CN113358680B - A method and application for differentiating and semi-quantitative analysis of different types of montmorillonite in geological samples - Google Patents

Abstract

The invention discloses a method and application for distinguishing and semi-quantitatively analyzing different types of montmorillonite in a geological sample, comprising the following steps: enriching and extracting clay minerals from the sample; preparing original oriented sheets before and after HCl dissolution and Mg ²⁺ and Ethylene glycol saturated directional sheet; XRD test and semi-quantitative analysis before and after HCl dissolution; relative content of all clay minerals including Na-montmorillonite and Ca-montmorillonite. The invention adopts the hydrochloric acid dissolution method to remove the Ca-montmorillonite, realizes the distinction and quantitative analysis of Na-montmorillonite and Ca-montmorillonite, and provides a new way for the identification and quantitative analysis of different types of montmorillonite.

Description

A method and application for differentiating and semi-quantitative analysis of different types of montmorillonite in geological samples

technical field

The invention belongs to the technical field of clay mineral analysis, and in particular relates to a method and application for distinguishing and semi-quantitatively analyzing different types of montmorillonite in geological samples.

Background technique

Clay minerals widely exist on the earth's surface, and as non-metallic resources, they are widely used in various fields such as medicine, chemical industry, and environmental management. At the same time, in the field of earth science, clay minerals are important weathering products of surface rock minerals, and their composition characteristics can reflect the climatic conditions and material sources during the formation period. Therefore, the study of clay minerals is an important way to explore the evolution history and development law of paleoclimate, and it is also an important method to trace sediment provenance (Velde, 1995).

The identification and quantitative analysis of different types of clay minerals are the basis for clay applications and research in various fields. The most extensive and effective identification method for clay minerals is X-ray diffraction (XRD). Peak areas were identified and semiquantitatively analyzed. However, due to the low-temperature genesis and layered characteristics of clay minerals, different minerals have the same diffraction peaks, which brings difficulties to the identification of clay minerals. For a long time, predecessors have proposed a variety of XRD pretreatment methods for different minerals, and realized the identification of some clay minerals with overlapping diffraction peaks. For example, dimethyl sulfoxide (DMSO) treatment distinguishes kaolinite from chlorite, ethylene glycol treatment distinguishes expansive minerals from chlorite, etc. (Abdel-Kader et al., 1975; Walker, 1958).

As a kind of expansive clay minerals, montmorillonite is a widely used raw material in chemical industries such as pharmaceuticals, pollution control and catalysts. Common montmorillonites in nature include Na-montmorillonite and Ca-montmorillonite, which are named after the main cations between the layers are Na ⁺ and Ca ²⁺ . The identification and quantitative analysis of two types of montmorillonite in the field of earth science has important theoretical and economic value.

和14

在没有其他黏土矿物的情况下能够直接区分两种蒙脱石。但在自然样品中往往还存在其他类型的黏土矿物，如绿泥石、伊利石和高岭石等。由于绿泥石的001峰同样在

左右，导致原始定向片无法有效区分Ca-蒙脱石和绿泥石。在通用方法中Mg²⁺和乙二醇饱和处理能够将膨胀性矿物蒙脱石的001衍射峰，以Mg²⁺替换其他层间阳离子和有机物乙二醇进入层间增大层间距的方式，将001衍射峰移向角度更低的

从而实现蒙脱石与绿泥石的区分。但如此一来，层间阳离子不同的Na-蒙脱石和Ca-蒙脱石均被Mg²⁺置换，导致这种处理之后的两种蒙脱石衍射谱峰完全相同。In the general clay mineral identification method, generally follow the steps of clay enrichment extraction, original oriented sheet preparation, Mg ²⁺ and ethylene glycol saturated oriented sheet preparation, XRD test analysis, at the same time, Mg ²⁺ and ethylene glycol Saturated oriented sheet preparation is a necessary step for semi-quantitative calculations of clay minerals (Moore and Reynolds, 1997; Zhang et al., 2014). In the original oriented sheet, the 001 diffraction peaks of Na-montmorillonite and Ca-montmorillonite are respectively

and 14

The two montmorillonites can be directly distinguished in the absence of other clay minerals. But other types of clay minerals, such as chlorite, illite, and kaolinite, are often present in natural samples. Since the 001 peak of chlorite is also in

left and right, resulting in the inability of the original oriented sheet to effectively distinguish Ca-montmorillonite from chlorite. In the general method, Mg ²⁺ and ethylene glycol saturation treatment can replace the 001 diffraction peak of the expansive mineral montmorillonite with Mg ²⁺ to replace other interlayer cations and organic ethylene glycol into the interlayer to increase the interlayer distance. Shift the 001 diffraction peak to a lower angle

So as to realize the distinction between montmorillonite and chlorite. However, in this way, Na-montmorillonite and Ca-montmorillonite with different interlayer cations are replaced by Mg ²⁺ , resulting in the same diffraction peaks of the two montmorillonite after this treatment.

Therefore, the existing identification and quantification methods cannot effectively distinguish the two kinds of montmorillonite minerals, and cannot analyze the content of two different montmorillonite minerals when there are multiple clay minerals mixed in natural samples.

At present, in the prior art, for example, the invention patent with the patent application number CN201810517982.X discloses a semi-quantitative method for indirectly testing the content of montmorillonite in coal minerals. First, the coal minerals are pulverized, and the coal minerals are separated by burning. Inorganic minerals, calculate the content of coal ash relative to coal, then measure the content of montmorillonite in coal ash by blue absorption method, and finally calculate the content of montmorillonite in coal according to coal ash content and montmorillonite content in coal ash. The invention adopts the burning method to separate the inorganic minerals in the coal, and measures the montmorillonite content in the coal ash. , but still cannot effectively distinguish the two montmorillonite minerals.

SUMMARY OF THE INVENTION

The invention provides a method for distinguishing and semi-quantitatively analyzing different types of montmorillonite in geological samples. The calibrated method enables the identification and quantification of two different types of montmorillonite in natural samples.

The invention discloses a method for distinguishing and semi-quantitatively analyzing different types of montmorillonite in geological samples, comprising the following steps:

(1) enrichment and extraction of clay minerals from geological samples;

(2) Prepare original oriented sheet, Mg saturated sheet, K saturated sheet and ethylene glycol saturated oriented sheet, and carry out XRD analysis;

(3) Remove the original oriented sheet and put it into HCl solution to dissolve and remove Ca-montmorillonite and chlorite;

(4) carrying out Mg-saturation and ethylene glycol atomization treatment on the samples from which Ca-montmorillonite and chlorite were removed in step (3), and re-prepared into original oriented sheets, Mg-saturated sheets and ethylene glycol-saturated oriented sheets;

(5) XRD test and semi-quantitative analysis were carried out on the Mg-saturated sheets and ethylene glycol-saturated oriented sheets prepared before and after HCl dissolving;

(6) Calculate the relative content of all clay minerals.

Preferably in any of the above solutions, after the geological sample in step (1) is crushed, organic matter cement and/or carbonate cement and/or gypsum minerals are removed, centrifuged, eluted to neutrality, and the extraction particle size is less than 2 μm. the clay component.

Preferably in any of the above solutions, hydrogen peroxide is used to remove organic cements, and an acetic acid reagent is added to remove carbonate cements.

Preferably in any of the above solutions, 20ml of 25% hydrogen peroxide is used to remove organic cements, and 0.5mol/L acetic acid reagent is added to remove carbonate cements.

Preferably in any of the above solutions, 20 ml of 30% hydrogen peroxide is used to remove organic cements, and 1 mol/L acetic acid reagent is added to remove carbonate cements.

Preferably in any of the above solutions, 20 ml of 35% hydrogen peroxide is used to remove organic cements, and 1.5 mol/L acetic acid reagent is added to remove carbonate cements.

Preferably in any of the above solutions, the method for preparing the original orientation sheet in the step (2) is as follows: sucking the clay-containing suspension droplets obtained in the step (1) onto a glass slide and coating it into a 2cm×2cm size. Squares, given original directional slices (original slices).

Preferably in any of the above-mentioned schemes, in the step (2), when the Mg-saturated sheet is prepared, a solution containing magnesium ions is added to the suspension containing the clay particles, and the Mg ²⁺ replacement interlayer cation treatment is carried out, until the Mg ^{2+ is} fully After replacing cations in the interlayer of 2:1 expansive clay minerals, centrifugation and elution were performed to prepare Mg-saturated sheets.

In any of the above solutions, preferably, the 2:1 type expansive clay minerals include any one of montmorillonite, nontronite, bailerite, vermiculite and saponite.

Preferably in any of the above solutions, the magnesium ion-containing solution is MgCl ₂ .

Preferably in any of the above solutions, the MgCl ₂ solution is 0.5-2 mol/L.

Preferably in any of the above solutions, the MgCl ₂ solution is 0.5 mol/L.

Preferably in any of the above solutions, the MgCl ₂ solution is 1 mol/L.

Preferably in any of the above solutions, the MgCl ₂ solution is 1.5 mol/L.

Preferably in any of the above solutions, the MgCl ₂ solution is 2 mol/L.

Preferably in any of the above-mentioned schemes, in the step (2), when the K-saturated sheet is prepared, a solution containing potassium ions is added to the clay-containing suspension, and the 2:1-type swelling clay mineral layer is fully replaced by K ⁺ . After the inter-cation, centrifugation, elution, and making K-saturated tablets.

Preferably in any of the above-mentioned schemes, the solution of the potassium ion is KCl.

Preferably in any of the above schemes, the KCl is 0.5-2 mol/L.

Preferably in any of the above solutions, the KCl is 0.5mol/L.

Preferably in any of the above solutions, the KCl is 1 mol/L.

Preferably in any of the above solutions, the KCl is 1.5mol/L.

Preferably in any of the above schemes, the KCl is 2 mol/L.

Preferably in any of the above solutions, in the step (2), the K sheet is heated at 140-160° C., 280-320° C., 540-560° C., respectively, and then subjected to XRD analysis, and compared with the original oriented sheet XRD results to identify Chlorite and Kaolinite.

Preferably in any of the above solutions, in the step (2), the K sheet is heated at 140° C., 280° C. and 540° C., respectively, and then subjected to XRD analysis, and compared with the XRD results of the original oriented sheet to identify chlorite and kaolinite. .

Preferably in any of the above solutions, in the step (2), the K sheet is heated at 150° C., 300° C. and 550° C., respectively, and then subjected to XRD analysis, and compared with the XRD results of the original oriented sheet to identify chlorite and kaolinite. .

Preferably in any of the above solutions, in the step (2), the K sheet is heated at 160° C., 320° C. and 560° C., respectively, and then subjected to XRD analysis, and compared with the XRD results of the original oriented sheet to identify chlorite and kaolinite. .

Preferably in any of the above-mentioned solutions, in the step (2), the ethylene glycol saturated directional sheet is obtained by using the prepared Mg saturated sheet to carry out ethylene glycol atomization treatment.

Preferably in any of the above-mentioned schemes, the preparation method of the ethylene glycol saturated directional sheet in the step (2) is: putting the prepared Mg saturated sheet into the ethylene glycol atomizing box, adding ethylene glycol under constant temperature conditions The alcohol solution was nebulized and kept for 4 days.

Preferably in any of the above solutions, the constant temperature is set at 40-50°C, 50ml of 95%-100% ethylene glycol solution is added, and the atomizer is turned on.

Preferably in any of the above solutions, the constant temperature is set to 40° C., 50 ml of 100% ethylene glycol solution is added, and the atomizer is turned on.

Preferably in any of the above solutions, the constant temperature is set to 45° C., 50 ml of 100% ethylene glycol solution is added, and the atomizer is turned on.

Preferably in any of the above solutions, the constant temperature is set to 50° C., 50 ml of 95% ethylene glycol solution is added, and the atomizer is turned on.

Above-mentioned any scheme is preferably, described in step (2) also comprises according to montmorillonite: (chlorite+kaolinite): illite=1:2:4, calculate and determine ethylene glycol saturated directional sheet The relative content of each clay mineral.

Preferably in any of the above solutions, the step (3) is to dissolve the original oriented sheet in HCl solution and heat to dissolve and remove Ca-montmorillonite and chlorite.

Preferably in any of the above solutions, the HCl solution is 2-4 mol/L, heated to 65-75° C. to dissolve and remove Ca-montmorillonite and chlorite.

Preferably in any of the above solutions, the HCl solution is 2 mol/L, heated to 75° C. to dissolve and remove Ca-montmorillonite and chlorite.

Preferably in any of the above solutions, the HCl solution is 3 mol/L, and the solution is heated to 70° C. to dissolve and remove Ca-montmorillonite and chlorite. After many experiments, it has been confirmed that when the concentration is higher than 3mol/L, Ca-montmorillonite can be removed, but if the concentration is too high, Na-montmorillonite will also be destroyed, so 3mol/L is the best.

Preferably in any of the above solutions, the HCl solution is 4 mol/L, and the solution is heated to 65° C. to dissolve and remove Ca-montmorillonite and chlorite.

In any of the above solutions, preferably, the samples from which Ca-montmorillonite and chlorite are removed in step (4) are placed in a solution containing magnesium ions for Mg ²⁺ replacement interlayer cation treatment to prepare Mg-saturated sheets.

Preferably in any of the above solutions, the magnesium ion-containing solution is MgCl ₂ .

Preferably in any of the above solutions, the MgCl ₂ solution is 0.5-2 mol/L.

Preferably in any of the above solutions, the MgCl ₂ solution is 0.5 mol/L.

Preferably in any of the above solutions, the MgCl ₂ solution is 1 mol/L.

Preferably in any of the above solutions, the MgCl ₂ solution is 1.5 mol/L.

Preferably in any of the above solutions, the MgCl ₂ solution is 2 mol/L.

Preferably in any of the above-mentioned solutions, in the step (4), the obtained Mg-saturated sheet is subjected to ethylene glycol atomization treatment to prepare the ethylene glycol-saturated directional sheet.

The present invention also discloses the above-mentioned method for distinguishing and identifying different types of montmorillonite.

The invention also discloses an atomization treatment device for clay mineral directional sheets, which is suitable for use in the preparation of ethylene glycol saturated directional sheets in the above steps, and specifically includes an atomization box. There are sensors and spray components. One end of the spray component is horizontally arranged in the atomization box, and the other end extends to the outside of the atomization box. The spray component can change the spray position through the servo motor and the moving component to achieve horizontal and vertical directions. Mobile spray, the bottom of the atomization box is equipped with a heating device.

Preferably, the sensor includes an air pressure sensor and a temperature sensor, and the air pressure sensor and the temperature sensor are arranged in the upper part of the atomizing box.

Preferably in any of the above solutions, the storage rack includes a plurality of L-shaped drawers arranged up and down.

In any of the above solutions, preferably, the drawer includes a horizontally arranged support plate, the support plate is horizontally arranged, and one end of the support plate is vertically connected with a sealing plate.

In any of the above solutions, preferably, the inner side of the sealing plate is provided with a sealing block, the sealing block is a triangular sealing block, and the outer surface of the sealing block is inclined.

In any of the above solutions, preferably, the sealing block is a right-angled triangular sealing block, and the outer plate surface of the sealing block is inclined.

In any of the above solutions, preferably, the upper end of the support plate is provided with a movable baffle assembly vertically, and the bottom side of the movable baffle assembly is provided with an inclined surface to facilitate the insertion of the support plate and also form a sealing effect. The upper end of the movable baffle assembly is connected with a fixed end through an elastic part. The lower end of the movable baffle assembly is sealed with a silicone layer or the like. The sealing block, the movable baffle assembly and the side wall of the atomizing box or the movable baffle assembly and the side wall of the atomizing box can be enclosed to form an isolation area and enhance the sealing effect in the atomizing box.

In any of the above solutions, preferably, the movable baffle assembly includes an inner baffle and an outer baffle, and the inner baffle and the outer baffle are integrally provided or separately provided.

In any of the above-mentioned solutions, it is preferred that, when the inner baffle and the outer baffle are arranged separately, the inner baffle and the outer baffle are adjacent and arranged in parallel, and the inner baffle and the outer baffle are arranged in parallel. The lengths are the same, and the outer surface of the bottom of the outer baffle is provided with an inclined surface, and the inclined surface is matched with the outer surface of the triangular sealing block.

Preferably in any of the above solutions, the elastic member is a spring.

In any of the above solutions, preferably, the fixed end is arranged on the upper part of the movable baffle assembly and fixed on the inner wall of the atomizing box.

In any of the above solutions, it is preferable that a plurality of placement slots are arranged in the support plate at intervals, the glass slides are arranged in the placement slots, and the support plates between adjacent slide glass are provided with anti-corrosion pads.

In any of the above solutions, preferably, the side wall of the atomizing box is provided with an insertion opening, and one end of the support plate can be inserted into the atomizing box through the insertion opening.

Preferably in any of the above solutions, the number of the drawers is 4, and the 4 drawers are arranged at intervals up and down.

In any of the above solutions, preferably, a cover plate is provided on the drawer, and the cover plate can be inserted from one side of the sealing plate and extend to the upper part of the support plate to seal the slide glass on the upper part of the support plate.

Preferably in any of the above solutions, the atomizer is arranged on the upper part of the atomization box, the ethylene glycol or glycerin solution is filled in the atomizer, and the upper part of the atomization box is provided with an air release valve.

Preferably in any of the above solutions, the sensor includes an air pressure sensor and a temperature sensor.

In any of the above solutions, preferably, a glass observation window is provided on the movable baffle assembly on the insertion side of each drawer and/or the side wall of the corresponding atomizing box.

Preferably in any of the above-mentioned schemes, the spray assembly includes a conduit, the upper end of the conduit is communicated with the atomizer, a plurality of horizontally arranged spray sub-pipes are communicated with the conduit, the end of the spray sub-pipe is connected to a spray head, and the conduit is provided with. Catheter valve.

In any of the above solutions, preferably, the spray branch pipe is a telescopic organ pipe, so as to be telescopic, stretchable and movable.

Preferably in any of the above-mentioned schemes, the moving assembly comprises an L-shaped x-direction bracket set on the upper and lower layers, a support rod and a y-direction bracket are also provided between the upper and lower layers of the x-direction bracket, and one of the x-direction brackets is provided. There is a first guide rail on one side, and a first screw rod on the other side. One end of the first screw rod is connected to the y-direction moving motor. The middle of the support rod is sleeved with a second screw rod. Move the motor connection.

Preferably in any of the above solutions, the L-shaped x-direction bracket includes a first fixing plate and a second fixing plate, the first fixing plate and the second fixing plate are vertically arranged in the same plane, and the first screw rod is arranged at On one side of the first fixing plate of the upper x-direction bracket, the first guide rail is arranged on one side of the second fixing plate and is fixed by the inner wall of the atomizing box.

In any of the above solutions, preferably, the x-direction support is driven by the x-direction moving motor and the first screw rod to move forward and backward, and the y-direction support is driven by the y-direction moving motor and the second screw rod to move left and right.

In any of the above solutions, preferably, the conduit y is connected to the shower head through a horizontally arranged fixing rod, so that when the conduit y moves towards the bracket, the shower head can be driven to move.

In any of the above solutions, it is preferable that a vacuuming assembly is provided on one side of the atomizing box, and the vacuuming assembly includes a liquid collecting tank. The air pipe valve, the lower end of the air suction pipe is connected with the condenser pipe, the condenser pipe extends into the liquid collection bottle, and one side of the liquid collection bottle is connected with the vacuum pump.

In any of the above solutions, preferably, both the water inlet and the water outlet of the condensation pipe are arranged outside the liquid collecting tank.

A processing method according to the above-mentioned clay mineral directional sheet atomization processing device, comprising the following steps:

(1) First check the air tightness of the atomization treatment device: insert the empty drawer directly into the atomization box, close the conduit valve and the air release valve, open the vacuum pump, open the valve of the exhaust pipe, do not need to open the cooling water, put the atomization box After pumping into negative pressure, close the valve of the exhaust pipe, turn off the vacuum pump, observe the reading of the air pressure sensor, and the vacuum degree in the atomizing box remains unchanged, then it can be used normally;

(2) Saturate the organic solvent ethylene glycol and glycerin: put the directional sheet coated with clay minerals into the drawer, insert the drawer into the atomization box, and draw the atomization box into 6.6 in accordance with the operation method of step (1). After Pa, close the valve and turn off the vacuum pump;

(3) Start the x-direction movement motor and the y-direction movement motor, so that the y-direction bracket and the x-direction bracket drive the catheter to move back and forth above the drawer as required, open the atomizer, set the valve according to the catheter to be used, and atomize the sample spray;

(4) Turn on the heating element and heat it to 30°C, keep the constant temperature and pressure closed for 48h to reach the saturation of the organic solvent in the clay mineral to be tested;

(5) Sampling for XRD test: open the vacuum pump, open the valve of the exhaust pipe, do not need to open the cooling water, remove the residual air in the atomization box, close the valve of the exhaust pipe, close the vacuum pump, open the exhaust valve, and take out the test in the drawer. The samples were tested by XRD;

(6) Clean up the atomization box after the saturation treatment: insert the empty drawer directly into the atomization box, close the conduit valve and the air release valve, turn on the vacuum pump, and open the valve of the exhaust pipe. It is not necessary to open the cooling water. After the residual air is evacuated, close the valve of the exhaust pipe and turn off the vacuum pump; use the heating element to heat the atomizing box, use the air pressure sensor and temperature sensor to understand the situation in the atomizing box, confirm the residual ethylene glycol through the glass observation window, and turn on the cooling water. Turn on the vacuum pump, open the valve of the suction pipe, and pump out the ethylene glycol vapor in the atomizing box.

beneficial effect

The invention discloses a method for distinguishing and semi-quantitatively analyzing different types of montmorillonite in geological samples. Alcohol-saturated oriented sheet; XRD test and semi-quantitative analysis before and after HCl dissolution; relative content of all clay minerals including Na-montmorillonite and Ca-montmorillonite. The invention adopts the hydrochloric acid (HCl) dissolution method to remove the Ca-montmorillonite, realizes the distinction and quantitative analysis of Na-montmorillonite and Ca-montmorillonite, and provides a new way for the identification and quantitative analysis of different types of montmorillonite .

At the same time, the invention discloses a clay mineral directional sheet atomization treatment device, which effectively solves the problem of XRD analysis errors caused by different expansive clay contents and drying time. At the same time, the non-contact ethylene glycol saturation treatment process is adopted to achieve the greatest protection for the personal health of the experimenters. The non-contact saturation treatment process prevents the experimenters from contacting toxic reagents and protects health and safety. The atomization treatment device of the invention can carry out the saturated atomization treatment of clay mineral crystal lattice organic molecules in batch and non-contact mode, and can process 200 samples at a time and batch process 200 samples. Greatly improve the efficiency of experimental testing; ensure that each sample to be tested has the same degree of organic saturation, reducing the error of different samples. Batch processing under uniform conditions ensures that each sample to be tested has the same degree of saturation of organic molecules; the samples waiting to be tested are in a closed environment to avoid changes in the degree of saturation caused by volatilization of organic solvents in the air; the device can also realize the recovery and recycling of organic reagents ,save resources.

Description of drawings

Fig. 1 is the analysis flow chart of a preferred embodiment of the method for distinguishing and semi-quantitatively analyzing different types of montmorillonite in geological samples according to the present invention;

Fig. 2 is the XRD diffraction pattern of Ca-montmorillonite before and after 3mol/L HCl treatment;

Fig. 3 is the XRD diffraction pattern of Na-montmorillonite before and after 3mol/L HCl treatment;

Figure 4 shows the TEM images of Ca-montmorillonite and Na-montmorillonite before and after 3 mol/L HCl treatment, in the figure a) is the crystal form and electron diffraction results of Ca-montmorillonite before HCl treatment, b) is after HCl treatment The crystal form and electron diffraction result of Ca-montmorillonite; c) is the crystal form and electron diffraction result of Na-montmorillonite before HCl treatment, d) is the crystal form and electron diffraction result of Na-montmorillonite after HCl treatment;

Fig. 5 is the structural representation of the clay mineral directional sheet atomization treatment device of the present invention;

6 is a partial structural cross-sectional view of a preferred embodiment of the clay mineral directional sheet atomization treatment device of the present invention;

FIG. 7 is a schematic diagram of the pull-out structure of the cover plate in FIG. 2;

8 is a partial structural cross-sectional view of another preferred embodiment of the clay mineral oriented sheet atomization treatment device of the present invention;

FIG. 9 is a schematic diagram of the pull-out structure of the cover plate in FIG. 4;

10 is a schematic diagram of a drawer structure of a preferred embodiment of the clay mineral oriented sheet atomization treatment device of the present invention;

Figure 11 is a top view of the structure of Figure 6;

Figure 12 is a schematic structural diagram of the mobile assembly in Figure 1;

Fig. 13 is the XRD diffractogram of adopting the clay mineral directional sheet atomization treatment device of the present invention and other methods for ethylene glycol saturation treatment;

Among them, the meanings of the symbols in the figure are as follows:

1. Air pressure sensor, 2. Catheter valve, 3. Temperature sensor, 4. Drawer, 41. Support plate, 5. Catheter, 6. Catheter support x-direction moving motor, 7. Catheter y-direction support, 8. Heating element, 9 , Vacuum pump, 10, Liquid collection bottle, 11, Condenser pipe, 12, Exhaust pipe, 13, Exhaust pipe valve, 14, Catheter support y-direction moving motor, 15, Catheter x-direction support, 151, First fixing plate, 152, Second fixing plate, 16, Nebulizer, 17, Glass slide (orientation sheet), 18, Anti-corrosion spacer, 20, Air release valve, 21, Glass observation window, 22, Nebulizer box, 221, Insertion port, 23, movable baffle assembly, 231, inner baffle, 232, outer baffle, 24, fixed end, 25, elastic part, 26, sprinkler head, 27, support rod, 28, first guide rail, 29, The first screw rod, 30, the second screw rod, 31, the liquid collecting tank, 32, the fixing rod, 33, the cover plate, 42, the sealing plate, 43, the sealing block.

Detailed ways

The following embodiments are further descriptions of the content of the present invention as an illustration of the technical content of the present invention, but the essential content of the present invention is not limited to the following embodiments, and those of ordinary skill in the art can and should know any Simple changes or substitutions of the essential spirit of the invention shall belong to the protection scope required by the present invention.

The X-ray diffractometer used in the present invention is produced by PANAlytical Company, the model is X'pert, the test uses Ni filter, Cu light pipe (40kV, 40mA), the test step is 0.020°, the resolution is 0.050°2θs ^-1 , Angular range 3° to 30° 2θ. The transmission electron microscope used JEM-2100 produced by JEOL.

The present invention is a method for distinguishing and quantitatively analyzing different types of montmorillonite in a geological sample. The analysis flowchart is shown in Figure 1, which includes the following steps in order:

(1), enrich and extract clay minerals from geological samples. Specifically, the sample was crushed to below 100 mesh, 10 g of the sample was weighed and 200 ml of deionized water was added. 20 ml of 30% hydrogen peroxide was added to react for 12 hours to remove organic cements, and 40 ml of 1 mol/L acetic acid reagent was added to react for 6 hours to remove carbonate cements. The samples from which organic matter and carbonate cements were removed were centrifuged at 3600 r/min for 5 min, the supernatant was removed, 450 ml of deionized water was added, and eluted repeatedly until the solution became neutral and deflocculation occurred. According to the Stocks sedimentation rule, the clay fraction with a particle size of less than 2 μm was suspended and extracted.

Na-蒙脱石001峰位于

)。(2), prepare oriented sheets with different pretreatment conditions. Pipette 1.5ml of the suspension containing the cosmid and drop it on the glass slide and coat it into a 2cm*2cm square to make the original piece. Add 80ml of 1mol/LMgCl ₂ solution to 10ml of the clay-containing suspension, and react for 10h. After Mg ²⁺ fully replaces the cations in the interlayer of 2:1 type expansive clay minerals, centrifuge at 4500r/min for 5min and deionized water. The introduced ^Cl- was sufficiently eluted 4 times to make Mg-saturated tablets. Add 80ml of 1mol/L KCl solution to 10ml of the clay-containing suspension, react for 10h, and after K ⁺ has fully replaced the cations in the interlayer of 2:1 type expansive clay minerals, centrifuge at 4500r/min for 5min, and deionized water is used to deionize the solution. The introduced ^Cl- was fully eluted 4 times to make a K-saturated sheet. The K-saturated sheets were heated at 150, 300, and 550 °C for XRD analysis and compared with the original sheet XRD results to identify chlorite and kaolinite. Preliminarily judge whether there are different types of montmorillonite (Ca-montmorillonite 001 peak is located in the

Na-montmorillonite peak 001 is located at

).

(3), carry out ethylene glycol atomization treatment to Mg saturated sheet. The specific steps are to put the prepared Mg sheet into the ethylene glycol atomization box, add 50ml of 100% ethylene glycol solution at a constant temperature of 45°C and turn on the atomizer, so that 30ml of the ethylene glycol solution is completely atomized and filled with The entire thermostatic sealed box, and kept for 5 days. After the swellable minerals in the Mg-saturated sheet fully absorb ethylene glycol molecules, the sample is transferred from the atomization chamber to the sampling chamber through the drawer device, and the Mg sheet after ethylene glycol atomization is taken out for XRD test.

峰面积代表Ca-蒙脱石和Na-蒙脱石总含量，

峰面积代表绿泥石和高岭石总含量，

峰面积代表伊利石含量，绿泥石和高岭石的比例通过绿泥石004峰

和高岭石002峰

面积比确定。计算相对含量是根据蒙脱石:(绿泥石+高岭石):伊利石＝1:2:4确定(Biscaye,1965)。上述衍射峰面积拟合使用Macdiff软件。(4) Calculate the relative content of each clay mineral in the Mg-saturated sheet treated by ethylene glycol atomization. Due to the substitution effect of Mg ions, the interlayer ions of expansive minerals such as montmorillonite in the samples were all replaced by Mg ²⁺ . Relative content calculations are based on the following diffraction peak areas:

The peak area represents the total content of Ca-montmorillonite and Na-montmorillonite,

The peak area represents the total content of chlorite and kaolinite,

The peak area represents the illite content, the ratio of chlorite and kaolinite through the chlorite 004 peak

and kaolinite 002 peak

Area ratio is determined. The relative content was calculated according to montmorillonite:(chlorite+kaolinite):illite=1:2:4 (Biscaye, 1965). The above diffraction peak areas were fitted using Macdiff software.

(5), remove Ca-montmorillonite and chlorite in the original sheet. The original sheet was put into 10 ml of 3 mol/L HCl solution, and heated to 70 °C to remove Ca-montmorillonite and chlorite in the original sheet, and Na-montmorillonite, kaolinite, and illite remained unchanged. The suspension from which Ca-montmorillonite and chlorite were removed was centrifuged with 50 ml of deionized water, centrifuged at 4500 r/min for 5 min, eluted 4 times, and eluted to neutrality.

(6) The samples from which Ca-montmorillonite and chlorite were removed were subjected to Mg saturation and ethylene glycol atomization. The sample obtained in step (5) from which Ca-montmorillonite and chlorite have been removed is subjected to Mg ²⁺ replacement interlayer cation treatment according to the method of step (2), and eluted to remove Cl ^- . According to the method of step (3), the sample treated with HCl and saturated with Mg was subjected to ethylene glycol atomization treatment, and then the XRD test was carried out.

(7) Calculate the relative content of each clay mineral after removing Ca-montmorillonite and chlorite. According to the method in step (4), the content of the Mg-saturated ethylene glycol atomized sample with Ca-montmorillonite and chlorite removed is calculated. The relative contents of Na-montmorillonite, kaolinite and illite were obtained.

(8) The difference between the content of montmorillonite calculated in steps (4) and (7), and the difference between the content of illite, is the sum of the content of dissolved Ca-montmorillonite and chlorite. This value minus the content of chlorite obtained in step (4) is the content of Ca-montmorillonite.

(9), in order to verify the accuracy of this method, prepare mixed standard samples of Ca-montmorillonite, Na-montmorillonite, kaolinite, chlorite and illite in known proportions, and use the above method to calculate the relative relative value of clay minerals. content to verify the accuracy of the present invention.

Example 1

The method of distinguishing and quantitatively analyzing different types of montmorillonite in geological samples of the present invention is used to analyze the loess samples in the Weinan area of Shaanxi, and the analysis process is shown in Figure 1, and the specific method is as follows:

(1) Clay minerals were enriched and extracted from Weinan loess samples. The sample was crushed with a geological hammer to below 100 mesh, 10 g of the sample was weighed and 200 ml of deionized water was added. 20 ml of 30% hydrogen peroxide was added to react for 12 hours to remove organic cements, and 40 ml of 1 mol/L acetic acid reagent was added to react for 6 hours to remove carbonate cements. The samples from which organic matter and carbonate cements were removed were centrifuged at 3600 r/min for 5 min, the supernatant was removed, 450 ml of deionized water was added, and eluted repeatedly until the solution became neutral and deflocculation occurred. According to the Stocks sedimentation rule, the clay fraction with a particle size of less than 2 μm was suspended and extracted.

Na-蒙脱石001峰位于

)。原始片XRD结果显示样品中含有Ca-蒙脱石、Na-蒙脱石、伊利石。K饱和片显示样品中含有绿泥石和高岭石。(2) Prepare oriented sheets with different pretreatment conditions, including original sheets, Mg-saturated sheets and K-saturated sheets. Use a pipette to draw 1.5 ml of the suspension containing the cosmid and drop it on a glass slide and coat it into a 2cm×2cm square to make the original sheet. Add 80 ml of 1 mol/L MgCl ₂ solution to 10 ml of the clay-containing suspension. After Mg ²⁺ fully replaces the cations in the interlayer of 2:1 type expansive clay minerals, centrifuge at 4500 r/min for 5 min, and use 250 ml of deionized water to remove the cations. The introduced ^Cl- elutes sufficiently to make Mg-saturated tablets. Add 80 ml of 1 mol/L KCl solution to 10 ml of the suspension containing clay particles, and treat for 10 hours. After K ⁺ has fully replaced the cations in the interlayer of 2:1 type expansive clay minerals, centrifuge at 4500 r/min for 5 min, and repeat the centrifugation for 5 times. Deionized water fully elutes the introduced ^Cl- to make a K-saturated sheet. The K-saturated sheets were heated at 150°C, 300°C, and 550°C for XRD analysis, and compared with the original sheet XRD results to identify chlorite and kaolinite. Preliminarily judge whether there are different types of montmorillonite (Ca-montmorillonite 001 peak is located in the

Na-montmorillonite peak 001 is located at

). The XRD results of the original sheet showed that the samples contained Ca-montmorillonite, Na-montmorillonite and illite. The K-saturated sheet shows that the sample contains chlorite and kaolinite.

(3), carry out ethylene glycol atomization treatment to Mg saturated sheet. The specific steps are to put the prepared Mg saturated tablet into the ethylene glycol atomization box, add 50ml of 100% ethylene glycol solution at a constant temperature of 45°C and turn on the atomizer, so that 30ml of the ethylene glycol solution is completely atomized and Fill the entire thermostatic sealed box and keep for 4 days. When the swellable minerals in the Mg-saturated sheet fully absorb the ethylene glycol molecules, the sample is transferred from the atomization chamber to the sampling chamber through the drawer device, and the Mg-saturated sheet (ethylene glycol-saturated directional sheet) after ethylene glycol atomization is taken out. ) for XRD testing.

峰面积代表Ca-蒙脱石和Na-蒙脱石总含量，

峰面积代表绿泥石和高岭石总含量，

峰面积代表伊利石含量，绿泥石和高岭石的比例通过绿泥石004峰(3.53

)和高岭石002峰

面积比确定。计算相对含量是根据蒙脱石:(绿泥石+高岭石):伊利石＝1:2:4确定(Biscaye,1965)。上述衍射峰面积拟合使用Macdiff软件。各衍射峰拟合面积为：蒙脱石13034，伊利石8281，绿泥石和高岭石1974。计算结果为：蒙脱石(Sm)26.01％，伊利石(Ill)66.11％，绿泥石(Chl)4.50％，高岭石(Kao)3.38％。(4) Calculate the relative content of each clay mineral in the Mg-saturated sheet treated by ethylene glycol atomization. in the sample

The peak area represents the total content of Ca-montmorillonite and Na-montmorillonite,

The peak area represents the total content of chlorite and kaolinite,

The peak area represents the illite content, and the ratio of chlorite to kaolinite passes through the chlorite 004 peak (3.53

) and kaolinite peak 002

Area ratio is determined. The relative content was calculated according to montmorillonite:(chlorite+kaolinite):illite=1:2:4 (Biscaye, 1965). The above diffraction peak areas were fitted using Macdiff software. The fitted area of each diffraction peak is: montmorillonite 13034, illite 8281, chlorite and kaolinite 1974. The calculated results are: montmorillonite (Sm) 26.01%, illite (Ill) 66.11%, chlorite (Chl) 4.50%, kaolinite (Kao) 3.38%.

(5), remove Ca-montmorillonite and chlorite in the original sheet. The original sheet was put into 3 mol/L HCl solution and heated to 70°C to remove Ca-montmorillonite and chlorite in the original sheet, and Na-montmorillonite, kaolinite and illite remained unchanged. The suspension from which Ca-montmorillonite and chlorite were removed was eluted to neutrality by centrifugation at 50 ml of deionized water at 4500 r/min for 5 min.

(6), performing Mg-saturation and ethylene glycol atomization on the samples from which the Ca-montmorillonite and chlorite were removed in step (5) to obtain new Mg-saturated sheets and ethylene glycol-saturated directional sheets. The sample obtained in step (5) from which Ca-montmorillonite and chlorite have been removed is subjected to Mg ²⁺ replacement interlayer cation treatment according to the method of step (2), and eluted to remove Cl ^- . Specifically, add 80 ml of 1 mol/L MgCl ₂ solution to 10 ml of the clay-containing suspension, and after about 10 hours, Mg ²⁺ fully replaces the cations in the interlayer of 2:1 type expansive clay minerals, and then centrifuge repeatedly at 4500 r/min. After centrifugation for 5 min, the introduced ^Cl- was fully eluted with deionized water to make Mg-saturated tablets.

According to the method of step (3), the HCl-treated and Mg-saturated samples were subjected to ethylene glycol atomization to obtain ethylene glycol-saturated oriented sheets, and then XRD tests were performed.

特征峰消失；如图3所示，3mol/L HCl处理前后Na-蒙脱石XRD衍射图，经过HCl溶液处理后Na-蒙脱石

特征峰无明显变化；如图4所示，3mol/L HCl处理前后Ca-蒙脱石和Na-蒙脱石透射电镜表征图，a)为HCl处理前Ca-蒙脱石晶型及电子衍射结果，显示了较为清晰的晶型及结晶特征，b)为HCl处理后Ca-蒙脱石晶型及电子衍射结果，晶型及结晶特征均被破坏；c)为HCl处理前Na-蒙脱石晶型及电子衍射结果，显示了较为清晰的晶型及结晶特征，d)为HCl处理后Na-蒙脱石晶型及电子衍射结果，晶型及结晶特征仍然清晰可见。As shown in Figure 2, the XRD diffraction patterns of Ca-montmorillonite before and after 3mol/L HCl treatment, it can be clearly seen that Ca-montmorillonite after treatment with HCl solution

The characteristic peak disappears; as shown in Figure 3, the XRD diffractogram of Na-montmorillonite before and after treatment with 3mol/L HCl, and the Na-montmorillonite after treatment with HCl solution

There is no obvious change in the characteristic peaks; as shown in Figure 4, the TEM images of Ca-montmorillonite and Na-montmorillonite before and after 3 mol/L HCl treatment, a) is the crystal form and electron diffraction results of Ca-montmorillonite before HCl treatment , showing relatively clear crystal form and crystal characteristics, b) is the crystal form and electron diffraction results of Ca-montmorillonite after HCl treatment, the crystal form and crystal characteristics are destroyed; c) is Na-montmorillonite before HCl treatment The crystal form and electron diffraction results show relatively clear crystal form and crystal characteristics. d) is the crystal form and electron diffraction results of Na-montmorillonite after HCl treatment, and the crystal form and crystal characteristics are still clearly visible.

(7) Calculate the relative content of each clay mineral after removing Ca-montmorillonite and chlorite. According to the method in step (4), the content of the Mg-saturated ethylene glycol atomized sample with Ca-montmorillonite and chlorite removed is calculated. The fitted area of each diffraction peak is: Na-montmorillonite 9142, illite 8281, and kaolinite 846. The calculated results are: Na-montmorillonite (NaSm) 20.8%, illite (Ill (HCl)) 75.35%, kaolinite (Kao (HCl)) 3.85%.

(8) The difference between the smectite content calculated in steps (4) and (7) is the smectite content: the Ca-montmorillonite (Ca-Sm) content is: Ca-Sm=Sm-NaSm= 26.01%-20.8%=5.21%.

(9) The Na-montmorillonite (NaSm) in the sample is 20.80%, the Ca-montmorillonite (CaSm) is 5.21%, the illite (Ill) is 66.11%, and the chlorite (Chl) is 4.50%, Kaolinite (Kao) was 3.85%, as shown in Table 1.

Table 1 Clay mineral content in loess samples from Weinan area, Shaanxi

In order to further verify the accuracy of this method, a mixed standard sample of Ca-montmorillonite, Na-montmorillonite, kaolinite, chlorite and illite (Ca-montmorillonite 20%, Na- Montmorillonite 20%, kaolinite 20%, chlorite 10%, illite 30%), the relative content of clay minerals calculated using the above method is (Ca-montmorillonite 22%, Na-montmorillonite 22%, Kaolinite 18%, Chlorite 9%, Illite 29%). It shows that the difference between the content of each mineral in this verification method and the original ratio is within the error range (6%).

Example 2

The Eocene gypsum sedimentary samples in Xining Basin are analyzed by the method of the present invention for distinguishing and semi-quantitatively analyzing different types of montmorillonite in geological samples, and the specific methods are as follows:

(1) Clay minerals are enriched and extracted from sedimentary strata samples in Xining Basin. The gypsum mudstone sample was crushed with a geological hammer to below 100 mesh, and 50 g of the sample was weighed and 200 ml of deionized water was added. 20ml of 30% hydrogen peroxide was added to react for 12h to remove organic cement. Add 0.32mol/L, 1L of disodium EDTA solution, and boil for 24h to remove gypsum minerals and release the cemented fine-grained components. Add deionized water again and repeat centrifugation, centrifuge at 3600r/min for 10min, elute until the solution is neutral, and anti-flocculation phenomenon occurs. According to the Stocks sedimentation rule, the clay fraction with a particle size of less than 2 μm was suspended and extracted.

Na-蒙脱石001峰位于

)。原始片XRD结果显示样品中含有Ca-蒙脱石、Na-蒙脱石、伊利石。K饱和片显示样品中含有绿泥石。(2), prepare oriented sheets with different pretreatment conditions. Use a pipette to draw 1.5 ml of the suspension containing the cosmid and drop it on a glass slide and coat it into a 2cm×2cm square to make the original sheet. Add 80 ml of 1mol/LMgCl ₂ solution to 10 ml of the clay-containing suspension, react for 10 h), after Mg ²⁺ fully replaces the cations in the interlayer of 2:1 type expansive clay minerals, repeat centrifugation and deionized water to introduce The ^Cl- was fully eluted, and centrifuged at 4500r/min for 5min to make Mg-saturated tablets. Add 80 ml of 1 mol/L KCl solution to the clay-containing suspension, and react for 10 hours. After K ⁺ has fully replaced the cations in the interlayer of 2:1 type expansive clay minerals, centrifuge repeatedly at 4500 r/min for 5 minutes, and use deionized water. The introduced ^Cl- was sufficiently eluted 4 times to make a K-saturated sheet. The K-saturated sheets were heated at 150°C, 300°C, and 550°C for XRD analysis, and compared with the original sheet XRD results to identify chlorite and kaolinite. Preliminarily judge whether there are different types of montmorillonite (Ca-montmorillonite 001 peak is located in the

Na-montmorillonite peak 001 is located at

). The XRD results of the original sheet showed that the samples contained Ca-montmorillonite, Na-montmorillonite and illite. The K-saturated sheet shows that the sample contains chlorite.

(3), carry out ethylene glycol atomization treatment to Mg saturated sheet. The specific steps are to put the prepared Mg saturated tablet into the ethylene glycol atomization box, add 50ml of 100% ethylene glycol solution at a constant temperature of 45°C and turn on the atomizer, so that 30ml of the ethylene glycol solution is completely atomized and Fill the entire thermostatic sealed box and keep for 4 days. After the swellable minerals in the Mg-saturated sheet fully absorb ethylene glycol molecules, the sample is transferred from the atomization chamber to the sampling chamber through the drawer device, and the Mg-saturated sheet after ethylene glycol atomization is taken out for XRD test.

峰面积代表Ca-蒙脱石和Na-蒙脱石总含量，

峰面积代表绿泥石和高岭石总含量，

峰面积代表伊利石含量，绿泥石和高岭石的比例通过绿泥石004峰

和高岭石002峰

面积比确定。计算相对含量是根据蒙脱石:(绿泥石+高岭石):伊利石＝1:2:4确定(Biscaye,1965)。上述衍射峰面积拟合使用Macdiff软件。各衍射峰拟合面积为：蒙脱石18845，伊利石28377，绿泥石12294。计算结果为：蒙脱石12.01％(Sm)，伊利石72.33％(Ill)，绿泥石15.67％(Chl)。(4) Calculate the relative content of each clay mineral in the Mg flakes treated by ethylene glycol atomization. 17-18 in the sample

The peak area represents the total content of Ca-montmorillonite and Na-montmorillonite,

The peak area represents the total content of chlorite and kaolinite,

The peak area represents the illite content, the ratio of chlorite and kaolinite through the chlorite 004 peak

And kaolinite 002 peak

Area ratio is determined. The relative content was calculated according to montmorillonite:(chlorite+kaolinite):illite=1:2:4 (Biscaye, 1965). The above diffraction peak areas were fitted using Macdiff software. The fitted area of each diffraction peak is 18845 for montmorillonite, 28377 for illite and 12294 for chlorite. The calculated results are: montmorillonite 12.01% (Sm), illite 72.33% (Ill), chlorite 15.67% (Chl).

(5), remove Ca-montmorillonite and chlorite in the original sheet. The original sheet was put into 3 mol/L HCl solution and heated to 70°C to remove Ca-montmorillonite and chlorite in the original sheet, and Na-montmorillonite and illite remained unchanged. The Ca-montmorillonite and chlorite-removed suspension was centrifuged to neutrality using deionized water.

(6), performing Mg saturation and ethylene glycol atomization on the sample from which the Ca-montmorillonite and chlorite were removed in step (5). The samples obtained in (5) from which Ca-montmorillonite and chlorite were removed were subjected to Mg ²⁺ replacement interlayer cation treatment in step (2), and eluted to remove Cl ^- . Add 80 ml of 1 mol/L MgCl ₂ solution to the clay-containing suspension, and react for 10 h. After Mg ²⁺ fully replaces the cations in the interlayer of 2:1 type expansive clay minerals, centrifuge repeatedly at 4500 r/min for 5 min. 200ml of ionized water, reacted for 10h, fully eluted the introduced ^Cl- to make Mg-saturated tablets.

According to step (3), the HCl-treated and Mg-saturated samples were subjected to ethylene glycol atomization. After that, XRD test was performed.

(7) Calculate the relative content of each clay mineral after removing Ca-montmorillonite and chlorite. According to the method in step (4), the content of the Mg-saturated ethylene glycol atomized sample with Ca-montmorillonite and chlorite removed is calculated. The diffraction peaks and areas are: Na-montmorillonite 9236, illite 28300. The calculated results are: Na-montmorillonite (NaSm) 7.54%, illite 92.46% (Ill (HCl)).

(8), the difference (Sm-NaSm) of the content of montmorillonite obtained by calculating in steps (4) and (7), and the difference of the content of illite (Ill (HCl)-Ill), is the dissolved Ca-montmorillonite The sum of delite and chlorite content (CaSm+Chl). Therefore, the sum of the contents of Ca-montmorillonite and chlorite is obtained as CaSm+Chl=Sm-NaSm+Ill(HCl)-Ill=12.01%-7.54%+92.46%-72.33%=24.6%. The content of Ca-montmorillonite is: CaSm=(CaSm+Chl)-Chl=24.6%-15.67%=8.93%.

(9) The Na-montmorillonite (NaSm) in the sample is 7.54%, the Ca-montmorillonite (CaSm) is 4.46%, the illite (Ill) is 72.33%, and the chlorite (Chl) is 15.67%, The specific results are shown in Table 2.

Table 2 Determination and standard addition method of free iron content in Eocene sedimentary samples from Xining Basin and clay mineral content of Xining Basin by ion exchange column method

In order to further verify the accuracy of this method, mixed standard samples of Ca-montmorillonite, Na-montmorillonite, kaolinite, chlorite and illite in known proportions (Ca-montmorillonite 10%, Na- 10% montmorillonite, 50% chlorite, 30% illite), using the above method to calculate the relative content of clay minerals to verify the accuracy of the present invention, the results are Ca-montmorillonite 13%, Na-montmorillonite 12 %, chlorite 48%, illite 27%). It shows that the difference between the content of each mineral in this verification method and the original ratio is within the error range (6%).

As can be seen from the experimental data in Table 2, the precision of the method for distinguishing and quantitatively analyzing different types of montmorillonite of the present invention can meet the requirements of scientific research, and has good feasibility. The steps are based on the general method, and the operation is relatively Convenient and easy to promote.

Example 3

The method of the present invention is used to analyze the fluvial and lacustrine sediment samples in Zhaotong Basin, Yunnan, and the specific method is as follows:

(1) Clay minerals were enriched and extracted from fluvial and lacustrine sediment samples in Zhaotong Basin. The sample was crushed with a geological hammer, 20 g of the sample was weighed and 200 ml of deionized water was added. 50ml of 30% hydrogen peroxide was added to react for 12h to remove organic cements, and 80ml of 1mol/L acetic acid reagent was added to react for 6h to remove carbonate cements. The samples from which organic matter and carbonate cements were removed were centrifuged at 3600 r/min for 5 min to remove the supernatant, and 450 ml of deionization was added, and the solution was repeatedly eluted with water until the solution was neutral and deflocculation occurred. According to the Stocks sedimentation rule, the clay fraction with a particle size of less than 2 μm was suspended and extracted.

Na-蒙脱石001峰位于

)。原始定向片XRD结果显示样品中含有Ca-蒙脱石、Na-蒙脱石、伊利石。K饱和片显示样品中含有绿泥石和高岭石。(2), prepare oriented sheets with different pretreatment conditions. Use a pipette to draw 1.5 ml of the suspension containing the cosmid and drop it on a glass slide and coat it into a 2cm×2cm square to make the original sheet. Add 80 ml of 1mol/LMgCl ₂ solution to 10 ml of the clay-containing suspension, and react for 10 hours. After Mg ²⁺ fully replaces the cations in the interlayer of 2:1 type expansive clay minerals, centrifuge at 4500 r/min for 5 min. The introduced ^Cl- was fully eluted 5 times with ionized water to make a Mg-saturated sheet. Add 80 ml of 1 mol/L KCl solution to 10 ml of the suspension containing clay particles, and react for 10 hours. After K ⁺ has fully replaced the cations in the interlayer of 2:1 type expansive clay minerals, centrifuge at 4500 r/min for 5 minutes, and deionized Water fully elutes the introduced Cl ^- to make a K-saturated sheet. The K-saturated sheets were heated at 150°C, 300°C, and 550°C for XRD analysis and compared with the original oriented sheet XRD results to identify chlorite and kaolinite. Preliminarily judge whether there are different types of montmorillonite (Ca-montmorillonite 001 peak is located in the

Na-montmorillonite peak 001 is located at

). The original oriented sheet XRD results show that the sample contains Ca-montmorillonite, Na-montmorillonite and illite. The K-saturated sheet shows that the sample contains chlorite and kaolinite.

(3), carry out ethylene glycol atomization treatment to Mg saturated sheet. The specific steps are to put the prepared Mg saturated tablet into the ethylene glycol atomization box, add 50ml of 100% ethylene glycol solution at a constant temperature of 45°C and turn on the atomizer, so that 30ml of the ethylene glycol solution is completely atomized and Fill the entire thermostatic sealed box and keep for 4 days. After the swellable minerals in the Mg-saturated sheet fully absorb ethylene glycol molecules, the sample is transferred from the atomization chamber to the sampling chamber through the drawer device, and the Mg-saturated sheet after ethylene glycol atomization is taken out for XRD test.

峰面积代表Ca-蒙脱石和Na-蒙脱石总含量，

峰面积代表绿泥石和高岭石总含量，

峰面积代表伊利石含量，绿泥石和高岭石的比例通过绿泥石004峰

和高岭石002峰

面积比确定。计算相对含量是根据蒙脱石:(绿泥石+高岭石):伊利石＝1:2:4确定(Biscaye,1965)。上述衍射峰面积拟合使用Macdiff软件。各衍射峰拟合面积为：蒙脱石13821，伊利石1242，绿泥石和高岭石5888。计算结果为：蒙脱石(Sm)58.32％，伊利石(Ill)12.37％，绿泥石(Chl)8.89％，高岭石(Kao)共20.42％。(4) Calculate the relative content of each clay mineral in the Mg flakes treated by ethylene glycol atomization. 17-18 in the sample

The peak area represents the total content of Ca-montmorillonite and Na-montmorillonite,

The peak area represents the total content of chlorite and kaolinite,

The peak area represents the illite content, the ratio of chlorite and kaolinite through the chlorite 004 peak

And kaolinite 002 peak

Area ratio is determined. The relative content was calculated according to montmorillonite:(chlorite+kaolinite):illite=1:2:4 (Biscaye, 1965). The above diffraction peak areas were fitted using Macdiff software. The fitted area of each diffraction peak is: montmorillonite 13821, illite 1242, chlorite and kaolinite 5888. The calculated results are: montmorillonite (Sm) 58.32%, illite (Ill) 12.37%, chlorite (Chl) 8.89%, kaolinite (Kao) 20.42% in total.

(5), remove Ca-montmorillonite and chlorite in the original orientation sheet. The original oriented sheet was put into 3 mol/L HCl solution and heated to 70 °C to remove Ca-montmorillonite and chlorite in the original oriented sheet, but Na-montmorillonite, kaolinite and illite remained unchanged. The Ca-montmorillonite and chlorite-removed suspension was centrifuged to neutrality using deionized water.

(6) The samples from which Ca-montmorillonite and chlorite were removed were subjected to Mg saturation and ethylene glycol atomization. The sample obtained in step (5) from which the Ca-montmorillonite and chlorite were removed was subjected to Mg ²⁺ replacement interlayer cation treatment according to the method of step (2), and the Cl ^- was removed by elution. According to step (3), the HCl-treated and Mg-saturated samples were subjected to ethylene glycol atomization treatment, and then the XRD test was carried out.

(7) Calculate the relative content of each clay mineral after removing Ca-montmorillonite and chlorite. According to the steps in (4), the content of the Mg-saturated ethylene glycol atomized sample with Ca-montmorillonite and chlorite removed was calculated. The diffraction peaks and areas are: Na-montmorillonite 13821, illite 1242, and kaolinite 10232. The calculated results are: Na-montmorillonite (NaSm) 35.21%, illite (Ill (HCl)) 12.37%.

(8) The difference between the content of montmorillonite calculated in step (4) and step (7): Sm-NaSm, which is the content of dissolved Ca-montmorillonite (CaSm). Therefore, the obtained Ca-montmorillonite is: CaSm=Sm-NaSm=58.32%-35.21%=23.11%.

(9) The Na-montmorillonite (NaSm) in the sample is 35.21%, the Ca-montmorillonite (CaSm) is 23.11%, the illite (Ill) is 12.37%, and the chlorite (Chl) is 8.89%, Kaolinite (Kao) was 20.42%, as shown in Table 3.

Table 3 Clay mineral content in fluvial and lacustrine sediment samples from Zhaotong Basin

In order to verify the accuracy of this method, a mixed standard sample of Ca-montmorillonite, Na-montmorillonite, kaolinite, chlorite and illite in known proportions was prepared (wherein Ca-montmorillonite 15%, Na- montmorillonite 15%, kaolinite 30%, chlorite 10%, illite 30%), the relative content of clay minerals was calculated by the above method to verify the accuracy of the present invention. The results were Ca-montmorillonite 14%, Na-montmorillonite 13%, kaolinite 29%, chlorite 12%, and illite 32% (the original contents here add up to 90). It shows that the difference between the content of each mineral in this verification method and the original ratio is within the error range (6%).

Example 4

A method for distinguishing and quantitatively analyzing different types of montmorillonite in geological samples is similar to Example 1, except that in step (1), 20ml of 25% hydrogen peroxide is used to remove organic cements, and 0.5mol/L acetic acid reagent is added to remove Carbonate cement.

Example 5

A method for distinguishing and quantitatively analyzing different types of montmorillonite in geological samples is similar to Example 1, except that in step (1), 20 ml of 35% hydrogen peroxide is used to remove organic cements, and 1.5 mol/L acetic acid reagent is added to remove Carbonate cement.

Example 6

A method for distinguishing and quantitatively analyzing different types of montmorillonite in geological samples is similar to Example 1, except that the MgCl ₂ solution in step (2) is 0.5mol/L.

Example 7

A method for distinguishing and quantitatively analyzing different types of montmorillonite in geological samples is similar to Example 1, except that the MgCl ₂ solution in step (2) is 1.5mol/L.

Example 8

A method for distinguishing and quantitatively analyzing different types of montmorillonite in geological samples is similar to Embodiment 1, except that the MgCl ₂ solution in step (2) is 2 mol/L.

Example 9

A method for distinguishing and quantitatively analyzing different types of montmorillonite in geological samples is similar to Example 1, except that KCl in step (2) is 0.5mol/L.

Example 10

A method for distinguishing and quantitatively analyzing different types of montmorillonite in geological samples is similar to Example 1, except that KCl in step (2) is 1.5mol/L.

Example 11

A method for distinguishing and quantitatively analyzing different types of montmorillonite in geological samples is similar to Embodiment 1, except that KCl in step (2) is 2 mol/L.

Example 12

A method for distinguishing and quantitatively analyzing different types of montmorillonite in geological samples, which is similar to Example 1, except that in step (2), the K-saturated sheet is heated at 140°C, 280°C, and 540°C, respectively, and then XRD analysis is performed , and compared with the original oriented sheet XRD results to identify chlorite and kaolinite.

Example 13

A method for distinguishing and quantitatively analyzing different types of montmorillonite in geological samples, which is similar to Example 1, except that in step (2), the K-saturated sheet is heated at 160°C, 320°C, and 560°C, respectively, and then XRD analysis is performed , and compared with the original oriented sheet XRD results to identify chlorite and kaolinite.

Example 14

A method for distinguishing and quantitatively analyzing different types of montmorillonite in geological samples, similar to Example 1, except that in step (3), the constant temperature is set to 40°C, 50ml of 100% ethylene glycol solution is added and atomization is turned on device.

Example 15

A method for distinguishing and quantitatively analyzing different types of montmorillonite in geological samples, similar to Example 1, except that in step (3), the constant temperature is set to 50°C, 50ml of 95% ethylene glycol solution is added and atomization is turned on device.

Example 16

A method for distinguishing and quantitatively analyzing different types of montmorillonite in geological samples, similar to Example 1, except that the HCl solution in step (5) is 2 mol/L, heated to 75 ° C to dissolve and remove Ca-montmorillonite Trifoliate and Chlorite.

Example 17

A method for distinguishing and quantitatively analyzing different types of montmorillonite in geological samples, similar to Example 1, except that the HCl solution in step (5) is 4 mol/L, heated to 65°C to dissolve and remove Ca-montmorillonite Trifoliate and Chlorite.

Example 18 As shown in Figures 5-7, a clay mineral directional sheet atomization treatment device, the device as a whole adopts a full set of corrosion-resistant materials, including an atomization box 22, and the atomization box 22 is a fully airtight sealed box body, atomization The outside of the box 22 is provided with an atomizer 16, and the inside of the atomization box 16 is provided with a sensor and a spray assembly. The sensor includes an air pressure sensor 1 and a temperature sensor 3. It is used to control the air pressure and temperature in the atomizing box. One end of the spray assembly is horizontally arranged in the atomization box 16, and the other end extends to the outside of the atomization box 16. The spray assembly can change the position of the spray through the servo motor and the moving assembly, so as to realize the horizontal and vertical movement of the spray in the same plane. A heating device 8 is provided at the inner bottom of the atomization box 22.

A further optimized technical solution of this embodiment is that the storage rack includes a plurality of L-shaped drawers 4 arranged at the top and bottom, so as to realize batch processing of samples. Specifically, the number of drawers 4 is four, and the four drawers 4 are arranged up and down and at intervals.

A further optimized technical solution of this embodiment is that the drawer 4 includes a support plate 41 , the support plate 41 is arranged horizontally, and a sealing plate 42 is arranged on the top of the support plate 41 . An insertion port 221 is provided on the wall of the atomizing box 22 . One end of the support plate 41 can be inserted into the atomization box 22 through the insertion port 221 .

A further optimized technical solution in this embodiment is that the upper end of the support plate 41 is provided with the movable baffle assembly 23 vertically. When specifically installed, the bottom side of the movable baffle assembly 23 is provided with an inclined surface to facilitate the insertion of the support plate 41 and to form a sealing effect. The upper end of the movable baffle assembly 23 is connected to the fixed end 24 through an elastic member 25 . Specifically, the fixed end 24 is arranged on the upper part of the movable baffle 23 and fixed on the inner wall of the atomization box 22, and the elastic member 25 can be arranged as a silicone rope or a spring. The lower end of the movable baffle assembly 23 is sealed by a silicone layer or the like. The movable baffle assembly 23, the side wall 22 of the atomization box and the support plate 41 are enclosed to form an isolation area.

A further optimized technical solution of this embodiment is that, as shown in FIG. 6 and FIG. 7 , the movable baffle assembly 23 specifically includes an inner baffle 231 and an outer baffle 232 , and the inner baffle 231 and the outer baffle 232 are All-in-one setup. The bottom end of the side surface of the outer baffle 232 is provided with an inclined surface. The lowermost ends of the inner baffle 231 and the outer baffle 232 are treated as sealing layers by elastic and corrosion-resistant materials such as silica gel layers.

A further optimized technical solution in this embodiment is that the sealing plate 42 of the drawer 4 is provided with a socket, the upper end of the support plate 41 is provided with a horizontal cover 33, and the horizontal cover 33 can be inserted horizontally from the socket in the sealing plate 42. After the organic saturation process is completed, it protects the to-be-determined sheet to prevent test errors caused by the volatilization of organic matter during the waiting test process. The specific use method of the cover plate is as follows: after the saturation process is completed, insert the cover plate 33 along the sealing plate 42 on one side of the drawer 4 and insert the cover plate 33. With the insertion of the cover plate 33, the top of the cover plate pushes open the movable baffle assembly 23 and gradually inserts it into the drawer 4. into the atomization box, and at this time, the elastic member 25 on the upper part of the movable baffle assembly 23 is compressed, thereby ensuring the tightness between the cover plate 33 and the movable baffle assembly 23 . On the contrary, when the drawer 4 is pulled out from the atomizing box, the elastic member 25 is stretched due to the gravity of the movable baffle assembly 23, and the movable baffle assembly 23 is pulled down until it is in contact with the support plate 41. Block the socket to seal the atomizer box.

A further optimized technical solution of this embodiment is that, as shown in FIG. 10 and FIG. 11 , the support plate 41 is provided with a plurality of placement grooves at intervals, the placement grooves are grooves, the slide glass 17 is arranged in the placement groove, and the adjacent support plate 41 is provided with a plurality of placement grooves. An anti-corrosion spacer 18 is provided on the support plate 41 between the glass slides 17 .

When in use, the clay mineral orientation sheet or glass slide to be processed is placed in the placement slot of the support plate 41, which can process 200 samples at a time, and a sealed movable baffle assembly 23 is added to the opening of the drawer 4, which can ensure that the drawer 4 is taken out. The airtightness of the chemical tank 22. The inner side of the drawer 4 is low and the outer side is high, to ensure that the drawer 4 will not rub against the sealing material and contaminate the sample when it is inserted into the atomization box 22. At the same time, the drawer itself has a cover plate 33 to ensure that the organic solvent in the sample to be tested is sampled after the atomization treatment. Does not evaporate.

A further optimized technical solution in this embodiment is that the atomizer 16 is arranged on the upper part of the atomization box 22, the atomizer 16 is filled with ethylene glycol or glycerin solution, and the upper part of the atomization box 22 is also provided with an air release valve 20 .

A further optimized technical solution in this embodiment is that a plurality of glass observation windows 21 are provided on the wall of the atomizing box 22 on the insertion side of the drawer 4, and the glass observation windows 21 are made of transparent materials. Of course, the glass observation windows 21 can also be arranged in Inside the movable baffle assembly 23 , it is convenient to observe the inside of the atomizing box 22 .

The further optimized technical solution of this embodiment is that, specifically, the spray assembly includes a conduit 5, the upper end of the conduit 5 is communicated with the atomizer 16, a plurality of horizontally arranged spray branch pipes 51 are communicated with the conduit 5, and the conduit 5 is connected to the sprayer 16. The branch pipes 51 are all hoses, so that they can be stretched during the movement. The end of the spray branch pipe 51 is connected to the spray head 26 , and the pipe valve 2 is provided on the pipe 5 . The other end of the conduit 5 is connected to an atomizer 16, and the atomizer 16 is filled with ethylene glycol or glycerin solution. The atomizer 16 is atomized at room temperature, which does not affect the performance of ethylene glycol and glycerin. In the process of organic solvent saturation, a low-pressure saturation method is adopted, and the air pressure in the atomization box is maintained at about 6.6Pa through a vacuum pump. The constant temperature of the atomizing box is 30°C.

A further optimized technical solution in this embodiment is that the spray branch pipe 51 can be set as a retractable organ pipe, so as to be retractable and stretchable.

A further optimized technical solution of this embodiment is that, as shown in FIG. 12 , the moving assembly includes L-shaped x-direction brackets 15 arranged on the upper and lower layers, and a support rod 27 is further provided between the upper and lower layers of the x-direction brackets 15 With the y-direction bracket 7, one side of the x-direction bracket 15 is provided with a first guide rail 28, and the other side is provided with a first screw rod 29, one end of the first screw rod 29 is connected with the y-direction moving motor 14, and the middle part of the support rod 27 is A second screw rod 30 is sleeved, and the other end of the second screw rod 30 is connected with the x-direction moving motor 6 .

A further optimized technical solution of this embodiment is that the L-shaped x-direction bracket 15 includes a first fixing plate 151 and a second fixing plate 152, the first fixing plate 151 and the second fixing plate 152 are vertically arranged in the same plane, and the first fixing plate 151 and the second fixing plate 152 are vertically arranged in the same plane. A rod 29 is arranged on the side of the first fixing plate 151 of the upper x-direction bracket 15 , and the first guide rail 28 is arranged on one side of the second fixing plate 152 and fixed by the inner wall of the atomizing box 22 . Guide rails are provided on one side of the first fixing plate 151 and the second fixing plate 152 of the upper x-direction bracket 15 .

The further optimized technical solution of this embodiment is that the x-direction bracket 15 is driven by the x-direction moving motor 6 and the second lead screw 30 to move forward and backward, and the y-direction bracket 7 is driven by the y-direction moving motor 14 and the first lead screw 14 Drive to move left and right. One end of the fixed rod 32 is fixedly connected to the y-direction bracket 7, and the other end is connected to the shower head 26, so that the movement of the x-direction bracket 15 or the y-direction movement motor 14 is controlled by a servo motor, such as the x-direction moving motor 6 or the y-direction moving motor 14 . The position of the spray head 5 is controlled by the servo motor (x-direction moving motor 6 and y-direction moving motor 14), so that the spraying can be moved horizontally and perpendicularly in the same plane to ensure that each position on the slide can be uniformly The ethylene glycol or glycerin water mist is sprayed, and the servo motor is controlled by an external controller (the controller controls the operation of the motor, etc., which belongs to common knowledge in the art, and will not be repeated again).

A further optimized technical solution of this embodiment is that a vacuuming assembly is provided on one side of the atomization box 22, and the vacuuming assembly is mainly used to remove the residual ethylene glycol in the atomization box 22 at the end of the saturation treatment. Low-pressure heating is used to reduce the boiling point of ethylene glycol to about 70°C. The bottom of the atomization box 22 is provided with a heating device, which can be specifically set as a heating element 8 for heating the temperature in the atomization box 22 to vaporize the ethylene glycol. After the ethylene glycol is vaporized, the vacuum pump 9 is turned on, and the ethylene glycol gas is pumped out of the atomization box 22 and can be recovered through the condensation device, thereby realizing recycling. The condensing device may be provided as a condensing pipe.

Specifically, the vacuuming assembly includes a liquid collecting tank 31. The liquid collecting tank 31 is connected to each other through the air extraction pipe 12 and the atomization tank 22. The upper part of the air extraction pipe 12 is provided with an air extraction pipe valve 13, and the lower end of the air extraction pipe 12 is connected with the condenser pipe 11. , the lower end of the condensation pipe 11 extends into the liquid collection bottle 10 , and one side of the liquid collection bottle 10 is connected to the vacuum pump 9 . Both the water inlet and the water outlet of the condensation pipe 11 are arranged outside the liquid collecting tank 31 .

Example 2

A method for the atomization treatment of the clay mineral directional sheet, which is carried out by the treatment equipment in Example 1, and specifically comprises the following steps:

(1), first check the air tightness of the atomization treatment device: insert the empty drawer 4 directly into the atomization box 22, close the conduit valve 2 and the air release valve 20, open the vacuum pump 9, open the air extraction pipe valve 13, do not need to open Cooling water, pump the inside of the atomizing box 22 to a negative pressure, then close the exhaust pipe valve 13, turn off the vacuum pump 9, observe the number of the air pressure sensor 1, and the vacuum degree in the atomizing box 22 remains unchanged, indicating that the air tightness is normal, then you can Normal use;

(2), carry out organic solvent ethylene glycol, glycerol saturation treatment: put the orientation sheet 17 coated with clay minerals into the drawer 4, insert the drawer 4 into the atomization box 22, and atomize the atomization according to the operation method of step (1). Close the valve 13 and close the vacuum pump 9 after pumping to 6.6Pa in the box 22;

(3), start the x-direction moving motor 6 and the y-direction moving motor 14, so that the y-direction support 7 and the x-direction support 15 drive the conduit 5 to move back and forth above the drawer 4 as required, open the atomizer 16, and use the conduit as required Set valve 2 to spray the sample with atomization;

(4), turn on the heating element 8 and heat it to 30°C, keep the constant temperature and pressure closed for 48h to reach the saturation of the organic solvent in the clay mineral to be tested;

(5), carry out XRD test by sampling: open vacuum pump 9, open air extraction pipe valve 13, do not have to open cooling water, close air extraction pipe valve 13 after the residual air in atomization box 22 is pumped away, close vacuum pump 9, open air release valve 20 , take out the sample to be tested in the drawer 4 for XRD test, put the sample to be tested back into the atomization box, and insert the cover plate 33 to prevent the organic molecules entering the mineral lattice from volatilizing;

(6), clean up the atomization box 22 after the saturation treatment: insert the empty drawer 19 directly into the atomization box 22, close the conduit valve 2 and the air release valve 20, open the vacuum pump 9, open the air extraction pipe valve 13, do not need to open Cooling water, after removing the residual air in the atomization box 22, close the air suction pipe valve 13, and close the vacuum pump 9;

The heating element 8 is used to heat the atomization box 22, the air pressure sensor 1 and the temperature sensor 3 are used to understand the situation in the atomization box 22, the residual ethylene glycol is confirmed through the glass observation window 21, the cooling water is turned on, the vacuum pump 9 is turned on, and the air extraction pipe is turned on. The valve 13 is used to draw away the ethylene glycol vapor in the atomization box 22 .

As shown in FIG. 13 , the XRD diffractograms of the clay mineral directional sheet atomization treatment device of the present invention and other methods of ethylene glycol saturation treatment are used. Using the XRD diffractogram of the device of the present invention and other methods of ethylene glycol saturation treatment, it can be seen that the saturation degree of ethylene glycol treated by the device of the present invention is significantly better than that of the traditional dropping method.

Example 3

A method for atomization treatment of clay mineral oriented sheets is similar to Embodiment 1, except that, as shown in Figures 8 and 9, a sealing block 43 is fixedly connected to the inner side of the sealing plate 42, and the sealing block 43 is a right-angled triangle sealing block, The outer plate surface of the sealing block 43 is inclined. Corresponding sockets are also provided at the corresponding insertion openings of the sealing block 43 and the sealing plate 42 to facilitate the insertion of the cover plate. A movable baffle assembly 23 is arranged on the inner side of the wall of the atomization box 22 located on the upper part of the sealing block 43 . The movable baffle assembly includes an inner baffle 231 and an outer baffle 232, and the inner baffle 231 and the outer baffle 232 are provided separately. The inner baffle 231 and the outer baffle 232 are adjacent and arranged in parallel, the inner baffle 231 and the outer baffle 232 have the same length, and the outer side of the bottom of the outer baffle 232 is provided with an inclined surface, which is connected to the triangular sealing block. The outside sloped decks match each other. When the drawer 4 is inserted from the insertion port 221, since the sealing block 43 and the outer baffle 232 are provided with inclined surfaces, the spring will gradually press upward as the drawer 4 gradually enters, and the adjacent inclined surfaces will be completely fitted. An isolation area is formed between the sealing block 43 , the outer baffle 232 and the inner baffle 231 , so as to realize the complete sealing of the atomizing box 4 and further strengthen the sealing effect in the atomizing box 4 .

It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: it is still The technical solutions recorded in the foregoing embodiments may be modified, or some or all of the technical features thereof may be equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention .

Claims (8)

1. A method for distinguishing and semi-quantitatively analyzing different types of montmorillonite in a geological sample, comprising the steps of:

(1) enriching and extracting clay minerals from geological samples;

(2) preparing an original orientation plate, an Mg saturation plate, a K saturation plate and an ethylene glycol saturation orientation plate, and carrying out XRD analysis, wherein the preparation method of the ethylene glycol saturation orientation plate comprises the following steps: putting the prepared Mg saturated sheet into an ethylene glycol atomization box, adding an ethylene glycol solution, and atomizing to obtain an ethylene glycol saturated oriented sheet;

(3) putting the original oriented sheet into HCl solution, heating to 65-75 ℃ to dissolve and remove Ca-montmorillonite and chlorite, wherein the HCl solution is 2-4 mol/L;

(4) carrying out Mg saturation and ethylene glycol atomization treatment on the sample from which Ca-montmorillonite and chlorite are removed in the step (3), and preparing an ethylene glycol saturation directional sheet again, wherein the ethylene glycol saturation directional sheet is prepared by using a clay mineral directional sheet atomization treatment device and specifically comprises an atomization box, an atomizer is arranged outside the atomization box, a sensor and a spray assembly are arranged in the atomization box, one end of the spray assembly is horizontally arranged in the atomization box, the other end of the spray assembly extends to the outside of the atomization box, the spray assembly can change the spraying position through a servo motor and a moving assembly to realize horizontal and vertical moving spraying, a heating device is arranged at the bottom in the atomization box, the sensor comprises an air pressure sensor and a temperature sensor, the air pressure sensor and the temperature sensor are arranged at the upper part in the atomization box, a storage rack is arranged in the atomization box, and the storage rack comprises a plurality of L-shaped drawers which are arranged up and down, the drawer comprises a horizontally arranged supporting plate, one end of the supporting plate is vertically connected with a sealing plate, a sealing block is arranged on the inner side of the sealing plate, the sealing block is a triangular sealing block, and the outer side plate surface of the sealing block is obliquely arranged;

(5) carrying out XRD test and semi-quantitative analysis on ethylene glycol saturated oriented sheets prepared before and after HCl is dissolved;

(6) calculating the relative content of all clay minerals:

(6.1) calculating the relative content of each clay mineral in the ethylene glycol saturated oriented sheets, the relative content being determined according to montmorillonite (chlorite + kaolinite) illite =1:2: 4;

(6.2) removing Ca-montmorillonite and chlorite in the original oriented sheets;

(6.3) subjecting the sample from which Ca-montmorillonite and chlorite were removed to Mg saturation and ethylene glycol atomization; (6.4) calculating the relative content of each clay mineral after the Ca-montmorillonite and the chlorite are removed, and calculating the content of the ethylene glycol saturated oriented sheets after the Ca-montmorillonite and the chlorite are removed according to the method in the step (6.1) to obtain the relative content of Na-montmorillonite, kaolinite and illite;

and (6.5) calculating according to the results of the steps (6.1) and (6.4) to obtain the relative content of each mineral.

2. The method according to claim 1, wherein the geological sample of step (1) is crushed to remove organic cement and/or carbonate cement and/or gypsum mineral, centrifuged, eluted to neutrality, and the clay fraction with a particle size of less than 2 μm is extracted.

3. The method of claim 2, wherein hydrogen peroxide is used to remove organic cements and acetic acid is used to remove carbonate cements.

4. The method for distinguishing and semi-quantitatively analyzing different types of montmorillonite in geological samples according to claim 1, wherein the Mg saturation sheet in the step (2) is prepared by adding a solution containing magnesium ions into a clay-containing suspension, performing Mg2+ interlayer cation replacement treatment, centrifuging and eluting after Mg2+ sufficiently replaces the interlayer cations of the 2:1 swelling clay minerals, and preparing the Mg saturation sheet.

5. The method according to claim 1, wherein the K saturation sheet in step (2) is prepared by adding a potassium ion-containing solution to a clay-containing suspension, centrifuging and eluting after K + has sufficiently replaced interlayer cations of the 2:1 swelling clay mineral, and preparing the K saturation sheet.

6. The method according to claim 1, wherein the K-saturation sheet in step (2) is heated at 150 ℃, 300 ℃ and 550 ℃ respectively and then subjected to XRD analysis, and compared with the XRD results of the original oriented sheets to identify chlorite and kaolinite.

7. The method for distinguishing and semi-quantitatively analyzing different types of montmorillonite in geological samples according to claim 1, wherein the glycol saturated oriented sheet prepared in step (2) is atomized by adding glycol solution under constant temperature condition and kept for 4 days.

8. Use of the method according to any one of claims 1 to 7 for the differentiation and identification of different types of smectites.

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