EP2089163A2 - Particule submicronique amorphe - Google Patents

Particule submicronique amorphe

Info

Publication number
EP2089163A2
EP2089163A2 EP07820693A EP07820693A EP2089163A2 EP 2089163 A2 EP2089163 A2 EP 2089163A2 EP 07820693 A EP07820693 A EP 07820693A EP 07820693 A EP07820693 A EP 07820693A EP 2089163 A2 EP2089163 A2 EP 2089163A2
Authority
EP
European Patent Office
Prior art keywords
grinding
classifier
amorphous
gas
mill
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.)
Granted
Application number
EP07820693A
Other languages
German (de)
English (en)
Other versions
EP2089163B1 (fr
Inventor
Karl Meier
Ulrich Brinkmann
Christian Panz
Doris Misselich
Christian Götz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Priority to PL07820693T priority Critical patent/PL2089163T3/pl
Publication of EP2089163A2 publication Critical patent/EP2089163A2/fr
Application granted granted Critical
Publication of EP2089163B1 publication Critical patent/EP2089163B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B02C19/06—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
    • B02C19/18—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
    • B02C19/0012—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 fine grinding in spiral or counter-jet mills is carried out with compressed air as the grinding gas, e.g. 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.
  • US Pat. No. 3,367,742 describes a process for grinding aerogels in which aerogels having a mean particle diameter of 1.8 to 2.2 ⁇ m are obtained. Milling to a mean particle diameter of less than 1 ⁇ m is not possible with this technique. Furthermore, the particles of US 3,367,742 have a broad Particle size distribution with particle diameters of 0.1 to 5.5 ⁇ m and a particle size> 2 ⁇ m of 15 to 20%.
  • the inventors have surprisingly found that it is possible to amorphous solids by means of a very specific to marry in claims 1 to 19 near the specified method to a mean particle size d 5 o of less than 1.5 microns and also a very narrow particle distribution to reach .
  • the object is thus achieved by the method specified in more detail in the claims and the description below and the amorphous solids specified there.
  • the invention accordingly provides a process for grinding amorphous solids by means of a grinding system (milling apparatus), preferably comprising a jet mill, characterized in that the mill in the milling phase with a resource selected from a group consisting of gas and / or steam, preferred Steam, and / or a gas containing water vapor, is, is operated and that the grinding chamber is heated in a heating phase, ie before the actual operation with the resources, such that the temperature in the grinding chamber and / or at the mill output higher than the dew point of Steam and / or resources is.
  • a grinding system milling apparatus
  • a jet mill characterized in that the mill in the milling phase with a resource selected from a group consisting of gas and / or steam, preferred Steam, and / or a gas containing water vapor, is, is operated and that the grinding chamber is heated in a heating phase, ie
  • the subject matter further amorphous solids having an average particle size d 5 o ⁇ 1.5 microns and / or a dgo value ⁇ 2 microns and / or a dgg value ⁇ 2 microns.
  • the amorphous solids may be gels but also those with different structure such.
  • Periodic Table of the Elements This applies both to the gels and to the other amorphous solids, in particular those containing particles of agglomerates and / or aggregates.
  • Particularly preferred are precipitated silicas, fumed silicas, silicates and silica gels, wherein silica gels include both hydro- and aerosol as well as xerogels.
  • the present invention relates to the use of the amorphous solids according to the invention having an average particle size d 5 o ⁇ 1.5 microns and / or a dgo value ⁇ 2 microns and / or a dgg value ⁇ 2 microns, z.
  • the amorphous solids according to the invention having an average particle size d 5 o ⁇ 1.5 microns and / or a dgo value ⁇ 2 microns and / or a dgg value ⁇ 2 microns, z.
  • surface coating systems In surface coating systems.
  • the inventive method is the first time succeeded, powdery amorphous solids having an average particle size d 5 o ⁇ 1.5 microns and a narrow Particle size distribution, expressed by the dgo value ⁇ 2 microns and / or the dgg ⁇ 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 reagglomeration of the amorphous particles, so that the effect of the milling was partially reversed and average particle sizes d 5 o ⁇ 1.5 microns and particle size distribution dgo value ⁇ 2 microns are not achieved in the dried, powdery solids could. In the case of drying of gels, 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 dgo value and dgg 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.
  • the very special preferred fluidized bed counter-jet mill 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 on the circumference of the preferred round
  • Grinder container arranged 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, more preferably a separator according to Figures 2 and 3.
  • a dynamic air classifier according to FIGS. 2a and 3a is used.
  • This dynamic air classifier includes a classifying wheel and a classifying wheel shaft as well as a classifier housing, between which
  • Classifying wheel and the classifier housing a classifier gap and between the reformradwelle and the classifier housing a shaft passage is formed, and is characterized in that a rinsing gap of the sifter gap and / or shaft passage is made with compressed low-energy gases.
  • a classifier in combination with the jet mill operated under the conditions according to the invention, 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 a
  • Heating phase is preceded, in which it is ensured that the grinding chamber, particularly preferably all essential components of the mill and / or the grinding system, where water and / or water vapor could condense, is heated so / that its / its temperature above the
  • the heating can be done in principle by any heating method. Preferably, however, 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 that
  • 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.
  • inlets or nozzles Preferably there are in the grinding chamber inlets or nozzles. 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). But it is also possible that in the grinding chamber separate inlets or nozzles (heating nozzles) are present, through which the hot gas and / or gas mixture can be introduced.
  • 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 equipment has a temperature of 200 to 800 0 C, more preferably 250 to 600 0 C and in particular 300 to 400 0 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. By these measures, a deposit of the ground material in the mill can be additionally prevented.
  • Specify and / or illustrated embodiments are not limited to these embodiments or the combination with the other features of these embodiments, but may in the context of technical possibilities, with any other variants, even if they are not treated separately in the present documents combined become.
  • 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 flushing gas with a temperature of about 80 to about 120 0 C, in particular approximately 100 0 C is used, and / or when flushing gas low-energy compressed air, in particular with about 0.3 bar to about 0, 4 bar is used.
  • amplification ratio see also Dr. med. R. Nied, "Fluid Mechanics and Thermodynamics in Mechanical Process Engineering", available from management consultancy Dr. Roland Nied, 86486 Bonstetten, Germany, also available from NETZSCH-CONDUX Mahltechnik GmbH, Rodenbacher Clice 1, 63457 Hanau, Germany.
  • the classifying rotor has a clear height increasing with decreasing radius, wherein preferably the area of the classifying rotor through which flow is at least approximately constant.
  • the classifying rotor has an exchangeable, co-rotating dip tube.
  • the jet mill according to the invention can advantageously contain, in particular, an air classifier which contains individual features or combinations of features of the air classifier according to EP 0 472 930 B1.
  • the air classifier may contain means for reducing the peripheral components of the flow according to EP 0 472 930 B1.
  • a discharge nozzle assigned to the classifying wheel of the air classifier which is designed as a dip tube, has a cross-sectional widening designed in the direction of flow, preferably rounded to avoid vortex formations.
  • FIGS. 1 to 3a and the associated description Preferred and / or advantageous embodiments of the grinding system or the mill which can be used in the method according to the invention emerge from FIGS. 1 to 3a and the associated description, it being emphasized once again that these embodiments merely illustrate the invention more closely by way of example, ie it is not these examples of application and application or on the respective Characteristic combinations within individual exemplary embodiments are limited.
  • FIG. 1 shows diagrammatically an exemplary embodiment of a jet mule in a partially sectioned schematic drawing
  • FIG. 2 shows an exemplary embodiment of an air classifier of a jet mill in a vertical arrangement and as a schematic center section, wherein the outlet wheel is associated with the outlet pipe for the mixture of classifying air and solid particles,
  • FIG. 2 a shows an exemplary embodiment of an air classifier analogous to FIG. 2, but with splitting winding of classifier gap 8 a and shaft passage 35 b, FIG.
  • Fig. 3 shows a schematic representation and a vertical section of a classifying wheel of an air classifier
  • Fig. 3a shows in a schematic representation and as
  • FIG. 4 shows the particle distribution of silica 1 (unmilled)
  • FIG. 5 shows a TEM image of Example 1
  • FIG. 6 shows a histogram of the equivalent diameter of Example 1
  • FIG. 7 shows a TEM image of Example 2
  • FIG. 8 shows a histogram of the equivalent diameter of Example 2
  • Figure 9 shows a TEM image of Example 3a
  • Figure 10 shows a histogram of the equivalent diameter of Example 3a
  • FIG. 11 shows a TEM image of Example 3b
  • Figure 12 shows a histogram of the equivalent diameter of Example 3b
  • 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 im Upper portion 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 eg in connection with FIG. 3) delimit radially extending blade channels, at whose outer ends the classifying air enters and particles of smaller grain size or mass to the central outlet and to the Product outlet 6 entrains, while larger particles or particles of larger mass are rejected under the influence of centrifugal force.
  • the air classifier 7 and / or at least its classifying wheel 8 are equipped with at least one design feature according to EP 0 472 930 B1.
  • 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 Mahlbehalters.
  • the inlets or nozzles are uniformly distributed over the circumference of the Mahlbehalters. 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 can, in addition to the grinding jet inlets, have heating openings 5a, preferably in the form of
  • the mill contains two Schudusen or - ⁇ Maschinenen and three Mahldusen 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 an already warm ground material, while avoiding heat losses in the Mahlgutiergabe 4 passes, to which a Zubowungsrohr 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.
  • the jet mill 1 is representative of any supply of a resource or medium B, a reservoir or generating device 18, for example, a tank 18a, from which the resource or operating medium B via conduit means 19 to the Mahlstrahleinlass 5 or the Mahlstrahleinashes. 5 to the formation of the grinding jet 10 and the grinding jets 10 is passed.
  • a jet mill 1 equipped with an air classifier 7 the relevant embodiments being intended and to be understood by way of example only and not by way of limitation, with this jet mill 1 having an integrated dynamic
  • Wind sifter 7 a method of producing finest particles performed.
  • the innovation compared to conventional jet mills, in addition to the fact that the grinding phase is preceded by a heating phase in which all the parts in contact with the steam to a temperature above the
  • Circumferential speed of a resource B on an immersion tube or outlet nozzle 20 associated with the preparerad 8 reaches up to 0.8 times, preferably up to 0.7 times and more preferably reaches up to 0.6 times the speed of sound of the operating medium or medium B.
  • 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
  • Operating means B it is advantageous to provide with expansion arcs (not shown) equipped line devices 19, which are then also called steam supply line to the inlet or grinding nozzles 9, so preferably when the steam supply line is connected to a source of steam as reservoir or generating means 18 .
  • 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.
  • Water vapor as resource B it is particularly advantageous to prevent heat exchange or heat loss and thus energy loss in the system.
  • This purpose is also served by the further alternative or additional design measure, namely the components of the jet mill 1 for avoiding
  • Impairment 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.
  • 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 can be seen from the schematic illustration in FIG. 2, an integrated air classifier 7, in which, for example in the case of types of the jet mill 1, as a fluid bed jet mill or as
  • Density bed jet mill or as a spiral jet mill is 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 surrounded 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 to 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 each other by a hinge 26 so that the upper housing part 22 after releasing the
  • Flange connecting means relative to the lower housing part 23 can be pivoted upward in the direction of the arrow 27 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 Austragskonus 29 and the reformraumgephaseuse 28 are at the top or bottom with
  • Flanges 30, 31 on each other and the two flanges 30, 31 of Austragkonus 29 and treatraumgeophuse 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 reformraumgephase 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 removal of the prepareradwelle 35 from the classifier housing 21 takes place in a
  • a pair of machined plates 36, 37 which terminate the classifier housing 21 at the upper end of an upwardly frusto-conical housing end portion 38, guide the classifying wheel shaft 35 and seal this shaft passage without obstruction to the rotational movements of the classifying wheel shaft 35.
  • the upper plate 36 as a rotatably associated with the prepareradwelle 35 and rotatable about pivot bearing 35a the lower plate 37 may be supported, which in turn is associated with a housing end portion 38.
  • the underside of the downstream cover disk 33 lies in the common plane between the peripheral flanges 24 and 25, so that the classifying wheel 8 is arranged in its entirety within the hinged housing upper part 22.
  • 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 withdrawradwelle 35, located on the upper housing part 22 is disposed radially outward.
  • the integrated dynamic air classifier 1 contains a
  • Classifying wheel 8 and a submitradwelle 35 and a classifier housing as already explained.
  • a classifier gap 8a is defined and between the sortradwelle and the classifier housing 21, a shaft passage 35b formed (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
  • Milling nozzles or therein grinding nozzles is charged. It At the same time, high-energy media and low-energy media are used.
  • the reactorgehause 21 takes the same axis to the classifying wheel 8 arranged rohrmundigen outlet nozzle 20 which lies with its upper end just below the downstream cover plate 33 of the classifying wheel 8, but without connected thereto to be.
  • an outlet chamber 41 is attached coaxially, which is also rohrformig whose
  • diameter is much larger 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 is.
  • 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.
  • the assembly of 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 crushergehause 21.
  • the outlet nozzle 20 is surrounded by a conical ring housing 45 whose lower, larger outer diameter at least approximately corresponds to the diameter of the outlet chamber 41 and its upper, smaller outer diameter at least approximately the diameter of the classifying wheel 8.
  • a conical ring housing 45 whose lower, larger outer diameter at least approximately corresponds 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 At the conical wall of the Ringgehauses 45 end the support arms 44 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 ring housing 45 are parts of the tufting device (not shown), wherein the Spul poverty 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 from the outside into the
  • Classifier housing 21 is inserted and is connected in 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 removably associated, wherein the lower end of the housing end portion 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 7 ready for sale is.
  • 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 "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, i.e. the product, passes
  • the fines, d. H. the particle fraction with lower mass is mixed with the classifying air, passes radially from outside to inside through the classifying wheel 8 into the
  • Outlet nozzle 20 in 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 which the operating means in the form of a fluid, such as air, and fines are separated from each other.
  • Fines are blown radially out of the classifying wheel 8 and added to 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 classifying wheel 8 still prevails in the discharge or outlet nozzle 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 dividing the crushergehauses 21 in the manner described and the assignment of the classifier components to the individual Generalgehausen and can be replaced damaged components with relatively little effort and within short maintenance times.
  • This classifying wheel 8 contains, in addition to the blade ring 59 with the blades 34, the upper cover disk 32 and the axially spaced lower downstream cover disk 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 plate 33 concentrically surrounds the outlet nozzle 20.
  • the blades 34 are connected to both cover plates 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 in such a way that pulverulent solids having an average particle size d 5 o ⁇ 1.5 ⁇ m and / or a dgo value ⁇ 2 ⁇ m and / or a dgg value ⁇ 2 microns are obtained.
  • pulverulent solids having an average particle size d 5 o ⁇ 1.5 ⁇ m and / or a dgo value ⁇ 2 ⁇ m and / or a dgg value ⁇ 2 microns are obtained.
  • the amorphous solids of the invention are characterized in that they have an average particle size (TEM) d 5 o ⁇ 1.5 microns, preferably d 5 o ⁇ 1 micron, more preferably d 5 o from 0.01 to 1 micron, very particularly preferably d 5 o from 0.05 to 0.9 microns, more preferably d 5 o 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 ⁇ m and / or a dgo value ⁇ 2 ⁇ m, preferably dgo ⁇ 1.8 ⁇ m, more preferably dgo from 0.1 to 1.5 ⁇ m, very particularly preferably dgo from 0.1 to 1.0 ⁇ m and in particular dgo preferably from 0.1 to 0.5 ⁇ m and / or a dgg value ⁇ 2 ⁇ m, preferably dgg ⁇ 1.8 ⁇ m, particularly preferably dgg ⁇ 1.5 ⁇ m, very particularly preferably
  • the amorphous solids according to the invention may be gels but also other types of amorphous solids. Preference is given to solids containing or consisting of at least one metal and / or metal oxide, in particular amorphous oxides of metals of the 3rd and 4th main group of the Periodic Table of the Elements. This applies to both the gels and the amorphous solids with a different structure. Particular preference is given to precipitated silicas, fumed silicas, silicates and silica gels, where silica gels include both hydro, aerosol and xerogels.
  • the amorphous solids according to the invention are particulate solids containing aggregates and / or agglomerates, in particular precipitated silicas and / or fumed silicic acid and / or silicates and / or mixtures thereof, having an average particle size d 5 o ⁇ 1.5 microns, preferably d 5 o ⁇ 1 micron, more preferably d 5 o from 0.01 to 1 micron, most preferably d 5 o from 0.05 to 0.9 microns, more preferably d 5 o of 0.05 to 0.8 microns, more preferably from 0.05 to 0.5 microns and most preferably from 0.1 to 0.25 microns and / or a dgo ⁇ value ⁇ 2 microns, preferably dgo ⁇ 1.8 ⁇ m, particularly preferably dgo from 0.1 to 1.5 ⁇ m, very particularly preferably dgo from 0.1 to 1.0 ⁇ m, particularly preferably dgo from 0.1 to 0.5 ⁇ m
  • the amorphous solids according to the invention are gels, preferably silica gels, in particular xerogels or aerogels, having an average particle size d 5 o ⁇ 1.5 ⁇ m, preferably d 5 o ⁇ 1 ⁇ m, particularly preferably d 5 o from 0.01 to 1 micron, most preferably d 5 o from 0.05 to 0.9 microns, more preferably d 5 o from 0.05 to 0.8 microns, especially preferably from 0.05 to 0 , 5 microns and most preferably from 0.1 to 0.25 microns and / or a dgo ⁇ value ⁇ 2 microns, preferably dgo 0.05 to 1.8 microns, more preferably dgo from 0.1 to 1.5 microns , very particularly preferably from 0.1 to 1.0 ⁇ m, particularly preferably from 0.1 to 0.5 ⁇ m and particularly preferably from 0.2 to 0.4 ⁇ m and / or a dgg value ⁇ 2 micro
  • embodiment 2a it is a narrow-pore xerogel which, in addition to the d 5 o, dg 0 and dgg values already contained in embodiment 2, additionally has a pore volume of from 0.2 to 0.7 ml / g , preferably 0.3 to 0.4 ml / g.
  • embodiment 2b it is a xerogel, in addition to the dso ⁇ , dgo ⁇ and dgg values already contained in embodiment 2, a pore volume of 0.8 to 1.4 ml / g, preferably 0, 9 to 1.2 ml / g.
  • embodiment 2c it is a xerogel which, in addition to the d 5 o, dgo and dgg values already contained in embodiment 2, additionally has a pore volume of from 1.5 to 2.1 ml / g, preferably 1.7 to 1.9 ml / g.
  • 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).
  • a very wide particle size range (-100 nm to 1000 ⁇ m).
  • 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.
  • TEM Transmission electron microscopy
  • the sieve fractions are determined by means of a shaker (Retsch AS 200 Basic).
  • test sieves are defined with
  • Dust pan 45 ⁇ m, 63 ⁇ m, 125 ⁇ m, 250 ⁇ m, 355 ⁇ m, 500 ⁇ m.
  • 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 particle distribution is determined according to the principle of laser diffraction on a laser diffractometer (Horiba, LA-920).
  • the sample of the amorphous solid is dispersed in 100 ml of water without addition of dispersing additives in a 150 ml beaker (diameter: 6 cm) so that a dispersion with a weight fraction of 1 wt .-% SiÜ2 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.
  • a partial sample of the dispersion subjected to ultrasound is irradiated with the laser diffractometer (Horiba LA-920)
  • the transmission electron micrographs are generated on the basis of ASTM D 3849-02.
  • Transmission electron microscope (Hitachi H-7500, with a maximum acceleration voltage of 120 KV) used.
  • the digital image processing is carried out by software of the company Soft Imaging Systems (SIS, Munster / 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 taken from the finished dispersion and then applied to the Tragernetzchen. The excess dispersion is absorbed with filter paper. Then the netting is dried.
  • magnification is described in ITEM WK 5338 (ASTM) and is dependent on the primary particle size of the amorphous solid to be tested. Typically, in the case of silicas, the electron optical magnification 50000: 1 and the final magnification 200000: 1 are selected. For the digital
  • ASTM D 3849 determines the appropriate resolution in nm / pixel.
  • the recording conditions must be arranged in such a way that the reproducibility of the measurements can be ensured.
  • 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 must be detected in order to arrive at an adequate statistical statement. For silicas, about 2500 individual particles are measured.
  • the measuring ranges are calibrated according to the large range of 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 flat 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 Flat sections of the particles must be adapted to those flat sections of the measurement mark, which are outside the particle boundary. If this adjustment has taken place, the actual payment process is triggered by actuating 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. There is a renewed adjustment and payment procedure. This is repeated until all of the evaluation statistics are characterized according to required particles.
  • the number of particles to pay depends on the range of the particle size: the larger this 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 5 o is the mean value of the equivalent diameter of all the particles analyzed.
  • Dgo to determine the particle Great and d 99 are the equivalent diameter of particles of all evaluated in classes (each 25 nm 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 size dgo (ie 90% of the particles evaluated have a smaller equivalent diameter) and dgg can be determined.
  • BET surface area The specific nitrogen surface area (hereinafter referred to as BET surface area) of the pulverulent solids is determined in accordance with 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 area 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 examined is predried 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 device ASAP 2400 and at 200 0 C for 60 minutes under vacuum
  • 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 measured by the measured
  • Nitrogen isotherms were calculated according to the BJH method (E.P.Barrett, L.G. Joyner, P.H. Halenda, J.Amer.Chem.Soc, vol. 73, 373 (1951)) and presented as a distribution curve.
  • the average pore size (pore diameter, APD) is calculated according to the Wheeler equation
  • APD [nm] 4000 * mesopore volume [cm 3 / g] / BET surface area [m 2 / g].
  • the moisture content of amorphous solids is in accordance with DIN EN ISO
  • 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 with the requirements of this standard, the initial weights were changed (5.00 g of SiO 2 to 100 ml of deionized water).
  • DBP number which is a measure of the absorbency of amorphous solids
  • dibutyl phthalate is added dropwise at room temperature through the "Dosimaten Brabender T 90/50" dibutyl phthalate into the mixture at a rate of 4 ml / min
  • the mixture becomes pasty, as indicated by a steep increase in power demand, and when 600 digits (torque of 0.6Nm) are displayed, an electrical contact shuts off both the kneader and the DBP dosing.
  • the synchronous motor for the DBP supply is coupled to a digital counter so that the consumption of DBP in ml can be read.
  • the DBP recording is in unit [g / 100g] without
  • the DBP image is defined for anhydrous, amorphous solids.
  • the correction value K for the calculation of the DBP recording to take into account 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.
  • 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 tamped density D (t) is calculated as follows:
  • V volume of silica after pounding [ml]
  • 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 temperature-controlled at 40 0 C measurement 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 / 1 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 starting material to be milled was prepared according to the following procedure:
  • 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 filter cake is dried in a spin-flash dryer.
  • silica 1 The data of silica 1 are given in Table 1.
  • 45% strength by weight sulfuric acid and sodium silicate glass are intensively mixed in such a way that a reactant ratio corresponding to an excess of acid (0.25 N) and a SiCl 2 concentration of 18.5% by weight is established.
  • the resulting hydrogel is stored overnight (about 12 h) and then broken to a particle size of about 1 cm. It is washed with deionized water at 30 - 50 0 C until the conductivity of the wash water is below 5 mS / cm.
  • the hydrogel prepared as described above is aged with ammonia addition at pH 9 and 80 0 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%. Then it is 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.
  • Silica 3b 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 0 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 0 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 In preparation for the actual grinding with superheated water vapor, a fluidized-bed counter jet mill according to Figure 1, 2a and 3a, first over the two heating nozzles 5a (of which shown in Figure 1 is only one), which are applied to 10 bar and 160 0 C hot compressed air, up to A mill outlet temperature of about 105 0 C heated.
  • the mill is for the separation of the ground material downstream of a filter unit (not shown in Figure 1), 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 separating filter, as well as the supply lines for steam and hot compressed air are particularly insulated.
  • water is injected in the starting phase and during grinding into the grinding chamber of the mill via a compressed air operated Zweistoffduse depending on the Muhlenaustrittstemperatur.
  • 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.
  • an entry member (4) acts a speed-controlled cell wheel, which doses the feedstock from a storage container via serving as a barometric conclusion cycle lock in the standing under pressure grinding chamber.
  • the crushing of the coarse material takes place in the expanding steam jets (grinding gas). Together with the expanded grinding gas, the product particles rise in the center of the mullet to the classifying wheel. Depending on the adjusted classifier speed and
  • Milled steam amount (see Table 1) get the particles that have a sufficient fineness with the grinding steam in the fine material outlet and from there into the downstream Separation system, while coarse particles get back into the grinding zone and subjected to a further comminution.
  • 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 connection with the speed of the dynamic Schaufelradsichters determine the fineness of the grain distribution function and the upper grain limit.
  • peripheral flange 24 peripheral flange 25 peripheral flange

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  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Disintegrating Or Milling (AREA)
  • Glanulating (AREA)
  • Crushing And Pulverization Processes (AREA)
  • Silicon Compounds (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Crushing And Grinding (AREA)

Abstract

L'invention concerne un nouveau procédé de fragmentation de matières solides chimiques amorphes, de sorte qu'on obtient des particules ayant un diamètre moyen de particules d<SUB>50</SUB> < 1,5 µm. L'invention concerne également l'utilisation des matières solides fragmentées dans des systèmes de revêtement.
EP07820693.5A 2006-10-16 2007-09-28 Particule submicronique amorphe Active EP2089163B1 (fr)

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PL07820693T PL2089163T3 (pl) 2006-10-16 2007-09-28 Amorficzne cząstki submikronowe

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DE102006048850A DE102006048850A1 (de) 2006-10-16 2006-10-16 Amorphe submicron Partikel
PCT/EP2007/060306 WO2008046727A2 (fr) 2006-10-16 2007-09-28 Particule submicronique amorphe

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EP2089163B1 EP2089163B1 (fr) 2017-12-27

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CN109806531B (zh) * 2019-01-30 2020-04-24 河南理工大学 一种低碳气体水合物粉碎抑爆装置
CN112337637A (zh) * 2019-08-07 2021-02-09 赣州力信达冶金科技有限公司 一种用于解决物料经气流粉碎后不夹粗的方法
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DE102017209874A1 (de) 2017-06-12 2018-12-13 Evonik Degussa Gmbh Verfahren zur Herstellung von wachsbeschichteter Kieselsäure
WO2018228878A1 (fr) 2017-06-12 2018-12-20 Evonik Degussa Gmbh Procédé pour produire de l'acide silicique recouvert de cire

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RU2009118341A (ru) 2010-11-27
US7850102B2 (en) 2010-12-14
CA2666099A1 (fr) 2008-04-24
EP2089163B1 (fr) 2017-12-27
JP5511384B2 (ja) 2014-06-04
UA98627C2 (ru) 2012-06-11
NO20091880L (no) 2009-07-14
DE102006048850A1 (de) 2008-04-17
US20100285317A1 (en) 2010-11-11
BRPI0717334A2 (pt) 2013-12-10
TWI446970B (zh) 2014-08-01
JP2010506708A (ja) 2010-03-04
TW200902153A (en) 2009-01-16
KR20090080971A (ko) 2009-07-27
US8039105B2 (en) 2011-10-18
US20080173739A1 (en) 2008-07-24
HUE038516T2 (hu) 2018-10-29
PT2089163T (pt) 2018-02-06
WO2008046727A2 (fr) 2008-04-24
CN101616743B (zh) 2014-03-05
PL2089163T3 (pl) 2018-06-29
MX2009003984A (es) 2009-04-28
RU2458741C2 (ru) 2012-08-20
WO2008046727A3 (fr) 2008-07-17
CN101244402A (zh) 2008-08-20
CN101616743A (zh) 2009-12-30
ZA200902603B (en) 2010-04-28
ES2658825T3 (es) 2018-03-12
KR101503936B1 (ko) 2015-03-18
BRPI0717334B1 (pt) 2019-05-21

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