CN101858902B - Soil alteration carbonate measuring method integrating carbon isotope ratio - Google Patents
Soil alteration carbonate measuring method integrating carbon isotope ratio Download PDFInfo
- Publication number
- CN101858902B CN101858902B CN 201010193506 CN201010193506A CN101858902B CN 101858902 B CN101858902 B CN 101858902B CN 201010193506 CN201010193506 CN 201010193506 CN 201010193506 A CN201010193506 A CN 201010193506A CN 101858902 B CN101858902 B CN 101858902B
- Authority
- CN
- China
- Prior art keywords
- carbon isotope
- sample
- content
- isotope ratio
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses a soil alteration carbonate measuring method integrating carbon isotope ratio, which comprises the following steps that: a sample is cracked in a golden tube sealing system; gas components after cracking are collected; the content of CO2 in a cracked product is determined; and the carbon isotope ratio of CO2 in the cracked product is determined. Compared with the prior art, the soil alteration carbonate measuring method integrating carbon isotope ratio increases the determination of the carbon isotope ratio of CO2 in the cracked product in a traditional soil Delta C measurement method so as to overcome the defects of the prior art that because other sources unrelated to hydrocarbon in underground oil and gas reservoirs, such as all CO2 produced in surface environment, are integrated with Ca2+, Fe2+ and other ions in surrounding media to form Delta C, indexes or methods which directly evaluate the underground oil and gas reservoirs only through the CO2 content in the cracked product under the condition of 600DEG C overestimate the contribution of Delta C to hydrocarbon in underground oil and gas reservoirs.
Description
Technical field:
The invention belongs to the hydrocarbon geochemical exploration field, relate to a kind of soil corrosion change carbonate (Δ C) measuring method, be specifically related to a kind of soil Δ C measuring method of combined carbon isotopic ratio.
Background technology:
Corrosion change carbonate (Δ C) is important index in the present oil-gas exploration.The ultimate principle of measuring Δ C among the oil and gas industry standard SY/T 6009.6-2003 of the People's Republic of China (PRC) (abbreviation rower) is: the low molecular hydrocarbon class in the hydrocarbon-bearing pool; Reducing environment makes progress when permeating or spreading the well-oxygenated environment of arrival near surface from the deep; A part is by soil particle absorption, and a part is oxidized to CO
2, it decomposes silicate and aluminosilicate in the sediment, generates certain stable special carbonate.Carbonate pyrolysis in specific temperature range (500-600 ℃) that this type is special can discharge CO again
2The SY/T 6009.6-2003 method that corrosion change carbonate (Δ C) is measured is: sample is removed organism and low-temperature decomposition carbonate at 500 ℃ ± 1 ℃ logical dioxygen oxidation.Decomposed 1 hour at 600 ℃ ± 1 ℃ then, the carbon dioxide that discharges is measured with infrared ray gas analyzer or gas chromatograph (TCD).
According to the measuring principle of above-mentioned Δ C, what mensuration obtained is all carbon dioxides that decomposed sample goes out under the 500-600 ℃ of condition.It not only comprises the hydro carbons source relevant with the subterranean oil gas reservoir, and promptly underground hydrocarbon component (like methane, ethane etc.) is penetrated into after the near surface, and part is oxidized to CO in soil
2, CO
2Again with surrounding medium in Ca
2+, Fe
2+Plasma combines, and forms a kind of special carbonate, i.e. Δ C; Also possibly comprise with irrelevant other source of subterranean oil gas reservoir hydro carbons, like the various CO that produce in the ground surface environment
2, they equally can with the Ca in the surrounding medium
2+, Fe
2+Plasma combines to form Δ C.The former is only really need look in the hydrocarbon geochemical exploration relevant with the subterranean oil gas reservoir unusual, the background value that the latter then is and the subterranean oil gas reservoir is irrelevant.Like this, only through the cracking under 600 ℃ of conditions, with CO in the pyrolysis product that records
2Content directly is used to estimate the index or the method for subterranean oil gas reservoir, has obviously over-evaluated the contribution of subterranean oil gas reservoir hydro carbons in the corrosion change carbonate (Δ C), and the stack of high background value has reduced the sensitivity and the validity of this index simultaneously.
Summary of the invention:
The measuring method that the purpose of this invention is to provide a kind of soil corrosion change carbonate of combined carbon isotopic ratio.
Because carbon isotope composition has abundant source-information, the organic matter in different origins and source has significant carbon isotope difference.The hydro carbons that the subterranean oil gas reservoir leaks into the face of land obviously has the carbon isotope composition characteristic close with underground oil and gas.Therefore, the CO that forms by underground hydrocarbon oxidation
2Has light partially carbon isotope ratio δ
13C value (＜-10 ‰).And the anorganogene CO in the face of land
2δ
13The C value generally lays particular stress on (＞-10 ‰).According to the CO that discharges under the 500-600 ℃ of condition
2Isotopics, can identify the part relevant in the corrosion change carbonate (Δ C) more reliably with the subterranean oil gas reservoir, for hydrocarbon geochemical exploration provides a relatively accurate index, so the present invention increases in traditional soil Δ C measuring method and measures CO in the pyrolysis product
2Carbon isotope ratio, thereby realized the object of the invention.
The measuring method of the soil corrosion change carbonate of combined carbon isotopic ratio of the present invention may further comprise the steps:
A) sample cracking in gold duct occlusion system;
B) gas composition after the collection cracking;
C) measure CO in the pyrolysis product
2Content;
D) measure CO in the pyrolysis product
2Carbon isotope ratio.
Because in the method for the oil and gas industry standard SY/T 6009.6-2003 of the People's Republic of China (PRC), the device of its cracking and the collection of component all are difficult to satisfy the mensuration requirement of carbon isotope composition; In addition, collect a large amount of N in the pyrolysis product
2The adding of gas, make original lower with regard to few carbon dioxide gas body burden, in the time of more can not satisfying carbon isotope composition and measure to the requirement of sample size.And at present in oil and gas geochemistry research, the gold duct occlusion system of often using can realize the cracking of pedotheque under 600 ± 1 ℃ of conditions.The mensuration of stipulating corrosion change carbonate (Δ C) in the rower is cracking one hour under 600 ± 1 ℃ of conditions.Yet under this cracking condition, corrosion change carbonate does not have complete cracking.For measuring CO in the pyrolysis product
2Content because assay is relative concept,, can compare according to pyrogenous origin relative quantity as long as pyrolytical condition is in full accord.For CO in the pyrolysis product
2Carbon isotope measure, must make the complete cracking of corrosion change carbonate because the existence of isotope effect, the 12C-12C key preferentially ruptures, thereby can produce isotope fractionation, influences CO in the pyrolysis product
2The mensuration of carbon isotope ratio.Because above-mentioned all restrictive conditions cause the carbon isotope ratio (δ that measures Δ C
13C) in the field of business is a very thing of difficulty.The inventor finds that sample is under 600 ± 1 ℃ condition, and cracking can make the complete cracking of corrosion change carbonate in the sample, CO in the pyrolysis product more than 6 hours in the gold pipe
2Content and carbon isotope value all reach a metastable value (seeing table 1).Therefore the cracking in the gold pipe of described sample is preferably sample under 600 ± 1 ℃ condition, and cracking was more preferably sample under 600 ℃ condition more than 6 hours in gold duct occlusion system, and cracking is 6 hours in gold duct occlusion system.
Table 1. sample is at the Δ C content and the isotopic ratio thereof of different temperature points and time point
CO in the described mensuration pyrolysis product
2Content preferably adopt vapor-phase chromatography to CO in the pyrolysis product
2It is quantitative that component is carried out external standard method;
CO in the described mensuration pyrolysis product
2Carbon isotope ratio preferably adopt mass spectrum-isotopic ratio mass spectrum (GC/IRMS) to CO in the pyrolysis product
2Carbon isotope ratio measure.
The measuring method of the soil corrosion change carbonate of combined carbon isotopic ratio of the present invention has compared with prior art increased CO in the pyrolysis product in traditional soil Δ C measuring method
2The mensuration of carbon isotope ratio, thereby overcome in the prior art because with irrelevant other source of subterranean oil gas reservoir hydro carbons, like the various CO that produce in the ground surface environment
2, the Ca in they and the surrounding medium
2+, Fe
2+Plasma combines to form Δ C, only uses CO in the pyrolysis product under 600 ℃ of conditions
2Content directly is used to estimate the index or the method for subterranean oil gas reservoir, and the shortcoming of having over-evaluated the contribution of subterranean oil gas reservoir hydro carbons in the corrosion change carbonate (Δ C) that causes.
The present invention is through conventional equipment (GC and GC/IRMS), and is simple, convenient and measure its carbon isotope ratio accurately in measuring pedotheque in the Δ C content, accurately explores the carbon source of Δ C, for oil-gas exploration provides foundation more accurately.
Embodiment:
Following examples are to further specify of the present invention, rather than limitation of the present invention.
Embodiment 1
Get about 2g particle diameter≤40 purpose samples and place clean vial, then vial is put into muffle furnace, heated at constant temperature is 2 hours under aerobic environment, and cooling is for use.
Get the above-mentioned burned sample of about 100mg and under argon shield, enclose gold pipe (40mm * 4.2mm i.d.) (weight of using precision to divide another name dress appearance front and back gold pipe, minusing draws the accurate weight of sample in the gold pipe) as the balance of 0.00001g.
Place temperature to be controlled in 600 ± 1 ℃ the pyrolysis oven gold pipe and carried out pyrolysis 6 hours.Be cooled to and take out the gold pipe after the room temperature, weigh after cleaning, and with burn before weight ratio, twice weight differs≤1mg for normal;＞1mg then representes golden tracheal rupture in the pyrolytic process, and is unavailable.
Gas composition in the gold sample tube is collected; Those skilled in the art can utilize prior art as gold sample tube being placed in the glass tube of having taken out vacuum according to external method; Rotating the needle-valve knob makes the needle point on knob top puncture the gold pipe; Gas and lighter hydrocarbons will be released out, and wherein lighter hydrocarbons are frozen and are deposited in the cold-trap, gas (C
1-C
5, CO
2Deng) through moving up and down repeatedly of mercury solution face in the mercury air pump gas is progressively shifted to gas compartment by glass tube, last, decide the amount of gas according to the height of mercury solution face, use gas chromatography gas is analyzed.Certainly those skilled in the art also can referenced patent number be the high precision collection device and the method for application of disclosed minimum gas among the ZL200710027876.5, the concentration of sample component in the mensuration gold pipe.Its concrete operation method is: the gold pipe is put into sample hose, open equalizing valve and vacuum valve and be evacuated to vacuum tightness≤0 that tensimeter shows.Close equalizing valve and puncture sample hose, leave standstill diffusive equilibrium, close vacuum valve, open equalizing valve and make the gaseous diffusion balance, treat that pressure gauge reading is stable after, close equalizing valve and use gas chromatography and carry out gas analysis, measure CO in the pyrolysis product
2Content (mg).Utilize following formula to ask for the content of corrosion change carbonate in the sample:
Corrosion change carbonate (Δ C) content (%)=W
CO2/ W
Sample* (12/44) * 100
W wherein
CO2Be the CO that records
2Content (mg), W
SampleBe corresponding sample size (mg).
After the gas chromatography GC of analytical gas component operation, (those skilled in the art can be according to CO in the pyrolysis product to extract 10 μ l-500 μ l with the gas sampling pin of being with airtight valve
2The sample size scope that content and isotope assay need is adjusted sample size or chromatogram injection port split ratio) the other a part of CO that has collected
2Gas advances GC/IRMS and analyzes its carbon isotope ratio.Owing to only contain CO in this gas composition
2, each run can advance 4 pins continuously, and the interval between every pin is about 30s, to shorten analysis time, improves analysis efficiency.Final isotope value is represented with PDB, is the mean value of repeatedly analyzing, and precision can reach 0.3 ‰.The CO that records
2Isotope value is directly as the δ of corrosion change carbonate
13The C value.
Therefore can study the Ground Response of oil gas accurately according to the content of corrosion change carbonate and the C isotopic ratio of corrosion change carbonate, the estimation range oil-gas bearing prospect is judged the existence of hydrocarbon-bearing pool.
For example, the sample D01 that gets the somewhere according to the method described above, after 6 hours, the content that records its Δ C is 5.55% 600 ℃ of heating.Single content from Δ C, this point is an abnormity point in this zone; And record its isotopic ratio is-6.2 ‰, obviously belongs to inorganic category, then can infer, among the Δ C of this point, inorganic CO
2Be its main source, and the CO of organic origin
2Contribution to it is little.
Claims (2)
1. the measuring method of the soil corrosion change carbonate of a combined carbon isotopic ratio is characterized in that, may further comprise the steps:
A) sample is under 600 ± 1 ℃ condition, and cracking is more than 6 hours in gold duct occlusion system;
B) gas composition after the collection cracking;
C) adopt vapor-phase chromatography to CO in the pyrolysis product
2Component is carried out external standard method quantitatively to measure CO in the pyrolysis product
2Content, utilize following formula to obtain corrosion change carbonate Δ C content: corrosion change carbonate Δ C content (%)=W
CO2/ W
Sample* (12/44) * 100, wherein W
CO2Be the CO that records
2Content, unit are mg, W
SampleBe corresponding sample size, unit is mg;
D) measure CO in the pyrolysis product
2Carbon isotope ratio: the gas sampling pin with the band airtight valve extracts the CO that has collected of 10 μ l-500 μ l
2Gas advances CO in mass spectrum-isotopic ratio mass spectrum GC/IRMS analytical pyrolysis product
2Carbon isotope ratio.
2. the measuring method of the soil corrosion change carbonate of combined carbon isotopic ratio according to claim 1 is characterized in that,
Step a) be sample under 600 ℃ condition, cracking is 6 hours in gold duct occlusion system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010193506 CN101858902B (en) | 2010-06-01 | 2010-06-01 | Soil alteration carbonate measuring method integrating carbon isotope ratio |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010193506 CN101858902B (en) | 2010-06-01 | 2010-06-01 | Soil alteration carbonate measuring method integrating carbon isotope ratio |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101858902A CN101858902A (en) | 2010-10-13 |
| CN101858902B true CN101858902B (en) | 2012-12-12 |
Family
ID=42944921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010193506 Expired - Fee Related CN101858902B (en) | 2010-06-01 | 2010-06-01 | Soil alteration carbonate measuring method integrating carbon isotope ratio |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101858902B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2477472C2 (en) * | 2010-12-24 | 2013-03-10 | Федеральное государственное бюджетное учреждение науки Институт биохимии и физиологии микроорганизмов им. Г.К. Скрябина Российской академии наук (ИБФМ РАН) | Method to detect efficiency of biodegradation of oil hydrocarbons in native and contaminated soils |
| US9618417B2 (en) * | 2011-10-20 | 2017-04-11 | Picarro, Inc. | Methods for gas leak detection and localization in populated areas using isotope ratio measurements |
| CN108469490B (en) * | 2018-03-20 | 2020-05-15 | 中国科学院广州地球化学研究所 | Automatic analysis device for components and carbon isotopes of gas in thermal simulation gold tube of hydrocarbon source rock |
| CN111856048A (en) * | 2019-04-30 | 2020-10-30 | 中国石油化工股份有限公司 | Altered carbonate automatic analysis device and analysis method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6660754B1 (en) * | 2000-02-15 | 2003-12-09 | Smithkline Beecham Corporation | Method for reducing or eliminating smoking |
| CN1249438C (en) * | 2001-02-02 | 2006-04-05 | 徐荣臻 | Protein chip |
| US6952650B2 (en) * | 2001-08-03 | 2005-10-04 | Yale University | Modulators of ribosomal function and identification thereof |
| CN1216291C (en) * | 2002-04-16 | 2005-08-24 | 浙江大学医学院附属第二医院 | Kit for real time fluorescence quantitative RT-RCR detection of human cancer embryoantigen |
-
2010
- 2010-06-01 CN CN 201010193506 patent/CN101858902B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101858902A (en) | 2010-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Merritt et al. | Carbon isotopic analysis of atmospheric methane by isotope‐ratio‐monitoring gas chromatography‐mass spectrometry | |
| CN104407089B (en) | The degassed highly sensitive gas chromatography of rock and mass spectrum Conjoint Analysis system and using method | |
| CN103245735B (en) | A kind of hydrocarbon source rock pyrolysis product light hydrocarbon monomer hydrocarbon carbon isotope on-line analysis | |
| CN101858902B (en) | Soil alteration carbonate measuring method integrating carbon isotope ratio | |
| CN105548416B (en) | Light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method and lighter hydrocarbons enriching apparatus | |
| CN105974007A (en) | Method for detecting phthalic acid ester in soil | |
| CN105021732A (en) | Method for fast determination of oxygen isotope composition of water in beverage wine | |
| CN105092687A (en) | Rare gas all-component content online analysis method | |
| CN105651912A (en) | Rock pyrologger and pyrolytic analysis method | |
| Fisseha et al. | Stable carbon isotope composition of secondary organic aerosol from β‐pinene oxidation | |
| CN109521126A (en) | A kind of thermal desorption/Gas Chromatography-Mass Spectrometry is burnt incense the methods of 16 kinds of polycyclic aromatic hydrocarbon contents in smog | |
| CN105866293A (en) | Method for identifying coal-formed gas and oil type gas by combining He and N2 and application of method | |
| CN107884481A (en) | For determining the detecting system and detection method of weight rare gas content in natural gas | |
| CN102706975B (en) | Method for identifying crude oil and fuel oil | |
| CN102735786A (en) | Online trapping and analyzing method for benzo[a]pyrene in thermal cracking products, and apparatus thereof | |
| CN109374810A (en) | A kind of hydrocarbon source rock Soluble Organic Matter light hydrocarbon component rapid analysis method | |
| Li et al. | Determination of isotope composition of dissolved inorganic carbon by gas chromatography-conventional isotope-ratio mass spectrometry | |
| CN111983062B (en) | Method for detecting trace DMAEA in air | |
| CN205388593U (en) | Rock pyrolysis analysis appearance | |
| Turner et al. | Calibration effects during natural gas analysis using a quadrupole mass spectrometer | |
| Smith et al. | A new automated method for high‐throughput carbon and hydrogen isotope analysis of gaseous and dissolved methane at atmospheric concentrations | |
| CN106680392A (en) | Method using gas chromatographic method to measure purity of tri-n-octylamine | |
| CN112730668A (en) | Method for measuring chloromethane in cigarette mainstream smoke | |
| Nazzari et al. | A simple and sensitive gas chromatography–electron capture detection method for analyzing perfluorocarbon tracers in soil gas samples for storage of carbon dioxide | |
| Sun et al. | Investigation and optimization of methane purification method for natural gas by two-column gas chromatography: A preliminary test for doubly substituted isotopologue (13CH3D) measurements |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121212 Termination date: 20140601 |