CN100513311C

CN100513311C - Modified smectite and method for producing the same and its application

Info

Publication number: CN100513311C
Application number: CNB2006800282478A
Authority: CN
Inventors: 吕光烈; 郑海辉; 胡秀荣; 夏志国; 陈绩馨
Original assignee: Zhejiag Hailisheng Pharmaceutical Co Ltd
Current assignee: Zhejiang Qianyuan hailisheng Pharmaceutical Co.,Ltd.
Priority date: 2005-11-04
Filing date: 2006-11-06
Publication date: 2009-07-15
Anticipated expiration: 2026-11-06
Also published as: CN101272986A

Abstract

Disclosed is an inorganic medicine, particularly modified montmorillonite, method for preparing the same and use thereof. The said modified montmorillonite means that dioctahedron of natural montmorillonite is not destroyed and basic chemical composition for the same is not changed, and the microstructure stacked from dioctahedron layer is changed to decrease the thickness of stacking layer and to expose and increase the end face charge and the interlayer charge of montmorillonite, thereby resulting in its lower degree of C axis order. The present medical use of montmorillonite is thus significantly strengthened, particularly the reversal treatment effect on chronic atrophic gastritis. Also disclosed are a medicine composition containing modified montmorillonite and the reversal treatment effect of natural montmorillonite on chronic atrophic gastritis.

Description

Modified montmorillonite used and preparation method thereof and its application

Technical field

The present invention relates to a kind of inorganic drug, particularly relate to modified montmorillonite used, modified na-montmorillonite and preparation method thereof and its application.

Background technology

(Chronic Atrophic Gastritis CAG) is a kind of common, obstinate digestive system to chronic atrophic gastritis, and the sickness rate in general crowd can reach 7.5-13.8%, and China has 100,015,000 chronic atrophic gastritis patients approximately.CAG also is the gastric precancerous lesion of generally acknowledging, its carninomatosis rate is up to about 10%, and especially with the incidence significant correlation of intestinal-type gastric cancer, WHO classifies it as the state in early stage of cancer of the stomach already, and it is classified as the I level prevention of cancer of the stomach.

The cause of disease complexity of CAG, and Hp (Helicobacter pylori, HP), bile, excessive drinking and NSAID (non-steroidal anti-inflammatory drug) etc. all be common paathogenic factors.China's medical science belongs to CAG categories such as " gastric abscess ", " noisy ", " ruffian is full ", is divided into insufficiency of the spleen, wet being stranded and three types of liver energy stagnation types etc. usually, and is wherein common with spleen-deficient.But also do not have to find the effectively treatment means of blocking-up chronic atrophic gastritis at present, more do not have to find that chronic atrophic gastritis is had the treatment means of reverse effect.

Natural montmorillonite is the silicates mineral with dioctahedron lamellar structure and interlayer heterogeneity charge distribution, by two one on folder structure unit's layers of forming of the alumina octahedral that connects of limit altogether in the tetrahedral si-o film that connects of top altogether, and repeat to stack the crystal that forms by the structural unit layer.Aluminium to the replacement at random of aluminium, makes it have electronegativity to silicon and magnesium in the structure, and is compensated by staying the commutative hydrated cation that stays in interlayer, to reach electrobalance.

The basic chemical constitution of montmorillonite is silicate or aluminosilicate, and outward appearance is earthy, the tool soapy feeling, and have changeable chemically reactive, and have intensive water-absorbent and swelling property, meet water after, dispersion and suspension, and between layer and layer, form trickle slit; In the aqueous solution, be suspended state and gelatinized, the multiple inside and outside borne pathogenic factor in the adsorbable digestive tube, and virulence factor is discharged with digestive tube self wriggling, can be used as gastral cause of disease scavenging agent, and do not absorbed, do not enter blood circulation, the human body nontoxicity by digestive tube.In addition, hydrated cation between montmorillonite layer has interchangeability, and its ion-exchange is not subject to the influence of medium potential of hydrogen, and montmorillonite can close digestive tube interior cholic acid, cholate by huge legendary turtle, toxin, gas and endogenous toxin etc. to virus, bacterium and generation thereof have extremely strong fixing, restraining effect, can make the above-mentioned former virulence that loses of causing a disease; And gastrointestinal mucosal had very strong covering protection ability, have reparation, improve defense function, balance flora and the local analgesic hemostatic effect of mucosal barrier attack factor.On February 10th, 2003, " daily magazine industry news " reported that pool, Japanese apricot woods university lecturer palace is rich in vitro tests result show: montmorillonite has the absorption allergen, has anti-allergic effects, and its adsorptive power specific activity charcoal is high 1 times.

The montmorillonite safety non-toxic, to people, animal and plant toxicological harmless and corrosive nature, non-stimulated to human body skin, neural, respiratory system there is not influence, as the choice drug for the treatment of infant diarrhea with as medical carrier, and serve many purposes at pharmacy field, can be used for treating illnesss such as hyperthyroidism, chronic renal failure, counteract oral malodour, diarrhoea and digestive tract ulcer as oral montmorillonite.

Montmorillonite can form complex body with multiple organic compound, and its goods show series of characteristics at aspects such as rheological, thixotropy, surface property and crystalline structure, had multiple industrial use.As in petroleum industry, being used as drilling mud, be used as the balling-up binding agent of molding sand and breeze in the foundary industry, textile industry is as slurry; Its mineral monomer is as the vehicle of producing medicine and prescription being dispensed, as pharmaceutical necessities, carrier, sustained release dosage or control-released agent etc., to improve stability of drug, and play the effect of slowly-releasing or controlled release drug, and the toxic side effect of reduction medicine, reduce dosage, strengthen the pharmacologically active of medicine; Regulate medicine release rate in vivo, reach the effect of controlled release or slowly-releasing; Minimizing is to toxic side effect such as GI stimulations.

Summary of the invention

The dioctahedron clay of laminar silicate mineral that natural montmorillonite is made up of tetrahedral si-o film and aluminum oxide octahedral sheet, aluminium and magnesium cause its charge unbalance to the replacement at random of silicon in the structure and aluminium, meet the distinctive expansion of water, absorption, charged and ion exchange property and give it.The difference that natural montmorillonite exists on quantity of electric charge size, charge distribution, interlayer cation kind makes it show physico-chemical property difference great disparities such as hydration swelling in the water, dispersion, and shows different pharmacological actions.

Purpose one of the present invention provides a kind ofly has the modified montmorillonite used of therapeutic action to the digestive tube illness, describedly modified montmorillonite usedly be meant the dioctahedron layer structure of not destroying natural montmorillonite and do not change its basic chemical constitution, and by changing the microtexture of dioctahedron stack layer, make its stack layer attenuation, expose and increase its end face electric charge and interlayer charge, and have the lower C axle degree of order.

The C axle degree of order of the present invention is meant that the d value is 12-100 in the X diffractogram of montmorillonite

The grain-size calculated of 001 diffraction peak.

Grain-size of the present invention claims relevant farmland size again, can be in order to weigh the degree of order of montmorillonite, and grain-size is big more, and the degree of order is high more, on the contrary the degree of order is low more.

The crystal grain of common unmodified montmorillonite is made up of 10-15 dioctahedron stack layer, thickness is 15-23nm, and modified montmorillonite used crystal grain is made up of 2-10 dioctahedron stack layer, thickness is 2-15nm, or 2-9 dioctahedron stack layer formed, thickness is 2-13.5nm, or is made up of 2-8 dioctahedron stack layer, and thickness is 2-12nm; Or form by 2-7 dioctahedron stack layer, thickness is 2-10.5nm, or is made up of 2-6 dioctahedron stack layer, thickness is 2-9nm, or 2-5 dioctahedron stack layer composition, and thickness is 2-7.5nm, or form by 2-4 dioctahedron stack layer, thickness is 2-6nm; Or form by 2-3 dioctahedron stack layer, thickness is 2-4.5nm; Or form by 3-10 dioctahedron stack layer, thickness is 3-15nm, or 3-9 dioctahedron stack layer form, and thickness is 3-13.5nm, or is made up of 3-8 dioctahedron stack layer, and thickness is 3-12nm; Or form by 3-7 dioctahedron stack layer, thickness is 3-10.5nm, or is made up of 3-6 dioctahedron stack layer, thickness is 3-9nm, or 3-5 dioctahedron stack layer composition, and thickness is 3-7.5nm, or form by 3-4 dioctahedron stack layer, thickness is 3-6nm; Or form by 4-10 dioctahedron stack layer, thickness is 4-15nm, or is made up of 4-9 dioctahedron stack layer, and thickness is 4-13.5nm, or form by 4-8 dioctahedron stack layer, thickness is 4-12nm, or is made up of 4-7 dioctahedron stack layer, and thickness is 4-10.5nm, or form by 4-6 dioctahedron stack layer, thickness is 4-9nm, or is made up of 4-5 dioctahedron stack layer, and thickness is 4-7.5nm; Or form by 5-10 dioctahedron stack layer, thickness is 5-15nm, or form by 5-9 dioctahedron stack layer, thickness is 5-13.5nm, or is made up of 5-8 dioctahedron stack layer, and thickness is 5-12nm, or form by 5-7 dioctahedron stack layer, thickness is 5-10.5nm, or is made up of 5-6 dioctahedron stack layer, and thickness is 5-9nm; Or form by 6-10 dioctahedron stack layer, thickness is 6-15nm, or is made up of 6-9 dioctahedron stack layer, thickness is 6-13.5nm, or is made up of 6-8 dioctahedron stack layer, and thickness is 6-12nm, or form by 6-7 dioctahedron stack layer, thickness is 6-10.5nm; Or form by 7-10 dioctahedron stack layer, thickness is 7-15nm, or is made up of 7-9 dioctahedron stack layer, and thickness is 7-13.5nm, or is made up of 7-8 dioctahedron stack layer, and thickness is 7-12nm; Or form by 8-10 dioctahedron stack layer, thickness is 8-15nm, or is made up of 8-9 dioctahedron stack layer, thickness is 8-13.5nm; Or form by 9-10 dioctahedron stack layer, thickness is 9-15nm.As seen, of the present inventionly modified montmorillonite usedly have the stack layer thinner than natural montmorillonite, end face is abundanter, behind hydration swelling, can form more " carriage-type " micelle, can produce thixotropy under lower concentration.

In addition, modified montmorillonite used not only have than natural montmorillonite thinner pile up synusia, end face is abundanter, and its interlayer charge and end face electric charge also significantly increase, thereby, greatly strengthened the medical function of natural montmorillonite.The total charge of described montmorillonite is formed by stacking by its layer charge and variable charge two portions.

Layer charge of the present invention claims " permanent charge " or " interlayer charge " again, comes from Al ³⁺To Si in the silicon-oxy tetrahedron ⁴⁺And Mg ²⁺, Fe ²⁺To Al in the alumina octahedral ³⁺The charge unbalance that causes of isomorphous substitution.

Variable charge of the present invention claims " end face electric charge " or " variable negative charge " again, comes from OH in the crystal ^-Group is H in alkaline medium ⁺Dissociate, aquation is disperseed Si-O in the tetrahedron of back, the scission of link of Al-O, Al-OH chemical bond exposes in the octahedron, lattice surfaces A l ³⁺Isoionic dissociating.

The carried charge measuring method of montmorillonite is divided into two big classes: a class is based on the crystalline structure of montmorillonite, the structural formula of calculating from its chemical constitution is to calculate its carried charge, can obtain total amount of electric charge and the electric charge distribution situation in tetrahedron and octahedral sheet, be called the structure of chemical composition computing method; Second class is based on the cation exchange capacity method serial alkylammonium exchange process different with carbonatoms that hydrated cation between montmorillonite layer has commutative characteristic.The cation exchange capacity method not only can exchange the interlayer hydrated cation, also can be adsorbed by electronegative end face, and the measured quantity of electric charge is interlayer negative charge and end face negative charge sum; Series straight chained alkyl ammonium method is used to measure interlayer charge amount and distribution situation thereof only to commutative hydrated cation of interlayer and number sensitivity thereof.

At present, the Chang Yong mensuration montmorillonite electric density and the method for charge distribution comprise:

1. structure of chemical composition computing method: measuring with silicate total analysis method that the back montmorillonite chemistry of purifying forms (mainly is SiO ₂, Al ₂O ₃, MgO, Fe ₂O ₃) atomic ratio, press dioctahedron general structure (E again _0.33) { [Al _2-x-y, Mg _xFe _y] (Si _4-zAl _z) O ₁₀(OH) ₂.nH ₂Negative charge total amount and positive charge total amount among the O (interlayer, octahedron and three positions of tetrahedron positively charged ion sum) equilibrated principle, naturalization becomes atomicity, be assigned to tetrahedral sheet and octahedral sheet, its zwitterion difference sum is montmorillonite hemihedral crystal born of the same parents total charge density value.The Ca that the electric charge of interlayer exchangable ion is recorded by the cation exchange capacity method ²⁺, Mg ²⁺, Na ⁺, K ⁺Sum obtains.

2. cation exchange capacity (CEC) method: measure cationic exchange total amount in the purification sample with cobalt chloride ammonium ion exchange process, plasma emission spectrometry is measured Ca wherein ²⁺, Mg ²⁺, Na ⁺, K ⁺Component.

3. straight chained alkyl ammonium positive ion exchange process: the montmorillonite sample ore through sodium, remove organic the processing after and C ₆-C ₁₈After straight chained alkyl ammonium muriate carried out permutoid reaction, with the unnecessary alkylammonium muriate of 95% ethanol flush away, vacuum-drying added SiO ₂Mark is 2-30 with X-ray diffraction method at 2 θ in doing ⁰Scope is measured 001 diffraction locations d ₀₀₁, draw d ₀₀₁With carbonatoms N _CGraph of a relation, mix the layer functions relational expression at random with MCEwan and calculate individual layer to the double-deck change ratio of double-deck transition each point, draw the layer charge density distribution histogram, obtain hemihedral crystal born of the same parents layer lotus and distribute and mean value.

4. end face variable charge assay method: based on montmorillonite end face electric charge variable characteristic under condition of different pH, measure the cation exchange capacity (CEC) of different pH scopes, draw the CEC-pH curve, therefrom calculate the end face quantity of electric charge with cobalt chloride ammonium ion exchange process.

The present invention adopts straight chained alkyl ammonium positive ion exchange process to measure the layer charge density and the charge distribution of montmorillonite, adopts the cation exchange capacity method to measure the variable charge and the layer charge of montmorillonite.

The layer charge of natural montmorillonite is generally at 0.30-0.40eq/[(Si, Al) ₄O ₁₀], variable charge 0.0072-0.058eq/[(Si, Al) ₄O ₁₀].

Further, limit the modified montmorillonite used interlayer charge of the present invention and be not less than 0.31eq/[(Si, Al) ₄O ₁₀], preferably be not less than 0.34eq/[(Si, Al) ₄O ₁₀], more preferably be not less than 0.40eq/[(Si, Al) ₄O ₁₀], most preferably be not less than 0.43eq/[(Si, Al) ₄O ₁₀].

Further, limit modified montmorillonite used variable charge of the present invention and be not less than 0.058eq/[(Si, Al) ₄O ₁₀], preferably be not less than 0.08eq/[(Si, Al) ₄O ₁₀], more preferably be not less than 0.10eq/[(Si, Al) ₄O ₁₀], most preferably be not less than 0.12eq/[(Si, Al) ₄O ₁₀].

The C axle degree of order of the present invention is the important parameter that shows the stacked configuration state of montmorillonite modular construction and its dispersion, viscosity, colloidal property.C axial unordered mainly be the layer pile up cause unordered, closely related with end face electric charge (variable charge).Modified montmorillonite used C axialite particle size of the present invention is little, the degree of order is low, variable negative charge is big, its 001 diffraction peak broadening disperse, its relevant farmland size is selected from the 2-10 layer, the 2-9 layer, the 2-8 layer, the 2-7 layer, the 2-6 layer, the 2-5 layer, layer 2-4, layer 2-3, the 3-10 layer, the 3-9 layer, the 3-8 layer, the 3-7 layer, the 3-6 layer, the 3-5 layer, the 3-4 layer, the 4-10 layer, the 4-9 layer, the 4-8 layer, the 4-7 layer, the 4-6 layer, the 4-5 layer, the 5-10 layer, the 5-9 layer, the 5-8 layer, the 5-7 layer, the 5-6 layer, the 6-10 layer, the 6-9 layer, the 6-8 layer, the 6-7 layer, the 7-10 layer, the 7-9 layer, the 7-8 layer, the 8-10 layer, 8-9 layer or 9-10 layer; And the C axialite particle size of natural montmorillonite is big, degree of order height, and variable negative charge is little, and 001 diffraction peak broadening is little, and its relevant farmland size reaches the 10-15 layer.

As far back as 1974, Toure will (Thorez) was just according to directed glycerine saturated sample, proposed to measure the peak height P of 001 diffraction peak, peak Qiangu V, and measure the C axle degree of order with the V/P value.The V/P value is big more, and the C axle degree of order is high more, otherwise then low.

Montmorillonite is to be to bear hexagonal crystal shape structure, sheet aluminium silicate mineral that structure is very not complete, its modular construction layer is often randomly with 60 ° of rotations or irregular the piling up of " turbulent flow " shape, and promptly montmorillonite is to have that turbulence structure, crystal are thin and tiny, the mineral of structural disorder.Octahedra center heart-yang ion A l ³⁺By the Mg of different ions radius ²⁺, Fe ²⁺, Fe ³⁺The isomorphous substitution and the existence in room cause octahedra distortion, shared rib shortens and elongates, and octahedraly tilts, and forces tetrahedral sheet rotation, elongation, twisted even scission of link, has caused structural unordered.The difference of this microstructure features has caused the difference of montmorillonite ore deposit on absorption property, colloidal property, electric density, charge distribution and application performance.In addition, the bottom surface portions of single montmorillonite stratiform crystal grain is negative electricity, and the edge can be electronegativity and positive polarity because of the variation of medium pH, and charging property is relevant with its colloidal property in water.The thickness of montmorillonite stratiform crystal grain extends the degree of order of arranging with vertical lamella C direction of principal axis pile up by its basic structural unit structure cell along lamella a, b direction of principal axis with the width size and is determined.And a, the b axle degree of order can show the degree of the distortion of montmorillonite crystalline, defective, fracture, and a, the b axle degree of order are low more, and its chemically reactive is big more.Di Kuang place, Nanjing late nineteen eighties was once studied 100 diffraction (dividing by past monocline structure cell the is 020 diffraction) height (h) at peak and the ratio h/W of 2/3 peak width (W) measures the b axle degree of order, its value is big more, and the degree of order is high more, but because of interfering factors is arranged, its peak type is extremely asymmetric, easily distortion.

The present invention adopts broadening peak Fourier to analyze and full figure match structure analysis method, and with grain-size as the index that characterizes structurally ordered degree, study the C axle degree of order of montmorillonite.

In addition, the modified montmorillonite used low charge layer that has of the present invention, characteristics such as layer charge skewness, interbed mineral partial order stacked structure at random appears, claim again " superstructure (superstructure) ", the unitary diffraction peak of periodicity that is made of a plurality of structural sheets appears in the low angle zone that shows its X-ray diffraction spectrum, and described structural sheet is selected from the 2-10 layer, the 2-9 layer, the 2-8 layer, the 2-7 layer, the 2-6 layer, the 2-5 layer, layer 2-4, layer 2-3, the 3-10 layer, the 3-9 layer, the 3-8 layer, the 3-7 layer, the 3-6 layer, the 3-5 layer, the 3-4 layer, the 4-10 layer, the 4-9 layer, the 4-8 layer, the 4-7 layer, the 4-6 layer, the 4-5 layer, the 5-10 layer, the 5-9 layer, the 5-8 layer, the 5-7 layer, the 5-6 layer, the 6-10 layer, the 6-9 layer, the 6-8 layer, the 6-7 layer, the 7-10 layer, the 7-9 layer, the 7-8 layer, the 8-10 layer, 8-9 layer or 9-10 layer.The appearance of " superstructure " is relevant with " (expanded-Collapsed-expanded) expands-cave in-expand " of structural sheet, because having four kinds of reactive forces between the stack layer of montmorillonite: the magnetism between 1. electronegative layer and its interlayer cation; 2. Van der Waals force; 3. the repulsive force between interlayer cation; 4. the repulsive force between the adjacent layers.When the interlayer negative charge density hour, the interlayer magnetism plays a leading role, stay the middle water Heyang ion migration stay in therebetween to adjacent layers and make, and between layer and layer, carry out ionic " distribution " again, " collapse and collapse " that causes the interlayer ion migrating layer, and the cationic adjacent layers of moving into increases " expansion " that causes layer because of its positively charged ion number, thereby form " superstructure " that comparatively orderly " expanding-cave in-expand " layer constitutes, and occur the d value of diffraction peak in the low angle zone of X-ray diffraction spectrum.Cave in layer because of no positively charged ion, and bed thickness is about 10

, and adjacent layers causes the slightly increase of interlamellar spacing because of the cationic expansion that causes layer of moving into, the increasing degree of bed thickness is relevant with move into cationic kind and quantity.When the aquation positively charged ion was calcium, its Laminate construction thickness was 15.3

About, when the aquation positively charged ion was sodium, the thickness of its structural sheet was 12.5

About.Therefore, can infer the number of plies of superstructure from the d value of the d value of 001 diffraction peak and superstructure diffraction peak.Simultaneously the superstructure middle level piles up and is unordered, the layer arrangement position therein that " cave in " also is at random, can be in any position of periodic structure, randomness stacked structure in this just cycle makes it first-order diffraction only occur in X-ray diffractogram, and secondary, three order diffractions do not occur.

Cationic type is relevant between the probability that superstructure forms and interlayer charge distribution layer.Interlayer low charge density layer is many more, distribution is irregular more even, and the probability of appearance is high more; The kind difference of interlayer cation, the complexity of its migration are also different.Though the migration of interlayer cation forms " superstructure ", total interlayer negative charge density and distribution remain unchanged, and only are that the distribution of interlayer cation changes.

Further, modified montmorillonite used modified na-montmorillonite, modification sodium ca-montmorillonite, modification hydrogen base montmorillonite, modification magnesium base montmorillonite or the modified calcium-base montmorillonite of being selected from of the present invention is preferably modified na-montmorillonite.

" modified na-montmorillonite " of the present invention claims " the sodium type is modified montmorillonite used ", " modification sodium matter montmorillonite ", " the sodium base is modified montmorillonite used " or " sodium modification montmorillonite " again, is meant that modified montmorillonite used interlayer interchangeability positively charged ion is mainly the modified montmorillonite used of sodium ion.

" modification sodium ca-montmorillonite " of the present invention claims " sodium calcium type is modified montmorillonite used ", " the calcareous montmorillonite of modification sodium ", " sodium calcium base is modified montmorillonite used " or " the sodium calcification is modified montmorillonite used " again, is meant that modified montmorillonite used interlayer interchangeability positively charged ion is mainly the modified montmorillonite used of sodium ion and calcium ion.

" modification hydrogen base montmorillonite " of the present invention claims " the hydrogen base is modified montmorillonite used ", " modification hydrogen matter montmorillonite ", " the hydrogen fundamental mode is modified montmorillonite used " or " the hydrogen baseization is modified montmorillonite used " again, is meant that modified montmorillonite used interlayer interchangeability positively charged ion is mainly hydrionic modified montmorillonite used.

" modification magnesium base montmorillonite " of the present invention claims " the magnesium base is modified montmorillonite used ", " modified magnesium montmorillonite ", " the magnesium type is modified montmorillonite used " or " magnesiumization is modified montmorillonite used " again, is meant that modified montmorillonite used interlayer interchangeability positively charged ion is mainly the modified montmorillonite used of magnesium ion.

" modified calcium-base montmorillonite " of the present invention claims " the calcium base is modified montmorillonite used ", " the calcium type is modified montmorillonite used ", " the calcareous montmorillonite of modification " or " calcification is modified montmorillonite used " again, is meant that modified montmorillonite used interlayer interchangeability positively charged ion is mainly the modified montmorillonite used of calcium ion.

Modified montmorillonite used synusia attenuation, end face electric charge (variable charge) increase, and can form the synusia end face of more positively charged behind its hydration swelling, and with electronegative synusia in the middle of interconnective carriage-type structure, improve its gel, thixotroping and hydrability.In addition, modified montmorillonite used layer charge increases (permanent charge) and increases, the synusia attenuation, and interlayer cation broadens its charge distribution scope by hydrated ion migration between oxonium ion or sodium hydrated ion genetic horizon.Therefore, modified montmorillonite used more natural montmorillonite of the present invention has better hydration swelling, can improve the delaminate separation of montmorillonite in water, " carriage-type " structure that increase aspect and edge constitute, the gel particles number that forms increases, and exposes more microcosmic electric charge, has better swelling property, adsorptive power, higher cation exchange capacity, wideer charge distribution, thereby, greatly improved the pharmacologically active of natural montmorillonite.

Further, slow because na-montmorillonite is superior than the physical and chemical performance and the process technology performance of ca-montmorillonite as absorption speed, but water-intake rate and expansion multiple are big, and colloidal property is good; Cation exchange capacity is big; Good dispersity in water.In addition, na-montmorillonite can be separated into single structure cell, its colloid index height, and the thixotropy of its soliquid, viscosity, oilness is good, pH is high, Heat stability is good, under higher temperature, keep its expansion character and certain cation exchange capacity, and stronger cohesiveness and higher plasticity-are arranged.As seen, na-montmorillonite is more superior than other montmorillonites (as ca-montmorillonite, sodium ca-montmorillonite, hydrogen base montmorillonite, magnesium base montmorillonite) at aspects such as swelling property, adsorptive power, cation exchange capacity, charge distribution, has better pharmacologically active.

CEC of the present invention is meant the quantity of clay mineral (if you would take off stone) absorption exchange cation, comprises exchangeable base and exchangeable hydrogen, and its unit is mmol/100g.The size of CEC is directly relevant with purity, aquation, expansion, the charging property of clay mineral (if you would take off stone), is the important indicator that characterizes, judges its character, purposes.

The method of measuring cation exchange capacity at present mainly contains NH4 ⁺Exchange process (ammonium acetate drip-rinsing process etc.), Mg ²⁺Exchange process (magnesium oxide extraction), Na ⁺Exchange processes (sodium-acetate drip-rinsing process) etc. are promptly used neutral salt drip washing mineral, its whole exchangeable cation exchanges are leached out, but behaviour's part of these measuring methods are loaded down with trivial details and time-consuming.

The present invention adopts cobalt chloride ammonium ion exchange process to measure CEC, promptly uses [Co (NH ₃) ₆] ³⁺Property positively charged ion is in return measured the cation exchange capacity of clay.Because of [Co (NH ₃) ₆] ³⁺Be electric charge height (3+), ionic radius big (0.2nm), maximum absorption arranged at the 474nm place, and good at pH1～14 scope internal stabilities, be the ideal exchange ion; And non-clay mineral is to not influence of permutoid reaction, and the free metal ion is not participated in permutoid reaction yet, and need not to stir and repeated exchanged when measuring.Thereby be the single-minded method of measuring CEC, have conveniently, characteristics such as sensitive, simple and direct, accuracy height.

The process that cobalt chloride ammonium ion exchange process is measured CEC comprises: the montmorillonite sample is pulverized, crossed 300 mesh sieves, 60 ℃ were dried by the fire 3 hours, standby; Again with montmorillonite sample and a certain amount of 0.025mol/L[Co (NH ₃) ₆] Cl ₃Solution mixes, transfer pH to 7～8, shake up, after treating ion-exchange equilibrium, survey its absorbancy at the 474.0nm place, by the difference AA of the absorbancy before and after the exchange, calculate the concentration C of ion-exchange correspondence, according to the cation exchange capacity of formula CEC=300CV/W calculating clay, V is that exchanging liquid is long-pending in the formula, and W is the sample size that takes by weighing.

Further, the cation exchange capacity (CEC) that limits montmorillonite of the present invention is 75-140mmol/100g, is preferably 80-135mmol/100g, and more preferably 90-130mmol/100g most preferably is 100-125mmol/100g.

Montmorillonite abundance (purity that claims montmorillonite again) is to weigh the key index of wilkinite quality and application performance, with its expansion, cation exchange properties, charging property, to peel off into characteristic such as nano-scale plate directly related.

The common method of measuring the montmorillonite abundance at present is methylene blue method (MB), alkylammonium method etc., but has shortcomings such as error is big, complex operation.

The present invention measures the method for montmorillonite abundance referring to document (Hu Xiurong, Lv Guanglie etc., " mineral journal ", in June, 2005,25 (2): 153-157, the quantivative approach research of montmorillonite abundance in the natural montmorillonite), it is very approaching and be characteristics such as linear positive correlation and measure its abundance in the whole scattering of falling spatial total amount and its abundance mainly to utilize the interlayer charge density value of same place of production montmorillonite and cation exchange capacity value to have specificity, unit mass montmorillonite.

Further, limit the modified montmorillonite used purity of the present invention and be not less than 95%, preferably be not less than 96%, more preferably be not less than 97%, also preferably be not less than 98%, preferably be not less than 99% in addition, most preferably be not less than 99.5%.

The present invention measures the method for modified montmorillonite used turgidity, adsorptive power, heavy metal, related substance referring to document (WS ₁-(X-165)-and 2004Z, the quality standard of montmorillonite).

Further, limit the modified montmorillonite used turgidity of the present invention and be not less than 4.0, preferably must not be less than 5.0, more preferably must not be less than 7.0, also preferably must not be less than 9.0, in addition preferably must not be less than 10.0, most preferably must not be less than 12.0.

Further, limiting the modified montmorillonite used adsorptive capacity to the sulfuric acid Strychnine of the every 1g of the present invention is 0.30-0.75g, is preferably 0.40-0.70g, and more preferably 0.45-0.65g most preferably is 0.50-0.60g.

Further, limit the modified montmorillonite used heavy metal of the present invention and must not surpass 10ppm, preferably must not surpass 7ppm, more preferably must not surpass 5ppm, most preferably be 3-4ppm.

Further, limiting the modified montmorillonite used related substance of the present invention must not surpass 5%, preferably must not surpass 4%, more preferably must not surpass 3%, also preferably must not surpass 2%, preferably must not surpass 1% in addition, most preferably must not surpass 0.5%.

" related substance " of the present invention is meant the impurity except that montmorillonite.

Another object of the present invention provides a kind of modified montmorillonite used method for preparing, comprise the steps: that purity is not less than 80% montmorillonite powder, with the mixing acid of 0.1-10mol/L with soil: the mass ratio of acid is 1: the 1-100 uniform mixing, heat is boiled, centrifugal or remove by filter mixing acid, wash, be drying to obtain.

Further, the purity of described montmorillonite is not less than 85%, more preferably is not less than 90%, most preferably is not less than 95%.

Further, the concentration of preferred mixing acid is 0.5-8mol/L, 0.8-6mol/L more preferably, and other is preferably 1-5mol/L, most preferably is 2-4mol/L.

Further, described mixing acid is mixed by mineral acid and organic acid.

Further, described mineral acid includes but are not limited to monoprotic acid, diprotic acid or triprotic acid.Described monoprotic acid is selected from hydrochloric acid, nitric acid, Hydrogen bromide or hydrofluoric acid, and diprotic acid is selected from sulfuric acid, and triprotic acid is selected from phosphoric acid or sulfonic acid; Preferred mineral acid is a monoprotic acid, most preferably is hydrochloric acid or nitric acid.

Further, described organic acid includes but are not limited to any or its combination of carboxylic acid, alcohol acid, ketone acid or tartaric acid, according to alkyl connect different, can be divided into lipid acid, aromatic acid, amino acid, nucleic acid, any or its combination of saturated acid or unsaturated acid.Preferred organic acid of the present invention is selected from any or its combination, more preferably any or its combination of acetic acid, oxalic acid, citric acid, succsinic acid, propionic acid, butyric acid, Succinic Acid or propanedioic acid of acetic acid, oxalic acid, citric acid, succsinic acid, formic acid, propionic acid, butyric acid, propanedioic acid, Succinic Acid, pyruvic acid, L-glutamic acid, tartrate, oxysuccinic acid, lactic acid, fumaric acid, methylene-succinic acid, xitix, fumaric acid, α-Tong Wuersuan or carboxylic acid.

Further, the mol ratio of described mixing acid is a mineral acid: mineral acid and/or organic acid: organic acid is 5-150:1-200:5-200, be preferably 10-120:5-150:10-150, more preferably 20-100:10-120:20-120 also is preferably 30-80:20-100:30-100; Hydrochloric acid most preferably: oxalic acid: acetic acid is the mixing acid of 30-80:20-100:30-100.

Further, preferred soil: the mass ratio of acid is 1:2-50, and more preferably 1:2.5-25 most preferably is 1:3-10.

Further, preferred heat was boiled 0.5-100 hour, also was preferably 2-70 hour, and more preferably 3-40 hour, most preferably 5-20 hour.

Further, it is 10-100 ℃ that heat is boiled temperature, is preferably 20-95 ℃, and other is preferably 30-90 ℃, more preferably 40-85 ℃, most preferably is 50-80 ℃.

Except as otherwise noted, per-cent of the present invention all is weight percentage.

Montmorillonite is carried out sodium modification can open stack between its layer and the layer, improve the characteristics such as expansion, absorption of montmorillonite, make it have the better application prospect.At present, montmorillonite sodium method has two kinds of dry method and wet methods usually.Dry method sodium method adopts sodium agent and montmorillonite directly to do and mixes, and handles promptly through milling, as stockyard method, extrusion process or suspension method etc.Be characterized in that technology is simple, but exist sodium inhomogeneous more, easily answer shortcomings such as calcification.

Wet method sodium method is meant various soluble sodium salts solutions and montmorillonite is disposed by a certain percentage that between the slightly acidic, heating, stir process are promptly in weakly alkaline for regulator solution pH.Be characterized in that sodium is thorough, but sodium fluid dewatering difficulty.

It is modified montmorillonite used that the present invention adopts hydrogenation sodium method or direct sodium legal system to be equipped with the sodium base.Can adopt the method for first purification, modification, hydrogenation, sodium, or adopt the method for first modification, hydrogenation, purification, sodium, or adopt the method for first purification, modification, sodium, to prepare highly purified modified na-montmorillonite.

Another object of the present invention is to provide a kind of modified montmorillonite used method of sodium base (hydrogenation sodium method) for preparing, comprise the steps: purity is not less than 95% modified calcium-base montmorillonite or modification magnesium base montmorillonite, add acid solution and be made into the acid solution slip that solid content is 10-50%, stir, remove by filter acid solution, washing leaching cake adds the sodium agent suitable with its cation exchange capacity to slightly acidic in the filter cake of solid content 30-70%, stir sodium, be drying to obtain.

Further, the purity of modified calcium-base montmorillonite or modification magnesium base montmorillonite is not less than 96%, preferably is not less than 97%, more preferably is not less than 98%, also preferably is not less than 99%, most preferably is not less than 99.5%.

Further, described acid solution is selected from mineral acid, organic acid any or its combination.

Further, described mineral acid includes but are not limited to monoprotic acid, diprotic acid or triprotic acid; Described monoprotic acid is selected from hydrochloric acid, nitric acid, Hydrogen bromide or hydrofluoric acid, and diprotic acid is selected from sulfuric acid, and triprotic acid is selected from phosphoric acid or sulfonic acid; Be preferably monoprotic acid, most preferably be hydrochloric acid, nitric acid.

Further, described organic acid includes but are not limited to carboxylic acid, alcohol acid, ketone acid, tartaric acid, lipid acid, aromatic acid, amino acid, nucleic acid, saturated acid, unsaturated acid etc., be preferably acetic acid, oxalic acid, citric acid, succsinic acid, formic acid, propionic acid, butyric acid, propanedioic acid, Succinic Acid, pyruvic acid, L-glutamic acid, tartrate, oxysuccinic acid, lactic acid, fumaric acid, methylene-succinic acid, xitix, fumaric acid, α-Tong Wuersuan or carboxylic acid, more preferably acetic acid, oxalic acid, citric acid, succsinic acid, propionic acid, butyric acid, Succinic Acid or propanedioic acid.

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

Further, the solid content of described acid solution slip is 15-45%, is preferably 20-40%, and more preferably 25-35% most preferably is 30%.

Further, described slightly acidic is meant that pH is 1.0-7.0, and preferred pH is 1.5-6.5, and more preferably pH is 2.0-6.0, and most preferably pH is 2.5-5.5.

Further, the solid content of preferred filter cake is 40-60%, more preferably 50%.

Further, sodium agent of the present invention claims " sodium salt properties-correcting agent " again, can be with the Ca in ca-montmorillonite, magnesium base montmorillonite or the hydrogen base montmorillonite ²⁺, Mg ²⁺Or H ⁺Be exchanged into Na ⁺Described sodium agent is this area soluble sodium salt commonly used, is selected from Sodium hexametaphosphate 99, Trisodium trimetaphosphate, heavy sodium-metaphosphate, sodium polyacrylate, trisodium phosphate, sodium polyphosphate, sodium acrylate, water glass, tertiary sodium phosphate, sodium hydroxide, yellow soda ash, sodium bicarbonate, Xylo-Mucine, Na ₂HPO ₄, NaH ₂PO ₄, NaCl, NaF, sodium sulfate, Trisodium Citrate any or its combination, be preferably Sodium hexametaphosphate 99, trisodium phosphate, sodium polyphosphate, Trisodium trimetaphosphate, heavy sodium-metaphosphate, sodium polyacrylate, tertiary sodium phosphate, Trisodium Citrate, Na ₂HPO ₄, NaH ₂PO ₄, NaCl, NaF, sodium sulfate, sodium hydroxide, yellow soda ash any or its combination.

Further, the consumption and the cation exchange capacity of described sodium agent are suitable, are meant the excessive 0.1-20% of amount ratio cation exchange capacity of sodium agent, in other words, the consumption of sodium agent is 0.5-15%, is preferably 1-12%, more preferably 3-10% most preferably is 4-7.5%.

Another object of the present invention is to provide a kind of modified montmorillonite used method of sodium base (directly sodium method) for preparing, comprise the steps: purity is not less than 95% modified calcium-base montmorillonite or modification magnesium base montmorillonite or modification hydrogen base montmorillonite, add the sodium agent suitable with cation exchange capacity, be made into the slip of solid content 30-70%, stir sodium, be drying to obtain.

Further, the purity of modified calcium-base montmorillonite, modification hydrogen base montmorillonite or modification magnesium base montmorillonite is not less than 96%, preferably is not less than 97%, more preferably is not less than 98%, also preferably is not less than 99%, most preferably is not less than 99.5%.

Further, described sodium agent is this area soluble sodium salt commonly used, is selected from Sodium hexametaphosphate 99, Trisodium trimetaphosphate, heavy sodium-metaphosphate, sodium polyacrylate, trisodium phosphate, sodium polyphosphate, sodium acrylate, water glass, tertiary sodium phosphate, sodium hydroxide, yellow soda ash, sodium bicarbonate, Xylo-Mucine, Na ₂HPO ₄, NaH ₂PO ₄, NaCl, NaF, sodium sulfate, Trisodium Citrate any or its combination, be preferably Sodium hexametaphosphate 99, trisodium phosphate, sodium polyphosphate, Trisodium trimetaphosphate, heavy sodium-metaphosphate, sodium polyacrylate, tertiary sodium phosphate, Trisodium Citrate, Na ₂HPO ₄, NaH ₂PO ₄, NaCl, NaF, sodium sulfate, sodium hydroxide, yellow soda ash any or its combination.

Further, the solid content of preferred slip is 40-60%, more preferably 50%.

Another object of the present invention is to provide a kind of highly purified modified na-montmorillonite, make by following method (hydrogenation sodium method): purity is not less than 95% modified calcium-base montmorillonite or modification magnesium base montmorillonite, add acid solution and be made into the acid solution slip that solid content is 10-50%, stir, remove by filter acid solution, washing leaching cake adds the sodium agent suitable with its cation exchange capacity to slightly acidic in the filter cake of solid content 30-70%, stir sodium, be drying to obtain.

Further, the purity of modified calcium-base montmorillonite or modification magnesium base montmorillonite is not less than 95%, preferably is not less than 96%, preferably is not less than 97% in addition, more preferably is not less than 98%, also preferably is not less than 99%, most preferably is not less than 99.5%.

Further, described slightly acidic is meant that pH is 1.0-7.0, is preferably 1.5-6.5, and more preferably 2.0-6.0 most preferably is 2.5-5.5.

Another object of the present invention is to provide a kind of highly purified modified na-montmorillonite, make by following method (directly sodium method): purity is not less than 95% modified calcium-base montmorillonite or modification magnesium base montmorillonite or modification hydrogen base montmorillonite, add the sodium agent suitable with cation exchange capacity, be made into the slip of solid content 30-70%, stir sodium, be drying to obtain.

Further, the purity of modified calcium-base montmorillonite, modification hydrogen base montmorillonite or modification magnesium base montmorillonite is not less than 95%, preferably is not less than 96%, preferably is not less than 97% in addition, more preferably is not less than 98%, also preferably is not less than 99%, most preferably is not less than 99.5%.

Further, the solid content of preferred slip is 40-60%, more preferably 50%.

Association has clay mineral and a spot of organic matters such as non-clay silicate mineralss such as silicon-dioxide, opal, feldspar, gypsum, calcite, perlite, zeolite and kaolinite, illite, chlorite in the natural montmorillonite, the mineral content of its montmorillonite is usually at 50%-70%, and part rich ore content can reach 80%-90%.Utilize montmorillonite expansible characteristic in water, reach with the symbiosis non-metallic minerals and separate, utilize the two globule size and density variation then, by eddy flow, mechanical means such as centrifugal the thick non-clay mineral of particle is separated, but granularity is tiny of tight symbiotic alpha-quartz of montmorillonite and the extremely tiny cristobalite that is embedded in montmorillonite of granularity, the hydration swelling power of montmorillonite still is not enough to open the high calcium base soil of the two parcel situation, particularly layer charge.According to the layer charge size, add an amount of different properties-correcting agent, under different pH, temperature condition, be aided with stirring, the last dispersion by force of quickening montmorillonite and impurity in the high speed centrifugation separating device is removed high-density, unexpansive impurity such as alpha-quartz with separation.In addition, can utilize montmorillonite wafer and the stability difference of cristobalite under different hydrothermal conditions, with basic solution with the cristobalite hydrolysis, become liquid phase, by high speed centrifugation its separation is removed.

Purpose one of the present invention provides a kind of method of purifying montmorillonite, comprises the steps: 1) the natural montmorillonite drying, pulverize, sieve, powder; 2) powder adds water-dispersion, is made into the slurry of solid content 10-50%, adds the dispersion agent of powder amount 0.05-1.2%, and making beating is sieved, and removes coarse sand; 3) after overflow slurry adds the suspension that water is made into solid content 0.5-12%, drop into the high speed centrifugation separating device, carry out high-speed separation, remove parcel or inlay impurity in the montmorillonite, centrifugal slurry; 4) centrifugal slurry is through concentrating, being drying to obtain.

Further, preferred 2) concentration of step slurry is 15～45%, more preferably 20～40%, most preferably be 25-35%.

Dispersion agent of the present invention is selected from Sodium hexametaphosphate 99, Trisodium trimetaphosphate, heavy sodium-metaphosphate, sodium polyacrylate, ammoniacal liquor, trisodium phosphate, sodium polyphosphate, vinylformic acid, sodium acrylate, water glass, tertiary sodium phosphate, sodium hydroxide, yellow soda ash, sodium bicarbonate, Xylo-Mucine, Trisodium Citrate, Na ₂HPO ₄, NaH ₂PO ₄, NaCl, NaF, sodium sulfate, silicon sol, urea, polysorbate, hydrochloric acid, acetic acid, mixing acid any or its combination, be preferably Sodium hexametaphosphate 99, trisodium phosphate, sodium polyphosphate, Trisodium trimetaphosphate, heavy sodium-metaphosphate, sodium polyacrylate, tertiary sodium phosphate, Trisodium Citrate, Na ₂HPO ₄, NaCl, NaF, urea, NaH ₂PO ₄, ammoniacal liquor, sodium sulfate, hydrochloric acid, acetic acid any or its combination.

Further, described mixing acid is mixed by mineral acid and organic acid; Described mineral acid includes but are not limited to monoprotic acid, diprotic acid or triprotic acid; Described monoprotic acid is selected from any or its combination of hydrochloric acid, nitric acid, Hydrogen bromide or hydrofluoric acid, and diprotic acid is selected from sulfuric acid, and triprotic acid is selected from phosphoric acid or sulfonic acid; Preferred mineral acid is a monoprotic acid, most preferably is hydrochloric acid or nitric acid.

Further, described organic acid includes but are not limited to carboxylic acid, alcohol acid, ketone acid, tartaric acid or acetic acid, according to alkyl connect different, can be divided into lipid acid, aromatic acid, amino acid, nucleic acid, saturated acid or unsaturated acid etc., can be selected from acetic acid as organic acid of the present invention, oxalic acid, citric acid, succsinic acid, formic acid, propionic acid, butyric acid, propanedioic acid, Succinic Acid, pyruvic acid, L-glutamic acid, tartrate, oxysuccinic acid, lactic acid, fumaric acid, methylene-succinic acid, xitix, fumaric acid, α-Tong Wuersuan or carboxylic acid, preferred organic acid is an acetic acid, oxalic acid, citric acid, succsinic acid, propionic acid, butyric acid, any of Succinic Acid or propanedioic acid or its combination.

For clear statement the present invention, " dispersion agent " of the present invention claims " dressing agent ", " high purity agent " or " high purity process agent " again.

Further, the consumption of preferred dispersants is the 0.10-1.0% of powder amount, also preferred 0.15-0.80%, more preferably 0.20-0.70%, most preferably 0.25-0.5%.

Further, preferred beating time 1-5h, more preferably 2-4h most preferably is 3h.

Further, 3) the slurry solid content is 1-10% the step, also is preferably 2-8%, and more preferably 3-6% most preferably is 4-5%.

Further, described high speed centrifugation separating device is selected from any or its combination of disk centrifugal separator, hydraulic vortex flow devices or horizontal centrifuge.

Further, 3) step described concentrate be selected from that high speed centrifugation concentrates, thin film concentration, concentrating under reduced pressure or filter-press dehydration.

Further, can be with 3) the centrifugal slurry of step gained directly carries out spraying drying.

Further, in order to separate the fine impurity of removing parcel or inlaying the montmorillonite intergranule, can be 3) step adopts the technology of delaminating of forcing, as adopt high-speed shearing machine, high speed dispersor, ball mill or high pressure homogenizer to force to delaminate, fully expose the impurity particle in the montmorillonite, remove the solid impurity that dissociates or expose through high speed centrifugation again, to obtain the higher montmorillonite of purity.

Further, the described pressure technology of delaminating is selected from the high speed dispersion and the shearing action of high-speed shearing machine, high speed dispersor, ball mill or high pressure homogenizer.Technical parameter that pressure is delaminated is selected mainly according to the detected result and deciding mutually of montmorillonite thing in the material phase analysis result of raw ore and the purification process.

High pressure homogenizer is transmission of power and material conveying mechanism with the high pressure reciprocating pump, with mass transport to operating valve (one-level homogenizing valve and secondary Emulsified valve) part.Want material handling in passing through the process of operating valve, formed high-intensity energy accumulating in the workspace, the intensive shearing, bump, turbulent flow and the cavitation that are produced when fluid is flowed through the small runner of homogenizing valve are that the solid particulate of carrier obtains the ultra micro refinement with fluent meterial or with liquid.

Further, described high-pressure homogeneous continuous homogeneous or the multistage homogeneous of can be is preferably multistage homogeneous, and more preferably 1-3 level homogeneous most preferably is 10-60MPa one-level homogeneous and 70-300MPa double-stage homogenization.

Further, can be 3) step carries out sodium modification to the montmorillonite slip and handles, to open the stack between montmorillonite crystal grain layer and the layer, increase its interlayer passage, expose the fine impurities between parcel or mosaic coating, remove the solid impurity that dissociates or expose through high speed centrifugation again, to obtain the higher montmorillonite of purity.

Further, described fine impurities or fine impurity are selected from the dirt of alpha-quartz or size 0.1-0.5 μ m.

Further, described sodium modification is hydrogenation sodium modification or direct sodium modification, is preferably the hydrogenation sodium modification.

Further, after described hydrogenation sodium modification is meant that the montmorillonite powder adds water-dispersion, after adding appropriate amount of acid solution is modified as hydrogen base montmorillonite with it, adds the sodium agent again and carry out sodium modification.

Further, after described direct sodium modification is meant that the montmorillonite powder adds water-dispersion, adds the sodium agent again and carry out sodium modification.

The principle of method of purification of the present invention is: the montmorillonite particle has characteristics such as surperficial electronegative and peripheral zone positive electricity, in water dispersion medium, lean on positive and negative electrical attraction between the particle, the bridging arrangement that formation is associated based on " worker " font, some trickle solid impurities are by this association institute's rest or parcel, be difficult to eliminate, bring very big difficulty for the purification of montmorillonite mineral.By the adding dispersion agent, conditions such as the pH of adjusting slurry, temperature, and be aided with stirring, make montmorillonite particle positive charge edge become the electronegativity edge, make the montmorillonite particle all become negative electrostatic double layer colloid, it is repelled mutually, associative structure disappears, colloid viscosity falls sharply simultaneously, make fine-grained solids impurity lose rest, sink rapidly by gravity, adopt leave standstill, filtration or mode such as centrifugal, quicken the dispersion by force of montmorillonite and impurity, to remove tiny solid impurity.

The electronegative major cause of montmorillonite particle surface has: 1) Al in the octahedral sheet ³⁺By Mg ²⁺, Fe ²⁺, Fe ³⁺Replace Deng at random; 2) Si in the tetrahedron ⁴⁺By Al ³⁺Replace; 3) surperficial O ^2-A key be connected with silicon, another key is free.The major cause of montmorillonite grain edges positively charged: 1) breaking portion is compared with the alumina particle surface on the octahedral sheet, positively charged in neutrality or acidic suspension, and reducing and increase positively charged amount with the pH value; 2) tetrahedron fracture place is compared with the alumina particle surface, though alumina surface is electronegative, clay particle slightly dissolves in the suspension, and the small amount of aluminum atom exists and makes fracture tetrahedral sheet positively charged; 3) in the tetrahedral sheet at the local preferential tear of aluminium substitution silicon so that the surface and the alumina surface that expose are suitable.

Montmorillonite method of purification of the present invention is wet purification, after the natural montmorillonite drying is pulverized, be made into certain density slip, add an amount of dispersion agent, pull an oar or delaminate, various mineral constituents in the wilkinite are become mixed uniformly slurry, so that utilize the qualitative difference of various mineral physicses, as granular size or density variation, utilize swirler or supercentrifuge (as disk centrifugal separator, horizontal centrifuge) again, heavy mineral constituent separation is removed, as natural zeolite, feldspar, lime carbonate, coarse particles quartz sand etc.

For the montmorillonite that contains cristobalite, then utilize the dissociate difference of ability of montmorillonite nano wafer and cristobalite aquation in alkaline medium, the cristobalite hydrolysis is become liquid phase, removed and it separates from montmorillonite.Therefore, the present invention also provides a kind of purification to contain the method for the montmorillonite of cristobalite, comprises the steps: 1) the montmorillonite powder is added the slip that water is made into solid content 10-50%, pull an oar, remove by filter coarse sand, must filter slurry; 2) filter add basic solution in the slurry after, place encloses container to carry out hydrothermal treatment consists, filter, washing, filter cake; 3) filter cake adds the slip that water is made into solid content 0.5-12%, drops into the high speed centrifugation separating device, and high speed centrifugation is removed impurity, gets centrifugal slurry; 4) centrifugal slurry is through concentrating, being drying to obtain.

Further, preferred 1) concentration of step slurry is 15～45%, more preferably 20～40%, most preferably be 25-35%.

Described basic solution is water-soluble and make by alkaline matter well known in the art, as an alkali metal salt, alkalimetal oxide, alkaline earth salt, alkaline earth metal oxide, weak acid strong alkali salt or ammoniacal liquor.

Further, preferred described alkaline matter is selected from any or its mixture of yellow soda ash, sodium bicarbonate, Sodium Fluoride, sodium-chlor, sodium sulfate, sodium hydroxide, sodium aluminate, ammoniacal liquor, salt of wormwood, saleratus, Potassium monofluoride, Repone K, vitriolate of tartar, potassium hydroxide, potassium aluminate, lime carbonate, Calcium hydrogen carbonate, Calcium Fluoride (Fluorspan), calcium chloride, calcium sulfate, calcium hydroxide or calcium aluminate, more preferably any or its mixture of ammoniacal liquor, yellow soda ash, sodium bicarbonate, Sodium Fluoride, sodium-chlor, sodium sulfate, sodium hydroxide or sodium aluminate.

Further, the concentration of described basic solution is 0.5-5N, is preferably 1-4.5N, and more preferably 1.5-4N also is preferably 2-3.5N, most preferably is 2.5-4N.

Further, described hydrothermal treatment consists temperature is 60-160 ℃, is preferably 70-140 ℃, more preferably 80-120 ℃, most preferably is 85-100 ℃.

Further, 2) pH7-10 of step gained filter cake is preferably pH7.5-9, more preferably about pH8-8.5.

Further, 4) step described concentrate be selected from that high speed centrifugation concentrates, thin film concentration, concentrating under reduced pressure or filter-press dehydration.

Wilkinite of the present invention claims otaylite, expansive rock, amargosite, bentonite, sweet soil, bentonite, potter's clay, white clay or white clay again.

Cristobalite of the present invention claims cristobalite again.

Further, the particle diameter of control wilkinite powder or montmorillonite powder is 50 orders-300 orders, is preferably 100 orders-200 order.

Further, slurry is crossed 50 orders-300 mesh sieve, is preferably 100 orders-200 mesh sieve.

Another object of the present invention is to provide the application of disk centrifugal separator in purification high-purity montmorillonite method, described disk centrifugal separator can conveniently be removed the fine particle in the hydration swelling wilkinite, as α quartz etc., and can conveniently solve the technical barriers such as thickening difficulty of purification liquid in the wet purification montmorillonite method.

Disk centrifugal separator of the present invention claims " disk centrifuge ", " disk plate centrifuge ", " disc separator " or " Thin-layer separation settling centrifuge " again, is a kind of vertical centrifugal machine, and separation factor can reach 3000-10000.Rotary drum is contained in vertical shaft upper end, by transmission mechanism by motor drive high speed rotating.One group of back taper dish part that is nested in mutually together is housed in the rotary drum, claims video disc again.Leave very little gap between video disc and the video disc, clearance between two dishes can be 0.5-1.5mm.Suspension (or emulsion) adds rotary drum by the feed-pipe that is positioned at the rotary drum center, is distributed in and forms laminar flows between the video disc.Under centrifugal action, particles settling is to video disc inner surface and outwards slip, and clear liquid then inwardly flows along the video disc outer surface.When suspension (or emulsion) during by the gap between the video disc, solid particulate (or drop) is deposited under the whizzer effect and forms sediment (or liquid layer) on the video disc.Sediment slides and the disengaging video disc along disc surface, and accumulates in the position of rotary drum interior diameter maximum, and the liquid after the separation is discharged rotary drum from liquid outlet.Video disc has shortened the settling height of solid particulate (or drop), the settling area of expansion rotary drum, improved the throughput and the separation efficiency of separating machine greatly because video disc has been installed in the rotary drum, be suitable for handling particle diameter 0.1～100mm, solid content less than 25% suspension.The solid that accumulates in the rotary drum is taken rotary drum apart by artificial removing after separating machine is shut down, or discharges from rotary drum under non-stop-machine situation by residue extraction machine.

Also have a kind of disk centrifugal separator to be " dish formula tubular-bowl centrifuge ", be characterized in that rotary drum (pipe) diameter is little, length is big, rotating speed is high, separation efficiency is very high, can handle suspension and difficult isolating emulsion that grain diameter is 0.01mm continuously.Suspension or emulsion are added by the rotary drum lower end, are rotated with circular frequency by moving the reaching rapidly with rotary drum of the longitudinal rib strip in the rotary drum.Under centrifugal action, particle or heavy-fluid layer get rid of to the drum wall and are drawn by heavy liquid exit, and light liquid then overflows from the rotary drum centre.Its centrifugation factor can reach 65000.Industrially can be used for oily water separation, can be used for separate microorganism and protein in the laboratory.

As seen, disk centrifuge can be finished clarification operation and lock out operation, promptly liquid-solid separation (being the separation of lower concentration suspension) and liquid-liquid (or liquid-liquid-solid) separate (separation that is emulsion), its linear velocity can reach 200 meter per seconds.Characteristics such as the used disk centrifuge of the present invention has compact construction, and floor space is little, and throughput is big.

Another object of the present invention is to provide the application of hydrocyclone in purification high-purity montmorillonite method, described hydrocyclone can conveniently be removed the fine particle in the hydration swelling wilkinite, as α quartz etc., and can conveniently solve the technical barriers such as thickening difficulty of purification liquid in the wet purification montmorillonite method.

Hydrocyclone is a kind ofly to carry out classification or isolating equipment by granularity, density.Material tangent line to be fractionated feeds at a high speed from garden tube inwall, medium, particulate mixture produce rotation and form centrifuge field, different grain size, the particle of different densities (or liquid phase) produces different movement locus, under the effect in the field of forces such as centrifugal force, medium viscous resistance, buoyancy, gravity, the particle of coarse particles, big density is discharged from spigot by cone-shaped body to peripolesis; Fine particle, low-density particle (or liquid phase) are discharged by upflow tube to central motion; The thickness grading of realization solid particulate is separated with the different densities fluidic.

Another object of the present invention is to provide the application of horizontal centrifuge in purification high-purity montmorillonite method, described horizontal centrifuge can conveniently be removed the fine particle in the hydration swelling wilkinite, as α quartz etc., and can conveniently solve the technical barriers such as thickening difficulty of purification liquid in the wet purification montmorillonite method.

The principle of work of horizontal centrifuge is: suspension adds continuously along feed-pipe, and 6 feed ports on the little end wall of spiral are distributed on the rotatory drum wall.Because action of centrifugal force, liquid is thrown out of by the hole on filter screen and the drum wall, and the filtrate outlet on casing is discharged from outside the machine; Solid then is trapped on the filter screen, forms filter cake layer.Because there are the difference rotating speed in spiral and rotary drum, and the effect of the spiral conveyer that forms is constantly pushed filter residue to big end by small end, the filter residue casing slag-drip opening that is pushed out the big end of rotary drum is discharged, and suspension comes to this automatically, is separated into continuously filtrate and filter residue.

The factors such as concentration of the separating effect of suspension and rotary drum rotating speed, rotary drum and spiral difference rotating speed, feeding rate, suspension are closely related, different suspension should be selected optimum parameter by test, rotary drum rotating speed and differential mechanism than constant situation under, regulate changing a rotating speed over to and can change poor rotating speed.

The present invention will remove the montmorillonite slip of coarse sand and other mineral, thin up becomes the slurry of solid content 1-6%, utilize disk centrifugal separator, hydrocyclone or horizontal centrifuge unexpansive α quartzy or other fine impurity from the montmorillonite viscose glue of expansion aquation, separated and removed, and eject with high linear velocity slave unit nozzle, improving the purity of montmorillonite, and can conveniently solve the technical barriers such as thickening difficulty of purification liquid in the wet purification montmorillonite method.

The present invention also provides a kind of highly purified smectite composition, it is characterized in that, the purity of described montmorillonite is not less than 95%, preferably be not less than 96%, more have choosing to be not less than 97%, also preferably be not less than 98%, preferably be not less than 99% in addition, most preferably be not less than 99.5%.

Further, the cation exchange capacity (CEC) that limits montmorillonite of the present invention is 75-140mmol/100g, is preferably 80-130mmol/100g, and more preferably 90-125mmol/100g most preferably is 100-120mmol/100g.

Further, the turgidity that limits purifying montmorillonite of the present invention is not less than 4.0, preferably must not be less than 5.0, more preferably must not be less than 7.0, and also preferably must not be less than 9.0, in addition preferably must not be less than 10.0, most preferably must not be less than 12.0.

Further, every 1g montmorillonite is 0.30-0.70g to the adsorptive capacity of sulfuric acid Strychnine in the composition, is preferably 0.40-0.65g, more preferably 0.5-0.6g.

Further, the heavy metal of montmorillonite must not surpass 10ppm in the composition, preferably must not surpass 7ppm, and more preferably 5ppm most preferably is 3-4ppm.

Further, the related substance of montmorillonite must not surpass 5% in the composition, preferably must not surpass 4%, more elect 3% as, and is also preferred 2%, and other is preferably 1%, most preferably is 0.5%.

Further, in the composition montmorillonite be selected from wilkinite through high purity montmorillonite, the high purity of purification processes modified montmorillonite used or nano modification montmorillonite.

Further, described modified montmorillonite used modified na-montmorillonite, modification sodium ca-montmorillonite, modification hydrogen base montmorillonite or the modified calcium-base montmorillonite of being selected from is preferably modified na-montmorillonite.

Another object of the present invention is to provide a kind of method for preparing the nano modification montmorillonite, comprise the steps: purity is not less than the 95% modified montmorillonite used aqueous solution that is mixed with solid content 0.5-60%, put carry out in high-speed shearing machine, high speed dispersor, ball mill or the high pressure homogenizer that high speed shear is disperseed, behind the homogeneous, dry, pulverize, promptly.

Further, described modified montmorillonite used purity is not less than 95%, preferably is not less than 96%, preferably is not less than 97% in addition, more preferably is not less than 98%, also preferably is not less than 99%, most preferably is not less than 99.5%.

Further, described modified montmorillonite used modified na-montmorillonite, modification sodium ca-montmorillonite, modification hydrogen base montmorillonite, modification magnesium base montmorillonite or the modified calcium-base montmorillonite of being selected from is preferably modified na-montmorillonite.

Further, the particle diameter of described nano modification montmorillonite is not more than 1 μ m, preferably is not more than 0.8 μ m, preferably is not more than 0.4 μ m in addition more preferably no more than 0.6 μ m, most preferably is not more than 0.2 μ m.

Further, the concentration of the described aqueous solution is 5-50%, 10-40% more preferably, and also preferred 15-30% most preferably is 20-25%.

Further, described homogenization pressure is not less than 10MPa, is preferably 20-800MPa, 30-600MPa more preferably, and also preferred 50-500MPa most preferably is 80-300MPa.

Further, described high pressure homogenizer is selected from any or its combination of mesohigh homogeneous, super-high-pressure homogenization machine, nm super high clarifixator, nanometer ram machine or high pressure microjet clarifixator.

Further, described pulverizing is that thick level is pulverized the back comminution by gas stream.

Further, described smashing fineness preferably is not less than 500 orders for being not less than 300 orders, preferably is not less than 1000 orders in addition, more preferably is not less than 3000 orders, most preferably is not less than 5000 orders.

Modified montmorillonite used solid particulate is medium with water, under the strong shearing action of high speed dispersor, carry out pre-dispersed, and through high-pressure homogeneous (also claim delaminate) by lower pressure to highly compressed behind the continuous or multistage homogeneous, obtain average particulate diameter and be not more than 1 μ m, purpose is to increase its edge by pulverizing by force, strengthen its aquation performance of delaminating, increase " compartment " quantity, improve absorption property and improve its medicinal effect.

Another object of the present invention is to provide a kind of nano modification montmorillonite, make by following method: the aqueous solution that purity is not less than the 95% modified montmorillonite used 0.5-60% of being mixed with, put carry out in high-speed shearing machine, high speed dispersor, ball mill or the high pressure homogenizer that high speed shear is disperseed, behind the homogeneous, dry, pulverize, promptly.

Further, described homogenization pressure is not less than 10MP, is preferably 20-800MPa, 30-600MPa more preferably, and also preferred 50-500MPa most preferably is 80-300MPa.

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

Further, the turgidity of nano modification montmorillonite is not less than 4.0, preferably must not be less than 5.0, more preferably must not be less than 7.0, and also preferably must not be less than 9.0, in addition preferably must not be less than 10.0, most preferably must not be less than 12.0.

Further, the every 1g nano modification of qualification the present invention montmorillonite is 0.30-0.70g to the adsorptive capacity of sulfuric acid Strychnine, is preferably 0.40-0.65g, more preferably 0.5-0.6g.

Further, the heavy metal that limits nano modification montmorillonite of the present invention must not surpass 10ppm, preferably must not surpass 7ppm, and more preferably 5ppm most preferably is 3-4ppm.

Further, the related substance that limits nano modification montmorillonite of the present invention must not surpass 5%, preferably must not surpass 4%, and more preferably 3%, also preferred 2%, other is preferably 1%, most preferably is 0.5%.

Another object of the present invention provides a kind of pharmaceutical composition that is used for the treatment of the enteron aisle illness, is made up of modified montmorillonite used and pharmaceutically acceptable carrier.

Further, described digestive tract diseases illness is selected from digestive tract ulcer, diarrhoea or gastritis, and preferred described gastritis is chronic gastritis, and more preferably chronic atrophic gastritis most preferably is the reversal therapies effect to chronic atrophic gastritis.

Further, modified montmorillonite used in the preferred composition: the weight ratio of auxiliary material (by dry product) is 0.001-99:1-99, is preferably 0.001-90:1-95, and more preferably 0.001-80:1-90 most preferably is 0.001-70:1-85.

Further, the weight percentage of montmorillonite is 1-100% in the composition, is preferably 5-95%, also is preferably 10-90%, and more preferably 15-85% most preferably is 20-80%.

Composition of the present invention can be various formulation well known in the art, and the preparation technique that can adopt this area routine is to prepare composition of the present invention.Be suitable for preparation of the present invention and be selected from oral preparations or external preparation, be preferably oral preparations.

Further, described oral preparations is selected from tablet, suspension, capsule, granule, pill, powder, dripping pill, syrup, mixture, distillate medicinal water, effervescent, paste, emulsion or medicinal tea etc.; Be preferably powder, suspension, granule, tablet, capsule or effervescent.

Further, it is optional from gelifying agent, emplastrum, plaster, creme, ointment, liniment, lotion, suppository, basting agent, paste or coagulate paste etc. to be suitable for external preparation of the present invention, is preferably gelifying agent.

Described pharmaceutically acceptable carrier is well known usual excipients or the auxiliary material that is used to prepare above-mentioned preparation, and vehicle that oral preparations or external preparation are commonly used or auxiliary material include but are not limited to weighting agent (claim not only thinner), lubricant (but also claiming glidant or antitack agent), dispersion agent, wetting agent, tackiness agent, conditioning agent, solubilizing agent, oxidation inhibitor, fungistat, emulsifying agent, correctives, reodorant etc.Tackiness agent, for example syrup, gum arabic, gelatin, sorbyl alcohol, tragacanth, Mierocrystalline cellulose and derivative thereof, gelatine size, syrup, starch slurry or polyvinylpyrrolidone, preferred derivatived cellulose is Microcrystalline Cellulose, Xylo-Mucine, ethyl cellulose, HPMC; Weighting agent, for example lactose, Icing Sugar, dextrin, starch and derivative thereof, Mierocrystalline cellulose and derivative thereof, inorganic calcium salt, sorbyl alcohol or glycine, preferred inorganic calcium salt is calcium sulfate, calcium phosphate, secondary calcium phosphate, precipitated calcium carbonate; Lubricant, for example micropowder silica gel, Magnesium Stearate, talcum powder, aluminium hydroxide, boric acid, hydrogenated vegetable oil, polyoxyethylene glycol; Disintegrating agent, for example starch and derivative thereof, polyvinylpyrrolidone, cross-linked polyvinylpyrrolidone or Microcrystalline Cellulose, preferred starch derivative is sodium starch glycolate, Explotab, pregelatinized Starch, modified starch, hydroxypropylated starch, W-Gum; Wetting agent, for example sodium lauryl sulphate, water or alcohol etc.

In addition, also activeconstituents can be mixed by its preparation requirement with pharmaceutically acceptable slow controlled release carrier, again according to the preparation method of sustained-release preparation well known in the art, as adding the retarding agent dressing or with making micropill after the active principle microcapsulesization again, as sustained release pellet or controlled release micro pill; Described slow controlled release carrier includes but are not limited to oil agent, hydrophilic colloid or the dressing retarding agent etc. of mixing, and described oil to mix agent be glyceryl monostearate, hydrogenated castor oil, Dormant oils, polysiloxane, dimethyl siloxane; Described hydrophilic colloid is derivatived celluloses such as Xylo-Mucine, hydroxypropylcellulose, Vltra tears, or PVP, gum arabic, tragcanth or carbopol etc.; Described dressing retarding agent is ethyl cellulose (EC), HPMC (HMPC), polyvinylpyrrolidone (PVP), cellulose acetate-phthalate (CAP), acrylic resin etc.

Another object of the present invention provides modified montmorillonite used application in the preparation medicine.

The modified montmorillonite used original medicinal use of natural montmorillonite that not only possesses reinforcement of the present invention, also special performance is to the reversal therapies effect of gastritis, especially the reversal therapies effect of chronic atrophic gastritis, its main medicinal use is as follows: (1) modified montmorillonite used application in the medicine of preparation treatment digestive tube illness, described digestive tract diseases includes but are not limited to acute and chronic diarrhea, reflux esophagitis, chronic gastritis, peptide ulceration, irritable bowel syndrome, inflammatory enteron aisle illness, gastritis etc., preferred described gastritis is chronic gastritis, more preferably chronic atrophic gastritis most preferably is the reversal therapies effect to chronic atrophic gastritis.Though montmorillonite does not have the direct sterilization of anti-microbial type medicine, bacteriostatic function, but can utilize the commutative characteristic of its interlayer ion, bacterium and the absorption of its metabolism toxin are exchanged to interlayer, promote the reparation of injured intestinal mucosa, and bacterial acute and chronic diarrhea illness is had good result of treatment, and result of treatment and its layer charge density of diarrhoea is proportionate; In addition, montmorillonite has unique synusia structure, and inhomogeneous charge distribution and slip visco-plasticity can evenly cover the digestive tube surface continuously, with static and materialization effect performance curative effect, the gi tract illness is had good preventive and therapeutic effect; (2) modified montmorillonite used in preparation treatment or prevent and treat application in the hyperthyroid medicine; (3) modified montmorillonite used application in the medicine of preparation treatment chronic renal failure; (4) modified montmorillonite used application in the medicine of preparation prevention or counteract oral malodour; (5) modified montmorillonite used application in preparation pharmaceutical carrier or excipient substance, modified montmorillonite used pharmaceutical carrier or the excipient substance of can be used as, mutually compound with some microbiotic or enzyme, make the complexing medicine, as Streptomycin sulphate-montmorillonite complex compound, drug component wherein has only when cation exchange reaction takes place just can discharge the performance property of medicine, strengthens montmorillonite to effects such as fixing, the inhibition of bacterium, virus etc., sterilizations; Be preferably used as the matrix of oral preparations, external preparation, sustained release preparation or controlled release preparation, more preferably as tablet, suspension, capsule, granule, pill, powder, dripping pill, syrup, mixture, distillate medicinal water, effervescent, paste, medicinal tea, biologic adhesion preparation, gelifying agent, ointment, creme, suppository, emulsion, paste, inorganic antiseptic, skin-use preparation, liniment, lotion, basting agent, coagulate the matrix of paste, makeup or suspension agent; Described medicine is selected from any or its combination of oral pharmaceutical, externally applied medicine, slow releasing pharmaceutical or controlled release drug; (6) modified montmorillonite used application in preparation treatment dermatosis treating medicine, pass through ion exchange method, sterilization, bacteriostatic metal ion or antibiotic can be exchanged, are adsorbed to the interlayer of montmorillonite, the montmorillonite that contains micro-sterilization metal ion or sterilization, bacteriostatic action with preparation, make it possess absorption and antibacterial or sterilization dual-use function, as the dermopathic externally applied agent of treatment; (7) modified montmorillonite used application in the preparation medicament for sobering up and protecting liver; (8) modified montmorillonite usedly remove or kill application in the helicobacter pylori medicine in preparation.

Modified montmorillonite used to chronic atrophic gastritis treatment and the reversal therapies effect based on following pharmacological action: modified montmorillonite used can the combination with the mucus in the digestive tube; strengthen mucous force of cohesion and visco-elasticity; synthesizing of stimulation of endogenous prostaglandin(PG); promote mucus secretion; reduce MGP sulfonyl composition; increase N-acetylgalactosamine and galactose component; and complexing cholate; fixing; suppress pathogenic pathogenic agent such as helicobacter pylori; aspect two of quality and quantities, strengthen mucous barrier action; prevent hydrochloric acid in gastric juice; stomach en-; cholate and nonsteroidal anti inflammatory medicine are to the erosion of gastrointestinal mucosal; help and quicken epithelial regeneration and reparation, promote the healing of impaired mucous membrane.The contriver is by discovering, montmorillonite and modified montmorillonite used distinctive microcosmic charging property, make it can bring into play good reverse effect in the process that atrophy of gastric mucosa takes place to develop, can be used for the reversal therapies of chronic atrophic gastritis, reverse effect and its microcosmic carried charge are proportionate.

Existing pharmacological research shows: natural montmorillonite does not have antibacterial or germicidal action, to bacterium mainly is adsorption, used as the medicine of treatment diarrhoea and digestive tract ulcer, the adsorbable fixation of bacteria of its " carriage-type " gel structure and its metabolism toxin are the pharmacological basis of its treatment diarrhoea clinically.Natural montmorillonite also all has adsorption preferably to intestinal bacteria, vibrio cholerae, campylobacter jejuni, golden Portugal bacterium and rotavirus and cholate; Bacterium and its metabolism toxin had good fixed action.Other has research also to show, the pathogenic charged pathogenic bacteria that montmorillonite only adsorbs, fixed surface has a proteins encoded (CS31A) does not have fixedly scavenging(action) with the normal microflora of CS31A to the surface, thereby nontoxicity.

Electronegative plate surface behind the montmorillonite hydration swelling is connected with the edge of positively charged, forms " compartment " the formula suspended substance of " marginal surface ", has " thixotropy " of " gel-sol-gel " sample.And " compartment " formula suspended particle locks onto bacterium in " compartment ", and it is removed.Of the present invention modified montmorillonite used by changing the microtexture of natural montmorillonite stack layer, the synusia attenuation, end face electric charge and variable charge all increase, charge distribution broadens, and exchanges the positively charged ion of easy aquation at interlayer, and pulverizes by force to increase the edge, strengthen that its aquation is delaminated, gellifying property, increase " compartment " quantity, strengthened the removing ability of natural montmorillonite greatly, and greatly strengthen and expand its medical applications bacterium and toxin.

Further, limiting the modified montmorillonite used day dosage of the present invention is 0.5-10g, is preferably 1-8g, and more preferably 1.5-6g also is preferably 2-4g, most preferably is 2-3g.The actual daily dosage of montmorillonite can suitably be adjusted according to factors such as patient's the state of an illness, physique, body weight, age, sexes.

Montmorillonite is based on its colloidal sol viscose properties and microcosmic charging property as the pharmacology of digestive tube medicine.Montmorillonite after modification is handled can increase the exposure of the hiding variable center of negative charge of natural montmorillonite, increases the end face electric charge, the Fe in the octahedra lamella structure of stripping simultaneously ²⁺, Mg ²⁺, Fe ³⁺, improve its layer charge, widen the distribution range of layer charge, improved the ununiformity of charge distribution, improve its delaminating property of hydration swelling and charge characteristic, strengthen its pharmacologically active.

Modified montmorillonite used CEC of the present invention, adsorptivity is more more superior than natural montmorillonite with swelling property, and soft tissue is (as the mucous membrane between stomach and intestine, the skin layer mucous membrane, oral mucosa etc.) the adhesion time prolongs greatly, prolong the residence time of activeconstituents at soft tissue, increase the swap time and the exchange efficiency of activeconstituents and body, fixed point administration and the controlled release of realizing activeconstituents discharge, can improve the bioavailability and the drug safety of effective constituent, therefore, modified montmorillonite used can be used for preparing medicine or edible adjuvant of the present invention: 1) as the carrier of biologic adhesion preparation, with control drug release, and reduce or minimizing surface-active substance confrontation skin irritation, described biologic adhesion preparation is selected from sucks bioadhesive polymer, the nose bioadhesive polymer, eye bioadhesive polymer, vagina bioadhesive polymer, rectum bioadhesive polymer or gi tract bioadhesive polymer etc.As adhering to drug transport system (AmDDS), can strengthen the interaction of the Saliva Orthana polymkeric substance of medicine and vaginal mucosa, prolong drug time of releasing with the vaginal mucosa of modified montmorillonite used preparation nonoxynolum of the present invention; Make the stomach bioadhesive polymer with Bismuth Potassium Citrate, both prolonged the residence time of Bismuth Potassium Citrate, and have synergistic function, can also significantly reduce the prominent phenomenon of releasing of bismuth agent, improve the security of medicine removing and killing helicobacter pylori at stomach and intestine; Make stomach and intestine (colon) location delivery formulations with antitumor drug (resistive connection bowelcancer medicine), can prolong the action time of antitumor drug at intestines and stomach, the rate of release of control antitumor drug improves drug bioavailability and security, and reduces or reduce the untoward reaction of medicine; 2) as the carrier of gelifying agent: the modified montmorillonite used aqueous solution of finite concentration scope can become good gel matrix, characteristics with water dispersible matrix, no greasy feeling, has good adhesion, the exclusive adsorptivity of film-forming properties and bacterium, be easy to be coated with the shop, to skin and mucous membrane nonirritant, and it is effective with skin adhesive, and can absorb and transudate is organized in removing, be the electrocardiographic diagnosis gelifying agent, the ultrasonic diagnosis gelifying agent, tooth section gelifying agent, become the dental cement, the tooth powder of treatment oral disease, toothpaste is used the good pharmaceutically acceptable carrier of gelifying agent with thickening material or skin; 3) utilize the characteristic of modified montmorillonite used suspending, adhesion and rheology improving agent, can be used as the matrix of semi-solid preparations such as water-soluble ointment, creme, suppository.Suppository as making with an amount of gum guaiacum, CMC, agar, PVP, oleic acid, glycerine, propylene glycol and distilled water has characteristic indeformable under the normal temperature, that do not liquefy, is beneficial to drug diffusion and absorption; 4) as the matrix of medical paste, inorganic antiseptic, skin paste, emulsion, add MgO as modified na-montmorillonite, have wetting ability, the dispersiveness of height, the anti Bacillus pyocyaneu Flugge effect of the inorganic antiseptic for preparing is better; 5) as good suspending agent, have a more negative charge because of modified montmorillonite used, water regain is big, have good gelation, thixotropy, oilness, and incompatibility is few, advantage such as adding preservative agent not, and its suspending effect obviously is better than sodium cellulose glycolate, sodium starch glycolate and sodium alginate; 6),,, form and be important cosmetic base as skin secretion, sweat, grease etc. because of adsorbable each organic molecular species of montmorillonite as the sorbent material of facial mask, face powder, pigment, sun care preparations etc.

The present invention also aims to provide a kind of Bismuth Potassium Citrate preparation of new bio adhesive type, said preparation is made up of Bismuth Potassium Citrate, modified montmorillonite used and other pharmaceutical excipients.

Further, the weight percentage of each composition is in the preparation: Bismuth Potassium Citrate 1-98%, and modified montmorillonite used 1-98%, surplus is other auxiliary materials.

Further, the weight percentage of each composition is in the preparation: Bismuth Potassium Citrate 5-90%, and modified montmorillonite used 5-90%, surplus is other auxiliary materials.

Further, the weight percentage of each composition is in the preparation: Bismuth Potassium Citrate 7.5-85%, and modified montmorillonite used 7.5-85%, surplus is other auxiliary materials.

In addition, limit in every dose of preparation of the present invention and contain Bismuth Potassium Citrate 50-2500mg, modified montmorillonite used 10-2500mg; Preferably contain Bismuth Potassium Citrate 100-2000mg, modified montmorillonite used 50-2000mg; More preferably contain Bismuth Potassium Citrate 150-1500mg, modified montmorillonite used 100-1500mg; Most preferably contain Bismuth Potassium Citrate 200-1200mg, modified montmorillonite used 150-1200mg.

Known Bismuth Potassium Citrate to the treatment machine of gastrointestinal tract disease (gastrointestinal dysfunction, diarrhoea, peptide ulceration or helicobacter pylori (HP) infect) built in: 1) in PH＜5 o'clock, huge legendary turtle is closed the protein of ulcer surface, covers ulcer surface, plays a protective role; 2) do not have antiacid effect, but can suppress pepsic activity, reduce pepsic degraded in the mucus and the feedback inhibition pepsinia; 3) promote mucous membrane PG synthetic, reduce the degraded of EGF in the mucus, stimulate the secretion of mucus and supercarbonate, increase mucosal blood flow; 4) promote that scavenger cell reassociates, be beneficial to ulcer healing; 5) effect of inhibition urease has the effect of killing HP.And montmorillonite has absorption, scavenging(action) to HP, with the Bismuth Potassium Citrate coupling, has synergistic function to killing and remove HP.

The present invention also aims to provide a kind of modified montmorillonite used makeup that contain, described makeup contain the modified montmorillonite used of 1-90%, and surplus is other auxiliary materials; Content modified montmorillonite used in the makeup is preferably 5-85%, and more preferably 7.5-80% most preferably is 10-75%.

The modified montmorillonite used construction industry that also can be used for of the present invention: 1) modified montmorillonite used as good water-proof material, modified montmorillonite used have an extremely strong water-swelling, the water that can adsorb 8～15 times of own vols, the volumetric expansion multiple can be up to 10～30 times, and can form thickness and metastable gelinite after the aquation, very strong water retention property is arranged, even long-term storage, after the moisture seasoning, chance water moisture absorption more still can expand and form gel once more, has dry shrinkage chance water and expands repeatedly, and can produce characteristic and thixotropy up to the 0.15MPa swelling pressure, has excellent waterproofness, waterproof self-styled and weather resistance become good water-proof material, but and winter construction; 2) modified montmorillonite usedly be used for preparing inorganic thickening agent: an OH, a COOH, a CH of coating organic molecule (as polyvinyl alcohol, Vinyl Acetate Copolymer, vinylformic acid, carboxymethyl cellulose, Natvosol etc.) ₂CH ₂OH isopolarity group is attracted by negative charge between montmorillonite layer, between interposed layer, form montmorillonite one organic double compound, montmorillonite and organism are cross-linked with each other, form netted three-dimensional arrangement, and montmorillonite is expanded, make it become the inorganic thickening agent that increases the coating denseness, and its thickening effectiveness is obvious, can significantly reduce cellulose thickener and emulsion-type thickening material or other fillers (as light calcium carbonate, polyvinyl alcohol) consumption, and, and has the good pigment that prevents to the abrasion resistance and the almost not influence of water tolerance of filming, the sedimentary effect of filler reduces the production cost of coating greatly; 3) modified montmorillonite usedly be used to prepare auxiliary adhesive: mainly utilize the multifrequency nature of montmorillonite, as hydrophilic, particle is tiny and irregularity, specific surface area is big, the variation of plane of crystal electric charge, hydroxyl and water form characteristics such as hydrogen bond or colloidal sol; 4) modified montmorillonite used as the suspension anti-settling agent, mainly based on its suspension good in water medium and dispersiveness.

The montmorillonite surface has adsorptivity, can form intensive physics or chemisorption with tensio-active agent.The hydroxyl on montmorillonite surface and Sauerstoffatom also can and surfactant molecule between form adsorption by hydrogen bond, can be used as petroleum drilling with the catalyzer in the mud, refining petroleum, discoloring agent, on-the-spot preparation drilling fluid etc.

In addition, modified montmorillonite usedly also can be used for following field: 1) modified montmorillonite used carrier with used as pesticides, chemical fertilizer, to reduce the water content of fertilizer, prevent fertilizer agglomeration, improve the granularity of fertilizer, or solve the too high or raw material generation chemical reaction of calcium superphosphate in the production of composite fertilizer contained moisture, free acid and produce granulation difficulty due to the excess moisture, be beneficial to production, transportation, preservation and the use of fertilizer; 2) modified montmorillonite used as soil improvement agent, because of its cation exchange capacity up to 120mmol/100g about, water-intake rate is up to more than 200%, dry-pressing intensity can reach 6kg/cm ², have stronger water retention capacity and good agglutinating value(of coal), change the ratio of solid, liquid, gas in the soil, improve the hydrothermal condition and the Soil structure of soil, make soil water-retaining, protect fertilizer contaminated soil environment not again, also can increase the surge capability of soil, the harmful element in the absorption soil; 3) modified montmorillonite used as fodder additives, contain multiple normal trace element and physiologically active substances such as Al, Si, Mg, Fe, K, Zn, Cu, Ca, P, Na, I, Se because of it, to domestic birds and animals have appetite stimulator, aid digestion, regulate organism balance, increase effects such as immunity function, disease-prevention health, improve the transformation efficiency of feed, reduce its cost, safe and reliable, also have good palatability, obviously prolong the quality guaranteed period of feed etc.; 4) modified montmorillonite used as premix carrier, because of it has better adsorptive power, fine and close fine and smooth, mobile big, be difficult for airborne dust, be difficult for layering in the course of processing, the uniform mixing performance is good, disperses adsorptive power strong to various VITAMIN, trace element, also can protection against the tide, mildew-resistant, anti-ly damage by worms, anti-go bad etc.; 5) modified montmorillonite used granulated feed and aquatic feeds sizing agent, because of it has stronger mineral products comprehensive utilization agglutinating value(of coal), the wet pressure of heat resistanceheat resistant, can replace the sizing agent as the feed moulding such as the carboxy cellulose of using always, inferior powder fully, and gluing is effective, plasticity-is strong, the grain type is neat, smooth surface, visual appearance is good, and is with low cost; 6) modified montmorillonite used as the feed toxinicide, can prevent the process of feeding because of the oxypathy that fine fodder is searched for food too much or maldigestion causes, and contained toxin or feed store the harm to domestic animal of the mycin that generated in the feed; 7) modified montmorillonite used thinner as fermented feed can prolong storage time of fermented feed; 8) modified montmorillonite used being mainly used in as the landfill impervious material effectively improved concrete water proof effect and antiseepage ability, prevents nuisance polluted underground water matter; 9) modified montmorillonite usedly can be used as Nuclear power plants nuclear waste disposal agent, cushioning material or backfilling material as high hazardness waste material are used to stop, cushion the diffusion of atomic waste, protection environment and the personal harm of avoiding radioactive pollutant; 10) modified montmorillonite used as air purifying preparation, energy airborne sulfur oxide of active adsorption and nitrogen oxide reach the effect that purifies air; 11) be used to prepare nano composite material, have mechanics, calorifics and the electricity, magnetic and the optical property that are different from general macroscopical matrix material; 12) as the finings of the decolorizing purification of multiple oils and drinks, fruit juice, and as the decolouring of vegetable and animals oils, remove stink and impurity is handled; 13) as industrial catalyst, carrier or sorbent material, to solve H ₂SO ₄, AlCl ₃Etc. problem of environmental pollutions such as a large amount of spent acid that cause in the acid catalysis technological process, equipment corrosion, product separation difficulty.

Description of drawings

The x ray diffraction material phase analysis figure of Fig. 1 embodiment 1 gained purifying montmorillonite;

The x ray diffraction material phase analysis figure of Fig. 2 embodiment 1 gained modified calcium-base montmorillonite;

The x ray diffraction material phase analysis figure of Fig. 3 embodiment 1 gained modified na-montmorillonite;

The x ray diffraction material phase analysis figure of Fig. 4 embodiment 2 purifying montmorillonites;

The x ray diffraction material phase analysis figure of Fig. 5 embodiment 2 gained modified calcium-base montmorillonites;

The x ray diffraction material phase analysis figure of Fig. 6 embodiment 2 gained modified na-montmorillonites;

The x ray diffraction material phase analysis figure of Fig. 7 embodiment 3 raw ores;

The x ray diffraction material phase analysis figure of Fig. 8 embodiment 3 purifying montmorillonites;

The x ray diffraction material phase analysis figure of Fig. 9 embodiment 3 gained modified calcium-base montmorillonites;

The x ray diffraction material phase analysis figure of Figure 10 embodiment 3 gained modified na-montmorillonites;

The x ray diffraction material phase analysis figure of Figure 11 embodiment 4 purifying montmorillonites;

The x ray diffraction material phase analysis figure of Figure 12 embodiment 4 gained modified calcium-base montmorillonites;

The x ray diffraction material phase analysis figure of Figure 13 embodiment 4 gained modified na-montmorillonites;

The x ray diffraction material phase analysis figure of Figure 14 embodiment 5 gained purifying montmorillonites;

The x ray diffraction material phase analysis figure of Figure 15 embodiment 5 gained modified calcium-base montmorillonites;

The x ray diffraction material phase analysis figure of Figure 16 embodiment 5 gained modified na-montmorillonites;

The x ray diffraction material phase analysis figure of Figure 17 embodiment 6 raw ores;

The x ray diffraction material phase analysis figure of Figure 18 embodiment 6 purifying montmorillonites;

The x ray diffraction material phase analysis figure of Figure 19 embodiment 6 gained modified calcium-base montmorillonites;

The x ray diffraction material phase analysis figure of Figure 20 embodiment 6 gained modified na-montmorillonites;

The x ray diffraction material phase analysis figure of Figure 21 embodiment 6 gained modification sodium ca-montmorillonites;

Figure 22: each group of test is to the influence of rat stomach hole mucous layer thickness level;

Figure 23: each group of test is to the influence of rat stomach hole portion mucous layer thickness/muscular layer of mucosa thickness (L1/L2) ratio;

Figure 24: each group of test is to the influence of rat stomach hole portion mucomembranous gland density;

Figure 25: each group of test is to the influence of rat stomach hole portion inflammation index;

Figure 26: each group of test is to the influence of gastric mucosa of rat hexosamine level;

Figure 27: each group of test is to gastric mucosa of rat PGE ₂The influence of level.

Embodiment

Specify the present invention below with reference to embodiment, embodiments of the invention only are used to technical scheme of the present invention is described, and non-limiting essence of the present invention.

Embodiment 1Modified montmorillonite used preparation

The material phase analysis of purifying montmorillonite is referring to Fig. 1.

In purifying montmorillonite, the mixing acid that adds 2mol/L, the consisting of of mixing acid (hydrochloric acid: oxalic acid: the mol ratio of acetic acid is 4:10:6), with soil: the mass ratio of acid is that 1:3 mixes, under 100 ℃ of conditions, heat was boiled 5-6 hour, removed by filter mixing acid, filter cake with deionized water wash to pH ≧ 4,100 ℃ of dryings, be ground into the 300-500 order, promptly get the modified calcium-base montmorillonite, its abundance or material phase analysis are referring to Fig. 2.

The modified calcium-base montmorillonite of gained is made into the slip of solid content 20% with the hydrochloric acid soln of 0.5N, stir 6h, remove by filter acid solution, filter cake with 60 ℃ of hot washes to PH about about 5, press filtration becomes the filter cake of solid content about 50%, add the yellow soda ash (as the 4.5-5% of modified calcium-base montmorillonite consumption) suitable with cation exchange capacity, stir sodium, making its PH is 7-8, sodium 34h 120 ℃ of dryings, is ground into the 300-500 order, promptly get modified na-montmorillonite, its abundance or material phase analysis are referring to Fig. 3.

Embodiment 2Modified montmorillonite used preparation

The material phase analysis of purifying montmorillonite is referring to Fig. 4.

In purifying montmorillonite, the mixing acid that adds concentration 1mol/L, the consisting of of mixing acid (hydrochloric acid: oxalic acid: the mol ratio of acetic acid is 3:4:3), with soil: the mass ratio of acid is that 1:4 mixes, under 90 ℃ of conditions, heat was boiled 6-8 hour, removed by filter mixing acid, filter cake with deionized water wash to pH ≧ 4,120 ℃ of dryings, be ground into the 300-500 order, promptly get the modified calcium-base montmorillonite, its abundance or material phase analysis are referring to Fig. 5.

Modified calcium-base montmorillonite with gained, be made into the slip of solid content 15% with the sulphuric acid soln of 0.5N, stir 6h, remove by filter acid solution, filter cake with 70 ℃ of hot washes to PH about about 5.5, press filtration becomes the filter cake of solid content about 40%, add the sodium hydroxide (as the 5-5.5% of modified calcium-base montmorillonite consumption) suitable with cation exchange capacity, stir sodium, making its PH is 8-9, sodium 34h, 115 ℃ of dryings, be ground into the 300-500 order, promptly get modified na-montmorillonite, its abundance or material phase analysis are referring to Fig. 6.

Embodiment 3Modified montmorillonite used preparation

The mineral composition of wilkinite raw ore: referring to Fig. 7.

The raw ore drying, 50 mesh sieves are crossed in pulverizing, add the Sodium hexametaphosphate 99 of the water and the 0.3% original ore powder scale of construction, form the slip of solid content 20%, stir after two hours, cross three grades of hydrocyclones, separate and remove coarse sand, get separating slurry; Separate the solvent or diluent slurry that slip adds water furnishing solid content 3%, entering disk centrifugal separator separates, the solvent or diluent slurry of separating enters another disk centrifugal separator again and concentrates, enriching slurry gets the filter cake of solid content 40-50% through filter press, filter cake is 125 ℃ of oven dry, be crushed to more than 500 orders, the mineral composition of purifying montmorillonite is referring to Fig. 8.

In purifying montmorillonite, the mixing acid (sulfuric acid: citric acid: the mol ratio of acetic acid consists of 6:8:6) that adds concentration 2mol/L, with soil: the mass ratio of acid is that 1:6 mixes, and under 80 ℃ of conditions, heat was boiled 7-8 hour, remove by filter mixing acid, filter cake with deionized water wash to pH be 4.5,115 ℃ of dryings, be ground into the 300-500 order, promptly get the modified calcium-base montmorillonite, its abundance or material phase analysis are referring to Fig. 9.

Modified calcium-base montmorillonite with gained, be made into the slip of solid content 25% with the hydrochloric acid soln of 1N, stir 7h, remove by filter acid solution, filter cake with 90 ℃ of hot washes to PH about about 5, press filtration becomes the filter cake of solid content about 60%, adds the sodium-chlor (as the 3.5-4% of modified calcium-base montmorillonite consumption) suitable with cation exchange capacity, stirs sodium 34h, 120 ℃ of dryings, be ground into the 300-500 order, promptly get modified na-montmorillonite, its abundance or material phase analysis are referring to Figure 10.

Embodiment 4Modified montmorillonite used preparation

The material phase analysis of purifying montmorillonite is referring to Figure 11.

In purifying montmorillonite, the mixing acid (phosphoric acid: tartrate: the mol ratio of oxalic acid consists of 10:12:12) that adds concentration 5mol/L, with soil: the mass ratio of acid is that 1:5 mixes, and under 70 ℃ of conditions, heat was boiled 9-10 hour, remove by filter mixing acid, filter cake with deionized water wash to pH be about 4.5,120 ℃ of dryings, be ground into the 300-500 order, promptly get the modified calcium-base montmorillonite, its abundance or material phase analysis are referring to Figure 12.

Modified calcium-base montmorillonite with gained, be made into the slip of solid content 30% with the salpeter solution of 0.5N, stir 6h, remove by filter acid solution, filter cake with 60 ℃ of hot washes to PH about about 5, press filtration becomes the filter cake of solid content about 65%, adds the sodium bicarbonate (as the 5-5.5% of modified calcium-base montmorillonite consumption) suitable with cation exchange capacity, stirs sodium 36h, 125 ℃ of dryings, be ground into the 300-500 order, promptly get modified na-montmorillonite, its abundance or material phase analysis are referring to Figure 13.

Embodiment 5Modified montmorillonite used preparation

The material phase analysis of purifying montmorillonite is referring to Figure 14.

In purifying montmorillonite, the mixing acid (nitric acid: oxysuccinic acid: the mol ratio of acetic acid consists of 75:120:105) that adds concentration 3mol/L, with soil: the mass ratio of acid is that 1:3 mixes, heat was boiled 7-8 hour under 90 ℃ of conditions, removed by filter mixing acid, filter cake with deionized water wash to pH ≧ 4,120 ℃ of dryings, be ground into the 300-500 order, promptly get the modified calcium-base montmorillonite, its abundance or material phase analysis are referring to Figure 15.

Modified calcium-base montmorillonite with gained, be made into the slip of solid content 20% with the hydrochloric acid soln of 0.5N, stir 6h, remove by filter acid solution, filter cake with 60 ℃ of hot washes to PH about about 5, press filtration becomes the filter cake of solid content about 50%, add the yellow soda ash (as the 4-4.5% of modified calcium-base montmorillonite consumption) suitable with cation exchange capacity, stir sodium, making its PH is 7-8, sodium 32h, 115 ℃ of dryings, be ground into the 300-500 order, promptly get modified na-montmorillonite, its abundance or material phase analysis are referring to Figure 16.

Embodiment 6Modified montmorillonite used preparation

The mineral composition of wilkinite raw ore is referring to Figure 17.

Wilkinite is formed the slip that mixing acid is made into 30% solid content with 0.9N acetic acid and 0.1N hydrochloric acid, handle 2h at 60 ℃, remove by filter mix acid liquor, to pH5, thin up becomes the solvent or diluent slurry of 5% solid content with 60 ℃ of hot wash filter cakes, after twice separation of disk centrifugal separator and once concentration, get enriching slurry, concentrate slurry and become the filter cake of solid content 40-50%, after 120 ℃ of oven dry, be crushed to more than 500 orders through filter press, the mineral facies of purifying montmorillonite are formed, referring to Figure 18.

In purifying montmorillonite, the mixing acid (methylsulfonic acid: oxalic acid: the mol ratio of propanedioic acid consists of 40:5:10) that adds concentration 5mol/L, with soil: the mass ratio of acid is that 1:4 mixes, heat was boiled 5-10 hour under 60 ℃ of conditions, removed by filter mixing acid, filter cake with deionized water wash to pH ≧ 4, at 120 ℃ of air dryings, be ground into the 300-500 order, promptly get the modified calcium-base montmorillonite, its abundance or material phase analysis are referring to Figure 19.

Modified calcium-base montmorillonite with gained, be made into the slip of solid content 30% with the hydrochloric acid soln of 0.5N, stir 6h, remove by filter acid solution, filter cake with 60 ℃ of hot washes to PH about about 5, press filtration becomes the filter cake of solid content about 50%, adds the Sodium Fluoride (as the 5-6% of modified calcium-base montmorillonite consumption) suitable with cation exchange capacity, stirs sodium 32h, 110 ℃ of dryings, be ground into the 300-500 order, promptly get modified na-montmorillonite, its abundance or material phase analysis are referring to Figure 20.

With the modified calcium-base montmorillonite of gained, be made into the slip of solid content 20% with the hydrochloric acid soln of 0.5N, stir 6h, remove by filter acid solution, filter cake is about about 5 to PH with 70 ℃ of hot washes, and press filtration becomes the filter cake of solid content about 50%, adds the Sodium Fluoride (as the 3-3.5% of modified calcium-base montmorillonite consumption) with half amount of cation exchange capacity, stir sodium, 32h 120 ℃ of dryings, is ground into the 300-500 order, promptly get modification sodium ca-montmorillonite, its abundance or material phase analysis are referring to Figure 21.

Embodiment 7Modified montmorillonite used electric charge is measured

Available structure of chemical composition analytical method, cation exchange capacity method and straight-chain paraffin base ammonium method are studied charge source, size, the distribution of montmorillonite, in the montmorillonite crystalline structure, aluminium is to the replacement of silicon in the tetrahedral si-o film, the magnesium replacement to aluminium in the aluminum oxide octahedral sheet, and crystal layer is at the scission of link-Si-OH of three-dimensional space fracture generation,-Al-OH makes its interlayer and end face present electronegativity.By measuring its cation exchange capacity, to calculate its carried charge.Measuring method is as follows:

1, the mensuration of interlayer charge

The montmorillonite sample ore through sodium, remove organic the processing after and C ₆-C ₁₈Straight chained alkyl ammonium muriate carries out permutoid reaction, and with the unnecessary alkylammonium muriate of 95% ethanol flush away, vacuum-drying adds SiO ₂Mark is that 2 ° of-30 ° of scopes are measured 001 diffraction locations d with X-ray diffraction method at 2 θ in doing ₀₀₁, draw d ₀₀₁With carbonatoms N _CGraph of a relation, mix the layer functions relational expression at random with MCEwan, calculate individual layer to the double-deck ratio that changes of double-deck transition each point, draw the layer charge density distribution histogram, obtain hemihedral crystal born of the same parents layer charge and distribute and mean value.

2, variable charge density (Eq./(Al.Si) ₄O ₁₀) mensuration

Variable charge claims the end face electric charge again, and its density changes with the pH value is different.With cobalt chloride ammonium ion exchange method, in the pH4-12 scope, measure the cation exchange capacity CEC of different pH, by relation curve between CEC and the pH, again in conjunction with formula LC (Eq./(Al, Si) ₄O ₁₀)=CEC * 360 * 10 ^-5, the unit (mmol/100g) of cation exchange capacity is converted into the (Eq./(Al.Si) of unit of layer charge ₄O ₁₀), LC presentation layer electric density in the formula, CEC represents cation exchange capacity.

The measurement result of modified montmorillonite used layer charge density, variable charge density, total charge density, turgidity, adsorptive capacity and the CEC for preparing according to the open method of the present invention is referring to table 1.

The measurement result of natural montmorillonite of table 1 and modified montmorillonite used physicochemical property parameter

The preparation that embodiment 8 is modified montmorillonite used

The material phase analysis of purifying montmorillonite is referring to Fig. 8.

In purifying montmorillonite, add the mixing acid (be hydrochloric acid: the mol ratio of acetic acid is 10:3) of concentration 3mol/L, with soil: the mass ratio of acid is that 1:3 mixes, under 80 ℃ of conditions, heated 3 hours, remove by filter mixing acid, filter cake with deionized water wash to PH 〉=4,100 ℃ of dryings are ground into the 300-500 order, promptly get the modified calcium-base montmorillonite, its purity is 96.7%, CEC is 106mmol/100g, and turgidity is 6.5, and the modified montmorillonite used adsorptive capacity to the sulfuric acid Strychnine of every 1g is 0.475g.

The modified calcium-base montmorillonite of gained is made into the slip of solid content 25% with the hydrochloric acid soln of 0.5N, stir 3h, remove by filter acid solution, filter cake with 60 ℃ of hot washes to PH about about 5, press filtration becomes the filter cake of solid content about 50%, add the 5-5.5% trisodium phosphate suitable with cation exchange capacity, stirred 30 hours, 120 ℃ of dryings, be ground into the 300-500 order, promptly get modified na-montmorillonite, its purity is 96.7%, CEC is 110mmol/100g, and turgidity is 11.5, and the modified montmorillonite used adsorptive capacity to the sulfuric acid Strychnine of every 1g is 0.491g.

The preparation that embodiment 9 is modified montmorillonite used

The material phase analysis of purifying montmorillonite is referring to Figure 18.

In purifying montmorillonite, add the mixing acid (hydrochloric acid: the mol ratio of acetic acid is 10:4) of concentration 1.5mol/L, with soil: the mass ratio of acid is that 1:4 mixes, under 90 ℃ of conditions, heated 3 hours, remove by filter mixing acid, filter cake with deionized water wash to 4 of PH, 100 ℃ of dryings are ground into the 300-500 order, promptly get the modified calcium-base montmorillonite, its purity is 98.1%, CEC is 95mmol/100g, and turgidity is 5.7, and the modified montmorillonite used adsorptive capacity to the sulfuric acid Strychnine of every 1g is 0.425g.

The modified calcium-base montmorillonite of gained is made into the slip of solid content 30% with the hydrochloric acid soln of 0.3N, stir 3h, remove by filter acid solution, filter cake with 40 ℃ of hot washes to PH about about 5, add the slip that water is made into solid content 10%, add the 7.0-7.5% Trisodium Citrate suitable, stirred 40 hours, through high speed centrifugation with cation exchange capacity, filter press one-tenth contains amount of solid 40-50% and gets filter cake, 120 ℃ of dryings are ground into the 300-500 order, promptly get modified na-montmorillonite, its purity is 98.1%, CEC is 101mmol/100g, and turgidity is 7.5, and the modified montmorillonite used adsorptive capacity to the sulfuric acid Strychnine of every 1g is 0.425g.

Embodiment 10The preparation of nano modification montmorillonite

With purity is 97.1% modified na-montmorillonite and the water proportional arrangement mud by 2:9, through high-speed shearing machine, high speed dispersor or ball mill are forced to shear, after mud is fully disperseed, under 50Mpa and the condition below 40 ℃, carry out the one-level homogeneous, again after carrying out double-stage homogenization under 100Mpa and the condition below 50 ℃, send into hot air drier, 90 ℃ carry out drying after, micronizer mill is crushed to more than 5000 orders, obtaining average particulate diameter is the nano modification na-montmorillonite of 0.6 μ m, CEC is 125mmol/100g, and turgidity is 13.5, and the modified montmorillonite used adsorptive capacity to the sulfuric acid Strychnine of every 1g is 0.546g.

Embodiment 11The preparation of nano modification montmorillonite

With purity is 98.5% modified na-montmorillonite and the water proportional arrangement mud by 1.2:9, through high-speed shearing machine, high speed dispersor or ball mill are forced to shear, after mud is fully disperseed, under 70Mpa and the condition below 40 ℃, carry out the one-level homogeneous, again under 150Mpa and the condition below 60 ℃, after carrying out double-stage homogenization, enter spray-dryer and carry out drying (180 ℃ of inlet temperature, 110 ℃ of temperature of charge) after, micronizer mill is crushed to more than 5000 orders, obtaining average particulate diameter is the nano modification na-montmorillonite of 0.3 μ m, CEC is 128mmol/100g, and turgidity is 15.8, and the modified montmorillonite used adsorptive capacity to the sulfuric acid Strychnine of every 1g is 0.575g.

Embodiment 12The preparation of powder

Modified montmorillonite used 300 mesh sieves of pulverizing of 3000g add 750g glucose, 6g soluble saccharin, 6g vanillin food grade,1000.000000ine mesh, mix 30 minutes, and packing promptly gets modified montmorillonite used powder.

Embodiment 13The preparation of granule

The modified montmorillonite used raw material of 2000g is crossed 300 mesh sieves, add 150g lactose, 300g starch, 5g soluble saccharin, 3g vanillin food grade,1000.000000ine mesh, after mixing 15 minutes, add 2%K4M (K4M is to measure the index of this material viscosity) Vltra tears slurry and mixed 15 minutes, 20 orders are granulated; Wet granular is 65 ℃ of dryings 10 hours, the whole grain of 20 orders, and packing promptly gets modified montmorillonite used granule.

Embodiment 14The preparation of capsule

The modified montmorillonite used raw material of 2000g is crossed 300 mesh sieves, adds 300g Icing Sugar, 100g starch, mix 15 minutes after, add 10% starch slurry and mixed 15 minutes, 20 eye mesh screens are granulated; Wet granular is 65 ℃ of dryings 10 hours, after the whole grain of 20 order nets, particle add 1% Magnesium Stearate uniform mixing, is fills up to Capsules, packing promptly gets modified montmorillonite used capsule.

Embodiment 15The preparation of suspensoid

The modified montmorillonite used raw material of 1000g is crossed 300 mesh sieves, add 250g Icing Sugar, 100g lactose, 10g polyvinylpyrrolidone K30 (K30 is this polymer molecule figureofmerit that draws to measure this polymer viscosity), 20g N.F,USP MANNITOL, after mixing 15 minutes, add 0.5%K4M Vltra tears slurry, mixed 15 minutes, 18 mesh sieves are granulated; Wet granular sprays lemon flavour 65 ℃ of dryings 10 hours, the whole grain of 20 mesh sieves, and packing promptly gets modified montmorillonite used dry suspensoid; Add packing again behind the water mixing, promptly get modified montmorillonite used suspension.

Embodiment 16The preparation of dispersible tablet

The modified montmorillonite used raw material of 3000g is crossed 300 eye mesh screens, add 10g Icing Sugar, 500g pregelatinized Starch, 30g polyvinylpyrrolidone K90 (K90 is this polymer molecule figureofmerit that draws to measure this polymer viscosity), 50g N.F,USP MANNITOL, after mixing 15 minutes, add 0.2%K4M Vltra tears slurry and mixed 15 minutes, 40 mesh sieves are granulated; Wet granular is 65 ℃ of dryings 12 hours, and the whole grain of 40 mesh sieves adds 1% Magnesium Stearate and 3% cross-linked polyvinylpyrrolidone, mixes, and compressing tablet promptly gets modified montmorillonite used dispersible tablet.

Embodiment 17The preparation of effervescent tablet

The modified montmorillonite used raw material of 3000g is crossed 300 mesh sieves, adds 50g glucose, 500g Citric Acid, usp, Anhydrous Powder, 390g lactose, 15g polyvinylpyrrolidone K90,1000g sodium bicarbonate, mix 15 minutes after, compressing tablet is 65 ℃ of dryings 13 hours, promptly.

Embodiment 18The preparation of paste

The heating of 1000g Vaseline is dissolved, and stirs, and slowly adds the modified montmorillonite used and 100g starch of 300 purpose 200g, fully grinds evenly, promptly.

Embodiment 19The preparation of gelifying agent

Get 10g polyvinylpyrrolidone K90,10g Vltra tears in the expansion of 1000g dissolved in distilled water, will cross the modified montmorillonite used slowly adding of 1000g of 300 eye mesh screens then, and mix, promptly.

Embodiment 20The preparation of adhesive type Bismuth Potassium Citrate particulate

Preparation method: take by weighing the Bismuth Potassium Citrate of formula ratio, modified montmorillonite used, starch, vanillin food grade,1000.000000ine mesh mixing, add the Vltra tears aqueous solution and mix thoroughly, granulate, under 65 ℃ of conditions dry 12 hours, make particle, behind the whole grain, the Magnesium Stearate that adds recipe quantity always mixes, and packing promptly.

Embodiment 21The preparation of adhesive type carmofur enteric coated capsule

The preparation method: take by weighing the carmofur of formula ratio, modified montmorillonite used, vanillin food grade,1000.000000ine mesh mixing, total mixing is filled to enteric (colon type) Capsules, promptly.

Embodiment 22Nourishing pack

Constituent mass mark (%) constituent mass mark (%)

Hyaluronate sodium 0.01 modified montmorillonite used 10

Squalane 1.8 sodium alginates 2.0

Glycerine 4.2 methyl p-hydroxybenzoates 0.2

Collagen protein 5 essence (jasmine perfume (or spice)) 0.1

Deionized water adds to 100

Preparation method: mix with deionized water modified montmorillonite used, behind adding glycerine, hyaluronate sodium and the collagen protein, be heated to 70 ℃, stir, make water; With methyl p-hydroxybenzoate, essence, squalane and sodium alginate uniform mixing, be heated to 40 ℃, to dissolving fully, make oil phase; Water and oil phase added in the vacuum tank mix, stir, after the homogeneous degassing, filter, cooling back can, promptly.

Below come to verify modified montmorillonite used reversal therapies effect of the present invention by test of pesticide effectiveness example chronic atrophic gastritis.Modified montmorillonite used or sucralfate are made the suspension liquid of 100mg/ml for examination with deionized water during test.Except as otherwise noted, the present invention tests the dosage standard of example all in the mineral crude drug.

Test example 1Montmorillonite is to the reversal therapies effect of chronic atrophic gastritis

Adopt healthy, sexually matured 8 age in week 120 of male SD rats, mean body weight 250g ± 50g adopts posture to raise in cages, 24 ± 2 ℃ of raising temperatures, humidity 55 ± 5%, per 12 hours light and shades of illumination are alternately fed with mixed fodder.

The comprehensive employing 60% alcohol, 20mmol/l sodium deoxycholate and 24 weeks of 0.1% ammonia treatment set up the CAG model according to the Si Shi modeling.Be to irritate stomach 20mmol/1 sodium deoxycholate every day, wherein on every Tuesdays, five irritate stomach (on every Mondays, four took feed away at late 9 o'clock, begin to irritate on an empty stomach stomach during m seq 9) on an empty stomach, dosage is as follows: rat body weight＜200g irritates stomach 1mL at every turn; Rat body weight 200～250g irritates stomach 1.5mL at every turn; Rat body weight〉250g irritates stomach 2mL at every turn.60% alcohol on every Tuesdays, five irritate on an empty stomach stomach, condition and the same sodium deoxycholate of dosage on an empty stomach; And freely drink 0.1% ammoniacal liquor, and record drink amount every day.The conventional raising slaughtered in 24 weeks.

120 SD rats are divided into 12 groups, 10 every group, are set to normal group, CAG group, NS group, sucralfate group, smectite in treatment group respectively and (comprise 2 natural smectite in treatment groups, be numbered MontE and MontF group; 4 modified calcium-base smectite in treatment groups are numbered MontA to MontD and organize; 1 modified na-montmorillonite treatment group is numbered MontG; 1 modification sodium ca-montmorillonite treatment group is numbered MontH).

Normal control group (normal group), after promptly mouse CAG became mould, the conventional raising slaughtered to the 24th weekend; Placebo group (physiological saline group, NS group) after promptly mouse CAG becomes mould, stops to stimulate and giving physiological saline, irritates stomach every day once, slaughters to the 28th weekend; Carafate for treating group (sucralfate group) after mouse CAG becomes mould, stops stimulation and gives sucralfate suspension liquid (100mg/mL) filling stomach, rat body weight＜200g irritates stomach 1mL//time, the rat administration 1.5ml/ of body weight 200-250g/time at every turn, rat body weight〉rat of 250g, administration 2ml/ only/time; Smectite in treatment group, dosage regimen, stop to stimulate also and irritate the suspension liquid (100mg/mL) that stomach gives montmorillonite every day after promptly mouse CAG becomes mould with the sucralfate group, and rat body weight＜200g irritates stomach 1mL//time at every turn; The rat administration 1.5ml/ of body weight 200-250g/time; Rat body weight〉rat of 250g, administration 2ml/ only/time, slaughter to the 28th weekend.

Can't help water after 24 hours in fasting, give 1% Sodital (40mg/kg) intraperitoneal anesthesia fixing after, cutting open the belly immediately exposes full stomach, takes out full stomach at distance orifice of the stomach and pylorus 1.5cm place from disconnected, cuts off along greater gastric curvature, ices normal saline flushing, spreads out after filter paper blots; The 1/2 usefulness slide glass of getting stomach hole portion is scraped and is got stomach mucous membrane, liquid nitrogen freezing ,-70 ℃ of preservations.Surplus stomach mucous membrane sample is liquid-solid fixed with 10% neutral formalin, and the greatly curved side slat shape in edge is drawn materials, conventional dehydration, and paraffin embedding, 5 μ m thickness serial section are copied to preventing on the slide glass of flake processing with poly-l-lysine, carry out Hematorylin-Yihong (HE) dyeing.

The observation and the result thereof of sample histopathology index:

1) the stomach lining inflammation situation is observed: adopt semiquantitative method, under low power lens, observe whole mucosa, observe 10 visuals field respectively in stomach hole portion and body of stomach for every, with reference to the gastritis Case definition in the houston, u.s.a proposition in 1994, the degree of cell infiltration is divided into 0,0.5,1.0,1.5,2.0,2.5,3.0 7 rank, write down the inflammation situation in 10 visuals field respectively in order to last method, the average inflammation index that obtains later every rat stomach body and stomach hole portion.

2) stomach mucous membrane body of gland layer thickness (L1) and muscular layer of mucosa thickness (L2) and ratio (L1/L2 ratio) thereof are observed: by the micrometer of microscopically, get 5 high power fields at hole, the body of every HE stained, calculate the mean of each mucomembranous gland layer and flesh layer thickness, compare with average simultaneously and obtain L1/L2.

3) observation of stomach mucous membrane body of gland density: on every PE stained apart between pyloric ring, glandular stomach and glandular stomach intersection 200-1200 μ m, utilize the microscopically micrometer, measure the intrinsic body of gland number of mucous membrane under the certain-length, thereby obtain the intrinsic body of gland density of mucous membrane (unit is individual/μ m) of stomach hole portion and body of stomach.

4) simultaneously every PE stained is noted observing the generation that has or not intestinal epithelial metaplasia, false pylorus glandular metaplasia, atypical hyperplasia, adenoma, carcinoid, gland cancer.

Obtain sample biochemical indicator and measuring method thereof:

1) mensuration of hexosamine: in frozen stomach mucous membrane, add ultrasonic homogenate after 500ul1 * PBS damping fluid, 4 ℃ of centrifugal (3000r/min, 5min), get supernatant, measure the absolute concentration of hexosamine with the Neuhaus method, and according to formula, hexosamine is proofreaied and correct content (mg/g albumen)=homogenate supernatant liquor hexosamine concentration (mg/L)/protein concentration (g/L), calculates hexosamine content.

2) the DC Protein Assay reagent that adopts Bio-Rad company to provide is measured protein.

3) PGE ₂(PGE ₂) mensuration: get the frozen mucosa tissue of part, add 500 μ l Krebs liquid and (add indomethacin in advance, to prevent PGE in the operating process ₂Release) ,-4 ℃ centrifugal, and (2000r/min 5min) gets supernatant, presses measured by radioimmunoassay PGE ₂, concentration represents with pg/ml, according to formula, and PGE ₂Proofread and correct content (pg/mg albumen)=homogenate supernatant liquor PGE ₂Concentration (pg/ml)/protein concentration (mg/ml) is calculated PGE ₂Content.

Test-results adopts the variance analysis method (One-Way ANOVA) of completely random design data to analyze, and uses the SPSS11.0 statistical software and assists statistics.

The present invention adopts the CAG model of Si Shi manufactured SD rat, has observed natural montmorillonite, the modified montmorillonite used and sucralfate reversal therapies effect to SD rat chronic atrophic gastritis.And by observing gastric mucosa of rat morphological change and mensuration gastric mucosa of rat biochemical indicator (hexosamine, PGE under the light microscopic ₂) level, the comparative studies medicine is to the reversal therapies effect of rat CAG model.

Result of study shows, through a treatment in month of montmorillonite of the present invention, the color of the mental status of SD rat, mobility, hair and gloss all have to a certain degree improvement latter stage than modeling; The stomach-tissue gross examination of skeletal muscle, visible mucous membrane color and luster is pink, the more mucus that is covered, mucosal surface is smooth, and pleat is walked line discipline, and general overall feeling has clear improvement than model control group; In the visible stomach hole of microscopically portion mucomembranous gland marshalling, gastric pit is clear, and inflammatory cell infiltration is few, and is congested, oedema is all not obvious.The measurement result of every quantitative target is as follows:

1, testing the influence of respectively organizing antrum layer thickness level can be referring to Figure 22.As seen, the stomach hole portion mucous layer thickness of smectite in treatment group is significantly higher than carafate for treating group (P＜0.01), particularly MontG treatment group and is higher than other montmorillonite group treatment groups (P＜0.01) very significantly, has reached normal control group level; The other treatment group still is lower than normal control group (P＜0.01) very significantly.

2. each group of test is to stomach hole portion mucous layer thickness/muscular layer of mucosa thickness (L1/L2) ratios affect can be referring to Figure 23.As seen, the L1/L2 ratio of CAG model control group significantly is lower than other each groups; The normal control group is significantly higher than other each groups; Property that there were significant differences between placebo and the carafate for treating group (P＜0.05); Smectite in treatment group highly significant is higher than CAG model control group and placebo (P＜0.01), and wherein MontG treatment group is higher than other montmorillonite group treatment groups (P＜0.01) very significantly.

3. (individual/mm) influence as shown in figure 24 to rat stomach hole portion mucomembranous gland density for each group of test.As seen, CAG model control group, placebo and carafate for treating group do not have significant difference each other, and three groups all significantly are lower than the normal control group; The smectite in treatment group is higher than CAG model control group, placebo and carafate for treating group significantly, and the MontG group is significantly higher than other smectite in treatment groups (P＜0.05).

Each group of test to the influence of antrum inflammation index level referring to Figure 25.The result shows that aspect rat stomach hole portion mucosal inflammation index, the smectite in treatment group significantly is lighter than CAG model control group and placebo; MontA group significantly is lighter than carafate for treating group (P＜0.05) with the MontG group, and and the normal control group between do not have significant difference (P〉0.05).

In addition, each group of test to the result that influences of body of stomach mucous membrane is: CAG control rats body of stomach is observed, the feature of the visible atrophic gastritis of mucomembranous gland, body of gland capsule sample has the expansion phenomenon, muscular layer of mucosa thickens, and between the dendritic insertion body of gland of proper mucous membrane composition, inflammation degree and stomach hole category are seemingly.The inflammation situation of placebo, carafate for treating group and the body of stomach of smectite in treatment group is compared with the CAG model control group, slightly take a favorable turn or take a turn for the better, all samples are not found phenomenons such as intestinal epithelial metaplasia, false pylorus glandular metaplasia, atypical hyperplasia, adenoma, carcinoid, gland cancer simultaneously.

Each group of test to the influence of stomach mucous membrane hexosamine level referring to Figure 26.As seen, aspect stomach mucous membrane hexosamine content, CAG model control group, placebo and carafate for treating group three do not have significant difference (P〉0.05) each other; The horizontal highly significant of stomach mucous membrane hexosamine of montmorillonite group rat is higher than other moduli groups (P＜0.01), and wherein the MontG group is significantly higher than other montmorillonite groups (P＜0.05), and highly significant is higher than montmorillonite F group.

6. each group of test is to stomach mucous membrane PGE ₂The influence of level as shown in figure 27.The result shows, the stomach mucous membrane PGE of smectite in treatment group rat ₂Level is higher than CAG model control group and carafate for treating group significantly, and MontG group highly significant is higher than montmorillonite F group (P＜0.01).

Conclusion: the CAG rat model is after the filling stomach treatment through a month montmorillonite, the atrophy of SD rat stomach hole portion mucous membrane and inflammation situation all have significant improvement than CAG group and placebo, simultaneously aspect the defence of mucous membrane and the synthesis capability significant recovery is being arranged all, show that the CAG rat model that montmorillonite is set up for the Si Shi method has the reversal therapies effect, and the precognition modified na-montmorillonite is to the reversal therapies more remarkable effect of chronic atrophic gastritis.

Than the smectite in treatment group, though the carafate for treating group has significant improvement than the CAG group on the indexs such as mucous membrane L1/L2 ratio, inflammation index and mucous membrane hexosamine content of mucous layer thickness (P＜0.01), mucous membrane L1/L2 ratio, inflammation index and the body of stomach of stomach hole portion, but only on stomach hole portion mucous layer thickness, be higher than placebo (P＜0.01) very significantly, and the montmorillonite group particularly the modified na-montmorillonite group at stomach hole portion mucous layer thickness, mucous membrane hexosamine content and mucous membrane PGE ₂Etc. the aspect, all be better than the sucralfate group very significantly.As seen, sucralfate has the mucous membrane protection effect to the CAG rat model, but does not have significant reversal therapies effect; And montmorillonite has significant reversal therapies effect to the CAG rat model, and modified montmorillonite used particularly modified na-montmorillonite is more more remarkable than natural montmorillonite to the reversal therapies effect of chronic atrophic gastritis.

Montmorillonite of the present invention is as follows to the reversal therapies mechanism of chronic atrophic gastritis:

(1) by between electric charge attract each other and with original mucous interaction, formed the gel protective layer that is covered in mucomembranous surface, promote the reparation of impaired mucous membrane.After montmorillonite was met water, by intergranular osmotic swelling and interlayer aquation, particles dispersed was peeled off between the lamination, and electronegative aspect and end face interact, and crosslinked association forms the aquation gel.These aquation gels remove significant adhesivity, can also combine with the mucus in the digestive tube, significantly strengthen mucous force of cohesion and visco-elasticity, be covered in the mucomembranous surface of damage securely, under the electrically charged constant situation of surface of a wound institute, this physical action intensity and montmorillonite gelling electronegative quantity be proportionate.And there are some researches show that montmorillonite reaches 93nm at the protection bed thickness that gastric mucosa surface forms, and can continue more than 6 hours.

Sucralfate is the alkaline aluminium salt of sucrose sulfuric ester, and is water-soluble hardly, but in pH＜4 o'clock, some Al ₂(OH) ₅ ⁺Dissociate out from sucrose eight sulfuric acid molecules, remaining mixture is electronegative, and aggregates into the gel-shaped material; attach to epithelial cell and damaged gastric mucosa surface securely; reach the protection stomach mucous membrane purpose, be a kind of medicine that depends on sour environment, thus can not with H ₂Receptor antagonist; proton pump inhibitors etc. suppress the drug combination of stomach inner acidic environment; and CAG patient's gastric acid secretion is obviously lowered; it secretes the atrophy of acid function with the gastric gland body; increasing the weight of of intestinesization and reducing; and CAG patient's stomach inner pH value usually can not reach the onset requirement of sucralfate; sucralfate only forms a kind of muddy liquid and is covered in gastric mucosa surface at this moment; interact between shortage and impaired mucous membrane and original mucus; be difficult to reach the effect of protection mucous membrane; by contrast; the electronegativity of montmorillonite aspect with become colloidality not to be subjected to the influence of environment pH value substantially; therefore, montmorillonite is more strong and lasting than sucralfate for the provide protection of CAG patient's stomach mucous membrane.And the powerful provide protection of montmorillonite gelling; can stop the coup injury of objectionable impuritiess such as hydrochloric acid in gastric juice, stomach en-, cholate and ethanol well to mucomembranous cell; for the gastric mucosal cell (especially stem cell) that is badly damaged and becomes very fragile provides the environment of stable safety, thereby created favourable condition for the regeneration of mucous membrane.

(2) absorption " being harmful to " material weakens their invasion and attack, damage stomach mucous membrane ability.The physical structure of montmorillonite uniqueness makes it have the not available cation exch ange adsorption ability of general gastric mucosa protectant; in stomach, can be adsorbed onto the surface to some organic cation (comprising ethanol, stomach en-, scleroproein segment, cholate etc.); finally secure it to interlayer; form montmorillonite-organic complex; to reduce of the direct injury of these deleterious aggressive materials, reached the effect of protection stomach mucous membrane from another aspect to stomach mucous membrane.This ion exchange of montmorillonite is subjected to the influence of its interlayer cation exchange capacity and various steric requirementss, and ion exchange and layer charge density are proportional, therefore, under other condition fixed prerequisites, the ion-exchange capacity of the montmorillonite that layer charge density is big is strong.

(3) interaction between microcosmic charging property and impaired mucous membrane improves its metabolic environment, promotes the synthetic and excretory effect of Saliva Orthana.

Test example 2Modified montmorillonite used effects of relieving alcoholism and protecting liver

Low alcohol consumption can promote metabolism, plays the effect of relaxing the muscles and stimulate the blood circulation, and can improve a poor appetite Ginseng Extract; But symptoms such as the excessive drinking meeting causes chronic alcoholism, mucosa injury, cardiac muscle is weak, blood vessel becomes fragile, the reduction of the defense function of respiratory system, renal failure, systems such as human consumption, nerve, circulation are caused serious harm, also can decrease internal organs, consumption qi and blood, cause the body physiological function disorder, the serious harm HUMAN HEALTH.The present invention is by irritating after drinking, and alcohol concn in observation different time sections mouse stomach, the intestinal contents and blood determining alcohol change studies modified montmorillonite used relieve the effect of alcohol effect and Antialcoholic liver-protecting mechanism thereof.

40 of the healthy male ICR kind mouse of body weight 25 ± 2g are divided into control group and treatment group at random, and control group is irritated stomach and given physiological saline, and treatment group filling stomach gives of the present invention modified montmorillonite used, is divided into 4 groups with every group at random by different time again, 5 of every groups.

Water is prohibited in the mouse fasting to spend the night, next day, irritate stomach by 0.10ml/25g mouse heavy prescription amount and give modified montmorillonite used suspension liquid of the present invention and 0.9% physiological saline, behind the 30min, irritate stomach by 0.15ml/25g mouse heavy prescription amount and give 56 ° of liquor, irritate after drinking, successively in 30,60,90,180min is from the about 1ml of eye socket blood sampling of each group, with gained blood sample 12000r/min centrifugation, get serum 200 μ l in the 1.5ml centrifuge tube, add people's methyl alcohol 1 μ l, 20% monochloroacetic acid solution respectively, mixing, the centrifugal 10min of 4000r/min gets supernatant liquor, freezing preservation.

With alcohol concn in the gas chromatograph test sample, the results are shown in Table 2.

Ethanol content measurement result (mg/ml) in the table 2 mouse blood

After drinking the time (minute)	The montmorillonite group (X ± S)	Control group (X ± S)	The P value
After drinking the time (minute)	The montmorillonite group (X ± S)	Control group (X ± S)	The P value	30	6.356±0.986	12.067±0 .886	<0.001
60	8.183±2.175	19.754±3 .602	<0.001	30	6.356±0.986	12.067±0 .886	<0.001
60	8.183±2.175	19.754±3 .602	<0.001	90	10.014±1.343	20.843±1 .897	<0.001
180	9.548±1.857	10.958±2 .012	>0.05	90	10.014±1.343	20.843±1 .897	<0.001

Test-results shows: mouse stomach is given after drinking in the 30min-180min, montmorillonite different time sections ethanol is absorbed and metabolism all influential, 4 time of administration group ethanol in blood concentration all significantly is lower than control group (P＜0.01); And the ethanol in blood measured value also shows as the administration group and descends significantly than control group.

Modified montmorillonite used effects of relieving alcoholism and protecting liver is based on its distinctive synusia structure; inhomogeneous charge distribution and slip visco-plasticity; can evenly cover the digestive tube surface continuously; with static and materialization effect performance curative effect; effectively suppress; delay and reduce ethanol in gastral absorption; effectively slow down and hinder ethanol and enter intravital speed and concentration; and by absorption; the metabolism and the drainage of parcel accelerating alcohol; strengthen ethanol at GI first pass effect; effectively reduce ethanol in vivo accumulate concentration; has good anti-intoxication and sober-up function; and can effectively protect gastrointestinal wall; reduce stimulation and the damage of ethanol, reduce the amount of bleeding of gastrointestinal wall, obviously reduce ethanol stomach and intestine to gastrointestinal wall; the harm of organs such as liver; and have good mucous membrane protection and mucous membrane repair, can be used as the medicine of treatment mucosa injury and Antialcoholic liver-protecting.

Test example 3Modified montmorillonite used to hyperthyroid prevention and treatment

Modified montmorillonite usedly be: after the containing thyroxinic bile and enter in the enteron aisle of hepatic secretion, be absorbed into blood again, constitute enterohepatic circulation by small intestinal mucosa to the hyperthyroid principle of preventing and treating.When the free thyroxine in the bile in enteron aisle, contacted by montmorillonite and the absorption of trying to be the first after, to no longer be absorbed by small intestinal mucosa, and discharge with digestive tube self wriggling, gradually reduce the thyroxine of reuptaking into blood, to reduce the thyroxine concentration in the circulation of body inner blood, reached the purpose of prevention with the treatment hyperthyroidism.

48 of hyperthyroidism small white mouses, be divided into high dose group (3g/kg), middle dosage group (1.5g/kg), low dose group (0.75g/kg) and control group, every group 12, irritate stomach and give modified montmorillonite used and respective amount physiological saline of the present invention, once a day, continuous 7 days, compare with control group, but significant prolongation hyperthyroidism small white mouse hypoxia endurance time, and can make the body weight of hyperthyroidism small white mouse be tending towards normal.

48 of hyperthyroidism big white mouse, be divided into high dose group (4g/kg), middle dosage group (2g/kg), low dose group (1g/kg) and control group, every group 12, irritate stomach and give modified montmorillonite used and respective amount physiological saline of the present invention, every day secondary, continuous 14 days, to compare with control group, each administration group highly significant reduces TT in the hyperthyroidism rat serum ₃, TT ₄, FT ₃And FT ₄Content, in, significantly the raise effect of thyrotropin (TSH) of low dose group, high, middle dosage group significantly reduces hyperthyroidism big white mouse body temperature, and can make the body weight of hyperthyroidism big white mouse be tending towards normal.

The result proves: modified montmorillonite used have remarkable influence to the relevant hypoxia tolerance of main pharmacodynamics, Triiodothyronine and thyrotropin (TSH), is beneficial to the control of hyperthyroidism.

Test example 4Modified montmorillonite used therapeutic action to chronic renal failure

Modified montmorillonite used treatment principle to chronic renal failure is: the protein,split blood urea nitrogen (BUN) that excretes via kidney, potassium ion etc. can not be discharged via chronic renal failure patient's kidney, pile up the excessive toxin that becomes in vivo, and form hyperpotassemia etc.Behind the oral intestinal canal sorbent material (as modified montmorillonite used); based on montmorillonite the digestion mucous membrane had very strong covering protection ability; repair, improve of the defence of mucous membrane barrier to attack factor; in enteron aisle, disperse and be attached to the intestinal mucosa surface; cause the change of intestinal mucosa surface seepage pressure reduction; make the interior toxin of intestinal mucosa, potassium ion etc. be adsorbed, dialyse out; and together excrete with intestinal contents; reach the intestinal dialysis effect, and the intestinal bleeding that the acute kidney merit declines is had the hemostasis and pain-relieving effect.

Through clinical diagnosis, the 36 routine chronic renal merits that the cause of disease, the state of an illness is the similar substantially patient's randomized, double-blind that declines is divided into treatment and organizes 20 examples and control group 16 examples.On the depleted conventional treatment of chronic renal merit basis, comprise treatment protopathy, hemodialysis, correction water, ionogen and acid base imbalance, keep nutrition of whole body etc., in the hemodialysis interval, oral montmorillonite of the present invention is organized in treatment, control group Orally active charcoal, beginning in second day is to hemodialysis next time the day before yesterday after the hemodialysis; With administration in 2-3 hour after meal, one time 3 gram of being grown up, three times on the one (8 hours 1 time).

The result shows: compare with control group, treatment group patient's plasma urea nitrogen (BUN) concentration level descends, and carbon dioxide combining power rises to some extent, shows dialysis curative effect in certain enteron aisle, analyzes by statistics, and two groups are not had significant difference.

In addition, the calamine lotion that is made into 2% montmorillonite is coated with puts the chronic renal merit skin of lower extremity that declines on the skin, its skin pruritus had tangible itching-relieving action, because of the depleted patient's of chronic renal merit skin of lower extremity has the accumulation of blood urea nitrogen to cause skin pruritus, montmorillonite adsorbs blood urea nitrogen (BUN) by skin to be played through the skin Dialysis.In addition, montmorillonite is used for medical ointment, can form film at skin surface, and antipruritic agent is had synergism.

Test example 5Modified montmorillonite used preventive and therapeutic effect to halitosis

Glycolysis, corruption, the alteration of intestinal flora of food in digestive tube, the excessive multiplication of aerogen and mass mortality, each internal organs chronic wasting disease of whole body, inflammation and digestive ferment shortage not of the same race, meta-bolites accumulation etc. all produce relevant through oral cavity exhalation gas with foreign flavor with digestive tube.Montmorillonite is as sorbent material efficiently, and adsorbable glycolysis, putrescible food and cover the aerogen surface adsorb the gas that produces in the digestive tube simultaneously, and changes the character that the oral cavity produces gas by ion-exchange, reach covering, filtration and deodorization.

The oral cavity does not have the exhalation foul gas, 20 of every biochemical indicator normal adults, and 10 of separating tests groups and control group are 10 at random, and food is received and is mixed living garlic 15-20 grams (3 lobe) of meal, at the 20th minute after the meal, the test group 3 gram montmorillonites of taking after mixing it with water, control group is taken orange juice; Compare with control group in 20 minutes in medication, simultaneously same people is subjective, and the sense of smell result is: the pernicious quantity of stimulus that exhalation garlic in test group oral cavity is hidden foul smell obviously alleviates, and control group is invalid.

Breathe out and produce 24 of the patients of foul gas by digestive tube in the oral cavity, 12 of separating tests groups and control group are 12 at random, work the back of gargling (avoiding the assorted bacterium in oral cavity to disturb) in morning, the test group 3 gram montmorillonites of taking after mixing it with water, and control group is taken orange juice; Compare with control group in 20 minutes in medication, simultaneously same people is subjective, and the sense of smell result is: the pernicious quantity of stimulus of test group oral cavity exhalation foul smell obviously alleviates, and control group is invalid.

Abundant, inexpensive, the safety non-toxic in montmorillonite of the present invention source, pharmacological action is strong, has very strong adsorption function, all types of virulence factors in the oral adsorbable digestive tube, strong as free thyroxine, blood urea nitrogen (BUN), potassium ion, oral cavity exhalation gas with foreign flavor and its adhesive property, be difficult for desorb, will discharge with digestive tube self wriggling together with adsorbed, fixed virulence factor, reach covering, filtration and deodorization, be cause of disease scavenging agent in the digestive tube of safety.

Test example 6Montmorillonite is to the external adsorption experiment of helicobacter pylori

1, to cultivate agar, contain PXB 5mg/l, amphotericin 2mg/l, vancomycin 10mg/l, TMP5mg/l, 1% W-Gum, 0.2% medicinal carbon powder, 5% fresh yolk makes the HP solid medium.

2, the 300g Pigs Hearts adds water 500ml, and soaked overnight is got supernatant liquor and boiled, and adds peptone 10g, and 5g NaCl adds water to 500ml, makes the heart and soaks basic meat soup; Scrape and get the about 50g of fresh pig stomach inwall slime layer, place 500ml distilled water, 100 ℃ of water-baths are dissolved, are filtered, protein quantification, and the 4 ℃ of refrigerations of sterilizing are standby, make Saliva Orthana solution.

The heart soaks in the basic meat soup and adds Saliva Orthana, and making its final concentration is 0.20%, is packed as the 16ml/ bottle, and 110 ℃ * 20min autoclaving is standby; Take by weighing Sodium.alpha.-ketopropionate, each 1g of ferrous sulfate, be dissolved in respectively in the 20ml water,, make its 5.0% solution through the degerming of 0.2um filter membrane; Draw 5.0% solution of 100ul Sodium.alpha.-ketopropionate, ferrous sulfate respectively, join in the 16ml substratum, add the 4ml horse serum again, behind the uniform mixing, add the microbiotic such as vancomycin that store concentration, make its ultimate density be: vancomycin 10mg/l, amphotericin B 5mg/l, Polymyxin B2 500IU/l makes the liquid nutrient medium of HP.

3, under the aseptic condition, prepare blank simulated gastric fluid, modified montmorillonite used (cation exchange capacity 120mmol/100 gram) simulated gastric fluid of 4%, 4% natural montmorillonite (cation exchange capacity 80mmol/100 gram) simulated gastric fluid and 4% mica (cation exchange capacity is 0) simulated gastric fluid.

4, HP is inoculated on the solid medium, cultivates 3-7d under 37 ℃ of conditions; An amount of HP bacterium colony of aseptic inoculation ring picking is inoculated in the liquid nutrient medium, at 37 ℃, 5%CO ₂After cultivating 2h; Cover tight bottleneck, place (37 ℃ 140-150r/min) are cultivated 48-72h on the constant temperature oscillator; Centrifugal, get supernatant liquor, equivalent adds blank simulated gastric fluid, 4% modified montmorillonite used simulated gastric fluid, 4% natural montmorillonite simulated gastric fluid and 4% mica simulated gastric fluid respectively, stirs 2h down at 37 ℃, the bacterial concentration in 30 minutes take a sample the observation substratum.The results are shown in Table 3:

The modified montmorillonite used external adsorption of table 3 (concentration is Cfu/ml) to helicobacter pylori

	0min	30min	60mi n	90mi n	120m in
	0min	30min	60mi n	90mi n	120m in	Blank	2.0×10 ⁵	2.0×10 ⁵	2.1×1 0 ⁵	2.1×1 0 ⁶	2.3×1 0 ⁵
Modified montmorillonite used	2.0×10 ⁵	7×10 ⁴	4×10 ⁴	2.8×1 0 ⁴	1×10 ⁴	Blank	2.0×10 ⁵	2.0×10 ⁵	2.1×1 0 ⁵	2.1×1 0 ⁶	2.3×1 0 ⁵
Modified montmorillonite used	2.0×10 ⁵	7×10 ⁴	4×10 ⁴	2.8×1 0 ⁴	1×10 ⁴	Natural montmorillonite	2.0×10 ⁵	1.1×10 ⁵	9×10 ⁴	6×10 ⁴	5×10 ⁴
Mica	2.0×10 ⁵	1.9×10 ⁵	1.8×1 0 ⁵	1.6×1 0 ⁵	1.6×1 0 ⁵	Natural montmorillonite	2.0×10 ⁵	1.1×10 ⁵	9×10 ⁴	6×10 ⁴	5×10 ⁴

The result shows: modified montmorillonite used adsorption rate to the helicobacter pylori in the simulated gastric fluid reaches 95.0%, the adsorption rate of natural montmorillonite is 75.3%, the micaceous adsorption rate is 30%, there are notable difference in montmorillonite and mica to the adsorptive power of helicobacter pylori, and modified montmorillonite usedly obviously are better than natural montmorillonite.

The dioctahedron clay of laminar silicate mineral that natural montmorillonite is made up of silicon-oxy tetrahedron and alumina octahedral, aluminium and magnesium replace the charge unbalance cause at random to silicon in the structure and aluminium, give it and meet the distinctive expansion of water, absorption, charged and ion exchange property.The montmorillonite of hydration swelling is that electronegative plate surface is connected with the edge of positively charged, be referred to as " compartment " the formula suspended substance at " a surperficial edge ", " thixotropy " with " gel one so-gel ", and " compartment " formula suspended particle is beneficial to helicobacter pylori locked onto in " compartment " and is removed.Montmorillonite after modification is handled, the laminated thickness attenuation, the end face electric charge increases, and has more " compartment " formula structure, and specific surface area significantly increases, thereby significantly strengthens the removing ability to bacterium such as helicobacter pylori and toxin.And the micaceous layer charge density is zero, and several nothings are disperseed the ability of delaminating, and laminated thickness is big, lacks the suspended particle of " compartment " formula structure, is unfavorable for absorption and removes HP.

Test example 7Modified montmorillonite used preventive and therapeutic effect research to acute impaired gastrointestinal mucosal

With purity is after 98% modified montmorillonite used, natural montmorillonite and mica are pulverized, to cross 400 mesh sieves.

80 of the SD healthy rats of body weight 187 ± 16g, ♀

Half and half, be divided into 8 groups at random, be respectively each 1 group of normal control, model contrast, each 3 groups of chemoprophylaxis and pharmacological agenies.

After the rat fasting 24 hours, by the difference of each big group of test objective, do following processing: the 1st group is the normal control group; The 2nd group is model group, and 1.0mL/ only irritates stomach and gives 0.9% NaCl once, only irritates stomach with dehydrated alcohol 5.0mL/kg/ behind the 3h; The chemoprophylaxis group is divided into 3 groups, irritates stomach respectively and only gives modified montmorillonite used, natural montmorillonite, each 0.15g/kg/ of mica sample, only irritates stomach with dehydrated alcohol 5.0mL/kg/ behind the administration 3h, and anesthesia (10.1mg/mL vetanarcol 1.0mL) is put to death behind the 1h; Medication therapy groups is divided into 3 groups, after stomach 1h only irritates with dehydrated alcohol 5.0mL/kg/ in elder generation, irritates stomach respectively and only gives modified montmorillonite used, natural montmorillonite, each 0.15g/kg/ of mica sample, and anesthesia (10.1mg/mL vetanarcol 1.0mL) is put to death behind the 3h.In the whole experiment, experimental animal is all normally drunk water, and after the execution, scrapes and gets gastric mucus postposition-18 ℃ refrigeration, after the lyophilize, weigh, and 4mol/L hydrochloric acid 2.0mL, the 4h that refluxes in the boiling water bath, deionized water is filtered to 5mL.

Adopt the hexosamine in the Neuhaus method mensuration gastric mucus: accurately draw and organize filtrate 1.0ml, add 1 0.5% phenolphthalein spirituous solution, 4mol/L NaOH dropwise is added to solution and reddens, and dropwise adds 0.5mol/L HCl again and disappears to solution is red.Add methyl ethyl diketone 1.0mL, airtight heating 20min in the boiling water bath, the cold water cooling adds dehydrated alcohol 2.5mL.Add Ehrlich reagent 1.0mL, CO is driven away in vibration gently ₂Move to behind the 1h in the 10mL volumetric flask, add dehydrated alcohol to 10mL scale place.The place measures its absorbancy at the 530nm wavelength.Blank pipe is with deionized water band sample, and treating processes is the same.According to the typical curve of hexosamine solution (1,2,5,7,10 μ g/mL), the hexosamine content in the determination test animal gastric mucus.Data are represented with x ± s, relatively check with t between group.The results are shown in Table 4:

The modified montmorillonite used preventive and therapeutic effect research of table 4 to acute impaired gastrointestinal mucosal

The result shows: layer silicate clay mineral mica, natural montmorillonite, modified montmorillonite used to the damage mucous membrane with do not damage the obvious difference that acts between mucous membrane, and modified montmorillonite used repair to the damage mucous membrane is significantly because natural montmorillonite.The charging property of montmorillonite and the interchangeability of interlayer cation are given it and are had the dual-use function that strengthens mucosal barrier and absorption invasion and attack mucous membrane; and electrical and the impaired mucomembranous cell interphase interaction of montmorillonite gelling microcosmic; improve the metabolic environment of impaired mucous membrane; and the ethanol molecule of low-pole, other stomach en-s, bile, pancreatic juice etc. of attacking stomach mucous membrane are adsorbed to interlayer, promoted the reparation and the protection stomach mucous membrane of impaired mucous membrane.The mica that layer charge is almost nil does not have the function of repairing the damage mucomembranous cell.

Test example 8Modified montmorillonite used provide protection research to acute impaired gastrointestinal mucosal volume of blood flow

Purity is after 98% modified montmorillonite used and mica is pulverized, to cross 400 mesh sieves.

40 of the SD healthy rats of body weight 190 ± 15g,

Half and half, be divided into 4 groups at random, be respectively normal control, model contrast, modified montmorillonite used prevention and mica prevention group.After the rat fasting 24 hours, model group is only irritated stomach once with 0.9%NaCl1.0mL/, only irritates stomach with dehydrated alcohol 5.0mL/kg/ behind the 3h, anaesthetizes with vetanarcol behind the 1h; The chemoprophylaxis group is only irritated stomach respectively by 0.15g/kg/ and is given modified montmorillonite used and mica, only irritates stomach with dehydrated alcohol 5.0mL/kg/ behind the administration 3h, anaesthetizes with vetanarcol behind the 1h.Xiphoid-process center is down cut off stomach wall, exposes the mouse stomach, and passivity is separated, and keeps the integrity of stomach supply of blood flow, cuts off the mouse stomach in skin stomach end, inserts the probe of mucosal blood flow instrument, measures greater gastric curvature mucosal blood flow value.The results are shown in Table 5:

The modified montmorillonite used influence of table 5 (mv) to the greater gastric curvature gastric mucosal blood flow

	Gastric mucosal blood flow (GMBF)
	Gastric mucosal blood flow (GMBF)	Normal control	56.02±5.12
The model contrast	32.71±5.96	Normal control	56.02±5.12
The model contrast	32.71±5.96	Mica	39.37±3.36
Modified montmorillonite used	56.41±3.15	Mica	39.37±3.36

The result shows: the interchangeability of modified montmorillonite used charging property and interlayer cation is given it and is had the dual-use function that strengthens mucosal barrier and absorption invasion and attack mucous membrane, can obviously increase mucosal blood flow, is beneficial to the reparation and the protection stomach mucous membrane of damage mucous membrane.And gastric mucosal blood flow not only is mucomembranous cell supply nutritive substance and oxygen, and can take away H in the tissue ⁺, and transport to mucomembranous surface, to regulate intracellular acid base equilibrium.And the almost nil mica of layer charge, several no mucosal blood flow improvement effects.

Test example 9The slow releasing function research of adhesive type bismuth citrate potassium tablets

8 of the Beagle dogs of body weight 9～10kg, in 11～December of monthly age, male and female half and half are divided into control group and test group, 4 every group.Control group is irritated stomach and is given Bismuth Potassium Citrate capsule (every contains the 55mg bismuth), and test group is irritated stomach and given the modified montmorillonite used Bismuth Potassium Citrate adhesive tablet (every contains the 55mg bismuth) that embodiment 12 prepares, and test dose is counted 11mg/kg with bismuth.After two weeks, two treated animals exchange medicine, two weeks again.

Fasting 12h before the experiment, 1,2,3,4,5,6,9,12,24,48,72, the 96h 3ml that respectively takes a blood sample adds 4ml mixing acid (HNO after the administration ₃HCl=3; 1), digestion is near on 180 ℃ of hot plates does, and residue is settled to 1Oml with 1mol/L hydrochloric acid solvent and makes liquid to be measured.Adopt the bismuth in the mobile injection of hydride generation aas determination blood.Get above-mentioned testing sample 400uL sample introduction, self-acting valve control injection length is 15s, and sample and sodium borohydride mix in current-carrying, and bismuth is reduced into BiH ₃Gas-liquid mixture is told gaseous state BiH through separator ₃, BiH ₃Be written in 800 ℃ of silica tube atomizers by carrier gas and carry out atomize, measure absorption value at wavelength 306.8nm place.

Article 8, after the Beagle dog is taken Bismuth Potassium Citrate capsule and modified montmorillonite used Bismuth Potassium Citrate adhesive tablet respectively, its pharmacokinetic parameters is respectively: Cmax is 0.28 ± 0.05 and 0.16 ± 0.06 μ mol/L, AUC is 4.51 ± 0.08 and 4.87 ± 0.11 μ mol.h/ml, and Tmax is 3.2 ± 0.6 and 5.6 ± 0.8h.As seen, be contrast with the Bismuth Potassium Citrate capsule, Beagle dog single dose is taken the modified montmorillonite used Bismuth Potassium Citrate adhesive tablet bioavailability of equivalence relatively, but peak time postpones, and peak concentration descends, and does not see that tool is prominent and release phenomenon, and slowly releasing effect is arranged.

Test example 10Modified montmorillonite used reversal therapies effect to chronic atrophic gastritis (CAG)

1, case is selected: turn out to be chronic atrophic gastritis treatment (CAG) through gastroscope, meet following condition person as the object of observation.1. biopsy pathology confirms to have CAG; 2. do not have upper digestive tract significant organic pathology, do not take important drugs in 1 week; 3. important diseases and pregnant lactation person such as cardiopulmonary liver kidney except; 4. the patient is ready that gastroscope follows up a case by regular visits to.Select 40 routine patients, be diagnosed as chronic atrophic gastritis, detect helicobacter pylori (HP), male 26 examples, women 14 examples, 34～65 years old age, medical history 1～12 year with rapid urease test through electronic gastroscope.

2, methods of treatment and result: 40 routine patients are divided into two groups at random, and 20 examples are organized in treatment, and oral modified montmorillonite used 4 grams divided and took for 2 times every day; Control group 20 examples, oral sucralfate 4 grams divided and took for 2 times every day.After treating for 8 weeks, carry out electronic gastroscope and HP experiment.The results are shown in Table 6:

The modified montmorillonite used reversal therapies effect of table 6 to CAG

	Reverse fully (%)	Part reverses (%)	No change (%)	Total effective rate (%)
	Reverse fully (%)	Part reverses (%)	No change (%)	Total effective rate (%)	The treatment group	15.0	35.0	50.0	50.0
Control group	0	15.0	85.0	15.0	The treatment group	15.0	35.0	50.0	50.0

Illustrate: 1) reverse fully: clinical symptom disappearance, stomach mucous membrane hyperemia under the electronic gastroscope, oedema and erosion are disappeared, and HP turns out cloudy; 2) part reverses: clinical symptom takes a turn for the better, and electronic gastroscope performance down takes a turn for the better the HP positive; 3) no change: clinical symptom does not have improvement.

Chronic atrophic gastritis (CAG) is a common disease, intestinal epithelial metaplasia that occurs together on the CAG basis (IM) and atypical hyperplasia (ATP) belong to gastric precancerous lesion (PC), obtain most scholars' approval by chronic gastritis-atrophy-intestinesization life-atypical hyperplasia-development of gastric carcinoma process.Modified montmorillonite used special charged ununiformity and hydration swelling, strengthen repairing the gastrointestinal mucosal barrier, fix and eliminate multiple pathogeny body and detoxifying function, oral back contacts with gastrointestinal mucosal, and combine with the digestive tube MGP, increase mucous elasticity force of cohesion and thicken slime layer, improve mucus from quality and quantity two aspects, also has the digestive tube local hemostasis simultaneously, gas in the absorption digestive tube promotes impaired mucomembranous epithelial cell reparation and regeneration, improves environment in the stomach, eliminate proinflammatory factors, recover defense mechanism in the stomach, can reverse or partly reverse CAG and PC fully.Simultaneously, modified montmorillonite used stomachache, turgor, the nausea and vomiting that also significantly improves the chronic atrophic gastritis patient, return malaise symptoms such as acid and hiccup.

Claims

1, a kind of have the modified montmorillonite used of therapeutic action to the digestive tube illness, it is characterized in that: do not destroy the dioctahedron layer structure of natural montmorillonite and do not change its basic chemical constitution, and by changing the microtexture of dioctahedron stack layer, make its stack layer attenuation, expose and increase its variable charge and interlayer charge, and have the lower C axle degree of order, the described C axle degree of order is meant that the d value is 12-100 in the X diffractogram of montmorillonite

The grain-size of the crystal grain that calculates of 001 diffraction peak, described modified montmorillonite used cation exchange capacity scope is 116mmol/100g＜cation exchange capacity≤140mmol/100g.

2, according to claim 1 modified montmorillonite used, described crystal grain is made up of 2-10 dioctahedron stack layer, and thickness is 2-15nm.

3, according to claim 2 modified montmorillonite used, described crystal grain is made up of 2-9 dioctahedron stack layer, and thickness is 2-13.5nm.

4, according to claim 3 modified montmorillonite used, described crystal grain is made up of 2-8 dioctahedron stack layer, and thickness is 2-12nm.

5, according to claim 4 modified montmorillonite used, described crystal grain is made up of 2-7 dioctahedron stack layer, and thickness is 2-10.5nm.

6, according to claim 5 modified montmorillonite used, described crystal grain is made up of 2-6 dioctahedron stack layer, and thickness is 2-9nm.

7, according to claim 6 modified montmorillonite used, described crystal grain is made up of 2-5 dioctahedron stack layer, and thickness is 2-7.5nm.

8, according to claim 7 modified montmorillonite used, described crystal grain is made up of 2-4 dioctahedron stack layer, and thickness is 2-6nm.

9, according to claim 8 modified montmorillonite used, described crystal grain is made up of 2-3 dioctahedron stack layer, and thickness is 2-4.5nm.

10, according to claim 1 modified montmorillonite used, described crystal grain is made up of 3-10 dioctahedron stack layer, and thickness is 3-15nm.

11, according to claim 10 modified montmorillonite used, described crystal grain is made up of 3-9 dioctahedron stack layer, and thickness is 3-13.5nm.

12, according to claim 11 modified montmorillonite used, described crystal grain is made up of 3-8 dioctahedron stack layer, and thickness is 3-12nm.

13, according to claim 12 modified montmorillonite used, described crystal grain is made up of 3-7 dioctahedron stack layer, and thickness is 3-10.5nm.

14, according to claim 13 modified montmorillonite used, described crystal grain is made up of 3-6 dioctahedron stack layer, and thickness is 3-9nm.

15, according to claim 14 modified montmorillonite used, described crystal grain is made up of 3-5 dioctahedron stack layer, and thickness is 3-7.5nm.

16, according to claim 15 modified montmorillonite used, described crystal grain is made up of 3-4 dioctahedron stack layer, and thickness is 3-6nm.

17, according to claim 1 modified montmorillonite used, described crystal grain is made up of 4-10 dioctahedron stack layer, and thickness is 4-15nm.

18, according to claim 17 modified montmorillonite used, described crystal grain is made up of 4-9 dioctahedron stack layer, and thickness is 4-13.5nm.

19, according to claim 18 modified montmorillonite used, described crystal grain is made up of 4-8 dioctahedron stack layer, and thickness is 4-12nm.

20, according to claim 19 modified montmorillonite used, described crystal grain is made up of 4-7 dioctahedron stack layer, and thickness is 4-10.5nm.

21, according to claim 20 modified montmorillonite used, described crystal grain is made up of 4-6 dioctahedron stack layer, and thickness is 4-9nm.

22, according to claim 21 modified montmorillonite used, described crystal grain is made up of 4-5 dioctahedron stack layer, and thickness is 4-7.5nm.

23, according to claim 1 modified montmorillonite used, described crystal grain is made up of 5-10 dioctahedron stack layer, and thickness is 5-15nm.

24, according to claim 23 modified montmorillonite used, described crystal grain is made up of 5-9 dioctahedron stack layer, and thickness is 5-13.5nm.

25, according to claim 24 modified montmorillonite used, described crystal grain is made up of 5-8 dioctahedron stack layer, and thickness is 5-12nm.

26, according to claim 25 modified montmorillonite used, described crystal grain is made up of 5-7 dioctahedron stack layer, and thickness is 5-10.5nm.

27, according to claim 26 modified montmorillonite used, described crystal grain is made up of 5-6 dioctahedron stack layer, and thickness is 5-9nm.

28, according to claim 1 modified montmorillonite used, described crystal grain is made up of 6-10 dioctahedron stack layer, and thickness is 6-15nm.

29, according to claim 28 modified montmorillonite used, described crystal grain is made up of 6-9 dioctahedron stack layer, and thickness is 6-13.5nm.

30, according to claim 29 modified montmorillonite used, described crystal grain is made up of 6-8 dioctahedron stack layer, and thickness is 6-12nm.

31, according to claim 30 modified montmorillonite used, described crystal grain is made up of 6-7 dioctahedron stack layer, and thickness is 6-10.5nm.

32, according to claim 1 modified montmorillonite used, described crystal grain is made up of 7-10 dioctahedron stack layer, and thickness is 7-15nm.

33, according to claim 32 modified montmorillonite used, described crystal grain is made up of 7-9 dioctahedron stack layer, and thickness is 7-13.5nm.

34, according to claim 33 modified montmorillonite used, described crystal grain is made up of 7-8 dioctahedron stack layer, and thickness is 7-12nm.

35, according to claim 1 modified montmorillonite used, described crystal grain is made up of 8-10 dioctahedron stack layer, and thickness is 8-15nm.

36, according to claim 35 modified montmorillonite used, described crystal grain is made up of 8-9 dioctahedron stack layer, and thickness is 8-13.5nm.

37, according to claim 1 modified montmorillonite used, described crystal grain is made up of 9-10 dioctahedron stack layer, and thickness is 9-15nm.

38, according to claim 1 modified montmorillonite used, described interlayer charge is not less than 0.31eq/[(Si, Al) ₄O ₁₀].

39, described modified montmorillonite used according to claim 38, described interlayer charge is not less than 0.34eq/[(Si, Al) ₄O ₁₀].

40, described modified montmorillonite used according to claim 39, described interlayer charge is not less than 0.40eq/[(Si, Al) ₄O ₁₀].

41, described modified montmorillonite used according to claim 40, described interlayer charge is not less than 0.43eq/[(Si, Al) ₄O ₁₀].

42, according to claim 1 modified montmorillonite used, described variable charge is not less than 0.058eq/[(Si, Al) ₄O ₁₀].

43, described modified montmorillonite used according to claim 42, described variable charge is not less than 0.08eq/[(Si, Al) ₄O ₁₀].

44, described modified montmorillonite used according to claim 43, described variable charge is not less than 0.10eq/[(Si, Al) ₄O ₁₀].

45, described modified montmorillonite used according to claim 44, described variable charge is not less than 0.12eq/[(Si, Al) ₄O ₁₀].

46, each is described modified montmorillonite used according to claim 1-45, described modified montmorillonite used modified calcium-base montmorillonite, modification sodium ca-montmorillonite, modification hydrogen base montmorillonite, modification magnesium base montmorillonite or the modified na-montmorillonite of being selected from.

47, described modified montmorillonite used according to claim 46, described modified montmorillonite used be modified na-montmorillonite.

48, described modified montmorillonite used according to claim 46, described modified montmorillonite used cation exchange capacity is 122-140mmol/100g.

49, described modified montmorillonite used according to claim 48, described modified montmorillonite used cation exchange capacity is 125-140mmol/100g.

50, described modified montmorillonite used according to claim 49, described modified montmorillonite used cation exchange capacity is 130-135mmol/100g.

51, described modified montmorillonite used according to claim 46, described modified montmorillonite used purity is not less than 95%.

52, described modified montmorillonite used according to claim 51, described modified montmorillonite used purity is not less than 96%.

53, described modified montmorillonite used according to claim 52, described modified montmorillonite used purity is not less than 97%.

54, described modified montmorillonite used according to claim 53, described modified montmorillonite used purity is not less than 98%.

55, described modified montmorillonite used according to claim 54, described modified montmorillonite used purity is not less than 99%.

56, described modified montmorillonite used according to claim 55, described modified montmorillonite used purity is not less than 99.5%.

57, described modified montmorillonite used according to claim 46, described modified montmorillonite used turgidity is not less than 4.0.

58, described modified montmorillonite used according to claim 57, described modified montmorillonite used turgidity is not less than 5.0.

59, described modified montmorillonite used according to claim 58, described modified montmorillonite used turgidity is not less than 7.0.

60, described modified montmorillonite used according to claim 59, described modified montmorillonite used turgidity is not less than 9.0.

61, described modified montmorillonite used according to claim 60, described modified montmorillonite used turgidity is not less than 10.0.

62, described modified montmorillonite used according to claim 61, described modified montmorillonite used turgidity is not less than 12.0.

63, described modified montmorillonite used according to claim 46, the modified montmorillonite used adsorptive capacity to the sulfuric acid Strychnine of every 1g is 0.30-0.75g.

64, described modified montmorillonite used according to claim 63, the modified montmorillonite used adsorptive capacity to the sulfuric acid Strychnine of every 1g is 0.40-0.70g.

65, described modified montmorillonite used according to claim 64, the modified montmorillonite used adsorptive capacity to the sulfuric acid Strychnine of every 1g is 0.45-0.65g.

66, described modified montmorillonite used according to claim 65, the modified montmorillonite used adsorptive capacity to the sulfuric acid Strychnine of every 1g is 0.50-0.60g.

67, described modified montmorillonite used according to claim 46, described modified montmorillonite used heavy metal is no more than 10ppm.

68, described modified montmorillonite used according to claim 67, described modified montmorillonite used heavy metal is no more than 7ppm.

69, described modified montmorillonite used according to claim 68, described modified montmorillonite used heavy metal is no more than 5ppm.

70, described modified montmorillonite used according to claim 69, described modified montmorillonite used heavy metal is 3-4ppm.

71, described modified montmorillonite used according to claim 46, described modified montmorillonite used related substance is no more than 5%, and described related substance is the impurity except that montmorillonite.

72, described modified montmorillonite used according to claim 71, described modified montmorillonite used related substance is no more than 4%.

73, described modified montmorillonite used according to claim 72, described modified montmorillonite used related substance is no more than 3%.

74, described modified montmorillonite used according to claim 73, described modified montmorillonite used related substance is no more than 2%.

75, described modified montmorillonite used according to claim 74, described modified montmorillonite used related substance is no more than 1%.

76, described modified montmorillonite used according to claim 75, described modified montmorillonite used related substance is no more than 0.5%.

77, described modified montmorillonite used according to claim 46, described modified montmorillonite used preparation method comprises the steps: purity is not less than 80% montmorillonite powder, with the mixing acid of 0.1-10mol/L with the montmorillonite powder: the mass ratio of mixing acid is the 1:1-100 uniform mixing, heat is boiled, centrifugal or remove by filter mixing acid, washing, drying, that is, described mixing acid is mixed by mineral acid and organic acid.

78, described modified montmorillonite used according to claim 77, the purity of described montmorillonite powder is not less than 85%.

79, described modified montmorillonite used according to claim 78, the purity of described montmorillonite powder is not less than 90%.

80, described modified montmorillonite used according to claim 79, the purity of described montmorillonite powder is not less than 95%.

81, described modified montmorillonite used according to claim 77, the concentration of described mixing acid is 0.5-8mol/L.

82,1 described modified montmorillonite used according to Claim 8, the concentration of described mixing acid is 0.8-6mol/L.

83,2 described modified montmorillonite used according to Claim 8, the concentration of described mixing acid is 1-5mol/L.

84,3 described modified montmorillonite used according to Claim 8, the concentration of described mixing acid is 2-4mol/L.

85, described modified montmorillonite used according to claim 77, described mineral acid is selected from monoprotic acid, diprotic acid or triprotic acid.

86,5 described modified montmorillonite used according to Claim 8, described mineral acid is a monoprotic acid.

87,5 described modified montmorillonite used according to Claim 8, described monoprotic acid is selected from hydrochloric acid, nitric acid, Hydrogen bromide or hydrofluoric acid.

88,7 described modified montmorillonite used according to Claim 8, described monoprotic acid is hydrochloric acid or nitric acid.

89,5 described modified montmorillonite used according to Claim 8, described diprotic acid is a sulfuric acid.

90,5 described modified montmorillonite used according to Claim 8, described triprotic acid is selected from phosphoric acid or sulfonic acid.

91, described modified montmorillonite used according to claim 77, described organic acid is selected from any or its combination of alcohol acid, ketone acid or tartaric acid.

92, described modified montmorillonite used according to claim 77, described organic acid is any or its combination of acetic acid, oxalic acid, citric acid, succsinic acid, formic acid, propionic acid, butyric acid, propanedioic acid, Succinic Acid, pyruvic acid, L-glutamic acid, tartrate, oxysuccinic acid, lactic acid, fumaric acid, methylene-succinic acid, xitix, fumaric acid, α-Tong Wuersuan.

93, described modified montmorillonite used according to claim 92, described organic acid is any or its combination of acetic acid, oxalic acid, citric acid, succsinic acid, propionic acid, butyric acid, Succinic Acid or propanedioic acid.

94, described modified montmorillonite used according to claim 77, described mixing acid is made up of hydrochloric acid, oxalic acid and acetic acid, and its mol ratio is a hydrochloric acid: oxalic acid: acetic acid equals 30-80:20-100:30-100.

95, described modified montmorillonite used according to claim 94, described mol ratio is a hydrochloric acid: oxalic acid: acetic acid equals 4:10:6.

96, described modified montmorillonite used according to claim 94, described mol ratio is a hydrochloric acid: oxalic acid: acetic acid equals 3:4:3.

97, described modified montmorillonite used according to claim 77, described mixing acid is made up of sulfuric acid, citric acid and acetic acid, and its mol ratio is a sulfuric acid: citric acid: acetic acid equals 6:8:6.

98, described modified montmorillonite used according to claim 77, described mixing acid is made up of phosphoric acid, tartrate and oxalic acid, and its mol ratio is a phosphoric acid: tartrate: oxalic acid equals 10:12:12.

99, described modified montmorillonite used according to claim 77, described mixing acid is made up of nitric acid, oxysuccinic acid and acetic acid, and its mol ratio is a nitric acid: oxysuccinic acid: acetic acid equals 75:120:105.

100, described modified montmorillonite used according to claim 77, described mixing acid is made up of methylsulfonic acid, oxalic acid and propanedioic acid, and its mol ratio is a methylsulfonic acid: oxalic acid: propanedioic acid equals 40:5:10.

101, described modified montmorillonite used according to claim 77, described mixing acid is made up of hydrochloric acid and acetic acid, and its mol ratio is a hydrochloric acid: acetic acid equals 10:3.

102, described modified montmorillonite used according to claim 77, described mixing acid is made up of hydrochloric acid and acetic acid, and its mol ratio is a hydrochloric acid: acetic acid equals 10:4.

103, described modified montmorillonite used according to claim 77, described montmorillonite powder: the mass ratio of mixing acid is 1:2-50.

104, described modified montmorillonite used according to claim 103, described montmorillonite powder: the mass ratio of mixing acid is 1:2.5-25.

105, described modified montmorillonite used according to claim 104, described montmorillonite powder: the mass ratio of mixing acid is 1:3-10.

106, described modified montmorillonite used according to claim 77, the described heat time of boiling is 0.5-100 hour.

107, described modified montmorillonite used according to claim 106, the described heat time of boiling is 2-70 hour.

108, described modified montmorillonite used according to claim 107, the described heat time of boiling is 3-40 hour.

109, described modified montmorillonite used according to claim 108, the described heat time of boiling is 5-20 hour.

110, described modified montmorillonite used according to claim 77, it is 10-100 ℃ that described heat is boiled temperature.

111, described modified montmorillonite used according to claim 110, it is 20-95 ℃ that described heat is boiled temperature.

112, described modified montmorillonite used according to claim 111, it is 30-90 ℃ that described heat is boiled temperature.

113, described modified montmorillonite used according to claim 112, it is 40-85 ℃ that described heat is boiled temperature.

114, described modified montmorillonite used according to claim 113, it is 50-80 ℃ that described heat is boiled temperature.

115, described modified montmorillonite used according to claim 47, the modified montmorillonite used preparation method of described sodium base comprises the steps: purity is not less than 95% described modified calcium-base montmorillonite or described modification magnesium base montmorillonite, add acid solution and be made into the acid solution slip that solid content is 10-50%, stir, remove by filter acid solution, wash to slightly acidic, in the filter cake of solid content 30-70%, add sodium agent than the excessive 0.1-20% of described cation exchange capacity, stir sodium, drying, promptly.

116, described modified montmorillonite used according to claim 115, the solid content of described acid solution slip is 15-45%.

117, described modified montmorillonite used according to claim 116, the solid content of described acid solution slip is 20-40%.

118, described modified montmorillonite used according to claim 117, the solid content of described acid solution slip is 25-35%.

119, described modified montmorillonite used according to claim 118, the solid content of described acid solution slip is 30%.

120, described modified montmorillonite used according to claim 115, described slightly acidic is meant that pH is 1.0-7.0.

121, described modified montmorillonite used according to claim 120, described slightly acidic is meant that pH is 1.5-6.5.

122, described modified montmorillonite used according to claim 121, described slightly acidic is meant that pH is 2.0-6.0.

123, described modified montmorillonite used according to claim 122, described slightly acidic is meant that pH is 2.5-5.5.

124, described modified montmorillonite used according to claim 115, described sodium agent is this area soluble sodium salt commonly used.

125, described modified montmorillonite used according to claim 124, described sodium agent is selected from Sodium hexametaphosphate 99, Trisodium trimetaphosphate, heavy sodium-metaphosphate, sodium polyacrylate, trisodium phosphate, sodium polyphosphate, sodium acrylate, water glass, tertiary sodium phosphate, yellow soda ash, sodium bicarbonate, Xylo-Mucine, Na ₂HPO ₄, NaH ₂PO ₄, NaCl, NaF, sodium sulfate, Trisodium Citrate any or its combination.

126, described modified montmorillonite used according to claim 125, described sodium agent is selected from Sodium hexametaphosphate 99, trisodium phosphate, sodium polyphosphate, Trisodium trimetaphosphate, heavy sodium-metaphosphate, sodium polyacrylate, tertiary sodium phosphate, Trisodium Citrate, Na ₂HPO ₄, NaH ₂PO ₄, NaCl, NaF, sodium sulfate, yellow soda ash any or its combination.

127, described modified montmorillonite used according to claim 115, described sodium agent is a sodium hydroxide.

128, described modified montmorillonite used according to claim 115, the purity for preparing used described modified calcium-base montmorillonite of described modified na-montmorillonite or described modification magnesium base montmorillonite is not less than 96%.

129, described modified montmorillonite used according to claim 128, the purity for preparing used described modified calcium-base montmorillonite of described modified na-montmorillonite or described modification magnesium base montmorillonite is not less than 97%.

130, described modified montmorillonite used according to claim 129, the purity for preparing used described modified calcium-base montmorillonite of described modified na-montmorillonite or described modification magnesium base montmorillonite is not less than 98%.

131, described modified montmorillonite used according to claim 130, the purity for preparing used described modified calcium-base montmorillonite of described modified na-montmorillonite or described modification magnesium base montmorillonite is not less than 99%.

132, described modified montmorillonite used according to claim 131, the purity for preparing used described modified calcium-base montmorillonite of described modified na-montmorillonite or described modification magnesium base montmorillonite is not less than 99.5%.

133, described modified montmorillonite used according to claim 115, the solid content of described filter cake is 40-60%.

134, described modified montmorillonite used according to claim 133, the solid content of described filter cake is 50%.

135, described modified montmorillonite used according to claim 47, described sodium base is modified montmorillonite used to be prepared by following method: be not less than the sodium agent that adds in 95% described modified calcium-base montmorillonite or described modification magnesium base montmorillonite or the described modification hydrogen base montmorillonite than the excessive 0.1-20% of described cation exchange capacity in purity, it is made into the slip of solid content 30-70%, stir sodium, drying, promptly.

136, described modified montmorillonite used according to claim 135, the purity for preparing the used described modified calcium-base montmorillonite of described modified na-montmorillonite, described modification hydrogen base montmorillonite or described modification magnesium base montmorillonite is not less than 96%.

137, described modified montmorillonite used according to claim 136, the purity for preparing the used described modified calcium-base montmorillonite of described modified na-montmorillonite, described modification hydrogen base montmorillonite or described modification magnesium base montmorillonite is not less than 97%.

138, described modified montmorillonite used according to claim 137, the purity for preparing the used described modified calcium-base montmorillonite of described modified na-montmorillonite, described modification hydrogen base montmorillonite or described modification magnesium base montmorillonite is not less than 98%.

139, described modified montmorillonite used according to claim 138, the purity for preparing the used described modified calcium-base montmorillonite of described modified na-montmorillonite, described modification hydrogen base montmorillonite or described modification magnesium base montmorillonite is not less than 99%.

140, described modified montmorillonite used according to claim 139, the purity for preparing the used described modified calcium-base montmorillonite of described modified na-montmorillonite, described modification hydrogen base montmorillonite or described modification magnesium base montmorillonite is not less than 99.5%.

141, described modified montmorillonite used according to claim 135, described sodium agent is this area soluble sodium salt commonly used.

142, described modified montmorillonite used according to claim 135, described sodium agent is selected from Sodium hexametaphosphate 99, Trisodium trimetaphosphate, heavy sodium-metaphosphate, sodium polyacrylate, trisodium phosphate, sodium polyphosphate, sodium acrylate, water glass, tertiary sodium phosphate, yellow soda ash, sodium bicarbonate, Xylo-Mucine, Na ₂HPO ₄, NaH ₂PO ₄, NaCl, NaF, sodium sulfate, Trisodium Citrate any or its combination.

143, described modified montmorillonite used according to claim 142, described sodium agent is selected from Sodium hexametaphosphate 99, trisodium phosphate, sodium polyphosphate, Trisodium trimetaphosphate, heavy sodium-metaphosphate, sodium polyacrylate, tertiary sodium phosphate, Trisodium Citrate, Na ₂HPO ₄, NaH ₂PO ₄, NaCl, NaF, sodium sulfate, yellow soda ash any or its combination.

144, described modified montmorillonite used according to claim 135, described sodium agent is a sodium hydroxide.

145, a kind of each described modified montmorillonite used method of claim 1-144 for preparing, comprise the steps: that purity is not less than 80% montmorillonite powder, with the mixing acid of 0.1-10mol/L with the montmorillonite powder: the mass ratio of mixing acid is the 1:1-100 uniform mixing, heat is boiled, centrifugal or remove by filter mixing acid, wash, be drying to obtain, described mixing acid is mixed by mineral acid and organic acid.

146, according to the described method of claim 145, the purity of described montmorillonite powder is not less than 85%.

147, according to the described method of claim 146, the purity of described montmorillonite powder is not less than 90%.

148, according to the described method of claim 147, the purity of described montmorillonite powder is not less than 95%.

149, according to the described method of claim 145, the concentration of described mixing acid is 0.5-8mol/L.

150, according to the described method of claim 149, the concentration of described mixing acid is 0.8-6mol/L.

151, according to the described method of claim 150, the concentration of described mixing acid is 1-5mol/L.

152, according to the described method of claim 151, the concentration of described mixing acid is 2-4mol/L.

153, according to the described method of claim 145, described mineral acid is selected from monoprotic acid, diprotic acid or triprotic acid.

154, according to the described method of claim 153, described mineral acid is a monoprotic acid.

155, according to the described method of claim 153, described monoprotic acid is selected from hydrochloric acid, nitric acid, Hydrogen bromide or hydrofluoric acid.

156, according to the described method of claim 155, described monoprotic acid is hydrochloric acid or nitric acid.

157, according to the described method of claim 153, described diprotic acid is a sulfuric acid.

158, according to the described method of claim 153, described triprotic acid is selected from phosphoric acid or sulfonic acid.

159, according to the described method of claim 145, described organic acid is a carboxylic acid.

160, according to the described method of claim 145, described organic acid is selected from any or its combination of alcohol acid, ketone acid or tartaric acid.

161, according to the described method of claim 145, described organic acid is any or its combination of acetic acid, oxalic acid, citric acid, succsinic acid, formic acid, propionic acid, butyric acid, propanedioic acid, Succinic Acid, pyruvic acid, L-glutamic acid, tartrate, oxysuccinic acid, lactic acid, fumaric acid, methylene-succinic acid, xitix, fumaric acid, α-Tong Wuersuan.

162, according to the described method of claim 161, described organic acid is any or its combination of acetic acid, oxalic acid, citric acid, succsinic acid, propionic acid, butyric acid, Succinic Acid or propanedioic acid.

163, according to the described method of claim 145, described mixing acid is made up of hydrochloric acid, oxalic acid and acetic acid, and its mol ratio is a hydrochloric acid: oxalic acid: acetic acid equals 30-80:20-100:30-100.

164, according to the described method of claim 163, described mol ratio is a hydrochloric acid: oxalic acid: acetic acid equals 4:10:6.

165, according to the described method of claim 163, described mol ratio is a hydrochloric acid: oxalic acid: acetic acid equals 3:4:3.

166, according to the described method of claim 145, described mixing acid is made up of sulfuric acid, citric acid and acetic acid, and its mol ratio is a sulfuric acid: citric acid: acetic acid equals 6:8:6.

167, according to the described method of claim 145, described mixing acid is made up of phosphoric acid, tartrate and oxalic acid, and its mol ratio is a phosphoric acid: tartrate: oxalic acid equals 10:12:12.

168, according to the described method of claim 145, described mixing acid is made up of nitric acid, oxysuccinic acid and acetic acid, and its mol ratio is a nitric acid: oxysuccinic acid: acetic acid equals 75:120:105.

169, according to the described method of claim 145, described mixing acid is made up of methylsulfonic acid, oxalic acid and propanedioic acid, and its mol ratio is a methylsulfonic acid: oxalic acid: propanedioic acid equals 40:5:10.

170, according to the described method of claim 145, described mixing acid is made up of hydrochloric acid and acetic acid, and its mol ratio is a hydrochloric acid: acetic acid equals 10:3.

171, according to the described method of claim 145, described mixing acid is made up of hydrochloric acid and acetic acid, and its mol ratio is a hydrochloric acid: acetic acid equals 10:4.

172, according to the described method of claim 145, described montmorillonite powder: the mass ratio of mixing acid is 1:2-50.

173, according to the described method of claim 172, described montmorillonite powder: the mass ratio of mixing acid is 1:2.5-25.

174, according to the described method of claim 173, described montmorillonite powder: the mass ratio of mixing acid is 1:3-10.

175, according to the described method of claim 145, the described heat time of boiling is 0.5-100 hour.

176, according to the described method of claim 175, the described heat time of boiling is 2-70 hour.

177, according to the described method of claim 176, the described heat time of boiling is 3-40 hour.

178, according to the described method of claim 177, the described heat time of boiling is 5-20 hour.

179, according to the described method of claim 145, it is 10-100 ℃ that described heat is boiled temperature.

180, according to the described method of claim 179, it is 20-95 ℃ that described heat is boiled temperature.

181, according to the described method of claim 180, it is 30-90 ℃ that described heat is boiled temperature.

182, according to the described method of claim 181, it is 40-85 ℃ that described heat is boiled temperature.

183, according to the described method of claim 182, it is 50-80 ℃ that described heat is boiled temperature.

184, a kind of pharmaceutical composition that is used for the treatment of the enteron aisle illness is made up of each described modified montmorillonite used and pharmaceutically acceptable carrier of claim 1-144.

185, according to the described pharmaceutical composition of claim 184, modified montmorillonite used in the composition: the dry product weight ratio of pharmaceutically acceptable carrier is 0.001-99:1-99.

186, according to the described pharmaceutical composition of claim 185, modified montmorillonite used in the composition: the dry product weight ratio of pharmaceutically acceptable carrier is 0.001-90:1-95.

187, according to the described pharmaceutical composition of claim 186, modified montmorillonite used in the composition: the dry product weight ratio of pharmaceutically acceptable carrier is 0.001-80: 1-90.

188, according to the described pharmaceutical composition of claim 187, modified montmorillonite used in the composition: the dry product weight ratio of pharmaceutically acceptable carrier is 0.001-70: 1-85.

189, according to the described pharmaceutical composition of claim 184, the weight percentage of montmorillonite is 1-95% in the composition.

190, according to the described pharmaceutical composition of claim 189, the weight percentage of montmorillonite is 5-90% in the composition.

191, according to the described pharmaceutical composition of claim 190, the weight percentage of montmorillonite is 10-85% in the composition.

192, according to the described pharmaceutical composition of claim 191, the weight percentage of montmorillonite is 15-80% in the composition.

193, according to each described pharmaceutical composition of claim 184-192, the dosage form of described composition is selected from oral preparations or external preparation.

194, according to the described pharmaceutical composition of claim 193, the dosage form of described composition is an oral preparations.

195, according to the described pharmaceutical composition of claim 193, described oral preparations is selected from tablet, suspension, capsule, granule, pill, powder, dripping pill, syrup, mixture, emulsion, distillate medicinal water, effervescent, paste or medicinal tea.

196, according to the described pharmaceutical composition of claim 195, described oral preparations is selected from powder, suspension, granule, tablet, capsule or effervescent.

197, according to the described pharmaceutical composition of claim 193, described external preparation is selected from gelifying agent, emplastrum, creme, ointment, liniment, lotion, suppository, basting agent or coagulates paste.

198, according to the described pharmaceutical composition of claim 197, described external preparation is a gelifying agent.

199, each described modified montmorillonite used or each described pharmaceutical composition of claim 184-198 application in preparation treatment disease medicament of claim 1-144.

200, each described modified montmorillonite used or each described pharmaceutical composition of claim 184-198 application in the medicine of preparation treatment digestive tube illness of claim 1-144.

201, according to the described application of claim 200, described digestive tract diseases is selected from acute and chronic diarrhea, reflux esophagitis, peptide ulceration, irritable bowel syndrome, inflammatory enteron aisle illness or gastritis.

202, according to the described application of claim 201, described gastritis is chronic gastritis.

203, according to the described application of claim 202, described chronic gastritis is a chronic atrophic gastritis.

204, according to the described application of claim 200, the therapeutic action of described digestive tube illness is the reversal therapies effect to chronic atrophic gastritis.

205, each described modified montmorillonite used or each described pharmaceutical composition of claim 184-198 of claim 1-144 is in the preparation treatment or prevent and treat application in the hyperthyroid medicine.

206, each described modified montmorillonite used or each described pharmaceutical composition of claim 184-198 application in the medicine of preparation treatment chronic renal failure of claim 1-144.

207, each described modified montmorillonite used or each described pharmaceutical composition of claim 184-198 application in the medicine of preparation prevention or counteract oral malodour of claim 1-144.

208, each described modified montmorillonite used application in preparation pharmaceutical carrier or excipient substance of claim 1-144.

209, according to the described application of claim 208, described pharmaceutical carrier or excipient substance are as the matrix of oral preparations, external preparation, sustained release preparation or controlled release preparation.

210, according to the described application of claim 208, described pharmaceutical carrier or excipient substance are used as tablet, suspension, capsule, granule, pill, powder, dripping pill, syrup, mixture, distillate medicinal water, effervescent, paste, medicinal tea, biologic adhesion preparation, gelifying agent, ointment, creme, suppository, emulsion, paste, inorganic antiseptic, coagulate the matrix of paste, makeup or suspension agent.

211, according to the described application of claim 208, described pharmaceutical carrier or excipient substance are as the matrix of skin-use preparation.

212, according to the described application of claim 211, described skin-use preparation is selected from liniment, lotion or basting agent.

213, according to each described application of claim 208-212, described medicine is selected from any or its combination of oral pharmaceutical, externally applied medicine, slow releasing pharmaceutical or controlled release drug.

214, each described modified montmorillonite used or each described pharmaceutical composition of claim 184-198 application in preparation treatment dermatosis treating medicine of claim 1-144.

215, each described modified montmorillonite used or each described pharmaceutical composition of claim 184-198 application in the preparation medicament for sobering up and protecting liver of claim 1-144.

216, application in the helicobacter pylori medicine is removed or killed to each described modified montmorillonite used or each described pharmaceutical composition of claim 184-198 of claim 1-144 in preparation.

217, a kind of method for preparing the nano modification montmorillonite, comprise the steps: purity is not less than each described modified montmorillonite used aqueous solution that is mixed with solid content 0.5-60% of claim 1-144 of 95%, put in high-speed shearing machine, high speed dispersor, ball mill or the high pressure homogenizer, after carrying out high speed shear dispersion, homogeneous, dry, pulverize, promptly.

218, according to the described method of claim 217, described modified montmorillonite used purity is not less than 96%.

219, according to the described method of claim 218, described modified montmorillonite used purity is not less than 97%.

220, according to the described method of claim 219, described modified montmorillonite used purity is not less than 98%.

221, according to the described method of claim 220, described modified montmorillonite used purity is not less than 99%.

222, according to the described method of claim 221, described modified montmorillonite used purity is not less than 99.5%.

223, according to the described method of claim 217, described modified montmorillonite used modified na-montmorillonite, modification sodium ca-montmorillonite, modification hydrogen base montmorillonite, modification magnesium base montmorillonite or the modified calcium-base montmorillonite of being selected from.

224, according to the described method of claim 223, described modified montmorillonite used be modified na-montmorillonite.

225, according to the described method of claim 217, the particle diameter of described nano modification montmorillonite is not more than 1 μ m.

226, according to the described method of claim 225, the particle diameter of described nano modification montmorillonite is not more than 0.8 μ m.

227, according to the described method of claim 226, the particle diameter of described nano modification montmorillonite is not more than 0.6 μ m.

228, according to the described method of claim 227, the particle diameter of described nano modification montmorillonite is not more than 0.4 μ m.

229, according to the described method of claim 228, the particle diameter of described nano modification montmorillonite is not more than 0.2 μ m.

230, according to the described method of claim 217, the solid content of the described aqueous solution is 5-50%.

231, according to the described method of claim 230, the solid content of the described aqueous solution is 10-40%.

232, according to the described method of claim 231, the solid content of the described aqueous solution is 15-30%.

233, according to the described method of claim 232, the solid content of the described aqueous solution is 20-25%.

234, according to the described method of claim 217, the homogenization pressure of described homogeneous is not less than 10MPa.

235, according to the described method of claim 234, the homogenization pressure of described homogeneous is 20-800MPa.

236, according to the described method of claim 235, the homogenization pressure of described homogeneous is 30-600MPa.

237, according to the described method of claim 236, the homogenization pressure of described homogeneous is 50-500MPa.

238, according to the described method of claim 237, the homogenization pressure of described homogeneous is 80-300MPa.

239, according to the described method of claim 217, described high pressure homogenizer is selected from any or its combination of mesohigh clarifixator, super-high-pressure homogenization machine, nanometer ram machine or high pressure microjet clarifixator.

240, according to the described method of claim 239, described super-high-pressure homogenization machine is the nm super high clarifixator.

241, according to each described method of claim 217-240, described pulverizing is that thick level is pulverized the back comminution by gas stream.

242, according to the described method of claim 241, the smashing fineness of described comminution by gas stream is not less than 300 orders.

243, according to the described method of claim 242, the smashing fineness of described comminution by gas stream is not less than 500 orders.

244, according to the described method of claim 243, the smashing fineness of described comminution by gas stream is not less than 1000 orders.

245, according to the described method of claim 244, the smashing fineness of described comminution by gas stream is not less than 3000 orders.

246, according to the described method of claim 245, the smashing fineness of described comminution by gas stream is not less than 5000 orders.

247, a kind of nano modification montmorillonite is prepared by each described method of claim 217-246.

248, according to the described nano modification montmorillonite of claim 247, the cation exchange capacity of described nano modification montmorillonite is 125-140mmol/100g.

249, according to the described nano modification montmorillonite of claim 248, described cation exchange capacity is 128-140mmol/100g.

250, according to the described nano modification montmorillonite of claim 249, described cation exchange capacity is 130-135mmol/100g.

251, according to each described nano modification montmorillonite of claim 247-250, the turgidity of described nano modification montmorillonite is not less than 4.0.

252, according to the described nano modification montmorillonite of claim 251, the turgidity of described nano modification montmorillonite is not less than 5.0.

253, according to the described nano modification montmorillonite of claim 252, the turgidity of described nano modification montmorillonite is not less than 7.0.

254, according to the described nano modification montmorillonite of claim 253, the turgidity of described nano modification montmorillonite is not less than 9.0.

255, according to the described nano modification montmorillonite of claim 254, the turgidity of described nano modification montmorillonite is not less than 10.0.

256, according to the described nano modification montmorillonite of claim 255, the turgidity of described nano modification montmorillonite is not less than 12.0.

257, a kind of Bismuth Potassium Citrate preparation of bioadhesion type, described preparation is made up of each described modified montmorillonite used and other pharmaceutical excipients of Bismuth Potassium Citrate, claim 1-144.

258, according to the described Bismuth Potassium Citrate preparation of claim 257, the weight percentage of each composition is in the preparation: Bismuth Potassium Citrate 1-98%, and modified montmorillonite used 1-98%, surplus is other auxiliary materials.

259, according to the described Bismuth Potassium Citrate preparation of claim 258, the weight percentage of each composition is in the preparation: Bismuth Potassium Citrate 5-90%, and modified montmorillonite used 5-90%, surplus is other auxiliary materials.

260, according to the described Bismuth Potassium Citrate preparation of claim 259, the weight percentage of each composition is in the preparation: Bismuth Potassium Citrate 7.5-85%, and modified montmorillonite used 7.5-85%, surplus is other auxiliary materials.

261, according to each described Bismuth Potassium Citrate preparation of claim 257-260, contain Bismuth Potassium Citrate 50-2500mg and modified montmorillonite used 10-2500mg in the preparation.

262, according to the described Bismuth Potassium Citrate preparation of claim 261, contain Bismuth Potassium Citrate 100-2000mg and modified montmorillonite used 50-2000mg in the preparation.

263, according to the described Bismuth Potassium Citrate preparation of claim 262, contain Bismuth Potassium Citrate 150-1500mg and modified montmorillonite used 100-1500mg in the preparation.

264, according to the described Bismuth Potassium Citrate preparation of claim 263, contain Bismuth Potassium Citrate 200-1200mg and modified montmorillonite used 150-1200mg in the preparation.

265, a kind of makeup, containing the claim 1-144 of 1-90% in the described makeup, each is described modified montmorillonite used, and surplus is other auxiliary materials.

266, according to the described makeup of claim 265, modified montmorillonite used content is 5-85% in the described makeup.

267, according to the described makeup of claim 266, modified montmorillonite used content is 7.5-80% in the described makeup.

268, according to the described makeup of claim 267, modified montmorillonite used content is 10-75% in the described makeup.

269, each described modified montmorillonite used application that is used for preparing material of construction of claim 1-144, described material of construction is selected from water-proof material, inorganic thickening agent, auxiliary adhesive or suspension anti-settling agent.

270, each described modified montmorillonite used application that is used for preparing the petroleum industry material of claim 1-144, described petroleum industry material are selected from petroleum drilling mud, petroleum catalyst, discoloring agent or drilling fluid.

271, each described modified montmorillonite used application that is used for preparing farm chemical carrier, chemical fertilizer carrier, fodder additives, feed toxinicide, soil improvement agent, premix carrier, waste disposal agent or nano composite material of claim 1-144.