WO2007090355A1

WO2007090355A1 - A method for purification of montmorillonit, purified montmorillonite and composition thereof

Info

Publication number: WO2007090355A1
Application number: PCT/CN2007/000463
Authority: WO
Inventors: Haihui Zheng; Guanglie Lv
Original assignee: Zhejiang Hailisheng Pharmaceutical Limited Co.
Priority date: 2006-02-09
Filing date: 2007-02-09
Publication date: 2007-08-16
Also published as: CN101016157A; CN101340979B; CN101340979A

Abstract

A method for purification and separation of inorganic mineral, especially for purification and separation of montmorillonite from natural bentonite is provided. The said method is simple, and uses high-speed centrifugal device to well solve the problems present in purification of montmorillonite that α-quartz and cristobalite are difficult to be separated and removed and purified slurry is difficult to be concentrated and dehydrated. The purity of montmorillonite thus obtained is not less than 95%.

Description

Method for purifying montmorillonite and purifying montmorillonite and its composition

The invention relates to a method for separating and purifying inorganic minerals, in particular to a method for separating and purifying montmorillonite from natural bentonite. Background technique

Natural bentonite is a mixture of clay and skeletal silicate minerals. The main mineral component is smectite that swells with water. In order to obtain montmorillonite of higher purity or higher quality, it is necessary to separate and remove other minerals from natural montmorillonite.

Natural montmorillonite is associated with non-clay silicate minerals such as silica, opal, feldspar, gypsum, calcite, perlite, zeolite, etc., and also contains clay minerals such as kaolinite, illite, chlorite, and a small amount. The organic matter, wherein the content of montmorillonite is usually 50%-70%, and the content of partially rich ore is 80%-90%. By utilizing the characteristics of smectite swelling in water, it can be separated from symbiotic non-metallic minerals, and then the coarse particle non-clay minerals can be separated and removed by means of mechanical means such as swirling or centrifugation using the difference in particle size and density. However, c-quartz with fine particle size and close symbiosis with montmorillonite and c-cristobalite with extremely fine particle size (0.1-0.5/mi) and montmorillonite are only dependent on the hydration expansion force of montmorillonite itself. It is not enough to open the symbiosis, inlay and enveloping conditions among the three, especially the calcium-based bentonite with high layer charge. Therefore, it cannot be separated and removed by ordinary hydrocyclones, which becomes the main factor affecting the quality of montmorillonite purification. It is also a difficult point in the purification technology of montmorillonite. In addition, the concentrated dehydration treatment of the purified liquid in the wet-purified montmorillonite method is also a technical difficulty.

Since the properties of purified montmorillonite are significantly improved compared with the original soil, such as adsorption, viscosity, expansion ratio and cation exchange capacity, the application properties and application fields of montmorillonite are significantly broadened. Therefore, the purification of montmorillonite has become a research hotspot. . At present, there are two kinds of purification methods for bentonite: dry method and wet method. The basic process of the dry process is as follows: raw ore 1 > hand selection > broken one > dry one > grinding one > dust collection > classification one > packaging. Although the process is simple, the product quality is difficult to control, because the impurity and smectite have similar specific gravity, which makes it difficult to separate fine particles and impurities, and it is difficult to obtain high-purity montmorillonite. This method is generally suitable for montmorillonite with a purity of 80% or more. Quality mineral selection, and purification of montmorillonite ore that does not require high purity of montmorillonite products. The wet method is suitable for the purification of montmorillonite with a purity of 30-80% and low-quality bentonite. The quality of the product is stable, but the purification period is long and the cost is high. The purity of the obtained montmorillonite is about 90%. Such as the early bromoform ethanol heavy liquid method, and Kong Qingchi et al ("rock test", 1999 3 Month, voU8(l): 62-64) The carbon tetrachloride-n-octylamine heavy liquid method, that is, the montmorillonite is immersed in an aqueous solution of n-octylamine, the density is reduced to 1.60xl0 ³ kg/m ³ or less. The separation of other clay minerals and impurities can be achieved by using CC1 ₄ as a heavy liquid, and montmorillonite containing n-octylamine can be treated with 7.5 mol/l NaOH solution to obtain high-purity montmorillonite. Li Yuling et al. (Journal of Xinyang Normal University (Natural Science Edition), October 2002, 15(4): 443-444) discloses a method for purifying calcium-based bentonite by flocculation, using inorganic, organic flocculants and homemade acetate shells. The solution of the bentonite slurry was flocculated and purified. The results showed that the purification effect of the self-made chitosan solution on bentonite was better than that of inorganic and organic flocculant. The whiteness of the purified bentonite reached 78.6% and the content of montmorillonite reached 90.1%. Yan Jinghui et al. (Non-Metallic Mines, May 2002, 25 (3): 8-9) From the structural analysis of montmorillonite, the purification route was studied. First, the calcium-based montmorillonite was soaked in water and soaked. Treatment, the layered structure is opened, because in the water dispersion medium, the montmorillonite particles are positively and negatively attracted, and there is a lap joint structure mainly composed of "work" type, some subtle The solid impurities of the granule are supported or wrapped by the association structure and are difficult to be removed. The lap structure is opened by adding a high-purity treatment agent (such as sodium pyrophosphate) to remove fine particle impurities for purification purposes. Remove high purity process agent, to restore the structure of montmorillonite.

In addition, there are many articles (Chinese Journal of Industrial Medicine, June 2002, 15 (3): 158-160 and Chinese Journal of Occupational Health and Occupational Diseases, February 2000, 18 (1): 60) Research results on the carcinogenicity of quartz and its carcinogenic mechanism. The International Agency for Research on Cancer (IARC) officially announced in October 1996 that quartz and cristobalite (SiO ₂ ) are human carcinogens (Environmental and Occupational Medicine, February 2005, 22 (1): 60-62), and research Researchers have obtained research results on the cellular and molecular mechanisms of quartz carcinogenesis: 1) Si0 ₂ induces the transformation, proliferation and proliferation of lung epithelial cells, directly causing damage to the damaged alveolar dysfunction, leading to destruction of the alveolar epithelium, and thus the proliferation of the alveolar wall fibroblasts, to proliferate and destruction of the alveolar epithelial cells of lung tissue repair and regeneration, pulmonary fibrosis key and carcinogenic; ₂₎ Si0 2 in A549 cells reduced space communication, and the SiO ₂ doses A good dose-response relationship is presented, and the downregulation of epithelial cell gap communication is also an important mechanism of the cancer-promoting phase; 3) Si0 ₂ mediates DNA damage and repair, and can exhibit significant concentration-dependent and time-dependent at lower doses. the role of DNA damage, mainly reactive oxygen species resulting in the target cell DNA strand breaks and base oxidation occurs; 4) SiO ₂ and tumor Of Concerning genes interfering cell growth, differentiation and / or apoptosis, ultimately leading to cancer.

Because of its specific structure and variable physical and chemical properties, montmorillonite has a variety of beneficial medical effects, and thus has many uses in the pharmaceutical and industrial fields. For example, montmorillonite can adsorb and encapsulate a variety of endogenous and exogenous pathogenic factors in the digestive tract, and cause the pathogenic factors to be excreted with the digestive tract itself, which can be used as a pathogen scavenger for the digestive tract without being digested by the digestive tract. Absorption, no entry into the blood circulation, no toxicity to the human body; can be combined into the digestive tract The bile acid and bile salt have strong immobilization and inhibition effects on viruses, bacteria and their produced toxins, gases and endogenous toxins, which can cause the above pathogens to lose pathogenicity; Strong coverage protection, repair, improve the defense function of mucosal barrier against attack factors, balance flora and local analgesic hemostasis; have allergens for adsorption, play an anti-allergic effect, and its adsorption capacity is 1 times higher than that of activated carbon It is non-toxic and corrosive to humans, animals and plants, has no irritation to human skin, has no effect on nerves and respiratory system, and has been used as the drug of choice for the treatment of infantile diarrhea; for the treatment of hyperthyroidism, chronic renal failure, elimination Oral odor, diarrhea and peptic ulcer; used as a pharmaceutical carrier.

Therefore, the montmorillonite is separated and purified, and the content of symbiotic minerals, 0;-quartz and cristobalite is reduced, and high-purity and high-quality montmorillonite is prepared to improve the medicinal quality and application performance of montmorillonite, thereby making it safer. Effective, becoming a technical problem that people urgently need to solve. Summary of the invention

The object of the present invention is to provide a high-purity montmorillonite. In order to minimize the original structure and properties of the montmorillonite, according to the results of the original ore identification, based on the general understanding of the impurity components of each sample, the use of the montmorillonite The characteristics of the stone swelling in water and the particle size and specific gravity of the smectite mineral are different from the impurity minerals, and the coarse non-clay minerals are separated and purified by mechanical means such as stripping, swirling, and centrifugation to separate and purify.

Natural montmorillonite is associated with non-clay silicate minerals such as silica, opal, feldspar, gypsum, calcite, perlite, zeolite, etc., and also contains clay minerals such as kaolinite, illite, chlorite, and a small amount. The organic matter, in which the mineral content of montmorillonite is usually 50%-70%, and the content of partially rich ore can reach 80%-90%. Using the characteristics of smectite swelling in water, it is separated from the symbiotic non-metallic minerals, and then the difference in particle size and density is utilized, by means of swirling and centrifugation. Mechanical equipment such as stripping removes coarse non-clay minerals, but α-quartz which is closely related to montmorillonite in 3⁄4 degree and cristobalite with extremely fine particle size and montmorillonite, 'Hydration of montmorillonite The expansion force is not enough to fight the condition of the two packages, especially the calcium-based soil with high layer charge. According to the size of the layer charge, plus the appropriate amount of modifier, under different conditions of Η, temperature, with stirring, and finally accelerate the dispersion of montmorillonite and impurities in high-speed centrifugal separation equipment to separate high density, non-separation Impurities such as expanded α-quartz. In addition, the difference in stability between the montmorillonite wafer and the cristobalite under different hydrothermal conditions can be utilized, and the cristobalite is hydrolyzed into a liquid phase with an alkaline solution, and separated and removed by high-speed centrifugation.

A first object of the present invention is to provide a method for purifying montmorillonite, comprising the following steps: 1) adding montmorillonite powder to water, and formulating a slurry having a solid content of 10-50%, and adding a powder amount of 0.05-1.2. % of dispersant, beating, sieving, removing coarse sand, and overflowing slurry; 2) overflowing slurry and water to form a suspension containing 0.5-12% solids, Into a high-speed centrifugal separation equipment for high-speed centrifugal separation, remove impurities in the package or inlaid montmorillonite, to obtain a centrifugal slurry; 3) Centrifugal slurry is concentrated and dried.

The smectite powder according to the present invention is obtained by drying, pulverizing and sieving natural bentonite or montmorillonite which requires improvement in purity. The bentonite powder or smectite powder is usually controlled to have a particle size of 50 mesh to 300 mesh, preferably 100 mesh to 200 mesh, and a powder of 50 mesh to 300 mesh, preferably 100 mesh to 200 mesh.

Further, it is preferred that the concentration of the step slurry is 15-45%, more preferably 20-40%, and most preferably 25-35.

%.

The dispersing agent of the present invention is selected from the group consisting of sodium hexametaphosphate, sodium trimetaphosphate, sodium metaphosphate, sodium polyacrylate, aqueous ammonia, sodium pyrophosphate, sodium polyphosphate, acrylic acid, sodium acrylate, sodium silicate, trisodium phosphate , sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium carboxymethylcellulose, sodium citrate, Na ₂ HPO ₄ , NaH ₂ PO ₄ NaCK NaF, sodium sulfate, silica sol, urea, Any one or a combination of polysorbate, hydrochloric acid, acetic acid, mixed acid, preferably sodium hexametaphosphate, sodium pyrophosphate, sodium polyphosphate, sodium trimite, sodium metaphosphate, sodium polyacrylate, Any one or a combination of trisodium phosphate, sodium citrate, Na ₂ HPO ₄ , NaCK NaF, urea, polysorbate, potassium hydroxide, potassium carbonate, NaH ₂ PO ₄ , ammonia water, sodium sulfate, hydrochloric acid, acetic acid .

Further, the mixed acid is prepared by mixing an inorganic acid and an organic acid; the inorganic acid includes but is not limited to a monobasic acid, a dibasic acid or a tribasic acid; and the monobasic acid is selected from the group consisting of hydrochloric acid, nitric acid, and hydrobromine. Any one or combination of acids or hydrofluoric acids, the dibasic acid is selected from the group consisting of sulfuric acid, the tribasic acid is selected from the group consisting of phosphoric acid or sulfonic acid; preferably the inorganic acid is a monobasic acid, most preferably hydrochloric acid or nitric acid.

Further, the organic acid includes, but is not limited to, a carboxylic acid, a hydroxy acid, a keto acid, an acid or an acetic acid, and may be classified into a fatty acid, an aromatic acid, an amino acid, a nucleic acid, a saturated acid or an unsaturated acid depending on the linkage with the hydrocarbon group. Etc., the organic acid according to the present invention may be selected from the group consisting of acetic acid, oxalic acid, citric acid, succinic acid, formic acid, propionic acid, butyric acid, malonic acid, succinic acid, pyruvic acid, glutamic acid, tartaric acid, malic acid, lactic acid. Any one or a combination of fumaric acid, itaconic acid, ascorbic acid, fumaric acid, α-ketoglutaric acid or carboxylic acid, preferably organic acid is acetic acid, oxalic acid, citric acid, succinic acid, propionic acid, butyric acid, Any one or combination of succinic acid or malonic acid.

In order to clearly describe the present invention, the "dispersant" of the present invention is also referred to as "selective agent", "high purity agent" or "high purity treatment agent".

Further, it is preferred that the dispersant be used in an amount of from 0.10 to 1.0%, more preferably from 0.15 to 0.80%, still more preferably from 0.20 to 0.70%, most preferably from 0.25 to 0.5%.

Further, the beating time is preferably from 1 to 5 h, more preferably from 2 to 4 h, and most preferably 3 h. Further, 2) the slurry has a solid content of from 1 to 10%, more preferably from 2 to 8%, still more preferably from 3 to 6%, most preferably from 4 to 5%.

Further, the high speed centrifugal separation apparatus is selected from any one or a combination of a disc centrifuge, a hydrocyclone or a horizontal centrifuge.

Further, in step 3), the concentration is selected from any one or a combination of high speed centrifugal concentration, thin film concentration, reduced pressure concentration or pressure filtration dehydration.

Further, the centrifugal slurry obtained in the second step can be directly spray-dried.

Further, in order to separate and remove fine impurities between the wrapped or inlaid montmorillonite grains, a forced stripping technique may be employed in step 3, such as forced stripping with a high speed shear, a high speed disperser, a ball mill or a high pressure homogenizer. The particles of impurities in the montmorillonite are fully exposed, and the dissociated or exposed solid impurities are removed by high-speed centrifugation to obtain montmorillonite having higher purity.

Further, the forced stripping technique is selected from the group consisting of a high speed shearing machine, a high speed dispersing machine, a ball mill or a high pressure homogenizer for high speed dispersion and shearing. The selection of technical parameters for forced stripping is mainly based on the phase analysis results of the ore and the results of the montmorillonite phase detection during the purification process.

The high-pressure homogenizer uses a high-pressure reciprocating pump as the power transmission and material conveying mechanism to deliver the material to the working valve (primary homogenizing valve and secondary emulsifying valve). In the process of passing the material through the working valve, a high-intensity energy accumulation is formed in the working area, and strong shear, impact, turbulence and cavitation are generated when the fluid flows through the small flow path of the homogenizing valve. The liquid substance or the solid particles which are supported by the liquid are ultra-fine, which is also called forced stripping.

Further, the high pressure homogenization is selected from continuous homogenization or multi-stage homogenization, preferably multi-stage homogenization, more preferably 1-3 grade homogenization, most preferably 5-60 MPa-class homogenization and 70-300 MPa. Secondary homogenization.

Further, the smectite slurry can be subjected to sodium modification treatment in step 2) to open the superposition of the montmorillonite grain layer and the layer, increase the interlayer channel, and expose the fine impurities between the coating or the mosaic layer. The dissociated or exposed solid impurities are removed by high speed centrifugation to obtain montmorillonite of higher purity.

Further, the fine impurities or fine impurities are selected from quartz or mineral impurities having a particle size of 0.1 / mi - 0.5 / mi.

Further, the sodium modification is a sodium hydride modification or a direct sodium modification, preferably a sodium hydride modification. Further, the sodium hydride modification means that the montmorillonite powder is added with water, and after adding an appropriate amount of an acid solution to the hydrogen-based montmorillonite, a sodiuming agent is added for sodium modification.

Further, the direct sodium modification means that the smectite powder is dispersed with water, and then a sodiumating agent is added for sodium. Transformation.

The principle of the purification method of the invention is as follows: utilizing the characteristics of negatively charged and positively charged on the surface of the montmorillonite particles, in the water dispersion medium, the montmorillonite particles are positively and negatively attracted to each other to form a "work" shape. Associative lap joint structure, some fine solid impurities are supported or wrapped by this association, it is difficult to remove, which brings great difficulty to the purification of montmorillonite minerals. By adding a dispersant, adjusting the pH, temperature and other conditions of the slurry, and supplementing with stirring, the positive charge edge of the montmorillonite particles becomes a negatively charged edge, so that all the montmorillonite particles become a negative electric double layer colloid, so that They are mutually exclusive, the association structure disappears, and the colloidal viscosity decreases sharply, so that the fine solid impurities lose support, and the gravity sinks quickly. The static dispersion, filtration or centrifugation is used to accelerate the forced dispersion of montmorillonite and impurities. To remove fine solid impurities.

The main reasons for the negative charge on the surface of montmorillonite particles are: 1) Al ^{3+ in} octahedral sheets is randomly substituted by Mg ²⁺ , Fe ²⁺ , Fe ^{3+ ,} etc. 2) Si ^{4+ in} tetrahedron is replaced by Al ³⁺ 3) One of the bonds of the surface O ² - is connected to the silicon, and the other is free. The main reasons for positive charge at the edge of montmorillonite particles are: 1) The fractured part of the octahedral piece is positively charged in the neutral or acidic suspension compared with the surface of the alumina particle, and increases positively with decreasing pH value. 2) The tetrahedral fracture is compared with the surface of the alumina particle. Although the surface of the alumina is negatively charged, when the clay particles in the suspension are slightly dissolved, a small amount of aluminum atoms are present to make the fractured tetrahedral piece positively charged; 3) The tetrahedral sheet preferentially ruptures where aluminum replaces silicon, so that the exposed surface is comparable to the alumina surface.

The montmorillonite purification method of the invention is wet purification, and after the natural bentonite is dried and pulverized, it is formulated into a certain concentration of slurry, and an appropriate amount of dispersant is added, beaten or peeled, and the various mineral components in the bentonite are uniformly formed. Mixing slurries to take advantage of differences in physical properties of various minerals, such as particle size or density differences, using cyclones or high-speed centrifuges (such as disc centrifuges, horizontal centrifuges) The components are separated and removed, such as natural zeolite, feldspar, calcium carbonate, coarse-grained quartz sand, and the like.

For smectite containing cristobalite, the difference in hydration dissociation ability of montmorillonite nanochips and cristobalite in an alkaline medium is utilized to hydrolyze cristobalite into a liquid phase, which is separated from montmorillonite. Therefore, the present invention also provides another method for purifying montmorillonite, comprising the following steps: 1) montmorillonite powder is dispersed with water, formulated into a slurry having a solid content of 10-50%, and is beaten and filtered to remove coarse sand. The slurry is filtered; 2) After adding an appropriate amount of alkaline solution to the filter slurry, it is placed in a closed container for hydrothermal treatment, filtered, and washed to obtain a filter cake; 3) The filter cake is added with water to form a solid content of 0.5-12%. The slurry is put into a high-speed centrifugal separation device, and the impurities are removed by high-speed centrifugation to obtain a centrifugal slurry; 4) The centrifugal slurry is concentrated and dried.

The smectite powder according to the present invention is obtained by drying, pulverizing and sieving natural bentonite or montmorillonite which needs to be improved in purity. Generally, the particle size of the bentonite powder or the smectite powder is controlled to be 50 mesh to 300 mesh, preferably 100. The mesh is -200 mesh, and the powder is passed through a 50 mesh-300 mesh sieve, preferably a 100 mesh to 200 mesh sieve.

%.

The alkaline solution is prepared by dissolving a basic substance well known in the art in water, such as an alkali metal salt, an alkali metal oxide, an alkaline earth metal salt, an alkaline earth metal oxide, a weak acid strong base salt or ammonia water.

Further, it is preferable that the alkaline substance is selected from the group consisting of sodium carbonate, sodium hydrogencarbonate, sodium fluoride, sodium chloride, sodium sulfate, sodium hydroxide, sodium aluminate, ammonia water, potassium carbonate, potassium hydrogencarbonate, potassium fluoride, Any one or a mixture of potassium chloride, potassium sulfate, potassium hydroxide, potassium aluminate, calcium carbonate, calcium hydrogencarbonate, calcium fluoride, calcium chloride, calcium sulfate, calcium hydroxide or calcium aluminate, more preferably It is any one of ammonia water, sodium carbonate, sodium hydrogencarbonate, sodium fluoride, sodium chloride, sodium sulfate, sodium hydroxide or sodium aluminate or a mixture thereof.

Further, the concentration of the alkaline solution is from 0.1 to 5 N, preferably from 0.5 to 4.5 N, more preferably from 1.0 to 4 N, still more preferably from 1.5 to 3.5 N, and most preferably from 2.0 to 3 N.

Further, the appropriate amount of the alkaline solution in the step 2) means that the alkaline solution is used in an amount sufficient to dissolve the cristobalite contained in the smectite powder.

Further, the hydrothermal treatment temperature is 60 to 160 ° C, preferably 70 to 140 ° C, more preferably 80 to 120 ° C, and most preferably 85 to 100 ° C.

Further, the filter cake obtained in the step 2) has a pH of 7 to 10, preferably a pH of 7.5 to 9, more preferably a pH of about 8 to 8.5. Further, the step slurry has a solid content of from 1 to 10%, more preferably from 2 to 8%, still more preferably from 3 to 6%, most preferably from 4 to 5%.

Further, in step 4), the concentration is selected from any one or a combination of high speed centrifugal concentration, film concentration, reduced pressure concentration or pressure filtration dehydration.

Further, the centrifugal slurry obtained in the third step can be directly spray-dried.

Further, in order to separate and remove the fine impurities between the wrapped or inlaid smectite grains, the forced stripping technique may be used in 3), such as using a high speed shear, a high speed disperser, a ball mill or a high pressure homogenizer. Stripping, fully exposing the impurity particles in the montmorillonite, and removing the dissociated or exposed solid impurities by high-speed centrifugation to obtain a montmorillonite of higher purity.

Further, the forced stripping technique is selected from the group consisting of a high speed shearing machine, a high speed dispersing machine, a ball mill or a high pressure homogenizer for high speed dispersion and shearing. The selection of technical parameters for forced stripping is mainly based on the phase analysis of the ore. The results of the montmorillonite phase detection during the fruit and purification process are determined.

Further, the smectite slurry may be subjected to sodium modification treatment in step 3 to open the superposition of the montmorillonite grain layer and the layer, increase the interlayer channel, and expose the fine impurities between the coating or the mosaic layer. The dissociated or exposed solid impurities are removed by high speed centrifugation to obtain montmorillonite of higher purity.

Further, the fine impurities or fine impurities are selected from quartz or mineral impurities having a particle size of 0.1 μm - 0.5 μm.

Further, the direct sodium modification means that the smectite powder is dispersed with water, and then a sodiuming agent is added for sodium modification. ..

The percentages stated herein are by weight unless otherwise indicated.

The bentonite of the present invention is also called porphyrite, expansive rock, bentonite, porphyrite, sweet earth, bentonite, clay, white mud or Guanyin soil; the cristobalite is also called cristobalite.

The montmorillonite abundance of the present invention, also known as the purity of montmorillonite, is a key index for measuring the quality and application properties of bentonite, and the expansion, adsorption, cation exchange characteristics, chargeability, stripping into nano-sized plates, etc. of montmorillonite. The characteristics are directly related.

At present, the common methods for determining the abundance of montmorillonite are methylene blue method, alkyl ammonium method, etc., but there are disadvantages such as large errors and cumbersome operations.

The present invention uses X-ray diffraction to determine the purity and phase composition of montmorillonite. The collected ore samples were pulverized, passed through a 200 mesh sieve, and placed on an X-ray diffractometer (RIGAK^D/Max-2550pc) to collect diffraction data to analyze the phase composition. For the determination method of montmorillonite abundance, please refer to the literature (Hu Xiurong, Lu Guanglie et al., Journal of Mineralogy, June 2005, 25 (2): 153-157, quantitative method for montmorillonite abundance in natural bentonite), mainly The interlayer charge density value and the cation exchange capacity value of the same origin montmorillonite are specific, and the total amount of scattering of the unit mass montmorillonite in the entire inverted space is very close to the abundance and linear positive correlation. Its abundance.

Further, the purity of the purified montmorillonite of the present invention is not less than 95%, preferably not less than 96%, more preferably not less than 97%, still more preferably not less than 98%, further preferably not less than 99%, most preferably Not less than 99.5%. The method for determining the degree of swelling, adsorption, heavy metals and related substances of the purified montmorillonite according to the invention is described in the literature.

(S (X- 165) -2004Z, quality standard for montmorillonite).

The cation exchange capacity (CEC) of the present invention refers to the amount of adsorbed exchange cations of clay minerals (e.g., montmorillonite), including exchangeable bases and exchangeable hydrogens, in units of mmol/100 g. The size of CEC is directly related to the purity, hydration, swelling, chargeability, adsorption and other properties of clay minerals (such as montmorillonite), and is an important indicator for characterizing and judging its properties and uses.

At present, the methods for determining the cation exchange capacity are mainly NH4+ exchange method (ammonium acetate leaching method, etc.), Mg ²⁺ exchange method (magnesium oxide extraction method), Na ⁺ exchange method (sodium acetate leaching method), etc. The salt is rinsed with minerals and all of the exchangeable cations are rinsed out, but the operation of these methods is cumbersome, time consuming and has many influencing factors.

In the present invention, CEC is measured by a cobalt chloride ammonia ion exchange method, that is, [Co(NH ₃ ) ₆ ] ^{3+ is} used as an exchange cation, and the cation exchange capacity of the clay is measured. Because [Co(NH ₃ ) ₆ ] ³⁺ is high in charge (3+), large in ionic radius (0.2nm), has maximum absorption at 474nm, and has good stability in the range of pH-1-14, which is an ideal exchange ion. And non-clay minerals have no effect on the exchange reaction, free metal ions do not participate in the exchange reaction, and do not need to be stirred and repeated exchange in the measurement, in order to determine the specific method of CEC, it is convenient, sensitive, simple, high accuracy.

The process of measuring CEC by cobalt chloride ammonia ion exchange method includes: crushing montmorillonite sample, passing through 300 mesh sieve, baking at 60 °C for 3 hours, and standby; and then montmorillonite sample with a certain amount of 0.025 mol/L [ Co(NH ₃ ) ₆ ]Cl ₃ solution was mixed, adjusted to pH 7-8, shaken, and after ion exchange equilibrium, the absorbance was measured at 474.0 nm, and the difference between the absorbances before and after the exchange was ΔΑ, and the ion exchange corresponding was calculated. At a concentration C, the cation exchange capacity of the clay is calculated according to the formula CEC=300 CV/W, where V is the volume of the exchange liquid and W is the amount of the sample weighed.

Further, the cation exchange capacity (CEC) of the purified montmorillonite of the present invention is defined to be 75-140 mmol/100 g, preferably 80-135 mmoI/100 g, more preferably 90-130 mmol/lOOg, most preferably 100-125 mmol/ 100g.

Further, the degree of expansion of the purified montmorillonite of the present invention is not less than 4.0, preferably not less than 5.0, more preferably not less than 7.0, still more preferably not less than 9.0, further preferably not less than 10.0, and most preferably not less than 12.0.

Further, the adsorption amount per lg of purified montmorillonite to the strychnine sulfate is limited to 0.30 to 0.75 g, preferably 0.40 to 0.70 g, more preferably 0.45 to 0.65 g, and most preferably 0.50 to 0.60 g.

Further, the heavy metal of the purified montmorillonite of the present invention is not more than 10 ppm, preferably not more than 7 ppm, more preferably not more than 5 ppm, and most preferably 3-4 ppm. Further, the relevant substance for purifying the montmorillonite of the present invention is not more than 5%, preferably not more than 4%, more preferably not more than 3%, still more preferably not more than 2%, further preferably not more than 1%, and most preferably not more than 0.5%.

The "related substance" as used in the present invention means an impurity other than montmorillonite.

In addition, conventional methods for purifying montmorillonite include dry purification methods such as hand selection and air selection. The hand-selected purification is mainly used for bentonite with a high content of ore montmorillonite. The large waste rock in the ore is manually selected, stacked separately and processed separately. The processing flow is: Bentonite 1>Fracture 1>Drying 1>Hand-selection 1>Pulverization 1 >Packing. Alternatively, the crushing method may be selected according to the original ore condition of the bentonite. If the soft bentonite is not broken, the hard bentonite is crushed by a jaw crusher or a Raymond mill, and the crushed to a particle size of about 2 cm; then dried by natural drying or heating. Remove the moisture, and then use a hand-selected or vibrating sieve to remove the clods with a particle size larger than 2 cm. Finally, the fine-grained ore is crushed by about 200 mesh using Raymond mill.

Wind selection is a commonly used montmorillonite purification method, which is suitable for montmorillonite ore with a montmorillonite content of more than 80% and a fine particle size, and which contains coarse quartz and feldspar. The process is as follows: bentonite ore-1>Drying> Breaking one> Airflow drying one> grinding one> wind selection grading one> packaging. The ore is dried to reduce its water content to less than 25% and crush it to 3-4cm _; then use a fluidized dryer, a rotary louver dryer, a cyclone dryer or a rotary dryer to make the water content It is 6%-12%, and after being ground to 100-325 mesh by Raymond mill, it is classified by a gas classifier to remove sand minerals such as feldspar and quartz.

For low-grade bentonite with a montmorillonite content of 30%-80% in the ore or a bentonite containing a small particle size of feldspar or quartz, a higher purity bentonite or montmorillonite is required, and a natural sedimentation method is often used. Wet purification is carried out by flocculation method, heavy liquid method, high-speed centrifugation method, secondary fractionation method or electrophoresis method. In the actual purification process, several purification methods can be combined as needed in different purification stages.

Natural sedimentation method refers to crushing bentonite ore to particles with a particle size of less than 5 mm, stirring with water at a ratio of about 3:1, making a slurry, and then standing still to make sand minerals such as quartz, feldspar and carbonate. Natural sedimentation; the remaining suspension continues to use natural sedimentation to further sediment the sandy minerals; or a polyacrylamide flocculant is added to promote further sedimentation of the montmorillonite.

The high-speed centrifugation method and the secondary fractionation method are carried out by separating the suspension after the natural sedimentation is removed by high-speed centrifugation, and further separating the fine-grained detrital minerals (such as feldspar, carbonate, etc.) to obtain bentonite having a particle size of less than 5 μm. The slurry or suspension is filtered, dried, and dispersed to obtain a solution.

Further, a dispersing agent may be added during the pulping process to precipitate the detrital mineral mass in the slurry; or after purifying and removing impurities, a flocculating agent may be added to the suspension for coagulation or flocculation to achieve solid-liquid separation. The process is as follows: Bentonite 1: Breaking 1> Pulping (plus dispersing agent) 1> Settling separation 1> Suspension centrifugation (flocculation) Agent) a>Filter a> Dry one> Disperse and depolymerize one> packaging.

Electrophoresis: Using the negative charge characteristics of montmorillonite particles, after dispersing the bentonite ore in water, it is placed in an electric field, and the negatively charged montmorillonite particles move toward the anode. Therefore, water and a dispersing agent can be added to the bentonite, which is slurried, and the negatively charged montmorillonite particles are collected on the anode by electrophoresis to separate and remove impurities therein. This method generally requires that the bentonite has a particle size of less than 2 nm, and the purified montmorillonite has a high purity.

Another object of the present invention is to provide the use of any one or a combination of a disc centrifuge, a hydrocyclone or a horizontal centrifuge in the purification of a high purity smectite process.

Another object of the present invention is to provide an application of a disc centrifuge in a method for purifying montmorillonite, which can conveniently remove fine particles in hydrated expanded bentonite, such as α-quartz, etc., and can be conveniently solved. Technical problems such as difficulty in concentration and dehydration of purified liquid in wet-purified montmorillonite method.

The disc centrifuge according to the present invention is also called a "disc separator", a "disc centrifuge", a "disc separator" or a "thin separation sedimentation centrifuge", which is a vertical centrifuge, which is separated. The factor can reach 3000-10000. The drum is mounted on the upper end of the vertical shaft and is driven by a motor to rotate at a high speed. The drum is provided with a set of inverted conical disc-shaped parts, also referred to as discs, which are nested together. There is a small gap between the disc and the disc, and the disc gap can be 0.5-1.5mm. The suspension (or emulsion) is added to the drum by a feed tube located at the center of the drum and distributed between the discs to form a thin layer flow. Under the action of centrifugal force, the particles settle to the inner surface of the disc and slide outward, and the clear liquid flows inward along the outer surface of the disc. When the suspension (or emulsion) passes through the gap between the discs, the solid particles (or droplets) settle to the disc under the action of the centrifuge to form a sediment (or liquid layer). The sediment slides along the surface of the disc to separate the disc and accumulates in the portion of the drum having the largest diameter, and the separated liquid is discharged from the outlet to the drum. The disc shortens the settlement distance of the solid particles (or droplets) and enlarges the settlement area of the drum. The drum is equipped with a disc to greatly improve the productivity and separation efficiency of the separator, and is suitable for processing particle size 0.1- 100mm suspension with a solids content of less than 25%. The solids accumulated in the drum are dismantled by the drum after the separator is stopped, or discharged from the drum by the slag discharge machine without stopping the machine.

There is also a disc centrifuge which is a "disc type tube centrifuge", which is characterized in that the drum (tube) has a small diameter, a large length, a high rotation speed, and a high separation efficiency, and can continuously treat a suspension having a particle diameter of 0.01 mm. Liquid and difficult to separate emulsion. The suspension or emulsion is added by the lower end of the drum and is driven by the longitudinal ribs in the drum to rapidly rotate at the same angular velocity as the drum. Under the action of centrifugal force, the granule or heavy liquid layer is led out from the heavy liquid outlet to the drum wall, and the light liquid overflows from the center of the drum. Its centrifugal separation factor can reach 65,000. It is industrially used for oil-water separation and can be used to separate microorganisms and proteins in the laboratory.

The disc separator of the present invention can perform clarification operation and separation operation, that is, liquid-solid separation (ie, low concentration suspension) Separation of the float liquid) and liquid-liquid (or liquid-liquid-solid) separation (ie separation of the emulsion), the linear velocity of up to 200 m / s, and compact structure, small footprint, large production capacity Features.

Another object of the present invention is to provide an application of a hydrocyclone in a method for purifying montmorillonite, which can conveniently remove fine particles in hydrated expanded bentonite, such as c-quartz, etc., and can be conveniently solved. Technical problems such as difficulty in concentration and dehydration of purified liquid in wet-purified montmorillonite method.

A hydrocyclone is a device that is classified or separated by particle size and density. The tangential line of the material to be graded is fed from the inner wall of the cylinder at a high speed, and the mixture of medium and particles is rotated to form a centrifugal force field. Particles (or liquid phases) of different particle sizes and different densities produce different trajectories, in centrifugal force, medium viscous resistance, Under the action of force fields such as buoyancy and gravity, coarse particles and large-density particles move to the periphery and are discharged from the grit chamber through the cone; fine particles, low-density particles (or liquid phase) move toward the center, and the overflow tube Discharge; achieve coarse subdivision of solid particles and separation of fluids of different densities.

Another object of the present invention is to provide an application of a horizontal centrifuge in the method of purifying montmorillonite, which can conveniently remove fine particles in hydrated expanded bentonite, such as α-quartz, etc., and can be conveniently solved. Technical problems such as difficulty in concentration and dehydration of purified liquid in wet-purified montmorillonite method.

The horizontal centrifuge works as follows: The suspension is continuously fed along the feed tube and dispersed through the six feed holes in the small end wall of the spiral onto the drum wall. Due to the centrifugal force, the liquid is pumped out through the filter and the hole in the drum wall, and is discharged out of the machine through the filtrate outlet on the casing; the solid is trapped on the filter screen to form a filter residue layer. Because the spiral and the drum have a differential speed, the formed screw conveyor pushes the filter residue from the small end to the big end, and is discharged from the slag discharge port of the filter drum at the big end of the drum. The suspension is automatically and continuously. It is separated into a filtrate and a filter residue.

The separation effect of the suspension is closely related to the drum speed of the horizontal centrifuge, the rotating speed of the drum and the spiral difference, the feed rate, and the concentration of the suspension. Different suspensions should be tested to select the most suitable parameters. When the drum speed and the differential ratio are constant, adjusting the speed of the turning shaft can change the differential speed.

The invention removes the smectite slurry of coarse sand and other minerals, dilutes it into a slurry containing 0.5-12% by weight with water, and uses non-expanded α- by a disc centrifuge, a hydrocyclone or a horizontal centrifuge. Quartz or other fine impurities are separated from the expanded hydrated montmorillonite viscose and discharged from the equipment nozzle at extremely high line speeds to improve the purity of the montmorillonite and to easily solve the wet-purified montmorillonite In the method, the technical problem of difficulty in concentration and dehydration of the purified liquid is difficult.

A first object of the present invention is to provide a high-purity montmorillonite obtained by the following method: 1) montmorillonite powder is dispersed with water, and is formulated into a slurry having a solid content of 10-50%, and a powder amount of 0.05 is added. -1.2% dispersant, firewood, over Screening, removing coarse sand, resulting in overflow slurry; 2) overflowing slurry with water to form a suspension with a solid content of 0.5-12%, then put into high-speed centrifugal separation equipment, high-speed separation, removal of parcel or mosaic montmorillonite In the impurities, the slurry is centrifuged; 3) The centrifuged slurry is concentrated and dried.

Further, it is preferred that the concentration of the step slurry is 15-45%, more preferably 20-40%, and most preferably 25-35%.

The dispersing agent of the present invention is selected from the group consisting of sodium hexametaphosphate, sodium trimetaphosphate, sodium metaphosphate, sodium polyacrylate, aqueous ammonia, sodium pyrophosphate, sodium polysodium sulphate, acrylic acid, sodium acrylate, sodium silicate, and phosphoric acid Sodium, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium carboxymethylcellulose, sodium citrate, Na ₂ HPO ₄ , Na3⁄4PO ₄ . NaCl, NaF, sodium sulfate, silica sol, urea Any one or a combination of polysorbate, hydrochloric acid, acetic acid, mixed acid, preferably sodium hexametaphosphate, sodium pyrophosphate, sodium polyphosphate, sodium trimetaphosphate, sodium metaphosphate, sodium polyacrylate, Any of trisodium phosphate, sodium citrate, Na ₂ HP0 ₄ , NaCl, NaF, urea, polysorbate, potassium hydroxide, potassium carbonate, NaH ₂ P0 ₄ , ammonia, sodium sulfate, hydrochloric acid, acetic acid or combination.

Further, the organic acid includes, but is not limited to, a carboxylic acid, a hydroxy acid, a keto acid, an acid or an acetic acid, and may be classified into a fatty acid, an aromatic acid, an amino acid, a nucleic acid, a saturated acid or an unsaturated acid depending on the linkage with the hydrocarbon group. Etc., the organic acid according to the present invention may be selected from the group consisting of acetic acid, oxalic acid, citric acid, succinic acid, formic acid, propionic acid, butyric acid, malonic acid, succinic acid, pyruvic acid, glutamic acid, tartaric acid, malic acid, lactic acid. Any one or a combination of fumaric acid, itaconic acid, ascorbic acid, fumaric acid, c-ketoglutaric acid or carboxylic acid, preferably the organic acid is acetic acid, oxalic acid, citric acid, succinic acid, propionic acid, butyric acid, Any one or combination of succinic acid or malonic acid.

Further, the beating time is preferably from 1 to 5 h, more preferably from 2 to 4 h, and most preferably from 3 h.

Further, 2) the step slurry has a solid content of from 1 to 10%, more preferably from 2 to 8%, still more preferably from 3 to 6%, most preferably from 4 to 5%.

Further, the high speed centrifugal separation apparatus is selected from any one or a combination of a disc centrifuge, a hydrocyclone or a horizontal centrifuge. Further, in step 3), the concentration is selected from any one or a combination of high-speed centrifugal concentration, thin film concentration, reduced pressure concentration or pressure filtration dehydration.

Further, the centrifugal slurry obtained in the step 2) can be directly spray-dried.

Further, in order to separate and remove fine impurities between the wrapped or inlaid montmorillonite grains, forced stripping may be performed in 2), such as forced shearing using a high speed shear, a high speed disperser, a ball mill or a high pressure homogenizer. The particles of impurities in the montmorillonite are fully exposed, and the dissociated or exposed solid impurities are removed by high-speed centrifugation to obtain montmorillonite having higher purity.

Further, the smectite slurry may be subjected to a sodium modification treatment in step 2) to open the superposition of the montmorillonite grain layer and the layer, to increase the interlayer passage, and to expose the fineness between the package or the mosaic layer. The impurities are removed by high-speed centrifugation to remove dissociated or exposed solid impurities to obtain montmorillonite of higher purity.

Further, the direct sodium modification means that the smectite powder is dispersed with water, and then a sodiuming agent is added for sodium modification.

An object of the present invention is to provide a high-purity smectite which is obtained by the following method: 1) dispersing the montmorillonite powder with water, formulating it into a slurry having a solid content of 10-50%, beating, The coarse sand is filtered to remove the slurry; 2) adding an appropriate amount of the alkaline solution to the filter slurry, placing it in a closed vessel for hydrothermal treatment, filtering and washing to obtain a filter cake; 3) adding water to the filter cake to form a solid 0.5-12% of the slurry is put into a high-speed centrifugal separation equipment, and the impurities are removed by high-speed centrifugation to obtain a centrifugal slurry; 4) The centrifugal slurry is concentrated and dried.

%.

The alkaline solution is prepared by dissolving a basic substance well known in the art in water, such as an alkali metal salt or an alkali metal. Oxide, alkaline earth metal salt, alkaline earth metal oxide, weak acid strong base salt or ammonia water.

Further, the concentration of the alkaline solution is from 0.1 to 5 N, preferably from 0.5 to 4.5 N, more preferably from 1.0 to 4 N, still more preferably from 1.5 to 3.5 N, and most preferably from 2 to 3 N.

Further, 4) the concentration is selected from the group consisting of high-speed centrifugal concentration, thin film concentration, reduced pressure concentration or pressure filtration dehydration. Further, the centrifugal slurry obtained in the step 3) can be directly spray-dried.

Further, in order to separate and remove fine impurities between the wrapped or inlaid montmorillonite grains, forced stripping may be employed in step 3), such as forced shearing using a high speed shear, a high speed disperser, a ball mill or a high pressure homogenizer. The impurity particles in the smectite are sufficiently exposed, and the dissociated or exposed solid impurities are removed by high-speed centrifugation to obtain a montmorillonite having a higher purity.

Further, the fine impurities or fine impurities are selected from α-quartz or mineral impurities having a particle size of 0.1-0.5 μm Quality.

Further, the purity of the purified montmorillonite obtained by the present invention is not less than 95%, preferably not less than 96%, more preferably not less than 97%, further preferably not less than 98%, further preferably not less than 99%, and most preferably Preferably it is not less than 99.5%.

Further, the cation exchange capacity (CEC) of the purified montmorillonite of the present invention is defined to be 75-140 mmol/100 g, preferably 80-135 mmol/100 g, more preferably 90-130 mmol/lOOg, most preferably 100-125 mmol/ 100g.

Further, the adsorption amount per lg of purified montmorillonite to the strychnine sulfate is 0.30-0.75 g, preferably 0.40-0.70 g, more preferably 0.45-0.65 g, and most preferably 0.50-0.60 g.

Further, the heavy metal of the purified montmorillonite of the present invention is not more than 10 ppm, preferably not more than 7 ppm, more preferably 5 ppm, and most preferably 3-4 ppm.

Further, the substance concerned with the purification of the smectite of the present invention is not more than 5%, preferably not more than 4%, more preferably 3%, still more preferably 2%, further preferably 1%, and most preferably 0.5%.

Another object of the present invention is to provide a method for preparing high-purity smectite, comprising the following steps: 1) adding montmorillonite powder to water, and formulating a slurry having a solid content of 10-50%, and adding an appropriate amount After the alkaline solution, it is placed in a closed container for hydrothermal treatment, filtered and washed to obtain a filter cake; 2) The filter cake is added with water to form a slurry containing 0.5-12% solids, and is put into a high-speed centrifugal separation device to remove impurities at high speed. , the slurry is centrifuged; 3) The centrifuged slurry is concentrated and dried.

Another object of the present invention is to provide a high-purity montmorillonite obtained by the following method: 1) montmorillonite powder is dispersed with water, and after being formulated into a slurry having a solid content of 10-50%, an appropriate amount is added. After the alkaline solution, it is placed in a closed container for hydrothermal treatment, filtered and washed to obtain a filter cake; 2) The filter cake is added with water to form a slurry containing 0.5-12% solids, and is put into a high-speed centrifugal separation device to remove impurities at high speed. , the centrifugal slurry is obtained; 3) the centrifugal slurry is concentrated and dried.

The purification method of montmorillonite can be based on the phase analysis results of bentonite or montmorillonite which needs to be purified, and needs to be divided. The purification method described in the present invention is selected or combined to obtain a smectite of a desired purity from factors such as impurities removed, purity requirements of montmorillonite, and the like.

The invention obtains high-purity montmorillonite, and significantly improves the physicochemical properties of montmorillonite, such as adsorption, swelling and abundance, which are extremely related to its pharmacological action and application performance, and thus has improved pharmacological properties than natural montmorillonite. Effects, better application performance and lower toxic side effects.

The sodium modification of montmorillonite can open up the superposition between layers and improve the characteristics of expansion, adsorption and cation exchange of montmorillonite, so that it has better application prospects. Currently, smectite sodiumation methods are usually available in both dry and wet methods. The dry sodium method is directly dry-mixed with a sodiuming agent and montmorillonite, and is obtained by milling, such as a yard method, an extrusion method or a suspension method. Its characteristic is that the process is simple, but there are many disadvantages such as uneven sodiumation and easy calcification. The wet sodiumation method refers to arranging various soluble sodium salt solutions and montmorillonite in a certain ratio, and adjusting the pH of the solution between weakly alkaline and weakly acidic, and heating and stirring are obtained. It is characterized by a deep sodiumation, but it is difficult to dehydrate sodium.

In the present invention, sodium-based high-purity montmorillonite is prepared by a sodium hydride method or a direct sodiumation method. The high-purity sodium montmorillonite can be obtained by a method of purification, hydrogenation or sodiumation, or by hydrogenation, purification, sodiumation or by purification or sodiumation.

Another object of the present invention is to provide a method for preparing high-purity sodium montmorillonite (hydrogenation sodiumation method) comprising the following steps: adding an acid solution to high-purity calcium-based montmorillonite or high-purity magnesium-based montmorillonite Prepare it into an acid slurry with a solid content of 10-50%, stir and filter the acid slurry, wash the filter cake to weak acidity, and add a slight excess of sodium salt to the filter cake. Stir the sodium and dry it.

Further, the purity of the high-purity calcium-based montmorillonite or the high-purity magnesium-based montmorillonite is not less than 95%, preferably not less than 96%, further preferably not less than 97%, more preferably not less than 98%, and further preferably Not less than 99%, most preferably not less than 99.5%, the preparation method is the same as the above purification method.

Further, the acid solution is selected from the group consisting of inorganic acids, organic acids, or mixtures thereof.

Further, the inorganic acid includes, but is not limited to, a monobasic acid, a dibasic acid or a tribasic acid.

Further, the monobasic acid is selected from the group consisting of hydrochloric acid, nitric acid, hydrobromic acid or hydrofluoric acid, the dibasic acid is selected from sulfuric acid, and the tribasic acid is selected from the group consisting of phosphoric acid or sulfonic acid; preferably a monobasic acid, most preferably hydrochloric acid or nitric acid.

Further, the organic acid includes, but is not limited to, a carboxylic acid, a hydroxy acid, a keto acid, an acid, a fatty acid, an aromatic acid, an amino acid, a nucleic acid, a saturated acid, an unsaturated acid, etc., preferably acetic acid, oxalic acid, citric acid, amber. Acid, formic acid, propionic acid, butyric acid, malonic acid, succinic acid, pyruvic acid, glutamic acid, tartaric acid, malic acid, lactic acid, fumaric acid, itaconic acid, ascorbic acid, fumaric acid, α-ketoglutaric acid Or a carboxylic acid, more preferably acetic acid, Oxalic acid, citric acid, succinic acid, propionic acid, butyric acid, succinic acid or malonic acid.

Further, the concentration of the acid solution is from 0.1 to 10 N, preferably from 0.2 to 8 N, more preferably from 0.3 to 6 N, and most preferably from 0 to 5 to 3 Torr.

Further, the acid slurry has a solid content of 15-45%, preferably 20-40%, more preferably 25-35 %, and most preferably 30%.

Further, the weakly acidic means that ρ Η is from 1.0 to 7.5, preferably from 1.5 to 7.0, more preferably from 2.0 to 6.5, most preferably from 2.5 to 6.0.

Further, the solid content of the filter cake is defined to be 30 to 70%, preferably 40 to 60%, more preferably 50%. Further, the sodiumating agent of the present invention is also called "sodium salt modifier", and can be Ca ²⁺ , Mg ²⁺ or H+ in calcium montmorillonite, magnesium montmorillonite or hydrogen montmorillonite. Exchanged to Na+, the sodiumating agent is a soluble sodium salt commonly used in the field, selected from sodium hexametaphosphate, sodium trimetaphosphate, sodium metametaphosphate, sodium polyacrylate, sodium pyrophosphate, sodium polyphosphate, sodium acrylate Any of sodium silicate, trisodium phosphate, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium carboxymethylcellulose, Na ₂ HPO ₄ , NaH ₂ PO ₄ , NaCl, NaF, sodium sulfate, sodium citrate Or a combination thereof, preferably sodium hexametaphosphate, sodium pyrophosphate, sodium polyphosphate, sodium trimetaphosphate, sodium metasilicate, sodium polyacrylate, trisodium phosphate, sodium citrate, Na ₂ HP0 ₄ , NaH ₂ Any one or combination of PO ₄ , NaCl, NaF, sodium sulfate, sodium hydroxide, sodium carbonate.

Further, the amount of the sodiumating agent is slightly more than the cation exchange capacity, which means that the amount of the sodiumating agent is 0.5-20% more than the cation exchange capacity, that is, the amount of the sodiumating agent is 1-20%, preferably 2-15. %, more preferably 3-10%, most preferably 4-7.5%.

Another object of the present invention is to provide a method for preparing high-purity sodium montmorillonite (direct sodiumation method) comprising the following steps: high-purity calcium-based montmorillonite or high-purity magnesium-based montmorillonite or hydrogen-based A desiccant solution having a slight excess amount of cation exchange capacity is added to the de-sparing stone to prepare a slurry having a solid content of 30-70%, stirred for sodiumation, and dried.

Further, the purity of the high-purity calcium-based montmorillonite, the high-purity hydrogen montmorillonite or the high-purity magnesium-based montmorillonite is not less than 95%, preferably not less than 96%, further preferably not less than 97%, more preferably Not less than 98%, still preferably not less than 99%, and most preferably not less than 99.5%.

Further, the sodiumating agent is a soluble sodium salt commonly used in the art, and is selected from the group consisting of sodium hexametaphosphate, sodium trimetaphosphate, sodium metametaphosphate, sodium polyacrylate, sodium pyrophosphate, sodium polyphosphate, sodium acrylate, and silicon. Any of sodium, trisodium phosphate, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium carboxymethylcellulose, Na ₂ HPO ₄ , NaH ₂ P0 ₄ , NaCl, NaF, sodium sulfate, sodium citrate or a combination thereof, preferably sodium hexametaphosphate, sodium pyrophosphate, poly Any of sodium phosphate, sodium trimetaphosphate, sodium metaphosphate, sodium polyacrylate, trisodium phosphate, sodium citrate, Na ₂ HPO ₄ , Na3⁄4P0 ₄ , NaC NaF, sodium sulfate, sodium hydroxide, sodium carbonate or Its combination.

Further, the amount of the sodiumating agent is slightly more than the cation exchange capacity, which means that the amount of the sodiumating agent is 0.5-10% more than the cation exchange capacity, that is, the amount of the sodiumating agent is 1-20%, preferably 2-15. %, more preferably 3-10%, most preferably 4-7.5%.

Further, it is preferred that the slurry has a solid content of 40 to 60%, more preferably 50%.

Another object of the present invention is to provide a high-purity sodium montmorillonite obtained by the following method (sodium hydride method): adding an acid solution to high-purity calcium-based montmorillonite or high-purity magnesium-based montmorillonite Prepare it into an acid slurry with a solid content of 10-50%, stir and filter the acid slurry, wash the filter cake to weak acidity, and add a slight excess of sodium salt to the filter cake. Stir in the sodium, dry and get.

Further, the concentration of the acid solution is from 0.1 to 10 N, preferably from 0.2 to 8 Torr, more preferably from 0.3 to 6 Torr, and most preferably from 0.5 to 3 Torr.

Further, the weakly acidic means that ρ Η is from 1.0 to 7.5, preferably from 1.5 to 7.0, more preferably from 2.0 to 6.5, most preferably from 2.5 to 6.0. .

Further, the gel cake is defined to have a solid content of 30 to 70%, preferably 40 to 60%, more preferably 50%.

Further, the sodiumating agent is a soluble sodium salt commonly used in the art, and is selected from the group consisting of sodium hexametaphosphate and trimetaphosphoric acid. Sodium, sodium metaphosphate, sodium polyacrylate, sodium pyrophosphate, sodium polyphosphate, sodium acrylate, sodium silicate, trisodium citrate, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium carboxymethylcellulose, Any one or a combination of Na ₂ HPO ₄ , Na 3⁄4PO ₄ , NaCl, NaF, sodium sulfate, sodium citrate or a combination thereof, preferably sodium hexametaphosphate, sodium pyrophosphate, sodium polyphosphate, sodium trimetaphosphate, heavy metaphosphoric acid Any of sodium, sodium polyacrylate, trisodium phosphate, sodium citrate, Na ₂ HPO ₄ , Na 3⁄4PO ₄ , NaC NaF, sodium sulfate, sodium hydroxide, sodium carbonate, or a combination thereof.

Another object of the present invention is to provide a high-purity sodium montmorillonite obtained by the following method (direct sodiumation method): high-purity calcium-based montmorillonite or high-purity magnesium-based montmorillonite or hydrogen-based monoxide A desiccant solution having a slight excess amount of cation exchange capacity is added to the de-sparing stone to prepare a slurry having a solid content of 30-70%, stirred for sodiumation, and dried.

Further, the sodiumating agent is a soluble sodium salt commonly used in the art, and is selected from the group consisting of sodium hexametaphosphate, sodium trimetaphosphate, sodium metametaphosphate, sodium polyacrylate, sodium pyrophosphate, sodium polyphosphate, sodium acrylate, and silicon. Any one or a combination of sodium, trisodium phosphate, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium carboxymethylcellulose, Na ₂ HP0 ₄ , NaH ₂ PO ₄ NaCK NaF, sodium sulfate, sodium citrate or sodium citrate Preferred are sodium hexametaphosphate, sodium pyrophosphate, sodium polyphosphate, sodium trimetaphosphate, sodium metaphosphate, sodium polyacrylate, trisodium phosphate, sodium citrate, Na ₂ HPO ₄ , NaH ₂ PO ₄ , NaC Any one or combination of NaF, sodium sulfate, sodium hydroxide, sodium carbonate.

Further, the purity of the purified sodium montmorillonite obtained by the present invention is not limited to 95%, preferably not less than 96%, more preferably not less than 97%, further preferably not less than 98%, and further preferably not less than 99%. Most preferably not less than 99.5%.

Further, the cation exchange capacity (CEC) of the purified sodium montmorillonite of the present invention is defined to be 75-140 mmol/100 g, preferably 80-135 mmol/100 g, more preferably 90-130 mmol/100 g, and most preferably 100-125. Mmmol/100g. Further, the degree of swelling of the purified sodium montmorillonite of the present invention is not less than 4.0, preferably not less than 5.0, more preferably not less than 7.0, still more preferably not less than 9.0, further preferably not less than 10.0, and most preferably not less than 12.0.

Further, the amount of adsorption of the sodium smectite per lg of the present invention to the strychnine sulfate is from 0.30 to 0.75 g, preferably from 0.40 to 0.70 g, more preferably from 0.45 to 0.65 g, and most preferably from 0.50 to 0.60 g.

Further, the heavy metal for purifying the sodium montmorillonite of the present invention is not more than 10 ppm, preferably not more than 7 ppm, more preferably 5 ppm, and most preferably 3-4 ppm.

Further, the substance related to the purification of the sodium montmorillonite of the present invention is not more than 5%, 'preferably not more than 4%, more preferably 3%, still more preferably 2%, further preferably 1%, and most preferably 0.5%.

The "purified montmorillonite" described in the present invention is also called "high-purity montmorillonite".

The "high-purity sodium-based montmorillonite" of the present invention is also called "sodium-type high-purity montmorillonite", "high-purity sodium montmorillonite", "sodium-based high-purity montmorillonite" or "sodium-based high-purity" "Mentite" refers to a high-purity montmorillonite in which the exchangeable cations between the layers are mainly sodium ions.

The "high-purity sodium-calcium montmorillonite" according to the present invention is also called "sodium-calcium-type high-purity montmorillonite", "high-purity sodium-calcium montmorillonite", "sodium-calcium-based high-purity montmorillonite" or " Sodium calcification high-purity montmorillonite" refers to a high-purity montmorillonite in which interlayer exchangeable cations are mainly sodium ions and calcium ions.

The "high-purity hydrogen montmorillonite" of the present invention is also called "hydrogen-based high-purity montmorillonite", "high-purity hydrogen montmorillonite", "hydrogen-based high-purity montmorillonite" or "hydrogenation" High-purity montmorillonite "is a high-purity montmorillonite that is a hydrogen ion in the exchange of cations between the layers."

The "high-purity magnesium-based montmorillonite" of the present invention is also called "magnesium-based high-purity montmorillonite", "high-purity magnesia montmorillonite", "magnesium-type high-purity montmorillonite" or "magnesium-based high-purity" "Montmorillonite" refers to a high-purity montmorillonite in which the exchangeable cations between the layers are mainly magnesium ions.

The "high-purity calcium-based montmorillonite" of the present invention is also called "calcium-based high-purity montmorillonite", "calcium-type high-purity montmorillonite", "high-purity calcium montmorillonite" or "calcified high-purity montmorillonite" "De-sparing" refers to high-purity montmorillonite in which the exchangeable cations between the layers are mainly calcium ions.

Another object of the present invention is to provide a method for preparing nano-purified montmorillonite, comprising the steps of: preparing purified montmorillonite into an aqueous solution having a solid content of 0.5-60%, placing a high-speed shearing machine, a high-speed dispersing machine, In a ball mill or a high-pressure homogenizer, high-speed shear dispersion, homogenization, drying, and pulverization are obtained.

Further, the purity of the purified montmorillonite is not less than 95%, preferably not less than 96%, further preferably not less than 97%, more preferably not less than 98%, still more preferably not less than 99%, and most preferably not Below 99.5%, the preparation method is the same as the above purification method. Further, the purified montmorillonite is selected from the group consisting of purifying sodium montmorillonite, purifying sodium calcium montmorillonite, purifying hydrogen montmorillonite, purifying magnesium montmorillonite or purifying calcium montmorillonite, preferably for purification. Sodium montmorillonite.

Further, the nano-purified smectite has a particle diameter of not more than 1 / m, preferably not more than 0.8 / xm, more preferably not more than 0.6 / mi, further preferably not more than 0.4 μηι, and most preferably not more than 0.2 / mi.

Further, the concentration of the aqueous solution is 5 to 50%, more preferably 10 to 40%, still more preferably 15 to 30%, and most preferably 20 to 25%.

Further, the high pressure homogenization is selected from continuous homogenization or multi-stage homogenization, preferably multi-stage homogenization, more preferably 1-3 grade homogenization, most preferably 10-60 MPa-class homogenization and 70-300 MPa. Secondary homogenization.

Further, the high pressure homogenization pressure is not less than 10 MPa, preferably 20 to 800 MPa, more preferably 30 to 600 MPa, still more preferably 50 to 500 MPa, and most preferably 80 to 300 MPa.

Further, the high pressure homogenizer is selected from any one or a combination of a medium and high pressure homogenizer, an ultrahigh pressure homogenizer, a nano ultrahigh pressure homogenizer, a nano collider or a high pressure micro jet homogenizer.

Further, the pulverization is a gas pulverization after coarse pulverization, and the purpose is to increase the edge thereof by forced pulverization, strengthen the hydration and flaking performance, increase the number of "cars", improve the adsorption performance and improve the medicinal effect.

Further, the pulverization fineness is not less than 300 mesh, preferably not less than 500 mesh, further preferably not less than 1000 mesh, more preferably not less than 3000 mesh, and most preferably not less than 5000 mesh.

The purified montmorillonite solid particles are pre-dispersed under the strong shearing action of a high-speed shearing machine, a high-speed dispersing machine or a ball mill with water as a medium, and are continuously homogenized or multi-stage homogenized by a high-pressure homogenizer to obtain The nano-purified montmorillonite with an average particle diameter of not more than I/mi aims to increase its edge by forcibly peeling off, strengthen its hydration and stripping performance, increase the number of "cars", improve the adsorption performance and improve its medicinal effect.

Another object of the present invention is to provide a nano-purified montmorillonite obtained by the following method: preparing purified montmorillonite into a 0.5-60% aqueous solution, placing a high-speed shearing machine, a high-speed dispersing machine, a ball mill or a high pressure After high-speed shear dispersion and homogenization in the machine, it is dried and pulverized.

Further, the purity of the purified montmorillonite is not less than 95%, preferably not less than 96%, further preferably not less than 97%, more preferably not less than 98%, still more preferably not less than 99%, and most preferably not Below 99.5%, the preparation method is the same as the above purification method.

Further, the purified montmorillonite is selected from the group consisting of purifying sodium montmorillonite, purifying sodium calcium montmorillonite, purifying hydrogen montmorillonite, purifying magnesium montmorillonite or purifying calcium montmorillonite, preferably purifying sodium Kemenite.

Further, the nano-purified smectite has a particle diameter of not more than 1/m, preferably not more than 0.8 μm, more preferably not more than 0.6 μm, further preferably not more than 0.4 μm, and most preferably not more than 0.2/mi. Further, the concentration of the aqueous solution is 5 to 50%, more preferably 10 to 40%, still more preferably 15 to 30%, and most preferably 20 to 25%.

Further, the homogenization pressure is not less than 10 ppm, preferably 20 to 800 MPa, more preferably 30 to 600 MPa, still more preferably 50 to 500 MPa, and most preferably 80 to 300 MPa.

Further, the high pressure homogenizer is selected from any one or a combination of a medium and high pressure homogenization, an ultrahigh pressure homogenizer, a nano ultrahigh pressure homogenizer, a nano collider or a high pressure microfluidizer.

Further, the pulverization is coarse pulverization and then pulverized by air flow.

Further, the nano-purified montmorillonite has a cation exchange capacity (CEC) of 75-140 mmol/100 g, preferably 80-135 mmol/100 g, more preferably 90-130 mmol/100 g, and most preferably 100-128 mmol/100 g.

Further, the nano-purified smectite has a degree of swelling of not less than 4.0, preferably not less than 5.0, more preferably not less than 7.0, further preferably not less than 9.0, further preferably not less than 10.0, and most preferably not less than 12.0.

Further, the adsorption amount per lg of nano-purified montmorillonite to the strychnine sulfate is defined to be 0.30 to 0.70 g, preferably 0.40 to 0.65 g, more preferably 0.5 to 0.6 g.

Further, the heavy metal defining the nano-purified smectite of the present invention is not more than 10 ppm, preferably not more than 7 ppm, more preferably 5 ppm, and most preferably 3-4 ppm.

Further, the substance related to the nano-purified smectite of the present invention is not more than 5%, preferably not more than 4%, more preferably 3%, still more preferably 2%, further preferably 1%, and most preferably 0.5%.

Another object of the present invention is to provide a pharmaceutical composition for treating intestinal disorders comprising high purity montmorillonite and a pharmaceutically acceptable carrier.

Further, the "high purity montmorillonite" is selected from the group consisting of high purity calcium montmorillonite, high purity magnesium montmorillonite, high purity hydrogen montmorillonite, high purity sodium calcium montmorillonite or high purity sodium base The smectite is preferably a high purity sodium montmorillonite.

Further, the digestive tract disease condition is selected from the group consisting of acute and chronic diarrhea, acute and chronic esophagitis, reflux esophagitis, acute and chronic gastritis, peptic ulcer, irritable bowel syndrome, inflammatory bowel disease or gastritis. The gastritis is chronic gastritis, more preferably chronic atrophic gastritis, and most preferably a reversal therapeutic effect on chronic atrophic gastritis. Further, it is preferred that the weight ratio (on a dry basis) of the high-purity smectite:auxene in the composition is from 0.001 to 99:1 to 99, preferably from 0.001 to 90:1 to 95, more preferably from 0.001 to 80:1 to 90. Most preferably 0.001 to 70: 1-85.

Further, the smectite has a weight percentage of 1-100%, preferably 5-95%, more preferably 10-90%, still more preferably 15-85%, most preferably 20-80%.

The compositions of the present invention can be prepared in a variety of dosage forms well known in the art and can be prepared by conventional formulation techniques in the art. The preparation suitable for the present invention is selected from an oral preparation or an external preparation, preferably an oral preparation.

Further, the oral preparation is selected from the group consisting of a tablet, a suspension, a capsule, a granule, a pill, a powder, a dropping syrup, a syrup, a mixture, an emulsion, an effervescent, a paste, an emulsion or a tea; Preference is given to powders, suspensions, granules, tablets, capsules or effervescent agents.

Further, the external preparation suitable for the present invention may be selected from a gel, a plaster, a plaster, a cream, an ointment, an elixir, a lotion, a suppository, an applicator or a gel, preferably a gel or an ointment.

The pharmaceutically acceptable carrier is a commonly used excipient or adjuvant commonly used in the preparation of the above preparations, and the excipients or excipients commonly used in oral preparations or external preparations include, but are not limited to, fillers (also known as diluents). , lubricants (also known as glidants or anti-adhesives), dispersants, wetting agents, binders, conditioners, solubilizers, antioxidants, bacteriostats, emulsifiers, flavoring agents, flavoring agents, etc. . Binder, such as syrup, gum arabic, gelatin, sorbitol, tragacanth, cellulose and its derivatives, gelatin syrup, syrup, starch syrup or polyvinylpyrrolidone, preferably cellulose derivatives are microcrystalline cellulose, carboxymethyl Cellulose sodium, ethyl cellulose, hydroxypropylmethylcellulose; fillers such as lactose, powdered sugar, dextrin, starch and its derivatives, cellulose and its derivatives, inorganic calcium salts, sorbitol or glycine Preferably, the inorganic calcium salt is calcium sulfate, calcium phosphate, calcium hydrogen phosphate, precipitated calcium carbonate; a lubricant such as micronized silica gel, magnesium stearate, talc, aluminum hydroxide, boric acid, hydrogenated vegetable oil or polyethylene glycol; Decomposing agents, such as starch and its derivatives, polyvinylpyrrolidone or microcrystalline cellulose, preferably starch derivatives are sodium carboxymethyl starch, sodium starch glycolate, pregelatinized starch, modified starch, hydroxypropyl starch or corn starch Wetting agent, such as sodium lauryl sulfate, water or alcohol.

In addition, the active ingredient may be mixed with a pharmaceutically acceptable controlled release carrier according to the preparation requirements thereof, and then prepared according to a preparation method of a controlled release preparation well known in the art, such as adding a retarder coating or microactive ingredient. After encapsulation, the pellets are prepared into a pellet, such as a sustained release pellet or a controlled release pellet; the sustained release carrier includes, but is not limited to, an oily incorporation agent, a hydrophilic colloid or a coating retarder, The oleaginous agent is selected from the group consisting of glyceryl monostearate, hydrogenated castor oil, mineral oil, polysiloxane or dimethyl siloxane; the hydrophilic colloid is selected from sodium carboxymethyl cellulose, hydroxypropyl a cellulose derivative such as cellulose or hydroxypropylmethylcellulose, or PVP, gum arabic, scutellaria or carbopol; the coating retarder is ethyl cellulose (EC), Hydroxypropylmethylcellulose (HMPC), polyethyl b Isopyrrolidone (PVP), cellulose acetate phthalate (CAP) or acrylic resin.

The high-purity montmorillonite of the present invention strengthens, enhances and improves the original medical use of natural montmorillonite: (1) the application of high-purity montmorillonite in preparing a medicament for preventing and treating digestive tract diseases, wherein the digestive tract diseases include It is limited to acute and chronic diarrhea, esophagitis, reflux esophagitis, acute and chronic gastritis, peptic ulcer, irritable bowel syndrome, inflammatory bowel disease, gastritis, etc. Preferably, the gastritis is chronic gastritis, more preferably Chronic atrophic gastritis is most preferably a reversal therapeutic effect on chronic atrophic gastritis. Although montmorillonite does not have the bactericidal or antibacterial function of antibacterial drugs, it can utilize the exchangeable properties of interlaminar ions to adsorb and exchange bacteria, viruses and their metabolic toxins to the layers, and promote the repair of damaged intestinal mucosa. It has a good control effect on acute and chronic diarrheal diseases caused by bacteria, and the control effect is positively correlated with its layer charge density; in addition, montmorillonite has a unique layer structure, uneven charge distribution and sliding viscoplasticity, which can be uniform Continuous coverage on the surface of the digestive tract, with electrostatic and physicochemical effects, has a good preventive effect on gastrointestinal disorders; (2) the application of high-purity montmorillonite in the preparation of drugs for the treatment or prevention of hyperthyroidism; 3) Application of high-purity montmorillonite in the preparation of drugs for the treatment of chronic renal failure; (4) Application of high-purity montmorillonite in the preparation of drugs for preventing or eliminating bad breath; (5) High-purity montmorillonite in For the preparation of pharmaceutical carriers or pharmaceutical excipients, high-purity montmorillonite can be used as a drug carrier or pharmaceutical adjuvant, complexed with certain antibiotics or enzymes. A complex drug, such as a streptomycin-montmorillonite complex, in which the drug component is released only when a cation exchange reaction occurs, and the montmorillonite is immobilized on the bacteria, the virus or its toxin, Inhibition, bactericidal action, etc.; preferably used as a base for oral preparations, external preparations, sustained release preparations or controlled release preparations, more preferably used as tablets, suspensions (dry mix or suspension), capsules, granules , pills, powders, dropping pills, syrups, mixtures, lotions, effervescent agents, pastes, teas, bioadhesive preparations, gels, ointments, creams, suppositories, emulsions, ointments, inorganic antibacterial agents, a substrate for a dermatological preparation, an expectorant, a lotion, a spread, a gel, a cosmetic or a suspension; the drug is selected from any one or a combination of an oral drug, a topical drug, a sustained release drug or a controlled release drug; 6) Purification of montmorillonite in the preparation of a medicament for treating dermatological diseases, by means of ion exchange, the bactericidal, bacteriostatic metal ions or antibiotics can be exchanged and adsorbed to the interlayer of montmorillonite. In order to prepare a smectite containing a trace amount of bactericidal metal ions or bactericidal or bacteriostatic action, it has the dual functions of adsorption, bacteriostatic or bactericidal action, and is preferably used as a medicine for treating skin diseases as a medicine for treating skin diseases; () Application of purified montmorillonite in the preparation of hangover and liver-protecting drugs; (8) Application of purified montmorillonite in the preparation of drugs for clearing or killing Helicobacter pylori; (9) Application of purified montmorillonite in preparation of antidote Purified montmorillonite can prevent the absorption of aflatoxin (AF), especially aflatoxin B1 (AFB1), against the acute and chronic toxicity of aflatoxin, reduce the acute poisoning mortality of animals, and restore animal performance. . Add 0.5% purified montmorillonite to broiler diet for chicken bone strength and chicken Calcium, phosphorus, copper, iron, and zinc deposits in bones have no adverse or no effect, and reduce lead and fluoride deposition in chicken bones, which is beneficial to prevent lead poisoning and fluorosis in animals, and improve animal product quality and production performance.

The treatment and reversal treatment of high-purity montmorillonite for chronic atrophic gastritis is based on the following pharmacological effects: High-purity montmorillonite can bind to mucus in the digestive tract, enhance mucus cohesion and viscoelasticity, and stimulate endogenous prostaglandin synthesis. Promotes mucus secretion, reduces mucin glycoprotein sulfurylation, increases N-acetylgalactosamine and galactose, and complexes bile salts to immobilize and inhibit pathogenic pathogens such as Helicobacter pylori, both in quality and quantity. Strengthen the barrier function of mucus, prevent gastric acid, pepsin, bile salts and non-organic anti-inflammatory drugs from attacking the digestive tract mucosa, help and accelerate the regeneration and repair of epithelial cells, and promote the healing of damaged mucosa. The inventors found through research that the microscopic chargeability of montmorillonite and high-purity montmorillonite can exert a good reversal effect in the process of gastric mucosal atrophy, which can be used for the reversal treatment of chronic atrophic gastritis. It is positively correlated with its microscopic charge.

Pharmacological studies have shown that: natural montmorillonite has adsorption, encapsulation, fixation and scavenging effects on bacteria and "hazardous substances". Its "vehicle-type" gel structure can adsorb bacteria and its metabolic toxins, and it is used clinically. A drug for treating diarrhea and peptic ulcers. Natural montmorillonite also has good adsorption and fixation effects on Escherichia coli, Vibrio cholerae, Campylobacter jejuni, Staphylococcus aureus, Rotavirus and bile salts. Other studies have also shown that montmorillonite only adsorbs and fixes pathogenic pathogenic bacteria with granule-encoded protein (CS31A) on the surface, and has no fixed scavenging effect on normal bacteria without CS31A on the surface, so it is non-toxic.

After hydration and expansion of montmorillonite, the surface of the negatively charged plate is connected with the positively charged edge to form a "carriage" type suspension with a "gel-sol-gel"-like "thixotropy" to lock the bacteria to " The carriage is in the middle and is removed. The high-purity montmorillonite of the invention improves the quality of the montmorillonite by purifying, and eliminates the influence of the impurities contained on the application and properties as much as possible, and then forcibly pulverizing and forcibly peeling off, to increase the edge and increase the number of "cars". Strengthening its hydration stripping and gel properties, significantly enhancing the ability of montmorillonite to remove bacteria, viruses, harmful substances and toxins, and broadening its application fields and application properties.

Further, the daily dosage of the high-purity smectite of the present invention is from 0.1 g to 10 _g , preferably from 0.5 g to 8 g, more preferably from lg to 6 g, still more preferably from 1.5 g to 4 g, and most preferably from 2 g to 3 g. The actual daily dose of montmorillonite can be adjusted according to the patient's condition, constitution, weight, age, sex and other factors.

The purified montmorillonite has better CEC, adsorption and swelling properties than natural montmorillonite, and the adhesion time with soft tissues (such as gastrointestinal mucosa, skin and mucous membranes, oral mucosa, etc.) is greatly prolonged, and the active ingredients are prolonged in soft tissues. The residence time increases the exchange time and exchange efficiency of the active ingredient with the body, and achieves the fixed-point administration and controlled-release release of the active ingredient, thereby improving the bioavailability and drug safety of the active ingredient. Therefore, the purification of the present invention Decalcification can be used to prepare pharmaceutical or edible excipients: 1) as a carrier for bioadhesive preparations to control drug release and reduce or reduce skin irritation to surfactants, said bioadhesive preparation being selected from the group consisting of Bioadhesives, nasal bioadhesives, ophthalmic bioadhesives, vaginal bioadhesives, rectal bioadhesives or gastrointestinal bioadhesives, and the like. The vaginal mucoadhesive drug transporter (AmDDS), which is prepared by using the purified montmorillonite of the present invention, can enhance the interaction between the drug and the mucin polymer of the vaginal mucosa, and prolong the drug release time; Potassium sulphate is used as a gastric bioadhesive agent to prolong the retention time of bismuth potassium citrate in the gastrointestinal tract, and synergistically remove and kill Helicobacter pylori with tincture, and improve the prevention and treatment of gastrointestinal diseases by bismuth potassium citrate The effect can also greatly reduce the burst release of tincture and improve the safety of the drug; and the anti-tumor drug (anti-colon cancer drug) can be made into a gastrointestinal (colon) localized release preparation, which can prolong the effect of anti-tumor drugs in the gastrointestinal tract. Time, control the release rate and localization release of anti-tumor drugs, improve drug bioavailability and safety, reduce or reduce adverse reactions and side effects of anticancer drugs, increase compliance of patients; 2) use as a carrier for gels : A certain concentration range of purified montmorillonite aqueous solution can be a good gel matrix, with the characteristics of water-dispersible matrix, no greasy feeling, good adhesion, film formation Sexual and bacterial-specific adsorption, easy to spread, no stimulation to the skin and mucous membranes, and good adhesion to the skin, and can absorb and remove tissue exudate, is an electrocardiographic diagnostic gel, ultrasonic diagnostic coagulation a pharmaceutically acceptable carrier for a formulation of a gel, a dental gel, a dental cement, a dentifrice, a toothpaste or a dermatological gel; 3) utilizing the suspension, adhesion and flow of purified montmorillonite The properties of the variant improver can be used as a matrix for semi-solid preparations such as water-soluble ointments, creams, suppositories, and the like. Such as suppository with appropriate amount of guaiac gum, CMC, agar, PVP, oleic acid, glycerin, propylene glycol and distilled water, it has the characteristics of no deformation and non-liquefaction at normal temperature, which is beneficial to drug diffusion and absorption; 4) for medical use A paste, an inorganic antibacterial agent, a skin cream, an emulsion matrix, such as purified sodium montmorillonite added to MgO, has high hydrophilicity and dispersibility, and the prepared inorganic antibacterial agent has a good effect against Pseudomonas aeruginosa; 5) Used as an excellent suspending agent, because the purified montmorillonite has more negative charge, has a large water absorption, has good gelation, thixotropic properties, lubricity, and has less compatibility and no preservatives. And other advantages, its suspending effect is significantly better than sodium carboxymethyl cellulose, sodium carboxymethyl starch and sodium alginate; 6) used as a sorbent for masks, powder, gouache, sunscreen cosmetics, etc., due to montmorillonite Adsorption of various organic molecules, such as skin secretions, sweat, oil, etc., becomes an important cosmetic base; 7) as an absorbent for oil drugs, the oil drugs are selected from oral drugs, more preferably aromatic Or volatile oils, and most preferably garlic oil.

It is also an object of the present invention to provide a novel bioadhesive potassium bismuth citrate formulation which comprises potassium bismuth citrate, purified montmorillonite and other pharmaceutically acceptable excipients.

Further, the weight percentage of each component in the preparation is: 98-potassium citrate 1-98%, purified montmorillonite 1-98%, the balance is other accessories.

Further, the weight percentage of each component in the preparation is: 5-90% potassium bismuth citrate, 5-90% purified montmorillonite, and the balance is other auxiliary materials.

Further, the weight percentage of each component in the preparation is: 7.5-85% potassium bismuth citrate, 7.5-85% purified montmorillonite, and the balance is other auxiliary materials.

In addition, each preparation of the preparation of the present invention contains 50-2500 mg of bismuth potassium citrate, and purified montmorillonite 10-2500 mg; preferably contains 100-2000 mg of bismuth potassium citrate, and purified montmorillonite 50-2000 mg; more preferably contains Potassium strontium citrate 150-1500 mg, purified montmorillonite 100-1500 m _g; most preferably contains 200-1200 mg of bismuth potassium citrate, and purified montmorillonite 150-1200 mg.

It is known that the treatment mechanism of bismuth potassium citrate for gastrointestinal diseases (gastrointestinal dysfunction, diarrhea, peptic ulcer or HP infection) is: 1) at pH < 5, the protein covering the ulcer surface covers the ulcer surface 2) It has no antacid effect, but it can inhibit the activity of pepsin, reduce the degradation of pepsin in mucus and feedback to inhibit the secretion of pepsin; 3) Promote the synthesis of mucosal PG, reduce the degradation of EGF in mucus, stimulate Mucus and bicarbonate secretion, increase mucosal blood flow; 4) promote macrophage re-aggregation, which is conducive to the healing of ulcers; 5) inhibit the action of urease, has the effect of killing HP. While montmorillonite has adsorption, scavenging and immobilization effects on HP, it is synergistic with bismuth potassium citrate and has synergistic effect on killing and purifying HP.

Another object of the present invention is to provide a cosmetic containing purified montmorillonite, the cosmetic containing 1-90% of purified montmorillonite, the balance being other auxiliary materials; preferably the content of purified montmorillonite in cosmetics is 5-85 %, more preferably 7.5-80%, most preferably 10-75%.

The purified montmorillonite of the invention can also be used in the construction industry: 1) Purifying montmorillonite as an excellent waterproof material, purifying montmorillonite has strong water swelling property, and can adsorb 8~5 times of water volume, volume The expansion ratio can be as high as 10-30 times, and it can form a viscous and relatively stable gel after hydration. It has strong water retention performance. Even after long-term storage, after the water is naturally dried, it can still swell and re-absorb with water. Forming a gel, having a dry shrinkage and repeated expansion with water, and capable of generating a swelling pressure of up to 0.15 MPa and thixotropy, having good water repellency, waterproof self-sealing property and durability, becoming an excellent waterproof material, and can be constructed in winter; 2) Purification of montmorillonite for the preparation of inorganic thickeners: one OH, one COOH in coating organic molecules (such as polyvinyl alcohol, polyvinyl acetate, acrylic acid, carboxymethyl cellulose, hydroxyethyl cellulose, etc.) CH _₂ CH ₂ OH a polar group such as montmorillonite are attracted to the negative charge, is inserted between the layers, the organic compound forming a montmorillonite, organic montmorillonite and crosslinked to form a three-dimensional net Configuration, and montmorillonite expands, making the coating increased consistency inorganic thickeners, and their thickening effect is obvious, it can significantly reduce the cellulose-based thickener or thickeners and other fillers emulsion (such as light calcium carbonate, polyvinyl alcohol), and has almost no effect on the washability and water resistance of the coating film, and has a good effect of preventing the precipitation of pigments and fillers, greatly reducing the production cost of the coating; 3) Purified montmorillonite is used to prepare auxiliary adhesives: It mainly utilizes various characteristics of montmorillonite, such as hydrophilicity, fine and irregular particles, large specific surface area, diversified surface charge of crystals, hydrogen bonds with water and sol. And other characteristics; 4) Purified montmorillonite is used as a suspension anti-settling agent, mainly based on its good suspension and dispersibility in aqueous media.

The surface of the purified montmorillonite is adsorbed and can form strong physical or chemical adsorption with the surfactant. The hydroxyl and oxygen atoms on the surface can also form hydrogen bond adsorption with the surfactant molecules, so it can be used for oil drilling. Mud, catalyst in refined petroleum, decolorizing agent or on-site preparation of drilling fluid.

In addition, purified montmorillonite can also be used in the following fields: 1) Purified montmorillonite is used as a carrier for pesticides and fertilizers to reduce the moisture content of fertilizers, prevent fertilizer agglomeration, increase the granularity of fertilizers, or solve compound fertilizers. The granulation difficulty caused by the excessive moisture or free acid in the production of calcium and calcium, or the chemical reaction of the raw material to produce excessive moisture, is beneficial to the production, transportation, preservation and use of fertilizer; 2) Purifying montmorillonite as soil The modifier has a cation exchange capacity of up to 120mmol/100g, a water absorption rate of more than 200%, a thousand-pressure strength of up to 6kg/cm ² , a strong water retention capacity and good adhesion, and a change in solids and liquids in the soil. The proportion of gas improves the hydrothermal conditions and soil structure of the soil, so that the soil retains water, protects the fertilizer and does not pollute the soil environment, and also increases the buffer capacity of the soil and adsorbs harmful elements in the soil; 3) Purifies montmorillonite as a feed additive Because it contains Al, Si, Mg, Fe, K, Zn, Cu, Ca, P, Na, I, Se and other trace elements and physiologically active substances, for poultry home Livestock has the functions of increasing appetite, helping digestion, regulating body balance, increasing immune function, preventing disease and health care, improving feed conversion rate, reducing its cost, being safe and reliable, and having good palatability, and obviously prolonging the shelf life of feed; 4 Purified montmorillonite is used as a premix carrier because of its better adsorption, compactness, fluidity, difficulty in dusting, delamination during processing, uniform mixing performance, and various vitamins and trace elements. Strong dispersion and adsorption, can also prevent moisture, mildew, insects, anti-deterioration, etc.; 5) Purify montmorillonite pellet feed and aquatic feed adhesive, because it has strong mineral comprehensive utilization, adhesion, heat and moisture resistance Pressure, can completely replace the commonly used carboxyl cellulose, secondary powder and other adhesives used as feed molding, and has good adhesive effect, strong plasticity, neat grain shape, smooth surface, good appearance quality and low cost; 6) Purification Desulphurization is used as a feed antidote to prevent acidosis caused by excessive intake of concentrate or indigestion during feeding, and poisoning in feed. The harm caused by the biochemical produced by the vegetarian or feed storage; 7) Purifying the montmorillonite as a diluent for the fermented feed, which can prolong the storage time of the fermented feed; 8) Purifying montmorillonite is mainly used as landfill seepage prevention Material, effectively improve the water-proof effect and anti-seepage ability of concrete, prevent harmful substances from polluting groundwater; 9) Purified montmorillonite can be used as nuclear waste treatment agent for nuclear power plants, used as cushioning material for high-hazard waste Material or backfill material, used to block and buffer the spread of radioactive waste, protect the environment and human body from radioactive contaminants; 10) Purify montmorillonite as an air purifier, which can effectively adsorb sulfur and nitrogen oxides in the air. To achieve the effect of purifying air; 11) Used to prepare nanocomposites, with different mechanical, thermal and electrical, magnetic and optical properties than general macrocomposites; 12) Used as decolorization and purification of various oils, alcohol, juice Clarifying agent, as well as decolorization, deodorization and impurity treatment for animal and vegetable oils; 13) Used as an industrial catalyst, carrier or adsorbent to solve the large number of acid-catalyzed processes such as H ₂ SO ₄ and A1C1 ₃ Environmental pollution problems such as waste acid, equipment corrosion, and difficult product separation.

The structural formula of the natural dioctahedral smectite of the present invention is {C _ai _ _a . _e Na _a KJ(Al _{4 y} M _gx F _e ²⁺ _y ) [Si _8-z Al _z ]O ₂₀ (OH) ₄ -nH ₂ O. DRAWINGS

Fig.1 X-ray diffraction pattern of purified montmorillonite with a purity of 90.0-99.9%. It can be seen that only the X-ray diffraction spectrum unique to the octahedral montmorillonite is shown in the diffraction pattern, and the diffraction lines of other symbiotic minerals are not detected;

Figure 2 Example 1 X-ray diffraction phase analysis of the ore,

Figure 3 is an X-ray diffraction phase analysis diagram of the purified montmorillonite obtained in Example 1,

Figure 4 is an _X -ray diffraction phase analysis diagram of the ore of Example 2,

Figure 5 is an X-ray diffraction phase analysis diagram of the purified montmorillonite obtained in Example 2,

Figure 6 Example 3 X-ray diffraction phase analysis of the ore,

Figure 7 is an X-ray diffraction phase analysis diagram of the purified montmorillonite obtained in Example 3,

Figure 8 is an X-ray diffraction phase analysis diagram of the purified montmorillonite obtained in Example 4,

Figure 9 Example 5 X-ray diffraction phase analysis of the ore,

Figure 10 shows an X-ray diffraction phase analysis of the purified montmorillonite obtained in Example 5,

Figure 11 shows an X-ray diffraction phase analysis of the purified montmorillonite obtained in Example 6;

Figure 12 Effect of each group on the thickness of gastric antral mucosa in rats;

Figure 13 The effect of each group on the ratio of mucosal thickness/mucosal thickness (L1/L2) in rat gastric antrum; Figure 14 The effect of each group on the density of mucosal glands in rat gastric antrum;

Figure 15 The effect of each group on the inflammatory index of gastric antrum in rats;

Figure 16 The effect of each group on the level of hexosamine in the gastric mucosa of rats;

Figure 17 Effect of each group on the level of PGE ₂ in the gastric mucosa of rats. detailed description

The invention will be specifically described with reference to the embodiments, which are intended to illustrate the technical scope of the invention and not to limit the invention.

Example 1 Purification of montmorillonite

The mineral composition of bentonite ore is 42.5% for montmorillonite, 33.9% for α-quartz, 12.0% for kaolin, 7.4% for feldspar, and 4.3% for calcite. See Figure 2.

The ore is dried, pulverized, passed through a 50 mesh sieve, added with water and 0.3% raw ore powder, sodium hexametaphosphate, to form a slurry containing 20% solids. After stirring for two hours, it passes through a three-stage hydrocyclone and is separated. The slurry is added with water to adjust to a solid slurry containing 3% solids, which is separated into a disc centrifuge, and the separated thin slurry is then concentrated into another dish centrifuge to concentrate the concentrated slurry through the plate frame. After press filtration, a filter cake having a solid content of 40-50% was obtained, and the filter cake was dried at 120 ° C and pulverized to 500 mesh or more.

The mineral composition of the montmorillonite is refined, 95.1% montmorillonite, 5.1% quartz, see Figure 3. Recovery rate 60%, heavy metals: Pb9.5ppm, As<lppm, Hg<0.01ppm, CEC 101.3 mmol/100g, lg purification The adsorption capacity of montmorillonite to sulphuric acid is 0.425g, and the degree of expansion is 7.0.

Example 2 Purification of montmorillonite

Mineral composition of bentonite ore: montmorillonite 46.8%, α-quartz 53.2%, see Figure 4.

The ore is dried, pulverized, passed through a 50 mesh sieve, and added with water and 0.5% of ore powder. The sodium polyacrylate is formulated into a slurry containing 15% solids. After stirring for 2.5 hours, it passes through a four-stage hydrocyclone. After separation, the ore is separated. The slurry is added with water to adjust to a solid slurry containing 3% solids. It is separated into a disc centrifuge twice, and the separated thin slurry is transferred to another disc centrifuge, concentrated, and the concentrated slurry is passed through the plate. After the filter press of the frame filter press, a filter cake having a solid content of 40-50% is obtained, and the filter cake is dried at 120 ° C and pulverized to 500 mesh or more.

The mineral composition of the purified montmorillonite: montmorillonite 96.7%, α-quartz 3.3%, see Figure 5. Recovery rate 65%, heavy metals: Pb8.5ppm, As<lppm, Hg<0.01ppm, CEC 105.9mmol/100g, lg purification montmorillonite adsorption to sulfate sulphate 0.47g, degree of expansion 7.0.

Example 3 Purification of montmorillonite

Mineral composition of bentonite ore: montmorillonite 86.5%, α-quartz 13.5%, see Figure 6.

The ore is dried, pulverized, passed through a 50 mesh sieve, added with water and 0.8% raw ore powder, sodium hexametaphosphate, formulated into a slurry containing 25% solids, stirred for two hours, and passed through a three-stage hydrocyclone. The separated slurry is adjusted to a solid slurry containing 3% solids, and separated into a disc centrifuge for separation once. The separated thin slurry is concentrated into another disc centrifuge, and the concentrated slurry is pressed through the frame. After filter press, a filter cake containing 40-50% solids is obtained. The filter cake was dried at 120 ° C and pulverized to 500 mesh or more.

Refined montmorillonite mineral composition: 97.0% montmorillonite, 3.0% quartz, see Figure 7. The recovery rate is 75%, heavy metal: Pb9.0ppm, As<lppm, Hg<0.01ppm, CEC is 107.6mmol/100g, lg purified montmorillonite has a nitrogen adsorption capacity of 0.519g and a swelling degree of 8.0.

Example 4 Purification of montmorillonite

The ore was the same as in Example 3.

The ore is dried, crushed, passed through a 50 mesh sieve, added with water and 0.8% raw ore powder, sodium hexametaphosphate, formulated into a slurry containing 25% solids, stirred for 3 hours, passed through a three-stage hydrocyclone, after separation The slurry is added with water to adjust the solid content of 3% solid waste, and is separated into the disc centrifuge twice. The separated thin slurry is then concentrated into another disc centrifuge to concentrate the concentrated slurry. After filter press filtration, a filter cake having a solid content of 40-50% is obtained, and the filter cake is dried at 120 ° C and pulverized to 500 mesh or more.

The mineral composition of the purified montmorillonite: 98.2% montmorillonite, 1.8% c-quartz, see Figure 8. Recovery rate 70%, heavy metals: Pb9.0ppm, As<lppm, Hg<0.01ppm, CEC 114.6mmol 00g, lg purification The adsorption capacity of montmorillonite to sulphuric acid is 0.532g, and the degree of expansion is 9.0.

Example 5 Purification of montmorillonite

The mineral composition of bentonite ore, 75.0% montmorillonite, 20.7% cristobalite, 4.3% feldspar, see Figure 9. The ore is dried, pulverized into a powder of about 50 mesh, and added to an IN NaOH solution to prepare a slurry having a solid content of 30%. The slurry is placed in a hydrothermal reactor, hydrothermally treated at 12 CTC for 1 hour, filtered, and the filter cake is washed with 60 ° C hot water to pH <8, and water is adjusted to 5% of a thin slurry, which is once separated and once by a disc centrifuge. After concentration treatment, the obtained slurry was subjected to pressure filtration through a plate frame to obtain a filter cake having a solid content of 40 to 50%, and after drying at 120 ° C, it was pulverized to 500 mesh or more.

The mineral composition of the purified montmorillonite: 99.9% montmorillonite, 0.1% c-quartz, see Figure 10. Recovery rate >80%, heavy metal: Pb8.0ppm, As<lppm, Hg<0.01ppm, CEC 125.1 mmol/100g, lg purification The adsorption capacity of montmorillonite to sulphuric acid is 0.562g, and the swelling degree is >12.0.

Example 6 Purification of montmorillonite

The ore was the same as in Example 3.

A mixed acid of 0.9 N acetic acid and 0.1 N hydrochloric acid was used to prepare a 30% solids slurry. After treatment at 60 ° C for 2 hours, remove the filter cake mixed with acid solution, wash with 60 ° C hot water to pH> 5, dilute with water to 3% solid content of the slurry, two times through the disc centrifuge The separated and once concentrated slurry is filtered by a plate frame to a filter cake having a solid content of 40-50%, and dried at 120 ° C, and pulverized to 500 mesh or more. The mineral phase composition of the purified montmorillonite: montmorillonite >99.0%, α-quartz <1.0%, see Figure 11. Recovery rate>70%, heavy metal: Pb is 3.5ppm, As<lppm, Hg<0.01ppm, CEC is 126.3mmol/lOOg, lg purified montmorillonite has a adsorption capacity of 0.565g for sulfate, and the degree of expansion is >10.0.

Example 7 Purification of montmorillonite

The content of ore montmorillonite is 70%, containing 20% cristobalite and 10% carbonate. After drying naturally, it is pulverized into 200 mesh, dispersed with water, stirred and soaked to make a paddle with a solid content of 15%. The slag is removed by centrifugation; the centrifuge slurry is redispersed in an aqueous medium, and after being immersed and ball-milled, a slurry having a solid content of 6% is prepared, and 3% Na ₂ CO _{3 is} added to adjust the pH to 10, and heated to 80. °C, stirring for 2 hours, cooling to room temperature, vacuum filtration, filter cake washed 4 times with deionized water, adding 0.5% sodium pyrophosphate, dispersed by ball mill, placed overnight, vacuum extraction of colloidal solution, washing with deionized water 2 After that, the precipitate was removed by high-speed centrifugation, washed, dried, and pulverized to 500 mesh or more. The purity of the obtained montmorillonite was 99.5%, containing 0.1% c-quartz, the recovery rate was 87%, the heavy metal was 7.5 ppm, and As <1 ppm, Hg< 0.01 ppm, CEC is 119.5 mmol/100g, lg purified montmorillonite has a adsorption capacity of 0.51g for sulphuric acid sulfate and an expansion capacity of 10.6.

Example 8 Purification of montmorillonite

The original ore has a montmorillonite content of 70%, contains 20% cristobalite and 10% carbonate. After natural drying, it is pulverized into 200 mesh, dispersed with water, stirred and soaked to form a paddle with a solid content of 25%. The slag is removed by centrifugation; the centrifugal slurry is redispersed in an aqueous medium, and after high-speed shearing or ball milling, a slurry having a solid content of 8% is prepared, and NaOH is added to a concentration of 1 mol/L, and stirred at 105 ° C for 1 hour. Cool to room temperature, filter, wash the filter cake to PH8-9; filter cake with water to disperse, to make a slurry containing 20% solids, add HC1 to a concentration of 0.5mol / L, stir at 45 ° C for 4 hours, filter, use Washed at 45 ° C deionized water to PH6; added 5.2% solids of Na ₂ CO _{3 in the} filter cake, sanded and mixed evenly, dried, pulverized to 500 mesh or more, the purity of the obtained montmorillonite was 99.0%, including c- Quartz <0.1%, recovery rate 80%, heavy metal <6.3ppm, As<lppm, Hg<0.01ppm, CEC is 121.4mmol/lOOg, lg purified montmorillonite has a stoichiometric adsorption capacity of 0.49g and an expansion capacity of 10.0.

Example 9 Preparation of High Purity Montmorillonite

The content of the original ore montmorillonite is 85.5%, containing 14.5% d of α-quartz, which is crushed by a roller mill to

10mm or less, dry to a moisture content of about 8%, sieve coarse slag with a particle size of 10mm or more; add deionized water to the powder, prepare it into a slurry with a solid content of 20%, centrifuge to remove slag; The paddle is added with 0.5% sodium hexametaphosphate, and is forcedly dispersed by a high-speed shearing machine, a ball mill or a high-speed disperser. The dispersion is placed in a high-pressure homogenizer, and after first-stage homogenization under conditions of 40 MPa and 45 ° C or less. After two-stage homogenization under the conditions of 90 MPa and 50 ° C or less, centrifugal centrifugation, washing, using a disc centrifuge, a horizontal centrifuge or a hydrocyclone Dry, the purity of the obtained montmorillonite is 99.2%, containing 0.8% α-quartz, recovery rate 60%, heavy metal 9.5ppm, As<lppm, HgO.Olppm, CEC is 121.3 mmol/100g, lg purified montmorillonite to sulfuric acid The adsorbed amount of strychnine is 0.48 g, and the expansion capacity is 7.0.

Example 10 Preparation of High Purity Montmorillonite

The mineral composition of bentonite ore, 75.0% montmorillonite, 20.7% cristobalite, 4.3% feldspar, see Figure 9. The ore is dried, pulverized into a powder of about 50 mesh, and added to an IN NaOH solution to prepare a slurry having a solid content of 30%. The slurry is placed in a hydrothermal reactor, hydrothermally treated at 12 CTC for 1 hour, filtered, and the filter cake is washed with 60 ° C hot water to pH <8, and water is added with a solid slurry containing 20% solids, passed through a high speed shear or high speed. The disperser is forcibly dispersed, and the dispersion is placed in a high-pressure homogenizer, and after first-stage homogenization under conditions of 50 MPa and 45 ° C, after secondary homogenization under conditions of 100 MPa and 50 ° C, After high-speed centrifugation, after removing fine impurities, spray drying (inlet air temperature of 180 ° C, material temperature of 110 ° C), and jet mill pulverization to more than 5,000 mesh. The obtained montmorillonite has a purity of 99.9%, Pb of 3.0 ppm, As<lppm, Hg<0.01 ppm, CEC of 126.2 mmol/100 g, and lg-purified montmorillonite has a nitrogen adsorption amount of 0.565 g, and a swelling degree of >12.1. . Example 11 Preparation of High Purity Montmorillonite

The mineral composition of bentonite ore is 75.0% for montmorillonite, 20.7% for α-quartz, and 4.3% for feldspar. See Figure 9. The ore is dried and pulverized into a powder of about 100 mesh, dispersed with water, and formulated into a slurry containing 30% solids, and centrifuged to remove slag; a centrifugal powder of 0.1% sodium phosphate is added to the slurry. Forced dispersion by shearing machine, ball mill or high-speed disperser, placing the dispersion in a high-pressure homogenizer, and homogenizing at 60Mpa and below 45°C, under conditions of 11OMPa and 50°C After the second-stage homogenization, fine impurities are removed by high-speed centrifugation, and then press-filtered, and the filter cake is sent to a hot air drying oven, dried at 90 ° C, and pulverized to 3000 mesh or more by a jet mill. The purity of the obtained montmorillonite is 99.1%, Pb is 4.0 ppm, As<lppm, Hg<O.Olppm, CEC is 121.3 mmol/100g, and the adsorption amount of lg-purified montmorillonite to sulphate is 0.565 g, and the degree of swelling is > 12.1.

Example 12 Preparation of High Purity Sodium Montmorillonite (Hydration Sodium Method)

A high purity calcium montmorillonite with a purity of 97% was added to a 5N hydrochloric acid solution, which was formulated into a slurry having a solid content of 30%, stirred at 40-50 ° C for 1.5 h, filtered, and the filter cake was heated. The water is washed to a pH of about 4.5, and is pressure-filtered into a filter cake having a solid content of 70%, and a solid weight of 5 % sodium hydroxide is added thereto, stirred for sodiumation for 32 hours, dried, and pulverized to 1000 mesh or more. The obtained lg sodium montmorillonite had a nitrogen adsorption amount of 0.53 g, an expansion capacity of 12.0, and a CEC of 123.1 mmol/100 g.

Example 13 Preparation of High Purity Sodium Montmorillonite (Direct Sodium Method) A high purity calcium montmorillonite with a purity of 98%, added with 5% sodium carbonate, and formulated into a slurry containing 50% solids, stirred at 100 ° C for 2 h, filtered, washed, dried That is, it is pulverized to more than 3,000 mesh. The obtained lg sodium montmorillonite has a stoichiometric adsorption amount of 0.56 g, an expansion capacity of 14.0, and a CEC of 126.2 mmol/lOOgo.

Example 14 Preparation of Nano-Purified Montmorillonite

The purified montmorillonite powder with a purity of 97.5% is dispersed with water, and is formulated into a slurry having a solid content of 50%. After being strongly sheared and fully dispersed by a high-speed shearing machine, a ball mill or a high-speed dispersing machine, the dispersed slurry is placed. In a high-pressure homogenizer, the first-stage homogenization is carried out under conditions of 60 MPa and 40 ° C or less, and after two-stage homogenization under conditions of llOMPa and 55 ° C or less, it is sent to a hot air drying oven and dried at 80 Torr. The jet mill was pulverized to more than 5,000 mesh to obtain nano-purified montmorillonite with an average particle diameter of 0.4/mi. The lg nano-purified montmorillonite adsorbed 0.56 g of sulphuric acid sulfate, the expansion capacity was 14.0, and the CEC was 125.3 mmol/100 g. .

Example 15 Preparation of Nano-Purified Montmorillonite

The purified montmorillonite powder with a purity of 98.5% is water-dispersed, and is formulated into a slurry having a solid content of 35%. After strong shearing and sufficient dispersion by a high-speed shearing machine, a ball mill or a high-speed dispersing machine, the dispersed slurry is placed. High-pressure homogenizer, first-class homogenization at 55Mpa and below 45°C, followed by secondary homogenization at 160Mpa and below 55°C, spray drying (inlet air temperature 180°C, material temperature 110°C) The jet mill was pulverized to more than 5,000 mesh to obtain nano-purified sodium-based montmorillonite with an average particle diameter of 0.25/mi. The lg nano-purified montmorillonite adsorbed 0.56 g of sulphuric acid sulfate, the expansion capacity was 14.0, and the CEC was 125.8 mmol. /100g.

Example 16 Preparation of Adhesive Potassium Citrate Tablets

Recipe:

Potassium bismuth citrate 150.0g High purity montmorillonite 300.0g Lactose 30.0g

2% hydroxypropyl methylcellulose (1500 cps) aqueous solution 6.3 g (as dry matter) magnesium stearate 3.0 g

Preparation of 1000 tablets of vanillin 0.5g: Weigh the formula amount of bismuth potassium citrate, high-purity montmorillonite, lactose, vanillin, and mix with hydroxypropyl methylcellulose solution. The granules were dried under conditions of 55 Torr for 12 hours to prepare granules, and the whole granules were mixed with a prescribed amount of magnesium stearate, and the tablets were obtained. T N2007/000463 Example 17 Preparation of Adhesive Enteric Capsules

Recipe:

5-fluorouracil 150.0g

Purified montmorillonite 300.0g

0.4g Preparation of 1000 tablets Preparation method: Weigh the formula amount of 5-fluorouracil, purified montmorillonite and vanillin, mix, add magnesium stearate, fill to enteric (colon type) hollow capsule That is.

Example 18 Preparation of Adhesive Deoxy fluorouridine enteric-coated capsules

Recipe:

Deoxyfluorouridine 200.0g

Purified montmorillonite 300.0g

0.4g made of 1000 capsules

Preparation method: Weigh the formula amount of deoxy fluorouridine, purified montmorillonite and vanillin, mix well, add appropriate amount of magnesium stearate, and fill it into enteric (colon type) hollow capsule.

Example 19 Preparation of Garlic Oil Adhesive Enteric Capsules

Recipe:

Garlic oil 40ml purified montmorillonite 300.0g

0.4g is made into 1000 capsules. Preparation method: Weigh the formula of garlic oil, purified montmorillonite and vanillin, mix well, add appropriate amount of magnesium stearate, and fill into enteric (colon type) hollow capsule.

Example 20 Nutrition Mask

Component ^ Fraction % Component mass fraction ° /. Sodium hyaluronate 0.01 purified montmorillonite 12 Squalane 2 Hydroxyethyl Cellulose 1.5 Glycerin 4 Ethyl p-Hydroxybenzoate 0.2% Hydrolyzed Protein 6 Fragrance (Lily) 0.1 % Deionized Water Add to 100

Preparation method: mixing the purified montmorillonite and deionized water uniformly, adding the formula amount of glycerin, sodium hyaluronate and hydrolyzed protein, stirring uniformly, heating to 75 ° C, until completely dissolved, to obtain an aqueous phase; The amount of ethyl p-hydroxybenzoate, flavor, squalane and hydroxyethyl cellulose are mixed and heated to 40 ° C until completely dissolved to obtain an oil phase; the aqueous phase and the oil phase are added to the vacuum tank Mix, stir, homogenize, degas, filter, cool and fill.

A variety of pharmaceutical uses for purifying montmorillonite are validated below by pharmacodynamic test examples. The test was carried out by using purified montmorillonite or sucralfate in a deionized water to prepare a suspension of 75 mg/ml. Unless otherwise stated, the test dosages of the test examples of the present invention are based on mineral crude drugs.

Test Example 1 Reversal effect of montmorillonite on chronic atrophic gastritis

70 healthy, sexually mature 8-week-old male Sprague-Dawley rats, with an average body weight of 250g±50g, were housed in cages, feeding at 24±2°C, humidity 55±5%, and light and dark every 12 hours. , fed with mixed feed.

The treatment was carried out for 24 weeks using 60% alcohol, 20 mmol/l sodium deoxycholate and 0.1% ammonia water. The CAG model was established according to the method of 姒氏. That is, 20mmol/l sodium deoxycholate is administered daily, and the stomach is administered on a fasting every Tuesday and Friday (the feed is taken every Monday and Thursday at 9:00, and the fasting is started at 9:00 the next day). The dose is as follows: Rat Body weight <200 per mL of intragastric administration; rat body weight 200-250g, 1.5mL per administration; rat body weight >250 per 2mg perfusion. 60% alcohol was given on a fasting stomach every Tuesday and Friday, with fasting conditions and a dose of sodium deoxycholate; while drinking 0.1% ammonia freely, and recording daily consumption. Regular feeding 24 weeks slaughter.

70 SD rats were divided into 7 groups, 10 in each group, which were set to normal group, CAG group, NS group, sucralfate group and montmorillonite treatment group (including 1 natural montmorillonite treatment group, numbered Monti group; one purified calcium-based montmorillonite treatment group, numbered Mont2 group; one purified sodium-based montmorillonite treatment group, numbered Mont3 group).

In the normal control group (normal group), after the mouse CAG was molded, the conventional words were raised to the 24th weekend; the placebo control group (saline group, NS group), ie, the mouse CAG was molded, the stimulation was stopped and the saline was stopped. , once a day, until the 28th weekend slaughter; sucralfate treatment group (sucralfide group), after the mouse CAG molding, stop stimulation and sucralfate suspending (100mg / mL), large The rats weighed <200 _§ , each time the rats were intragastrically administered lmL/time/time, the rats weighing 200-250g were administered 1.5ml/time/time, and the rats with the body weight >250 _§ were administered 2ml/time/time; In the montmorillonite treatment group, after the dosage regimen was modeled with the sucralfate group, ie, the mouse CAG, the stimulation was stopped and the suspension of montmorillonite (100 m _g /mL) was administered daily, and the body weight of the rats was <200 per Rats were administered with a dose of 1.5 mL/mouse/time; rats weighing 200-250 g; rats weighing >250 _§ , administered 2 ml/time/time, slaughtered at the 28th weekend.

After fasting for 24 hours, after 1% pentobarbital (40mg/kg) was fixed by abdominal anesthesia, the whole stomach was immediately expelled by laparotomy. The whole stomach was removed at 1.5cm from the cardia and pylorus. Cut open, rinse with ice physiological saline, spread the filter paper and spread it out; take 1/2 of the antrum and scrape the gastric mucosa with a glass slide, freeze it with liquid nitrogen, and store at -70 °C. The remaining gastric mucosa specimens were fixed with 10% neutral formaldehyde solution, taken along the large curved side strips, routinely dehydrated, embedded in paraffin, serially sliced at 5/mi thickness, and copied to poly-L-lysine anti-offset tablets. Hematoxylin-eosin (HE) staining was performed on the treated slides.

Observation of the histopathological indicators of the sample and its results:

1) Observation of gastric mucosal inflammation: Using the semi-quantitative method, the whole gastric mucosa was observed under a low magnification microscope, and 10 fields were observed in each of the gastric antrum and the corpus, respectively, according to the diagnostic criteria for gastritis proposed in 1994 in Houston, USA. The degree of inflammatory cell infiltration was divided into seven levels of 0, 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0. The inflammatory conditions of 10 visual fields were recorded by the above methods, and the corpus and stomach of each rat were obtained after the average. Inflammation index of the sinus. .

2) Gastric mucosal gland layer thickness (L1) and mucosal muscle layer thickness (L2) and their ratio (L1/L2 ratio) observation: With the micrometer under the microscope, the sinus and body of each HE stained section were observed. Take 5 high power fields, calculate the mean of the mucosal gland layer and muscle layer thickness of each part, and obtain Ll/L2 by the mean value.

3) Observation of gastric mucosal density: On each PE stained section, between the pyloric ring, the anterior stomach and the glandular stomach at 200-1200 μm, the microscopic device was used to measure the number of mucosal intrinsic glands at a certain length. Thereby, the mucosal intrinsic gland density (in units per μπι) of the gastric antrum and the corpus corpus is obtained.

4) At the same time, each PE stained section should be observed to observe the occurrence of intestinal metaplasia, pseudo-pyloric gland metaplasia, atypical hyperplasia, adenoma, carcinoid and adenocarcinoma.

Obtain sample biochemical indicators and their determination methods:

1) Determination of hexosamine: After adding 500W lxPBS buffer to the frozen gastric mucosa, ultrasonically paddle, centrifuge at 4 °C (3000r/min, 5min), take the supernatant, and determine the absolute content of hexose in the Neuhaus method. Concentration, and according to the formula, aminoglycol corrected content (mg / g protein) two homogenate supernatant aminohexose concentration (mg / L) I protein concentration (g / L), calculate the aminohexose content.

2) Protein was determined using the DC Protein Assay reagent supplied by Bio-Rad. 3) Determination of prostaglandin E ₂ (PGE ₂ ): Take partially frozen gastric mucosal tissue, add 500/ l Krebs solution (pre-added indomethacin to prevent release of PGE ₂ during operation), -4° C centrifugation (2000r/min, 5min) The supernatant was taken and PGE ₂ was determined by radioimmunoassay. The concentration was expressed in pg/ml. According to the formula, PGE ₂ corrected content (pg/mg protein) = pulping supernatant PGE ₂ concentration (pg/ml) / protein concentration (mg/ml), the content of PGE ₂ was calculated. '

The test results were analyzed by one-Way ANOVA with completely random design data, and statistical data was assisted by SPSS 11.0 statistical software.

The invention adopts the CAG model of SD rats to prepare the CAG model of SD rats, and observes the reversal effect of natural montmorillonite, purified calcium montmorillonite, purified sodium montmorillonite and sucralfate on chronic atrophic gastritis in SD rats. . The effects of drug on the reversal of rat CAG model were compared by observing the morphological changes of rat gastric mucosa under light microscope and measuring the biochemical indexes (aminohexose, prostaglandin E ₂ ) of gastric mucosa in rats.

The results of the study showed that after one month of purification of montmorillonite according to the present invention, the mental state, activity ability, hair color and gloss of the SD rats were improved to some extent than the end of the model; the mucosal color was observed in the stomach tissue. Pink, covered with more mucus, smooth mucosal surface, wrinkle walking rules, the overall feeling is significantly improved compared with the model control group; under the microscope, the gastric sinus mucosa is arranged neatly, the gastric pit is clear, the inflammatory cells infiltrate less, congestion, Edema is not obvious. The results of the various quantitative indicators are as follows:

1. The effect of the thickness of the antral mucosa layer in each group was as shown in Fig. 12. It can be seen that the thickness of the gastric antrum mucosa in the montmorillonite treatment group was significantly higher than that in the sucralfate treatment group (P<0.05), and the purified sodium-based montmorillonite group was significantly higher than the sucralfate treatment group (P<0.01). The purified calcium-based montmorillonite was significantly higher than the natural montmorillonite group (P<0.05), and the purified sodium-based montmorillonite group was close to the normal control group.

2. The effect of each group on the thickness of the mucosal layer of the gastric antrum / the thickness of the mucosal muscle layer (L1/L2) is shown in Fig. 13. It can be seen that the L1/L2 ratio of the CAG model control group was significantly lower than that of the other groups; the normal control group was significantly higher than the other groups; there was a significant difference between the placebo group and the sucralfate treatment group (PO.05); The decalcification group was significantly higher than the CAG model control group and the placebo group (P<0.01). The purified sodium montmorillonite group was significantly higher than the natural montmorillonite (PO.01), and the purified calcium-based montmorillonite was significantly There is a significant difference between the natural montmorillonite group (PO.05).

3. The effect of each group on the mucosal gland density (number/mm) of the gastric antrum of rats is shown in Fig. 14. It can be seen that there was no significant difference between the CAG model control group, the placebo group and the sucralfate treatment group, and the three groups were significantly lower than the normal control group; the montmorillonite treatment group was significantly higher than the CAG model control group and the placebo group. In the treatment group with sucralfate, the purified sodium-based montmorillonite group was significantly better than the natural montmorillonite (P<0.05), and the purified calcium-based montmorillonite was higher than the natural montmorillonite group. 4. The effect of each group on the inflammatory index of gastric mucosa is shown in Figure 15. The results showed that in the antral mucosal inflammation index of rats, the montmorillonite treatment group was significantly lighter than the CAG model control group and the placebo group.

(P<0.05), the purified sodium montmorillonite group was significantly better than the sucralfate group (P<0.05), and there was no significant difference between the control group and the normal control group (P>0.05).

In addition, the effects of the test groups on the mucosa of the stomach and body were as follows: The characteristics of atrophic gastritis were seen in the mucosa of the gastric mucosa of the CAG control group, the cystic gland of the gland was dilated, the mucous membrane was thickened, and the mucosa was inherently The layer components are intercalated between the glands, and the degree of inflammation is similar to that of the antrum. In the placebo group, the inflammatory condition of the stomach was slightly improved compared with the CAG model control group; the indicators in the sucralfate treatment group and the montmorillonite treatment group were better than those in the CAG model group. At the same time, no intestinal metaplasia, pseudo-pyloric gland metaplasia, atypical hyperplasia, adenoma, carcinoid and adenocarcinoma were found in all samples.

5. The effect of each group on the level of hexosamine in the gastric mucosa is shown in Figure 16. It can be seen that there is no significant difference between the CAG model control group, the placebo group and the sucralfate treatment group in the aminoglycoside content of the gastric mucosa (P>0.05); the gastric mucosa of the montmorillonite group Sugar levels are significantly higher than other modules

(P<0.01), in which the purified sodium-based montmorillonite group and the purified calcium-based montmorillonite group were significantly higher than the natural montmorillonite group (P<0.05), and the purified sodium-based montmorillonite group was significantly higher than the purified calcium-based montmorillonite group. Desilicide group (P<0.05).

6. The effect of each group on the gastric mucosal PGE ₂ level is shown in Figure 17. The results showed that the PGE ₂ level of gastric mucosa in the montmorillonite treatment group was significantly higher than that in the CAG model control group and the sucralfate treatment group. Among them, the purified sodium-based montmorillonite group and the purified calcium-based montmorillonite group were significantly better than the natural montmorillonite (P<0.05), and the purified sodium-based montmorillonite group was significantly better than the natural montmorillonite (P<0.01). .

Conclusion: After a month of smectite treatment in CAG model rats, the atrophy and inflammation of the gastric antrum mucosa of SD rats were significantly improved compared with the CAG group and the placebo group, and the mucosal defense and There was a significant recovery in the synthesis ability, indicating that montmorillonite has a reversal effect on the CAG rat model established by the Weishi method, and the effect of purifying sodium-based montmorillonite on the reversal of chronic atrophic gastritis is more significant.

Compared with the montmorillonite treatment group, the sucralfate treatment group had a mucosal layer thickness (P<0.01), a mucosal L1/L2 ratio, an inflammation index, and a mucosal, inflammatory index, and mucosal amino group in the gastric antrum. The sugar content and other indicators were significantly improved compared with the CAG group, but only in the gastric mucosal layer thickness was significantly higher than the placebo group (P <0.01), and the montmorillonite group especially purified sodium montmorillonite The group was significantly superior to the sucralfate group in mucosal layer thickness, mucosal hexose content and mucosal PGE ₂ in the gastric antrum. It can be seen that sucralfate has a mucosal protective effect on the CAG rat model, but does not have a significant reversal effect; while montmorillonite has a significant reversal effect on the CAG rat model, and the montmorillonite is purified, especially the sodium base. Montmorillonite for chronic atrophy The reversal treatment of gastritis is more pronounced than natural montmorillonite.

Test Example 2 Study on the effect of montmorillonite on hangover and liver protection

A small amount of alcohol can promote metabolism, play a role in relaxing the muscles and promoting blood circulation, and increase appetite and eliminate fatigue. However, excessive drinking can cause chronic alcoholism, mucosal damage, myocardial weakness, blood vessel brittleness, decreased respiratory function, kidney failure and other symptoms, causing serious damage to the body's digestion, nerves, circulation and other systems, and also damage the organs, It consumes qi and blood, causing disturbance of physiological functions of the body and seriously endangering human health.

The invention studies the hangover effect of montmorillonite purification and the mechanism of hangover and liver protection by observing the changes of ethanol concentration and blood alcohol concentration in the stomach and intestinal contents of mice at different time points after drinking alcohol.

Sixty healthy male ICR rats weighing 25±2 g were randomly divided into control group and treatment group. The control group was intragastrically administered with physiological saline, and the treatment group was intragastrically administered with the purified montmorillonite and natural montmorillonite of the present invention, and each group was randomly divided into 4 groups at a time, 5 in each group.

The mice were fasted and banned overnight. On the next day, the purified montmorillonite suspension of the present invention, the natural montmorillonite suspension and 0.9% physiological saline were administered by weighting 0.10 ml/25 g of the mouse. After 30 minutes, 0.15ml/25g rats were given 56° liquor by intragastric administration. After the alcohol was poured, about 1 ml of blood was collected from the eyelids of each group at 30, 60, 90, and 180 minutes. The obtained blood sample was centrifuged at 12000 r/min, and serum 200 μl was taken in a 1.5 ml centrifuge tube, and respectively, methanol 1 μ1, 20% chloroacetic acid solution was added, mixed, centrifuged at 4000 r/min for 10 min, and the supernatant was taken and stored frozen. The concentration of ethanol in the sample was measured by gas chromatography, and the results are shown in Table 1.

Table 1 Determination of ethanol content in blood of mice (mg/ml)

The results showed that: montmorillonite had effects on ethanol absorption and metabolism in different time periods from 30 min to 180 min after drinking. The concentration of ethanol in the blood of the drug-administered group was significantly lower than that of the control group (PO.01). The measured value of ethanol in the blood was significantly lower in the drug-administered group than in the control group (PO.001), while the concentration of ethanol in the purified montmorillonite group was significantly lower than that in the natural montmorillonite group (P<0.05).

The hangover and hepatoprotective effect of montmorillonite is based on its unique layer structure, uneven charge distribution, sliding viscoplasticity, cation exchange and gel properties. It can uniformly cover the surface of the digestive tract and play a role in electrostatic and physicochemical treatment. Effectively inhibits, delays and reduces the absorption of ethanol in the digestive tract, slows down and hinders the rate and concentration of ethanol into the body, and accelerates the metabolism and excretion of ethanol through adsorption, encapsulation and immobilization, accelerating the first step of ethanol in the gastrointestinal tract. Over-effect, effectively reduce the accumulation of ethanol in the body, has good anti-drunk and hangover effects, and can effectively protect the gastrointestinal wall, reduce the stimulation and damage of the gastrointestinal wall of ethanol, reduce the amount of bleeding in the gastrointestinal wall, significantly reduce Ethanol has harmful effects on organs such as gastrointestinal and liver, and has good mucosal protection and mucosal repair. It can be used as a drug for treating mucosal damage and hangover and liver protection.

The purified montmorillonite forms more "carriage" rubber particles than natural montmorillonite, which can produce thixotropic properties at lower concentrations, and its expansion and adsorption properties are also greatly improved. The hangover effect is significantly better than natural montmorillonite.

Test Example 3 Purification and treatment of montmorillonite for hyperthyroidism

The principle of the prevention and treatment of montmorillonite on hyperthyroidism is as follows: After the thyroid hormone secreted by the liver is discharged into the intestine, it is reabsorbed into the blood by the small intestine mucosa, which constitutes the intestinal hepatic circulation. When the free thyroxine in the bile is contacted by the montmorillonite in the intestine and adsorbed first, it will no longer be absorbed by the small intestine mucosa, and will be discharged as the digestive tract itself creeps, gradually reducing the thyroxine reabsorbed into the blood to reduce The concentration of thyroxine in the blood circulation of the body achieves the purpose of preventing and treating hyperthyroidism.

48 hyperthyroid mice, divided into high dose group (0.8g/kg), middle dose group (0.4g/kg), low dose group

(0.2g/kg) and the control group, 12 rats in each group, the purified montmorillonite of the present invention and the corresponding amount of physiological saline were intragastrically administered once a day for 7 consecutive days, and the hyperthyroidism mice were significantly prolonged compared with the control group. It is resistant to hypoxia and can make the body weight of the nail white mice normal.

48 hyperthyroid rats were divided into high dose group (2g/kg), middle dose group (lg/kg), low dose group (0.5g/kg) and control group, 12 rats in each group. The invention was administered by gavage. The montmorillonite and the corresponding amount of normal saline were purified twice a day for 14 consecutive days. Compared with the control group, each administration group significantly reduced the contents of TT ₃ , TT ₄ , FT ₃ and FT ₄ in the serum of hyperthyroidism rats. The medium and low dose groups had a significant increase in thyrotropin (TSH). The high and middle dose groups also significantly reduced the body temperature of hyperthyroidism rats, and the body weight of hyperthyroidism rats became normal.

The results prove that the purified montmorillonite of the present invention has a significant effect on the main pharmacodynamics-related hypoxia tolerance, thyroid hormone and thyrotropin (TSH), and is beneficial to the prevention and treatment of hyperthyroidism.

Test Example 4 Therapeutic effect of montmorillonite on chronic renal failure

The therapeutic effect of purified montmorillonite on chronic renal failure is: The proteolytic products such as urea nitrogen (BU) and potassium ions that have been excreted through the kidneys are not excreted by the kidneys of patients with chronic renal failure, and excessive accumulation of toxins in the body And form hyperkalemia and so on. After oral montmorillonite purification, montmorillonite has strong coverage protection ability on the digestive tract mucosa, repairing and improving the defense of the mucosal barrier against attack factors, in the intestine Dispersed and attached to the surface of the intestinal mucosa, causing a change in the osmotic pressure difference on the surface of the intestinal mucosa, so that the toxins and potassium ions in the intestinal mucosa are adsorbed, dialyzed, and excreted with the contents of the intestine to reach the intestinal tract. Dialysis, and hemostasis for intestinal bleeding in acute renal failure.

After clinical diagnosis, 28 patients with chronic renal failure who had similar etiology and similar conditions were divided into treatment group (n=16) and control group (n=12). On the basis of conventional treatment of chronic renal failure, including treatment of primary disease, hemodialysis, correction of water, electrolytes and acid-base balance disorders, maintenance of systemic nutrition, etc., in the hemodialysis treatment interval, the treatment group is orally purified by the present invention. Stone, control group oral activated carbon, the day after hemodialysis from the first day to the next day of hemodialysis; 2-3 hours after the meal, 2 grams a day, three times a day (8 hours a day).

The results showed that compared with the control group, the plasma urea nitrogen (BUN) concentration of the treatment group decreased, the carbon dioxide binding capacity increased, and the intestinal dialysis effect was demonstrated. After statistical analysis, there was no significant difference between the two groups.

In addition, the calf lotion formulated with 2% purified montmorillonite is used to coat the lower limb skin of chronic renal failure, which has obvious antipruritic effect on skin itching. Because of the accumulation of urea nitrogen in the lower limb skin of patients with chronic renal failure It causes itching of the skin, and montmorillonite adsorbs urea nitrogen (BUN) through the skin for percutaneous dialysis.

In addition, purified montmorillonite is used to prepare a medical ointment containing an antipruritic drug, which can form a film on the skin surface and has a synergistic effect on other antipruritic drugs.

Test Example 5 The effect of montmorillonite on the prevention and treatment of oral odor

The digestive tract produces glycolysis and odor in the digestive tract, and the glycolysis, decay, intestinal flora imbalance, overproduction and a large number of deaths of the gas-producing bacteria, chronic wasting diseases of various organs, inflammation and different kinds of digestive enzymes Lack of accumulation of metabolites. As a highly efficient adsorbent, montmorillonite covers the surface of glycolysis, decayed food and gas-producing bacteria, absorbs the gas generated in the digestive tract, and changes the properties of the gas produced by the oral cavity through ion exchange to achieve covering, filtering and deodorization. effect.

No oral odorous gas in the mouth, 16 normal adult biochemical indicators, 8 randomly selected test groups and 8 control groups, 15-20 grams of raw garlic mixed food, 3 petals, 20 minutes after meal, test The group was given 2 grams of purified montmorillonite, and the control group took orange juice. Compared with the control group within 20 minutes of treatment, the subjective olfactory result of the same person was: The malignant stimulation of the oral cavity exhaled garlic odor was significantly reduced in the test group. The group is invalid.

20 patients with oral exhalation and malodorous gas produced by the digestive tract were randomly divided into 10 groups in the test group and 10 in the control group. After the mouthwash in the morning (to avoid oral bacteria interference), the test group was blunt 2 g of montmorillonite, the control group. Taking orange juice; comparing with the control group within 20 minutes of treatment, and the subjective olfactory result of the same person is: The malignant stimulation of the oral odor of the test group was significantly reduced, while the control group was ineffective.

Montmorillonite has abundant sources, low cost, safe and non-toxic, strong pharmacological action, and strong adsorption function. Oral can absorb various types of pathogenic factors in the digestive tract, such as free thyroxine, urea nitrogen (BUN), potassium ions, oral exhaled odor gas and its strong binding property, not easy to desorb, together with the adsorbed, fixed pathogenic factors It is discharged with the digestive tract itself to achieve the function of covering, filtering and deodorizing, and is a safe pathogen in the digestive tract. Test Example 6 In vitro adsorption experiment of montmorillonite on Helicobacter pylori

1. Based on culture agar, containing polymyxin B5mg/1, amphotericin 2mg/l, vancomycin 10mg/l,

TMP 5 mg/l, 1% corn starch, 0.2% medicinal carbon, 5% fresh egg yolk, to prepare HP solid medium.

2, 300g pig heart plus water 500ml, soaked overnight, take the supernatant to boil, add peptone 10g, 5g NaCl, add water to 500ml, to obtain heart soaked base broth; scrape fresh mucus stomach inner wall mucus layer about 50g, placed in 500ml Distilled water, dissolved in a water bath at 100 ° C, filtered, protein quantified, sterilized at 4 ° C for storage, to obtain a mucin solution.

The mucin was added to the heart immersed base broth to a final concentration of 0.20%, and the mixture was packed into 16 ml/bottle. After autoclaving for 20 min at 110 Torr, it was reserved; the sodium sulphate and the ferrous sulfate were weighed separately. Dissolved in 20ml water, sterilized by 0.2um filter to prepare 5.0% solution; separately absorb lOOul sodium pyruvate, ferrous sulfate 5.0% solution, add to 16ml medium, then add 4ml horse serum, evenly mix Thereafter, an antibiotic such as vancomycin at a storage concentration was added to give a final concentration of vancomycin 10 m _g /l, amphotericin B 5 mg/1, polymyxin B 2500 IU/1, and a liquid medium of HP was prepared.

3. Under sterile conditions, prepare blank artificial gastric juice, 4% purified montmorillonite (cation exchange capacity 120mmol/100g) artificial gastric juice, 4% natural montmorillonite (cation exchange capacity 80mmol/100g) artificial gastric juice and 4% of mica (cation exchange capacity is 0) artificial gastric juice.

4, HP inoculated on solid medium, cultured at 37 ° C for 3-7 days; a sterile inoculating loop pick the right amount of HP colonies, inoculated in liquid medium, incubated at 37 ° C, 5 % CO _{2 for} 2h Close the bottle mouth, place on a constant temperature shaker (37 ° C, 140-150r / min) for 48-72h; Centrifuge, take the supernatant, add the same amount of artificial gastric juice, 4% purified montmorillonite Gastric juice, 4% natural montmorillonite artificial gastric juice and 4% mica artificial gastric juice were stirred at 37 °C for 2 h, and the concentration of bacteria in the medium was observed every 30 minutes. The results are shown in Table 2 _:

Table 2 Purification of montmorillonite by montmorillonite in vitro (concentration is Cfo/ml)

The results showed that the adsorption rate of montmorillonite on artificial Helicobacter pylori in artificial gastric juice reached 90.2%. The adsorption rate of decalcification is 75.3%, and the adsorption rate of mica is 30%. The adsorption capacity of montmorillonite and mica on Helicobacter pylori (HP) is significantly different, and the purified montmorillonite is obviously superior to natural montmorillonite.

Natural montmorillonite is a dioctahedral layered silicate clay mineral composed of a silicon oxytetrahedron and an aluminoxy octahedron. The charge imbalance caused by the random substitution of aluminum and magnesium in the structure of silicon and aluminum gives it water. Unique expansion, adsorption, charge and ion exchange characteristics. The hydrated expanded montmorillonite is a "carriage" type suspension of a negatively charged plate surface connected to a positively charged edge, and has a "gel-sol-gel" "Tactile variability", while "carriage" type suspended particles facilitate the locking of Helicobacter pylori and toxins into the "carriage" for removal. Mica has a layer charge density of zero, a few dispersive stripping ability, a large stack thickness, and a lack of "carriage" structure of suspended particles, which is not conducive to adsorption and removal of HP.

In addition, the test proves that: purified montmorillonite has the function of inhibiting toxic bacterial proteins and bacterial products (such as protease, lipase, phospholipase), reacts with HP adhesin, interferes with the coagulation of Helicobacter pylori, and can reduce 20 %-60% cryptotoxicity caused by Helicobacter pylori infection, also blocking the adsorption of HP and gastric epithelial cells, inhibiting the proliferation of HP in the gastrointestinal tract, and promoting the prevention and treatment of gastric ulcer and duodenal ulcer It can effectively reduce the medical use of gastric ulcer and recurrence of duodenal ulcer.

Test Example 7 Study on sustained release of adhesive bismuth potassium citrate tablets

8 Beagle dogs weighing 9-10 kg, aged 11-12 months, male and female, divided into control group and experimental group, 4 in each group. The control group was intragastrically administered with bismuth potassium citrate capsules (containing 55 mg sputum per capsule), and the experimental group was administered with smectite bismuth potassium lanthanum citrate potassium-attached tablets prepared in Example 12 (each containing 55 mg bismuth). The test dose is in the range of l lmg/kg. Two weeks later, the animals in the two groups were exchanged for two weeks.

Fasting for 12 h before the experiment, 3 ml of blood was collected at 1, 2, 3, 4, 5, 6, 9, 12, 24, 48, 72, 96 h after administration, and the force f] 4 ml mixed acid (HNO _{3 ;} HCl = 3; 1), digested on a hot plate at 180 ° C, and the residue was made up to 10 ml with 1 mol/L hydrochloric acid solvent for the test solution. Determination of strontium in the blood by flow injection hydride generation atomic absorption spectrometry. Take the above sample to be tested 400 uL injection, the automatic valve control injection time is 15s, the sample and sodium borohydride are mixed in the carrier stream, the hydrazine is reduced to 13⁄4 gas-liquid mixture, the gas is separated by the separator Bi3⁄4, BiH ₃ is carrier gas Atomization was carried out in an 800 ° C quartz tube atomizer. The absorbance was measured at a wavelength of 306.8 nm.

After 8 Beagle dogs were treated with bismuth potassium citrate capsules and purified montmorillonite bismuth potassium citrate adherent tablets, the pharmacokinetic parameters Cmax were 0.24±0.07 and 0.18±0.05/miol/L, respectively. For 4.11 ± 0.10 and 4.38 ± 0.11/xmol.h/ml, Tmax was 3.4 ± 0.8 and 4.8 ± 0.9 h, respectively. It can be seen that the use of bismuth potassium citrate capsule as a control, Beagle dog single-dose purified montmorillonite bismuth potassium citrate adhesive tablets relatively equivalent bioavailability, but the peak time delay, peak concentration decreased, and not See the sudden release, there is a slow release effect. Test Example 8 Study on the prevention and treatment of montmorillonite on acute damaged gastrointestinal mucosa

The purified montmorillonite, natural montmorillonite and mica having a purity of 98% were pulverized and passed through a 400 mesh sieve.

Sprague-Dawley (SD) healthy rats, 80, each half, weighing 187 ± 16g. They were randomly divided into 8 groups, which were subordinate to the control group (normal control, preventive control, treatment control), drug prevention, and drug treatment. After fasting for 24 hours, the rats were treated as follows according to the purpose of each group: Group 1 was the normal control group; Group 2 was the model group, and was intragastrically administered with 0.9% NaC11.0 mL/3 h after 3 h. With absolute ethanol 5.0mL / kg / only intragastric; drug prevention group: There are 3 groups, respectively, purified montmorillonite, natural montmorillonite, mica samples each 0.15g / kg / only, 3h After the operation, the rats were intragastrically anesthetized with anhydrous ethanol (5.0 mL/kg/mouse), and anesthetized with lh (1.10 mg/mL sodium pentobarbital l.OmL) was sacrificed, and gastric mucus was scraped off. There were 3 groups in the drug treatment group. After the oral administration of 5.0 mL/kg/kg of absolute ethanol for 1 hour, each group was given a purified montmorillonite, natural montmorillonite and mica samples each 0.15g/kg/ After 3h, anesthesia (10.1mg/mL pentobarbital sodium l.OmL) was sacrificed, gastric mucus was scraped off, then -18 ^Q C was chilled, then lyophilized, weighed, 4mol/L hydrochloric acid 2.0mL, placed in boiling water bath Reflux for 4 h. Filter to 5 mL with deionized water.

The test animals were given normal water throughout the experiment.

Determination of hexose in gastric mucus by Neuhaus method: Accurately absorb 1.0ml of tissue filtrate, add 1 drop of 0.5% phenolphthalein alcohol solution, add 4mol/L NaOH dropwise to the solution and turn red, then add 0.5mol/L HC1 dropwise. The solution red disappears. 1.0 mL of acetylacetone was added, and the mixture was heated in a boiling water bath for 20 min, cooled in cold water, and added with anhydrous ethanol (2.5 mL). Add Ehrlich reagent 1.0 mL and gently shake to remove CO ₂ . After lh, transfer to a 10 mL volumetric flask and add absolute ethanol to the lOmL scale. The absorbance was measured at a wavelength of 530 nm. The blank tube is labeled with deionized water and the process is the same as before. At the same time, a standard curve was prepared using an aminohexose solution (1, 2, 5, 7, lO^g/mL), and the absorbance of the sample was determined on the standard curve to obtain the aminohexose content. The results are shown in Table 3:

Table 3 Effect of purified montmorillonite on acute damaged gastrointestinal mucosa

The results show that: layered structure silicate clay mineral mica, natural montmorillonite, modified montmorillonite The difference between the membrane and the undamaged mucosa is obvious, and the repairing effect of the modified montmorillonite on the damaged mucosa is significantly due to the natural montmorillonite. The chargeability of montmorillonite and the exchangeability of interlayer cations give it a dual function of enhancing mucosal barrier and adsorbing invading mucosa, and the microscopic electrical properties of montmorillonite gel interact with damaged mucosal cells to improve damage. The metabolic environment of the mucous membrane adsorbs weakly polar ethanol molecules, other pepsin, bile, pancreatic juice, etc. that attack the gastric mucosa to the layers, promoting the repair of the damaged mucosa and protecting the gastric mucosa. Mica with almost zero layer charge has no function to repair damaged mucosal cells.

Test Example 9 Study on the protective effect of montmorillonite on blood flow of acutely damaged gastrointestinal mucosa

Purified montmorillonite and mica with a purity of 98% were crushed and passed through a 400 mesh sieve.

Forty SD healthy rats weighing 190±15g were randomly divided into 4 groups: normal control and model control. The drug prevention was purified by montmorillonite and mica. After fasting for 24 hours, the rats were treated as follows according to the purpose of each group: Group 1 was the normal control group; Group 2 was the model group, and was administered once with 0.9% NaCll.OmL/3 h after 3 h. The purified montmorillonite-like and mica samples were administered to the drug-preventive group at a dose of 0.15 g/kg/dose, respectively, and administered at a dose of 5.0 mL/kg/dose for 3 hours. Absolute ethanol, anesthetized with sodium pentobarbital after 1 h. Under the xiphoid process, the abdominal wall was cut open, the rat stomach was exposed, the blunt dissection was separated, and the integrity of the blood supply to the stomach was maintained. The rat stomach was cut at the stomach end, and the probe of the mucosal blood flow meter was inserted to measure the blood of the large curved mucosa. Stream value. The results are shown in Table 4:

Table 4 Effect of purified montmorillonite on blood flow of gastric mucosa (mv)

The results show that the chargeability of purified montmorillonite and the exchangeability of interlayer cations have the dual functions of enhancing mucosal barrier and adsorbing harmful substances invading mucous membranes, which can significantly increase mucosal blood flow, which is beneficial to repairing damaged mucosa and protecting gastric mucosa. The gastric mucosal blood flow not only supplies nutrients and oxygen to the mucosal cells, but also carries away the H+ in the tissue and transports it to the mucosal surface to regulate the acid-base balance in the cells. The mica with almost zero layer charge has no mucosal blood flow improvement effect.

Claims

Rights request

1. A method for purifying montmorillonite, comprising the following steps: 1) montmorillonite powder is dispersed with water, and is formulated into a slurry having a solid content of 10-50%, and the powder is added in an amount of 0.05-1.

2% dispersant, beating, sieving, removing coarse sand, resulting in overflow slurry; 2) overflow slurry is added with water to form a suspension with a solid content of 0.5-12%, and then put into high-speed centrifugal separation equipment for high-speed separation , remove the impurities in the package or inlaid montmorillonite, and obtain the centrifugal slurry; 3) The centrifugal slurry is concentrated and dried.

2. The method according to claim 1, wherein the dispersing agent is selected from the group consisting of sodium hexametaphosphate, sodium trimetaphosphate, sodium metacoxide, sodium polyacrylate, aqueous ammonia, sodium pyrophosphate, sodium polyphosphate, acrylic acid , sodium acrylate, sodium silicate, trisodium phosphate, uranium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium carboxymethyl cellulose, sodium citrate, Na ₂ HPO ₄ , NaCK NaF, sodium sulphide, silica sol, urea, Any one of polysorbate, hydrochloric acid, acetic acid, mixed acid or a mixture thereof, preferably sodium hexametaphosphate, sodium pyrophosphate, sodium polyphosphate, sodium trimetaphosphate, sodium metaphosphate, sodium polyacrylate, phosphoric acid Any of trisodium, sodium citrate, Na ₂ HPO ₄ , NaCK NaF, urea, polysorbate, sodium sulfate, hydrochloric acid, acetic acid or a mixture thereof.

3. The method according to claim 1, wherein the mixed acid is a mixture of a mineral acid and an organic acid.

4. The method according to claim 3, wherein the inorganic acid is selected from any one or a combination of a monobasic acid, a dibasic acid or a tribasic acid; and the monobasic acid is selected from the group consisting of hydrochloric acid, nitric acid, hydrobromic acid or hydrogen. Any one or combination of hydrofluoric acid, the dibasic acid being selected from the group consisting of sulfuric acid; 'the tribasic acid is selected from the group consisting of phosphoric acid or sulfonic acid; preferably the inorganic acid is a monobasic acid, most preferably hydrochloric acid or nitric acid. ·

5. The method according to claim 3, wherein the organic acid is selected from the group consisting of acetic acid, oxalic acid, citric acid, succinic acid, formic acid, propionic acid, butyric acid, malonic acid, succinic acid, pyruvic acid, glutamic acid, Any one or a combination of tartaric acid, malic acid, lactic acid, fumaric acid, itaconic acid, ascorbic acid, fumaric acid, 0!-ketoglutaric acid or carboxylic acid, preferably acetic acid, oxalic acid, citric acid, succinic acid, or C Any one or combination of acid, butyric acid, succinic acid or malonic acid.

6. The method according to claim 1, wherein the dispersant is used in an amount of from 0.10 to 1.0%, more preferably from 0.15 to 0.80%, still more preferably from 0.20 to 0.70%, most preferably from 0.25 to 0.5%.

7. The method according to claim 1, wherein the step 1) is beaten for a period of from 1 to 5 hours, preferably from 2 to 4 hours, more preferably from 3 hours.

8. A method for purifying montmorillonite, comprising the following steps: 1) montmorillonite powder is dispersed with water, and is formulated into a slurry having a solid content of 10-50%, and is beaten and filtered to remove coarse sand, and the slurry is obtained. Material; 2) Adding suitable filter slurry After the amount of the alkaline solution, it is placed in a closed container for hydrothermal treatment, and then filtered and washed to obtain a filter cake; 3) The filter cake is added with water to form a mass containing 0.5-12% of the solid, and is put into a high-speed centrifugal separation device for high speed. The impurities are removed by centrifugation to obtain a centrifugal slurry; 4) The centrifuged slurry is concentrated and dried.

9. Process according to claim 1 or 8, said slurry having a concentration of from 15 to 45%, preferably from 20 to 40%, more preferably from 25 to 35%.

10. The method according to claim 8, wherein the alkaline solution is prepared by dissolving a basic substance well known in the art in water, the alkaline substance being selected from the group consisting of alkali metal salts, alkali metal oxides, alkaline earth metal salts, Any one or combination of alkaline earth metal oxides, weak acid strong base salts or ammonia water.

11. The method according to claim 10, wherein the alkaline substance is selected from the group consisting of sodium carbonate, sodium hydrogencarbonate, sodium fluoride, sodium chloride, sodium sulfate, sodium hydroxide, sodium aluminate, aqueous ammonia, potassium carbonate, and carbonic acid. Any of potassium hydrogen, potassium fluoride, potassium chloride, potassium sulfate, potassium hydroxide, potassium aluminate, calcium carbonate, calcium hydrogencarbonate, calcium fluoride, calcium chloride, calcium sulfate, calcium hydroxide or calcium aluminate Or a mixture thereof, preferably any one of aqueous ammonia, sodium carbonate, sodium hydrogencarbonate, sodium fluoride, sodium chloride, sodium sulfate, sodium hydroxide or sodium aluminate or a mixture thereof.

12. The method according to claim 8, wherein the concentration of the alkaline solution is from 0.1 to 5 N, preferably from 0.5 to 4.5 N, more preferably from 1.0 to 4 N, still more preferably from 1.5 to 3.5 N, most preferably from 2.0 to - 3N,.

13. The method according to claim 8, wherein the hydrothermal treatment temperature is from 60 ° C to 160 ° C, preferably from 70 ° C to 140 ° C, more preferably from 80 ° C to 120 ° C, most preferably 85 °C-100 °C.

14. Process according to claim 8, wherein the filter cake obtained in step 2 has a pH of from 7 to 10, preferably from pH 7.5 to 9, more preferably from pH 8 to 8.5.

15. The method according to claim 1 or 8, wherein the step slurry has a solid content of from 1 to 10%, preferably from 2 to 8%, more preferably from 3 to 6%, most preferably from 4 to 5%. .

16. The method of claim 1 or 8, wherein said high speed centrifugal separation apparatus is selected from any one or combination of a disc centrifuge, a hydrocyclone or a horizontal centrifuge.

17. The method according to claim 1 or 8, wherein the concentration is selected from any one of the group consisting of high speed centrifugal concentration, thin film concentration, reduced pressure concentration or pressure filtration dehydration or a combination thereof.

18. The method according to claim 1 or 8, wherein the centrifugal slurry obtained in step 3) can also be directly spray-dried.

19. The method according to claim 1 or 8, wherein the forced stripping technique is further employed in step 3) to dissociate or expose impurities between the wrapped or inlaid smectite grains, and then to remove impurities by high speed centrifugation.

20. The method according to claim 19, wherein the forced stripping technique is selected from the group consisting of a high speed shearing machine and a high speed High-speed dispersion and shearing of dispersers, ball mills or high-pressure homogenizers.

21. The method according to claim 19, wherein the high pressure homogenization is selected from continuous homogenization or multi-stage homogenization, preferably multi-stage homogenization, more preferably 1-3 grade homogenization, and most preferably 5-60 MPa. - Grade homogenization and 70-300 MPa secondary homogenization.

22. A method according to claim 1 or claim 8 wherein the smectite slurry is subjected to a sodium modification in step 3).

23. The method of claim 22, wherein the sodium modification is a sodium hydride modification or a direct sodium modification, preferably a sodium hydride modification.

24. The method according to claim 23, wherein the sodium hydride modification refers to adding a smectite powder to the water after dispersing it, adding a suitable amount of an acid solution to the hydrogen montmorillonite, and then adding the sodium hydride agent. Perform a sodium modification.

25. The method according to claim 23, wherein the direct sodium modification means that the smectite powder is added with moisture and then added with a sodiuming agent for sodium modification.

26. Use of any one or a combination of a disc centrifuge, a hydrocyclone or a horizontal centrifuge in the purification of a high purity montmorillonite process.

27. A high-purity montmorillonite obtained by the following method: 1) montmorillonite powder is dispersed with water, and is formulated into a slurry having a solid content of 10-50%, and a powder having a powder content of 0.05-1.2% is dispersed. Agent, beating, sieving, removing coarse sand, and overflowing slurry; 2) adding overflow water to form a suspension with a solid content of 0.5-12%, then putting it into high-speed centrifugal separation equipment for high-speed separation, removing the package or Incorporating impurities in the montmorillonite to obtain a centrifugal slurry; 3) The centrifugal slurry is concentrated and dried.

28. A high-purity montmorillonite obtained by the following method: 1) adding smectite powder to water to form a slurry having a solid content of 10-50%, paddle, filtering to remove coarse sand, and obtaining a filter paddle 2) After adding an appropriate amount of alkaline solution to the filter slurry, it is placed in a closed container for hydrothermal treatment, filtered, and washed to obtain a filter cake; 3) The filter cake is added with water to form a slurry having a solid content of 0.5-12%. , put into high-speed centrifugal separation equipment, remove impurities by high-speed centrifugation, and obtain the centrifugal slurry; 4) Centrifugal slurry is concentrated and dried.

The high-purity montmorillonite according to claim 27 or 28, wherein the high-purity montmorillonite has a cation exchange capacity of 75 mmol/100 g to 140 mmol/100 g, preferably 80 mmol/100 g to 135 mmol/100 g, more preferably It is from 90 mmol/100 g to 130 mmol/100 g, most preferably from 100 mmol/lOOg to 125 mmol/100 g _o

The high-purity smectite according to claim 27 or 28, wherein the high-purity smectite has a degree of swelling of not less than 4.0, preferably not less than 5.0, more preferably not less than 7.0, still more preferably not less than 9.0, and further preferably Not less than 10.0, most preferably not less than 12.0.

31. The high purity smectite according to claim 27 or 28, wherein said lg high purity montmorillonite pair The adsorption amount of strychnine sulfate is from 0.30 g to 0.75 g, preferably from 0.40 g to 0.70 g, more preferably from 0.45 g to 0.65 g, and most preferably from 0.50 g to 0.60 g.

The high-purity smectite according to claim 27 or 28, wherein the high-purity smectite has a heavy metal of not more than 10 ppm, preferably not more than 7 ppm, more preferably not more than 5 ppm, and most preferably 3-4 ppm.

The high-purity smectite according to claim 27 or 28, wherein the high-purity smectite has a substance of not more than 5%, preferably not more than 4%, more preferably not more than 3%, and further preferably not more than 2%, further preferably not more than 1%, most preferably not more than 0.5%.

The high-purity smectite according to claim 27 or 28, wherein the high-purity smectite has a purity of not less than 95%, preferably not less than 96%, more preferably not less than 97%, and further preferably not It is less than 98%, further preferably not less than 99%, and most preferably not less than 99.5%.

35. A method for preparing high-purity sodium-based montmorillonite, comprising the steps of: adding an acid solution to a high-purity calcium-based montmorillonite or a high-purity magnesium-based montmorillonite, and formulating the solid content into 10-50 % acid slurry, stir, filter, wash the filter cake to weak acidity, add a slight excess of sodium hydride agent to the filter cake, stir it, and dry it.

36. The method of claim 35, wherein the acid solution is selected from the group consisting of inorganic acids, organic acids, or mixtures thereof.

37. The method of claim 36, wherein the mineral acid is selected from any one or a combination of a monobasic acid, a dibasic acid, or a tribasic acid.

38. The method according to claim 37, wherein the monobasic acid is selected from the group consisting of hydrochloric acid, nitric acid, hydrobromic acid or hydrofluoric acid, the dibasic acid is selected from the group consisting of sulfuric acid, and the tribasic acid is selected from the group consisting of phosphoric acid or sulfonic acid; preferably a monobasic acid. Most preferred is hydrochloric acid or nitric acid.

39. The method according to claim 36, wherein the organic acid is selected from any one of a carboxylic acid, a hydroxy acid, a keto acid, an acid, a fatty acid, an aromatic acid, an amino acid, a nucleic acid, a saturated acid or an unsaturated acid or Combination, preferably acetic acid, oxalic acid, citric acid, succinic acid, formic acid, propionic acid, butyric acid, malonic acid, succinic acid, pyruvic acid, glutamic acid, tartaric acid, malic acid, lactic acid, fumaric acid, itacon Acid, ascorbic acid, fumaric acid, c-ketoglutaric acid or carboxylic acid, more preferably any one or a combination of acetic acid, oxalic acid, citric acid, succinic acid, propionic acid, butyric acid, succinic acid or malonic acid.

40. The method of claim 35, wherein the acid solution has a concentration of from 0.1 to 10 N, preferably from 0.2 to 8 N, more preferably from 0.3 to 6 N, most preferably from 0.5 to 3 N.

41. The method according to claim 35, wherein the acid solution slurry has a solid content of 15-45%, preferably It is 20-40%, more preferably 25-35 %, and most preferably 30%.

42. The method of claim 35, said weakly acidic means a pH of from 1.0 to 7.5, preferably from 1.5 to 7.0, more preferably from 2.0 to 6.5, most preferably from 2.5 to 6.0.

43. A method for preparing high-purity sodium montmorillonite comprising the steps of: adding a slight excess of sodium to a cation exchange capacity in a high purity calcium montmorillonite or a high purity magnesium montmorillonite or hydrogen montmorillonite The chemical solution is formulated into a slurry containing 30-70% solids, stirred for sodiumation, filtered, washed, and dried.

44. The method according to claim 35 or 43, wherein the high purity calcium montmorillonite, the high purity magnesium montmorillonite or the high purity hydrogen montmorillonite has a purity of not less than 95%, preferably not less than 96%, further preferably not less than 97%, more preferably not less than 98%, still more preferably not less than 99%, and most preferably not less than 99.5%.

45. The method according to claim 35 or 43, wherein the filter cake has a solids content of from 30 to 70%, preferably from 40 to 60%, more preferably 50%.

46. The method according to claim 35 or 43, wherein the sodiumating agent is a soluble sodium salt commonly used in the art, selected from the group consisting of sodium hexametaphosphate, sodium trimetaphosphate, sodium metametaphosphate, sodium polyacrylate, pyrophosphate Sodium, sodium polyphosphate, sodium acrylate, sodium silicate, trisodium phosphate, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium carboxymethylcellulose, Na ₂ HPO ₄ , NaH ₂ PO ₄ , NaC NaF, sulfuric acid Any one or a combination of sodium or sodium citrate, preferably sodium hexametaphosphate, sodium pyrophosphate, sodium polyphosphate, sodium trimite, sodium metaphosphate, sodium polyacrylate, trisodium phosphate, citric acid Any one or combination of sodium, Na ₂ HP0 ₄ , Na 3⁄4 P0 ₄ , NaCK NaF, sodium sulfate, sodium hydroxide, sodium carbonate.

47. The method according to claim 35 or 43, wherein the amount of the sodiumating agent is slightly more than the cation exchange capacity, and the amount of the sodiumating agent is 0.5 to 20% greater than the cation exchange capacity.

48. The method according to claim 47, wherein the amount of the sodiumating agent is from 1 to 20%, preferably from 2 to 15%, more preferably from 3 to 10%, most preferably from 4 to 7.5%.

49. A high-purity sodium-based montmorillonite obtained by the following method: adding an acid solution to a high-purity calcium-based montmorillonite or a high-purity magnesium-based montmorillonite, and formulating the solid content into 10-50 % acid slurry, stir, filter the acid slurry, add water to wash the filter cake to weak acidity, add a slight excess of sodium hydride agent to the filter cake, stir it, and dry it.

50. A high-purity sodium-based montmorillonite obtained by the following method: high-purity calcium-based montmorillonite or high-purity magnesium-based montmorillonite or hydrogen montmorillonite is added with a slight excess of sodium than the cation exchange capacity The solution is prepared into a slurry containing 30-70% solids, stirred and desirably dried, and obtained.

51. A method for preparing nano-purified montmorillonite, comprising the steps of: preparing purified montmorillonite into A 0.5-60% solid solution is placed in a high-speed shearing machine, a high-speed dispersing machine, a ball mill or a high-pressure homogenizer for high-speed shear dispersion, homogenization, drying, and pulverization.

52. A nano-purified montmorillonite obtained by the following method: preparing purified montmorillonite into 0.5-60% aqueous solution, and setting high speed shearing machine, high speed dispersing machine, ball mill or high pressure homogenizing machine for high speed shearing After dispersing and homogenizing, drying and pulverizing, it is obtained.

The nano-purified smectite according to claim 52, wherein the purified montmorillonite has a purity of not less than 95%, preferably not less than 96%, further preferably not less than 97%, more preferably not less than 98. % is also preferably not less than 99%, and most preferably not less than 99.5%.

54. The nano-purified smectite according to claim 52, wherein the purified montmorillonite is selected from the group consisting of purifying sodium montmorillonite, purifying sodium calcium montmorillonite, purifying hydrogen montmorillonite, and purifying magnesium montmorillonite. Stone or purified calcium montmorillonite, preferably purified sodium montmorillonite.

55. The nano-purified smectite according to claim 52, wherein the nano-purified smectite has a particle diameter of not more than 1 μm, preferably not more than 0.8 μm, more preferably not more than 0.6/mi, and further preferably not more than 0.4 μm. Most preferably it is not more than 0.2 μm.

56. The nano-purified smectite according to claim 52, wherein the aqueous solution has a concentration of 5 to 50%, more preferably 10 to 40%, still more preferably 15 to 30%, most preferably 20 to 25%.

57. The nano-purified smectite according to claim 52, wherein the high pressure homogenization is selected from continuous homogeneity or multi-stage homogenization, preferably multi-stage homogenization, more preferably 1-3 grade homogenization, most preferably It is 5-60MPa-grade homogenization and 70-300MPa second-level homogenization.

58. The nano-purified montmorillonite according to claim 52, wherein the high-pressure homogenizer is selected from the group consisting of a medium-high pressure homogenization, an ultra-high pressure homogenizer, a nano-super high pressure homogenizer, a nano collider, or a high pressure microjet. Any one or combination of qualities.

59. The nano-purified smectite according to claim 52, wherein the pulverization is coarse pulverization and the air flow is pulverized.

60. The nano-purified smectite according to claim 52, wherein the pulverization fineness of the pulverization is not lower than

300 mesh, preferably not less than 500 mesh, further preferably not less than 1000 mesh, more preferably not less than 3000 mesh, and most preferably not less than 5000 mesh.

61. A pharmaceutical composition for treating intestinal disorders comprising high purity montmorillonite and a pharmaceutically acceptable carrier.

62. The pharmaceutical composition according to claim 61, wherein the composition is selected from the group consisting of an oral preparation or a topical preparation The agent is preferably an oral preparation.

63. The pharmaceutical composition according to claim 62, wherein the oral preparation is selected from the group consisting of a tablet, a suspension, a capsule, a granule, a pill, a powder, a dropping pill, a syrup, a mixture, an excipient, and an effervescent agent. , an emulsion, a paste or a tea, preferably a powder, a suspension, a granule, a tablet, a capsule or an effervescent.

The pharmaceutical composition according to claim 62, wherein the external preparation is selected from the group consisting of a gel, a plaster, a plaster, a cream, an ointment, an expectorant, a lotion, a suppository, an applicator or a gel, preferably a coagulant. Glue or ointment.

The pharmaceutical composition according to claim 61, wherein the weight ratio of the high-purity smectite:the auxiliary material is 0.001-99: 1-99, preferably 0.001-90: 1-95, more It is preferably 0.001 to 80: 1-90, and most preferably 0.001 to 0: 1-85.

66. The pharmaceutical composition according to claim 61, wherein the composition has a smectite weight percentage of from 1 to 100%, preferably from 5 to 95%, more preferably from 10 to 90%, still more preferably from 15 to 90%. 85 %, most preferably 20-80%.

67. Application of purified montmorillonite in preparing medicine for treating digestive tract diseases.

68. The use according to claim 67, wherein the digestive tract disease is selected from the group consisting of acute and chronic diarrhea, acute and chronic esophagitis, reflux esophagitis, acute and chronic gastritis, peptic ulcer, irritable bowel syndrome, inflammatory In case of intestinal disease or gastritis, it is preferred that the gastritis is chronic gastritis, more preferably chronic atrophic gastritis, and most preferably a reversal therapeutic effect on chronic atrophic gastritis.

69. Application of purified montmorillonite in preparing medicine for treating or preventing hyperthyroidism.

70. Application of purified montmorillonite in preparing medicine for treating chronic renal failure.

71. The application of purified montmorillonite in preparing a medicament for preventing or eliminating bad breath.

72. The use of purified montmorillonite in the preparation of a pharmaceutical carrier or a pharmaceutical adjuvant, preferably used as a base for an oral preparation, a external preparation, a sustained release preparation or a controlled release preparation, more preferably used as a tablet, a suspension, a capsule, Granules, pills, powders, dropping pills, syrups, mixtures, lotions, effervescent agents, pastes, teas, bioadhesive preparations, gels, ointments, creams, suppositories, emulsions, ointments, inorganic antibacterials A matrix of a dermatological, dermatological, elixirs, lotion, spread, gel, cosmetic or suspending agent.

73. The use according to claim 72, wherein the drug is selected from any one or a combination of an oral drug, a topical drug, a sustained release drug or a controlled release drug.

74. Purification of montmorillonite for the preparation of a medicament for treating dermatological diseases.

75. Purification of montmorillonite in the preparation of hangover and liver-protecting drugs.

76. Purification of montmorillonite for the preparation of a medicament for removing or killing Helicobacter pylori.

77. Application of purified montmorillonite in the preparation of antidote.

78. A novel bioadhesive potassium bismuth citrate preparation, the preparation consisting of bismuth potassium citrate, purified montmorillonite and other medicinal adjuvants, preferably the weight percentage of each component in the preparation is: 枸Potassium bismuth citrate 1-98%, purified montmorillonite 1-98%, the balance is other auxiliary materials; more preferably, the weight percentage of each component in the preparation is: 5-90% potassium bismuth citrate, purified montmorillonite Stone 5-90%, the balance is other auxiliary materials; the most preferred content of the components in the preparation is: 7.5-85% potassium bismuth citrate, 7.5-85% purified montmorillonite, the balance is other auxiliary materials.

79. A novel bioadhesive potassium bismuth citrate preparation, wherein the preparation comprises 50-2500 mg of bismuth potassium citrate, 10-2500 mg of montmorillonite purified; preferably 100-2000 mg of bismuth potassium citrate, The montmorillonite is purified by 50-2000 mg; more preferably, it contains 150-1500 mg of bismuth potassium citrate, and 100-1500 mg of montmorillonite is purified; most preferably, it contains 200-1200 mg of bismuth potassium citrate, and 150-1200 mg of montmorillonite is purified.

80. A cosmetic containing purified montmorillonite, wherein the cosmetic contains 1-90% of purified montmorillonite, and the balance is other auxiliary materials, preferably the content of purified montmorillonite in cosmetics is 5-85%, more preferably It is 7.5-80%, and most preferably 10-75%.

81. Use of purified montmorillonite for the preparation of a building material selected from the group consisting of a waterproof material, an inorganic thickener, an auxiliary binder or a suspension anti-settling agent, or a combination thereof.

82. Use of purified montmorillonite for the preparation of a petroleum industry material selected from the group consisting of oil drilling mud, petroleum catalyst, decolorizing agent or drilling fluid, or a combination thereof.

83. Use of purified montmorillonite for preparing a pesticide carrier, a fertilizer carrier, a feed additive, a word antidote, a soil conditioner, a premix carrier, a waste treatment agent or a nanocomposite.

84. A high-purity montmorillonite is prepared by the following method: 1) montmorillonite powder is dispersed with water, and is formulated into a slurry having a solid content of 10-50%, and then added with an appropriate amount of an alkaline solution. The mixture is hydrothermally treated in a closed vessel, filtered and washed to obtain a filter cake; 2) the filter cake is added with water to form a slurry having a solid content of 0.5-12%, and is put into a high-speed centrifugal separation device, and the impurities are removed by high-speed centrifugation to obtain a centrifugal slurry; 3) The centrifuged slurry is concentrated and dried.