Ramp extremely
130 DEG C, and keep 60min, it is cooled to room temperature, to remove the physical absorption water in sample；The sample analysis program of DSC is with 15
℃ min-1Speed rise to 1000 DEG C from room temperature.
In DSC experimentation, aluminum dish is not added a cover, to reduce gaseous products and sample generation secondary response band in experimentation
Carry out the uncertainty of result.
In a kind of continental sedimentary basin provided the embodiment of the present invention above, Organic Matter In Sediments early diagenesis develops
The hot authentication method of degree, is described in detail, and specific case used herein is to the principle of the present invention and embodiment
Being set forth, the explanation of above example is only intended to help to understand method and the core concept thereof of the present invention；Simultaneously for
One of ordinary skill in the art, according to the thought of the present invention, the most all can change it
Place, in sum, this specification content should not be construed as limitation of the present invention.
Claims (10)
1. the hot authentication method of Organic Matter In Sediments early diagenesis evolution grade in continental sedimentary basin, it is characterised in that include
Following steps:
Step one, the pretreatment of sediment sample
The column core of sediments collected is separated respectively, is respectively charged into expendable sealing bag, weighs after lyophilization, grind
Mill, freezing is sealed up for safekeeping standby；
Step 2, sediment sample thermogravimetric analysis
Sediment sample through pretreatment is placed among platinum pallet, thermogravimetric analyzer carries out heat and analyze acquisition TGA song
Line；
Step 3, sediment sample differential calorimetric scan
Sediment sample through pretreatment is placed among standard aluminum dish, differential calorimetric scan instrument carries out heat and analyze acquisition
DSC collection of illustrative plates；
Step 4, TGA collection of illustrative plates interpret, and obtain heating index
The TGA curve that step 2 obtains, obtains DTG curve by derivative analysis, is analyzed by onset and obtains main thermal weight loss peak
Starting point, terminal and peak temperature, then by line integral analysis obtain main thermal weight loss peak weight loss；
Step 5, DSC collection of illustrative plates interpret, and obtain heating index
The DSC collection of illustrative plates that step 4 obtains, is analyzed by onset and obtains principal endothermic peak and the starting point of exothermic peak, terminal and peak temperature
Degree, then obtains the energy variation of main thermal process by line integral analysis；
Step 6, the organic quantitative analysis being combined peak with mineral
DSC has two main endothermic peaks that the weightless peak main with DTG two is relative, and in the main heat absorption of the two
Before peak occurs, there are two secondary endothermic peaks, be not accompanied by the most weightless process；
The main endothermic peak of said two represents the pyrolysis situation of organic matter, and the endothermic peak that said two is secondary represents organic matter
With the combination situation of clay mineral, they exist only in the sediment sample that deeper the sedimentary age is more long, and it is fixed to carry out it
Component analysis, is used for evaluating Organic Matter In Sediments early diagenesis evolution grade.
Method the most according to claim 1, it is characterised in that described method also includes that the TOC to deposit measures, and
XRD is utilized to detect Clay Minerals in Sediments component.
Method the most according to claim 1, it is characterised in that described column core of sediments is separated with 1-3cm.
Method the most according to claim 1, it is characterised in that in described step one, polished sediment sample, mistake
80-100 mesh sieve.
Method the most according to claim 1, it is characterised in that the deposit of the pretreatment in described step 2 and step 3
Amount be 9.5-10.5mg, preferably 9.8-10.2mg.
Method the most according to claim 1, it is characterised in that described step 4 uses Universal Analysis
2000 softwares carry out Treatment Analysis to TGA curve；Described step 5 uses Universal Analysis 2000 software to DSC
Collection of illustrative plates carries out Treatment Analysis.
Method the most according to claim 1, it is characterised in that described thermogravimetric analysis, scans sample, often in a nitrogen atmosphere
Individual specimen disc from room temperature with 10-20 DEG C of min-1Ramp to 110-130 DEG C, and keep 30-60min, be cooled to room
Temperature；Thermogravimetric analysis program is with 10-15 DEG C of min-1Speed from room temperature to 600-1000 DEG C.
Method the most according to claim 7, it is characterised in that in described thermogravimetric analysis, the flow of nitrogen is 80-
100mlmin-1, improve the accuracy of result.
Method the most according to claim 7, it is characterised in that described differential scanning calorimetry, under nitrogen atmosphere encloses
Carrying out, put into by the powder sample through pretreatment in standard aluminum dish, the weight of specimen disc and comparing disk is all passed through and is weighed；Each
Specimen disc from room temperature with 10-20 DEG C of min-1Ramp to 110-130 DEG C, and keep 30-60min, be cooled to room temperature；
The sample analysis program of DSC is with 10-15 DEG C of min-1Speed rise to 600-1000 DEG C from room temperature；
In described differential scanning calorimetry, specimen disc heating rate, warming temperature and analyze program heating rate,
With in thermogravimetric analysis specimen disc programming rate rate, warming temperature and analyze program heating rate corresponding identical.
Method the most according to claim 9, it is characterised in that described differential scanning calorimetry, in DSC experimentation
Aluminum dish is not added a cover, and uses bigger nitrogen flow 80-100ml min-1, to reduce gaseous products and sample in experimentation
Secondary response is occurred to bring the uncertainty of result.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106896033A (en) * | 2017-04-26 | 2017-06-27 | 安徽理工大学 | A kind of method of the content of organic matter in measure gangue |
| CN107560994A (en) * | 2017-09-05 | 2018-01-09 | 中国石油大学(华东) | Aperture location mode in one kind evaluation mud shale organic matter, clay and other mineral |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4345913A (en) * | 1980-01-18 | 1982-08-24 | Eur-Control Kalle Ab | Method and apparatus for determining the lignin content in pulp |
| CN1837798A (en) * | 2006-04-27 | 2006-09-27 | 国家海洋局第一海洋研究所 | Measurer for oceanic sediment thermal conductivity in-situ measuring system |
| CN102706911A (en) * | 2011-05-11 | 2012-10-03 | 浙江长生鸟珍珠生物科技有限公司 | Method for detecting quality of pearl powder by using thermal transformation hemodynamic difference combined with X-ray diffraction (XRD) and application thereof |
| CN105203579A (en) * | 2015-09-14 | 2015-12-30 | 中国环境科学研究院 | Thermal analysis determination method for plant biomass lignin content |
-
2016
- 2016-07-11 CN CN201610542638.7A patent/CN106248521B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4345913A (en) * | 1980-01-18 | 1982-08-24 | Eur-Control Kalle Ab | Method and apparatus for determining the lignin content in pulp |
| CN1837798A (en) * | 2006-04-27 | 2006-09-27 | 国家海洋局第一海洋研究所 | Measurer for oceanic sediment thermal conductivity in-situ measuring system |
| CN102706911A (en) * | 2011-05-11 | 2012-10-03 | 浙江长生鸟珍珠生物科技有限公司 | Method for detecting quality of pearl powder by using thermal transformation hemodynamic difference combined with X-ray diffraction (XRD) and application thereof |
| CN105203579A (en) * | 2015-09-14 | 2015-12-30 | 中国环境科学研究院 | Thermal analysis determination method for plant biomass lignin content |
Non-Patent Citations (1)
| Title |
|---|
| 赵伟涛等: "《森林泥炭的热解特性及热解动力学》", 《物理化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106896033A (en) * | 2017-04-26 | 2017-06-27 | 安徽理工大学 | A kind of method of the content of organic matter in measure gangue |
| CN107560994A (en) * | 2017-09-05 | 2018-01-09 | 中国石油大学(华东) | Aperture location mode in one kind evaluation mud shale organic matter, clay and other mineral |
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