WO2017122049A1 - Procédé de compaction de nano-silice - Google Patents

Procédé de compaction de nano-silice Download PDF

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Publication number
WO2017122049A1
WO2017122049A1 PCT/IB2016/050193 IB2016050193W WO2017122049A1 WO 2017122049 A1 WO2017122049 A1 WO 2017122049A1 IB 2016050193 W IB2016050193 W IB 2016050193W WO 2017122049 A1 WO2017122049 A1 WO 2017122049A1
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WO
WIPO (PCT)
Prior art keywords
silica
nano
water
compacted
bulk density
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PCT/IB2016/050193
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English (en)
Inventor
Liudmila SUVOROVA
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Iį "Macrosorb.Lt"
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Priority to PCT/IB2016/050193 priority Critical patent/WO2017122049A1/fr
Publication of WO2017122049A1 publication Critical patent/WO2017122049A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof

Definitions

  • the invention belongs to the chemical technology and relates to the method of increasing the bulk density in order to receive compacted nano-silica while saving its physical-chemical properties.
  • Such nano-silica may be used as the sorbent and carrier of the medical preparations in many areas of medicine, pharmacology, veterinary science. It also may be used as filler in the production of oils, lacquers, paints, adhesives, rubber, silicon rubber, sealers, polymeric materials, abrasives under chemical-mechanical polishing of the mono-crystals of the electronics, for preparation of new adsorbents and catalyzers [Medicinal chemistry and clinical application of silica dioxide / ed. by Chuiko A. A. - Kyiv. - Naukova dumka. - 2003.
  • nano-silica is obtained by burning halides and organosilicon substances in hydrogen-air flame.
  • Pyrogenic synthesis method allows receive powder material (nano-silica), the size of the particles of which is 5-20 nm. Under the synthesis due to the coalescence the noncoherent components appear in the reactor, they form agglomerates, the volume of which consists of 98% air. Major space between agglomerates causes their low bulk density, which leads to the excessive dust formation, adverse working conditions, considerable expenses for packing, storage and transportation of the production and clean out of the technological equipment. It also requires the larger equipment for usage of nano-silicas in the production of different preparations and products.
  • nano-silica compaction is based on the vacuous compaction by the means of the pressure below atmospheric (300-900 mbar), applied to the filter in the form of the tube, in which the nano-silica is mixed and transferred by the rotating auger [US Patent N° 4326852 ].
  • the disadvantage of this method is insignificant increase of the bulk density to 120 g/1 and significant dust formation.
  • Vacuous systems are fairly expensive and complicated, as a rule.
  • the present invention aims to increase the bulk density of nano-silica, to reduce the dust formation and to preserve the other standardized physico-chemical properties, inter alia, the adsorptive characteristics, of the initial uncompacted product.
  • the application task is solved through the method of nano-silica compaction claimed which comprises: loading nano-silica into the reactor with stirring mechanism and water pulverization device, which includes the water injection system and sprayer; pumping water under the pressure and pulverization it in the form of aerosol while stirring the mixture continuously and intensively over a period of time, then switching off the mixer remaining compacted nano-silica for equilibration, then unloading, drying and sieving. Water forces air out of the powder volume and forms hydrated film of the nano-silica particles. Consequently, the dispersion of water in nano-sized silica leads to the microencapsulation.
  • the nano-sized silica is capable of stabilizing the water nano-drops.
  • Appliance of the present method claimed for the compaction of nano-silicas is important and sufficient for achievement of technical result which consists in the increase of the bulk density of nano-silica and the decrease of dust formation and preservation the adsorptive properties of nano-silica.
  • the bulk density was determined by volumetric method. For that purpose 25 ml of silica (after it has been dried out) was put into the 100 ml glass graduated in 25 and 50 ml, and weighted by using electronic scales with relative mean errors ⁇ 0,01 mg at 290 K.
  • NMR-spectroscopy The NMR spectra were recorded using a NMR spectrometer of high- resolution Varian Mercury (operating frequency 400 MHz). The 90° probe pulse with a duration of 3 and bandwidth of 20 khz was used. The temperature was controlled by Bruker VT-1000 device with relative mean errors ⁇ 1 K. The intensity of signals was determined by measurement of area of peaks in the assumption of their Gaussian shape with relative mean errors ⁇ 10%. To prevent super-cooling of water in the studied objects, the measurements of the concentration of unfrozen water were carried out on heating of samples preliminarily cooled to 210 K.
  • Interfacial energy of water on the boundary with solid particles or in its aqueous solutions was determined as the module of total decrease of water free energy, conditional upon the presence of the phase boundary [Gun'ko V.M., Turov V.V., Gorbyk P.P. Water on Interface. Kyiv. Naukova Dumka - 2009. - 694 p.; Gun'ko V.M., Turov V.V. Nuclear Magnetic Resonance Studies of Interfacial Phenomena. - New York: Taylor & Francis, 2013. - 1040 p.; Turov V.V., Gun'ko V.M. Clustered water and its application. - Kyiv: Naukova Dumka, 2011.
  • the samples of nano-silicas weighing 0,2 g were dispersed and shook over a period of 1 hour together with 25 ml 0,6 % wt of gelatin succeeded by the settling of the sorbent in centrifuge and determination of the adsorbate equilibrium concentration in centrifugate.
  • the adsorption value was calculated as the difference between the initial and equilibrium concentration - mass of silica in the sample ratio.
  • the supernatant fluid was collected and the amount of gelatin was determined by using the biuret reaction. This method is based on the formation of a biuret complex of protein peptide bonds with bivalent copper ions.
  • biuret reagent consisting of KOH, CuSQ-i and sodium citrate was used.
  • copper is bound to four nitrogens by the coordination bonds, and to two oxygens by the electrostatic interactions.
  • the full complex is formed only with peptides consisting of more than 4 residues.
  • the equilibrium concentration was determined by the colorimetric method by using KFK-2MP device [The Ukranian State Pharmacopoeia / SE «Scientific and Expert Pharmacopoeial center».— 1 ed.— Kharkov: RIREG, 2001.— Add. 1.— 2004.— 520 p.; FC42U-82/224-889-00 Si ks].
  • optical density of the solution was determined under the wavelength of 540 nm in 10 mm basin in 30 minutes after the probe selection. Simultaneously, the optical density of the received solution was determined by using the spectrophotometer Specord M-40 (Karl Zeiss Iena, Germany) under the wavelength of 560 nm in 10 mm basin.
  • Fig. 1 SEM micrograph of the nano-silica A-300 with the bulk density of 45 mg/ml .
  • Fig. 2 The dependency of bulk density of the dry nano-silica A-300 powder on the degree of its wetness.
  • Fig.5. The dependency of the maximum gelatin adsorption value on the concentration of water used for the hydraulic compaction of nano-silica in accordance with FEK (1 ) and spectrophotometer (2) data.
  • Fig. 7 Reactor equipped with a stirring mechanism and a water pulverization device, which includes a water injection system and a sprayer.
  • Example 3 The compaction of nano-silica was performed similarly to the example 1.
  • the correlation watennano-silica was 3 : 1.
  • Example 4 The compaction of nano-silica was performed similarly to the example 1.
  • the correlation watennano-silica was 4: 1.
  • Example 5 The compaction of nano-silica was performed similarly to the example 1.
  • the correlation water :nano-silica was 5: 1.
  • Example 6 (by the prototype).
  • 3,5 kg of silica dioxide were delivered by applying the rotating auger (40 rotations per minute) to the surface of the filter "Siperm" with pores of 20 ⁇ , which has the tube form (length 2000 mm, diameter 303 mm) and is situated in a closed chamber, then the vacuum pump was switched on to create the pressure of 840 mbar ; the product was unloaded by applying the rotating auger through the cross outlet.
  • Nanosilica leads to the loss in the flowability of the powder and the increase in the energy consumption while drying without changing the bulk density.
  • Nano-silica, compacted by the claimed method is characterized by the bulk density of 175-250 g/1, reduced dust formation while preserving the physico-chemical properties of the initial un-compacted product.
  • the textural porosity of nanosilica is conditional upon the pore spaces between nanoparticles in aggregates (nanopores of the radius R ⁇ 1 nm and mesopores of the radius 1 ⁇ R ⁇ 25 nm) and hollownesses between aggregates in agglomerates (macropores of the radius R > 25 nm).
  • Fig. 2 Bulk density of nanosilica dependance on the degree of its wetness diagram is given in Fig. 2 which shows that with a rise of wetness the bulk density increases monotonically and reaches its maximum of 250 g/1, which is roughly 5 times higher than the bulk density of the initial silica.
  • thermodynamic characteristics of the bound water for silica samples with different bulk densities is listed in the table 2, in which the values of the amount of strongly and weakly bound water (Cuw s and C m v respectively), maximal decrease of the Gibbs free in the layer of bound water (Ag" 1 "*) and value of interfacial energy (ys) are given.
  • the interfacial energy which characterizes the total interaction between silica and aqueous medium, is within the range from 1 1 to 15 J/g, which affirms a relatively weak change in the structure of aggregates of silica in the process of its hydraulic compaction.
  • IR-spectra of the nanosilica A-300 samples with different amounts of water, which was used for the hydraulic compaction, are given in Fig. 6 a,b.
  • the dependence of the signal intensity of free OH-groups (calculated in accordance with the peak area) on the amount of wetting liquid (C(H 2 0)) is given in Fig. 6c.
  • the hydraulic compaction of amorphous nano-silicas allows to increase the bulk density from 0.05 to 0.25 g/ml without considerable loss of protein holding adsorption capacity.
  • the further growth of the amount of wetting water may reduce the adsorption capacity to 25% of the initial.
  • the process of compaction goes along with some changes in the radial distributions of adsorbed on the silica surface water polyassociates (nanodrops), consisting in the growth of contribution from nanodrops of the radius 0.6-2 nm.
  • the protein adsorptive capacity of the nano-silica A-300 in relation to gelatin decreases with the increase of the bulk density no more than by 30%, which allows to actively use the compacted forms of silica as enterosorbents and carriers of medications.

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

Abstract

La présente invention concerne un procédé de compaction de nano-silice comprenant les étapes suivantes : charge de la nano-silice dans le réacteur avec un mécanisme d'agitation et un dispositif de pulvérisation d'eau, alimentation d'une quantité appropriée d'eau sous la pression de 0,5 à 1 atm, le rapport en masse de l'eau et de la nano-silice étant de 2:1 à 5:1, agitation du mélange de manière continue et intensive, en le laissant pour équilibrage, séchage à 450 K et tamisage. La nano-silice compactée obtenue est caractérisée par une densité en vrac supérieure et conserve ses caractéristiques d'adsorption.
PCT/IB2016/050193 2016-01-15 2016-01-15 Procédé de compaction de nano-silice WO2017122049A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2414478A1 (de) * 1974-03-26 1975-10-02 Degussa Verfahren zur herstellung aerogelartiger strukturierter kieselsaeuren
US4326852A (en) 1978-10-12 1982-04-27 Wacker-Chemie Gmbh Method for increasing the bulk weight of silicon dioxide
GB2329893A (en) * 1997-10-02 1999-04-07 Samsung Electronics Co Ltd Sol-gel method of manufacturing a silica glass article from silica with two particle sizes
EP1316589A2 (fr) * 2001-11-30 2003-06-04 Shin-Etsu Chemical Co., Ltd. Poudre fine de silice hydrophobe et sa préparation
JP2003192331A (ja) * 2001-12-26 2003-07-09 Shin Etsu Chem Co Ltd 親水性シリカ微粉末及びその製造方法
EP1813574A1 (fr) * 2006-01-25 2007-08-01 Degussa GmbH Silice pyrogénée sous forme d'écaille
WO2009015967A2 (fr) 2007-07-31 2009-02-05 Evonik Degussa Gmbh Procédés de compression d'oxydes préparés par voie pyrogénique
DE102012211121A1 (de) * 2012-06-28 2014-01-02 Evonik Industries Ag Granuläre, funktionalisierte Kieselsäure, Verfahren zu deren Herstellung und deren Verwendung

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2414478A1 (de) * 1974-03-26 1975-10-02 Degussa Verfahren zur herstellung aerogelartiger strukturierter kieselsaeuren
US4326852A (en) 1978-10-12 1982-04-27 Wacker-Chemie Gmbh Method for increasing the bulk weight of silicon dioxide
GB2329893A (en) * 1997-10-02 1999-04-07 Samsung Electronics Co Ltd Sol-gel method of manufacturing a silica glass article from silica with two particle sizes
EP1316589A2 (fr) * 2001-11-30 2003-06-04 Shin-Etsu Chemical Co., Ltd. Poudre fine de silice hydrophobe et sa préparation
JP2003192331A (ja) * 2001-12-26 2003-07-09 Shin Etsu Chem Co Ltd 親水性シリカ微粉末及びその製造方法
EP1813574A1 (fr) * 2006-01-25 2007-08-01 Degussa GmbH Silice pyrogénée sous forme d'écaille
WO2009015967A2 (fr) 2007-07-31 2009-02-05 Evonik Degussa Gmbh Procédés de compression d'oxydes préparés par voie pyrogénique
DE102012211121A1 (de) * 2012-06-28 2014-01-02 Evonik Industries Ag Granuläre, funktionalisierte Kieselsäure, Verfahren zu deren Herstellung und deren Verwendung

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