EP2089163B1 - Particule submicronique amorphe - Google Patents

Particule submicronique amorphe Download PDF

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Publication number
EP2089163B1
EP2089163B1 EP07820693.5A EP07820693A EP2089163B1 EP 2089163 B1 EP2089163 B1 EP 2089163B1 EP 07820693 A EP07820693 A EP 07820693A EP 2089163 B1 EP2089163 B1 EP 2089163B1
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EP
European Patent Office
Prior art keywords
classifier
milling
grinding
mill
process according
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EP07820693.5A
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German (de)
English (en)
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EP2089163A2 (fr
Inventor
Karl Meier
Ulrich Brinkmann
Christian Panz
Doris Misselich
Christian Götz
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Evonik Operations GmbH
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Evonik Degussa GmbH
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Priority to PL07820693T priority Critical patent/PL2089163T3/pl
Publication of EP2089163A2 publication Critical patent/EP2089163A2/fr
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Classifications

    • 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
    • B02C19/18—Use of auxiliary physical effects, e.g. ultrasonics, irradiation, for disintegrating
    • B02C19/186—Use of cold or heat for disintegrating
    • 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
    • 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
    • B02C19/0012—Devices for disintegrating materials by collision of these materials against a breaking surface or breaking body and/or by friction between the material particles (also for grain)
    • B02C19/005—Devices for disintegrating materials by collision of these materials against a breaking surface or breaking body and/or by friction between the material particles (also for grain) the materials to be pulverised being disintegrated by collision of, or friction between, the material particles
    • 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
    • B02C19/068—Jet mills of the fluidised-bed type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C21/00—Disintegrating plant with or without drying of the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/08—Separating or sorting of material, associated with crushing or disintegrating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/259—Silicic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the invention relates to powdery amorphous solids having a very small average particle size and a narrow particle size distribution, a process for their preparation, and their use.
  • Fine-particle, amorphous silicic acid and silicates have been industrially produced for decades.
  • the finest grinding in spiral or counter-jet mills with compressed air is carried out as a grinding gas, eg EP 0139279 ,
  • the achievable particle diameter is proportional to the root of the reciprocal of the collision velocity of the particles.
  • the impact velocity in turn is determined by the jet velocity of the expanding gas jets of the respective grinding medium from the nozzles used.
  • superheated steam can be used to generate very small particle sizes, since the acceleration capacity of steam is about 50% greater than that of air.
  • the use of steam has the disadvantage that, in particular during the startup of the mill, condensation can occur in the entire grinding system, which generally results in the formation of agglomerates and crusts during the grinding process.
  • the average particle diameter d 50 obtained using conventional jet mills in the milling of amorphous silica, silicates or silica gels was therefore far above 1 ⁇ m.
  • So z. B. in the US 3,367,742 describes a process for the milling of aerogels, in which aerogels are obtained with a mean particle diameter of 1.8 to 2.2 microns. Milling to a mean particle diameter of less than 1 ⁇ m is not possible with this technique.
  • the particles of the US 3,367,742 a wide one Particle size distribution with particle diameters of 0.1 to 5.5 microns and a proportion of particles> 2 microns from 15 to 20%.
  • Vermahlungsschw provides the wet comminution, z. B. in ball mills, is. It leads to very finely divided suspensions of the products to be ground, see, for. B. WO 200002814 , It is not possible with the help of this technology to isolate a finely divided, agglomerate-free dry product, in particular without changing the porosimetric properties, from these suspensions.
  • the inventors have surprisingly found that it is possible to grind amorphous solids by means of a very special, further specified in the claims 2 to 14 method to a mean particle size d 50 of less than 1.5 microns and also a very narrow particle distribution to reach.
  • the invention relates to amorphous powdered solids having an average particle size d 50 (TEM) ⁇ 1.5 microns and a d 90 value (TEM) ⁇ 1.8 microns and a d 99 value (TEM) ⁇ 2 microns and it itself are silica gels, which also have a pore volume of 0.2 to 0.7 ml / g, or are silica gels which also have a pore volume of 0.8 to 1.5 ml / g or are silica gels , which also have a pore volume of 1.5 to 2.1 ml / g.
  • the invention also provides a process for producing the amorphous pulverulent solids according to the invention by grinding amorphous solids by means of a grinding system (milling apparatus), preferably comprising a jet mill, particularly preferably a milling system comprising a fluidized bed counter-jet mill or a dense bed jet mill or a spiral jet mill, characterized in that the mill in the milling phase with a resource selected from a group consisting of gas and steam, preferably water vapor, and a gas containing water vapor, is operated, and that the grinding chamber in a heating phase, ie before the actual operation with the operating means, so heated is that the temperature in the grinding chamber and at the mill outlet is higher than the dew point of the steam and / or equipment.
  • a grinding system milling apparatus
  • the present invention relates to the use of the amorphous solids according to the invention having an average particle size d 50 ⁇ 1.5 microns and a d 90 value ⁇ 1.8 microns and a d 99 value ⁇ 2 microns, z.
  • the inventive method is the first time succeeded, powdery amorphous solids having an average particle size d 50 ⁇ 1.5 microns and a narrow Particle size distribution, expressed by the d 90 value ⁇ 1.8 microns and / or the d 99 value ⁇ 2 microns to produce.
  • amorphous solids in particular those containing a metal and / or metal oxide, for.
  • metals of the 3rd and 4th main group of the Periodic Table of the Elements such as.
  • precipitated silicas, fumed silicas, silicates and silica gels to achieve such small average particle sizes was previously possible only by wet milling. As a result, only dispersions could be obtained.
  • the drying of these dispersions led to re-agglomeration of the amorphous particles, so that the effect of grinding was partially reversed and average particle sizes d 50 ⁇ 1.5 microns, and particle size distribution d 90 value can not be reached ⁇ 2 microns in the dried, powdered solids could.
  • the porosity was also adversely affected.
  • the process according to the invention has the advantage that it is a dry milling process which leads directly to pulverulent products with a very small mean particle size, which can also have a high porosity in a particularly advantageous manner ,
  • the problem of reagglomeration during drying is eliminated because no grinding of the downstream drying step is necessary.
  • Another advantage of the method according to the invention in one of its preferred embodiments is the fact that the grinding can take place simultaneously with the drying, so that z. B. a filter cake can be further processed directly. This saves an additional drying step and at the same time increases the space-time yield.
  • the inventive method also has the advantage that when starting up the grinding system no or only very small amounts of condensate in the grinding system, especially in the mill arise. On cooling, dried gas can be used. As a result, no condensate is produced in the grinding system during cooling and the cooling phase is significantly shortened. The effective machine running times can thus be increased.
  • the amorphous pulverulent solids produced by means of the process according to the invention have particularly good properties when used in surface coating systems, for example because of the very special and unique average particle sizes and particle size distributions.
  • the products of the invention allow z. B. due to the very small average particle size and in particular the low d 90 value and d 99 value to produce very thin coatings.
  • powder and pulverulent solids are used interchangeably in the context of the present invention and each denote finely comminuted, solid substances from small dry particles, dry particles meaning that they are externally dry particles. Although these particles usually have a water content, this water is so firmly bound to the particles or in their capillaries that it is not released at room temperature and atmospheric pressure. In other words, it is perceptible by optical methods particulate matter and not suspensions or dispersions. Furthermore, these may be both surface-modified and non-surface-modified solids. The surface modification is preferably carried out with carbon-containing coating agents and can be carried out both before and after the grinding.
  • the solids according to the invention can be present as gel or as particles containing agglomerates and / or aggregates.
  • Gel means that the solids are composed of a stable, three-dimensional, preferably homogeneous network of primary particles. Examples are silica gels.
  • Particles comprising aggregates and / or agglomerates in the sense of the present invention have no three-dimensional network or at least no network of primary particles extending over the entire particle. Instead, they have aggregates and agglomerates of primary particles. Examples of these are precipitated silicas and fumed silicas.
  • the process according to the invention is carried out in a milling system (milling apparatus), preferably in a milling system comprising a jet mill, particularly preferably comprising an opposed jet mill.
  • a feed to be crushed is accelerated in expanding high-speed gas jets and comminuted by particle-particle collisions.
  • jet mills very particular preference is given to using fluid bed counter-jet mills or dense-bed jet mills or spiral jet mills.
  • Mahlstrahleinlässe located in the lower third of the grinding chamber two or more Mahlstrahleinlässe, preferably in the form of grinding nozzles, which are preferably in a horizontal plane.
  • the Mahlstrahleinlässe are particularly preferably arranged on the circumference of the preferably round mill container, that the grinding jets all meet at a point inside the grinding container.
  • the grinding jet inlets are distributed uniformly over the circumference of the grinding container. In the case of three Mahlstrahleinlässe the distance would thus each be 120 °.
  • the grinding system comprises a separator, preferably a dynamic separator, particularly preferably a dynamic Schaufelradsichter, particularly preferably a separator according to Figure 2 and 3 ,
  • a dynamic air classifier according to Figure 2a and 3a used.
  • This dynamic air classifier includes a classifying wheel and a bombardradwelle and a classifier housing, wherein between the classifying wheel and the classifier housing a classifier gap and between the prepareradwelle and the classifier housing a shaft passage is formed, and is characterized in that a rinsing gap of the classifier gap and / or shaft passage with compressed Low energy gases take place.
  • the upper particle is confined, the product particles rising together with the expanded gas jets being passed through the classifier from the center of the grinding container and subsequently the product having a sufficient fineness , from the sifter and from the mill is executed. Too coarse particles return to the milling zone and are subjected to further comminution.
  • a classifier can be connected downstream as a separate unit of the mill, but preferably an integrated classifier is used.
  • An essential feature of the method according to the invention is that the actual grinding step is preceded by a heating phase, in which it is ensured that the grinding chamber, particularly preferably all essential components of the mill and / or the grinding system, at which water and / or water vapor could condense, is heated so / that its temperature is above the dew point of the vapor.
  • the heating can be done in principle by any heating method.
  • the heating takes place in that hot gas is passed through the mill and / or the entire grinding system, so that the temperature of the gas at the mill outlet is higher than the dew point of the vapor.
  • the hot gas preferably heats all essential components of the mill and / or the entire grinding system, which come into contact with the steam, sufficiently.
  • any gas and / or gas mixtures can be used as the heating gas, but hot air and / or combustion gases and / or inert gases are preferably used.
  • the temperature of the hot gas is above the dew point of the water vapor.
  • the hot gas can in principle be introduced into the milling space as desired.
  • These inlets or nozzles can be the same inlets or nozzles through which the grinding jets are also passed during the grinding phase (grinding nozzles).
  • the heating gas or heating gas mixture is introduced through at least two, preferably three or more, in-plane inlets or nozzles, which are so arranged on the circumference of the preferably round mill container that the rays all meet at a point inside the grinding container.
  • the inlets or nozzles are distributed uniformly over the circumference of the grinding container.
  • a gas and / or a vapor preferably water vapor and / or a gas / steam mixture is depressurized by the grinding jet inlets, preferably in the form of grinding nozzles.
  • This equipment usually has a much higher speed of sound than air (343 m / s), preferably at least 450 m / s on.
  • the equipment comprises water vapor and / or hydrogen gas and / or argon and / or helium. Particularly preferred is superheated steam.
  • the operating means at a pressure of 15 to 250 bar, more preferably from 20 to 150 bar, most preferably 30 to 70 bar and particularly preferably 40 to 65 bar relaxed in the mill.
  • the operating means has a temperature of 200 to 800 ° C, particularly preferably 250 to 600 ° C and in particular 300 to 400 ° C.
  • the surface of the jet mill has the smallest possible value and / or the flow paths are at least largely free of projections and / or if the components of the jet mill are designed to prevent mass accumulation.
  • the air classifier includes a classifying wheel and a classifying wheel shaft and a classifier housing, wherein between the classifying wheel and the classifier housing a classifier gap and between the classifying wheel shaft and the classifier housing a shaft passage is formed and is operated in such a way that a gap cooling of the separator gap and / or shaft passage with compressed low-energy gases takes place.
  • the purge gas is used at a pressure of not more than at least approximately 0.4 bar, particularly preferably not more than at least approximately 0.3 bar and in particular not more than approximately 0.2 bar above the internal mill pressure.
  • the internal mill pressure can be at least approximately in the range of 0.1 to 0.5 bar.
  • the purge gas is used at a temperature of about 80 to about 120 ° C., in particular approximately 100 ° C., and / or if low-pressure compressed air, in particular from about 0.3 bar to about 0, is used as the purge gas. 4 bar is used.
  • the amplification ratio see also Dr. med. R.
  • the sifting rotor has a clear height which increases with decreasing radius, wherein preferably the throughflow area of the sifting rotor is at least approximately constant.
  • the classifier rotor may also have an exchangeable, co-rotating dip tube.
  • the jet mill according to the invention can advantageously contain, in particular, an air classifier which can combine individual characteristics or combinations of features of the air classifier according to the EP 0 472 930 B1 contains.
  • the air classifier may comprise means for reducing the peripheral components of the flow according to the EP 0 472 930 B1 contain.
  • a discharge nozzle assigned to the classifying wheel of the air classifier which is constructed as a dip tube, has a cross-sectional widening designed to be rounded in the direction of flow, preferably in order to avoid vortex formations.
  • Fig. 1 is an embodiment of a jet mill 1 with a cylindrical housing 2, which encloses a grinding chamber 3, a Mahlgutholzgabe 4 approximately half the height of the grinding chamber 3, at least one Mahlstrahleneinlass 5 in the lower region of the grinding chamber 3 and a product outlet 6 in the upper region of the grinding chamber. 3 shown.
  • an air classifier 7 is arranged with a rotatable classifying wheel 8, with which the ground material (Not shown) is classified to dissipate only regrind below a certain grain size through the product outlet 6 from the grinding chamber 3 and feed millbase with a grain size above the selected value to another grinding process.
  • the classifying wheel 8 can be a classifying wheel which is common in air classifiers and whose blades (see later, for example, in connection with FIG Fig. 3 ) define radially extending blade channels, at the outer ends of which the classifying air enters and entrains particles of smaller grain size or mass to the central outlet and to the product outlet 6, while larger particles or particles of larger mass are rejected under the influence of centrifugal force.
  • Particularly preferred are the air classifier 7 and / or at least its classifying wheel 8 with at least one design feature according to the EP 0 472 930 B1 fitted.
  • Mahlstrahleinlass 5 z. B. consisting of a single, radially directed inlet opening or inlet nozzle 9 may be provided to impinge a single grinding jet 10 on the Mahlgutpiety that get from the Mahlgutiergabe 4 in the area of the grinding jet 10, with high energy and disassemble the Mahlgutpelle into smaller particles to let in, sucked by the classifying wheel 8 and, as far as they have a correspondingly small size or mass, are conveyed through the product outlet 6 to the outside.
  • two or more Mahlstrahleinlässe preferably grinding nozzles, in particular 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 Mahlstrahleinlässe used, which are mounted in the lower third of, preferably cylindrical housing of the grinding chamber.
  • Mahlstrahleinlässe are ideally in a plane and evenly distributed over the circumference of the grinding container arranged so that the grinding jets all meet at a point inside the grinding container.
  • the inlets or nozzles are distributed uniformly over the circumference of the grinding container. With three grinding jets this would be an angle of 120 ° between the respective inlets or nozzles. In general one can say that the larger the grinding chamber, the more inlets or grinding nozzles are used.
  • the grinding chamber may contain, in addition to the grinding jet inlets, heating openings 5a, preferably in the form of heating nozzles, through which hot gas can be passed into the mill in the heating phase.
  • heating openings 5a preferably in the form of heating nozzles, through which hot gas can be passed into the mill in the heating phase.
  • These nozzles or openings can - as already described above - be arranged in the same plane as the grinding openings or nozzles 5. It can one, but preferably several, more preferably 2, 3, 4, 5, 6, 7 or 8 heating openings or nozzles 5a may be included.
  • the mill contains two heating nozzles or openings and three grinding nozzles or openings.
  • the processing temperature can be influenced by using an internal heat source 11 between Mahlgutiergabe 4 and the range of grinding jets 10 or a corresponding heat source 12 in the area outside the Mahlgutiergabe 4 or by processing particles of already warm ground material, while avoiding heat loss in the Mahlgutiergabe 4 passes, to which a feed tube 13 is surrounded by a temperature-insulating jacket 14.
  • the heating source 11 or 12, when used, may be arbitrary in nature and therefore purposely operational and selected according to market availability, so that further explanation is not required.
  • the temperature of the grinding jet or the grinding jets 10 is relevant and the Temperature of the ground material should at least approximately correspond to this grinding jet temperature.
  • Representing the present embodiment of the jet mill 1 is representative of any supply of a resource or medium B, a reservoir or generating means 18, for example, a tank 18a, from which the operating medium or operating medium B via line 19 to the Mahlstrahleinlass 5 or the Mahlstrahleinlässen to the formation of the grinding jet 10 and the grinding jets 10 is passed.
  • a method for producing very fine particles is carried out with this jet mill 1 with an integrated dynamic air classifier 7.
  • gases or vapors B which have a higher and in particular significantly higher speed of sound than air (343 m / s).
  • gases or vapors B having an acoustic velocity of at least 450 m / s are used as the operating means.
  • a fluid is used, preferably the water vapor already mentioned, but also hydrogen gas or helium gas.
  • the jet mill 1 is preferably equipped with a source, for example the reservoir or generating device 18 for steam or superheated steam or other suitable reservoir or generating device, for a resource B or is associated with such a resource source, resulting in a resource B for operation with a higher and in particular much higher speed of sound than air (343 m / s), such as preferably a speed of sound of at least 450 m / s, is fed.
  • a source for example the reservoir or generating device 18 for steam or superheated steam or other suitable reservoir or generating device, for a resource B or is associated with such a resource source, resulting in a resource B for operation with a higher and in particular much higher speed of sound than air (343 m / s), such as preferably a speed of sound of at least 450 m / s, is fed.
  • This resource such as the steam or hot steam reservoir or generator 18, contains gases or vapors B for use in operation of the jet mill 1, particularly the water vapor already mentioned above, but hydrogen gas or
  • Another advantageous aspect when using steam as operating medium B is to provide the jet mill 1 with as small a surface as possible, or in other words, to optimize the jet mill 1 with regard to the smallest possible surface area.
  • This purpose is also served by the further alternative or additional design measure, namely to design or optimize the components of the jet mill 1 in order to avoid mass accumulations. This can be realized, for example, by using as thin as possible flanges in and for connecting the line devices 19.
  • Energy loss and other flow-related impairments can also be contained or avoided if the components of the jet mill 1 are designed or optimized to avoid condensation. It may even be included for this purpose special equipment (not shown) for condensation prevention. Furthermore, it is advantageous if the flow paths are optimized at least largely free of projections or to that extent. In other words, with these design variants, individually or in any combination, the principle is implemented to avoid as much as possible or anything that can become cold and thus where condensation can occur.
  • the classifying rotor has a clear height which increases with decreasing radius, that is to say towards its axis, wherein in particular the throughflow area of the classifying rotor is at least approximately constant.
  • a fine-material outlet chamber can be provided, which has a cross-sectional widening in the flow direction.
  • a particularly preferred embodiment of the jet mill 1 is that the sifting rotor 8 has a replaceable, with rotating dip tube 20.
  • the jet mill 1 preferably contains, as the schematic representation in the Fig. 2 it can be seen, an integrated air classifier 7, which is, for example, in types of jet mill 1 as fluidized bed jet mill or as a dense bed jet mill or as a spiral jet mill to a dynamic air classifier 7, which is advantageously arranged in the center of the grinding chamber 3 of the jet mill 1.
  • an integrated air classifier 7 which is, for example, in types of jet mill 1 as fluidized bed jet mill or as a dense bed jet mill or as a spiral jet mill to a dynamic air classifier 7, which is advantageously arranged in the center of the grinding chamber 3 of the jet mill 1.
  • the desired fineness of the material to be ground can be influenced.
  • the entire vertical air classifier 7 is enclosed by a classifier housing 21, which consists essentially of the upper housing part 22 and the lower housing part 23.
  • the upper housing part 22 and the lower housing part 23 are provided at the upper or lower edge, each with an outwardly directed peripheral flange 24 and 25 respectively.
  • the two peripheral flanges 24, 25 are in the installation or functional state of the air classifier 8 on each other and are fixed by suitable means against each other. Suitable means for fixing are, for example, screw connections (not shown). As releasable fastening means may also serve brackets (not shown) or the like.
  • both circumferential flanges 24 and 25 are connected to one another by a hinge 26 so that the upper housing part 22 can be pivoted upward in the direction of the arrow 27 after loosening the flange connecting means relative to the lower housing part 23 and the upper housing part 22 from below and the lower housing part 23 are accessible from above.
  • the housing base 23 in turn is formed in two parts and it consists essentially of the cylindrical withdrawraumgephaseuse 28 with the peripheral flange 25 at its upper open end and a discharge cone 29, which tapers conically downwards.
  • the discharge cone 29 and the reformraumgephasepuruse 28 are at the upper and lower ends with flanges 30, 31 to each other and the two flanges 30, 31 of discharge cone 29 and reformraumgephase 28 are like the peripheral flanges 24, 25 connected by releasable fastening means (not shown).
  • the thus assembled classifier housing 21 is suspended in or on support arms 28a, of which several as evenly spaced around the circumference of the classifier or compressor housing 21 of the air classifier 7 of the jet mill 1 are distributed and attack the cylindrical withdrawraumgephase 28.
  • An essential part of the housing installations of the air classifier 7 is in turn the classifying wheel 8 with an upper cover plate 32, with an axially spaced lower downstream cover plate 33 and arranged between the outer edges of the two cover plates 32 and 33, fixedly connected to these and evenly around the circumference of Classifying wheel 8 distributed blades 34 with appropriate contour.
  • the drive of the classifying wheel 8 is effected via the upper cover disk 32, while the lower cover disk 33 is the downstream cover disk.
  • the storage of the classifying wheel 8 comprises a positively driven forcibly digestradwelle 35, which is led out with the upper end of the classifier housing 21 and rotatably supports the classifying wheel 8 with its lower end within the classifier housing 21 in flying storage.
  • the upper housing part 22 also has a tubular product feed nozzle 39 of the Mahlgutholzgabe 4, the longitudinal axis parallel to the axis of rotation 40 of the classifying wheel 8 and its drive or withdrawradwelle 35 and as far as possible from this axis of rotation 40 of the classifying wheel 8 and its Drive or prepareradwelle removed 35, the housing upper part 22 is disposed radially outboard.
  • the integrated dynamic air classifier 1 includes a classifying wheel 8 and a classifying wheel shaft 35 as well as a classifier housing, as already explained.
  • a classifier gap 8a is defined between the classifying wheel 8 and the classifier housing 21, and a shaft bushing 35b is formed between the classifying wheel shaft and the classifier housing 21 (see Fig. 2a and 3a ).
  • a method for producing very fine particles is carried out with this jet mill 1 with an integrated dynamic air classifier 7.
  • the innovation compared to conventional jet mills is in addition to the fact that the grinding chamber is heated to a temperature above the dew point of the steam before the grinding phase, in that there is a gap mulling of classifier gap 8a and / or shaft passage 35b with compressed low-energy gases.
  • the special feature of this embodiment is precisely the combination of the use of these compressed low-energy gases with the high-energy superheated steam, with which the mill through the Mahlstrahleinlässe, in particular grinding nozzles or therein grinding nozzles, is charged. It At the same time, high-energy media and low-energy media are used.
  • the classifier housing 21 receives the coaxial with the classifying wheel 8 arranged tubular outlet nozzle 20 which lies with its upper end just below the downstream cover plate 33 of the classifying wheel 8, but without being connected to this.
  • an outlet chamber 41 is attached coaxially, which is also tubular, but whose diameter is substantially greater than the diameter of the outlet nozzle 20 and in the present embodiment, at least twice as large as the diameter of the outlet nozzle 20.
  • the outlet nozzle 20 is inserted into an upper cover plate 42 of the outlet chamber 41. Below the outlet chamber 41 is closed by a removable cover 43.
  • outlet nozzle 20 and outlet chamber 41 is held in a plurality of support arms 44 which are evenly distributed star-shaped around the circumference of the unit, connected with their inner ends in the region of the outlet nozzle 20 fixed to the unit and secured with their outer ends on the classifier housing 21.
  • the outlet nozzle 20 is surrounded by a conical annular housing 45 whose lower, larger outer diameter corresponds at least approximately to the diameter of the outlet chamber 41 and its upper, smaller outer diameter at least approximately the diameter of the classifying wheel 8.
  • the support arms 44 terminate and are firmly connected to this wall, which in turn is part of the assembly of outlet nozzle 20 and outlet chamber 41.
  • the support arms 44 and the annular housing 45 are parts of the scavenging air device (not shown), wherein the scavenging air the Penetration of matter from the interior of the classifier housing 21 in the gap between the classifying wheel 8 or more precisely its lower cover plate 3 and the outlet nozzle 20 prevents.
  • the support arms 44 are formed as tubes, with their outer end portions passed through the wall of the classifier housing 21 and connected via a suction filter 46 to a purge air source (not shown) ,
  • the annular housing 45 is closed at the top by a perforated plate 47 and the gap itself can be adjusted by an axially adjustable annular disc in the area between perforated plate 47 and lower cover plate 33 of the classifying wheel 8.
  • the outlet from the outlet chamber 41 is formed by a fines discharge pipe 48, which is led into the separator housing 21 from the outside and is connected in a tangential arrangement to the outlet chamber 41.
  • the fine material discharge pipe 48 is part of the product outlet 6.
  • the lining of the junction of the fine material discharge pipe 48 with the outlet chamber 41 serves as a deflecting cone 49.
  • a sighting air inlet spiral 50 and a coarse material discharge 51 are assigned to the housing end section 38 in a horizontal arrangement.
  • the direction of rotation of the sighting air inlet spiral 50 is opposite to the direction of rotation of the classifying wheel 8.
  • Grobgutaustrag 51 is the housing end portion 38 detachably associated with the lower end of the Gescousendabiteses 38 a flange 52 and the upper end of Grobgutaustrages 51 assigned a flange 53 and both flanges 52 and 53 are in turn releasably connected together by known means when the air classifier ready to be sold.
  • the dispersing zone to be designed is designated 54.
  • Flanges machined on the inner edge (chamfered) for a clean flow guidance and a simple lining are designated with 55.
  • a replaceable protective tube 56 is still applied to the inner wall of the outlet nozzle 20 as a wearing part and a corresponding replaceable protective tube 57 may be applied to the inner wall of the outlet chamber 41.
  • view air is introduced into the air classifier 7 at a pressure gradient and at a suitably chosen entry speed via the sighting air inlet spiral 50.
  • the classifying air rises spirally upward into the region of the classifying wheel 8.
  • the "product" of solid particles of different mass is introduced into the classifier housing 21 via the product feed port 39. From this product, the coarse material, d. H. the proportion of particles with greater mass against the classifying air in the region of the coarse material output 51 and is provided for further processing.
  • the proportion of particles of lesser mass is mixed with the classifying air, passes from the outside to the inside radially through the classifying wheel 8 into the outlet nozzle 20, into the outlet chamber 41 and finally via a fine material outlet pipe 48 into a fine material outlet or outlet 58, and from there into a filter in that the resources are separated from each other in the form of a fluid, such as air, and fines.
  • Coarser fines constituents are thrown radially out of the classifying wheel 8 and mixed with the coarse material in order to leave the classifier housing 21 with the coarse material or to circle in the classifier housing 21 until it has become fines of such a grain size that it is discharged with the classifying air.
  • the protective tube 57 is only a highly precautionary measure.
  • the reasons for a good separation technology high flow velocity in the classifying wheel 8 still prevails in the discharge or outlet pipe 20, therefore, the protective tube 56 is more important than the protective tube 57.
  • Particularly significant is the diameter jump with a diameter extension in the transition from the outlet nozzle 20 into the outlet chamber 41st
  • the air classifier 7 can again be well maintained by the division of the classifier housing 21 in the manner described and the assignment of the classifier components to the individual sub-housings and defective components can be replaced with relatively little effort and within short maintenance times.
  • the classifying wheel 8 While in the schematic representation of Fig. 2 2a, the classifying wheel 8 with the two cover disks 32 and 33 and the blade ring 59 arranged therebetween with the blades 34 is shown in already known, conventional form with parallel and parallel-sided cover disks 32 and 33 Fig. 3 or 3a, the classifying wheel 8 is shown for a further embodiment of the air classifier 7 of an advantageous development.
  • This classifying wheel 8 contains in addition to the blade ring 59 with the blades 34, the upper cover plate 32 and the axially downstream lower downstream cover plate 33 and is rotatable about the axis of rotation 40 and thus the longitudinal axis of the air classifier 7.
  • the diametrical extent of the classifying wheel 8 is perpendicular to the axis of rotation 40, ie to the longitudinal axis of the air classifier 7, regardless of whether the axis of rotation 40 and thus said longitudinal axis is vertical or horizontal.
  • the lower downstream cover disk 33 concentrically encloses the outlet nozzle 20.
  • the blades 34 are connected to both cover disks 33 and 32.
  • the two cover plates 32 and 33 are conical and preferably such that the distance between the upper cover plate 32 from the outflow side cover 33 from the rim 59 of the blades 34 inwards, ie toward the axis of rotation 40, and although preferably continuous, such as linear or non-linear, and with further preference so that the surface of the flow-through cylinder jacket for each radius between the blade outlet edges and outlet nozzle 20 remains at least approximately constant.
  • the decreasing due to the decreasing radius in known solutions outflow rate remains at least approximately constant in this solution.
  • the shape of the non-parallel-sided cover disk may be such that at least approximately so that the surface of the cylinder jacket through which flows through remains constant for each radius between blade outlet edges and outlet nozzle 20.
  • any particles, in particular amorphous particles can be ground so that powdered solids having an average particle size d 50 (TEM) ⁇ 1.5 microns and a d 90 value (TEM) ⁇ 1.8 microns and a d 99 value (TEM) ⁇ 2 ⁇ m.
  • TEM average particle size
  • TEM d 90 value
  • TEM d 99 value
  • the amorphous solids according to the invention are characterized in that they have an average particle size (TEM) d 50 ⁇ 1.5 ⁇ m, preferably d 50 ⁇ 1 ⁇ m, particularly preferably d 50 from 0.01 to 1 ⁇ m, very particularly preferably d 50 from 0.05 to 0.9 microns, more preferably d 50 from 0.05 to 0.8 microns, more preferably from 0.05 to 0.5 microns and most preferably from 0.08 to 0.25 microns and a d 90 value (TEM) ⁇ 1.8 ⁇ m, preferably d 90 from 0.1 to 1.5 ⁇ m, more preferably d 90 from 0.1 to 1.0 ⁇ m, and very particularly preferably d 90 from 0.1 to 0 , 5 microns and a d 99 value (TEM) ⁇ 2 microns, preferably d 99 ⁇ 1.8 microns, more preferably d 99 ⁇ 1.5 microns, most preferably d 99 from 0.1 to 1.0 microns and particularly preferably have d 99 of 0.
  • the amorphous solids of the invention are silica gels, where silica gels include both hydro, aerosol and xerogels.
  • the amorphous solids according to the invention are silica gels, in particular xerogels or aerogels, having an average particle size d 50 (TEM) ⁇ 1.5 ⁇ m, preferably d 50 ⁇ 1 ⁇ m, particularly preferably d 50 of 0 , 01 to 1 .mu.m, most preferably d 50 from 0.05 to 0.9 microns, more preferably d 50 from 0.05 to 0.8 microns, more preferably from 0.05 to 0.5 microns and most preferably of 0.1 to 0.25 microns and a d 90 value (TEM) of ⁇ 1.8 microns, preferably d 90 0.05 to 1.8 .mu.m, particularly preferably d 90 of 0.1 to 1.5 microns, most preferably d 90 is from 0.1 to 1.0 ⁇ m, particularly preferably d 90 from 0.1 to 0.5 ⁇ m and especially preferably d 90 from 0.2 to 0.4 ⁇ m and a d 99 value (TEM ) ⁇
  • TEM average
  • reaction conditions and the physical / chemical data of the precipitated silicas according to the invention are determined by the following methods:
  • particle sizes are named at various points, which were measured by one of the three following methods.
  • the reason for this is that the particle sizes mentioned there extend over a very wide particle size range ( ⁇ 100 nm to 1000 ⁇ m).
  • ⁇ 100 nm to 1000 ⁇ m the expected particle size of the sample to be examined therefore each of a different one of the three particle size measurement methods come into question.
  • Particles with an expected average particle size of approx.> 50 ⁇ m were determined by sieving. Particles with an expected average particle size of approx. 1 - 50 ⁇ m were examined by means of the laser diffraction method and for particles with an expected average particle size ⁇ 1.5 ⁇ m the TEM analysis + image processing was used.
  • the sieve fractions are determined by means of a shaker (Retsch AS 200 Basic).
  • the resulting sieve tower is mounted on the screening machine. For sieving, 100 g of solid are weighed to the nearest 0.1 g and added to the top sieve of the sieve tower. It is shaken for 5 minutes at an amplitude of 85.
  • the individual fractions are weighed back to 0.1 g.
  • the fractions must be weighed immediately after shaking, otherwise it can lead to distorted results due to moisture losses.
  • the combined weights of the individual fractions should be at least 95 g to evaluate the result.
  • the determination of the particle distribution is based on the principle of laser diffraction on a laser diffractometer (Horiba, LA-920).
  • the sample of the amorphous solid in 100 ml of water without the addition of dispersing additives in a 150 ml beaker (diameter: 6 cm) is dispersed so that a dispersion with a weight fraction of 1 wt .-% SiO 2 is formed.
  • This dispersion is then dispersed intensively (300 W, not pulsed) with an ultrasonic finger (Dr. Hielscher UP400s, Sonotrode H7) over a period of 5 min.
  • the ultrasound finger is to be mounted in such a way that its lower end dips to about 1 cm above the bottom of the beaker.
  • the particle size distribution is determined from a partial sample of the dispersion subjected to ultrasound with the laser diffractometer (Horiba LA-920).
  • Horiba LA-920 For evaluation with the supplied standard software of the Horiba LA-920, a refractive index of 1.09 must be selected.
  • the transmission electron micrographs are generated on the basis of ASTM D 3849-02.
  • a transmission electron microscope (Hitachi H-7500, with a maximum acceleration voltage of 120 KV) is used.
  • the digital image processing is done by a software of the company Soft Imaging Systems (SIS, Weg / Westphalia).
  • the program version iTEM 5.0 is used.
  • amorphous solid For the determinations, about 10-15 mg of the amorphous solid are dispersed in an isopropanol / water mixture (20 ml isopropanol / 10 ml distilled water) and ultrasonicated for 15 min (ultrasound processor UP 100, Dr. Hielscher GmbH, HF - power 100 W, HF frequency 35 kHz). Thereafter, a small amount (about 1 ml) is removed from the finished dispersion and then applied to the carrier mesh. The excess dispersion is absorbed with filter paper. Then the netting is dried.
  • the choice of magnification is described in ITEM WK 5338 (ASTM) and depends on the primary particle size of the amorphous solid to be investigated. Typically, in the case of silicas, the electron optical magnification 50,000: 1 and the final magnification 200,000: 1 are selected. For digital imaging systems, ASTM D 3849 specifies the appropriate resolution in nm / pixel depending on the primary particle size of the amorphous solid to be measured.
  • the recording conditions must be arranged in such a way that the reproducibility of the measurements can be guaranteed.
  • the individual particles to be characterized on the basis of the TEM images must be imaged with sufficiently sharp contours be.
  • the distribution of the particles should not be too dense.
  • the particles should be as separate as possible. There should be as few overlaps as possible.
  • the total number of aggregates to be measured depends on the range of aggregate sizes: the larger this is, the more particles have to be detected in order to arrive at an adequate statistical statement. For silicas, about 2500 individual particles are measured.
  • the primary particle sizes and size distributions are determined on the basis of TEM images specially prepared for this purpose; these are analyzed by means of a particle size analyzer TGZ3 according to Endter and Gebauer (Sales: Carl Zeiss). The entire measurement process is supported by the analysis software DASYLab 6.0 - 32.
  • the measuring ranges are calibrated according to the size range of the particles to be examined (determination of the smallest and largest particles), after which the measurements are made.
  • An enlarged transparency of a TEM image is positioned on the evaluation desk so that the center of gravity of a particle lies approximately in the middle of the measurement mark. Then, by turning the handwheel on the TGZ3, the diameter of the circular measuring mark is changed until the best possible surface alignment with the image object to be analyzed is achieved.
  • the structures to be analyzed are not circular. Then it is true that they project beyond the measuring mark Surface portions of the particles must be adapted to those surface portions of the measurement mark, which are outside the particle boundary. If this adjustment has taken place, the actual counting process is triggered by actuation of a foot switch.
  • the particle in the area of the measuring mark is perforated by a knock-down marking pen.
  • the TEM film is again shifted on the evaluation lectern until a new particle is adjusted below the measurement mark. A new adjustment and counting procedure takes place. This is repeated until all of the evaluation statistics are characterized according to required particles.
  • the number of particles to be counted depends on the range of the particle size: the larger it is, the more particles must be detected in order to arrive at an adequate statistical statement. For silicas, about 2500 individual particles are measured.
  • the average particle size d 50 is the mean value of the equivalence diameter of all particles evaluated.
  • the equivalent diameters of all the particles evaluated are in classes of 25 nm each (0-25 nm, 25-50 nm, 50-100 nm, ... 925-950 nm, 950-975 nm, 975-1000 nm) and the frequencies in the respective classes are determined. From the cumulative representation of this frequency distribution, the particle sizes d 90 (ie 90% of the particles evaluated have a smaller equivalent diameter) and d 99 can be determined.
  • the specific nitrogen surface area (hereinafter referred to as the BET surface area) of the pulverulent solids is determined on the basis of ISO 5794-1 / Annex D with the TRISTAR 3000 device (Micromeritics) after the multipoint determination in accordance with DIN ISO 9277.
  • the measuring principle is based on nitrogen sorption at 77 K (volumetric method) and can be used for mesoporous solids (2 nm to 50 nm pore diameter).
  • the determination of the pore size distribution is carried out according to DIN 66134 (determination of the pore size distribution and the specific surface of mesoporous solids by nitrogen sorption, according to Barrett, Joyner and Halenda (BJH)).
  • Drying of the amorphous solids takes place in a drying cabinet. Sample preparation and measurement are carried out with the ASAP 2400 device (Micromeritics). As measuring gases nitrogen 5.0 and helium 5.0 are used. The cooling bath is liquid nitrogen. Weighing weights are precisely determined with an analytical balance in [mg] to one decimal place.
  • the sample to be tested is pre-dried at 105 ° C for 15-20 h. Of these, 0.3 to 1 g are weighed into a sample vessel.
  • the sample vessel is connected to the ASAP 2400 device and baked at 200 ° C. for 60 minutes under vacuum (final vacuum ⁇ 10 ⁇ m Hg).
  • the sample cools to room temperature under vacuum, is blanketed with nitrogen and weighed. The difference to the weight of the filled with nitrogen sample vessel without solid results in the exact weight.
  • the measurement is carried out according to the operating instructions of the ASAP 2400.
  • the adsorbed volume is determined on the basis of the desorption branch (pore volume for pores with a pore diameter ⁇ 50 nm).
  • the pore radius distribution is calculated from the measured nitrogen isotherms according to the BJH method ( EP Barett, LG Joyner, PH Halenda, J. Amer. Chem. Soc., Vol. 73, 373 (1951 )) and displayed as a distribution curve.
  • the moisture of amorphous solids is determined according to DIN EN ISO 787-2 after drying for 2 hours in a convection oven at 105 ° C. This drying loss consists predominantly of water moisture.
  • the determination of the pH of the amorphous solids is carried out as a 5% aqueous suspension at room temperature based on DIN EN ISO 787-9. Compared to the specifications of this standard, the initial weights were changed (5.00 g SiO 2 to 100 ml deionized water).
  • the DBP image is defined for anhydrous, amorphous solids.
  • the correction value K for the calculation of the To consider DBP inclusion can be determined from the following correction table, eg. For example, a water content of the silica of 5.8% would mean a 33 g / (100 g) addition for DBP uptake.
  • the moisture content of the silica or of the silica gel is determined according to the method "Determination of the moisture or the drying loss" described below.
  • Moisture correction table for dibutyl phthalate uptake - anhydrous % Moisture % Humidity .0 .2 .4 .6 .8th 0 0 2 4 5 7 1 9 10 12 13 15 2 16 18 19 20 22 3 23 24 26 27 28 4 28 29 29 30 31 5 31 32 32 33 33 6 34 34 35 35 36 7 36 37 38 38 39 8th 39 40 40 41 41 9 42 43 43 44 44 10 45 45 46 46 47
  • the determination of the tamped density is based on DIN EN ISO 787-11.
  • a defined amount of a previously unsorted sample is filled into a graduated glass cylinder and subjected to a fixed number of stacks by means of a tamping volumeter. During the stamping, the sample condenses. As a result of the examination, the tamped density is obtained.
  • the measurements are carried out on a tamping volumeter with counter from Engelsmann, Ludwigshafen, type STAV 2003.
  • a 250 ml glass cylinder is tared on a precision balance. Subsequently, 200 ml of the amorphous solid are filled with the aid of a powder funnel in the tared measuring cylinder so that no cavities form. The sample quantity is then weighed to the nearest 0.01 g. Thereafter, lightly tapping the cylinder so that the surface of the silica in the cylinder is horizontal. The measuring cylinder is in The measuring cylinder holder of the tamping volumeter used and tamped 1250 times. The volume of the mashed sample is read to 1 ml after a single ramming pass.
  • the alkali number determination is understood to mean the consumption of hydrochloric acid in ml (at 50 ml test volume, 50 ml distilled water and a hydrochloric acid used of concentration 0.5 mol / l) in a direct potentiometric titration of alkaline solutions or suspensions up to a pH of 8.30.
  • the free alkali content of the solution or suspension is hereby recorded.
  • the pH device Kernick, type: 766 pH meter Calimatic with temperature sensor
  • the pH electrode combination electrode from Schott, type N7680
  • the combination electrode is immersed in the 40 ° C tempered solution or suspension consisting of 50.0 ml of sample and 50.0 ml of deionized water.
  • hydrochloric acid solution of concentration 0.5 mol / l dropwise until a constant pH of 8.30 is reached. Due to the slowly adjusting equilibrium between the silica and the free alkali content it takes a waiting time of 15 minutes until a final reading of the Acid consumption.
  • the read-out hydrochloric acid consumption in ml corresponds directly to the alkali number, which is given dimensionlessly.
  • the precipitated silica used as the starting material to be ground was prepared according to the following procedure:
  • the water glass and the sulfuric acid used at various points in the following recipe for the preparation of the silica 1 are characterized as follows: Water glass: Density 1.348 kg / l, 27.0 wt% SiO 2 , 8.05 wt% Na 2 O Sulfuric acid: Density 1.83 kg / l, 94% by weight
  • the resulting suspension is filtered with a membrane filter press and the filter cake washed with deionized water until a conductivity of ⁇ 10 mS / cm is observed in the wash water.
  • the filter cake is then present with a solids content of ⁇ 25%.
  • the drying of the filter cake takes place in a spin-flash dryer.
  • silica 1 The data of silica 1 are given in Table 1.
  • the hydrogel prepared as described above is aged with ammonia addition at pH 9 and 80 ° C for 10-12 hours, and then adjusted to pH 3 with 45 wt .-% sulfuric acid.
  • the hydrogel then has a solids content of 34-35%. It is then coarsely ground on a pin mill (Alpine Type 160Z) to a particle size of approx. 150 ⁇ m.
  • the hydrogel has a residual moisture of 67%.
  • silica 2 The data of silica 2 are given in Table 1.
  • silica 3a The data of silica 3a are given in Table 1.
  • the hydrogel prepared as described above is further washed at about 80 ° C until the conductivity of the wash water is below 2 mS / cm and dried in a convection oven (Fresenberger POH 1600.200) at 160 ° C to a residual moisture content of ⁇ 5%.
  • the xerogel is pre-shredded to a particle size ⁇ 100 ⁇ m (Alpine AFG 200).
  • silica 3b The data of silica 3b are given in Table 1.
  • the hydrogel prepared as described above is aged with addition of ammonia at pH 9 and 80 ° C for 4 hours, then adjusted with 45 wt .-% sulfuric acid to about pH 3 and in a convection oven (Fresenberger POH 1600.200) at 160 ° C to a Residual moisture of ⁇ 5% dried.
  • the xerogel is pre-shredded to a particle size ⁇ 100 ⁇ m (Alpine AFG 200).
  • silica 3c The data of silica 3c are given in Table 1.
  • a fluidized bed counter-jet mill according to FIG. 1 . 2a and 3a first via the two heating nozzles 5a (of which in FIG. 1 only one shown), which are charged with 10 bar and 160 ° C hot compressed air, heated to a mill outlet temperature of about 105 ° C.
  • the mill is downstream of the filtration of the ground material a filter unit (not in FIG. 1 shown), the filter housing is heated in the lower third indirectly via attached heating coils by means of 6 bar saturated steam also to prevent condensation. All equipment surfaces in the area of the mill, the separation filter, as well as the supply lines for steam and hot compressed air are particularly insulated.
  • the supply of the heating nozzles with hot compressed air is switched off and the admission of the three grinding nozzles with superheated steam (38 bar (abs), 330 ° C) started.
  • water is injected in the starting phase and during grinding in the grinding chamber of the mill via a two-fluid nozzle operated with compressed air in dependence on the mill outlet temperature.
  • the product task is started when the relevant process parameters (see Table 2) are constant.
  • the regulation of the feed quantity is dependent on the self-adjusting stream.
  • the classifier flow regulates the feed quantity such that approx. 70% of the nominal flow can not be exceeded.
  • the crushing of the coarse material takes place in the expanding steam jets (grinding gas). Together with the expanded grinding gas, the product particles in the center of the mill container rise to the classifying wheel. Depending on the set speed of the sifter and the amount of grinding steam (see Table 1), the particles which have a sufficient fineness pass with the grinding steam into the fine-material outlet and from there into the downstream one Separation system, while too coarse particles go back into the grinding zone and subjected to a further crushing.
  • the discharge of the separated fine material from the separation filter in the subsequent ensiling and packaging is done by means of rotary valve.
  • the grinding pressure of the grinding gas prevailing at the grinding nozzles, or the resulting amount of grinding gas in conjunction with the speed of the dynamic Schaufelradsichters determine the fineness of the grain distribution function and the upper grain limit.

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  • Food Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
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Claims (16)

  1. Matières solides pulvérulentes amorphes ayant une taille de particule moyenne d50 (MET) < 1,5 µm et une valeur d90 (MET) < 1,8 µm et une valeur d99 (MET) < 2 µm, et consistant en des gels de silice qui présentent en outre un volume poreux de 0,2 à 0,7 ml/g ou qu'ils consistent en des gels de silice qui présentent en outre un volume poreux de 0,8 à 1,5 ml/g ou consistant en des gels de silice qui présentent en outre un volume poreux de 1,5 à 2,1 ml/g.
  2. Procédé de fabrication de matières solides amorphes selon la revendication 1 par broyage de matières solides amorphes au moyen d'un système de broyage (appareil de broyage), de préférence d'un système de broyage comprenant un broyeur à jet, de manière particulièrement préférée d'un système de broyage comprenant un broyeur à jets opposés et lit fluidisé ou un broyeur à jet à lit dense ou un broyeur à jet à spirale, caractérisé en ce que le broyeur est exploité pendant la phase de broyage avec un agent d'exploitation choisi dans le groupe constitué par un gaz et/ou une vapeur, de préférence de la vapeur d'eau et/ou un gaz contenant de la vapeur d'eau, et en ce que la chambre de broyage est chauffée pendant un phase de chauffage, c'est-à-dire avant l'exploitation propre avec l'agent d'exploitation, de sorte que la température dans la chambre de broyage et/ou à la sortie du broyeur soit supérieure au point de condensation de la vapeur et/ou de l'agent d'exploitation.
  3. Procédé selon la revendication 2, caractérisé en ce que le système de broyage ou le broyeur est exploité pendant la phase de chauffage avec un gaz et/ou un mélange de gaz chaud, de préférence avec de l'air chaud et/ou des gaz de combustion et/ou des gaz inertes et/ou des mélanges de ceux-ci.
  4. Procédé selon la revendication 3, caractérisé en ce que le gaz et/ou mélange de gaz chaud est introduit dans la chambre de broyage pendant la phase de chauffage par des entrées, de préférence des buses, qui sont différentes de celles par lesquelles l'agent d'exploitation est détendu pendant la phase de broyage et/ou le gaz et/ou mélange de gaz chaud est introduit dans la chambre de broyage pendant la phase de chauffage par les entrées, de préférence des buses, par lesquelles l'agent d'exploitation est également détendu pendant la phase de broyage.
  5. Procédé selon l'une quelconque des revendications 2 à 4, caractérisé en ce qu'un gaz sec et/ou un mélange de gaz sec, de préférence de l'air sec et/ou un gaz de combustion et/ou un gaz inerte et/ou un mélange de ceux-ci est introduit dans le broyeur pour le refroidissement.
  6. Procédé selon l'une quelconque des revendications 2 à 5, caractérisé en ce qu'une condensation de la vapeur d'eau sur des éléments et/ou des composants du système de broyage ou du broyeur est empêchée.
  7. Procédé selon l'une quelconque des revendications 2 à 6, caractérisé en ce que la température de l'agent d'exploitation pendant la phase de broyage se situe dans la plage allant de 200 à 800 °C et/ou en ce que la pression de l'agent d'exploitation pendant la phase de broyage se situe dans la plage allant de 15 à 250 bar.
  8. Procédé selon l'une quelconque des revendications 2 à 7, caractérisé en ce qu'un tamisage, de préférence au moyen d'un tamiseur intégré et/ou dynamique, de manière particulièrement préférée au moyen d'un tamiseur à roue à aubes et/ou d'un tamiseur pneumatique dynamique intégré, du produit broyé a lieu.
  9. Procédé selon la revendication 8, caractérisé en ce qu'un broyeur à jet (1) muni d'un tamiseur pneumatique dynamique intégré (7) est utilisé, la vitesse de rotation d'un rotor ou d'une roue de tamisage (8) du tamiseur pneumatique (7) et le rapport d'amplification intérieur V (= Di/DF) étant choisis ou ajustés de sorte que la vitesse périphérique de l'agent d'exploitation (B) au niveau d'un tube d'immersion ou d'un embout de sortie (20) attribué à la roue de tamisage atteigne jusqu'à 0,8 fois la vitesse du son de l'agent d'exploitation (B).
  10. Procédé selon l'une quelconque des revendications 8 ou 9, caractérisé en ce qu'un système de broyage est utilisé, dans lequel un rinçage de la fente entre la roue de tamisage et le boîtier du tamiseur (fente du tamiseur) et/ou du passage d'arbre entre l'arbre de la roue de tamisage et le boîtier du tamiseur est possible et/ou est réalisé.
  11. Procédé selon l'une quelconque des revendications 8 à 10, caractérisé en ce qu'un broyeur à jet (1) muni d'un tamiseur pneumatique dynamique intégré (7), qui contient une roue de tamisage (8) et un arbre de roue de tamisage (35), ainsi qu'un boîtier de roue de tamisage (21), une fente de tamiseur (8a) étant formée entre la roue de tamisage (8) et le boîtier de roue de tamisage (21) et un passage d'arbre (35b) étant formé entre l'arbre de roue de tamisage (35) et le boîtier du tamiseur (21), est utilisé et en ce qu'un rinçage de la fente du tamiseur (8a) et/ou du passage d'arbre (35b) a lieu avec des gaz comprimés à faible teneur en énergie.
  12. Procédé selon l'une quelconque des revendications 8 à 11, caractérisé en ce que la quantité de gaz de broyage qui atteint le tamiseur est ajustée de sorte que la taille de particule moyenne (MET) d50 du produit broyé obtenu soit inférieure à 1,5 µm et/ou que la valeur d90 soit < 2 µm et/ou que la valeur d99 soit < 2 µm.
  13. Procédé selon l'une quelconque des revendications 2 à 12, caractérisé en ce que les matières solides amorphes sont des gels ou des particules contenant des agrégats et/ou des agglomérats, de préférence des matières solides amorphes contenant ou constitués par au moins un métal et/ou au moins un oxyde de métal, de manière particulièrement préférée des oxydes amorphes de métaux du 3e et du 4e groupe principal du tableau périodique des éléments.
  14. Procédé selon l'une quelconque des revendications 2 à 13, caractérisé en ce que des particules amorphes, qui ont déjà été soumises à une étape de séchage, sont broyées ou en ce qu'un gâteau de filtration constitué de particules amorphes ou un hydrogène est broyé ou simultanément broyé et séché.
  15. Utilisation des matières solides amorphes selon la revendication 1 dans des systèmes de revêtement.
  16. Agent de revêtement contenant au moins une matière solide amorphe selon la revendication 1.
EP07820693.5A 2006-10-16 2007-09-28 Particule submicronique amorphe Active EP2089163B1 (fr)

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BRPI0717334B1 (pt) 2019-05-21
WO2008046727A3 (fr) 2008-07-17
ES2658825T3 (es) 2018-03-12
NO20091880L (no) 2009-07-14
US7850102B2 (en) 2010-12-14
CN101616743B (zh) 2014-03-05
EP2089163A2 (fr) 2009-08-19
DE102006048850A1 (de) 2008-04-17
MX2009003984A (es) 2009-04-28
WO2008046727A2 (fr) 2008-04-24
US20100285317A1 (en) 2010-11-11
TW200902153A (en) 2009-01-16
US8039105B2 (en) 2011-10-18
ZA200902603B (en) 2010-04-28
RU2458741C2 (ru) 2012-08-20
BRPI0717334A2 (pt) 2013-12-10
TWI446970B (zh) 2014-08-01
JP5511384B2 (ja) 2014-06-04
US20080173739A1 (en) 2008-07-24
PL2089163T3 (pl) 2018-06-29
PT2089163T (pt) 2018-02-06
CA2666099A1 (fr) 2008-04-24
CN101616743A (zh) 2009-12-30
KR101503936B1 (ko) 2015-03-18
KR20090080971A (ko) 2009-07-27
HUE038516T2 (hu) 2018-10-29
RU2009118341A (ru) 2010-11-27
JP2010506708A (ja) 2010-03-04
CN101244402A (zh) 2008-08-20

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