CN1320962C - Process for conversion and size reduction of solid particles - Google Patents
Process for conversion and size reduction of solid particles Download PDFInfo
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- CN1320962C CN1320962C CNB2003801047984A CN200380104798A CN1320962C CN 1320962 C CN1320962 C CN 1320962C CN B2003801047984 A CNB2003801047984 A CN B2003801047984A CN 200380104798 A CN200380104798 A CN 200380104798A CN 1320962 C CN1320962 C CN 1320962C
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Abstract
A combined process for the conversion of solid starting particles into solid intermediate particles and reducing the median diameter of the intermediate particles to obtain product particles. This process involves flowing a suspension of starting particles through a series of at least two conversion vessels, thereby converting at least part of the starting particles into intermediate particles, adding a supercritical fluid to one or more of the conversion vessels, thereby forming a supercritical suspension, and releasing pressure from the supercritical suspension, thereby expanding the suspension and converting the intermediate particles into product particles.
Description
The present invention relates to the method that a kind of solid particle that will have specific median particle diameter is converted into the solid product particle with less median particle diameter.
One of most popular method that reduces particle size is to grind.Yet median particle diameter can not obtain by conventional polish process usually less than about 1 micron particle.Nowadays, nanometer technology is a research field in the development of high expectation value.The so-called nano particle of this Technology Need, nano particle is defined as median particle less than about 1 micron particle in this manual.Such particle can not obtain by the simple grinding to larger particles usually.
United States Patent (USP) 5810267 disclose a kind of by with powder suspension in the fluid of above-critical state, to suspended substance pressurization, inject this fluid, reduce the pressure of suspension and under overcritical or subcritical neutron, fluid separated from solid particle with gaseous state and the method for this powder being carried out meticulous pulverizing by nozzle.Embodiment in this document is reduced to 10 microns SiC particle 1 micron SiC particle.The size of these particles changes, but their chemical constitution and the degree of order remain unchanged.
United States Patent (USP) 5921478 discloses a kind ofly sends the mixture of dispersion and solvent into overcritical container by (i), (ii) supercritical solvent is sent in the overcritical container, (iii) heat and compress supercritical solvent to be converted into supercritical fluid from gaseous state, (iv) in overcritical container, mix described mixture and supercritical fluid with obtain supercritical mixtures and (thereby v) supercritical mixtures is introduced that blast-bump jar is discharged into supercritical mixtures under the atmospheric pressure and with the collision of overcritical jar partly collide supercritical mixtures with the dispersion of realization dispersion the method for discrete particles.This method has produced the bump and the dispersion of particle.The chemical constitution and the degree of order thereof of particle remain unchanged.
Yet, need in a technology, to integrate (a) and change the degree of order of particle and (b) size of these particles is reduced to nanometer range (if need).The present invention has provided such method.
Method of the present invention relates to the median particle diameter that the solid material particle is converted into the solid intermediate particle and reduces midbody particle to obtain the integrated processes of product particle, and this method relates to the following step:
A) make the suspended substance of feed particles flow through a series of at least two conversion vessel, thereby at least a portion feed particles be converted into midbody particle,
B) supercritical fluid is added in one or more conversion vessel, thus form overcritical suspended substance and
C) release pressure from overcritical suspended substance, thus make the suspended substance expansion and midbody particle is converted into the product particle.
Solid material particle or for amorphous or have a specific degree of order.The solid material particle preferably is converted into (i) and has the specific degree of order when being amorphous when feed particles in the methods of the invention, or (ii) when feed particles has the specific degree of order, have different ordered structures, the different degree of order or the midbody particle of disordered structure.Term " degree of order " is defined as existence can be by the crystallization or accurate crystallization (the being non-amorphous) phase of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope inspection art (TEM) or extended X-ray absorption fine structure (EXAFS) detection.Usually, the degree of order can detect (as peak or broad peak) by X ray, but (promptly is lower than the limit that XRD detects) under very little crystal grain situation, just needs to adopt more advanced technology to detect the degree of order: SEM, TEM or EXAFS.On the other hand, the amorphous degree of order that is defined as with above-mentioned definition.If crystal grain can detect by X ray, then can for example estimate the degree of order from the width of XRD peak (or broad peak).The peak is narrow more, and the degree of order will be high more.Follow the tracks of different ordered structures by crystal structure or morphosis that above-mentioned technology for detection is different.Disordered structure is represented amorphous.
Method of the present invention is particularly suitable for producing nano particle.Therefore the inventive method can be advantageously used in the preparation median particle diameter less than 1 micron product particle, more specifically is 1-500nm, further is specially to be lower than 1-200nm, most preferably 1-100nm.Midbody particle and in most of the cases also have feed particles to have the median particle diameter bigger than product particle.Preferably, the median particle diameter of feed particles is higher than 1 micron, 1-1000 micron preferably approximately, more preferably 1-500 micron, further preferred 1-200 micron.The diameter of particle is determined by measuring with the particle diameter of the observed representative quantity of electronic microscopy.Median particle diameter is the median that particle diameter distributes: the particle grain size of 50% quantity is more than median particle diameter, and 50% below median particle diameter.
Raw material, intermediate and product particle are preferably made by inorganic material.Feed particles is lower cost materials such as aluminium oxide or aluminium hydroxide preferably, for example bauxite, crystallization aluminum trihydrate (ATH), gibbsite, bauxitic ore condensation product (BOC) or its treated forms (for example calcining and/or quick burning form); Synthesize and natural clay such as kaolin, sepiolite, hydrotalcite, terre verte or bentonite; Silica ore such as sand or diatomite; Magnesium source such as magnesium salts, magnesia or magnesium hydroxide such as shepardite, magnesium carbonate, magnesium hydroxide magnesium carbonate double salt; Zirconium compounds such as zirconia, zircon or baddeleyite; Titanium oxide or titanium hydroxide; Adsorbent, catalyst or catalyst precarsor are spray-dired particle form with microballoon for example, or the like.If desired, feed particles can be used for carrying out mechanical treatment (for example grinding) to reduce its granularity before the inventive method.
The example that feed particles is converted into midbody particle has the precipitation mixture with aluminum sulfate and aluminum nitrate to be converted into boehmite, (BOC) is converted into boehmite with the bauxitic ore condensation product, accurate crystalline boehmite is converted into the crystallite boehmite, cheap silicate ore (for example sand) is converted into silica or based on the material of silica, with silicon source (sand for example, Ludox, waterglass, diatomite) and solid magnesium source (MgO for example, shepardite, hydromagnesite or magnesium salts) be converted into layered magnesium silicate, zirconia ore (as zircon or baddeleyite) is recrystallised to the zirconia of highly crystalline, silicon source and solid aluminium source (for example aluminium oxide or aluminium hydroxide) and optional crystal seed and/or template are converted into molecular sieve (X zeolite for example, the Y zeolite, the A zeolite, ZSM type zeolite, the β zeolite, mesoporous molecular sieve), the solid metal source (for example aluminium source and magnesium source) of trivalent and divalence is converted into anionic clay (for example hydrotalcite), two kinds of divalence solid metal sources are converted into stratiform hydroxyl (answering) salt, with silicon source and solid aluminium source and optional bentonite crystal seed is converted into bentonite and with the silicon source, solid aluminium source and solid magnesium source are converted into terre verte.In addition, the various combinations of above-mentioned conversion can be used for forming the composite that various composites for example contain anionic clay and boehmite, or contain the composite of anionic clay, boehmite and zeolite.
Usually by forming with the midbody particle identical materials, different is that they have less granularity to the product particle.Yet, if midbody particle is stratified material such as anionic clay (for example hydrotalcite), cationic clay (for example terre verte, kaolin, bentonite, sepiolite etc.) or stratiform hydroxyl (answering) salt, pressure release can cause the delamination of layer structure and/or peel off.
The inventive method relates to the suspended substance that makes feed particles and flows through a series of at least two conversion vessel as the first step, and the pressure of release suspended substance is as final step.Can change the time that supercritical fluid is introduced according to following three embodiments.
In first embodiment, for example adopting at first one, two or three conversion vessel in non-supercritical liquid, feed particles to be converted into midbody particle under atmospheric pressure or the superatmospheric pressure.The suitable non-supercritical liquid of Cai Yonging comprises water, alcohol (as methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol etc.) and hydrocarbon liquids (as toluene, hexane, petroleum solvent, gasoline etc.) in the methods of the invention.In conversion vessel subsequently, to choose wantonly behind its content liquid of minimizing and/or after carrying out mechanical treatment, the suspended substance that will contain midbody particle combines with supercritical fluid and obtains overcritical suspended substance.Then, overcritical suspended substance is pumped in subsequently the container, thereby overcritical suspended substance is expanded and forms the product particle by nozzle or aperture.
In second embodiment, in the process that feed particles is converted into midbody particle, add supercritical fluid.Therefore the part conversion to midbody particle takes place under super critical condition.Have again, before with suspended substance and supercritical fluid combination, can for example pass through drying or dehydration, and can carry out mechanical treatment (for example grinding) suspended substance with the content liquid in the minimizing suspended substance.After reaching required transforming degree, by nozzle or aperture overcritical suspended substance is pumped in subsequently the container, thereby overcritical suspended substance is expanded and forms the product particle.
At these two formerly in the embodiment, the conversion vessel that does not contain supercritical fluid remains on usually than under the lower pressure of the container that supercritical fluid is housed.In order to produce big pressure reduction between each container, described equipment can be equipped with the high pressure slush pump.This can realize continuous processing.Perhaps can semi-continuously carry out this method by interrupting the preparation of midbody particle in the sequential steps of supercritical fluid being packed into one of them container at (a) and (b) overcritical suspended substance being expanded.During disconnected hereinto, the conversion vessel under conversion vessel under the super critical condition and the non-supercritical condition disconnects.
In the 3rd embodiment, the whole technology that feed particles is converted into midbody particle is carried out under super critical condition.Therefore supercritical fluid is added in first container of a series of two conversion vessel at least.At last, after forming midbody particle, overcritical suspended substance is pumped in subsequently the container by nozzle or aperture, thereby overcritical suspended substance is expanded and forms the product particle.
The example of supercritical fluid has supercritical CO
2, overcritical nitrogen, overcritical ethene, overcritical xenon, overcritical ethane, overcritical nitrous oxide, supercritical propane, supercritical ammine, overcritical pentane, overcritical isopropyl alcohol, supercritical methanol, overcritical toluene and supercritical water.Supercritical CO
2It is the preferred supercritical fluid that is used for the inventive method.CO
2Have gentle critical-temperature (31 ℃), it is inflammable and nontoxic.And it can and can further not encourage greenhouse effects from existing commercial run acquisition.Supercritical carbon dioxide has high diffusion coefficient, low viscosity and low surface tension.Adopt supercritical CO
2Another advantage be gaseous state CO
2Can evaporate, and make dry solid product particle be easy to collect.
Comprise at least two conversion vessel and thereby the example that is suitable for the equipment of the inventive method be equipment according to United States Patent (USP) 2003-0003035 and WO03/078055.This equipment can comprise the feed preparation container, wherein can add the raw material solid particle and mix with optional crystal seed, corrodent and/or acid and with liquid.The gained suspended substance can be pumped in first container of a series of two but preferred 3-5 conversion vessel by feed pump at least.Each conversion vessel all can contain syringe (can introduce other liquid, acid, alkali, crystal seed and other composition by syringe) and blender, and preferred axes is to blender or coaxial hybrid, for example with EKATO-INTERMIG
In conjunction with double helix impeller or dasher (being suitable for mixing the impeller of low viscosity slurries, the wherein downward pumping of outer leafs pumping) and intra vane makes progress.
Because supercritical fluid requires superatmospheric pressure (at CO
2Situation under be higher than about 73 the crust), the conversion vessel of working under super critical condition must be an autoclave.The typical pressures range of super critical condition is about 200-300 crust.The exemplary that can be used for the autoclave of this purpose is the AHPT autoclave of AHPT Ltd. (P.O.Box11807, Tel Aviv61116, Israel) supply.
Preferably by overcritical suspended substance is sprayed in the container subsequently and release pressure by nozzle or aperture (can cool off solidifying of causing to prevent joule-Thomsons to nozzle or aperture heating).The method also is called the rapid expansion (RESS) of overcritical suspended substance.Container subsequently can remain near atmospheric pressure or slightly under the condition of high pressure such as 40-50 crust.The latter can realize the recirculation of Energy Efficient more and economic supercritical fluid.
In order to realize the conversion of feed particles, in the process of suspended substance, additional compounds (crystal seed, template, additive, other feed particles) can be added in one or more conversion vessel to midbody particle.In addition, the temperature in each conversion vessel can be different.
And, can in suspended substance, add surfactant such as acetate or gluconate, thus the interaction between the interaction between minimizing non-supercritical liquid and the solid particle and enhancing solid particle and the supercritical fluid.If have polar liquid such as water in the suspended substance, then need this operation especially.
In addition, can in suspended substance, add metallic additions, to obtain metal-doped midbody particle and/or feed particles.The example of this metallic additions has the compound that comprises the element that is selected from alkaline-earth metal (as Mg, Ca and Ba), transition metal (as Mn, Fe, Co, Ti, Zr, Cu, Ni, Zn, Mo, W, V, Sn, Nb), actinide metals, rare earth metal such as La and Ce, noble metal such as Pt and Pd, silicon, gallium, boron, titanium, phosphorus and composition thereof.Metallic additions can (for example pass through metallic additions is added in the container subsequently) in adding suspended substance with feed particles or respectively.If stratified material forms as midbody particle, then may need to be present in intercalator in the suspended substance to form the stratified material of intercalation.Term " intercalator " thus be defined as and can be used as main body is present in increases the interval between each layer between each layer of stratified material compound.The example of intercalator has organic compound, for example comprises aromatic ring and/or is selected from the organic compound of the functional group of carbonyl, carboxyl, hydroxyl, amide groups, ether, ammonium and ester group.The example of these compounds has amino acid (as glycine, serine, the L-aspartic acid), oleate, gluconate, carboxymethylated carbohydrate (for example carboxymethyl cellulose), organic solvent is (as methyl-sulfoxide, isophorone, gamma-butyrolacton, the N-methyl pyrrolidone, 2-Pyrrolidone, diethylene glycol dimethyl ether, caprolactam, furfuryl alcohol, oxolane), quaternary ammonium cation, alkyl sulfate (as lauryl sodium sulfate), alkylsulfonate is (as styrene sulfonate, poly styrene sulfonate), reach other ionic alkyl chain compound or surfactant.The example that can be used as the anionic inorganic compound of intercalator is column anion such as Fe (CN)
6 3-, HVO
4 -, V
2O
7 4-, HV
2O
12 4-, V
3O
9 3-, V
10O
28 6-, Mo
7O
24 6-, PW
12O
40 3-, B (OH)
4 -, [B
3O
3(OH)
4]
-, [B
3O
3(OH)
5]
2-, B
4O
5(OH)
4 2-, HBO
4 2-, HGaO
3 2-, CrO
4 2-, Cr
2O
7 2-Or Keggin ion.
The non-supercritical suspended substance that flows through conversion vessel can have high solid-liquid than (SLR).The SLR of suspended substance is defined as solid (comprising the crystallization water) in the suspended substance to the weight ratio of liquid.The rheological property that best SLR depends on suspended substance is as tending to form the performance of gel, and can be in the scope of 0.1-1.33, more preferably 0.3-1.33, further preferred 0.5-1.33, most preferably 0.65-1.00.The viscosity of non-supercritical suspended substance is preferably at 0.1s
-1Shear rate under be 1-500Pas.
Adopt method of the present invention can make the product particle that is fit to various application.The size of type of material and particle is depended in their application.For example nano particle can be used for preserving (for example preserving history file), polymer (as filler) etc. as molecular electronic device (for example molecular electric wire, diode, transistor, memory), sensor, nanometer pump, catalysis (as catalyst, catalyst additive, catalyst carrier etc.), adsorbent, coating composition (for example priming paint of metal and/or plastic basis material, subcoat and/or clear coat), papermaking, paper.
Embodiment
Embodiment 1
The inventive method that this embodiment explanation is converted into aluminum trihydrate and raw materials of magnesium oxide particle the anionic clay midbody particle and these anionic clay midbody particles is converted into anionic clay product nano particle.
In 250 liters feed preparation container, mix the 24.2kg aluminum trihydrate (from the ATHM6 of Alcoa
), 25kg MgO is (from the Zolitho40 of Martin Marietta
) and 150.8kg water.The solid-liquid ratio is 0.33.MgO/Al
2O
3Mol ratio be 4.
Suspended substance is pumped in first conversion vessel.By the steam injection suspended substance is heated to 170 ℃, thereby the solid-liquid ratio is reduced to 0.25.Making suspended substance is two conversion vessel by subsequently under the about 45 minutes flow at mean residence time.Suspended substance in all conversion vessel all adopts the double helix impeller to stir under the rotating speed of 76-83rpm.Since slight exothermic reaction, 170 ℃ 180 ℃ of being elevated in second conversion vessel of temperature from first conversion vessel.The pressure of whole system is by just being positioned at the 3rd the pressure valve control outside the conversion vessel.System pressure in this experiment maintains 12 crust.The measurement result of X-ray diffraction (XRD) shows and has formed the Mg-Al anionic clay.The midbody particle of this anionic clay has about 4 microns median particle diameter.
After the 3rd conversion vessel, with suspended substance the 4th conversion vessel of packing into, this container utilizes supercritical CO
2Pump CO
2(T＞304.2K is under the required condition of p＞73atm) to be pressurized to supercriticality.Before the supercritical fluid of packing into, the 4th conversion vessel and the 3rd conversion vessel disconnect and interrupt the preparation of anionic clay feed particles.The overcritical suspended substance of gained was stirring 10 minutes under (1000-2000rpm) at a high speed.CO in the suspended substance
2/ H
2The weight ratio of O is higher than 5, thereby the solid-liquid ratio is reduced to less than 0.054.Then, suspended substance is discharged in subsequently the container by nozzle, and this container remains under the condition near atmosphere, thereby will wet CO
2Gas is discharged into CO
2In gas recovery and the drying system.Dry CO
2Gas adopts supercritical CO
2Compressor/pump recycles.According to the semicontinuous pattern of the inventive method, reconnect the 3rd and the 4th conversion vessel, recover the production of product particle, and the 4th conversion vessel of once more feed particles being packed into.
The product particle that analysis is collected from last container is the Mg-Al anionic clay particles of median particle less than 500nm.
Embodiment 2
Repeat embodiment 1, different is to adopt overcritical nitrogen (126K, 33.5atm) alternative supercritical CO
2Have again, the product particle comprises the Mg-Al anionic clay and has median particle less than 500nm.
Embodiment 3
The method that this embodiment explanation is converted into the feed particles of sodium metasilicate and quick burning aluminium oxide the zeolite midbody particle and these midbody particles is converted into zeolite product particle.
The 3.73kg sodium silicate aqueous solution that contains 28wt% solid (with sol particle) is mixed with 40g aluminium CP-3 (aluminum trihydrate of quick burning) and 2.80kg water to form suspended substance.The solid-liquid of this suspended substance is 0.20 than (SLR).When calculating SLR, 28wt% sodium metasilicate Mass Calculation is a solid, and remaining 72wt% is calculated as liquid.Add ZSM-5 crystal seed (10wt%).Suspended substance is heated to 170 ℃ and kept 300 minutes under this temperature.Suspended substance adopts the double helix impeller to stir under 76-83rpm.The zeolite midbody particle of Xing Chenging has about 7 microns median particle diameter like this.
With suspended substance second container of packing into, this container utilizes supercritical CO
2Pump CO
2(T＞304.2K is under the required condition of p＞73atm) to be pressurized to supercriticality.The overcritical suspended substance of gained was stirring 10 minutes under (1000-2000rpm) at a high speed.CO in the suspended substance
2/ H
2The weight ratio of O is higher than 5, thereby the solid-liquid ratio is reduced to less than 0.033.Then, suspended substance is discharged in the 3rd container by nozzle, and this container remains under the condition near atmosphere, thereby will wet CO
2Gas is discharged into CO
2In gas recovery and the drying system.Dry CO
2Gas adopts supercritical CO
2Compressor/pump recycles.The product particle that analysis is collected from the 3rd container is that silicon/aluminum ratio (SAR) is 55.90% ZSM-5, and these product particles have the granularity less than 1 micron.
Embodiment 4
Repeat embodiment 1 and 2, before different is in the 4th conversion vessel of packing into, adopts the high-pressure filteration step to make the suspended substance dehydration, thereby the water content (LOI) of suspended substance is reduced to less than 10wt%.This has increased the ratio of supercritical fluid/water in the 4th conversion vessel.
Embodiment 5
Repeat embodiment 3, before different is in second container of packing into, adopts the high-pressure filteration step to make the suspended substance dehydration, thereby the water content (LOI) of suspended substance is reduced to less than 10wt%.This has increased the ratio of supercritical fluid/water in second container.
Embodiment 6
Repeat embodiment 1-5, different is to add gluconic acid sodium salt in suspended substance.
Embodiment 7
Repeat embodiment 1-6, before different was in being discharged near the container of atmospheric conditions, overcritical suspended substance at first was discharged into slightly under the high pressure (at supercritical CO
2Situation under: in container 40-50 crust), thereby can realize supercritical fluid Energy Efficient and economic recirculation more.
Claims (10)
1. the median particle diameter that the solid material particle is converted into the solid intermediate particle and reduces midbody particle is to obtain the method for product particle, and this method comprises the following steps:
A) make the suspended substance of feed particles flow through a series of at least two conversion vessel, thereby at least a portion feed particles is converted into midbody particle, this midbody particle
(i) have the specific degree of order when being amorphous when feed particles, or
(ii) when having the specific degree of order, feed particles has different ordered structures, the different degree of order or disordered structure,
B) supercritical fluid is added in one or more conversion vessel, thus form overcritical suspended substance and
C) release pressure from overcritical suspended substance, thus make the suspended substance expansion and midbody particle is converted into the product particle.
2. according to the process of claim 1 wherein that the solid product particle has the median particle diameter less than 1 micron.
3. according to the method for claim 2, wherein the solid product particle has the median particle diameter of 1-500nm.
4. according to the method for claim 3, wherein the solid product particle has the median particle diameter of 1-200nm.
5. according to the method for aforementioned any claim, wherein the solid material particle is an inorganic solid particles.
According to the process of claim 1 wherein midbody particle comprise be selected from anionic clay, terre verte, zeolite, boehmite, silica, cationic clay, layered hydroxy salts with and the material of combination.
7. according to the process of claim 1 wherein that supercritical fluid is a supercritical carbon dioxide.
8. according to the process of claim 1 wherein that feed particles occurs under the super critical condition to transforming to small part of midbody particle.
9. according to the process of claim 1 wherein that overcritical suspended substance adds in first of a series of conversion vessel.
10. supercritical fluid is added in the suspended substance of feed particles after feed particles is converted into midbody particle according to the process of claim 1 wherein.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US43022702P | 2002-12-02 | 2002-12-02 | |
| US60/430,227 | 2002-12-02 | ||
| EP02027486.6 | 2002-12-10 |
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| Publication Number | Publication Date |
|---|---|
| CN1720103A CN1720103A (en) | 2006-01-11 |
| CN1320962C true CN1320962C (en) | 2007-06-13 |
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| TWI486474B (en) * | 2012-02-15 | 2015-06-01 | 陳柏頴 | A low-temperature optimizing materials method and the device thereof |
| CN107697930B (en) * | 2017-03-14 | 2021-04-09 | 中国石油大学(北京) | SAPO-11 molecular sieve, preparation method thereof and application thereof in hydrocarbon isomerization |
| CN108704588B (en) * | 2018-06-29 | 2020-10-09 | 广西壮族自治区林业科学研究院 | Preparation method of microencapsulated acidic aqueous solution |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1202258B (en) * | 1960-11-14 | 1965-10-07 | Almasfuezitoei Timfoeldgyar | Method for breaking down alumina-containing materials, in particular bauxite, using caustic soda |
| US5810267A (en) * | 1995-09-29 | 1998-09-22 | Karasawa; Yukihiko | Method and apparatus for pulverizing solid particles |
| US5921478A (en) * | 1996-12-27 | 1999-07-13 | Inoue Mfg., Inc. | Dispersion method and dispersing apparatus using supercritical state |
-
2003
- 2003-12-02 CN CNB2003801047984A patent/CN1320962C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1202258B (en) * | 1960-11-14 | 1965-10-07 | Almasfuezitoei Timfoeldgyar | Method for breaking down alumina-containing materials, in particular bauxite, using caustic soda |
| US5810267A (en) * | 1995-09-29 | 1998-09-22 | Karasawa; Yukihiko | Method and apparatus for pulverizing solid particles |
| US5921478A (en) * | 1996-12-27 | 1999-07-13 | Inoue Mfg., Inc. | Dispersion method and dispersing apparatus using supercritical state |
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