CN110346197B - Preparation method of shale carrier for adsorbing petroleum liquid hydrocarbon - Google Patents
Preparation method of shale carrier for adsorbing petroleum liquid hydrocarbon Download PDFInfo
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- CN110346197B CN110346197B CN201910502128.0A CN201910502128A CN110346197B CN 110346197 B CN110346197 B CN 110346197B CN 201910502128 A CN201910502128 A CN 201910502128A CN 110346197 B CN110346197 B CN 110346197B
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
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- G—PHYSICS
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- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4022—Concentrating samples by thermal techniques; Phase changes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4044—Concentrating samples by chemical techniques; Digestion; Chemical decomposition
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
- G01N2001/4061—Solvent extraction
Abstract
The invention relates to a preparation method of a shale carrier for adsorbing petroleum liquid hydrocarbon, belonging to the field of shale oil. In the treatment method, firstly, hydrochloric acid is used for treating and removing carbonate minerals in a shale sample, and residues are washed to be neutral and equally divided into three parts; then, a tubular furnace is used for respectively carrying out heat release, pyrolysis and ignition treatment, soluble organic matters (300 ℃), active kerogen (650 ℃) and inert kerogen (1200 ℃) in the shale sample are respectively removed, and finally chloroform extraction and methanol-acetone-benzene ternary extraction are respectively carried out to remove residual hydrocarbon possibly generated in the treatment process; thus preparing three types of shale residue samples of active kerogen retention, active kerogen removal, inert kerogen retention and inert kerogen removal (namely organic matter). The three types of shale residue samples as the adsorption carriers have important significance for carrying out tests and related researches on adsorption of liquid hydrocarbon on organic matters containing kerogen with different structures.
Description
Technical Field
The invention relates to the field of shale oil, in particular to a preparation method of a shale carrier for adsorbing petroleum liquid hydrocarbon.
Background
The shale oil is a liquid petroleum resource which is retained in a shale system after hydrocarbon generation and discharge, is more and more emphasized by people along with the progress of exploration and development technology, and is an important oil-gas replacing resource in the future. Shale oil mainly exists in a free state and an adsorption state, and the former is a main contributor to the productivity, so the characterization of the free oil is one of the key problems of shale oil exploration and development. The current methods for obtaining free oil can be generally divided into direct characterization methods and indirect calculation methods. The direct characterization method can be classified into an extraction method and a heat release method, and the indirect calculation method tends to be used due to the complex flow and high cost. The indirect calculation method is mainly obtained by measuring the difference value between the total oil content and the oil absorption amount of the shale. And because the total oil quantity of the shale is easy and accurate to obtain, the accuracy of calculating the free oil quantity by using the method mainly depends on the determination of the oil quantity absorbed by the shale. This method has also received increasing attention in recent years.
Since the adsorption capacity of the organic matter on the shale oil (liquid hydrocarbon) is far higher than that of the mineral matter, the adsorption effect of the organic matter on the liquid hydrocarbon is focused on, and the adsorption capacity of the total organic matter (total organic carbon content) on the liquid hydrocarbon is researched, however, the shale oil potential evaluated according to the method sometimes does not accord well with the actual exploration result. It is known that organic matter in shale consists of insoluble organic matter-kerogen (> 90%) and soluble organic matter-bitumen (< 10%), so that the adsorption of liquid hydrocarbons by organic matter in shale is actually the adsorption of liquid hydrocarbons by kerogen. The structure of kerogen is very complex, the exact chemical structure is not available at present, and the kerogen is a conceptual model, and Cools et al (1986) classify the kerogen into chemically active kerogen and chemically inert kerogen. Therefore, organic matter in the shale can be processed into three parts by a pyrolysis method, namely soluble organic matter, active kerogen and inert kerogen.
At present, organic carriers for adsorbing liquid hydrocarbon are reported to be general organic matters or kerogen, and no special report for further subdividing the adsorption effect of active kerogen and inert kerogen on the liquid hydrocarbon is seen. Zhang Y et al reported that the oil adsorption test using the shale residue after ternary extraction resulted in the recognition that the crude oil adsorption amount of kerogen is much greater than that of inorganic mineral adsorption, but the test only developed the oil adsorption capacity test of the shale residue after chloroform and ternary extraction, i.e., the shale residue after removal of soluble organic matter, and did not further develop the liquid hydrocarbon adsorption test of shale residue after removal of active kerogen, retention of inert kerogen and removal of inert kerogen.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a shale carrier for adsorbing petroleum liquid hydrocarbon, which comprises the steps of further processing and subdividing a shale sample into three shale residue samples for removing soluble organic matters, active kerogen and inert kerogen through a specific processing method, wherein the three shale residue samples are used as carriers for adsorbing petroleum liquid hydrocarbon, and are used for developing the mechanism research of the adsorption of petroleum liquid hydrocarbon by organic matters containing kerogen with different structures.
The invention provides a preparation method of a shale carrier for adsorbing petroleum liquid hydrocarbon, which comprises the following steps:
s1, collecting a shale sample containing petroleum liquid hydrocarbon, treating the shale sample with hydrochloric acid to remove carbonate minerals in the shale sample, washing the residue left after the reaction with distilled water to be neutral, and equally dividing the shale residue sample into three parts;
s2, taking the first residue obtained in the step S1, and performing heat release treatment in a tube furnace to remove soluble organic matters in the shale residue;
performing pyrolysis treatment on the second part of residue obtained in the step S1 in a tube furnace to remove active kerogen in the shale residue;
taking the third residue obtained in the step S1, and burning the third residue in a tube furnace to remove inert kerogen in the shale residue;
s3, respectively adopting chloroform extraction and methanol-acetone-benzene ternary extraction to sequentially extract the first, second and third shale residue samples processed by the three methods in the step S2 for removing residual hydrocarbon possibly generated in the processing process in the step S2, and further preparing a first shale residue sample retaining active kerogen, a second shale residue sample removing active kerogen and retaining inert kerogen and a third shale residue sample removing inert kerogen (organic matter), wherein the obtained three shale residue samples can be used as shale carriers for carrying out tests of adsorbing petroleum liquid hydrocarbon by organic matters containing kerogen with different structures.
Firstly, treating with hydrochloric acid to remove carbonate minerals in a shale sample, washing residues after reaction to be neutral, and equally dividing into three parts; then, respectively carrying out heat release, pyrolysis and ignition treatment by using a tube furnace to respectively remove soluble organic matters, active kerogen and inert kerogen in the shale residue sample, and finally respectively using chloroform extraction and methanol-acetone-benzene ternary extraction to remove residual hydrocarbon possibly generated in the treatment process; thus preparing shale residue samples of three types of active kerogen retention, active kerogen removal, inert kerogen retention and inert kerogen removal (organic matter) as shale carriers for petroleum liquid hydrocarbon adsorption tests.
Further, in step S1, the specific process of removing carbonate minerals in the shale sample by hydrochloric acid treatment is as follows: crushing the shale sample, adding hydrochloric acid, fully stirring the mixture until the mixture is uniform, and placing the mixture in a water bath kettle to be heated and stirred for reaction.
Further, after step S1, the method further includes drying the shale residue sample for use.
Further, in step S2, the temperature of the tubular furnace for the thermolysis process is 300 ℃, the temperature of the tubular furnace for the thermolysis process is 650 ℃, and the temperature of the tubular furnace for the burning process is 1200 ℃; the time for carrying out heat release, pyrolysis and ignition in the tube furnace is 1 h.
Further, in step S3, the chloroform extraction and the methanol-acetone-benzene ternary extraction time are both 24 hours.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects: according to the preparation method of the shale carrier for adsorbing the petroleum liquid hydrocarbon, provided by the invention, a shale residue sample which is prepared by subdividing a shale sample through a specific treatment method and retains three types of active kerogen, active kerogen-removed shale, inert kerogen-removed shale (organic matter) and the like is used as an adsorption carrier, so that the preparation method has important significance for developing a liquid hydrocarbon adsorption test and related researches on organic matters containing kerogen with different structures.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention.
FIG. 1 is a flow chart of a processing method according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the accompanying drawings.
Examples
In the embodiment of the invention, the typical maturity of three upper sections, namely a shale oil enrichment region, a sunless depressed deep concave region and a nucleus, in China is selected to be within the range of an oil producing window (R)o＝0.55％About 0.75%) of a mashed bean curd type kerogen (I-II)1Type), considering that high-temperature ignition (1200 ℃ +/-may cause most of carbonate minerals in the sample to be decomposed, in order to make the subsequent heat release and pyrolysis treatment method and the adsorption carrier obtained by high-temperature ignition consistent as much as possible in inorganic mineral composition, before heat release, pyrolysis and ignition, the carbonate minerals in the shale are firstly removed by hydrochloric acid treatment, then the shale is treated by the heat release, pyrolysis and ignition method, and finally chloroform and ternary extraction are used to remove residual hydrocarbons possibly generated in the heat release, pyrolysis and ignition process. The final purpose is to prepare mud shale residue samples of three types of active kerogen retention, active kerogen removal, inert kerogen removal (organic matter) retention and inert kerogen removal as adsorption carriers. The specific process is as follows:
referring to fig. 1, an embodiment of the present invention provides a method for preparing a shale carrier for adsorbing petroleum liquid hydrocarbons, including the following steps:
1. crushing a shale sample collected in a deep concave area of a sunrise depression to 120 meshes, weighing 150g of the sample, placing the sample in a 400ml beaker, adding 200ml of hydrochloric acid with the volume fraction of 10%, fully and uniformly stirring, placing the sample in a water bath kettle at 50 ℃ for heating while stirring, washing residues left after the reaction to be neutral by using distilled water after the reaction is completed, and drying the residues at 110 ℃.
2. Dividing the dried residue sample treated by hydrochloric acid into three equal parts, placing one part in a Kabolat-Gammf Roman MTF type tube furnace, heating at 300 ℃ for 1h in a high-purity nitrogen atmosphere to remove soluble organic matters thermally, taking out the sample after cooling, placing the sample in a YSC type full-automatic multifunctional extractor, respectively extracting for 24h by using chloroform and methanol-acetone-benzene (MAB, 15%: 15%: 70%), taking out the residue and drying for later use, thus preparing the first shale residue sample retaining active kerogen as an adsorption carrier.
3. And placing the second sample in a Kaibozite-Gama Roman MTF type tube furnace, heating at 650 ℃ for 1h in a high-purity nitrogen atmosphere to remove active kerogen through pyrolysis, taking out the sample after cooling, placing the sample in a YSC type full-automatic multifunctional extractor, respectively extracting for 24h by using chloroform and methanol-acetone-benzene (MAB, 15%: 15%: 70%), and taking out and drying the residue for later use to obtain a second shale residue sample with the active kerogen removed and the inert kerogen remained as an adsorption carrier.
4. And placing the third sample in a Kaibozite-Gama Roman MTF type tube furnace, heating at 1200 ℃ for 1h in an oxygen atmosphere to burn out the active inert kerogen, cooling, taking out the sample, placing the sample in a YSC type full-automatic multifunctional extractor, respectively extracting for 24h by using chloroform and methanol-acetone-benzene (MAB, 15%: 15%: 70%), taking out the residue, and drying for later use to obtain a third shale residue sample with the inert kerogen (organic matter) removed as an adsorption carrier.
The features of the embodiments and embodiments described herein above may be combined with each other without conflict.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. The preparation method of the shale carrier for adsorbing the petroleum liquid hydrocarbon is characterized by comprising the following steps of:
s1, collecting a shale sample containing petroleum liquid hydrocarbon, treating the shale sample with hydrochloric acid to remove carbonate minerals in the shale sample, washing the residue left after the reaction with distilled water to be neutral, and equally dividing the shale residue sample into three parts;
s2, taking the first residue obtained in the step S1, and performing heat release treatment in a tube furnace at 300 ℃ to remove soluble organic matters in the shale residue;
performing pyrolysis treatment on the second part of residue obtained in the step S1 in a tube furnace at 650 ℃ to remove active kerogen in the shale residue;
taking the third residue obtained in the step S1, and burning the third residue in a tubular furnace at 1200 ℃ to remove inert kerogen in the shale residue;
s3, respectively adopting chloroform extraction and methanol-acetone-benzene ternary extraction to sequentially extract the first, second and third shale residue samples processed by the three methods in the step S2 for removing residual hydrocarbon possibly generated in the processing process in the step S2, and further preparing a first shale residue sample for retaining active kerogen, a second shale residue sample for removing active kerogen and retaining inert kerogen and a third shale residue sample for removing inert kerogen, wherein the obtained three shale residue samples can be used as shale carriers for carrying out tests of petroleum liquid hydrocarbon adsorption of organic matters containing kerogen with different structures.
2. The method for preparing a shale carrier for adsorbing petroleum liquid hydrocarbons as claimed in claim 1, wherein the removing carbonate minerals in the shale sample by hydrochloric acid treatment in step S1 comprises: crushing the shale sample, adding hydrochloric acid, fully stirring the mixture until the mixture is uniform, and placing the mixture in a water bath kettle to be heated and stirred for reaction.
3. The method of claim 1, further comprising drying the shale residue sample for further use after step S1.
4. The method for preparing a shale carrier for adsorbing petroleum liquid hydrocarbons as claimed in claim 1, wherein in step S2, the time for heat release, pyrolysis and burning in the tube furnace is 1 h.
5. The method for preparing a shale carrier for adsorbing petroleum liquid hydrocarbons as claimed in claim 1, wherein in step S3, the time for chloroform extraction and methanol-acetone-benzene ternary extraction are both 24 h.
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| CN112304799B (en) * | 2020-06-24 | 2021-06-22 | 成都理工大学 | Method for quantitatively analyzing organic matters in different occurrence states of shale oil reservoir |
| CN112016032B (en) * | 2020-07-24 | 2023-06-27 | 中国地质大学（武汉） | Hydrocarbon source rock hydrocarbon discharge efficiency calculation method and system based on pyrolysis parameter diagram format |
| CN111912960B (en) * | 2020-08-24 | 2022-11-08 | 东北石油大学 | Quantitative evaluation method and system for kerogen free oil in shale |
| CN112349356B (en) * | 2020-11-06 | 2022-09-23 | 中国石油大学(华东) | Shale oil absorption quantity evaluation model, method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104130818A (en) * | 2013-12-25 | 2014-11-05 | 吉林市东燃新能源科技有限责任公司 | Oil shale semi-coke activator, and preparation method and application thereof |
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| EP2895887B1 (en) * | 2012-09-12 | 2019-11-06 | BP Exploration Operating Company Limited | System and method for determining retained hydrocarbon fluid |
| CN104307415A (en) * | 2014-11-11 | 2015-01-28 | 四川省科源工程技术测试中心 | Kerogen separation equipment |
| CN105107590A (en) * | 2015-07-16 | 2015-12-02 | 中国地质大学（武汉） | Grinding device and method for oil gas-containing rock inclusion |
| CN106596605B (en) * | 2016-11-29 | 2019-11-08 | 中国石油天然气股份有限公司 | It is a kind of to prepare high-purity kerogenic method |
| CN108034650A (en) * | 2017-12-27 | 2018-05-15 | 北京嘉博文生物科技有限公司 | A kind of microbial bacteria agent carrier and preparation method and application |
| CN108982286B (en) * | 2018-08-28 | 2021-09-03 | 同济大学 | Separation and quantification method for soluble organic matters in different occurrence states in shale |
| CN109612794B (en) * | 2018-12-06 | 2021-05-11 | 同济大学 | Method for separating and quantifying organic matters in different occurrence states in hydrocarbon source rock |
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| CN104130818A (en) * | 2013-12-25 | 2014-11-05 | 吉林市东燃新能源科技有限责任公司 | Oil shale semi-coke activator, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
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| A. G. Ivanova 等."Mössbauer study of products of the thermocatalytic treatment of kerogen-containing rocks".《Bulletin of the Russian Academy of Sciences: Physics》.2017,第81卷 * |
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