An extraction separation device and separation method for deep brittle shale graptolite fossils

Abstract

The invention relates to a kind of extraction separation device and separation method for deep brittle shale graptolite fossil, the device includes: screening mechanism, for loading and screening shale sample;Container mechanism is used to accommodate screening mechanism;The screening mechanism is located in the container mechanism, and the shale sample to be separated is loaded in the screening mechanism, and the separation method comprises the following steps: (1) in small cup-shaped screen (5) loading shale sample containing shale graptolite fossil;(2) pour separation liquid into cup body (2), liquid just covers shale sample;After sealing by tightening upper cup cover (6), it is stationary;(3) open upper valve (7) and lower valve (9), inject distilled water and carry out circulating flushing, remove residue, and obtain graptolite fossil after separation.Compared with prior art, the method of the invention can completely separate graptolite fossil, and the graptolite fossil integrity can be maintained.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of paleontological fossils, in particular to a kind of extraction separation device and separation method for deep brittle shale graptolite fossils. BACKGROUND

[0002] Shale gas is a kind of natural gas in adsorbed, free or dissolved state in shale, which has important development value. Graptolite is a kind of soft body biological remains or remains of ancient semi-cord animals. Graptolite evolved very rapidly in the Paleozoic era and is widely distributed, which is one of the important biological fossils for stratigraphic division and correlation. With the exploration and development of shale gas to a depth of more than 3500m, shale graptolite fossils are continuously exposed by drilling core. It has become an important basic work for deep shale gas exploration and development to determine unknown horizon by graptolite identification and correlation. Graptolite fossil photographing and description are usually required in the identification process. Since two-dimensional plane photography cannot meet the needs of shale graptolite research, it is difficult to fully characterize graptolite structure, initial end development and cell tube morphology due to the scale and accuracy of two-dimensional characterization, which seriously affects the identification accuracy and scientificity of graptolite. Therefore, it is necessary to separate graptolite from rock and extract single graptolite three-dimensional individual, and then image research under scanning electron microscope or microscope, so as to obtain more information related to graptolite fossils, especially the initial end development characteristics of graptolite.

[0003] The commonly used fossil separation method at present is hand grinding method, which is to cut the fossils from the rock by using hammer head, cutting tool, saw blade, etc. The separation effect of this method is good for fossils such as brachiopods and dinosaurs with large individual, but it is difficult to apply to graptolite fossils due to the following reasons. The individual of graptolite fossil is generally several millimeters to several centimeters, the brittleness of deep shale is greater, the microcracks are more developed, and the graptolite fossil body is relatively fragile and easy to break after being hit. In addition, acid etching method is also used for super-micro fossils such as spores, but it is difficult to separate graptolite fossils. Since the composition of graptolite fossils is less different from the mineral composition of surrounding rock, strong acid used in acid etching method can dissolve the calcareous graptolite fossils and rock.

[0004] CN1810725A mentions a kind of separation method for dissolving treatment of carbonate rock sample by using chelating agent solution. Through field use, it is found that the above two methods mainly have the following defects: 1. The graptolite fossil is easily damaged and it is difficult to obtain complete sample due to the brittleness of graptolite body and the difficulty in controlling force and strength during hand grinding of rock. 2. The residues generated by acid etching method are almost composed of organic matter and microfossils resistant to acid, so it is impossible to obtain calcareous graptolite fossils. 3. The acid etching method and chelating agent dissolution method widely used at present generally use ordinary glassware, so that the sample treatment lacks specific device, the treatment efficiency is low, and the time consumption is long.

[0005] Therefore, the existing shale sample pre-treatment method and device have defects and need to be improved. SUMMARY

[0006] The present application aims to overcome the defects of the prior art and provide a method for completely separating graptolite fossils, as well as an extraction and separation device for deep brittle shale graptolite fossils that can maintain the integrity of graptolite fossils.

[0007] The object of the present application can be achieved by the following technical solutions:

[0008] The present application belongs to the field of shale graptolite extraction and separation, and can separate and extract graptolite fossils for identification and recognition of graptolite fossils, and is an important fossil extraction technology in the field of paleontological research, and specifically as follows:

[0009] An extraction and separation device for deep brittle shale graptolite fossils, comprising:

[0010] A screening mechanism for loading and screening shale samples;

[0011] A container mechanism for containing the screening mechanism;

[0012] The screening mechanism is located in the container mechanism, and the shale samples to be separated are loaded into the screening mechanism.

[0013] Further, the screening mechanism comprises a plurality of cup-shaped screens stacked one on top of another, with the screen hole diameters decreasing in sequence, and the shale samples to be separated are loaded into the uppermost cup-shaped screen.

[0014] Further, the screening mechanism comprises a small cup-shaped screen, a medium cup-shaped screen, and a large cup-shaped screen stacked one on top of another in sequence from top to bottom.

[0015] Further, the upper edges of the small cup-shaped screen and the medium cup-shaped screen are provided with a plurality of clamps, and the lower side of the large cup-shaped screen is provided with a plurality of legs.

[0016] Further, the mesh diameter of the small cup-shaped screen is 0.8-1.2mm, the mesh diameter of the medium cup-shaped screen is 400-600μm, and the mesh diameter of the large cup-shaped screen is 60-70μm.

[0017] Further, the container mechanism comprises a cup body and a cup cover connected in a screwing manner, the cup cover is provided with an upper valve, and the cup body is provided with a lower valve. The cup body and the cup cover are made of S304 stainless steel.

[0018] Further, an O-ring is provided between the cup body and the cup cover. The O-ring is made of silicone rubber.

[0019] A separation method using the extraction separation device for deep brittle shale graptolite fossils as described above, the method comprising the following steps:

[0020] (1) loading a shale sample containing shale graptolite fossils into a small cup-shaped sieve;

[0021] (2) pouring a separation liquid into the cup, with the liquid just covering the shale sample; after sealing with the upper cup cover, standing still;

[0022] (3) opening the upper valve and the lower valve, injecting distilled water for circulating flushing, taking out the residues, and obtaining graptolite fossils after separation.

[0023] Further, the specific operation of step (3) is:

[0024] (3-1) collecting the residues on each sieve respectively, and adding ethanol to reduce foam;

[0025] (3-2) collecting the floating graptolite fossils with a pipette, and storing the graptolite fossils in glycerol;

[0026] (3-3) after drying, using a sodium polytungstate ultrasonic high-speed centrifugal method to extract phosphate microfossils, and then washing the remaining calcareous fossils in an ultrasonic bath, to obtain phosphate microfossils and calcareous microfossils respectively.

[0027] Further, the separation liquid comprises 70-80 wt% of a cationic active agent and 20-30 wt% of a solvent; the cationic active agent comprises 1-methyl-1-oleamide ethyl-2-oleato imidazoline methyl sulfate ammonium, and the solvent is propylene glycol.

[0028] Compared with the prior art, the present application has the following advantages:

[0029] (1) In the present application, the cup cover and the cup body are sealed with an O-shaped sealing ring and connected in a screwing manner. The structure is compact, and the nested cup-shaped sieve makes it more convenient to disassemble and assemble. The box cover and the cup body have valves, which facilitate the injection and discharge of fluid;

[0030] (2) In the present application, the graptolite fossils generally have an extremely thin chitin on their surface, and the -OH bond can react with the oleic acid group and the unsaturated amine ethyl group of 1-methyl-1-oleamide ethyl-2-oleato imidazoline methyl sulfate ammonium to form a compound that can be dissolved in propylene glycol. With the passage of time, the reaction continues, and eventually a void space is formed along the surface of the graptolite, thereby separating the graptolite fossils from the rock. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 is a cross-sectional view of the extraction separation device in the embodiment;

[0032] Figure 2 Side view of nested cup-shaped screen in an embodiment;

[0033] Figure 3 Shale sample containing shale graptolite fossils in an embodiment;

[0034] Figure 4 Graptolite fossils collected in an embodiment;

[0035] Reference signs in the figure: leg 1, cup body 2, large cup-shaped sieve 3, medium cup-shaped sieve 4, small cup-shaped sieve 5, cup lid 6, upper valve 7, clamp 8, lower valve 9. DETAILED DESCRIPTION

[0036] The application will be described in detail below with reference to the drawings and specific embodiments. The embodiments are implemented on the premise of the technical solution of the application, and detailed implementation modes and specific operation processes are given, but the protection scope of the application is not limited to the following embodiments.

[0037] Active agent separation effect comparison test:

[0038] 1. Separation method of 1-methyl-1-oleamide ethyl-2-oleylimidazoline methyl sulfate ammonium (70-80 wt%) and propylene glycol (20-30 wt%)

[0039] Take 1000 grams of sample (fossil content 5 wt%), put it into the cup, inject 2 liters of 1-methyl-1-oleamide ethyl-2-oleylimidazoline methyl sulfate ammonium 75 wt% and propylene glycol 25 wt%, and stand for 10 days after injection. Then, use distilled water to rinse. Collect the residues on each sieve, dry the residues at 30°C, extract the phosphate microfossils by using the multi-tungsten sodium ultrasonic high-speed centrifugation method, and then clean the remaining calcareous fossils in an ultrasonic bath to obtain phosphate microbodies and calcareous microbodies of fossils, respectively.

[0040] 2. Pluronic PE10500 active agent separation method

[0041] Take 1000 grams of sample (fossil content 5 wt%), put it into the cup, inject 2 liters of Pluronic PE10500 active agent solution, and stand for 10 days after injection. Then, use distilled water to rinse. Collect the residues on each sieve, dry the residues at 30°C, extract the phosphate microfossils by using the multi-tungsten sodium ultrasonic high-speed centrifugation method, and then clean the remaining calcareous fossils in an ultrasonic bath to obtain phosphate microbodies and calcareous microbodies of fossils, respectively.

[0042] The comparison of the extraction and separation effects of two active agents: 1-methyl-1-oleamide ethyl-2-oleic imidazoline methyl sulfate ammonium (70-80 wt%) and propylene glycol (20-30 wt%) separation method and Pluronic PE10500 active agent separation method. The residues recovered by extraction are 30 grams and 5 grams, respectively, and the fossil extraction rates are 60% and 10%, respectively. The main body of the extraction residue of 1-methyl-1-oleamide ethyl-2-oleic imidazoline methyl sulfate ammonium (70-80 wt%) and propylene glycol (20-30 wt%) separation method is graptolite fossils (20 grams), the purity of which is more than 98%, calcareous microfossils such as insect teeth and sponge spicules (5 grams), the purity of which is 95%, and the shells of other epigenetic organisms (5 grams), the purity of which is 95%. The residues recovered by extraction of the Pluronic PE10500 active agent separation method are mainly clay rock fragments, only a small amount of graptolite fragments (2 grams), the purity of which is about 70%, and a small amount of chitinous animals and insect teeth (3 grams), the purity of which is less than 60%, and no calcareous fossils are detected.

[0043] Under the same conditions, the active agent and the ratio of the present application can separate more graptolite fossils with higher purity. The above comparison shows that the active agent and the formula used in the present application have more obvious separation effect.

[0044] Embodiment

[0045] An extraction and separation device for deep brittle shale graptolite fossils, as shown in Figure 1 , the device comprises: a screening mechanism for loading and screening shale samples; a container mechanism for containing the screening mechanism; the screening mechanism is located in the container mechanism, and the shale samples to be separated are loaded in the screening mechanism.

[0046] As shown in Figure 2 , the screening mechanism comprises a small cup-shaped sieve 5, a medium cup-shaped sieve 4 and a large cup-shaped sieve 3 stacked in order from top to bottom. The upper edges of the small cup-shaped sieve 5 and the medium cup-shaped sieve 4 are provided with a plurality of clamps 8, and the lower side of the large cup-shaped sieve 3 is provided with a plurality of legs. The mesh diameter of the small cup-shaped sieve 5 is 0.8-1.2 mm, the mesh diameter of the medium cup-shaped sieve 4 is 400-600 μm, and the mesh diameter of the large cup-shaped sieve 3 is 60-70 μm.

[0047] In most cases, graptolite fossils are not complete, and there are graptolite fragments, residues or partial organizations in the rock. The volume of this part is smaller than that of the graptolite body, so three layers of screens are set. The purpose is to collect as much information as possible about graptolite fossils, including fragments, residues or partial organizations. Practice has proved that the three layers of screens can achieve the above-mentioned goal.

[0048] The container mechanism comprises a cup body 2 and a cup cover 6 connected in a screwing manner, the cup cover 6 is provided with an upper valve 7, and the cup body 2 is provided with a lower valve 9. The cup body 2 and the cup cover 6 are made of S304 stainless steel. An O-shaped sealing ring is arranged between the cup body 2 and the cup cover 6. The O-shaped sealing ring is made of silicone rubber.

[0049] A separation method, comprising the steps of:

[0050] (1) loading a shale sample containing shale graptolite fossils into a small cup-shaped sieve 5, such as Figure 3 ;

[0051] (2) pouring a separation liquid into the cup body 2, the liquid just covers the shale sample; after the upper cup cover 6 is tightly screwed and sealed, it is placed for 10 days; the separation liquid comprises 75wt% of a cationic active agent and 25wt% of a solvent; the cationic active agent is 1-methyl-1-oleamide ethyl-2-oleic imidazoline ammonium sulfate, and the solvent is propylene glycol.

[0052] 1-methyl-1-oleamide ethyl-2-oleic imidazoline ammonium sulfate is a macromolecular compound, and the molecular structure thereof has unsaturated groups such as an oleic acid group and an oleic amine ethyl group. The graptolite fossils generally have an extremely thin chitin on the surface, and the -OH bond thereof can react with the unsaturated groups such as the oleic acid group and the oleic amine ethyl group of 1-methyl-1-oleamide ethyl-2-oleic imidazoline ammonium sulfate to generate a compound that can be dissolved in propylene glycol. With the passage of time, the reaction continuously proceeds, and eventually a void space is formed along the surface of the graptolite, thereby separating the graptolite fossils from the rock.

[0053] (3) opening the upper valve 7 and the lower valve 9, injecting distilled water for circulating flushing, taking out the residues, and obtaining the graptolite fossils after separation, the specific operation being:

[0054] (3-1) collecting the residues on each sieve respectively, and adding ethanol to reduce foam;

[0055] (3-2) collecting the floating graptolite fossils by using a pipette, such as Figure 4 , and storing the graptolite fossils in glycerol;

[0056] (3-3) after drying the other residues, using a multi-tungsten sodium ultrasonic high-speed centrifugal method to extract phosphate microfossils, and then cleaning the remaining calcareous fossils in an ultrasonic bath, to obtain phosphate microbodies and calcareous microfossils respectively.

[0057] The graptolite fossils are composed of tholus, graptolite branch, mouth spine, wire tube and other parts, therefore, the comparison of the above parameters of the graptolite fossils before and after extraction can reflect the advantages of the method, the graptolite completeness is more than 90%, and the integrity is well maintained. The present application takes single graptolite as an example to illustrate that the integrity of graptolite is not affected before and after extraction, and it is proved that the method can maintain the integrity of graptolite.

[0058] Comparison table of single graptolite shape parameters before and after extraction

[0059]

[0060] The above description is only a preferred embodiment of the present application, and does not limit other forms of the present application. Any person skilled in the art can modify or change the above disclosed technical content into equivalent embodiments with equivalent changes. However, any simple modification, equivalent change and modification of the above embodiments made according to the technical essence of the present application without departing from the technical scheme of the present application still belongs to the protection scope of the present application.

Claims

1. A method for the isolation of deep-burial brittle shale graptolite fossils, characterized by, The method comprises the following steps: (1) loading shale samples containing shale graptolite fossils into small cup-shaped screens (5); (2) pouring a separating liquid into the cup body (2), the liquid just covering the shale samples, the separating liquid comprising 70-80 wt% of a cationic active agent and 20-30 wt% of a solvent; the cationic active agent comprising 1-methyl-1-oleylamidoethyl-2-oleylimidazoline methyl sulfate ammonium, and the solvent being propylene glycol; after the upper cup cover (6) is screwed tightly to seal, standing still; (3) opening the upper valve (7) and the lower valve (9), injecting distilled water for circulating flushing, taking out the residues, and obtaining graptolite fossils after separation; The separating method is based on an extraction separation device for deep brittle shale graptolite fossils, which comprises: a screening mechanism for loading and screening shale samples; the screening mechanism comprises small cup-shaped screens (5), medium cup-shaped screens (4) and large cup-shaped screens (3) stacked from top to bottom, shale samples to be separated are loaded on the uppermost cup-shaped screen, the small cup-shaped screens (5) and the medium cup-shaped screens (4) are provided with a plurality of clamps (8) at the upper edges, the large cup-shaped screens (3) are provided with a plurality of supporting legs (1) below, the mesh diameter of the small cup-shaped screens (5) is 0.8-1.2 mm, the mesh diameter of the medium cup-shaped screens (4) is 400-600 μm, and the mesh diameter of the large cup-shaped screens (3) is 60-70 μm; a container mechanism for accommodating the screening mechanism; the container mechanism comprises a cup body (2) and a cup cover (6) connected in a screwing manner, the cup cover (6) is provided with an upper valve (7), the cup body (2) is provided with a lower valve (9), and an O-shaped sealing ring is arranged between the cup body (2) and the cup cover (6); the screening mechanism is located in the container mechanism, and shale samples to be separated are loaded in the screening mechanism.

2. The method for extraction and separation of deep-buried brittle shale graptolite fossils according to claim 1, characterized in that, The specific operation of step (3) is as follows: (3-1) collecting the residues on each screen respectively, and adding ethanol to reduce foam; (3-2) collecting floating graptolite fossils, and storing the graptolite fossils in glycerol; (3-3) after drying, using a multi-tungsten sodium ultrasonic high-speed centrifugal method to extract phosphate microfossils, and then washing the remaining calcareous fossils in an ultrasonic bath to obtain phosphate microfossils and calcareous microfossils respectively.

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