CN104628809B - Molecular sieve combination separation and concentration biomarker gonane and the method for hopance - Google Patents
Molecular sieve combination separation and concentration biomarker gonane and the method for hopance Download PDFInfo
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- CN104628809B CN104628809B CN201310571888.XA CN201310571888A CN104628809B CN 104628809 B CN104628809 B CN 104628809B CN 201310571888 A CN201310571888 A CN 201310571888A CN 104628809 B CN104628809 B CN 104628809B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J63/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by expansion of only one ring by one or two atoms
- C07J63/008—Expansion of ring D by one atom, e.g. D homo steroids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
Abstract
The present invention relates to a kind of molecular sieve combination separation and concentration biomarker gonane and the method for hopance；1) weigh sample to be added on particulate unmodified packed column, use n-hexane drip washing, isolate saturated hydrocarbon component, 2) through ZSM 5 molecular sieve filling pillar, isooctane drip washing, isolate the ring-type of saturated hydrocarbons and isomeric component；3) through 13X molecular sieve filling pillar, after pentane drip washing pillar, nitrogen dries up pillar；4) 10X molecular sieve filling pillar, is concentrated into step 3) gained solution on post, and two parts of pentane drip washing are collected, and obtain two cuts of gonane；5) isooctane extracting 13X molecular sieve 10h, obtains hopance component；6) concentration step 4), 5) gained solution, upper machine measure；This method can efficiently separate and be enriched with gonane and hopance, makes the mensuration of the detailed hydrocarbon stable carbon isotope of biomarker gonane and hopance be possibly realized.
Description
Technical field:
The present invention relates to biomarker gonane and the method for separating and preparing of hopance in petroleum geology sample.
Background technology:
China's Midwest oil-gas bearing basin, based on Superimposed Basins, is grown many set hydrocarbon source rocks and preserves series of strata, oily system
Unite more complicated.Owing to major part basin hydrocarbon source rock has, the epoch are old, Organic Material Thermal Evolution history length, maturity are high, depression is deep
The body distribution of hydrocarbon source, district of portion is not clear, and a lot of prospect pits cannot obtain the hydrocarbon source rock matched with crude maturity, it has to uses and appears
Hydrocarbon source rock carry out OIL SOURCE CORRELATION.Due to the difference of maturity, the mass spectral analysis TuPu method of biomarker changes relatively
Greatly, OIL SOURCE CORRELATION result is the most multifarious；The appearance of normal hydrocarbon detailed hydrocarbon stable carbon isotope, the most once made it is seen that
Solve the hope of this problem, but normal hydrocarbon is more due to its constructive ways, constantly have cracking to wait other in maturation
The normal hydrocarbon that form is formed occurs, the stable carbon isotope analysis result of monomer whose hydrocarbon also is difficult to mate with crude oil, and this is just to surveying
The confirmation visiting direction and exploration targets causes certain puzzlement.And the biomarker monomer in crude oil or hydrocarbon source rock
The stable carbon isotope of hydrocarbon is a time dependent parameter, is affected the least by maturity change, this parameter can deeper into,
Precisely, reflection eobiont thing feature, effectively solution Special section OIL SOURCE CORRELATION, biological precursor sentence the conventional earth such as knowledge all sidedly
The insurmountable difficult problem of chemical experiment means [1]；In crude oil to be set up or hydrocarbon source rock, biomarker detailed hydrocarbon is stable
The analytical technology that carbon isotope composition measures first has to set up the separation and concentration technology of biomarker, therefore biological marker
The fine separation of compound is key issue.
Gonane and hopance are class Biological Mark Compounds critically important in crude oil and rock extracts, are by nature respectively
The biosynthetic sterol in boundary and leaves of pulse plants tetrol are transformed, and are under the jurisdiction of saturated hydrocarbon component, are oil and gas geochemistry worker research
Oil-gas formation and the important compound of Filling process, be possible not only to provide the Organic matter type of crude oil, depositional environment and maturity
Etc. the information of aspect, and be the main target compound of the research such as OIL SOURCE CORRELATION and oil and gas secondary migration.Along with detailed hydrocarbon is steady
Determining the development of Radioisotope Measuring Technology, oil and gas geochemistry worker starts the isotopic research of Biological Mark Compounds, with
To more, more detailed information, solve an indeterminable difficult problem in the past.Owing to they percentages in saturated hydrocarbons are relatively low,
The stable carbon isotope of gonane to be realized and hopance measures, it is necessary to it is isolated the purest from oil or rock extracts
Clean gonane and hopance, get rid of the interference of its condistillation component.Abroad, Kenig F. etc. utilize ultra-steady Y molecular sieve filler at height
Gonane and hopance is isolated, it is achieved that its isotopic mensuration [2] on effect liquid phase chromatogram.But the super steady Y that Keniing F etc. are used
Molecular sieve is domestic cannot be bought, and domestic super steady Y molecular sieve cannot repeat its result.Another family realizes gonane and hopance is stable
What carbon isotope measured is the oil gas earth laboratory of Stanford Univ USA, the AAPG that Moldowan J.M. holds in Beijing
Illustrate result in geochemistry international conference, but how the gonane hopance of isolated belongs to secrecy technology, provides only externally
Service.At home, Wang Huitong etc. utilize domestic molecular sieve to do a large amount of fruitful work in terms of gonane, hopance separation and concentration
Make [3-7], be successfully separated out gonane and hopance cluster compound.But the biological marker of Y type molecular sieve separation and concentration used
Monomer adduct hydrocarbon carbon isotope value repeatability poor [8-9], the biomarker technology of X-type molecular sieve separation and concentration used
Also have and promote the space improved；The molecular sieve that can be enriched with and isolate hopance has two kinds, i.e. 10X and 13X.10X molecular sieve can
So that gonane is separated into two groups of components, the beneficially mensuration of monomer whose hydrocarbon stable carbon isotope, it it is the optimal selection separating gonane；
10X and 13X molecular sieve can effective adsorption and enrichment hopance compound, molecular sieve can be desorbed with isooctane extracting molecular sieve
The hopance of absorption.But carefully compare the two enrichment absorption biomarker difference it appeared that: on 13X molecular sieve adsorb
β-daucane than absorption the most more on 10X molecular sieve, the hopance S configuration of absorption and R configuration are more complete, this
The reason of one difference is that the passage aperture of 10X molecular sieve is slightly less than 13X molecular sieve so that the hopance of S configuration is easily eluted, and
β-daucane molecule is relatively big, is directly leached out between molecular sieve without duct.Therefore, 13X molecular sieve divides than 10X
Son sieve concentration and separation hopance is more suitable.Just by the accumulation of years of work, inventors herein propose with 10X and 13X molecule screen banks
The way separation and concentration gonane closed and hopance, measure for biomarker detailed hydrocarbon stable carbon isotope and provide preferably
Technological means.
Bibliography:
1.Moldowan J M, Dahl J.Combining isotopes with biomarkers and
Diamondoids:A two-dimensional approach to paleoenvironmental
Charactreization.AAAPG-2004 proceeding .Beijing, China, 2004:135-137
2.Kenig, F., Popp, B.N.and Summons, R.E.Preparative HPLC with
ultrastable-Y zeolite for compound-specific carbon isotopic analyses.Organic
Geochem.,2000,31,1087-1094.
3. Wang Hui is red, the separation side of steroid in Wei Caiyun, Zhang Shuichang .REUSY molecular sieve separation saturated hydrocarbon component
Method .ZL200710065580.2 patent of invention
4. Wang Hui is red, Wei Caiyun Zhang Shuichang, waits the method for steroid in .MOY molecular sieve separation saturated hydrocarbon component
.ZL200710065581.7 patent of invention
5. Wang Hui is red, Wei Caiyun, Zhang Shuichang, waits the gonane in .10X molecular sieve separation crude oil or rock extracts and hopance
Method .ZL200710065582.1 patent of invention
6. Wang Hui is red, Wei Caiyun, Zhang Shuichang, waits gonane and hopance in .13X molecular sieve separation crude oil or rock extracts
Method .ZL200710065583.6 patent of invention
7. bright cloud Wei, Wang Huitong, Huang Ling, etc. a kind of gonane separated in crude oil or rock extracts and the method for hopance
.ZL200910242741.X patent of invention
8. Wang Hui is red, Wei Caiyun, Zhang Shuichang, waits .MOY molecular sieve same to separation and the detailed hydrocarbon thereof of biomarker
Position element measures research. oil experiment geology, and 2010,32:513-516
9. Wang Hui is red, Wei Caiyun, Zhang Shuichang, etc. domestic Y type molecular sieve is to gonane, the absorption of hopance and desorption research. stone
Oil experiment geology, 2010,32:73-75
Summary of the invention
It is an object of the invention to provide a kind of molecular sieve combination separation and concentration biomarker gonane and the side of hopance
Method.Gonane and hopance are all polycyclic naphthene hydrocarbon compounds, structure the most close (as shown in Figure 1).Gonane and hopance with carbon number
Retention behavior in adsorption chromatography is the most close, and traditional method is difficult to separate gonane close for structure with hopance.This
The bright difference utilizing gonane and the difference of hopance molecular diameter and 10X and 13X molecular sieve internal channel aperture, utilizes two kinds of molecules
The combination of sieve, it is achieved gonane and the separation of hopance, enrichment.
Gonane, hopance separation and concentration flow process as follows:
1) weighing sample 60mg, join on particulate unmodified packed column, with 12ml n-hexane drip washing, separation is prepared saturated
Hydrocarbon component, solvent flashing, weighs；
2) taking the ZSM-5 molecular sieve filling pillar of 100 times of saturated hydrocarbons quality, 20ml isooctane drip washing, separation is prepared full
With the ring-type of hydrocarbon and isomeric component, solvent flashing, weigh；
3) 300 times of steps 2 are weighed) the 13X molecular sieve filling pillar of prepared product quality, after 60ml pentane drip washing pillar,
Nitrogen dries up pillar.
4) 300 times of steps 2 are weighed) the 10X molecular sieve filling pillar of prepared product quality, step 3) gained solution is concentrated into
On post, the pentane drip washing of two parts of 5ml is also collected respectively, obtains two cuts of gonane；
5) isooctane extracting 13X molecular sieve 10h, obtains hopance component；
6) concentration step 4), 5) gained solution, treat that machine measures.
The pillar leacheate rate of outflow used by front four step column chromatographies is not more than 30 droplets/point.Filling filler used by pillar
Need before use to activate 10 hours, activation temperature respectively: silica gel, 220 DEG C；ZSM molecular sieve, 450 DEG C；13X molecular sieve, 470
℃；10X molecular sieve, 470 DEG C.
The core of invention is the 3rd, 4,5 steps, i.e. apply domestic 10X, 13X molecular sieve to do filler, be individually separated and prepare
Gonane and hopance.
Invention effect:
The gonane going out 10X, 13X molecular sieve combination concentration and separation and hopance carry out chromatographic mass spectrometry qualification and (select ion
Contain all ions of saturated hydrocarbon component detection), accompanying drawing 2 is shown in by the qualification collection of illustrative plates of gonane, and accompanying drawing 3 is shown in by the qualification collection of illustrative plates of hopance.With
Total ion current figure before 10X, 13X molecular sieve combination separation and concentration compares and can be seen that the present invention can efficiently separate and be enriched with
Gonane and hopance, the determination data of the detailed hydrocarbon stable carbon isotope of gonane and hopance biomarker is reproducible.Point
The spectrogram effect shown in AAPG geochemistry international conference with Moldowan J.M. from effect compares (bibliography 2) base
This is consistent, illustrates that it is feasible for utilizing domestic 10X, 13X molecular sieve combination separation gonane and hopance, it is possible to efficiently separate richness
Collection gonane and hopance.The method of the be enriched with hopance of this method is compared than the method for document 3, simple, convenient, it is easy to promote.
Accompanying drawing and accompanying drawing explanation:
Fig. 1. remove sample chromatogram-mass spectrum total ion current figure that n-alkane processes without molecular sieve
The chromatography-mass spectroscopy total ion current figure of gonane isolated by Fig. 2 .10X molecular sieve
The chromatography-mass spectroscopy total ion current figure of hopance isolated by Fig. 3 .13X molecular sieve
Fig. 4 splitter structural representation
Detailed description of the invention:
Embodiment 1
1, crude oil or rock extracts 60mg, loads pillar, 12ml n-hexane with the silica gel of 6g particle diameter 40 microns
Saturated hydrocarbons is prepared in drip washing.
2, solvent flashing on Nitrogen evaporator, weighs the quality of saturated hydrocarbons, takes the ZSM-5 molecule of saturated hydrocarbons quality about 100 times
Sieve filling pillar, cyclic hydrocarbon is prepared in 20ml isooctane drip washing.
3, solvent flashing on Nitrogen evaporator, weighs the quality of cyclic hydrocarbon, takes the 13X molecular sieve of cyclic hydrocarbon quality about 300 times
Filling pillar, prepared cut Z with 60ml pentane drip washing after 30 minutes.
4, at recovery, the solvent of volatile fraction Z, weigh its quality, take the 10X molecular sieve filling pillar of 300 times, by step
3 gained solution are concentrated on post, and the pentane drip washing of two parts of 5ml is also collected respectively, obtains two cuts of gonane, and concentrates.
5, after the column packing nitrogen of step 3 dries up, after extracting 10 hours with isooctane, hopance is obtained.
6, concentration step 4,5 gained solution.
7, the machine on step 2, step 6 gained solution that takes measures.
Pillar used by front four step column chromatographies requires to connect nitrogen pressurization (accompanying drawing 4 is shown in by pillar schematic diagram), and leacheate flows out speed
Degree is not more than 30 droplets/point.Filling filler used by pillar needs to activate 10 hours before use, activation temperature respectively: silica gel,
220℃；ZSM molecular sieve, 450 DEG C；13X molecular sieve, 470 DEG C；10X molecular sieve, 470 DEG C.
Step 2 is removed the chromatography-mass spectroscopy total ion current figure of the sample of positive structure and is seen accompanying drawing 1.
The chromatography-mass spectroscopy total ion current figure of the isolated gonane of 10X molecular sieve is shown in accompanying drawing 2.
Wherein:
(1) 5 α, 14 α, 17 α-C27Gonane 20S；(2) 5 α, 14 β, 17 β-C27Gonane 20R；
(3) 5 α, 14 β, 17 β-C27Gonane 20S；(4) 5 α, 14 α, 17 α-C27Gonane 20R；
(5) 13 α, 17 β-C27Diasterane 20S；(6) 5 α, 14 α, 17 α-C28Gonane 20S；
(7) 5 α, 14 β, 17 β-C28Gonane 20R；(8) 5 α, 14 β, 17 β-C28Gonane 20S；
(9) 5 α, 14 α, 17 α-C28Gonane 20R；(10) 5 α, 14 α, 17 α-C29Gonane 20S；
(11) 5 α, 14 β, 17 β-C29Gonane 20R；(12) 5 α, 14 β, 17 β-C29Gonane 20S；
(13) 5 α, 14 α, 17 α-C29Gonane 20R；
The chromatography-mass spectroscopy total ion current figure of the isolated hopance of 13X molecular sieve is shown in accompanying drawing 3
(1) 18 α (H)-22,29,30-trisnorhopane (Ts)；(2) 17 α (H)-22,29,30-trisnorhopanes (Tm)；
(3) 17 α (H), 21 β (H)-C29Hopance；(4) 17 α (H), 21 α (H)-C29Moretane；
(5) 17 α (H), 21 β (H)-C30Hopance；(6) 17 β (H), 21 α (H)-C30Moretane；
(7) 17 α (H), 21 β (H)-29-C31Homohopane 22S；(8) 17 α (H), 21 β (H)-29-C31Homohopane 22R；
(9) 17 α (H), 21 β (H)-29-C32Two homohopane 22S；(10) 17 α (H), 21 β (H)-29-C32Two homohopane 22R；
(11) 17 α (H), 21 β (H)-29-C33Trishomohopane 22S；(12) 17 α (H), 21 β (H)-29-C33Trishomohopane 22R；
(13) 17a (H), 21b (H)-29-C34Tetrakishomohopane 22S；(14) 17a (H), 21b (H)-29-C34Tetrakishomohopane 22R；
Embodiment 2
1, choose Yumen Oilfield willow 43 well crude oil sample 60mg, load pillar with the silica gel of 6g particle diameter 40 microns,
Saturated hydrocarbons is prepared in 12ml n-hexane drip washing.
2, solvent flashing on Nitrogen evaporator, weighs the quality of saturated hydrocarbons, takes the ZSM-5 molecule of saturated hydrocarbons quality about 100 times
Sieve filling pillar, cyclic hydrocarbon is prepared in 20ml isooctane drip washing.
3, solvent flashing on Nitrogen evaporator, weighs the quality of cyclic hydrocarbon, takes the 13X molecular sieve of cyclic hydrocarbon quality about 300 times
Filling pillar, prepared cut Z with 60ml pentane drip washing after 30 minutes.
4, at recovery, the solvent of volatile fraction Z, weigh its quality, take the 10X molecular sieve filling pillar of 300 times, by step
3 gained solution are concentrated on post, and the pentane drip washing of two parts of 5ml is also collected respectively, obtains two cuts of gonane, and concentrates.
5, after the column packing nitrogen of step 3 dries up, after extracting 10 hours with isooctane, hopance is obtained.
6, concentration step 4,5 gained solution, and do isotope analysis, obtain the isotope knot of gonane and hopanoid compound
Really.
Pillar used by front four step column chromatographies requires to connect nitrogen pressurization (accompanying drawing 4 is shown in by pillar schematic diagram), and leacheate flows out speed
Degree is not more than 30 droplets/point.Filling filler used by pillar needs to activate 10 hours before use, activation temperature respectively: silica gel,
220℃；ZSM molecular sieve, 450 DEG C；13X molecular sieve, 470 DEG C；10X molecular sieve, 470 DEG C.
7, repeat step 1-6, again obtain the carbon isotope knot of gonane and hopanoid compound in willow 43 well crude oil sample
Really, and the result of twice experiment is compared (be shown in Table 1, table 2), from table data it can be seen that twice pre-treating method obtains
Testing result relative deviation all within 5%, meet conventional detection requirement.The separation method repeatability that the present invention provides is described
Good, it is worthy to be popularized.
The gonane carbon isotope repeatability result of twice enrichment and separation method of table 1a)
A) in table, compound number is corresponding with accompanying drawing 2
The hopance carbon isotope repeatability result of twice enrichment and separation method of table 2b)
B) in table, compound number is corresponding with accompanying drawing 3.
Claims (1)
1. a molecular sieve combination separation and concentration biomarker gonane and the method for hopance, it is characterised in that:
1) weigh sample 60mg, join on particulate unmodified packed column, with 12ml n-hexane drip washing, separate and prepare saturated hydrocarbons group
Point, solvent flashing, weigh；
2) take the ZSM-5 molecular sieve filling pillar of 100 times of saturated hydrocarbons quality, 20ml isooctane drip washing, separate and prepare saturated hydrocarbons
Ring-type and isomeric component, solvent flashing, weigh；
3) 300 times of steps 2 are weighed) the 13X molecular sieve filling pillar of prepared product quality, after 60ml pentane drip washing pillar, nitrogen
Dry up pillar；
4) 300 times of steps 2 are weighed) the 10X molecular sieve filling pillar of prepared product quality, by step 3) gained solution is concentrated into post
On, the pentane drip washing of two parts of 5ml is also collected respectively, obtains two cuts of gonane；
5) isooctane extracting 13X molecular sieve 10h, obtains hopance component；
6) concentration step 4), 5) gained solution, treat that machine measures；
The pillar leacheate rate of outflow used by front four step column chromatographies is 30 droplets/point, and filling filler used by pillar is before use
10 hours need to be activated, activation temperature respectively: silica gel, 220 DEG C；ZSM-5 molecular sieve, 450 DEG C；13X molecular sieve, 470 DEG C；10X
Molecular sieve, 470 DEG C.
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| CN110940790B (en) * | 2018-09-21 | 2022-08-12 | 中国石油化工股份有限公司 | Method and device for identifying efficient hydrocarbon source rock |
| CN110672739A (en) * | 2019-09-29 | 2020-01-10 | 中国海洋石油集团有限公司 | Rapid crude oil and organic matter saturated hydrocarbon complex analysis method |
| CN112625082B (en) * | 2020-12-14 | 2022-05-24 | 长江大学 | Method for separating and purifying hopane by neutral alumina |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289492A (en) * | 2007-04-17 | 2008-10-22 | 中国石油天然气股份有限公司 | Process for separating sterane and hopane form mother oil or rock extract by 13X molecular sieve |
| CN101289491A (en) * | 2007-04-17 | 2008-10-22 | 中国石油天然气股份有限公司 | Process for separating sterane and hopane form mother oil or rock extract by 10X molecular sieve |
| CN102101877A (en) * | 2009-12-16 | 2011-06-22 | 中国石油天然气股份有限公司 | Method for separating gonane and hopane from crude oil or rock extract |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289492A (en) * | 2007-04-17 | 2008-10-22 | 中国石油天然气股份有限公司 | Process for separating sterane and hopane form mother oil or rock extract by 13X molecular sieve |
| CN101289491A (en) * | 2007-04-17 | 2008-10-22 | 中国石油天然气股份有限公司 | Process for separating sterane and hopane form mother oil or rock extract by 10X molecular sieve |
| CN102101877A (en) * | 2009-12-16 | 2011-06-22 | 中国石油天然气股份有限公司 | Method for separating gonane and hopane from crude oil or rock extract |
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