CN101049580A - Technique and equipment for preparing Nano granules in high purity by using method of comminution by gas stream - Google Patents
Technique and equipment for preparing Nano granules in high purity by using method of comminution by gas stream Download PDFInfo
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Abstract
An apparatus for preparing high-purity nanoparticles by airflow pulverizing method is composed of an air source system, a pulverizing system consisting of left and right reflux pipes and flow-up pipe to form a circulating loop of material, and air-solid separating system. Its process features that the raw material is carried by two supersonic jets for mutual and cyclic collision to obtain nanoparticles.
Description
Technical field
The present invention relates to a kind of pulverizing preparation technology and device of particle, more particularly say, be meant that a kind of air-flow continuous grinding mode that circulates that adopts prepares the technology and the device of Nano granules in high purity.
Background technology
Nano-particle material is because the many special natures of himself have application very widely in a lot of fields.At present, the preparation method about nano particle mainly is divided into synthetic method and breaking method two classes on the whole.Synthetic method prepares nano particle and mainly comprises gas evaporation method, liquid-phase precipitation method, sol-gel process etc.And breaking method to prepare nano particle mainly be to adopt the mechanical force and chemical method to prepare nano particle at present.When adopting synthetic method to prepare nano particle, the material of preparation is very restricted, and adopt mechanical force and chemical method such as medium mill to prepare nano particle, because the wearing and tearing of medium ball are arranged in preparation process, prepared nano particle purity is not very high, have certain pollution, prepared material also has significant limitation.
Airflow pulverization method is present a kind of preparation method of granules commonly used, in the process of its preparation particle, owing to there is not the existence of other medium, just utilizes the mutual collision between the material and make the material fragmentation, thereby this method also is a kind of free of contamination high purity granular preparation method.But because mostly general air-flow disintegrating apparatus is to adopt grading wheel that the particle after pulverizing is carried out the classification processing at present, the fine powder that granularity is qualified separates from meal, and underproof meal then continues to pulverize in airslide disintegrating mill and obtains the qualified fine particle of granularity.Be subjected to the restriction of grading wheel classification principle and effectiveness of classification, the method by grading wheel want is nano particle and air separation, still is difficult to realize industrial at present.
Summary of the invention
One of purpose of the present invention is to propose a kind of technology that adopts airflow pulverization method to prepare Nano granules in high purity, material is carried in two bursts of supersonic jets of this technology utilization, head-on collision, pulverizing by band material jet, and material is circulated pulverize continuously, prepare the high-purity nano particle in crushing chamber.
Another object of the present invention provides a kind of device that adopts airflow pulverization method to prepare Nano granules in high purity, this device can be made up of air supply system, the gentle solid separation system of crushing system, perhaps spray into the gentle solid separation system of system and form by air supply system, crushing system, modifier, air supply system and crushing system by pipeline be connected, crushing system is connected by pipeline with the modifier system that sprays into.
Described air supply system includes air compressor machine, drier, heater, temperature sensor and temperature controller; Temperature sensor links to each other with temperature controller, and the sensitivity end of temperature sensor is installed in the heater; The gases at high pressure that produce by air compressor machine enter carry out in the drier dryly handling, the heater via heating obtains 20～200 ℃ of temperature then dry gases at high pressure;
Described gas solid separation system includes filter, blow-back device, air-introduced machine, described air-introduced machine is connected with the air-introduced machine interface, the blow-back device is connected with blow-back device A interface, blow-back device B interface respectively, filter is installed in top, gas solid separation chamber, and this gas solid separation system can make in the crushing chamber material and air realize separating;
Described crushing system includes cylindrical shell, left tapering, right tapering, right return duct, tedge, left return duct, left nozzle, right nozzle, crushing chamber, and the top of cylindrical shell is provided with air-introduced machine interface, blow-back device A interface, blow-back device B interface; The bottom of cylindrical shell is connected with left tapering, tedge, right tapering, between tapering, a left side and the right tapering A shape groove is arranged, tedge is placed in the A shape groove, tapering, the left side other end is connected with left return duct, the left side return duct other end is connected on the crushing chamber, the right tapering other end is connected with right return duct, and the right return duct other end is connected on the crushing chamber, and left nozzle, right nozzle are connected to the left inlet end of crushing chamber, right inlet end; Be provided with the gas solid separation chamber in the cylindrical shell.
The advantage that the present invention adopts airflow pulverization method to prepare the Nano granules in high purity device is:
(1) two taper design of symmetry are adopted in the crushing system bottom, made things convenient for material to enter crushing chamber by left and right sides return duct, and make respectively that to enter the quality of material of crushing chamber by left return duct and right return duct suitable, help the collision of material in crushing chamber and pulverize;
(2) left return duct, right return duct and tedge constitute the material closed circuit of air-flow crushing process, gone out from crushing chamber by tedge by pulverized particles, then again by left and right sides return duct, make the particle of having been pulverized enter in the jet respectively, be accelerated simultaneously and clash, realize pulverizing again; Such process is back and forth carried out continuously, behind the certain hour, just can obtain nano-scale particle;
(3) left and right sides nozzle adopts Laval nozzle, can produce supersonic jet, and the material that quickens in the crushing chamber collides mutually;
(4) two ends of crushing chamber connect Laval nozzle, and the material in the crushing chamber is the outside at jet expansion, the ejector action by high-speed jet enters jet, and are carried acceleration, by nozzle, can not caused wearing and tearing to nozzle by comminuting matter;
(5) filter adopts pottery or processing of high molecular material to be made into capillary, can realize separating of nano-scale particle and air;
(6) high pressure dry air that is provided by air supply system has uniform temperature, absorption on the material surface has facilitation to modifier, can coat the modifier film of one deck densification at particle surface, improved the flowability of particle, reduce the surface free energy of pulverizing the back nano particle, prevented to pulverize the reunion of back nano particle.Simultaneously also can improve crush efficiency;
(7) in crushing process, can in crushing chamber, add modifier in the material pulverizing, also can before pulverizing, modifier and material be carried out prior premixed;
(8) in apparatus of the present invention, material is the continuous pulverizing of circulation, and therefore, the pulverizing time can be regulated in a big way, with the granularity of control crushing rear material particle.
Description of drawings
Fig. 1 is that the present invention adopts airflow pulverization method to prepare the structured flowchart of Nano granules in high purity.
Fig. 2 is the external structure of crushing system of the present invention.
Fig. 3 is material and a gas flow schematic diagram in the crushing chamber of the present invention.
Fig. 4 is the stereoscan photograph before aluminium oxide granulation ball is pulverized.
Fig. 5 is the transmission electron microscope photo after aluminium oxide granulation ball is pulverized.
Fig. 6 is that aluminium oxide granulation ball is being pulverized the transmission electron microscope photo after titanate coupling agent modification, pulverizing simultaneously.
Among the figure: 1. the right tapering of 111. cylindrical shells 112., the right inlet end of the left inlet end of the left return duct of the right return duct of crushing system 101. 102. tedges 103. 104. left nozzles 105. right nozzles 106. crushing chambers 107. 108. 109. gas solid separation chambeies 113. left tapering 114.A shape grooves, 115. air-introduced machine interfaces, 116. blow-back device B interface, 117. blow-back device A interfaces, 2. air supply systems, 201. air compressor machines, 202. driers, 203. heaters, 204. temperature sensors, 205. temperature controllers, 3. gas solid separation systems 301. filters
The specific embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
The present invention is a kind of technology that adopts airflow pulverization method to prepare Nano granules in high purity, comprises the following steps:
The first step: material is positioned in the crushing chamber 106, and the material consumption of putting is 1/5～3/5 of crushing chamber 106 volumes;
Second step: the gases at high pressure that air compressor machine 201 is produced (pressure 0.1～1MPa) carries out drying processing in drier 202 after, export to and carry out heat treated in the heater 203 and obtain dry gases at high pressure; Described dry gases at high pressure temperature is 20～200 ℃, adopts temperature sensor 204 and temperature controller 205 to realize that described temperature sensor 204 is thermocouples to the temperature survey and the temperature control of the dry gas in the heater 203;
The 3rd step: continuous comminuting matter circulates
(A) left nozzle 104 of crushing system 1, right nozzle 105 receive the dry gases at high pressure that made by second step, described dry gases at high pressure form two bursts of supersonic jets and enter in the crushing chamber 106 behind left nozzle 104, right nozzle 105, the material in the crushing chamber 106 is carried in described two bursts of supersonic jets, head-on collision by band material jet realizes high-purity pulverizing of material;
(B) material after pulverizing enters in the gas solid separation chamber 109 by tedge 102, under the air inducing effect that air-introduced machine produces, realizes separating of materials and air by filter 301; Material after the separation utilizes the ejector action of gas jet to enter in the crushing chamber 106 by left tapering 113, left return duct 103 in turn and pulverizes once more, and the material after perhaps separating utilizes the ejector action of gas jet to enter in the crushing chamber 106 by right tapering 112, right return duct 101 in turn and pulverizes once more;
(C) (B) step of going round and beginning again realizes that the circulation of material is pulverized continuously; The continuous comminuting matter time of described circulation is 0.5～8h.
The present invention adopts air-flow to pulverize the technology of preparation nano particle, material is carried in two bursts of supersonic jets that utilize supersonic jet left and right sides nozzle to produce, and the head-on collision by band material jet realizes high-purity pulverizing, because the circulation of material powder is pulverized continuously, obtains nano-scale particle thus.When particle being carried out the pulverizing of nanoscale jet, the specific cycle loop of adopting left return duct, tedge, right return duct to constitute, utilize the ejector action of gas jet to realize the purpose that particle is pulverized continuously, can pulverize the time by the air-flow of control particle like this, particle is pulverized continuously and obtained nano-scale particle.In the crushing process, nano particle was realized with separating by pottery or macromolecular material filter of air.
For the better dispersiveness of raising material in crushing chamber 106 that obtain, preparation technology of the present invention can also carry out the modification processing to the material surface by the modifier of interpolation doses when pulverizing or in the crushing process.Particle is disperseed and surface modification treatment, increase the flowability of particle, prevent to pulverize the reunion of back nano particle, finally obtain the nano particle of favorable dispersibility.
When third step, in crushing chamber 106, be added with modifier, the interpolation of described modifier reduces the surface free energy of pulverizing the back nano particle in order to improve the flowability of material, prevents to pulverize the reunion of back nano particle, improves crush efficiency.Described modifier is silane coupling agent, titante coupling agent, stearic acid, aluminium esters of gallic acid coupling agent or surfactant, and its addition is about 1.5% of weight of material part.
The granularity of the material particles 40～80% after preparation technology of the present invention pulverizes is at 20～1000nm.
The present invention is a kind of device that adopts airflow pulverization method to prepare Nano granules in high purity, this device is formed (referring to shown in Figure 1) by air supply system 2, crushing system 1 gentle solid separation system 3, perhaps spray into system's 4 gentle solid separation systems 3 and form (shown in Figure 1A) by air supply system 2, crushing system 1, modifier, air supply system 2 and crushing system 1 are connected by pipeline, and crushing system 1 and modifier spray into system 4 and is connected by pipeline.One provided by the invention is can add modifier modification is carried out on the material surface, and purpose provides and obtain better good material fluidity in crushing chamber 106, improves crushing effect; Another is modification not to be carried out on the material surface.These two devices of the present invention can be realized identical pulverizing function.
Described air supply system 1 includes air compressor machine 201, drier 202, heater 203, temperature sensor 204 and temperature controller 205; Temperature sensor 204 links to each other with temperature controller 205, and the sensitivity end of temperature sensor 204 is installed in the heater 203; The gases at high pressure that produce by air compressor machine 201 enter carry out in the drier 202 dryly handling, heater via 203 heating obtain uniform temperatures (20～200 ℃ scope between adjustable continuously) then dry gases at high pressure.
Described gas solid separation system 3 includes filter 301, blow-back device, air-introduced machine, described air-introduced machine is connected with air-introduced machine interface 115, the blow-back device is connected with blow-back device A interface 117, blow-back device B interface 116 respectively, filter 301 is installed in 109 tops, gas solid separation chamber, and described filter 301 is the capillary-like structures that pottery or macromolecular material are made.This gas solid separation system 3 can make in the crushing chamber material and air realize separating.In the present invention, the dry gases at high pressure of air supply system 1 output, the air that produces with the blow-back device, and the interaction between the air that siphons away of air-introduced machine can make material form in crushing chamber 106, tedge 102, left return duct 103, right return duct 101 and circulate.
Referring to shown in Figure 2, described crushing system 1 includes cylindrical shell 111, left tapering 113, right tapering 112, right return duct 101, tedge 102, left return duct 103, left nozzle 104, right nozzle 105, crushing chamber 106, and the top of cylindrical shell 111 is provided with air-introduced machine interface 115, blow-back device A interface 117, blow-back device B interface 116; The bottom of cylindrical shell 111 is connected with left tapering 113, tedge 102, right tapering 112, between tapering 113, a left side and the right tapering 112 an A shape groove 114 is arranged, tedge 102 is placed in the A shape groove 114, tapering, a left side 113 other ends are connected with left return duct 103, left side return duct 103 other ends are connected on the crushing chamber 106, right tapering 112 other ends are connected with right return duct 101, right return duct 101 other ends are connected on the crushing chamber 106, and left nozzle 104, right nozzle 105 are connected to left inlet end 107, the right inlet end 108 of crushing chamber 106; Be provided with gas solid separation chamber 109, filter 301 in the cylindrical shell 111.Described left return duct 103, right return duct 101 and tedge 102 constitute the material closed circuit (referring to shown in Figure 3) of air-flow crushing process.
1 pair of aluminium oxide granulation of embodiment ball adopts airflow pulverization method to prepare nano-scale aluminum oxide particle
The stereoscan photograph of aluminium oxide granulation ball among the figure, is pulverized the spheric granules that preceding aluminium oxide granulation ball is rendered as tens microns as shown in Figure 4 before pulverizing, and granularity does not almost have less than 1 micron alumina particle.Adopting Ma Erwen 2000 type particle size analyzers to record the granularity of pulverizing preceding aluminium oxide granulation ball is 1～50 μ m.
Adopting preparation technology of the present invention and preparation facilities that aluminium oxide granulation ball (material) is carried out pulverising step has:
The first step: aluminium oxide granulation ball (material) is positioned in the crushing chamber 106, and the consumption of the aluminium oxide granulation ball of putting is 500g;
Second step: the gases at high pressure (pressure 0.6MPa) that air compressor machine 201 is produced carry out in drier 202 after drying handle, and exporting to heats in the heater 203 handles the dry gases at high pressure of acquisition; Described dry gases at high pressure temperature is 25 ℃, temperature survey and temperature control to the dry gas in the heater 203 adopt temperature sensor 204 and temperature controller 205 to realize, described temperature sensor 204 adopts XMT-101T type thermocouple, and described temperature controller 205 adopts KTF1-30 type silicon-controlled voltage regulation device.
The 3rd step: aluminium oxide granulation ball is pulverized in circulation continuously
The left nozzle 104 of crushing system 1, right nozzle 105 receive the described dry gases at high pressure that made by second step, described dry gases at high pressure form two bursts of supersonic jets and enter in the crushing chamber 106 behind left nozzle 104, right nozzle 105, material is carried in described two bursts of supersonic jets, head-on collision by band material jet realizes high-purity pulverizing of material; Material after the pulverizing enters in the gas solid separation chamber 109 by tedge 102, under the air inducing effect that air-introduced machine produces, realizes separating of materials and air by filter 301; Material after the separation utilizes the ejector action of gas jet to enter the circulation that realizes material in the crushing chamber 106 by left return duct 103, right return duct 101 and pulverizes continuously.Aluminium oxide granulation ball transmission electron microscope photo after the pulverizing among the figure, contains a large amount of nano-scale aluminum oxide particles as shown in Figure 5.Adopt in the aluminium oxide granulation ball after Ma Erwen 2000 type particle size analyzers record pulverizing 41% grain graininess at 20～1000nm.In this step, it is 1h that circulation is pulverized the aluminium oxide granulation ball time continuously.
The principle of technology of the present invention is to adopt supersonic jet nozzle (left nozzle 104, right nozzle 105), utilize two bursts of supersonic jets to carry the material powder, the head-on collision by band material jet realizes high-purity pulverizing, because the circulation of material powder is pulverized continuously, obtains nano-scale particle thus.Particle being carried out the nanoscale jet when pulverizing, adopts capable of circulation, continuous grinding mode to carry out solid jet and pulverize, like this can be by controlling the pulverizing time of particle, particle is pulverized continuously and obtained nano-scale particle.In the crushing process, nano particle was realized with separating by pottery or macromolecular material filter of air.
Owing to adopt this technology that particle is pulverized, be to utilize the collision between the material to pulverize, there are not the wearing and tearing of other medium, thereby can obtain highly purified nano particle.This technology can realize industrialized Nano granules in high purity pulverizing preparation, is particularly useful for the fragile material of high-purity, high rigidity is pulverized, and obtains nano-scale particle in batches.
2 pairs of aluminium oxide granulations of embodiment ball adopts airflow pulverization method to prepare modified Nano grade aluminum oxide particle
The first step: identical with embodiment 1;
Second step: similar to embodiment 1, difference is: described dry gases at high pressure temperature is 60 ℃;
The 3rd step: similar to embodiment 1, difference is: crushing system 1 is connected with modifier and sprays into system 4 (shown in Figure 1A), pulverizing simultaneously, spray into titanate coupling agent NDZ-401 alumina material is carried out surface modification treatment, to increase the flowability of particle, prevent to pulverize the reunion of back particle.The weight portion consumption of described titanate coupling agent NDZ-401 is 1.5% of a material.
Adopt in the aluminium oxide granulation ball after Ma Erwen 2000 type particle size analyzers record pulverizing 45% grain graininess at 20～1000nm to the above-mentioned modified Nano grade aluminum oxide particle for preparing.Modified aluminas granulation ball transmission electron microscope photo after the pulverizing is compared with pulverizing rear oxidation aluminium granulation ball shown in Figure 5 as shown in Figure 6, and its dispersiveness of nano-scale aluminum oxide particle that contains modifier is better than the nano-scale aluminum oxide particle that does not contain modifier.
Under identical process conditions, by adopting different modifier (silane coupling agent, stearic acid, aluminium esters of gallic acid coupling agent or surfactant) to experimentize, when addition was about 1.5% (material of 100 weight portions adds 1.5 parts of modifier), its particle crushing effect was more or less the same.
The interpolation of modifier makes alumina surface form Modified Membrane, when conducting powder is broken, aluminium oxide is disperseed and surface modification treatment, increase the flowability of alumina particle, prevent to pulverize the reunion of rear oxidation aluminium nano particle, finally obtain the aluminum oxide nanoparticle of favorable dispersibility.
3 pairs of silica of embodiment adopt airflow pulverization method to prepare the nanometer grade silica particle
The first step, second goes on foot identical with embodiment 1;
The 3rd step: similar to embodiment 1, difference is: the pulverizing time is 2h.
To the above-mentioned nanometer grade silica (SiO for preparing
2) particle adopts the silica (SiO after Ma Erwen 2000 type particle size analyzers record pulverizing
2) in 54% grain graininess at 20～1000nm.
Among the preparation technology of the present invention, long more when the time of pulverizing, the grain graininess of its material is just littler.
Claims (10)
1, a kind of technology that adopts airflow pulverization method to prepare Nano granules in high purity is characterized in that comprising the following steps:
The first step: material is positioned in the crushing chamber (106), and the material consumption of putting is 1/5～3/5 of crushing chamber (a 106) volume;
Second step: the gases at high pressure that air compressor machine (201) is produced carry out drying processing in drier (202) after, export to and carry out heat treated in the heater (203) and obtain dry gases at high pressure;
Described dry gases at high pressure temperature is 20～200 ℃, adopts temperature sensor (204) and temperature controller (205) to realize that described temperature sensor (204) is a thermocouple to the temperature survey and the temperature control of gas in the heater (203);
The pressure of the gases at high pressure that described air compressor machine (201) produces is 0.1～1MPa;
The 3rd step: continuous comminuting matter circulates
(A) left nozzle (104) of crushing system (1), right nozzle (105) receive the dry gases at high pressure that made by second step, and described dry gases at high pressure form two bursts of supersonic jets and enter in the crushing chamber (106) behind left nozzle (104), right nozzle (105); The material in the crushing chamber (106) is carried in described two bursts of supersonic jets, and the head-on collision by band material jet realizes high-purity pulverizing of material;
(B) material after pulverizing enters in the gas solid separation chamber (109) by tedge (102), under the air inducing effect that air-introduced machine produces, by separating of filter (301) realization material and air; Material after the separation utilizes the ejector action of gas jet to enter in the crushing chamber (106) by left tapering (113), left return duct (103) in turn and pulverizes once more, and the material after perhaps separating utilizes the ejector action of gas jet to enter in the crushing chamber (106) by right tapering (112), right return duct (101) in turn and pulverizes once more;
(C) (B) step of going round and beginning again realizes that the circulation of material is pulverized continuously; The continuous comminuting matter time of described circulation is 0.5～8h.
2, employing airflow pulverization method according to claim 1 prepares the technology of Nano granules in high purity, it is characterized in that: when third step, in crushing chamber (106), be added with modifier, the interpolation of described modifier is in order to improve the flowability of material, reduce the surface free energy of pulverizing the back nano particle, prevent to pulverize the reunion of back nano particle, improve crush efficiency.
3, employing airflow pulverization method according to claim 2 prepares the technology of Nano granules in high purity, it is characterized in that: the described modifier interpolation time is to add simultaneously with the material premixed or in the process that material is pulverized before pulverizing.
4, employing airflow pulverization method according to claim 2 prepares the technology of Nano granules in high purity, it is characterized in that: described modifier is silane coupling agent, titante coupling agent, stearic acid, aluminium esters of gallic acid coupling agent or surfactant.
5, employing airflow pulverization method according to claim 1 and 2 prepares the technology of Nano granules in high purity, it is characterized in that: in the material after the described pulverizing, 40～80% grain graininess is at 20～1000nm.
6, employing airflow pulverization method according to claim 1 and 2 prepares the technology of Nano granules in high purity, it is characterized in that: described material is aluminium oxide granulation ball, silica dioxide granule or diatomite.
7, a kind ofly be applied to the device that employing airflow pulverization method as claimed in claim 1 prepares Nano granules in high purity technology, it is characterized in that: be made up of air supply system (2), the gentle solid separation system of crushing system (1) (3), air supply system (2) is connected by pipeline with crushing system (1);
Described air supply system (1) includes air compressor machine (201), drier (202), heater (203), temperature sensor (204) and temperature controller (205); Temperature sensor (204) links to each other with temperature controller (205), and the sensitivity end of temperature sensor (204) is installed in the heater (203); Air compressor machine (201) is connected with drier (202) by pipeline, and drier (202) is connected with heater (203) by pipeline;
Described gas solid separation system (3) includes filter (301), blow-back device, air-introduced machine, described air-introduced machine is connected with air-introduced machine interface (115), the blow-back device is connected with blow-back device A interface (117), blow-back device B interface (116) respectively, filter (301) is installed in top, gas solid separation chamber (109), and this gas solid separation system (3) realizes material and air separation;
Described crushing system (1) includes cylindrical shell (111), left tapering (113), right tapering (112), right return duct (101), tedge (102), left return duct (103), left nozzle (104), right nozzle (105), crushing chamber (106), and the top of cylindrical shell (111) is provided with air-introduced machine interface (115), blow-back device A interface (117), blow-back device B interface (116); The bottom of cylindrical shell (111) is connected with left tapering (113), tedge (102), right tapering (112), between tapering (113), a left side and right tapering (112) an A shape groove (114) is arranged, tedge (102) is placed in the A shape groove (114), tapering (113), the left side other end is connected with left return duct (103), left side return duct (103) other end is connected on the crushing chamber (106), right tapering (112) other end is connected with right return duct (101), right return duct (101) other end is connected on the crushing chamber (106) left nozzle (104), right nozzle (105) is connected to the left inlet end (107) of crushing chamber (106), on the right inlet end (108); Be provided with gas solid separation chamber (109) in the cylindrical shell (111).
8, employing airflow pulverization method according to claim 7 prepares the device of Nano granules in high purity, it is characterized in that: described crushing system (1) is connected with modifier by pipeline and sprays into system (4).
9, prepare the device of Nano granules in high purity according to claim 7 or 8 described employing airflow pulverization methods, it is characterized in that: described left return duct (103), right return duct (101) and tedge (102) constitute the material closed circuit of air-flow crushing process.
10, prepare the device of Nano granules in high purity according to claim 7 or 8 described employing airflow pulverization methods, it is characterized in that: described filter (301) adopts pottery or processing of high molecular material to make tubular structure.
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| CN1038396C (en) * | 1994-10-06 | 1998-05-20 | 石油大学(北京) | Fluid-bed opposite-jetting superthin air flow crusher |
| CN2227526Y (en) * | 1994-11-01 | 1996-05-22 | 宋海滨 | Crushing and grading machine |
| CN2299662Y (en) * | 1997-06-20 | 1998-12-09 | 盖国胜 | Composite jet mill |
| JP2004121958A (en) * | 2002-10-01 | 2004-04-22 | Ricoh Co Ltd | Fluidized vessel jet crusher |
| US7032849B2 (en) * | 2003-01-23 | 2006-04-25 | Ricoh Company, Ltd. | Fluidized bed pulverizing and classifying apparatus, and method of pulverizing and classifying solids |
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