CN103073010B - Environment-friendly production process for high-purity montmorillonite - Google Patents
Environment-friendly production process for high-purity montmorillonite Download PDFInfo
- Publication number
- CN103073010B CN103073010B CN201310042071.3A CN201310042071A CN103073010B CN 103073010 B CN103073010 B CN 103073010B CN 201310042071 A CN201310042071 A CN 201310042071A CN 103073010 B CN103073010 B CN 103073010B
- Authority
- CN
- China
- Prior art keywords
- montmorillonite
- environment
- relative density
- ultrasonic
- production process
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to an environment-friendly production process for high-purity montmorillonite. The production process comprises the following steps: (1) drying, soaking, dispersing and sieving a bentonite raw material to obtain a crude solution of montmorillonite; (2) performing ultrasonic dispersion on the crude solution to obtain suspended emulsion; (3) performing cyclone separation on the suspended emulsion to remove a material with the relative density of more than 2.5g/cm<3>, sieving, standing, and removing water on the upper layer to obtain a material on the lower layer; (4) performing high temperature and high pressure cooperative ultrasonic sterilization on the material on the lower layer to obtain a sterilized material; and (5) performing centrifugal separation on the sterilized material, collecting a material with the relative density of less than or equal to 2.5g/cm<3>, drying, grinding until the average grain diameter of less than or equal to 45mu m, and sieving by using a 325-400-mesh sieve to obtain the montmorillonite. The environment-friendly production process ensures medication safety, clinical effectiveness and controlled quality, the process is simple and environment-friendly, the production efficiency is high, the production cost is low, the product quality is high, and industrial montmorillonite production is easily realized; and high temperature, high pressure and ultrasonic waves are combined for sterilization to ensure safety, reliability and a good sterilization effect.
Description
Technical field
The present invention relates to a kind of high purity montmorillonite environment-friendly production process, particularly relate to a kind of environment-friendly production process extracting high-purity montmorillonite from wilkinite.Belong to the technical field that medication chemistry is produced.
Background technology
Montmorillonite (Montmorillonite) is the layer mineral be made up of the hydrous alumino silicates that particle is superfine, and title derives from the Montmorillon of the place of production-France first found.Montmorillonite subtribe belongs to one of smectite race (smectite) mineral (another subtribe is saponite saponite), is important clay mineral, is generally bulk or earthy.The molecular formula of montmorillonite is (Al, Mg)
2[Si
4o
10] (OH)
2nH
2o, centre is alumina octahedral, the clay mineral of the three-layer tablet shape structure formed for silicon-oxy tetrahedron up and down, Montmorillonite Crystal belongs to monoclinic moisture layer silicate mineral, moisture and some exchange cations at crystal structure interlayer, there is higher loading capacity, there is higher water-swelling ability.Utilize its cation exchange property to make montmorillonite organic complex, be widely used in high gentle fat, rubber, plastics, paint; Utilize its absorption property, for edible oil refinery decolorization except poison, purification oil, nuclear waste disposal, sewage disposal; Utilize its cohesiveness can make foundry sand binding agent etc.; Utilize its dispersion suspension for drilling mud.Montmorillonite is widely used in medicine, can do medical carrier, play control-released agent, and have antidiarrheal efficacy.Montmorillonite has fine application in domestic animals cultivation, especially the yellowish-white dysentery of son, sucking pig, and having loose bowels of rabbit, plays prevention effects, in view of the characteristic of montmorillonite, can also take off mould dose as classic feed.
Montmorillonite is mainly present in natural wilkinite, is bentonitic main component, containing mineral such as cristobalite, quartzite, calcite, feldspar, illites in wilkinite.Cristobalite is indefiniteness silicon-dioxide, and normal and wilkinite association, its occupational exposure limit (threshold limit value) is 0.05mg/m
3(can dust be breathed) (ACGIH, 1997); Carcinogens classification is I level; Dominant touch approach is by absorbing in body, and when suction danger is 20 DEG C, evaporation can be ignored, but can reach particulate in air adverse concentration quickly during diffusion; Contact and can have impact to lung for a long time or repeatedly, cause pneumoconiosis (silicosis); The content of cristobalite is controlled according in the standard of " national drug standards XGB2011-079 " at present.About other mineral contents also have certain content restriction at national medical standards in montmorillonite; Therefore, from wilkinite, purifying montmorillonite is the key of field of medicaments.
The domestic general production method of current process for purifying montmorillonite mainly contains four kinds, and dry purification, chemical method are purified, centrifuging is purified and the centrifugal purification again of first sodium method.Chinese patent literature CN1803607A(200510120588.5) disclose a kind of preparation method of high-purity montmorillonite, but the method utilizes and adds the effect that chemical reagent reaches separation montmorillonite, cause montmorillonite to contain a large amount of harmful chemicals, the montmorillonite of purifying is not suitable for being applied to medicine and food service industry.Chinese patent literature CN101049940A(200710067840.X) disclose a kind of method for purifying superfine montmorillonite, the method is in production montmorillonite technological process, each production stage does not state the Con trolling index of processing parameter and the intermediate of material in each link, thus technique is uncontrollable when making production, cause the montmorillonite quality of output unstable, particularly do not state the sterilising method of material, cannot use at medicine and food service industry.Chinese patent literature CN101844772A(201010185479.2) disclose a kind of Montmorillonite Purification technique, the method overcomes the defect of above-mentioned method of purification to a certain extent, but following points are not enough: 1, this invention adopts and directly pulverizes in the pre-treatment of raw material, causing the mineral powders such as the cristobalite in a large amount of raw ores, quartzite, calcite, feldspar and illite to be broken into fine powder enters in whole extraction process, add the difficulty of aftertreatment, affect quality product; 2, this contriver's sterilizing adopts Co
60method of radiating, according to the relevant Co of health ministry
60in irradiation sterilization dosage standard " defend medicine and send out 1997 No. 38 " notice, Co
60irradiation sterilization maximal dose is 6KGY, and this contriver executes Co
60irradiation sterilization dosage is 15KGY, considerably beyond the 6KGY maximum dose level that health ministry specifies, is not suitable for medicine and food service industry use; 3, this invention spray-drying process, does not indicate the material concentration entering spray-dryer, make the production capacity of material and moisture uncontrollable; And spray-dryer intake air temperature is higher, temperature consumes a large amount of energy at 400 ~ 430 DEG C, the particle of spraying out does not meet standard according to national montmorillonite drug standard grain diameter, micronizing must be carried out again, make whole production operation complicated, and high temperature can make the change of montmorillonite chemical structure generation essence.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of high purity montmorillonite environment-friendly production process.
Term explanation
Purified water: the water of the hyoscine that tap water obtains through distillation method, ion exchange method, reverse osmosis method or other suitable methods.
Relative density: according to Chinese Pharmacopoeia version in 2010 two annex VI A, refer to the ratio of the density of material and the density of reference material, reference material is water.
Bentonite material: bentonite material of the present invention refers to unpretreated bentonite origin mineral aggregate.
Technical scheme of the present invention is as follows:
A kind of montmorillonite environment-friendly production process, step is as follows:
(1) bentonite material 90 ~ 160 DEG C being dried to water content is 0.5 ~ 10wt%, and after soaking 1 ~ 3h by purified water, dispersed with stirring is even, leaves standstill 30 ~ 50min, crosses 200 ~ 300 mesh sieves, obtain montmorillonite coarse fodder liquid; Described bentonite material: purified water is 1:5 ~ 10, mass ratio;
(2) by coarse fodder liquid 20 ~ 60 DEG C of ultrasonic disperse 10 ~ 50min, ultrasonic frequency is 15 ~ 40KHz, obtains suspended emulsion;
(3) suspended emulsion rotary filter press is removed relative density > 2.5g/cm
3material after cross 325 ~ 400 mesh sieves, standing sedimentation 2 ~ 10h, obtains sedimentation feed liquid; Remove sedimentation feed liquid upper strata moisture, when obtaining 25 DEG C, coefficient of dynamic viscosity is lower floor's material of 20 ~ 40Pas;
(4) by lower floor's material in 130 ~ 151 DEG C of temperature and 3 ~ 5Kg sterilized under pressure, 30 ~ 50min, be then cooled to 35 ~ 60 DEG C, the ultrasonic sterilizing 10 ~ 50min of 15 ~ 30KHz, obtains sterilizing material;
(5) sterilizing material is carried out centrifugation, collect relative density≤2.5g/cm
3material, 90 ~ 160 DEG C of drying 120 ~ 240min; Be crushed to median size≤45 μm; Cross 325 ~ 400 mesh sieves and carry out always mixing 20 ~ 40min, then packing at mixer, obtaining montmorillonite of the present invention.
According to the present invention, preferably, in described step (1), drying mode is for adopting rotary drum drying machine dry, and rotating cylinder rotating speed is 6 ~ 20r/min, and the inlet air temperature of warm air is 130 ~ 160 DEG C, and air outlet temperature is 90 ~ 120 DEG C;
More preferably, be fed in rotary drum drying machine with the feeding manner of following current, being dried to water content is 0.5 ~ 10wt%;
Preferably, dispersed with stirring mode is for adopting dispersion machine dispersion, and dispersion machine dispersion axle rotating speed is 1000 ~ 1400r/min, and dispersion machine dispersion impeller diameter is 350 ~ 600mm, and jitter time controls at 10 ~ 15min.
According to the present invention, preferably, in described step (2) with ultrasonic generator to coarse fodder liquid ultrasonic disperse, ultrasonic frequency is 25 ~ 35KHz.
According to the present invention, preferably, in described step (3), the mode of rotary filter press is adopt three grades of separation in rotary filter press machine; First step eddy flow machine specification is FXJ-75, and control pressure is 2.5Kpa, and first step eddy flow goes out relative density≤3.5g/cm
3material enter second stage eddy flow machine; Second stage eddy flow machine specification is FXJ-50, and control pressure is 2.0Kpa, and second stage eddy flow goes out relative density≤2.8g/cm
3material enter third stage eddy flow machine; Third stage eddy flow machine specification is FXJ-25, and control pressure is 1.5Kpa, and third stage eddy flow goes out relative density≤2.5g/cm
3material cross 325 ~ 400 mesh sieves.
According to the present invention, preferably, in described step (4) by lower floor's material in 135 ~ 145 DEG C of temperature and 3 ~ 4Kg sterilized under pressure, 30 ~ 50min, be then cooled to 35 ~ 60 DEG C, the ultrasonic sterilizing 10 ~ 50min of 20 ~ 30KHz.
According to the present invention, preferably, the mode of centrifugation in described step (5) carries out centrifugation for adopting horizontal screw centrifuge; Feeding rate controls at 0.1 ~ 0.3m
3/ min, collection relative density is 2.0 ~ 2.5g/cm
3material;
Preferably, grinding mode be first coarse reduction to median size≤5mm, recycling supper micron mill micronizing is to median size≤45 μm, and supper micron mill rotating speed controls at 1000 ~ 1400r/min; Cross 325 ~ 400 mesh sieves after pulverizing and carry out always mixing 20 ~ 40min, then packing at mixer.
It is vital that bentonite material product confrontation montmorillonite uses in different field, according to " national drug standards XGB2011-079 ", cristobalite standard in medicinal smectite standard is the ratio of cristobalite diffraction peak height and montmorillonite feature peak height, must not more than 50.0%; The inventive method processes cristobalite in bentonite material emphatically, the ratio < 50.0% of cristobalite diffraction peak height and montmorillonite feature peak height after the inventive method process, meet national medical standards, the industries such as medicine, food, fodder additives and makeup can be widely used in.
Method of the present invention is suitable for the bentonite material of different areas, and it is better that water content is that the bentonite material of 10 ~ 50wt% is suitable for effect.
Montmorillonite forms primarily of basic igneous rock weathering in alkaline environment, Mohs' hardness 2 ~ 2.5, relative density 2 ~ 2.5g/cm
3, add water expansion, and volume energy increases several times to tens times, and becomes mashed prod; Cristobalite is a kind of mineral polymorph of silicon-dioxide, and point α-cristobalite and two mutation of β-cristobalite, cristobalite belongs to tesseral system, relative density 2.20g/cm
3, Mohs' hardness 6.0 ~ 6.5; Montmorillonite relative density 2 ~ 2.5g/cm
3, cristobalite relative density 2.20g/cm
3, two material relative densities relatively, adopt settling process to be separated and are separated montmorillonite with additive method, cristobalite difficulty is larger.
The present invention becomes in marked difference according to montmorillonite Mohs' hardness 2 ~ 2.5, cristobalite Mohs' hardness 6.0 ~ 6.5, two material Mohs' hardness.Supersound process is carried out to montmorillonite, under hyperacoustic effect, sound wave cavatition is produced between water and montmorillonite, cause the formation of bubble in slurry of mineral, growth and explosion compression, the solid montmorillonite volumetric expansion that particle is tiny, dispersion and produce hydration phenomena, montmorillonite Particle Phase after emulsification reduces proportion, and is dispersed in water formation soliquid.
The present invention has following beneficial effect:
1, the present invention is according to the limit of national medicinal smectite interested party cristobalite content, carries out a large amount of technological experiments and research, obtain method steps of the present invention to the bentonite material in the whole nation; Through process rear of the present invention, cristobalite content meets national medical standards, has wide range of applications.
2, the water-absorbent of montmorillonite is very strong, water-absorbent is primarily of the moisture content of montmorillonite itself, when montmorillonite water content is at below 10wt%, its volumetric expansion and increase several times to tens times after water suction, when water content is at more than 10wt%, montmorillonite water-absorbent, volumetric expansion are very little, are unfavorable for that montmorillonite grain expansion scatters, thus the separation difficulty of other mineral making it wrap up; The present invention carries out drying and processing to bentonite material, and make water content at below 10wt%, turgidity reaches 2.0 ~ 5.0, and montmorillonite is better separated with impurity.Cross 200 ~ 300 mesh sieves after soaking by purified water, remove the impurity of particle diameter >=75 μm, be conducive to the separation and purification of follow-up montmorillonite, make the follow-up montmorillonite purity obtained high.
3, montmorillonite is minimum at occurring in nature particle diameter, and particle diameter is within 2 μm, and its surface energy is larger, generally be gathered into larger particle, the particle diameter of other dirts mainly distributes > 2 μm, together with mutually reuniting, is difficult to separate with montmorillonite; The present invention utilizes ultrasonic wave agglomerated montmorillonite Granular composite and forms suspension, ultrasonic wave produces sound wave cavatition between water and montmorillonite, cause the formation of bubble in slurry of mineral, growth and explosion compression, solid montmorillonite is disperseed, thus its montmorillonite is pulverized in the liquid phase, dispersion; Other dirt is greater than montmorillonite due to proportion and particle diameter, is sunken to material lower floor and is separated, and is more conducive to being separated of montmorillonite and impurity.
4, the present invention utilizes High Temperature High Pressure and ultrasonic synergistic sterilizing, avoids and uses Co
60irradiation sterilization, makes montmorillonite product both meet requirement and the safety of the national drug standards, can reach again the object of sterilizing.
5, the requirement of tool drug safety of the present invention, Clinical efficacy and quality controllability, the simple environmental protection of technique, production efficiency is high, and production cost is low, and quality product is high, is easy to realize industrialized montmorillonite and produces.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of the embodiment of the present invention 5, and X-coordinate is 2 θ (°), and ordinate zou is intensity (arbitrary unit).
Fig. 2 is the X-ray diffraction spectrogram of comparative example 1 of the present invention, and X-coordinate is 2 θ (°), and ordinate zou is intensity (arbitrary unit).
Fig. 3 is the X-ray diffraction spectrogram of comparative example 2 of the present invention, and X-coordinate is 2 θ (°), and ordinate zou is intensity (arbitrary unit).
Fig. 4 is the X ray diffracting spectrum of the montmorillonite that the embodiment of the present invention 7 obtains, and X-coordinate is 2 θ (°), and ordinate zou is intensity (arbitrary unit).
Fig. 5 is the X-ray diffracting spectrum of montmorillonite standard substance, and X-coordinate is 2 θ (°), and ordinate zou is intensity (arbitrary unit).
Fig. 6 is the X-ray diffracting spectrum of the montmorillonite that comparative example 4 of the present invention obtains, and X-coordinate is 2 θ (°), and ordinate zou is intensity (arbitrary unit).
Fig. 7 is the electron micrograph that the present invention tests the suspended emulsion that ultrasonic front bentonite material is formed in 1, and enlargement ratio is 20,000 times.
Fig. 8 is the electron micrograph that the present invention tests the suspended emulsion that ultrasonic rear bentonite material is formed in 1, and enlargement ratio is 20,000 times.
Embodiment
Below by specific embodiment, also the present invention will be further described by reference to the accompanying drawings, but be not limited thereto.
Embodiment 1 ~ 3, in embodiment 5 ~ 7 and comparative example 1 ~ 4, bentonite material takes from Shandong, and water content is 23.2wt%, commercial products, and Weifang Yong Lian wilkinite company limited is on sale.
In embodiment 1 ~ 7, comparative example 1 ~ 4 and effect experimental, purified water used is conventional pharmaceutical water, and Shandong Sibangde Pharmaceutical Co., Ltd. provides; Equipment used is conventional equipment, commercial products.
Embodiment 1, a kind of high purity montmorillonite environment-friendly production process, step is as follows:
(1) bentonite material heating-type circular rotary drum drying machine is dried, drum speed controls at 20r/min, opening for feed is with downbeam charging (warm air approach axis is identical with material approach axis), HAI Heated Air Intake temperature is 130 DEG C, air outlet temperature is 90 DEG C, drying 120 minutes in drying machine, being dried to water content is 1wt%;
The mensuration of turgidity is carried out with reference to " Chinese Pharmacopoeia version in 2010 annex IX O ", get dried sample 5.0g, put in 100ml tool plug graduated cylinder, add water 90ml, and jolting mixes, place 10 minutes, jolting therebetween 5 times, is diluted with water to 100ml, then puts upside down shake 20 times, place 30 minutes, recording turgidity is 3.0;
Soak 3h by purified water after drying, the mass ratio of dried bentonite material and purified water is 1:10; Then disperse in dispersion machine, dispersion machine dispersion axle rotating speed is 1400r/min, and dispersion impeller diameter is 500mm, and jitter time controls at 15 minutes; Disperse latter standing 50 minutes, crossed 300 mesh sieves, obtain coarse fodder liquid;
Montmorillonite mean particle size≤35 μm in coarse fodder liquid are measured with Mastersizer2000 particle size analysis instrument;
(2) by coarse fodder liquid 20 DEG C of ultrasonic disperse 50min, ultrasonic frequency is 40KHz, obtains suspended emulsion;
According to " Chinese Pharmacopoeia version in 2010 two annex IX E the 3rd methods ", measure suspended emulsion median size≤8 μm with Mastersizer2000 particle size analysis instrument;
(3) suspended emulsion is carried out three grades of rotary filter press in rotary filter press machine, first step eddy flow machine is FXJ-75, and control pressure is 2.5Kpa, and the first step separates relative density≤3.5g/cm
3material enter second stage eddy flow machine; Second stage eddy flow machine specification is FXJ-50, and control pressure is 2.0Kpa, and the second stage separates relative density≤2.8g/cm
3material enter third stage eddy flow machine; Third stage eddy flow machine specification is FXJ-25, and control pressure is 1.5Kpa, and the third stage separates relative density≤2.5g/cm
3material cross 325 mesh sieves; Standing sedimentation 10h, obtains sedimentation feed liquid; Remove sedimentation feed liquid upper strata moisture, when obtaining 25 DEG C, coefficient of dynamic viscosity is lower floor's material of 20 ~ 40Pas;
Adopt NDJ-1 type Rotary Viscosimeter according to " Chinese Pharmacopoeia version in 2010 two annex VI G second methods ", with No. 4 rotors, rotating speed is per minute 6 turns, and measuring the viscosity of lower floor's material, is 30Pas at the coefficient of dynamic viscosity of 25 DEG CShi lower floor materials;
(4) by lower floor's material in 130 DEG C of temperature and 5Kg sterilized under pressure 50min, be then cooled to 35 DEG C, recycling 30KHz ultrasonic echography sterilizing 50min, obtains sterilizing material;
According to " Chinese Pharmacopoeia version annex XIJ in 2010 " microbial decolorization, measure microbial limit in sterilizing material, meet the regulation of national standard;
(5) utilize horizontal screw centrifuge to carry out centrifugation sterilizing material, feeding rate controls at 0.1m
3/ min, collects relative density≤2.5g/cm
3material, 160 DEG C of dry 240min;
Measure according to " Chinese Pharmacopoeia version annex VIIIL in 2010 " dry weightless mensuration, moisture≤3wt%;
Be crushed to median size≤5mm with primary crusher after drying completes, then cross 325 mesh sieves after being crushed to median size≤45 μm with supper micron mill, obtain montmorillonite of the present invention;
Detect according to " national drug standards XGB2011-079 " relevant particle size determination, the weight not crossing 325 mesh sieve particles is no more than 1wt%;
After having sieved, put in mixer and always mix, always doing time is 40 minutes, then packing finished product.
Embodiment 2, a kind of high purity montmorillonite environment-friendly production process, step is as follows:
(1) bentonite material 90 DEG C being dried to water content is 10wt%, is uniformly dispersed, leaves standstill 30min, cross 200 mesh sieves, obtain coarse fodder liquid by purified water after soaking 1h; Described bentonite material: purified water is 1:5, mass ratio;
(2) by coarse fodder liquid 20 DEG C of ultrasonic disperse 10min, ultrasonic frequency is 15KHz, obtains suspended emulsion;
(3) suspended emulsion rotary filter press is removed relative density > 2.5g/cm
3material after, cross 325 mesh sieves, standing sedimentation 2h, obtains sedimentation feed liquid; Remove sedimentation feed liquid upper strata moisture, when obtaining 25 DEG C, coefficient of dynamic viscosity is lower floor's material of 20 ~ 40Pas;
(4) by lower floor's material in 130 DEG C of temperature and 3Kg sterilized under pressure 50min, be then cooled to 35 DEG C, the ultrasonic sterilizing 50min of 15KHz, obtains sterilizing material;
(5) sterilizing material is carried out centrifugation, collecting relative density is≤2.5g/cm
3material, 90 DEG C of dry 240min; Be crushed to median size≤5mm with primary crusher after drying completes, then cross 325 mesh sieves after being crushed to median size≤45 μm with supper micron mill, obtain montmorillonite of the present invention.
Embodiment 3, a kind of high purity montmorillonite environment-friendly production process, step is as follows:
(1) bentonite material 160 DEG C being dried to water content is 0.5wt%, is uniformly dispersed, leaves standstill 50min, cross 300 mesh sieves, obtain coarse fodder liquid by purified water after soaking 3h; Described bentonite material: purified water is 1:10, mass ratio;
(2) by coarse fodder liquid 60 DEG C of ultrasonic disperse 50min, ultrasonic frequency is 40KHz, obtains suspended emulsion;
(3) suspended emulsion rotary filter press is removed relative density > 2.5g/cm
3material after cross 400 mesh sieves, standing sedimentation 10h, obtains sedimentation feed liquid; Remove sedimentation feed liquid upper strata moisture, when obtaining 25 DEG C, coefficient of dynamic viscosity is lower floor's material of 20 ~ 40Pas;
(4) by lower floor's material in 151 DEG C of temperature and 5Kg sterilized under pressure 30min, be then cooled to 60 DEG C, the ultrasonic sterilizing 10min of 30KHz, obtains sterilizing material;
(5) sterilizing material is carried out centrifugation, collecting relative density is≤2.5g/cm
3material, 160 DEG C of dry 120min; Be crushed to median size≤5mm with primary crusher after drying completes, then cross 400 mesh sieves after being crushed to median size≤35 μm with supper micron mill, obtain montmorillonite of the present invention.
Embodiment 4, with different areas wilkinite for feedstock purification montmorillonite:
Select the Inner Mongol, Shandong, Guangxi, each three places, Sichuan to get bentonite material, bentonite material quality is as shown in table 1:
The quality of montmorillonite in table 1 different areas, different bentonite material
Step is as follows:
(1) by the bentonite material of above-mentioned different areas, different quality, dry 4 hours for 105 DEG C, mensuration water content is 0.51 ~ 1.02wt%; Taking the above-mentioned bentonite material of having dried of 100g respectively joins in the beaker of 2000ml, and the purified water adding 1000ml soaks 2h, is uniformly dispersed with electromagnetism dispersion machine, controlling electromagnetic dispersion machine rotating speed is 1000r/min, jitter time is 12min, crosses 300 mesh sieves, obtain coarse fodder liquid after leaving standstill 30min;
(2) by coarse fodder liquid ultrasonic disperse 30min in ultrasonic generator, temperature controls at 60 DEG C, and ultrasonic frequency is 30KHz, obtains suspended emulsion;
(3) suspended emulsion wet cyclone is removed relative density > 2.5g/cm
3material after cross 325 mesh sieves, standing sedimentation 2h, obtains sedimentation feed liquid; Remove sedimentation feed liquid upper strata moisture with suction pipe, when obtaining 25 DEG C, coefficient of dynamic viscosity is lower floor's material of 20 ~ 40Pas;
(4) by lower floor's material in 151 DEG C of temperature and 5Kg sterilized under pressure 30min, be then cooled to 60 DEG C, the ultrasonic sterilizing 30min of 20KHz, obtains sterilizing material;
(5) getting sterilizing material 90ml is respectively charged in 3 centrifuge tubes, and often pipe loads 30ml, and with laboratory tube centrifuge 10 minutes, controls centrifuge speed was 2000r/min, removes the water layer on upper strata after centrifugal end with suction pipe, collection relative density≤2.5g/cm
3the material being in middle level 105 DEG C dry 4 hours; Be crushed to mean particle size≤40 μm, cross 325 mesh sieves, obtain montmorillonite of the present invention.
X-ray powder diffraction is tested:
Get montmorillonite sample obtained above and carry out the experiment of X-ray powder diffraction, record diffracting spectrum, with the baseline of collection of illustrative plates for bottom line, measure montmorillonite characteristic peak, cristobalite diffraction peak summit respectively to the height of bottom line, calculate the ratio of each peak height relative to montmorillonite feature peak height, result is as shown in table 2:
The result of cristobalite in table 2 different areas, different bentonite material montmorillonite
According to the ratio of the cristobalite X-ray powder diffraction peak height in " national drug standards XGB2011-079 " medicinal smectite standard and montmorillonite feature peak height, must not more than 50.0%.After the inventive method process, the ratio < 50% of cristobalite X-ray powder diffraction peak height and montmorillonite feature peak height, meets national standard, can be applied to the industries such as medicine, food, fodder additives and makeup.
The drying of embodiment 5, bentonite material, the impact processed product montmorillonite yield and foreign matter content that pulverizes and sieves, step is as follows:
(1) by 300g bentonite material, water content is 23.2wt%, and the peak height of other impurity diffraction peaks and the ratio of montmorillonite feature peak height are 90%; Dry 4 hours with chamber oven 105 DEG C, mensuration water content is 0.51 ~ 1.02wt%; Taking the above-mentioned bentonite material of having dried of 100g joins in the beaker of 2000ml, the purified water adding 1000ml soaks 3h, be uniformly dispersed with electromagnetism dispersion machine, controlling electromagnetic dispersion machine rotating speed is 1000r/min, jitter time is 10min, cross 300 mesh sieves after leaving standstill 30min, obtain coarse fodder liquid, montmorillonite grain diameter Mastersizer2000 particle size analysis instrument measures particle diameter≤48 μm;
(2) by coarse fodder liquid ultrasonic disperse 50min in ultrasonic generator, temperature controls at 60 DEG C, and ultrasonic frequency is 35KHz, obtains suspended emulsion;
(3) suspended emulsion wet cyclone is removed relative density > 2.5g/cm
3material after cross 325 mesh sieves, standing sedimentation 2h, obtains sedimentation feed liquid; Remove sedimentation feed liquid upper strata moisture with suction pipe, when obtaining 25 DEG C, coefficient of dynamic viscosity is lower floor's material of 20 ~ 40Pas;
(4) by lower floor's material in 150 DEG C of temperature and 5Kg sterilized under pressure 30min, be then cooled to 60 DEG C, the ultrasonic sterilizing 30min of 20KHz, obtains sterilizing material;
(5) getting sterilizing material 90ml is respectively charged in 3 centrifuge tubes, often pipe loads 30ml, and with laboratory tube centrifuge 10 minutes, control centrifuge speed was 2000r/min, remove the water layer on upper strata after centrifugal end with suction pipe, collection density is 2.0 ~ 2.5g/cm
3the material being in middle level 105 DEG C dry 4 hours; Be crushed to mean particle size≤45 μm, cross 325 mesh sieves, obtain montmorillonite of the present invention.
Get montmorillonite sample obtained above and carry out the experiment of X-ray powder diffraction, Fig. 1 is the X-ray diffraction spectrogram of embodiment 5.
Comparative example 1,
This comparative example step, with embodiment 5, is pulverized and crosses 325 mesh sieves after drying unlike bentonite material in step (1).
Get the montmorillonite sample after above-mentioned purification and carry out the experiment of X-ray powder diffraction, Fig. 2 is the X-ray diffraction spectrogram of comparative example 1.
Comparative example 2,
This comparative example step, with embodiment 5, does not carry out drying and processing unlike bentonite material in step (1).
Get montmorillonite sample obtained above and carry out the experiment of X-ray powder diffraction, Fig. 3 is the X-ray diffraction spectrogram of comparative example 2.
Calculate the yield (the montmorillonite quality of output and the ratio of bentonite material quality) of montmorillonite in embodiment 5, comparative example 1 and comparative example 2, result is as shown in table 3.
Measure according to other impurity in " national drug standards XGB2011-079 " medicinal smectite standard in embodiment 5, comparative example 1 and comparative example 2, the peak height of other impurity diffraction peaks and the ratio of montmorillonite feature peak height must not more than 70%.
Table 3
As can be seen from Table 3, montmorillonite very easily hydration swelling in embodiment 5, form suspension, and there is not aquation in other impurity such as quartz, and the proportion of the sandstone such as the quartz that particle is larger is greater than montmorillonite, subsidence rate is very fast, sedimentation voluntarily in solution system, in solution after dispersion, montmorillonite suspension and quartz wait sandstone throw out interface clear, good separating effect, and yield is high, the montmorillonite quality obtained is better, the ratio of other impurity diffraction peaks and montmorillonite feature peak height is 28.6%, meets national medical standards.
After in comparative example 1, bentonite material is pulverized, the sandstone such as the quartz that particle is larger are pulverized too, form tiny particle, after montmorillonite aquation, surface-area increases the particle forming carrier tiny with sandstone such as quartz and jointly forms suspensoid, the particle settling rates that the sandstone such as quartz are tiny is caused to reduce, in solution after dispersion, montmorillonite suspension and quartz wait sandstone throw out interface fuzzy, inferior separating effect, in the montmorillonite be separated, quartz waits sandstone content high, the montmorillonite obtained is second-rate, the ratio of other impurity diffraction peaks and montmorillonite feature peak height is 72.1%, exceed national medical standards.
In comparative example 2, montmorillonite moisture content is lower, and extent of hydration is higher, and more easily meet water disintegration and expand, when montmorillonite moisture content is higher than more than 10wt%, extent of hydration is very low, and montmorillonite turgidity is low; In solution after dispersion, montmorillonite suspension and quartz wait sandstone throw out interface clear, and the ratio of other impurity diffraction peaks and montmorillonite feature peak height is 19.5%, meets national medical standards.But there is the non-disintegration of a large amount of montmorillonites to expand, with the sandstone coprecipitation such as quartz in beaker bottom, montmorillonite yield is very low.
Embodiment 6, high temperature high pressure process and supersonic synergetic effect are on the impact of sterilising effect, and step is as follows:
(1) by 300g bentonite material, water content is 23.2wt%, with chamber oven 105 DEG C dry to water content be 8wt%; Taking the above-mentioned bentonite material of having dried of 100g joins in the beaker of 2000ml, and the purified water adding 1000ml soaks 3h, is uniformly dispersed with electromagnetism dispersion machine, controlling electromagnetic dispersion machine rotating speed is 1200r/min, jitter time is 15min, crosses 300 mesh sieves, obtain coarse fodder liquid after leaving standstill 50min;
(2) by coarse fodder liquid ultrasonic disperse 50min in ultrasonic generator, temperature controls at 60 DEG C, and ultrasonic frequency is 40KHz, obtains suspended emulsion;
(3) suspended emulsion wet cyclone is removed relative density > 2.5g/cm
3material after cross 325 mesh sieves, standing sedimentation 1h, obtains sedimentation feed liquid; Remove sedimentation feed liquid upper strata moisture with suction pipe, when obtaining 25 DEG C, coefficient of dynamic viscosity is lower floor's material of 20 ~ 40Pas;
(4) by lower floor's material in 150 DEG C of temperature and 5Kg sterilized under pressure 30min, be then cooled to 60 DEG C, the ultrasonic sterilizing 30min of 20KHz, obtains sterilizing material;
(5) getting sterilizing material 90ml is respectively charged in 3 centrifuge tubes, often pipe loads 30ml, and with laboratory tube centrifuge 10 minutes, control centrifuge speed was 2000r/min, remove the water layer on upper strata after centrifugal end with suction pipe, collection relative density is 2.0 ~ 2.5g/cm
3the material being in middle level 105 DEG C dry 4 hours; Be crushed to mean particle size≤45 μm, cross 325 mesh sieves, obtain montmorillonite of the present invention.
Get 10g montmorillonite obtained above according to " Chinese Pharmacopoeia version annex XIJ in 2010 " microbial decolorization, carry out limit test of microbe, record detected result.
Comparative example 3,
The step of this comparative example, with embodiment 6, does not carry out ultrasonic sterilizing unlike in step (4) after 150 DEG C of temperature and 5Kg sterilized under pressure.
Get 10g montmorillonite obtained above according to " Chinese Pharmacopoeia version annex XIJ in 2010 " microbial decolorization, carry out limit test of microbe, record detected result.
The microorganism detection result of embodiment 6 and comparative example 3 is as shown in table 5.
Table 5
Analyzed from table 5, the successful of high temperature high pressure process and supersonic synergic sterilizing is better than the effect of only carrying out autoclave sterilization process.
Embodiment 7, drying temperature are on the impact of smectite structure, and step is as follows:
(1) by 300g bentonite material, water content is 23.2wt%, dries 1 hour with chamber oven 160 DEG C; Taking the above-mentioned bentonite material of having dried of 100g joins in the beaker of 2000ml, and the purified water adding 1000ml soaks 3h, is uniformly dispersed with electromagnetism dispersion machine, controlling electromagnetic dispersion machine rotating speed is 1400r/min, jitter time is 14min, crosses 300 mesh sieves, obtain coarse fodder liquid after leaving standstill 30min;
(2) by coarse fodder liquid ultrasonic disperse 50min in ultrasonic generator, temperature controls at 60 DEG C, and ultrasonic frequency is 40KHz, obtains suspended emulsion;
(3) suspended emulsion wet cyclone is removed relative density > 2.5g/cm
3material after cross 325 mesh sieves, standing sedimentation 2h, obtains sedimentation feed liquid; Remove sedimentation feed liquid upper strata moisture with suction pipe, when obtaining 25 DEG C, coefficient of dynamic viscosity is lower floor's material of 20 ~ 40Pas;
(4) by lower floor's material in 150 DEG C of temperature and 5Kg sterilized under pressure 30min, be then cooled to 60 DEG C, the ultrasonic sterilizing 30min of 20KHz, obtains sterilizing material;
(5) getting sterilizing material 90ml is respectively charged in 3 centrifuge tubes, often pipe loads 30ml, and with laboratory tube centrifuge 10 minutes, control centrifuge speed was 2000r/min, remove the water layer on upper strata after centrifugal end with suction pipe, collection relative density is 2.0 ~ 2.5g/cm
3the material being in middle level 160 DEG C dry 4 hours; Be crushed to mean particle size≤45 μm, cross 325 mesh sieves, obtain montmorillonite of the present invention.
Get 4g montmorillonite obtained above and grind to form fine powder; Get fine powder appropriate, be placed on load sample frame, load sample frame is put into moisture eliminator (containing saturated nacl aqueous solution, relative humidity about 75% when 20 DEG C) in after about 12 hours take out, sample on load sample frame is flattened, measure according to x-ray powder diffraction (Chinese Pharmacopoeia version in 2010 two annex IX F), in the scope interscan of diffraction angle (2 θ) 2 ° to 80 °, Fig. 4 is the montmorillonite X-ray diffracting spectrum that embodiment 7 obtains.Fig. 4 is consistent with the montmorillonite characteristic peak (diffraction angle (2 θ) is about 5.8 °, 19.8 ° and 61.9 ° respectively) in montmorillonite standard substance X-ray diffracting spectrum (Fig. 5), shows that drying does not destroy montmorillonite chemical structure under 160 DEG C of conditions.
Comparative example 4,
This comparative example step, with embodiment 7, is 400 DEG C unlike bentonite material bake out temperature.Get montmorillonite that this comparative example of 4g obtains to grind to form fine powder and do X-ray diffracting spectrum, as shown in Figure 6; Montmorillonite characteristic peak (diffraction angle (2 θ) is about 5.8 °, 19.8 ° and 61.9 ° respectively) wherein (2 θ) is about 5.8 ° of diffraction angle disappearances, shows under 400 DEG C of conditions, dry the destruction to montmorillonite chemical structure generation essence.
Effect experimental
Experiment 1, supersound process are on the impact of montmorillonite in bentonite material and magazins' layout effect:
This experiment carries out supersound process to the suspended emulsion that the bentonite material after soaking is formed, and ultrasonic frequency is 40KHz, with the change of particle in ultrasonic rear suspended emulsion before ultrasonic with electron microscope scanning analysis.Fig. 7 is the electron micrograph of the suspended emulsion that ultrasonic front bentonite material is formed, and Fig. 8 is the electron micrograph of the suspended emulsion that ultrasonic rear bentonite material is formed; The enlargement ratio of electron micrograph is 20,000 times.
Because cristobalite Mohs' hardness is comparatively large, as shown in Figure 7, under this frequency condition, produce sound wave cavatition less, pulverize in liquid phase and dispersion effect poor, cause solid cristobalite particle larger, volume does not expand, and does not produce hydration phenomena, and relative montmorillonite proportion in water is comparatively large and produce precipitation.And montmorillonite Mohs' hardness is less, as shown in Figure 8, under this frequency condition, sound wave cavatition is obvious, produces hydration phenomena, pulverize in liquid phase and dispersion effect better.
Experiment 2, the water content of bentonite material before immersion are on the impact of montmorillonite turgidity:
Take the bentonite material trial-product 7 parts that water content is 23.2wt% respectively, every part is 7g, be respectively sample 1, sample 2, sample 3, sample 4, sample 5, sample 6, sample 7, sample 1-6 chamber oven dry respectively under 130 DEG C, 120 DEG C, 110 DEG C, 100 DEG C, 90 DEG C, 80 DEG C temperature condition, drying time is 1 hour, and sample 7 is dried; Concrete steps are as follows:
Sample thief 7 and each 5.0g of sample 1-6 after drying, be placed in 100ml tool plug graduated cylinder respectively, add water 90ml, powerful jolting, and mixing, places 10 minutes, and jolting therebetween for several times, is diluted with water to 100ml, then puts upside down shake 20 times, place 30 minutes; Put upside down shake again 20 times, place 24 hours, carry out the mensuration of turgidity with reference to " Chinese Pharmacopoeia version in 2010 annex IX O ", measurement result is as shown in table 4.
Table 4
Measure turgidity and should be 2.0 ~ 5.0, as shown in Table 4, when bentonite material water content constantly increases, turgidity constantly reduces, and when bentonite material water content is at 9.8wt%, turgidity is close to bottom line 2.0.
Claims (6)
1. a montmorillonite environment-friendly production process, is characterized in that, step is as follows:
(1) bentonite material 90 ~ 160 DEG C being dried to water content is 0.5 ~ 10wt%, and after soaking 1 ~ 3 h by purified water, dispersed with stirring is even, leaves standstill 30 ~ 50 min, crosses 200 ~ 300 mesh sieves, obtain montmorillonite coarse fodder liquid; Described bentonite material: purified water is 1:5 ~ 10, mass ratio;
Described drying mode is for adopting rotary drum drying machine dry, and rotating cylinder rotating speed is 6 ~ 20r/min, and the inlet air temperature of warm air is 130 ~ 160 DEG C, and air outlet temperature is 90 ~ 120 DEG C;
(2) by coarse fodder liquid 20 ~ 60 DEG C of ultrasonic disperse 10 ~ 50 min, ultrasonic frequency is 15 ~ 40 KHz, obtains suspended emulsion;
(3) suspended emulsion rotary filter press is removed relative density > 2.5g/cm
3material after cross 325 ~ 400 mesh sieves, standing sedimentation 2 ~ 10 h, obtains sedimentation feed liquid; Remove sedimentation feed liquid upper strata moisture, when obtaining 25 DEG C, coefficient of dynamic viscosity is lower floor's material of 20 ~ 40Pas;
The mode of described rotary filter press is adopt three grades of separation in rotary filter press machine; First step eddy flow machine specification is FXJ-75, and control pressure is 2.5Kpa, and first step eddy flow goes out relative density≤3.5 g/cm
3material enter second stage eddy flow machine; Second stage eddy flow machine specification is FXJ-50, and control pressure is 2.0Kpa, and second stage eddy flow goes out relative density≤2.8 g/cm
3material enter third stage eddy flow machine; Third stage eddy flow machine specification is FXJ-25, and control pressure is 1.5Kpa, and third stage eddy flow goes out relative density≤2.5g/cm
3material;
(4) by lower floor's material in 130 ~ 151 DEG C of temperature and 3 ~ 5 Kg sterilized under pressure 30 ~ 50 min, be then cooled to 35 ~ 60 DEG C, 15 ~ 30 KHz ultrasonic sterilizing 10 ~ 50 min, obtains sterilizing material;
(5) sterilizing material is carried out centrifugation, collect relative density≤2.5 g/cm
3material, 90 ~ 160 DEG C of drying 120 ~ 240 min; Be crushed to median size≤45 μm; Cross 325 ~ 400 mesh sieves and carry out always mixing 20 ~ 40 min, then packing at mixer, obtaining montmorillonite.
2. montmorillonite environment-friendly production process according to claim 1, it is characterized in that, in described step (1), dispersed with stirring mode is for adopting dispersion machine dispersion, dispersion machine dispersion axle rotating speed is 1000 ~ 1400 r/min, dispersion machine dispersion impeller diameter is 350 ~ 600 mm, and jitter time controls at 10 ~ 15 min.
3. montmorillonite environment-friendly production process according to claim 1, is characterized in that, in described step (2) with ultrasonic generator to coarse fodder liquid ultrasonic disperse, ultrasonic frequency is 15 ~ 40KHz.
4. montmorillonite environment-friendly production process according to claim 1, it is characterized in that, in described step (4) by lower floor's material in 135 ~ 145 DEG C of temperature and 3 ~ 4 Kg sterilized under pressure 30 ~ 50 min, be then cooled to 35 ~ 60 DEG C, 20 ~ 30 KHz ultrasonic sterilizing 10 ~ 50 min.
5. montmorillonite environment-friendly production process according to claim 1, is characterized in that, the mode of centrifugation in described step (5) carries out centrifugation for adopting horizontal screw centrifuge; Feeding rate controls at 0.1 ~ 0.3 m
3/ min, collecting relative density is 2.0 ~ 2.5 g/cm
3material.
6. montmorillonite environment-friendly production process according to claim 1, it is characterized in that, in described step (5), grinding mode is that first coarse reduction is to median size≤5 mm, recycling supper micron mill micronizing is to median size≤45 μm, and supper micron mill rotating speed controls at 1000 ~ 1400r/min; Cross 325 ~ 400 mesh sieves after pulverizing and carry out always mixing 20 ~ 40 min, then packing at mixer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310042071.3A CN103073010B (en) | 2013-02-04 | 2013-02-04 | Environment-friendly production process for high-purity montmorillonite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310042071.3A CN103073010B (en) | 2013-02-04 | 2013-02-04 | Environment-friendly production process for high-purity montmorillonite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103073010A CN103073010A (en) | 2013-05-01 |
| CN103073010B true CN103073010B (en) | 2015-03-04 |
Family
ID=48149735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310042071.3A Active CN103073010B (en) | 2013-02-04 | 2013-02-04 | Environment-friendly production process for high-purity montmorillonite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103073010B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103962251A (en) * | 2014-04-18 | 2014-08-06 | 松阳县中奇环境工程有限公司 | Shearing emulsifying smashing device for processing materials containing ferrites |
| CN107051715A (en) * | 2017-05-22 | 2017-08-18 | 句容康泰膨润土有限公司 | The enrichment method of low-grade bentonite |
| CN107179327A (en) * | 2017-07-12 | 2017-09-19 | 四川维奥制药有限公司 | A kind of quality determining method of montmorillonite |
| CN107399742A (en) * | 2017-08-25 | 2017-11-28 | 芜湖飞尚非金属材料有限公司 | A kind of preparation technology of ultra-fine montmorillonite |
| CN108405204A (en) * | 2018-03-19 | 2018-08-17 | 田东昊润新材料科技有限公司 | A kind of New type cyclone group production technology suitable for high-purity montmorillonite industrialization processing |
| CN108996514A (en) * | 2018-07-20 | 2018-12-14 | 东北大学 | The method of chlorite crystal is prepared under a kind of hydrothermal condition |
| CN113122611A (en) * | 2019-12-30 | 2021-07-16 | 海南先声药业有限公司 | Method for checking microbial limit of montmorillonite powder |
| CN111686399B (en) * | 2020-05-29 | 2022-05-24 | 华南理工大学 | Reagent for inhibiting expression of antibiotic resistance genes of bacteria under metal induction and preparation method and application thereof |
| CN116077437A (en) * | 2022-12-29 | 2023-05-09 | 合肥久诺医药科技有限公司 | Montmorillonite suspension and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016157A (en) * | 2006-02-09 | 2007-08-15 | 浙江海力生制药有限公司 | Method of purifying montmorillonite, purified montmorillonite and composition thereof |
| CN100500563C (en) * | 2007-03-29 | 2009-06-17 | 浙江三鼎科技有限公司 | Method for purifying superfine montmorillonite |
| CN101129326A (en) * | 2007-08-15 | 2008-02-27 | 济南康众医药科技开发有限公司 | Method of preparing smectite suspension agent |
| CN101844772B (en) * | 2010-05-28 | 2012-02-29 | 四川思迈特药业科技有限公司 | Process for purifying montmorillonite |
| CN102583418A (en) * | 2012-02-11 | 2012-07-18 | 济南康众医药科技开发有限公司 | Preparation method for asbestos-free montmorillonites |
-
2013
- 2013-02-04 CN CN201310042071.3A patent/CN103073010B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103073010A (en) | 2013-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103073010B (en) | Environment-friendly production process for high-purity montmorillonite | |
| CN105344428B (en) | A kind of wonderful mill prepared slices of Chinese crude drugs breaking cellular wall micronizing technique and its equipment | |
| CN102897783A (en) | Preparation method of bentonite for slurry | |
| CN106622482A (en) | Chinese herbal medicine grinding, crushing and dehumidifying device | |
| CN101844772B (en) | Process for purifying montmorillonite | |
| CN102205972A (en) | Modification method of attapulgite | |
| Sarkar et al. | Biomass derived palygorskite–carbon nanocomposites: Synthesis, characterisation and affinity to dye compounds | |
| JP2007501180A (en) | High oil-absorbing amorphous silica particles | |
| Filio et al. | A study on talc ground by tumbling and planetary ball mills | |
| CN103663481A (en) | Purification technology for low-grade bentonite | |
| Ford et al. | Separation of the light fraction from soils by ultrasonic dispersion in halogenated hydrocarbons containing a surfactant | |
| CN105289487B (en) | A kind of preparation method of red mud base weight metal ion adsorption material | |
| CN110092386A (en) | A kind of method of purification of attapulgite clay | |
| JP2015229621A (en) | Hydrophobic aerogel powder, method of manufacturing thereof, and filler using thereof | |
| CN101002805B (en) | Method for breaking trachytectum of glossy ganoderma | |
| Toraman | Effect of chemical additive on stirred bead milling of calcite powder | |
| CN101559402B (en) | Method for purifying high-ash coke powder | |
| Hu et al. | An study on preparation and utilization of tourmaline from tailings of an iron-ore processing plant | |
| CN102951651A (en) | Preparation technology of high-purity fine white montmorillonite | |
| CN108295808A (en) | A kind for the treatment of agent for papermaking wastewater | |
| CN106745014A (en) | A kind of method of purification of low taste sepiolite | |
| Ajemba | Structural alteration of bentonite from nkaliki by acid treatment: studies of the kinetics and properties of the modified samples | |
| CN102583418A (en) | Preparation method for asbestos-free montmorillonites | |
| Du et al. | Improving thickener bed density by ultrasonic treatment | |
| JM et al. | Effect of dry grinding on the structures and physical properties of pyrophyllite and talc by a planetary ball mill |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: SHANDONG SIBANGDE PHARMACEUTICAL CO., LTD. SHANDON Effective date: 20130524 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20130524 Address after: 250216, Shandong, Ji'nan, Zhangqiu Longshan office, Longhu Road, East Shandong Pharmaceutical Co., Ltd. Applicant after: Qiao Min Applicant after: Shandong Sibangde Pharmaceutical Co., Ltd. Applicant after: Shandong Xianhe Pharmaceutical Co., Ltd. Address before: 250216, Shandong, Ji'nan, Zhangqiu Longshan office, Longhu Road, East Shandong Pharmaceutical Co., Ltd. Applicant before: Qiao Min |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |