WO2013079377A1 - Granulated materials based on titanium dioxide particles with high mechanical stability, manufacturing method and usage - Google Patents

Granulated materials based on titanium dioxide particles with high mechanical stability, manufacturing method and usage Download PDF

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Publication number
WO2013079377A1
WO2013079377A1 PCT/EP2012/073213 EP2012073213W WO2013079377A1 WO 2013079377 A1 WO2013079377 A1 WO 2013079377A1 EP 2012073213 W EP2012073213 W EP 2012073213W WO 2013079377 A1 WO2013079377 A1 WO 2013079377A1
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Prior art keywords
titanium dioxide
granules
dioxide particles
mechanical stability
predispersion
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PCT/EP2012/073213
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German (de)
French (fr)
Inventor
Maximilian CORNELIUS
Jürgen Meyer
Wolfgang Lortz
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Evonik Degussa Gmbh
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Publication of WO2013079377A1 publication Critical patent/WO2013079377A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3615—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C09C1/3638—Agglomeration, granulation, pelleting
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Definitions

  • the invention relates to granules based on aggregated titanium dioxide particles with high mechanical stability, as well as their preparation and use.
  • DE 19601415 discloses granules of pyrogenically prepared silica particles, which by means of spray-drying an aqueous dispersion and
  • Catalyst supports can be used.
  • the proportion of silicon dioxide in the dispersion is 5 to 25 wt .-%.
  • DE 10138574 discloses granules of pyrogenically produced aluminum oxide particles, which by means of spray-drying an aqueous dispersion and
  • the metal oxide content is 3 - 25 wt .-%.
  • DE 19928851 discloses granules of pyrogenic titanium dioxide particles, which are prepared by spray-drying an aqueous dispersion and
  • the proportion of titanium dioxide in the dispersion is 3 - 25 wt .-%.
  • Granules based on titanium dioxide particles are increasingly being used as catalyst or catalyst support.
  • the separation and recovery of the catalyst or catalyst support plays a crucial role. Usually it comes during the reaction by mechanical stress to the abrasion of the catalyst material or the carrier material and thus to a reduction of the average
  • the object of the invention is therefore to provide granules containing these
  • An object of the invention are granules based on aggregated titanium dioxide particles having a mean grain diameter of 5 - 100 ⁇ and a BET specific surface area of 10 - 120 m 2 / g, the a. a tamped density of 1350 - 1800 g / l,
  • Granules are to be understood as meaning the compact arrangement of the aggregated titanium dioxide particles, the granules having essentially a spherical morphology.
  • Essentially spherical means that a majority of the particles has a spherical, that is spherical, morphology, while the remaining portion may also have a rather elliptical or bulbous morphology.
  • the granules can also be understood as meaning the compact arrangement of the aggregated titanium dioxide particles, the granules having essentially a spherical morphology.
  • Essentially spherical means that a majority of the particles has a spherical, that is spherical, morphology, while the remaining portion may also have a rather elliptical or bulbous morphology.
  • the granules can also
  • the aggregated form of the titanium dioxide particles is still present in the granules and causes a porosity of the granules, which is also referred to as pore or Eisenkornvolumen.
  • the available free pore volume within the granules can be used to absorb foreign substances.
  • the particle size of granules is commonly referred to as the grain diameter.
  • the average particle diameter or the average particle size of the granules according to the invention, the d 5 o value, is 5-100 ⁇ m.
  • the value is determined after the thermal treatment by means of static light scattering. Any device known to those skilled in the art can be used for this purpose.
  • Aggregates are to be understood as meaning, for example, sintered necks, interconnected primary particles.
  • the type of aggregated titanium dioxide particles used is not limited, but it is preferred that the aggregated titanium dioxide particles are pyrogenic Origin. Pyrogen in this case comprises those particles which are obtainable by flame oxidation, flame hydrolysis or flame pyrolysis from suitable titanium compounds. As a rule, titanium tetrachloride is emitted in a flame
  • the granules preferably have a pH of 1-7, more preferably 1-5, most preferably 3-4. It is measured in a 4% dispersion in water on the basis of DIN ISO 787/9, ASTM D1208, JIS K 5101/24.
  • the BET specific surface area of the granules according to the invention after the thermal treatment is 10-120 m 2 / g.
  • the specific BET surface area after the thermal treatment is preferably 15-40 m 2 / g, more preferably 20-30 m 2 / g.
  • the BET specific surface area is determined according to DIN 66131.
  • the tamped density of the granules according to the invention is 1350-1800 g / l, preferably 1400-1500 g / l.
  • the tamped density is determined according to DIN 53194.
  • the pore volume of the granules according to the invention is 0.10-0.50 cm 3 / g, preferably the granules have a pore volume of 0.15-0.25 cm 3 / g. It is calculated from the sum of micro, meso and macro pore volumes.
  • the determination of the micropores and mesopores is carried out by measuring the nitrogen physisorption isotherm according to DIN 66131 / DIN 66134.
  • the determination of the macropores is carried out by the
  • Sorption data can be determined by the method according to Barret, Joyner and Halenda (BJH method), the pore size distribution, which in turn can calculate the average pore diameter.
  • the average pore diameter of the granules according to the invention is 5 to 45 nm, preferably 10 to 40 nm, more preferably 15 to 35 nm.
  • a particular embodiment of the invention provides that the stability of the granules after ultrasonic treatment has a DIF value of 0.85-0.99, preferably 0.9-0.99, very particularly preferably 0.95-0.99.
  • the DIF value is 0.95-0.99 after 130 seconds, 0.90-0.99 seconds in 300 seconds, and 0.85-0.99 after 500 seconds.
  • the DIF value after 130 seconds of ultrasonic treatment is 0.95-0.99, after 300 seconds the DIF value is 0.9-0.99 and after 550 seconds the DIF value is 0.85. 0.99.
  • the mechanical stability, DIF disintegration factor, results after a pulsed ultrasonic treatment from the ratio of the mean
  • US 2005/0032965 A1 discloses a stability test for silica granules, in which the destruction rate is determined by pulsed ultrasonic treatment and particle size measurement ([0109-01 10]).
  • Ultrasonic treatment means that the granules are exposed to ultrasonic pulses in water for a certain period of time. Under suitable conditions, ultrasonic waves are able to mechanically stress solid bodies which are suspended in liquid media. If necessary, this stress can be so strong that the energy input caused by the ultrasonic treatment causes the solids to be comminuted and thus the mean grain size, the d 5 o value, is reduced.
  • Another object of the invention is a process for the preparation of the granules of the invention in which aggregated titanium dioxide particles with a mean aggregate diameter of 100 nm to 10 ⁇ first mixed with water, this mixture to a pH of 1-7 brings and by shearing to an aqueous predispersion having a solids content of 30 to 70 wt .-% processed, this predispersion then a
  • the resulting dispersion is then spray-dried, and the resulting product for 1 - 8 h at 400 - 800 ° C thermally treated.
  • the predispersion of aggregated titanium dioxide particles in water has a concentration of titanium dioxide of 30-70% by weight, preferred are 35% by weight.
  • shear units that operate on the rotor-stator principle.
  • shear energy is applied by the application of shear forces in the millbase, which causes a dispersion. This is achieved, for example, by rotating disks in a static stirred tank.
  • the pH of the predispersion is adjusted to a value of 1-7, preferably 1-5, more preferably of 1.5- 2.5, most preferably of 2. This is usually achieved with monoprotic acids which do not form sparingly soluble salts.
  • nitric acid is used.
  • the predispersion is divided into at least two dispersion streams, these are brought under a pressure of 500 to 4000 bar, expanded via a nozzle and in a gas or liquid-filled reactor chamber collided, so that the particles grind themselves.
  • dispersions having a mean aggregate diameter of 50-100 nm are obtained.
  • any high-energy mill which is known to those skilled in the art, and with which a corresponding aggregate diameter of the particles can be achieved.
  • the spray-drying is preferably carried out at temperatures of 200-600 ° C., more preferably of 250-500 ° C., very particularly preferably of 300-400 ° C.
  • the exhaust air temperature is preferably 100-200 ° C., particularly preferably 110-1080 ° C., very particularly preferably 120-150 ° C.
  • Any spray-drying apparatus known to those skilled in the art can be used for this purpose; disc, nozzle or ultrasonic atomisers are preferably used.
  • the thermal treatment of the granules can be carried out both in static bed, such as in chamber furnaces, as well as in moving bed, such as in rotary kilns. It is carried out for 1 - 8 h at 400 - 800 ° C. Times of 2-7 hours are preferred, more preferably 4-6 hours.
  • the temperature is advantageously 500-700 ° C, more preferably a temperature of 550-650 ° C.
  • the combinations of 2 to 7 hours at 400 to 800 ° C. have proved to be advantageous.
  • Preference is given to annealing at 500-700 ° C. for 2 to 7 h, more preferably for 2 to 7 h at 550 to 650 ° C., and very particularly preferably for 4 to 6 h at 550 to 650 ° C.
  • the granules are at 300-400 ° C
  • the granules are spray dried at 350-400 ° C and then annealed for 4-6 h at 550-650 ° C.
  • Titanium dioxide particles are not limited, preferably the BET surface area is 20-120 m 2 / g. Particularly preferred for the granules are those Titanium dioxide particles with a specific surface area of 50 ⁇ 15 m 2 / g or 90 ⁇ 20 m 2 / g used.
  • the size of the aggregated titanium dioxide particles is considered a mean
  • Diameter indicated which is called mean aggregate diameter.
  • the d 5 o-value of the mean aggregate diameter of the titanium dioxide particles that are used for the preparation of the granules according to the invention lies in front of the high-energy grinding with 100 nm - 10 m, and after the
  • High energy milling at 70 - 100 nm The average aggregate diameter after high energy milling is measured by means of dynamic light scattering. Any device known to those skilled in the art can be used for this purpose.
  • Another object of the invention is the use of the granules as a carrier material, as a catalyst or catalyst support, as grinding and
  • Polishes as a raw material for glass and ceramic production and in cosmetics, as sunscreen, in silicone rubber, in toner powder, in paints and inks.
  • the experiments are with a pyrogenic titanium dioxide having a BET surface area of about 50 m 2 / g, a pH of about 3.5, a
  • Tamped density of about 130 g / l and a primary particle size of 21 nm
  • Example 1 (inventive granules):
  • the high-energy mill milled dispersion b) is sprayed with a spray drying unit and dried.
  • the spray is generated by means of a disk atomization.
  • the disc rotation is adjusted to values of 12000 rpm.
  • the drying temperature is 380 ° C.
  • the exhaust air temperature is 125 ° C.
  • the throughput of titanium dioxide suspension is set to 100 l / h.
  • the dried granules are separated from the gas stream by means of a fabric filter.
  • the described spray-drying process produces essentially spherical granules. d) Thermal aftertreatment:
  • Granules stored at 600 ° C for 4 h in a chamber furnace. It is then cooled to room temperature.
  • Examples 2 and 3 (comparative examples):
  • examples 2 and 3 a commercially available titanium dioxide granules having a BET surface area of 50 m 2 / g, an average grain diameter of about 20 ⁇ , a tapped density of about 700 g / l and a pH of 3, 0 - 4.5, which is sold by Evonik Degussa under the name VP AEROPERL® P25 / 20.
  • This granulate was prepared according to DE 19928851 A1 from a dispersion of pyrogenically produced, aggregated titanium dioxide particles having a BET surface area of 50 ⁇ 15 m 2 / g, a primary particle size of 21 nm, a tamped density of about 130 g / l and a pH Value of 3.5-4.5 sold by Evonik Degussa under the name AEROXIDE® TiO 2 P25.
  • Example 2 the untreated granules are used, there is no thermal aftertreatment.
  • Example 3 the granules are thermally post-treated at 600 ° C for 4 h. Measurement of mechanical stability:
  • the sample dispersing unit for small volumes MSX1 with pump / stirrer speed control, each by the company Malvern Instruments Ltd ..
  • the ultrasonic treatment is the
  • Granules produced in the dispersion The concentration of the solid is chosen so that the optical shading of the granules is not too large.
  • the dispersion will now be throughout the measurement process pumped continuously through the apparatus, the power of the pump is regulated to 2000 rev / min.
  • the continuous grain size measurement is started, whereby first the mean grain size (d50o) is determined three times by means of static light scattering and the mean value is formed from these values.
  • the pulsed ultrasonic treatment is started.
  • the sample is sonicated continuously in 1 second intervals with ultrasound: 1 second "on” followed by 1 second "off”.
  • the dispersion is cooled during sonication in the flow cell. For this purpose, water is pumped through the cooling jacket, which is tempered by means of cryostat to 18 ° C. After every 10 seconds of pulsed ultrasound treatment, the
  • volume-weighted particle size distribution recorded, which consists of 2000 individual measurements. From the measured data by means of
  • Grain diameter (d50us) calculated. The determination of the mechanical stability ends depending on how fast the granules during the
  • Grain diameter remains constant with continuous ultrasonic treatment.
  • the granule stability factors are then calculated as follows: Each measured value of the mean grain diameter d50us is divided by the previously determined initial value d50o and then plotted against the duration of the ultrasound treatment. A granule stability factor of 1.0 indicates that there is no change in the mean
  • Grain diameter came through the ultrasonic treatment and thus no crushing of the granules took place.
  • a granule stability factor of 0.2 indicates that the original value of the mean grain diameter has decreased by 80%.
  • Figure 1 shows a diagram by means of which the mechanical stability of the exemplary titanium dioxide granules can be compared. It is possible to increase the curve already at the beginning of the measurement
  • Example 1 recognize.
  • the DIF value of the titanium dioxide granules according to the invention also remains at a significantly higher level with time as compared to the comparative examples.
  • the time in seconds is plotted on the x-axis.
  • the ratio D50us / D50o is plotted on the y-axis.
  • Table 2 shows the measured values for Figure 1.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Cosmetics (AREA)

Abstract

The invention relates to granulated materials based on aggregated titanium dioxide particles with a mean grain diameter of 5-100 µm and a specific surface of 10-120 m2/g according to BET, with a tamped density of 1350-1800 g/l, a pore volume of 0.10-0.50 cm3/g and a mean pore diameter of 5-45 nm. Another subject matter of the invention is a method for producing granulated materials based on titanium dioxide, in which aggregated titanium dioxide particles with a mean aggregate diameter of 100 nm to 10 µm are first mixed with water, this mixture is brought to a pH value of 1-7 and is processed by shearing into an aqueous pre-dispersion with a solids content of 30-70 wt%, this pre-dispersion is subsequently subjected to a high-energy grinding step, the dispersion created thereby is subsequently spray-dried, and the obtained product is thermally post treated for 1-8 h at 400-800°C.

Description

GRANULATE AUF DER BASIS VON TITANDIOXID - PARTIKELN MIT HOHER  GRANULES BASED ON TITANIUM DIOXIDE - PARTICULARS WITH HIGHER
MECHANISCHER STABILITÄT, DAS HERSTELLVERFAHREN UND VERWENDUNG  MECHANICAL STABILITY, MANUFACTURING METHOD AND USE
Die Erfindung betrifft Granulate auf der Basis von aggregierten Titandioxid- Partikeln mit hoher mechanischer Stabilität, sowie deren Herstellung und Verwendung. The invention relates to granules based on aggregated titanium dioxide particles with high mechanical stability, as well as their preparation and use.
DE 19601415 offenbart Granulate aus pyrogen hergestellten Siliciumdioxid- Partikeln, die mittels Sprühtrocknung einer wässrigen Dispersion und DE 19601415 discloses granules of pyrogenically prepared silica particles, which by means of spray-drying an aqueous dispersion and
anschließender thermischer Behandlung erhalten werden und als subsequent thermal treatment and as
Katalysatorträger verwendet werden können. Der Anteil an Siliciumdioxid in der Dispersion beträgt 5 - 25 Gew.-%. Catalyst supports can be used. The proportion of silicon dioxide in the dispersion is 5 to 25 wt .-%.
DE 10138574 offenbart Granulate aus pyrogen hergestellten Aluminiumoxid- Partikeln, die mittels Sprühtrocknung einer wässrigen Dispersion und DE 10138574 discloses granules of pyrogenically produced aluminum oxide particles, which by means of spray-drying an aqueous dispersion and
gegebenenfalls anschließender thermischer Behandlung erhalten werden. Der Metalloxidgehalt beträgt 3 - 25 Gew.-%. DE 19928851 offenbart Granulate aus pyrogen hergestellten Titandioxid- Partikeln, die mittels Sprühtrocknung einer wässrigen Dispersion und optionally subsequent thermal treatment can be obtained. The metal oxide content is 3 - 25 wt .-%. DE 19928851 discloses granules of pyrogenic titanium dioxide particles, which are prepared by spray-drying an aqueous dispersion and
gegebenenfalls anschließender thermischer Behandlung erhalten werden. Der Anteil an Titandioxid in der Dispersion beträgt 3 - 25 Gew.-%. optionally subsequent thermal treatment can be obtained. The proportion of titanium dioxide in the dispersion is 3 - 25 wt .-%.
Granulate auf der Basis von Titandioxid-Partikeln werden zunehmend als Katalysator oder Katalysatorträger eingesetzt. Granules based on titanium dioxide particles are increasingly being used as catalyst or catalyst support.
Insbesondere bei heterogen katalysierten Reaktionen kommt der Abtrennung und der Rückgewinnung des Katalysators oder Katalysatorträgers eine entscheidende Rolle zu. Üblicherweise kommt es während der Umsetzung durch mechanische Beanspruchung zum Abrieb des Katalysatormaterials oder des Trägermaterials und somit zu einer Verkleinerung der mittleren Especially in heterogeneously catalyzed reactions, the separation and recovery of the catalyst or catalyst support plays a crucial role. Usually it comes during the reaction by mechanical stress to the abrasion of the catalyst material or the carrier material and thus to a reduction of the average
Partikelgröße. Eine Abtrennung kleiner Partikel aus dem Reaktionsgemisch gestaltet sich meist schwierig und ist zudem zeit- und kostenintensiv. Aufgabe der Erfindung ist es daher, Granulate bereitzustellen, die diese Particle size. A separation of small particles from the reaction mixture is usually difficult and is also time consuming and costly. The object of the invention is therefore to provide granules containing these
Nachteile nicht aufweisen. Do not have disadvantages.
Ein Gegenstand der Erfindung sind Granulate auf der Basis von aggregierten Titandioxid-Partikeln mit einem mittleren Korndurchmesser von 5 - 100 μιτι und einer spezifischen Oberfläche nach BET von 10 - 120 m2/g, die a. eine Stampfdichte von 1350 - 1800 g/l, An object of the invention are granules based on aggregated titanium dioxide particles having a mean grain diameter of 5 - 100 μιτι and a BET specific surface area of 10 - 120 m 2 / g, the a. a tamped density of 1350 - 1800 g / l,
b. ein Porenvolumen von 0,10 - 0,50 cm3/g b. a pore volume of 0.10 - 0.50 cm 3 / g
c. und einen mittleren Porendurchmesser von 5 - 45 nm aufweisen.  c. and have an average pore diameter of 5 - 45 nm.
Unter Granulaten ist die kompakte Anordnung der aggregierten Titandioxid- Partikel zu verstehen, wobei die Granulate im Wesentlichen eine sphärische Morphologie aufweisen. Im Wesentlichen sphärisch heißt dabei, dass ein Großteil der Partikel eine sphärische, also kugelförmige, Morphologie aufweist, während der restliche Anteil auch eine eher elliptische oder knollenartige Morphologie aufweisen kann. Weiterhin können die Granulate auch Granules are to be understood as meaning the compact arrangement of the aggregated titanium dioxide particles, the granules having essentially a spherical morphology. Essentially spherical means that a majority of the particles has a spherical, that is spherical, morphology, while the remaining portion may also have a rather elliptical or bulbous morphology. Furthermore, the granules can also
Einbuchtungen aufweisen. Die aggregierte Form der Titandioxid-Partikel ist in den Granulaten weiterhin vorhanden und bewirkt eine Porosität der Granulate, die auch als Poren- oder Zwischenkornvolumen bezeichnet wird. Das so zur Verfügung stehende freie Porenvolumen innerhalb der Granulate kann zur Aufnahme von Fremdstoffen genutzt werden. Have indentations. The aggregated form of the titanium dioxide particles is still present in the granules and causes a porosity of the granules, which is also referred to as pore or Zwischenkornvolumen. The available free pore volume within the granules can be used to absorb foreign substances.
Die Teilchengröße von Granulaten wird üblicherweise als Korndurchmesser bezeichnet. Der mittlere Korndurchmesser beziehungsweise die mittlere Teilchengröße der erfindungsgemäßen Granulate, der d5o-Wert, beträgt 5 - 100 μιτι. Der Wert wird nach der thermischen Behandlung mittels statischer Lichtstreuung bestimmt. Dazu kann jedes Gerät verwendet werden, das dem Fachmann auf diesem Gebiet bekannt ist. The particle size of granules is commonly referred to as the grain diameter. The average particle diameter or the average particle size of the granules according to the invention, the d 5 o value, is 5-100 μm. The value is determined after the thermal treatment by means of static light scattering. Any device known to those skilled in the art can be used for this purpose.
Unter Aggregaten sind fest, beispielsweise über Sinterhälse, miteinander verbundene Primärpartikel zu verstehen. Aggregates are to be understood as meaning, for example, sintered necks, interconnected primary particles.
Die Art der eingesetzten, aggregierten Titandioxid-Partikel ist nicht beschränkt, bevorzugt handelt es sich jedoch um aggregierte Titandioxid-Partikel pyrogener Herkunft. Pyrogen umfasst dabei solche Partikel, die durch Flammenoxidation, Flammenhydrolyse oder Flammenpyrolyse aus geeigneten Titanverbindungen erhältlich sind. In der Regel wird Titantetrachlorid in einer Flamme aus The type of aggregated titanium dioxide particles used is not limited, but it is preferred that the aggregated titanium dioxide particles are pyrogenic Origin. Pyrogen in this case comprises those particles which are obtainable by flame oxidation, flame hydrolysis or flame pyrolysis from suitable titanium compounds. As a rule, titanium tetrachloride is emitted in a flame
Wasserstoff und Sauerstoff zu Titandioxid hydrolysiert. Beispiele für Hydrogen and oxygen hydrolyzed to titanium dioxide. examples for
kommerziell erhältliche aggregierte, pyrogene Titandioxidpartikel sind are commercially available aggregated, fumed titania particles
AEROXIDE® TiO2 P25 und AEROXIDE® TiO2 P90 von Evonik Degussa. AEROXIDE® TiO 2 P25 and AEROXIDE® TiO 2 P90 from Evonik Degussa.
Die Granulate weisen bevorzugt einen pH-Wert von 1 - 7, besonders bevorzugt von 1 - 5, ganz besonders bevorzugt von 3 - 4, auf. Er wird in einer 4 %-igen Dispersion in Wasser in Anlehnung an DIN ISO 787/9, ASTM D1208, JIS K 5101 /24 gemessen. The granules preferably have a pH of 1-7, more preferably 1-5, most preferably 3-4. It is measured in a 4% dispersion in water on the basis of DIN ISO 787/9, ASTM D1208, JIS K 5101/24.
Die spezifische BET-Oberfläche der erfindungsgemäßen Granulate nach der thermischen Behandlung beträgt 10 - 120 m2/g. Bevorzugt beträgt die spezifische BET-Oberfläche nach der thermischen Behandlung 15 - 40 m2/g, besonders bevorzugt beträgt sie 20 - 30 m2/g . Die spezifische BET-Oberfläche wird gemäß DIN 66131 bestimmt. The BET specific surface area of the granules according to the invention after the thermal treatment is 10-120 m 2 / g. The specific BET surface area after the thermal treatment is preferably 15-40 m 2 / g, more preferably 20-30 m 2 / g. The BET specific surface area is determined according to DIN 66131.
Die Stampfdichte der erfindungsgemäßen Granulate beträgt 1350 - 1800 g/l, bevorzugt sind 1400 - 1500 g/l. Die Stampfdichte wird gemäß DIN 53194 bestimmt. The tamped density of the granules according to the invention is 1350-1800 g / l, preferably 1400-1500 g / l. The tamped density is determined according to DIN 53194.
Das Porenvolumen der erfindungsgemäßen Granulate beträgt 0,10 - 0,50 cm3/g, bevorzugt weisen die Granulate ein Porenvolumen von 0,15 - 0,25 cm3/g auf. Es wird rechnerisch aus der Summe von Mikro-, Meso- und Makroporenvolumen bestimmt. Die Bestimmung der Mikro- und Mesoporen erfolgt durch Messung der Stickstoff-Physisorption-Isotherme gemäß DIN 66131 /DIN 66134. Die Bestimmung der Makroporen erfolgt durch das The pore volume of the granules according to the invention is 0.10-0.50 cm 3 / g, preferably the granules have a pore volume of 0.15-0.25 cm 3 / g. It is calculated from the sum of micro, meso and macro pore volumes. The determination of the micropores and mesopores is carried out by measuring the nitrogen physisorption isotherm according to DIN 66131 / DIN 66134. The determination of the macropores is carried out by the
Quecksilber-Einpressverfahren gemäß DIN 66133. Aus den gemessenenMercury injection molding according to DIN 66133. From the measured
Sorptionsdaten lässt sich mittels der Methode nach Barret, Joyner und Halenda (BJH-Methode) die Porengroßenverteilung ermitteln, woraus sich wiederum der mittlere Porendurchmesser berechnen lässt. Der mittlere Porendurchmesser der erfindungsgemäßen Granulate beträgt 5 - 45 nm, bevorzugt beträgt er 10 - 40 nm, besonders bevorzugt beträgt er 15 - 35 nm. Eine besondere Ausführungsform der Erfindung sieht vor, dass die Stabilität der Granulate nach Ultraschallbehandlung einen DIF-Wert von 0,85 - 0,99, bevorzugt von 0,9 - 0,99, ganz besonders bevorzugt 0,95 - 0,99 aufweist. Sorption data can be determined by the method according to Barret, Joyner and Halenda (BJH method), the pore size distribution, which in turn can calculate the average pore diameter. The average pore diameter of the granules according to the invention is 5 to 45 nm, preferably 10 to 40 nm, more preferably 15 to 35 nm. A particular embodiment of the invention provides that the stability of the granules after ultrasonic treatment has a DIF value of 0.85-0.99, preferably 0.9-0.99, very particularly preferably 0.95-0.99.
In weiteren Ausführungsformen beträgt der DIF-Wert nach 130 Sekunden 0,95 - 0,99, 300 Sekunden 0,90 - 0,99 und nach 500 Sekunden 0,85 - 0,99. In further embodiments, the DIF value is 0.95-0.99 after 130 seconds, 0.90-0.99 seconds in 300 seconds, and 0.85-0.99 after 500 seconds.
In einer besonderen bevorzugten Ausführungsform beträgt der DIF-Wert nach 130 Sekunden Ultraschallbehandlung 0,95 - 0,99, nach 300 Sekunden beträgt der DIF-Wert 0,9 - 0,99 und nach 550 Sekunden beträgt der DIF-Wert 0,85 - 0,99. Die mechanische Stabilität, DIF = disintegration factor, ergibt sich nach einer gepulsten Ultraschallbehandlung aus dem Verhältnis des mittleren In a particular preferred embodiment, the DIF value after 130 seconds of ultrasonic treatment is 0.95-0.99, after 300 seconds the DIF value is 0.9-0.99 and after 550 seconds the DIF value is 0.85. 0.99. The mechanical stability, DIF = disintegration factor, results after a pulsed ultrasonic treatment from the ratio of the mean
Korndurchmessers nach der Ultraschallbehandlung zu dem mittleren Grain diameter after the ultrasonic treatment to the middle
Korndurchmesser vor der Ultraschallbehandlung, gemäß DIF = dso.us/dso.o, aus der statischen Lichtstreuung. Durch Auftragung dieses Verhältnisses gegen die Beschallungsdauer lassen sich Stabilitätsdiagramme erzeugen, die einenGrain diameter before the ultrasonic treatment, according to DIF = dso.us/dso.o, from the static light scattering. By plotting this ratio against the duration of the sonication, stability diagrams can be generated which produce a
Vergleich der mechanischen Stabilität verschiedener Granulate ermöglichen. Je länger der d50us-Wert konstant auf dem Ausgangswert verbleibt, desto stabiler sind die Granulate, oder je steiler die Ultraschall-Stabilitätskurve abfällt, desto geringer ist die mechanische Belastbarkeit. Ein Endwert von 1 ,0 bedeutet keine Änderung der Korngröße der Granulate, während ein Wert von 0,2 eine Allow comparison of the mechanical stability of different granules. The longer the d50us value remains constant at the initial value, the more stable the granules are, or the steeper the ultrasonic stability curve falls, the lower the mechanical load capacity. A final value of 1.0 means no change in the granule size, while a value of 0.2 means
Abnahme des d500-Wertes um 80 % bedeutet. Aus US 2005/0032965 A1 ist ein Stabilitätstest für Siliziumdioxid-Granulate bekannt, bei dem durch gepulste Ultraschallbehandlung und Partikelgrößenmessung die Zerstörungsrate bestimmt wird ([0109-01 10]). Ultraschallbehandlung bedeutet, dass die Granulate in Wasser für eine bestimmte Zeit Ultraschallpulsen ausgesetzt werden. Ultraschallwellen sind unter geeigneten Bedingungen in der Lage Festkörper, welche in flüssigen Medien suspendiert vorliegen, mechanisch stark zu beanspruchen. Diese Beanspruchung kann gegebenenfalls so stark sein, dass der Energieeintrag durch die Ultraschallbehandlung dazu führt, dass die Feststoffe zerkleinert werden und somit die mittlere Korngröße, der d5o-Wert, reduziert wird. So können durch die Stärke und die Dauer der Ultraschallbehandlung und die kontinuierliche Bestimmung der Korngröße Rückschlüsse auf die mechanische Stabilität der Granulate gezogen werden. Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung der erfindungsgemäßen Granulate bei dem man aggregierte Titandioxid-Partikel mit einem mittleren Aggregatdurchmesser von 100 nm bis 10 μιτι zunächst mit Wasser versetzt, dieses Gemisch auf einen pH-Wert von 1 - 7 bringt und durch Scherung zu einer wässrigen Vordispersion mit einem Feststoffgehalt von 30 - 70 Gew.-% verarbeitet, diese Vordispersion anschließend einem Decrease of the d50 0 value by 80% means. US 2005/0032965 A1 discloses a stability test for silica granules, in which the destruction rate is determined by pulsed ultrasonic treatment and particle size measurement ([0109-01 10]). Ultrasonic treatment means that the granules are exposed to ultrasonic pulses in water for a certain period of time. Under suitable conditions, ultrasonic waves are able to mechanically stress solid bodies which are suspended in liquid media. If necessary, this stress can be so strong that the energy input caused by the ultrasonic treatment causes the solids to be comminuted and thus the mean grain size, the d 5 o value, is reduced. Thus, conclusions can be drawn on the mechanical stability of the granules by the strength and the duration of the ultrasonic treatment and the continuous determination of the grain size. Another object of the invention is a process for the preparation of the granules of the invention in which aggregated titanium dioxide particles with a mean aggregate diameter of 100 nm to 10 μιτι first mixed with water, this mixture to a pH of 1-7 brings and by shearing to an aqueous predispersion having a solids content of 30 to 70 wt .-% processed, this predispersion then a
Hochenergievermahlungsschritt unterzieht, die dadurch entstandene Dispersion anschließend sprühtrocknet, und das erhaltene Produkt für 1 - 8 h bei 400 - 800 °C thermisch nachbehandelt.  Subjected to high energy milling step, the resulting dispersion is then spray-dried, and the resulting product for 1 - 8 h at 400 - 800 ° C thermally treated.
Die Vordispersion von aggregierten Titandioxid-Partikeln in Wasser weist eine Konzentration an Titandioxid von 30 - 70 Gew.-% auf, bevorzugt sind 35 -The predispersion of aggregated titanium dioxide particles in water has a concentration of titanium dioxide of 30-70% by weight, preferred are 35% by weight.
55 Gew.-%, besonders bevorzugt 38 - 45 Gew.-%, ganz besonders bevorzugt sind 40 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Dispersion. Die Herstellung dieser Vordispersion erfolgt mit dem Fachmann bekannten 55 wt .-%, particularly preferably 38 to 45 wt .-%, most preferably 40 wt .-%, each based on the total weight of the dispersion. The preparation of this predispersion is known to those skilled in the art
Methoden zur Dispergierung von Pulvern in Flüssigkeiten. Besonders geeignet sind Scheraggregate, die nach dem Rotor-Stator-Prinzip arbeiten. Bei der Scherung wird durch das Ausüben von Scherkräften Energie in das Mahlgut eingebracht, die eine Dispergierung bewirkt. Dies wird zum Beispiel durch rotierende Scheiben in einem statischen Rührbehälter erreicht. Methods for dispersing powders in liquids. Particularly suitable are shear units that operate on the rotor-stator principle. In the shear energy is applied by the application of shear forces in the millbase, which causes a dispersion. This is achieved, for example, by rotating disks in a static stirred tank.
Der pH-Wert der Vordispersion wird auf einen Wert von 1 - 7, bevorzugt von 1 - 5, besonders bevorzugt von 1 ,5 - 2,5, ganz besonders bevorzugt von 2, eingestellt. Dies wird üblicherweise mit einprotonigen Säuren erreicht, die keine schwerlöslichen Salze bilden. Bevorzugt wird Salpetersäure verwendet. The pH of the predispersion is adjusted to a value of 1-7, preferably 1-5, more preferably of 1.5- 2.5, most preferably of 2. This is usually achieved with monoprotic acids which do not form sparingly soluble salts. Preferably, nitric acid is used.
Bei der Hochenergievermahlung wird die Vordispersion in mindestens zwei Dispersionsströme aufgeteilt, diese werden unter einen Druck von 500 bis 4000 bar gebracht, über eine Düse entspannt und in einer gas- oder flüssigkeitsgefüllten Reaktorkammer zur Kollision gebracht, so dass sich die Teilchen selbst mahlen. Auf diese Weise werden Dispersionen mit einem mittleren Aggregatdurchmesser von 50 - 100 nm erhalten. Hierzu kann jede Hochenergiemühle verwendet werden, die dem Fachmann auf diesem Gebiet bekannt ist, und mit der ein entsprechender Aggregatdurchmesser der Partikel erreicht werden kann. In the high-energy milling, the predispersion is divided into at least two dispersion streams, these are brought under a pressure of 500 to 4000 bar, expanded via a nozzle and in a gas or liquid-filled reactor chamber collided, so that the particles grind themselves. In this way, dispersions having a mean aggregate diameter of 50-100 nm are obtained. For this purpose, any high-energy mill, which is known to those skilled in the art, and with which a corresponding aggregate diameter of the particles can be achieved.
Die Sprühtrocknung wird bevorzugt bei Temperaturen von 200 - 600 °C besonders bevorzugt von 250 - 500 °C, ganz besonders bevorzugt von 300 - 400°C durchgeführt. Die Ablufttemperatur beträgt dabei bevorzugt 100 - 200 °C, besonders bevorzugt 1 10 - 180 °C, ganz besonders bevorzugt 120 - 150 °C. Hierzu kann jedes Sprühtrocknungsgerät verwendet werden, das dem Fachmann auf diesem Gebiet bekannt ist, bevorzugt werden Scheiben-, Düsenoder Ultraschallzerstäuber eingesetzt. The spray-drying is preferably carried out at temperatures of 200-600 ° C., more preferably of 250-500 ° C., very particularly preferably of 300-400 ° C. The exhaust air temperature is preferably 100-200 ° C., particularly preferably 110-1080 ° C., very particularly preferably 120-150 ° C. Any spray-drying apparatus known to those skilled in the art can be used for this purpose; disc, nozzle or ultrasonic atomisers are preferably used.
Die thermische Behandlung der Granulate kann man sowohl in ruhender Schüttung, wie zum Beispiel in Kammeröfen, als auch in bewegter Schüttung, wie zum Beispiel in Drehrohröfen, durchführen. Sie wird für 1 - 8 h bei 400 - 800 °C durchgeführt. Bevorzugt sind Zeiten von 2 - 7 h, besonders bevorzugt sind 4 - 6 h. Die Temperatur beträgt vorteilhafterweise 500 - 700°C, besonders bevorzugt ist eine Temperatur von 550 - 650°C. Als vorteilhaft haben sich die Kombinationen von 2 - 7 h bei 400 - 800°C herausgestellt. Bevorzugt wird für 2 - 7 h bei 500 - 700°C getempert, besonders bevorzugt für 2 - 7 h bei 550 - 650°C und ganz besonders bevorzugt für 4 - 6 h bei 550 - 650 °C. The thermal treatment of the granules can be carried out both in static bed, such as in chamber furnaces, as well as in moving bed, such as in rotary kilns. It is carried out for 1 - 8 h at 400 - 800 ° C. Times of 2-7 hours are preferred, more preferably 4-6 hours. The temperature is advantageously 500-700 ° C, more preferably a temperature of 550-650 ° C. The combinations of 2 to 7 hours at 400 to 800 ° C. have proved to be advantageous. Preference is given to annealing at 500-700 ° C. for 2 to 7 h, more preferably for 2 to 7 h at 550 to 650 ° C., and very particularly preferably for 4 to 6 h at 550 to 650 ° C.
In einer Ausführungsform werden die Granulate bei 300 - 400°C In one embodiment, the granules are at 300-400 ° C
sprühgetrocknet und anschließend für 2 - 7 h bei 500 - 700 °C getempert. In einer besonderen Ausführungsform werden die Granulate bei 350 - 400 °C sprühgetrocknet und anschließend für 4 - 6 h bei 550 - 650 °C getempert. spray-dried and then annealed for 2 - 7 h at 500 - 700 ° C. In a particular embodiment, the granules are spray dried at 350-400 ° C and then annealed for 4-6 h at 550-650 ° C.
Die spezifische Oberfläche nach BET der eingesetzten, aggregierten The BET specific surface area of the used, aggregated
Titandioxid-Partikel ist nicht beschränkt, bevorzugt beträgt die BET-Oberfläche 20 - 120 m2/g. Besonders bevorzugt werden für die Granulate solche Titandioxid-Partikel mit einer spezifischen Oberfläche von 50 ± 15 m2/g oder 90 ± 20 m2/g verwendet. Titanium dioxide particles are not limited, preferably the BET surface area is 20-120 m 2 / g. Particularly preferred for the granules are those Titanium dioxide particles with a specific surface area of 50 ± 15 m 2 / g or 90 ± 20 m 2 / g used.
Die Größe der aggregierten Titandioxid-Partikel wird als ein mittlerer The size of the aggregated titanium dioxide particles is considered a mean
Durchmesser angegeben, der mittlerer Aggregatdurchmesser genannt wird. Der d5o-Wert des mittleren Aggregatdurchmessers der Titandioxid-Partikel, die zur Herstellung der erfindungsgemäßen Granulate verwendet werden, liegt vor der Hochenergievermahlung bei 100 nm - 10 m und nach der Diameter indicated, which is called mean aggregate diameter. The d 5 o-value of the mean aggregate diameter of the titanium dioxide particles that are used for the preparation of the granules according to the invention lies in front of the high-energy grinding with 100 nm - 10 m, and after the
Hochenergievermahlung bei 50 - 100 nm, bevorzugt liegt er nach der Hochenergievermahlung at 50 - 100 nm, preferably it is after the
Hochenergievermahlung bei 70 - 100 nm. Der mittlere Aggregatdurchmesser nach der Hochenergievermahlung wird mittels dynamischer Lichtstreuung gemessen. Dazu kann jedes Gerät verwendet werden, das dem Fachmann auf diesem Gebiet bekannt ist. High energy milling at 70 - 100 nm. The average aggregate diameter after high energy milling is measured by means of dynamic light scattering. Any device known to those skilled in the art can be used for this purpose.
Ein weiterer Gegenstand der Erfindung ist die Verwendung der Granulate als Trägermaterial, als Katalysator oder Katalysatorträger, als Schleif- und Another object of the invention is the use of the granules as a carrier material, as a catalyst or catalyst support, as grinding and
Poliermittel, als Rohstoff zur Glas- und Keramikherstellung sowie in Kosmetika, als Sonnenschutz, in Silikonkautschuk, in Tonerpulver, in Lacken und Farben. Polishes, as a raw material for glass and ceramic production and in cosmetics, as sunscreen, in silicone rubber, in toner powder, in paints and inks.
Beispiele Examples
Die Versuche werden mit einem pyrogen hergestellten Titandioxid mit einer BET-Oberfläche von ca. 50 m2/g, einem pH-Wert von ca. 3,5, einer The experiments are with a pyrogenic titanium dioxide having a BET surface area of about 50 m 2 / g, a pH of about 3.5, a
Stampfdichte von ca. 130 g/l und einer Primärpartikelgröße von 21 nm Tamped density of about 130 g / l and a primary particle size of 21 nm
(AEROXIDE® TiO2 P25 von Evonik Degussa) durchgeführt. (AEROXIDE TiO2 P25 ® from Evonik Degussa) performed.
Die verwendeten Geräte stehen nur beispielhaft für mögliche Gerätschaften und sind in keinem Fall als Einschränkung für die Erfindung zu verstehen. The devices used are only examples of possible equipment and are in no way to be construed as limiting the invention.
Beispiel 1 (erfindungsgemäße Granulate): Example 1 (inventive granules):
a) Herstellung der Vordispersion: a) Preparation of predispersion:
150 kg vollentsalztes Wasser werden in einem geeigneten Behälter vorgelegt. Zum Einstellen des pH-Wertes auf 2 wird verdünnte Salpetersäure verwendet. 100 kg aggregierte Titandioxid-Partikel werden über den Saugrüssel eines Scheraggregats vom Typ Conti-TDS 3 der Firma Ystral unter Scherung bei 3000 U/min bis zu einem Gewichtsanteil von 40 % eingezogen. Ein 150 kg of demineralized water are placed in a suitable container. To adjust the pH to 2, dilute nitric acid is used. 100 kg of aggregated titanium dioxide particles are conveyed under shear through the proboscis of a scissor unit of the Conti-TDS 3 type from Ystral 3000 U / min drawn up to a weight of 40%. One
ansteigender pH-Wert wird durch weitere Zugabe von verdünnter Salpetersäure wieder auf 2 gesenkt. Nach Beendigung des Einziehens wird die Vordispersion noch bei 3000 U/min 15 min lang nachgeschert. b) Herstellung der Dispersion durch Hochenergievermahlung: increasing pH is reduced to 2 by further addition of dilute nitric acid. After completion of the retraction, the predispersion is post-sheared at 3000 rpm for 15 minutes. b) Preparation of the dispersion by high energy milling:
Es wird eine Hochenergiemühle vom Typ Ultimaizer HJP-25050 der Firma Sugino Machine Ltd. eingesetzt. Die unter a) beschriebene Vordispersion wird bei einem Druck von 2500 bar und einem Diamantdüsendurchmesser von 0,3 mm zweimal durch die Hochenergiemühle geführt. Der mittlere  It is a high energy mill type Ultimaizer HJP-25050 Sugino Machine Ltd. used. The predispersion described under a) is passed twice through the high-energy mill at a pressure of 2500 bar and a diamond nozzle diameter of 0.3 mm. The middle one
Aggregatdurchmesser des Titandioxids weist nun einen d5o-Wert von 70 - 100 nm auf. c) Herstellung der Granulate: Aggregate diameter of the titanium dioxide now has a d 5 o value of 70 - 100 nm. c) Preparation of the granules:
Die mit einer Hochenergiemühle vermahlene Dispersion b) wird mit einem Sprühtrocknungsaggregat versprüht und getrocknet. Der Sprühnebel wird mittels einer Scheibenzerstäubung erzeugt. Dabei wird die Scheibenumdrehung auf werte von 12000 U/min eingestellt. Die Trocknungstemperatur liegt bei 380°C. Die Ablufttemperatur beträgt 125°C. Der Durchsatz an Titandioxid- Suspension wird auf 100 l/h eingestellt. Die getrockneten Granulate werden mittels eines Gewebefilters vom Gasstrom abgetrennt. Bei dem beschriebenen Sprühtrocknungsvorgang entstehen im Wesentlichen sphärische Granulate. d) Thermische Nachbehandlung: The high-energy mill milled dispersion b) is sprayed with a spray drying unit and dried. The spray is generated by means of a disk atomization. The disc rotation is adjusted to values of 12000 rpm. The drying temperature is 380 ° C. The exhaust air temperature is 125 ° C. The throughput of titanium dioxide suspension is set to 100 l / h. The dried granules are separated from the gas stream by means of a fabric filter. The described spray-drying process produces essentially spherical granules. d) Thermal aftertreatment:
Für die thermische Nachbehandlung werden 10 kg der sprühgetrocknetenFor the thermal aftertreatment, 10 kg of the spray-dried
Granulate bei 600 °C für 4 h in einem Kammerofen gelagert. Anschließend wird auf Raumtemperatur abgekühlt. Granules stored at 600 ° C for 4 h in a chamber furnace. It is then cooled to room temperature.
Beispiele 2 und 3 (Vergleichsbeispiele): Für die Beispiele 2 und 3 wird ein konnnnerziell erhältliches Titandioxid-Granulat mit einer BET-Oberfläche von 50 m2/g, einem mittleren Korndurchmesser von etwa 20 μιτη, einer Stampfdichte von ca. 700 g/l und einem pH-Wert von 3,0 - 4,5 eingesetzt, das von Evonik Degussa unter dem Namen VP AEROPERL® P25/20 vertrieben wird. Dieses Granulat wurde entsprechend DE 19928851 A1 aus einer Dispersion von pyrogen hergestellten, aggregierten Titandioxid- Partikeln mit einer BET-Oberfläche von 50 ± 15 m2/g, einer Primärpartikelgröße von 21 nm, einer Stampfdichte von ca. 130 g/l und einem pH-Wert von 3,5 - 4,5, das von Evonik Degussa unter dem Namen AEROXIDE® TiO2 P25 vertrieben wird, hergestellt. Examples 2 and 3 (comparative examples): For examples 2 and 3, a commercially available titanium dioxide granules having a BET surface area of 50 m 2 / g, an average grain diameter of about 20 μιτη, a tapped density of about 700 g / l and a pH of 3, 0 - 4.5, which is sold by Evonik Degussa under the name VP AEROPERL® P25 / 20. This granulate was prepared according to DE 19928851 A1 from a dispersion of pyrogenically produced, aggregated titanium dioxide particles having a BET surface area of 50 ± 15 m 2 / g, a primary particle size of 21 nm, a tamped density of about 130 g / l and a pH Value of 3.5-4.5 sold by Evonik Degussa under the name AEROXIDE® TiO 2 P25.
Für Beispiel 2 wird das unbehandelte Granulat verwendet, es erfolgt keine thermische Nachbehandlung. In Beispiel 3 wird das Granulat bei 600 °C für 4 h thermisch nachbehandelt. Messung der mechanischen Stabilität:  For example 2, the untreated granules are used, there is no thermal aftertreatment. In Example 3, the granules are thermally post-treated at 600 ° C for 4 h. Measurement of mechanical stability:
Zur statischen Lichtstreuung wird ein Partikelgrößenmessgerät vom Typ „Mastersizer S" mit Durchflusszelle der Firma Malvern Instruments Ltd.  For static light scattering, a particle sizer of the type "Mastersizer S" with flow cell from Malvern Instruments Ltd. is used.
eingesetzt. Als Pumpeneinheit dient die Probendispergiereinheit für kleine Volumina MSX1 mit Pumpen-/Rührerdrehzahlkontrolle, jeweils von der Firma Malvern Instruments Ltd.. In der Ultraschallbehandlung kommt der used. As a pump unit, the sample dispersing unit for small volumes MSX1 with pump / stirrer speed control, each by the company Malvern Instruments Ltd .. In the ultrasonic treatment is the
Ultraschallprozessor GEX 750 mit 750 Watt Generatorleistung und einer Frequenz von 20 kHz der Firma G. Heinemann, Schwäbisch Gmünd, bestückt mit Ultraschall konverter CV 33 inklusive 13 mm Resonator mit wechselbaren Titan-Tellern zum Einsatz. Die Beschallung der Probe findet in einer  Ultrasonic processor GEX 750 with 750 watts generator power and a frequency of 20 kHz from G. Heinemann, Schwäbisch Gmünd, equipped with ultrasonic converter CV 33 including 13 mm resonator with exchangeable titanium plates for use. The sonication of the sample takes place in one
Durchflusszelle mit Kühlmantel und mit 1/ "-Gewinde zum Aufschrauben auf den Resonator der Firma G. Heinemann statt. Die Ultraschall-Amplitude beträgt 100 %, wobei ein Ultraschallpuls von 1 Sekunde eingestellt wird. Flow cell with cooling jacket and with 1 / "thread for screwing onto the resonator of G. Heinemann The ultrasonic amplitude is 100%, whereby an ultrasonic pulse of 1 second is set.
Vor der Messung wird eine wässrige Dispersion der zu untersuchenden Before the measurement, an aqueous dispersion of the to be examined
Granulate in der Dispergiereinheit hergestellt. Die Konzentration des Feststoffs wird dabei so gewählt, dass die optische Abschattung der Granulate nicht zu groß wird. Die Dispersion wird nun während des gesamten Messvorgangs kontinuierlich durch die Apparatur gepumpt, die Leistung der Pumpe wird dabei auf 2000 U/min geregelt. Zuerst wird die kontinuierliche Korngrößenmessung gestartet, wobei zunächst die mittlere Korngröße (d50o) dreimal mittels statischer Lichtstreuung bestimmt und aus diesen Werten der Mittelwert gebildet wird. Danach wird die gepulste Ultraschallbehandlung gestartet. Die Probe wird nun kontinuierlich im 1 Sekundentakt mit Ultraschall beschallt: 1 Sekunde„an" gefolgt von 1 Sekunde„aus". Die Dispersion wird während der Beschallung in der Durchflusszelle gekühlt. Dazu wird Wasser durch den Kühlmantel gepumpt, das mittels Kryostat auf 18°C temperiert wird. Nach jeweils 10 Sekunden gepulster Ultraschall-Behandlung wird die Granules produced in the dispersion. The concentration of the solid is chosen so that the optical shading of the granules is not too large. The dispersion will now be throughout the measurement process pumped continuously through the apparatus, the power of the pump is regulated to 2000 rev / min. First, the continuous grain size measurement is started, whereby first the mean grain size (d50o) is determined three times by means of static light scattering and the mean value is formed from these values. Thereafter, the pulsed ultrasonic treatment is started. The sample is sonicated continuously in 1 second intervals with ultrasound: 1 second "on" followed by 1 second "off". The dispersion is cooled during sonication in the flow cell. For this purpose, water is pumped through the cooling jacket, which is tempered by means of cryostat to 18 ° C. After every 10 seconds of pulsed ultrasound treatment, the
volumengewichtete Teilchengrößenverteilung aufgezeichnet, welche aus 2000 Einzelmessungen besteht. Aus den gemessenen Daten wird mittels Volume-weighted particle size distribution recorded, which consists of 2000 individual measurements. From the measured data by means of
Auswertesoftware anhand der Fraunhofer-Theorie der mittlere Evaluation software based on the Fraunhofer theory of the middle
Korndurchmesser (d50us) berechnet. Die Bestimmung der mechanischen Stabilität endet je nachdem wie schnell die Granulate während der Grain diameter (d50us) calculated. The determination of the mechanical stability ends depending on how fast the granules during the
Ultraschallbehandlung zerfallen, spätestens jedoch, wenn der mittlere Ultrasonic treatment decay, but no later than when the middle
Korndurchmesser bei fortlaufender Ultraschallbehandlung konstant bleibt. Grain diameter remains constant with continuous ultrasonic treatment.
Anschließend werden die Granulat-Stabilitäts-Faktoren folgendermaßen errechnet: Jeder Messwert des mittleren Korndurchmessers d50us wird durch den zuvor bestimmten Ausgangswert d50o dividiert und anschließend gegen die Zeitdauer der Ultraschall-Behandlung aufgetragen. Ein Granulat-Stabilitäts- Faktor von 1 ,0 gibt an, dass es zu keiner Veränderung des mittleren The granule stability factors are then calculated as follows: Each measured value of the mean grain diameter d50us is divided by the previously determined initial value d50o and then plotted against the duration of the ultrasound treatment. A granule stability factor of 1.0 indicates that there is no change in the mean
Korndurchmessers durch die Ultraschallbehandlung kam und somit keine Zerkleinerung der Granulate stattfand. Ein Granulat-Stabilitäts-Faktor von 0,2 gibt an, dass der ursprüngliche Wert des mittleren Korndurchmessers um 80 % abgenommen hat. Grain diameter came through the ultrasonic treatment and thus no crushing of the granules took place. A granule stability factor of 0.2 indicates that the original value of the mean grain diameter has decreased by 80%.
Die Parameter zur Herstellung der Granulate und deren physikalische- chemische Daten sind in Tabelle 1 dargestellt. In Abbildung 1 ist ein Diagrannnn dargestellt, anhand dessen die mechanische Stabilität der beispielhaften Titandioxid-Granulate verglichen werden kann. Man kann am Kurvenverlauf bereits zu Beginn der Messung eine höhere The parameters for the preparation of the granules and their physical-chemical data are shown in Table 1. Figure 1 shows a diagram by means of which the mechanical stability of the exemplary titanium dioxide granules can be compared. It is possible to increase the curve already at the beginning of the measurement
mechanische Stabilität des erfindungsgemäßen Titandioxid-Granulates mechanical stability of the titanium dioxide granules according to the invention
(Beispiel 1 ) erkennen. Der DIF-Wert des erfindungsgemäßen Titandioxid- Granulates bleibt auch mit fortschreitender Zeit auf einem deutlich höheren Niveau als die Vergleichsbeispiele. (Example 1) recognize. The DIF value of the titanium dioxide granules according to the invention also remains at a significantly higher level with time as compared to the comparative examples.
Legende: Quadrat - Beispiel 1 , Legend: Square - Example 1,
Dreieck - Beispiel 2,  Triangle - Example 2,
Kreis - Beispiel 3.  Circle - Example 3.
Auf der x-Achse ist die Zeit in Sekunden aufgetragen. Auf der y-Achse ist das Verhältnis D50us/D50o aufgetragen.  The time in seconds is plotted on the x-axis. The ratio D50us / D50o is plotted on the y-axis.
In Tabelle 2 sind die Meßwerte zu Abbildung 1 wiedergegeben. Table 2 shows the measured values for Figure 1.
Tabelle 1 : Parameter zur Herstellung der Granulate und deren mechanische Stabilität DIF Table 1: Parameters for the preparation of the granules and their mechanical stability DIF
Beispiel 1 2 3 Example 1 2 3
Konzentration in Concentration in
Gew.-% 40 3-25 3-25 Dispersion  Weight% 40 3-25 3-25 dispersion
Scherparameter U/min 3000 3000 3000 min 15 15 15 Shear parameters rpm 3000 3000 3000 min 15 15 15
Hochenergiemühle bar 2500 - - High energy mill bar 2500 - -
Thermische °C 600 600 Thermal ° C 600 600
- Behandlung h 4 4 spez. Oberfläche  - Treatment h 4 4 spec. surface
m2/g 20 50 18 (BET) m 2 / g 20 50 18 (BET)
Porenvolumen ml/g 0,17 0,47 0,26 mittlerer Pore volume ml / g 0.17 0.47 0.26 average
nm 25 26 48 nm 25 26 48
Porendurchmesser Pore diameter
Stampfdichte g/i 1492 ca. 700 1297 Tamped density g / i 1492 approx. 700 1297
DIF nach 132 sec 0,96 0,18 0,7 DIF after 132 sec 0.96 0.18 0.7
Tabelle 2: Wertetabelle zu Abbildung 1 Table 2: Value table for Figure 1
D50us/D50o D50us/D50o D50 us / D50o D50 us / D50o
Zeit in Zeit in  Time in time
Beispiel Beispiel Beispiel Beispiel Beispiel Beispiel Sekunden Sekunden  Example Example Example Example Example Example Seconds Seconds
1 2 3 1 2 3 1 2 3 1 2 3
0 1 1 1 282 0,430 1 1 1 282 0.43
12 1 ,00 0,94 1 292 0,4212 1, 00 0.94 1 292 0.42
22 0,86 0,96 302 0,4122 0.86 0.96 302 0.41
32 0,74 0,91 312 0,91 0,3632 0.74 0.91 312 0.91 0.36
42 0,67 0,89 322 0,3442 0.67 0.89 322 0.34
52 0,59 332 0,3252 0.59 332 0.32
62 0,52 0,90 342 0,3062 0.52 0.90 342 0.30
72 1 ,00 0,46 0,88 352 0,2672 1, 00 0.46 0.88 352 0.26
82 0,40 0,82 362 0,2482 0.40 0.82 362 0.24
92 0,35 0,80 372 0,93 92 0.35 0.80 372 0.93
102 0,30 0,76 382  102 0.30 0.76 382
1 12 0,26 0,73 392  1 12 0.26 0.73 392
122 0,22 0,71 402  122 0.22 0.71 402
132 0,96 0,18 0,70 412  132 0.96 0.18 0.70 412
142 0,67 422  142 0.67 422
152 0,66 432 0,93  152 0.66 432 0.93
162 0,64 442  162 0.64 442
172 0,61 452  172 0.61 452
182 0,59 462  182 0.59 462
192 0,99 0,63 472  192 0.99 0.63 472
202 0,61 482  202 0.61 482
212 0,57 492 0,89  212 0.57 492 0.89
222 0,54 502  222 0.54 502
232 0,54 512  232 0.54 512
242 0,54 522  242 0.54 522
252 0,94 0,45 532  252 0.94 0.45 532
262 0,49 542  262 0.49 542
272 0,45 552 0,89  272 0.45 552 0.89

Claims

Patentansprüche claims
1 . Granulate auf der Basis von aggregierten Titandioxid-Partikeln mit einem mittleren Korndurchmesser von 5 - 100 μιτι und einer spezifischen 1 . Granules based on aggregated titanium dioxide particles having a mean particle diameter of 5 to 100 μm and a specific particle size
Oberfläche nach BET von 10 - 120 m2/g, dadurch gekennzeichnet, dass sie BET surface area of 10 to 120 m 2 / g, characterized in that it
a. eine Stampfdichte von 1350 - 1800 g/l,  a. a tamped density of 1350 - 1800 g / l,
b. ein Porenvolumen von 0,10 - 0,50 cm3/g und b. a pore volume of 0.10 - 0.50 cm 3 / g and
c. einen mittleren Porendurchmesser von 5 - 45 nm aufweisen.  c. have a mean pore diameter of 5 - 45 nm.
2. Granulate nach Anspruch 1 , dadurch gekennzeichnet, dass sie nach 2. Granules according to claim 1, characterized in that they are after
Ultraschallbehandlung eine mechanische Stabilität von 0,85 - 0,99 aufweisen.  Ultrasonic treatment have a mechanical stability of 0.85 - 0.99.
3. Granulate nach Anspruch 2, dadurch gekennzeichnet, dass sie nach 130 Sekunden Ultraschallbehandlung eine mechanische Stabilität von 0,95 - 0,99 aufweisen. 3. Granules according to claim 2, characterized in that they have a mechanical stability of 0.95 to 0.99 after 130 seconds of ultrasonic treatment.
4. Granulate nach Anspruch 2, dadurch gekennzeichnet, dass sie nach 300 Sekunden eine mechanische Stabilität von 0,9 - 0,99 aufweisen 4. Granules according to claim 2, characterized in that they have a mechanical stability of 0.9 - 0.99 after 300 seconds
5. Granulate nach Anspruch 2, dadurch gekennzeichnet, dass sie nach 550 Sekunden eine mechanische Stabilität von 0,85 - 0,99 aufweisen. 6. Verfahren zur Herstellung von Granulaten auf der Basis von Titandioxid, dadurch gekennzeichnet, dass man aggregierte Titandioxid-Partikel mit einem mittleren Aggregatdurchmesser von 100 nm bis 10 μιτι zunächst mit Wasser versetzt, dieses Gemisch auf einen pH-Wert von 1 - 7 bringt und durch Scherung zu einer wässrigen Vordispersion mit einem 5. Granules according to claim 2, characterized in that they have a mechanical stability of 0.85 - 0.99 after 550 seconds. 6. A process for the preparation of granules based on titanium dioxide, which comprises adding aggregated titanium dioxide particles having a mean aggregate diameter of 100 nm to 10 μm initially with water, bringing this mixture to a pH of 1-7 and by shearing to an aqueous predispersion with a
Feststoffgehalt von 30 - 70 Gew.-% verarbeitet, diese Vordispersion anschließend einem Hochenergievermahlungsschritt unterzieht, die dadurch entstandene Dispersion anschließend sprühtrocknet und das erhaltene Produkt für 1 - 8 h bei 400 - 800 °C thermisch nachbehandelt. Processed solids content of 30 to 70 wt .-%, this predispersion then subjected to a Hochenergievermahlungsschritt, the The resulting dispersion is then spray-dried and the resulting product thermally post-treated for 1 to 8 hours at 400 to 800 ° C.
Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass aggregierte Titandioxid-Partikel verwendet werden, die pyrogen hergestellt sind. A method according to claim 6, characterized in that aggregated titanium dioxide particles are used which are produced pyrogenically.
8. Verfahren nach Anspruch 6 oder 7, dadurch gekennzeichnet, dass der pH- Wert der Titandioxid-Vordispersion mit Säure auf 1 bis 5 eingestellt wird. 8. The method according to claim 6 or 7, characterized in that the pH of the titanium dioxide predispersion is adjusted to 1 to 5 with acid.
9. Verfahren nach den Ansprüchen 6 oder 7, dadurch gekennzeichnet, dass der pH-Wert der Titandioxid-Vordispersion mit Säure auf 1 ,5 bis 2,5 eingestellt wird. 9. The method according to claims 6 or 7, characterized in that the pH of the titanium dioxide predispersion with acid to 1, 5 to 2.5 is set.
10. Verfahren nach den Ansprüchen 6 bis 9, dadurch gekennzeichnet, dass der pH-Wert mit Salpetersäure eingestellt wird. 10. The method according to claims 6 to 9, characterized in that the pH is adjusted with nitric acid.
1 1 . Verwendung der Granulate gemäß der Ansprüche 1 bis 5 als 1 1. Use of the granules according to claims 1 to 5 as
Trägermaterial, als Katalysator oder Katalysatorträger, sowie in  Support material, as a catalyst or catalyst support, as well as in
Kosmetika, Sonnenschutzformulierungen, Silikonkautschuk, Tonerpulver, Lacken, Farben, als Schleif-/Poliermittel, als Rohstoff zur Glas- und Cosmetics, sunscreen formulations, silicone rubber, toner powder, paints, paints, as grinding / polishing agents, as a raw material for glass and
Keramikherstellung. Ceramics.
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