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EP3097153A1 - Mélange contenant des particules d'oxyde de zinc ayant une tendance réduite à l'agglutination lors du stockage - Google Patents

Mélange contenant des particules d'oxyde de zinc ayant une tendance réduite à l'agglutination lors du stockage

Info

Publication number
EP3097153A1
EP3097153A1 EP15701199.0A EP15701199A EP3097153A1 EP 3097153 A1 EP3097153 A1 EP 3097153A1 EP 15701199 A EP15701199 A EP 15701199A EP 3097153 A1 EP3097153 A1 EP 3097153A1
Authority
EP
European Patent Office
Prior art keywords
zinc oxide
particles
zinc
mixture according
oxide
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.)
Withdrawn
Application number
EP15701199.0A
Other languages
German (de)
English (en)
Inventor
Florian WALTZ
Jürgen BEZLER
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.)
Grillo Zinkoxid GmbH
Original Assignee
Grillo Zinkoxid 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 Grillo Zinkoxid GmbH filed Critical Grillo Zinkoxid GmbH
Priority to EP15701199.0A priority Critical patent/EP3097153A1/fr
Publication of EP3097153A1 publication Critical patent/EP3097153A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Definitions

  • the invention relates to a mixture of particles of zinc oxide and other oxide particles, and to the use thereof for reducing the tendency of caking upon storage.
  • Zinc oxide is a substance that is employed in many forms in many fields, for example, utilized as a pigment under the designation of zinc white. Being a semiconductor, zinc oxide is employed as a transparent conducting layer in the production of blue light emitting diodes (LEDs), liquid crystal displays (TFT; thin- film transistor), varistors (VDR; voltage dependent resistor), and thin-film solar cells. As semiconducting nanowires, zinc oxide is employed in measuring technology because of its piezoelectric properties and UV light transparency. As a component of pharmaceutical zinc ointments, pastes, plasters (Leukoplast) and dressings, zinc oxide causes the skin surface to dry out. This is used, for example, in intertrigo, diaper dermatitis and other exuding wounds.
  • Zinc oxide In athlete's feet and other dermatomycoses, zinc oxide promotes healing. Zinc oxide is also employed in sunscreens and as an additive in the vulcanization of rubber. Since zinc is an essential trace element for humans and animals, zinc oxide as a source thereof is employed both in food supplements for humans and in animal nutrition. In addition, it is employed as a phosphor in fluorescent lamps.
  • Zinc oxide is produced industrially on the order of 1-2 megatons a year.
  • Customers include the pharmaceutical and chemical industries, and feed producers.
  • the biggest customer of ZnO is the tire industry, zinc oxide usually being added to the raw rubber within a range of from 0.5 to 10 phr, its main task being the activation of sulfur-cured vulcanization.
  • some storage of supplies of zinc oxide is indispensable for undertakings.
  • moisture deposition/condensation may occur.
  • Water bridges form between the zinc oxide particles, and under the pressure of the zinc oxide's own weight, for example, in a storage silo, caking of the zinc oxide occurs. This leads to dosing problems and problems with the admixing/incorporating of the zinc oxide.
  • pipelines may clog as a consequence of caking, and in such a case, they must be beaten free tediously, in part manually.
  • Zinc oxide which is usually produced with particle sizes of below 10 prn on an industrial scale, falls under the bulk material category of highly dispersed powders, for which very poor free-flowing properties are expected [Tomas J., Leinschmidt S., Chem. Ing. Tech. 2009, 81 (6), 717-733]. In practice, the flow characteristics of zinc oxide considerably complicate the conveying and transport from silos and through pipelines, and the further processing.
  • EP 2 409 952 Al, US 2010/047590 Al, US 2006/073092 Al and Zhou et al. described zinc oxide particles doped with other elements, but not mixtures of discrete zinc oxide particles with discrete other oxide particles.
  • US 2012/0233929 Al discloses discrete hydrophobically modified nanoparticles, which are to be added to a wide variety of other particles to prevent absorption of moisture in a powder, whereby the powder can be stored even at an increased humidity.
  • An object of the invention is to provide a zinc oxide having a reduced tendency of caking upon storage. According to the invention, this problem is solved by a mixture containing particles of zinc oxide and other oxide particles selected from the group consisting of oxides of silicon, aluminum, titanium, magnesium, calcium, or combinations thereof.
  • the particles of zinc oxide cannot be doped with an element selected from the group consisting of Sc, Y, In, Ga, Al, Ti, B, Ge, Sn, and lanthanides.
  • it may contain said other oxide particles in amounts of from 0.1% by weight to 25% by weight.
  • the size of said other oxide particles may orient itself by the particle size of the zinc oxide employed, and they may have a primary particle size that is smaller than that of the zinc oxide employed by a factor of at least 10 or by a factor of at least 50.
  • the term primary particle is understood according to the definition of DIN 53206.
  • the mixture according to the invention has zinc oxide particles with a particle size of from 0.03 to 500 prn.
  • particle size relates to d50 values of the volume-weighted particle size distribution of an aqueous suspension of the particles as determinable by means of laser diffraction. Such values can be determined with suitable devices, for example, Malvern Mastersizer 2000.
  • the particles of zinc oxide are agglomerated and are not in the form of discrete particles.
  • the size of the other oxide particles in the mixture 1 to 3 according to the invention may be from 0.003 to 1 prn.
  • the size of the other particles of oxides of silicon in the mixture may be ⁇ 1000 nm, especially ⁇ 300 nm, especially from 1 nm to 300 nm. Because the primary particles are frequently in a strongly agglomerated/aggregated form, it may be more appropriate to state specific N 2 surface areas (BET) according to DIN 66132.
  • the N 2 surface area of the oxides of silicon in the mixture may be > 50 m 2 /g, especially > 100 m 2 /g, especially from 150 to 350 m 2 /g.
  • the origin of the zinc oxide is of less importance.
  • the zinc oxide of the zinc oxide particles may be obtainable, in particular, as the product of a thermal or wet-chemical process.
  • the invention also relates to the use of the mixture according to the invention for reducing the tendency of caking upon storage.
  • the mixture according to the invention is advantageous because, in addition to the reduction of the tendency of caking upon storage, there is also a good flowability of the mixture.
  • Figure 1 Graphical plot of the free-flowing capabilities (ffc) for different consolidation stresses (sigma 1) of pure pharma grade zinc oxide and of mixtures thereof with different silicas.
  • Figure 2 Graphical plot of the free-flowing capabilities (ffc) of different zinc oxides and mixtures of such zinc oxides with pyrogenic silica as determined at consolidation stresses of about 5000 Pa, and after three days of storage at such consolidation stress.
  • the present invention discloses a mixture containing particles of zinc oxide and other oxide particles selected from the group consisting of oxides of silicon, aluminum, titanium, magnesium, calcium, or combinations thereof.
  • the mixture according to the invention contains said other oxide particles in amounts of from 0.1% by weight to 25% by weight.
  • said addition of said other oxide particles leads to reduced caking upon storage, and to an increased flow property of the mixture.
  • the described properties do not change linearly with the amount of other oxide particles added, but a plateau effect is seen.
  • a significant improvement of caking upon storage and of the flow behavior of the mixture is obtained already when less than 2% by weight of the other oxide particles are admixed.
  • the mixture according to the invention has zinc oxide particles with a particle size of from 0.03 to 500 prn.
  • particle size relates to d50 values of the volume-weighted particle size distribution of an aqueous suspension of the particles as determinable by means of laser diffraction. Such values can be determined with suitable devices, for example, Malvern Mastersizer 2000.
  • volume-weighted d50 values according to measurement by laser diffraction of industrially produced zinc oxide are ⁇ 5 prn.
  • feed grade zinc oxide for example, Grillo zinc oxide F72 and F80
  • d50 values above 10 pm are already have a clearly lower tendency to caking upon storage and a higher flowability of the powders as compared to other grade zinc oxides.
  • the selection of the size of said other oxide particles may orient itself, for example, by the particle size of the zinc oxide employed. In particular, they may have a primary particle size that is smaller by a factor of at least 10 or by a factor of at least 50. According to one embodiment of the invention, the size of the other oxide particles in the mixture according to the invention may be from 0.003 to 1 pm.
  • the size of the particles of oxides of silicon in the mixture is typically ⁇ 1000 nm, especially ⁇ 300 nm, especially from 1 nm to 300 nm. Because the particles are frequently in a strongly agglomerated/aggregated form, it may be more appropriate in practice to state specific N 2 surface areas (BET) according to DIN 66132.
  • the N 2 surface area of the oxides of silicon in the mixture is > 50 m 2 /g, especially > 100 m 2 /g, especially from 150 to 350 m 2 /g-
  • the origin of the zinc oxide is of less importance.
  • the zinc oxide of the zinc oxide particles may be obtainable as the product of a thermal or wet-chemical process.
  • thermal processes are classified into two basic processes, a direct one (also referred to as an American process), and an indirect one (also referred to as a French process).
  • oxidic precursors so-called white ashes
  • the zinc oxide obtained usually has a star-shaped morphology and N 2 surface areas according to DIN 66132 of 1-2.5 m 2 /g - Examples of a zinc oxide produced by this process include zinc oxide 2011 from Grillo Zinkoxid GmbH, Goslar.
  • metallic zinc precursors for example, hard zinc, refined zinc, floats from strip galvanizing, SHG zinc, and remelted zinc are employed. These are heated above the boiling temperature of zinc by means of a furnace, such as a column, retort, muffle kiln and rotary kiln. The vaporous zinc is subsequently oxidized by atmospheric oxygen and collected in a filter.
  • Industrial examples of zinc oxides produced by this method by means of a rotary kiln include Rotsiegel, Grunsiegel and Weisssiegel from the Grillo Zinkoxid GmbH Goslar, which are distinguished by their purity, the purity increasing towards the Weisssiegel.
  • These zinc oxide types usually have N 2 surface areas according to DIN 66132 of 3- 7 m 2 /g-
  • Examples of zinc oxides produced by the French process using a retort include the so-called pharma grades from the Grillo Zinkoxid GmbH. These are characterized by very little contamination with heavy metals, wherein the ZnO content according to DIN 55908 > 99.9%.
  • the N 2 surface areas of these types are usually from 3 to 20 m 2 /g-
  • Another thermal process for producing zinc oxide is the clinker process, in which so-called zinc ashes obtained from galvanizing processes are employed as raw materials.
  • a rotary kiln contaminants are discharged in gaseous form at temperatures of > 1000 °C, and any metallic zinc present is oxidized.
  • a brownish zinc oxide with zinc contents of from 70 to 80% is obtained as a product.
  • the thus obtainable zinc oxide is usually employed in animal nutrition (also referred to as feed grade zinc oxide), where it serves as a zinc source for preventing zinc deficiency symptom.
  • Examples of zinc oxide produced by the clinker process include the feed grades F72 and F80 from the Grillo Zinkoxid GmbH.
  • Zinc oxide obtained by this production process is characterized by relatively large particle sizes of > 10 prn, corresponding to N 2 surface areas according to DIN 66132 of ⁇ 1 m 2 /g.
  • the invention also relates to the use of the mixture according to the invention for reducing the tendency of caking upon storage.
  • the mixture according to the invention avoids the disadvantages arising from the above described caking.
  • the addition of oxides of silicon to zinc oxide should not create any further problems in the tire industry since oxides of silicon are present as fillers in many rubber blends with filling rates of more than 50 phr. Therefore, no contamination occurs, but rather the amount of oxide of silicon employed as a filler can simply be reduced optionally.
  • the mixture according to the invention is advantageous because, in addition to the reduction of the tendency of caking upon storage, there is also a good flowability of the mixture.
  • Example 1 The invention is further illustrated by means of the following Examples.
  • Example 1 Example 1 :
  • Table 1 Flowabilities (ffc) at different consolidation stresses (sigma 1) of pure Grillo Pharma 4 zinc oxide and of mixtures thereof with different silicas.
  • Figure 1 shows a graphical plot of the free-flowing capabilities (ffc) for different consolidation stresses (sigma 1) of pure pharma grade zinc oxide and of mixtures thereof with different silicas.
  • Table 2 Free-flowing capabilities (ffc) of different zinc oxides and mixtures of such zinc oxides with pyrogenic silica as determined at consolidation stresses of about 5000 Pa, and after three days of storage at such consolidation stress.
  • Figure 2 shows a graphical plot of the free-flowing capabilities (ffc) of different zinc oxides and mixtures of such zinc oxides with pyrogenic silica as determined at consolidation stresses of about 5000 Pa, and after three days of storage at such consolidation stress.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention concerne un mélange contenant des particules d'oxyde de zinc et d'autres particules d'oxyde choisi dans le groupe constitué par les oxydes de silicium, d'aluminium, de titane, de magnésium, de calcium, ou des combinaisons de ceux-ci. L'invention concerne également l'utilisation de ce mélange pour réduire la tendance à l'agglutination lors du stockage.
EP15701199.0A 2014-01-24 2015-01-23 Mélange contenant des particules d'oxyde de zinc ayant une tendance réduite à l'agglutination lors du stockage Withdrawn EP3097153A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP15701199.0A EP3097153A1 (fr) 2014-01-24 2015-01-23 Mélange contenant des particules d'oxyde de zinc ayant une tendance réduite à l'agglutination lors du stockage

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP14152377 2014-01-24
EP15701199.0A EP3097153A1 (fr) 2014-01-24 2015-01-23 Mélange contenant des particules d'oxyde de zinc ayant une tendance réduite à l'agglutination lors du stockage
PCT/EP2015/051348 WO2015110575A1 (fr) 2014-01-24 2015-01-23 Mélange contenant des particules d'oxyde de zinc ayant une tendance réduite à l'agglutination lors du stockage

Publications (1)

Publication Number Publication Date
EP3097153A1 true EP3097153A1 (fr) 2016-11-30

Family

ID=49998117

Family Applications (1)

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EP15701199.0A Withdrawn EP3097153A1 (fr) 2014-01-24 2015-01-23 Mélange contenant des particules d'oxyde de zinc ayant une tendance réduite à l'agglutination lors du stockage

Country Status (2)

Country Link
EP (1) EP3097153A1 (fr)
WO (1) WO2015110575A1 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10235758A1 (de) * 2002-08-05 2004-02-26 Degussa Ag Dotiertes Zinkoxidpulver, Verfahren zu seiner Herstellung und Verwendung
KR101455419B1 (ko) * 2006-10-06 2014-10-28 사까이가가꾸고오교가부시끼가이샤 초미립자 산화아연 및 그의 제조 방법
WO2011043207A1 (fr) * 2009-10-07 2011-04-14 堺化学工業株式会社 Particules d'oxyde de zinc, procédé pour la production des particules, charge dissipant la chaleur, composition de résine dissipant la chaleur, graisse dissipant la chaleur et composition de revêtement dissipant la chaleur
WO2011068742A1 (fr) * 2009-12-03 2011-06-09 3M Innovative Properties Company Procédé d'inhibition d'adsorption d'eau par une poudre par ajout de nanoparticules hydrophobes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2015110575A1 *

Also Published As

Publication number Publication date
WO2015110575A1 (fr) 2015-07-30

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