CN104749303A - Mud shale thermal release C5-C14 hydrocarbon preparation and online chromatographic analysis method - Google Patents
Mud shale thermal release C5-C14 hydrocarbon preparation and online chromatographic analysis method Download PDFInfo
- Publication number
- CN104749303A CN104749303A CN201310729635.0A CN201310729635A CN104749303A CN 104749303 A CN104749303 A CN 104749303A CN 201310729635 A CN201310729635 A CN 201310729635A CN 104749303 A CN104749303 A CN 104749303A
- Authority
- CN
- China
- Prior art keywords
- hydrocarbon
- mud shale
- preparation
- releases
- line
- 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.)
- Pending
Links
Landscapes
- Sampling And Sample Adjustment (AREA)
Abstract
The present invention provides a mud shale thermal release C5-C14 hydrocarbon preparation and online chromatographic analysis method, which comprises that: 1, a mud shale sample is grinded into particles, and are in the quartz sample boat of a tubular furnace; 2, the tubular furnace is heated under helium gas purging, and hydrocarbon components of the sample are enriched in a liquid nitrogen cold trap; and 3, after completing the enriching, a chromatograph is started, the online enriching tube is rapidly heated, and the thermal release hydrocarbon enters the chromatographic column through a high temperature six-way valve along with carrier gas so as to separate. With the mud shale thermal release C5-C14 hydrocarbon preparation and online chromatographic analysis method of the present invention, the incomplete heavy-component thermal release caused by the large sample particles or the low thermal release temperature is avoided, the online chromatographic analysis and the sample preparation for other analysis items can be concurrently performed, the oil-rock comparative study can be performed, the mud shale can be subjected to quantitative evaluation, and advantages of convenience and environmental protection are provided.
Description
Technical field
The present invention relates to oil-field development technical field, particularly relate to a kind of mud shale heat and release C
5~ C
14the preparation of hydrocarbon and on-line chromatograph analytical approach.
Background technology
Oil shale fuel is a kind of important emerging energy, C in shale
5~ C
14light hydrocarbon is the important component part of oil shale fuel, and its content not only determines the resource potential of shale oil gas, also determine the mobility of shale oil gas and can employ feature, C in addition
5~ C
14contain a large amount of geochemical informations in light hydrocarbon, the deficiency that other geochemical analysis methods exist can be made up.
Because traditional method for extracting can only obtain C in mud shale
15above hydrocarbon compound, to the research relative difficulty compared with light constituent in mud shale.2004, Southwest Petroleum Institute invented a kind of method (patent No. ZL 02113247.X) of extracting all hydrocarbons from hydrocarbon rock, obtains C in rock
1~ C
25the information of hydrocarbon component.The weak point of the method is: releasing in heat can be comparatively large because of sample particle diameter (30 order ~ 60 order) in process, and heavy component release not exclusively; Ask for the total hydrocarbon content in hydrocarbon source rock with weight method, total hydrocarbon content can be caused to be forbidden because of impurity, directly can not obtain the content of single component.2005, Petroleum Geology Institute experimental study center, exploratory development research institute of China Petrochemical Industry Wuxi have developed rock sealing hydrocarbon extraction instrument (patent No. ZL 02160133.X), obtains C in rock
6~ C
15the information of hydrocarbon component.The method can only be carried out by the restriction of environment temperature winter, uses freon extracting to there is environmental issue in experiment.2011, a kind of analytical approach and equipment (patent No. 200710119460.6) thereof of light fraction compounds in petroleum hydrocarbon source rock were invented by exploratory development research institute of PetroChina Company Limited., obtain C in rock
5~ C
13the information of hydrocarbon component.The weak point of the method is: heat is released temperature and only had 200 DEG C, n C
13boiling point 234 DEG C, can cause comparatively heavy hydrocarbon component remain; Can not be quantitative, on-line analysis can only carry out oil, rock comparative study.We have invented a kind of new mud shale heat for this reason and release C
5~ C
14the preparation of hydrocarbon and on-line chromatograph analytical approach, solve above technical matters.
Summary of the invention
The object of this invention is to provide one to have taken into account on-line chromatograph analysis and prepared sample for other analysis project, with the C that interior mark can be quantitatively residual in mud shale more accurately
5~ C
14the mud shale heat of hydrocarbon releases C
5~ C
14the preparation of hydrocarbon and on-line chromatograph analytical approach.
Object of the present invention realizes by following technical measures: mud shale heat releases C
5~ C
14the preparation of hydrocarbon and on-line chromatograph analytical approach, this mud shale heat releases C
5~ C
14preparation and the on-line chromatograph analytical approach of hydrocarbon comprise: step 1, after mud shale sample is ground to form particle, put into the quartz specimen boat of tubular furnace; Step 2, heated Tube-furnace under helium purge, the hydrocarbon component in sample is enriched in liquid nitrogen cold trap; And step 3, startup chromatograph after enrichment completes, Fast Heating on-line preconcentration pipe, heat is released hydrocarbon and is entered chromatographic column with carrier gas through high temperature six-way valve and be separated.
Object of the present invention also realizes by following technical measures:
In step 1, mud shale sample is ground to form 60 order ~ 80 object particles.
This mud shale heat releases C
5~ C
14preparation and the on-line chromatograph analytical approach of hydrocarbon also comprise, after step 1, on-line preconcentration pipe is immersed the liquid nitrogen in vacuum cup, collection tube is immersed the liquid nitrogen in vacuum cup, collection tube is connected to tubular furnace, high temperature six-way valve is connected to tubular furnace, chromatograph is connected to high temperature six-way valve, on-line preconcentration pipe is connected to high temperature six-way valve.
Step 3 also comprises, and takes off collection tube after enrichment completes, freezing for subsequent use after sealing.
In step 2, when heated Tube-furnace, heat releases temperature 280 DEG C, constant temperature 30min.
Chromatograph is Agilent 6890N gas chromatograph.
Mud shale heat in the present invention releases C
5~ C
14the preparation of hydrocarbon and on-line chromatograph analytical approach, overcome the large and heat of the sample particle that exists in prior art release temperature low heavy component is remained, quantitatively inaccurate, preparation and on-line analysis, the problem being unfavorable for environmental protection can not be taken into account.This method avoid the comparatively large or heat of sample particle to release the temperature heavy component heat caused on the low side and release not exclusively, taken into account on-line chromatograph analysis and prepared sample for other analysis project, the C that can remain in quantitative mud shale more accurately with interior mark
5~ C
14hydrocarbon, not only can carry out oil, rock comparative study but also can quantitative evaluation mud shale, convenient and environmental protection.Stratographic analysis result can be seen, the method effectively can obtain the C in mud shale
5~ C
14component.
Accompanying drawing explanation
Fig. 1 is that in mud shale of the present invention, heat releases C
5~ C
14the preparation of hydrocarbon and the process flow diagram of on-line chromatograph analytical approach;
Fig. 2 is that in mud shale of the present invention, heat releases C
5~ C
14the preparation of hydrocarbon and on-line chromatograph analytical equipment schematic diagram;
Fig. 3 is that mud shale heat releases C
5~ C
14the stratographic analysis result figure of hydrocarbon.
Embodiment
For making above and other object of the present invention, feature and advantage can become apparent, cited below particularly go out preferred embodiment, and coordinate institute's accompanying drawings, be described in detail below.
As shown in Figure 1, Fig. 1 is that in mud shale of the present invention, heat releases C
5~ C
14the preparation of hydrocarbon and the process flow diagram of on-line chromatograph analytical approach.
In step 101, mud shale sample is ground to form 60 order ~ 80 object particles, put into quartz specimen boat, add interior mark, quartz specimen boat is placed in the middle part of tubular furnace reducing quartz ampoule.Flow process enters into step 102.
In step 102, on-line preconcentration pipe is immersed the liquid nitrogen in vacuum cup, collection tube is immersed the liquid nitrogen in vacuum cup, collection tube is connected to tubular furnace, high temperature six-way valve is connected to tubular furnace, chromatograph is connected to high temperature six-way valve, and on-line preconcentration pipe is connected to high temperature six-way valve.Flow process enters into step 103.
In step 103, heat under helium purge, the hydrocarbon component in sample is enriched in liquid nitrogen cold trap, and heat releases temperature 280 DEG C, constant temperature 30min.Flow process enters into step 104.
In step 104, after enrichment completes, take off collection tube, freezing for subsequent use after sealing; Startup chromatograph after enrichment completes, Fast Heating on-line preconcentration pipe, heat is released hydrocarbon and is entered chromatographic column with carrier gas through high temperature six-way valve and be separated.Flow process terminates.
In an application specific embodiment of the present invention, Fig. 2 is that mud shale heat of the present invention releases C
5~ C
14the preparation of hydrocarbon and on-line chromatograph analytical equipment schematic diagram.The present embodiment is that mud shale heat releases C
5~ C
14the on-line chromatograph analysis of hydrocarbon, specimen in use is SHENGLI PETROLEUM AREA mud shale sample.
(1) mud shale sample is ground to form 60 order ~ 80 object particles, the pyrolysis S1 value of reference sample, take 100mg and put into quartz specimen boat 3, add interior mark, quartz specimen boat 3 is placed in the middle part of tubular furnace 5 reducing quartz ampoule 4, be stoppered high temperature silicon plug 2, the carrier gas flux arranging packed column injection port 1 is 7ml/min.
(2) on-line preconcentration pipe 10 is immersed the liquid nitrogen 9 in vacuum cup 11, collection tube 7 is immersed the liquid nitrogen 6 in vacuum cup 8, start tubular furnace 5, constant temperature 30 minutes after being warming up to 280 DEG C.
(3) start chromatograph, remove vacuum cup 11, Fast Heating on-line preconcentration pipe 10, heat is released hydrocarbon and is entered shunting/Splitless injecting samples mouth 13 through high temperature six-way valve 12 with carrier gas, is separated through capillary column 14, detects at flame ionization detector 15.Stratographic analysis the results are shown in Figure 3, and the method effectively can obtain the C in mud shale
5~ C
14component.
In one embodiment, have employed Agilent 6890N gas chromatograph.
Claims (6)
1. mud shale heat releases C
5~ C
14the preparation of hydrocarbon and on-line chromatograph analytical approach, is characterized in that, this mud shale heat releases C
5~ C
14preparation and the on-line chromatograph analytical approach of hydrocarbon comprise:
Step 1, after mud shale sample is ground to form particle, puts into the quartz specimen boat of tubular furnace;
Step 2, heated Tube-furnace under helium purge, the hydrocarbon component in sample is enriched in liquid nitrogen cold trap; And
Step 3, startup chromatograph after enrichment completes, Fast Heating on-line preconcentration pipe, heat is released hydrocarbon and is entered chromatographic column with carrier gas through high temperature six-way valve and be separated.
2. mud shale heat according to claim 1 releases C
5~ C
14the preparation of hydrocarbon and on-line chromatograph analytical approach, is characterized in that, in step 1, mud shale sample ground to form 60 order ~ 80 object particles.
3. mud shale heat according to claim 1 releases C
5~ C
14the preparation of hydrocarbon and on-line chromatograph analytical approach, is characterized in that, this mud shale heat releases C
5~ C
14preparation and the on-line chromatograph analytical approach of hydrocarbon also comprise, after step 1, on-line preconcentration pipe is immersed the liquid nitrogen in vacuum cup, collection tube is immersed the liquid nitrogen in vacuum cup, collection tube is connected to tubular furnace, high temperature six-way valve is connected to tubular furnace, chromatograph is connected to high temperature six-way valve, on-line preconcentration pipe is connected to high temperature six-way valve.
4. mud shale heat according to claim 3 releases C
5~ C
14the preparation of hydrocarbon and on-line chromatograph analytical approach, it is characterized in that, step 3 also comprises, and takes off collection tube after enrichment completes, freezing for subsequent use after sealing.
5. mud shale heat according to claim 1 releases C
5~ C
14the preparation of hydrocarbon and on-line chromatograph analytical approach, is characterized in that, in step 2, when heated Tube-furnace, heat releases temperature 280 DEG C, constant temperature 30min.
6. mud shale heat according to claim 1 releases C
5~ C
14the preparation of hydrocarbon and on-line chromatograph analytical approach, is characterized in that, chromatograph is Agilent 6890N gas chromatograph.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310729635.0A CN104749303A (en) | 2013-12-26 | 2013-12-26 | Mud shale thermal release C5-C14 hydrocarbon preparation and online chromatographic analysis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310729635.0A CN104749303A (en) | 2013-12-26 | 2013-12-26 | Mud shale thermal release C5-C14 hydrocarbon preparation and online chromatographic analysis method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104749303A true CN104749303A (en) | 2015-07-01 |
Family
ID=53589297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310729635.0A Pending CN104749303A (en) | 2013-12-26 | 2013-12-26 | Mud shale thermal release C5-C14 hydrocarbon preparation and online chromatographic analysis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104749303A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106996966A (en) * | 2017-05-26 | 2017-08-01 | 中国科学院广州地球化学研究所 | A kind of apparatus and method of online quick analysis oil component |
| CN109374810A (en) * | 2018-12-05 | 2019-02-22 | 中国科学院地质与地球物理研究所兰州油气资源研究中心 | A kind of hydrocarbon source rock Soluble Organic Matter light hydrocarbon component rapid analysis method |
| CN110095545A (en) * | 2019-05-25 | 2019-08-06 | 东北石油大学 | A kind of compact reservoir grade sample oil sources directly analyzes comparison system |
| CN111610265A (en) * | 2020-05-30 | 2020-09-01 | 中国石油天然气股份有限公司 | Synchronous analysis method for oil content and molecular composition of shale fraction |
| CN111610267A (en) * | 2020-05-30 | 2020-09-01 | 中国石油天然气股份有限公司 | Shale oil content and fine component synchronous experimental analysis device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5288310A (en) * | 1992-09-30 | 1994-02-22 | The Regents Of The University Of Michigan | Adsorbent trap for gas chromatography |
| US5390529A (en) * | 1993-03-19 | 1995-02-21 | Agip S.P.A. | Method for determining heavy hydrocarbons in rock matrices and the apparatus for the purpose |
| CN1370812A (en) * | 2002-01-15 | 2002-09-25 | 西南石油学院 | Method of extracting all hydrocarbons from hydrocarbon rock |
| CN101354383A (en) * | 2007-07-25 | 2009-01-28 | 中国石油天然气股份有限公司 | Method and device for analyzing light fraction compounds in petroleum hydrocarbon source rock |
| CN101900713A (en) * | 2010-05-18 | 2010-12-01 | 中国石油天然气股份有限公司 | Chromatograph on-line analysis method for source rock by closed ball milling, heating analysis and cold trap trapping |
| CN102721590A (en) * | 2012-06-28 | 2012-10-10 | 中国石油天然气股份有限公司 | Continuous lossless whole rock natural gas generation simulation method |
-
2013
- 2013-12-26 CN CN201310729635.0A patent/CN104749303A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5288310A (en) * | 1992-09-30 | 1994-02-22 | The Regents Of The University Of Michigan | Adsorbent trap for gas chromatography |
| US5390529A (en) * | 1993-03-19 | 1995-02-21 | Agip S.P.A. | Method for determining heavy hydrocarbons in rock matrices and the apparatus for the purpose |
| CN1370812A (en) * | 2002-01-15 | 2002-09-25 | 西南石油学院 | Method of extracting all hydrocarbons from hydrocarbon rock |
| CN101354383A (en) * | 2007-07-25 | 2009-01-28 | 中国石油天然气股份有限公司 | Method and device for analyzing light fraction compounds in petroleum hydrocarbon source rock |
| CN101900713A (en) * | 2010-05-18 | 2010-12-01 | 中国石油天然气股份有限公司 | Chromatograph on-line analysis method for source rock by closed ball milling, heating analysis and cold trap trapping |
| CN102721590A (en) * | 2012-06-28 | 2012-10-10 | 中国石油天然气股份有限公司 | Continuous lossless whole rock natural gas generation simulation method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106996966A (en) * | 2017-05-26 | 2017-08-01 | 中国科学院广州地球化学研究所 | A kind of apparatus and method of online quick analysis oil component |
| CN106996966B (en) * | 2017-05-26 | 2019-07-02 | 中国科学院广州地球化学研究所 | A kind of device and method of online quickly analysis oil component |
| CN109374810A (en) * | 2018-12-05 | 2019-02-22 | 中国科学院地质与地球物理研究所兰州油气资源研究中心 | A kind of hydrocarbon source rock Soluble Organic Matter light hydrocarbon component rapid analysis method |
| CN110095545A (en) * | 2019-05-25 | 2019-08-06 | 东北石油大学 | A kind of compact reservoir grade sample oil sources directly analyzes comparison system |
| CN110095545B (en) * | 2019-05-25 | 2021-11-23 | 东北石油大学 | Millimeter-level sample oil source direct analysis and comparison system for tight reservoir |
| CN111610265A (en) * | 2020-05-30 | 2020-09-01 | 中国石油天然气股份有限公司 | Synchronous analysis method for oil content and molecular composition of shale fraction |
| CN111610267A (en) * | 2020-05-30 | 2020-09-01 | 中国石油天然气股份有限公司 | Shale oil content and fine component synchronous experimental analysis device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11119085B2 (en) | Methods and devices for detecting mercury isotopes in oil-gas sources | |
| CN104749303A (en) | Mud shale thermal release C5-C14 hydrocarbon preparation and online chromatographic analysis method | |
| US8492152B2 (en) | Method and apparatus for determining formation fluid composition | |
| CN109253996B (en) | Mercury isotope testing method and device for crude oil | |
| CN105548416B (en) | Light hydrocarbon in natural gas detailed hydrocarbon hydrogen isotope analysis method and lighter hydrocarbons enriching apparatus | |
| CN102253136A (en) | Method for analyzing carbon isotopes of micro single hydrocarbons in natural gas | |
| CN105974007A (en) | Method for detecting phthalic acid ester in soil | |
| WO2012051109A3 (en) | Fluid compositional analysis by combined gas chromatographic and direct flash methods | |
| CN103278589A (en) | Detection method and device for volatile and semi-volatile components | |
| CN104062368A (en) | Vapor headspace enrichment detection method for trace amount of volatile organic pollutants in seawater | |
| CN112345667A (en) | Gaseous hydrocarbon preparation and online carbon isotope analysis device and method | |
| CN104931613A (en) | Method for detecting volatile components in tobacco leaves | |
| CN106525768A (en) | Non-methane total hydrocarbon detection device and detection method | |
| CN103293246B (en) | Method for rapidly detecting oil-bearing rate of oil shale | |
| CN101858902B (en) | Soil alteration carbonate measuring method integrating carbon isotope ratio | |
| CN104391063A (en) | New purpose of miniature-needle trapping device | |
| TAO et al. | Carbon isotope fractionation characteristics during shale gas release | |
| CN103869027B (en) | A kind of method being separated n-alkane in oil geology sample | |
| Narros et al. | Determination of siloxanes in landfill gas by adsorption on Tenax tubes and TD-GC-MS | |
| CN107179372B (en) | Hydrocarbon extraction system and extraction method thereof | |
| CN105548376B (en) | A kind of method that gas chromatography determines impurity in 2,3,3,3 tetrafluoropropene products | |
| CN101587100A (en) | Method for determining benzene compounds in coked lean and fat oil by capillary gas chromatography | |
| CN103675157B (en) | A kind of quick pretreatment method of crude oil sample | |
| CN210269738U (en) | Trace volatile organic compound enrichment and sampling device | |
| CN104198639A (en) | Quantitative analysis method for micromolecular organic acids in fluid extracted from oil field |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150701 |