EP0603602B1 - Method and apparatus for jet milling in a fluidised bed - Google Patents
Method and apparatus for jet milling in a fluidised bed Download PDFInfo
- Publication number
- EP0603602B1 EP0603602B1 EP93119416A EP93119416A EP0603602B1 EP 0603602 B1 EP0603602 B1 EP 0603602B1 EP 93119416 A EP93119416 A EP 93119416A EP 93119416 A EP93119416 A EP 93119416A EP 0603602 B1 EP0603602 B1 EP 0603602B1
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- European Patent Office
- Prior art keywords
- nozzle
- jet
- section
- cross
- process according
- 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.)
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C19/00—Other disintegrating devices or methods
- B02C19/06—Jet mills
Definitions
- the invention relates to the process of so-called fluidized bed jet milling, in which a gas or steam jet emerging from a nozzle is introduced at high speed into a fluidized bed made of granular material.
- the particles in the vicinity of the jet are accelerated to such a high speed that they burst upon impact with resting or flying particles.
- Such a method which is particularly suitable for fine grinding, is e.g. already known from DE-PS 598 421.
- a disadvantage of the known method is that the kinetic energy introduced by the jet is only partially used for comminution.
- the jet enters the material bed 3 with a uniform velocity distribution 2 over the outlet cross section 1. Because of the negative pressure in the jet compared to the material bed, particles 4 are immediately sucked into the jet and accelerated from the material bed. This is made clear by the increasing distance between two particles 4. As could be determined, such an exchange of impulses only takes place in the outer edge region of the beam, for example between lines 5 and 6, which are to be thought of as surface lines of the edge region.
- the jet speed also decreases significantly as the jet progresses, as can be seen from the speed distributions 2a, 2b and 2c in the beam cross sections 1a, 1b and 1c.
- the core area 7 of the beam remains practically free of regrind, so that the kinetic beam energy remains largely unused in this area and this results in an unsatisfactory efficiency in the comminution.
- the invention is therefore based on the object of increasing the loading of the gas or steam jets used for grinding in the fluidized bed with the material to be comminuted, so as to improve it To achieve utilization of the kinetic energy introduced with the rays.
- a possibility is to be created to bring the regrind into the core area of the beams in order to be able to optimally use the kinetic energy available here.
- the solution to the problem is that in the case of a high-speed gas or steam jet introduced for impact crushing in a fluidized mill bed, the size of the jet pulse is changed locally while maintaining the size of the outlet cross section of the known nozzle, so that zones with high and low jet pulses are formed. and that they are arranged such that the size of the jet pulse in the peripheral region of the outlet cross section changes at least twice between a minimum and a maximum value and in the core region of the cross section is equal to or less than the minimum values.
- FIG. 2 schematically shows a perspective representation of the flow conditions at the outlet cross section 10 and in the beam cross section 11c, in which a normal speed distribution has already been established as in the beam cross section 1c of FIG. 1.
- the suction effect to the core area is optimal.
- FIG. 3 shows the flow conditions as they occur in the plane 13, which is placed in the central nozzle axis 9 and in the middle between two outlet openings 8, which are shown in FIG. 3.
- 8 radially directed flow channels are formed directly at the outlet cross section 10 between two outlet openings, which flow channels extend in the jet direction up to the jet cross section 11 (with speed distribution 12), in which the individual jet areas begin to overlap.
- 3 shows the speed distributions 12a, 12b and 12c in the beam cross sections 11a, 11b and 11c.
- the arrows 14 in FIG. 2 indicate the transverse flow which forms as a result of the flow channels described above and which transports the particles 4 to the central nozzle axis 9.
- Comparative grinding on a fluidized bed counter jet mill which was initially equipped with normal and then with nozzle elements designed according to the invention, has shown that with otherwise the same operating parameters and approximately the same specific energy requirement (in kWh / t), the mill equipped according to the invention with the same grinding fineness more than that double throughput compared to the normally equipped mill could be achieved, ie the grinding efficiency could be improved by a factor of almost 2.5.
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- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Disintegrating Or Milling (AREA)
- Crushing And Grinding (AREA)
- Perforating, Stamping-Out Or Severing By Means Other Than Cutting (AREA)
Abstract
Description
Die Erfindung bezieht sich auf das Verfahren der sog. Fließbett-Strahlmahlung, bei dem ein aus einer Düse austretender Gas- oder Dampfstrahl hoher Geschwindigkeit in ein fluidisiertes Bett aus körnigem Material eingeleitet wird. Die Partikel in der Umgebung des Strahls werden dabei auf eine so hohe Geschwindigkeit beschleunigt, daß sie beim Aufprallen auf ruhende oder entgegenfliegende Partikel zerbersten. Ein solches, insbesondere für die Feinzerkleinerung geeignetes Verfahren ist z.B. schon durch die DE-PS 598 421 bekannt geworden.The invention relates to the process of so-called fluidized bed jet milling, in which a gas or steam jet emerging from a nozzle is introduced at high speed into a fluidized bed made of granular material. The particles in the vicinity of the jet are accelerated to such a high speed that they burst upon impact with resting or flying particles. Such a method, which is particularly suitable for fine grinding, is e.g. already known from DE-PS 598 421.
Nachteilig bei dem bekannten Verfahren ist jedoch, daß die durch den Strahl eingebrachte kinetische Energie nur zum Teil für die Zerkleinerung genutzt wird. Wie in Fig. 1 schematisch dargestellt ist, tritt der Strahl mit über den Austrittsquerschnitt 1 gleichmäßiger Geschwindigkeitsverteilung 2 in das Gutbett 3 ein. Wegen des Unterdrucks im Strahl gegenüber dem Gutbett werden sofort Partikel 4 aus dem Gutbett in den Strahl eingesaugt und beschleunigt. Dies ist durch den zunehmenden Abstand zwischen zwei Partikeln 4 deutlich gemacht. Wie festgestellt werden konnte, erfolgt ein solcher Impulsaustausch jedoch nur in dem äußeren Randbereich des Strahls, etwa zwischen den Linien 5 und 6, die als Mantellinien des Randbereichs zu denken sind. Hier nimmt auch die Strahlgeschwindigkeit beim Fortschreiten des Strahls deutlich ab, wie aus den Geschwindigkeitsverteilungen 2a, 2b und 2c in den Strahlquerschnitten 1a, 1b und 1c zu erkennen ist. Der Kernbereich 7 des Strahls bleibt praktisch frei von Mahlgut, so daß die kinetische Strahlenergie in diesem Bereich weitgehend ungenutzt bleibt und daraus ein unbefriedigender Wirkungsgrad bei der Zerkleinerung resultiert.A disadvantage of the known method, however, is that the kinetic energy introduced by the jet is only partially used for comminution. As is shown schematically in FIG. 1, the jet enters the material bed 3 with a
Der Erfindung liegt daher die Aufgabe zugrunde, die Beladung der für die Mahlung im Fließbett eingesetzten Gas- oder Dampfstrahlen mit dem zu zerkleinernden Material zu erhöhen, um so eine bessere Nutzung der mit den Strahlen eingebrachten kinetischen Energie zu erreichen. Insbesondere soll eine Möglichkeit geschaffen werden, das Mahlgut in den Kernbereich der Strahlen zu bringen, um die hier zur Verfügung stehende kinetische Energie optimal nutzen zu können.The invention is therefore based on the object of increasing the loading of the gas or steam jets used for grinding in the fluidized bed with the material to be comminuted, so as to improve it To achieve utilization of the kinetic energy introduced with the rays. In particular, a possibility is to be created to bring the regrind into the core area of the beams in order to be able to optimally use the kinetic energy available here.
Es ist zwar schon in der DE-OS 20 40 519 vorgeschlagen worden, das Mahlgut mit mechanischen Fördermitteln von der Seite her in den Strahl zu drücken, dabei muß aber mit starkem Verschleiß an den Fördermitteln gerechnet werden. Um diesen Verschleiß zu verhindern, wurde als Lösung eine Anordnung aus der DE-OS-26 28 612 bekannt, wobei zusätzliche Fluidstrahlen als Fördermittel dienen, um das Mahlgut in den Strahl zu drücken. Beide Maßnahmen erfordern jedoch einen erheblichen apparativen und energetischen Aufwand. Die gleichen Nachteile weisen die bekannten Injektor-Strahlmühlen z.B. nach US-PS 1 935 344 oder US-PS 2 704 635 auf, bei denen das Mahlgut vor der Strahlausbildung in einer Beschleunigungsdüse mit dem Gas oder Dampf gemischt wird.It has already been proposed in DE-OS 20 40 519 to press the regrind into the jet from the side using mechanical conveying means, but heavy wear on the conveying means must be expected. In order to prevent this wear, an arrangement from DE-OS-26 28 612 was known as a solution, with additional fluid jets serving as conveying means to press the ground material into the jet. However, both measures require a considerable amount of equipment and energy. The known disadvantages of the known injector jet mills e.g. according to US Pat. No. 1,935,344 or US Pat. No. 2,704,635, in which the millbase is mixed with the gas or steam in an acceleration nozzle before the jet formation.
Die Lösung der Aufgabe besteht darin, daß bei einem zur Prallzerkleinerung in ein fluidisiertes Mahlgutbett eingeleiteten Gas- oder Dampfstrahl hoher Geschwindigkeit die Größe des Strahlimpulses unter Beibehaltung der Größe des Austrittsquerschnitts der bekannten Düse örtlich geändert wird, so daß Zonen mit hohem und niedrigem Strahlimpuls entstehen, und daß diese so angeordnet werden, daß die Größe des Strahlimpulses im Umfangsbereich des Austrittsquerschnitts mindestens zweimal zwischen einem Minimal- und einem Maximalwert wechselt und im Kernbereich des Querschnitts gleich den Minimalwerten oder kleiner als diese ist. In überraschender Weise hat sich gezeigt, daß damit in den Bereichen mit niedrigem Strahlimpuls unmittelbar nach Austritt des Strahls aus der Düse gewissermaßen Strömungskanäle quer zur Strömungsrichtung des Strahls geschaffen werden mit einem Druckgefälle von der Umgebung zum Kernbereich des Strahls, so daß hier die Partikel 4 des Mahlgutes bis zum Strahlzentrum eingesaugt werden. Hier werden sie dann auf die für ihre Zerkleinerung erforderliche Prallgeschwindigkeit beschleunigt, wenn sich im weiteren Verlauf des Strahls durch Mischvorgänge infolge Überschneidung der einzelnen Strahlbereiche eine Vergleichmäßigung des Strahlimpulses über den Strahlquerschnitt einstellt und sich eine Geschwindigkeitsverteilung über den Strahlquerschnitt wie bei dem einfachen Strahl (entsprechend Fig. 1) ergibt. Durch das Einsaugen von Mahlgut in den Kernbereich des Strahls wird eine deutlich höhere Gutmenge erfaßt als bei einem einfachen Strahl und die Gutpartikel werden auf eine höhere Geschwindigkeit beschleunigt.
Eine Möglichkeit der Realisierung besteht beispielsweise darin, daß noch innerhalb der Düse, also bevor der Strahl aus der Düse austritt, örtlich abgesaugt wird.
Vorteilhafte Ausgestaltungen der Erfindung sind in den Unteransprüchen beschrieben, wobei sich die Ansprüche 2 bis 4 auf die Größenverhältnisse von Strahlimpuls und Strahlzonen und Ansprüche 5 bis 8 auf die Strahlrichtung in den einzelnen Strahlzonen beziehen. Diese Maßnahmen dienen dazu, den Öffnungswinkel des Strahls zu beeinflussen bzw. den Strahlquerschnitt 11c mit der normalisierten Geschwindigkeitsverteilung in Strahlrichtung zu verschieben, um so eine Änderung der Strahlform zur Anpassung an die Mahlkammergröße bzw. die Mahlguteigenschaften zu erreichen.
Die technisch einfachste und bevorzugte Lösung stellt die Verwendung von gleichmäßig über den Austrittsquerschnitt verteilten Austrittsöffnungen dar. Als ausgeführte und erprobte Düse wird beispielsweise ein in eine Halterung einsetzbares Düsenelement mit vier Austrittsöffnungen 8 mit kreisförmigem Querschnitt verwendet, deren Mitten auf einem Kreis angeordnet sind, dessen Durchmesser etwa dem 2,5fachen Durchmesser einer Austrittsöffnung entspricht. Die aus jeder Öffnung austretende Strömung ist dabei auf einen gemeinsamen Punkt auf der zentralen Düsenachse 9 gerichtet. Fig. 2 zeigt schematisch in perspektivischer Darstellung die Strömungsverhältnisse am Austrittsquerschnitt 10 und im Strahlquerschnitt 11c, in dem sich bereits eine normale Geschwindigkeitsverteilung wie im Strahlquerschnitt 1c von Fig. 1 eingestellt hat. Die Saugwirkung zum Kernbereich ist hierbei optimal.The solution to the problem is that in the case of a high-speed gas or steam jet introduced for impact crushing in a fluidized mill bed, the size of the jet pulse is changed locally while maintaining the size of the outlet cross section of the known nozzle, so that zones with high and low jet pulses are formed. and that they are arranged such that the size of the jet pulse in the peripheral region of the outlet cross section changes at least twice between a minimum and a maximum value and in the core region of the cross section is equal to or less than the minimum values. Surprisingly, it has been shown that flow channels transverse to the flow direction of the jet are created with a pressure gradient from the environment to the core area of the jet in the areas with low jet impulses immediately after the jet emerges from the nozzle, so that here the
One possible implementation is, for example, that local suction is carried out inside the nozzle, ie before the jet emerges from the nozzle.
Advantageous embodiments of the invention are described in the subclaims, claims 2 to 4 relating to the size relationships of the beam pulse and beam zones and claims 5 to 8 relating to the beam direction in the individual beam zones. These measures serve to influence the opening angle of the beam or to shift the
The technically simplest and preferred solution is the use of outlet openings evenly distributed over the outlet cross section. For example, a nozzle element that can be inserted into a holder and has four
Die Strömungsverhältnisse, wie sie sich in der Ebene 13 einstellen, die in die zentrale Düsenachse 9 und in die Mitte zwischen zwei Austrittsöffnungen 8 gelegt ist, sind in Fig. 3 dargestellt. Wie zu erkennen ist, bilden sich unmittelbar am Austrittsquerschnitt 10 zwischen je zwei Austrittsöffnungen 8 radial gerichtete Strömungskanäle aus, die in Strahlrichtung bis zu dem Strahlquerschnitt 11 (mit Geschwindigkeitsverteilung 12) reichen, in dem sich die einzelnen Strahlbereiche zu überschneiden beginnen. Den weiteren Strahlverlauf zeigen in Fig. 3 die Geschwindigkeitsverteilungen 12a, 12b und 12c in den Strahlquerschnitten 11a, 11b und 11c. Die Pfeile 14 in Fig. 2 deuten die sich infolge der vorstehend beschriebenen Strömungskanäle ausbildende Querströmung an, die die Partikel 4 bis zur zentralen Düsenachse 9 transportiert.The flow conditions as they occur in the
Vergleichsmahlungen auf einer Fließbett-Gegenstrahlmühle` die zuerst mit normalen und dann mit erfindungsgemäß ausgebildeten Düsenelementen ausgerüstet war, haben ergeben, daß bei sonst gleichen Betriebsparametern und etwa gleichem spezifischen Energiebedarf (in kWh/t) mit der erfindungsgemäß ausgerüsteten Mühle bei gleicher Mahlfeinheit mehr als der doppelte Durchsatz gegenüber der normal ausgerüsteten Mühle erzielt werden konnte, d.h. der Mahlwirkungsgrad konnte um einen Faktor von fast 2,5 verbessert werden.Comparative grinding on a fluidized bed counter jet mill, which was initially equipped with normal and then with nozzle elements designed according to the invention, has shown that with otherwise the same operating parameters and approximately the same specific energy requirement (in kWh / t), the mill equipped according to the invention with the same grinding fineness more than that double throughput compared to the normally equipped mill could be achieved, ie the grinding efficiency could be improved by a factor of almost 2.5.
Claims (11)
- Process designed for impact comminution by means of introducing at least one gas or steam jet exiting a nozzle at high speed into a fluidised bed of material, the cross-section of the jet having a core zone and a peripheral zone circumferential to the core zone characterized in that the level of jet momentum of the gas or steam jet upon exiting the nozzle changes in the peripheral zone of the nozzle cross-section at least twice between a minimum and maximum value and is the same or smaller than the minimum values of the peripheral zone in the core zone of the nozzle cross-section.
- Process according to Claim 1, characterized in that the level of jet momentum has the value zero at the points where the minimum values exist.
- Process according to Claim 1 or 2, characterized in that all sub-sections of the nozzle cross-section with mutual maximum and minimum jet momentum have more or less the same value upon exiting the nozzle.
- Process according to one of the Claims 1 - 3, characterized in that the transition from a minimum jet momentum to a maximum occurs discontinuously.
- Process according to one of the Claims 1 - 4, characterized in that the emission flow upon exiting the nozzle in every sub-section of the nozzle cross-section occurs parallel to the central nozzle axis (9).
- Process according to one of the Claims 1 - 4, characterized in that the emission flow upon exiting the nozzle in every sub-section of the nozzle cross-section is aimed away from the central nozzle axis (9).
- Process according to one of the Claims 1 - 4, characterized in that the emission flow upon exiting the nozzle in every sub-section of the nozzle cross-section points towards the central nozzle axis (9).
- Process according to Claim 7, characterized in that the emission flow upon exiting the nozzle from every sub-section of the nozzle cross-section is aimed at a common point on the central nozzle axis (9).
- Device to carry out the process according to one of the Claims 1 - 8, characterized by a nozzle element to be mounted in a holder to generate the jet, which has at least two emission points (8) of different form and size distributed uniformly across the cross-section of the nozzle element.
- Device according to Claim 9, characterized in that the emission points (8) are arranged within an area whose boundary represents a inflexion-point-free envelope curve which encloses the emission points (8).
- Device according to Claim 9 or 10, characterized in that the emission points (8) are designed with circular cross-sections.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4243438 | 1992-12-22 | ||
DE4243438A DE4243438C2 (en) | 1992-12-22 | 1992-12-22 | Method and device for fluid bed jet grinding |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0603602A1 EP0603602A1 (en) | 1994-06-29 |
EP0603602B1 true EP0603602B1 (en) | 1997-05-14 |
Family
ID=6476080
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93119416A Expired - Lifetime EP0603602B1 (en) | 1992-12-22 | 1993-12-02 | Method and apparatus for jet milling in a fluidised bed |
Country Status (10)
Country | Link |
---|---|
US (1) | US5423490A (en) |
EP (1) | EP0603602B1 (en) |
JP (1) | JP3095937B2 (en) |
KR (1) | KR970001784B1 (en) |
CN (1) | CN1051254C (en) |
AT (1) | ATE152933T1 (en) |
DE (2) | DE4243438C2 (en) |
ES (1) | ES2104024T3 (en) |
MY (1) | MY112091A (en) |
TW (1) | TW246650B (en) |
Families Citing this family (22)
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DE19513034A1 (en) * | 1995-04-06 | 1996-10-10 | Nied Roland | Fluid bed jet milling device |
DE19513035C2 (en) * | 1995-04-06 | 1998-07-30 | Nied Roland | Fluid bed jet grinding |
DE19728382C2 (en) * | 1997-07-03 | 2003-03-13 | Hosokawa Alpine Ag & Co | Method and device for fluid bed jet grinding |
US6038987A (en) * | 1999-01-11 | 2000-03-21 | Pittsburgh Mineral And Environmental Technology, Inc. | Method and apparatus for reducing the carbon content of combustion ash and related products |
CN1287023A (en) * | 1999-09-08 | 2001-03-14 | 株式会社威士诺 | Jet mill |
DE10007794A1 (en) | 2000-02-21 | 2001-06-28 | Zimmer Ag | Composition useful for making containers, films, membranes and fibers, comprises a biodegradable polymer and a marine plant or shell material |
US6951312B2 (en) * | 2002-07-23 | 2005-10-04 | Xerox Corporation | Particle entraining eductor-spike nozzle device for a fluidized bed jet mill |
US6942170B2 (en) * | 2002-07-23 | 2005-09-13 | Xerox Corporation | Plural odd number bell-like openings nozzle device for a fluidized bed jet mill |
DE102005039118A1 (en) * | 2005-08-18 | 2007-02-22 | Wacker Chemie Ag | Method and device for comminuting silicon |
DE102006017472A1 (en) * | 2006-04-13 | 2007-10-18 | Nied, Roland, Dr. Ing. | Method for producing finest particles by means of a jet mill |
US8858699B2 (en) * | 2006-07-13 | 2014-10-14 | Unimin Corporation | Ultra fine nepheline syenite powder and products for using same |
US20080040980A1 (en) * | 2006-07-13 | 2008-02-21 | Unimin Corporation | Method of processing nepheline syenite |
US20080015104A1 (en) | 2006-07-13 | 2008-01-17 | Unimin Corporation | Ultrafine nepheline syenite |
ES2378898T3 (en) | 2006-12-14 | 2012-04-18 | Tronox Llc | Enhanced jet nozzle for use in a jet mill micronizer |
US7757976B2 (en) * | 2007-02-07 | 2010-07-20 | Unimin Corporation | Method of processing nepheline syenite powder to produce an ultra-fine grain size product |
US7959095B2 (en) * | 2007-06-27 | 2011-06-14 | E. I. Du Pont De Nemours And Company | Center-feed nozzle in a contained cylindrical feed-inlet tube for improved fluid-energy mill grinding efficiency |
JP5275345B2 (en) * | 2007-07-09 | 2013-08-28 | ユニミン コーポレーション | Meteorite syenite powder with controlled particle size and its new production method |
WO2009128857A1 (en) | 2008-04-17 | 2009-10-22 | Unimin Corporation | Powder formed from mineral or rock material with controlled particle size distribution for thermal films |
DE102014211037A1 (en) * | 2014-06-10 | 2015-12-17 | Wacker Chemie Ag | Silicon seed particles for the production of polycrystalline silicon granules in a fluidized bed reactor |
KR102149323B1 (en) * | 2016-11-07 | 2020-08-31 | 와커 헤미 아게 | How to pulverize solids containing silicon |
CN108543605B (en) * | 2018-04-28 | 2019-04-16 | 中国计量大学 | The method of the lossless depolymerization of free shear turbulence array and fine grading LED fluorescent powder |
DE102021002671A1 (en) | 2021-05-21 | 2022-11-24 | Hosokawa Alpine Aktiengesellschaft | Process for determining the optimum nozzle spacing in jet mills and grinding processes for producing the finest particles |
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US1935344A (en) * | 1931-06-16 | 1933-11-14 | American Pulverizing Corp Camd | Impact pulverizer |
US1948609A (en) * | 1932-01-18 | 1934-02-27 | American Pulverizing Corp | Method of pulverizing minerals and similar materials |
DE598421C (en) * | 1932-01-18 | 1934-06-13 | Internat Pulverizing Corp | Method and device for impact crushing |
US2309036A (en) * | 1940-09-12 | 1943-01-19 | Beardsley & Piper Co | Apparatus for conditioning molding sand |
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US2704635A (en) * | 1951-06-02 | 1955-03-22 | Conrad M Trost | Pulverizing mill having opposed jets and circulatory classification |
US2846150A (en) * | 1955-09-29 | 1958-08-05 | Texaco Development Corp | Fluid energy grinding |
CA919370A (en) * | 1968-04-19 | 1973-01-23 | Spray Steelmaking Limited | Atomization of molten material with provision of clearing gas orifice |
DE2040519C2 (en) * | 1970-08-14 | 1984-04-12 | Alpine Ag, 8900 Augsburg | Fluidized bed jet mill |
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SU1168288A1 (en) * | 1982-08-19 | 1985-07-23 | Министерство Мелиорации И Водного Хозяйства Северо-Осетинской Асср | Apparatus for mincing filamentous algae |
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JP3031923B2 (en) * | 1989-07-07 | 2000-04-10 | フロイント産業株式会社 | Granulation coating apparatus and granulation coating method using the same |
-
1992
- 1992-12-22 DE DE4243438A patent/DE4243438C2/en not_active Expired - Fee Related
-
1993
- 1993-12-02 EP EP93119416A patent/EP0603602B1/en not_active Expired - Lifetime
- 1993-12-02 AT AT93119416T patent/ATE152933T1/en not_active IP Right Cessation
- 1993-12-02 ES ES93119416T patent/ES2104024T3/en not_active Expired - Lifetime
- 1993-12-02 DE DE59306446T patent/DE59306446D1/en not_active Expired - Lifetime
- 1993-12-20 TW TW082110798A patent/TW246650B/zh active
- 1993-12-21 US US08/172,445 patent/US5423490A/en not_active Expired - Lifetime
- 1993-12-21 JP JP05321787A patent/JP3095937B2/en not_active Expired - Lifetime
- 1993-12-21 MY MYPI93002795A patent/MY112091A/en unknown
- 1993-12-22 CN CN93119950A patent/CN1051254C/en not_active Expired - Lifetime
- 1993-12-22 KR KR1019930029023A patent/KR970001784B1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
TW246650B (en) | 1995-05-01 |
KR970001784B1 (en) | 1997-02-15 |
ES2104024T3 (en) | 1997-10-01 |
ATE152933T1 (en) | 1997-05-15 |
CN1051254C (en) | 2000-04-12 |
DE4243438A1 (en) | 1994-06-23 |
DE4243438C2 (en) | 1996-06-05 |
MY112091A (en) | 2001-04-30 |
DE59306446D1 (en) | 1997-06-19 |
EP0603602A1 (en) | 1994-06-29 |
JP3095937B2 (en) | 2000-10-10 |
JPH0747298A (en) | 1995-02-21 |
US5423490A (en) | 1995-06-13 |
CN1091338A (en) | 1994-08-31 |
KR940013611A (en) | 1994-07-15 |
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