WO2016186455A1 - Procédé et appareil de purification de nanodiamant à l'aide d'un lit fluidisé par un milieu - Google Patents

Procédé et appareil de purification de nanodiamant à l'aide d'un lit fluidisé par un milieu Download PDF

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Publication number
WO2016186455A1
WO2016186455A1 PCT/KR2016/005279 KR2016005279W WO2016186455A1 WO 2016186455 A1 WO2016186455 A1 WO 2016186455A1 KR 2016005279 W KR2016005279 W KR 2016005279W WO 2016186455 A1 WO2016186455 A1 WO 2016186455A1
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WIPO (PCT)
Prior art keywords
nanodiamond
fluidized bed
bed reactor
oxidizing gas
aggregates
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PCT/KR2016/005279
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English (en)
Korean (ko)
Inventor
이동현
정승우
권명택
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나노리소스 주식회사
성균관대학교산학협력단
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Publication of WO2016186455A1 publication Critical patent/WO2016186455A1/fr

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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
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/16—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by suspending the powder material in a gas, e.g. in fluidised beds or as a falling curtain
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles

Definitions

  • the present invention relates to a nanodiamond purification method and apparatus using a medium fluidized bed. More specifically, the present invention relates to a nanodiamond purification method and apparatus for selectively removing a graphite layer by fluidizing raw nanodiamond aggregates formed by an explosion method.
  • DND Detonation Nano Diamond
  • SWCNT single wall
  • DWCNT double wall
  • MWCNT multiwall carbon nanotubes
  • DND occurs instantaneously when an explosive substance reacts with a mixture of explosive trinitrotoluene (TNT) and white crystalline non-aqueous explosive (RDX), at a certain ratio, for example, in the tens percent by weight.
  • TNT explosive trinitrotoluene
  • RDX white crystalline non-aqueous explosive
  • the carbon component of the composition generates nuclei (carbon SP3 structure) of diamond crystal phase, and the nucleus grows to a certain size.
  • DND has little toxicity in vivo and is biocompatible due to the stability of the structure, and has a very small particle diameter of several nm in size and a specific surface area of 250 m 2 / g to 450 m 2 / g, which is usually about tens of times higher than that of diamond. It is known to exhibit unique electrical, chemical and optical characteristics, such as being several hundred times larger and including a large number of hydrophilic functional groups on its surface. In particular, recently, researches for attaching a functional group to a surface to have a biomedical function or to attach a useful substance having an anti-biomedical function have been in the spotlight as a drug delivery material. For this purpose, high purity and uniform nanodiamonds are essential.
  • DND has a very short explosion process and contraction occurs at the same time, which makes it difficult to separate single or several particle clusters due to the strong aggregation of single diamond particles. Impurities contained in were also difficult to purify.
  • the raw nanodiamond obtained by the explosion reaction in the reaction chamber contains not only diamond particles but also metals, metal oxides and other impurities.
  • chemicals are used to remove impurities by the wet method, but the wet method is not environmentally friendly and requires a high processing cost.
  • U.S. Patent No. 8,940,267 discloses a method for purifying raw nanodiamonds in a liquid phase, and Japanese Patent Application JP 2006-273704 uses a mechanical method.
  • US Patent Publication No. US2010 / 0028675 uses a method of heating nanodiamonds at 375 to 630 ° C. under the presence of oxygen gas.
  • the method disclosed in the U.S. Patent Application has a problem that it is difficult to purify a large amount of nanodiamonds with a uniform quality because it is simply heated in air.
  • the present invention is to provide a method for securing a uniform oxidation temperature to purify the nanodiamonds to a uniform quality.
  • the present invention provides a method for selectively removing amorphous carbon and other impurities including graphite layers present on the surface of nanodiamond aggregates.
  • the present invention is to provide a method for reducing the purification time and temperature of the raw nanodiamond aggregates.
  • It relates to a nanodiamond purification method using a medium fluidized bed comprising separating and recovering the gas discharged to the top of the fluidized bed reactor and the nanodiamond aggregates.
  • a fluidized bed reactor formed on the oxidizing gas and flowing media particles and raw material nanodiamond aggregates to the oxidizing gas introduced from the oxidizing gas supply unit;
  • a raw material supply unit supplying raw nanodiamond aggregates to the fluidized bed reactor
  • nanodiamond purification device including a separation unit for separating the gas and the nanodiamond aggregates are connected to the fluidized bed reactor upper side.
  • the method and apparatus of the present invention use a fluidized bed reactor, it is possible to ensure a uniform oxidation temperature and to improve the contact efficiency between the oxidizing gas and the raw material nanodiamond aggregates.
  • the present invention can increase the mixing and contact efficiency by using a fluid medium such as diamond, it is possible to remove impurities such as graphite layer more quickly.
  • Figure 2 shows a nanodiamond purification apparatus using a medium fluidized bed according to an embodiment of the present invention.
  • FIG 3 shows a nanodiamond purification apparatus using a fluidized bed according to another embodiment of the present invention.
  • FIG. 4 shows a nanodiamond purification apparatus using a medium fluidized bed according to another embodiment of the present invention.
  • the present invention relates to a nanodiamond purification method and apparatus using a medium fluidized bed.
  • FIG. 1 shows the structure of nanodiamond aggregates formed by explosion.
  • Figure 2 shows a nanodiamond purification apparatus using a medium fluidized bed according to an embodiment of the present invention.
  • a graphite layer (sp2 structure) 20 forms a shell along the surface thereof.
  • the nanodiamond of the single particle shape 10 is typically formed by including a core 1 having a diamond crystal structure (SP3) and a graphite layer (sp2 structure, 2) surrounding it, the size of the core is 4 ⁇ 7nm
  • the graphite layer is about 1 nm.
  • the nanodiamond aggregate 100 includes a portion of amorphous carbon such as carbon, soot, coke, and graphene in addition to the graphite layer 20 on the surface.
  • amorphous carbon such as carbon, soot, coke, and graphene
  • the present invention describes only the graphite layer, which occupies most of the amorphous carbon formed on the surface of the nanodiamond aggregate, and does not remove carbon, soot, coke and other amorphous carbons and graphene by the method of the present invention. It is not impossible. That is, in the present invention, “graphite removal” is used to encompass that amorphous carbons and graphene that may be formed on the nanodiamond surface may also be removed.
  • Nanodiamond purification method and apparatus of the present invention is a method and apparatus for separating and removing the graphite layer 20 surrounding the nanodiamond aggregate (100).
  • the present invention oxidizes the graphite layer 20 by fluidizing the nanodiamond aggregates 100.
  • the nanodiamond purification method of the present invention includes a feeding step, a fluidization step and a separation recovery step.
  • the nanodiamond purification method of the present invention can use the apparatus of FIG. 2 comprising a fluidized bed reactor.
  • the nanodiamond purification apparatus of the present invention includes an oxidizing gas supply unit 10, a fluidized bed reactor 20, a raw material supply unit 30, and a separation unit 40.
  • the feeding step is to inject the oxidizing gas and the raw material nanodiamond aggregates 31 into the fluidized bed reactor 20.
  • the oxidizing gas may be supplied to the oxidizing gas supply unit 10 and the raw material nanodiamond aggregates 31 through the raw material supply unit 30.
  • oxidizing gas air, oxygen, water vapor, or the like may be used.
  • the fluidization step is a step of flowing the media particles and the nanodiamond aggregates into the oxidizing gas in the fluidized bed reactor (20).
  • the fluidization step is an oxidation reaction between the oxidizing gas and the graphite layer surrounding the nanodiamond aggregates.
  • the oxidation reaction in the fluidized bed reactor takes place as follows.
  • Carbon monoxide (CO) may also be generated in the oxidation reaction.
  • the flow rate of the oxidizing gas in the fluidized bed, the reaction temperature, etc. may be appropriately adjusted according to the size, content, and the like of the nanodiamond injected.
  • the oxidation reaction can be carried out in the range of 200 ⁇ 650 °C, the flow rate of the oxidizing gas can be varied depending on the size and processing speed of the media particles.
  • the surface of the nanodiamond aggregate is a carbon material having a graphite (sp2) structure.
  • the nanodiamond aggregates are fluidized to efficiently perform oxidation reaction between the graphite layer and the oxidizing gas. That is, fluidization using a fluidized bed reactor rapidly mixes the nanodiamond aggregated particles so that a uniform temperature can be applied to the entirety of the reactor and consequently the surface of the nanodiamond aggregates flowing in the reactor. Since the contact efficiency with the oxidizing gas is improved, the reaction rate between the oxidizing gas and the graphite layer can also be increased. In addition, the use of a fluidization reactor allows large-scale oxidation reactions that can be mass produced.
  • the present invention can more efficiently perform the oxidation reaction of the nanodiamond aggregates using the media particles 60 in the fluidization step.
  • the media particles may correspond to Geldart A or B particles and may be particles which are no longer oxidized in the above temperature range.
  • the media particles may be any material that does not have a chemical reaction at high temperatures such as diamond, SiO 2, TiO 2, zirconia, steel balls, and the like and has good wear resistance.
  • the size of the media particles may be larger than the size of the raw material nanodiamond aggregates.
  • the fluidized bed reactor 20 is composed of a medium fluidized bed 21 in which most of the media particles flow and a lean layer 22 in which the media solid is present in a very small amount.
  • media particles and the nanodiamond aggregates are suspended by the oxidizing gas flow rate to form a fluidized bed.
  • the present invention uses media particles larger in size than the nanodiamond aggregates, wherein the media particles and the nanoparticles are bonded to each other by van der Waals forces and flow together. Referring to FIG. 1, it is conceptually shown that the nanodiamond aggregate 31 is wrapped around the media particle 60.
  • the fluidization step may be mainly carried out in the medium fluidized bed 21 of the fluidized bed reactor 20.
  • the flow rate of the oxidizing gas in the medium fluidized bed, the reaction temperature, etc. may be appropriately adjusted according to the size, content, etc. of the raw nanodiamond and the medium particles to be injected.
  • the present invention improves heat transfer and mass transfer between the media particles in the fluidized bed and aggregates including nanodiamonds, thereby effectively oxidizing the graphite layer and graphene attached to the surface of the nanodiamonds to be removed in the gas phase with carbon dioxide or carbon monoxide.
  • the separation recovery step is a step of separating and recovering the nanodiamond aggregates from which gas and graphite discharged to the fluidized bed reactor are removed.
  • Separation recovery step may use the cyclone 40 as the separation unit 40, and may further use a water trap (70). Cyclones can be used to capture unreacted nanodiamond aggregates or media particles, and purified nanodiamond aggregates can also be collected according to particle size.
  • the water trap 70 is capable of separating from the gas the purified nanodiamond aggregates having a particle size of 100 nm or less in sun nano. That is, when the gas containing the nanodiamond aggregates passes through the water trap, the nanodiamond aggregates may be dispersed in the water, and the gas may be discharged upward.
  • the method may increase the fluidity of the medium and the nanodiamond aggregates by vibrating the fluidized bed reactor.
  • the fluidity of the media particles having a relatively large particle size may be further increased, and thus the fluidity of the nanodiamond aggregates may be increased.
  • the vibration is periodically applied to the entire fluidized bed, even when the size of the medium particles is large, the minimum fluidization rate of the particles can be lowered.
  • the method may vibrate the fluidized bed reactor by adding a vibrator 80 to the bottom outer surface of the fluidized bed reactor.
  • the vibrator 80 is shown in FIG. 3.
  • the intensity of the vibration applied to the vibrator 80 may be appropriately controlled according to the size of the refining apparatus or the size, density of particles to be injected.
  • the vibration unit may apply a vibration of 0.01 ⁇ 100 Hz to the purification apparatus.
  • the method may increase the fluidity of the medium by additionally supplying air to the bottom of the fluidized bed reactor periodically (pulsed-air). Further supply of air may use the air supply unit 90, as shown in FIG.
  • the method of the present invention can periodically inject air into the medium fluidized bed 21 in a pulsed manner to eliminate channeling phenomenon and the like.
  • the fluidity of the media particles can be increased, and the amount of oxidizing gas per unit time can be reduced. Therefore, supplying air in pulses improves the fluidity of the media particles and effectively purifies the nanodiamonds from the fluidized bed.
  • the present invention provides a nanodiamond purification device.
  • the purification apparatus of the present invention includes an oxidizing gas supply unit 10, a fluidized bed reactor 20, a raw material supply unit 30, and a separation unit 40.
  • the oxidizing gas supply unit 10 supplies the oxidizing gas into the purification apparatus.
  • the fluidized bed reactor 20 is formed on the oxidizing gas and flows media particles and raw nanodiamond aggregates to the oxidizing gas introduced from the oxidizing gas supply unit.
  • the purification apparatus includes a dispersion plate 50 located between the oxidizing gas supply unit 10 and the fluidized bed reactor 20.
  • the oxidizing gas is supplied from an external source and provided at a constant flow rate to the fluidized bed reactor 20 through the dispersion plate 50.
  • the dispersion plate may be a bubble cap type dispersion plate.
  • the raw material supply unit 30 supplies the raw material nanodiamond aggregates to the fluidized bed reactor.
  • the separation unit is connected to the fluidized bed reactor upper side to separate the discharged gas and the nanodiamond aggregates.
  • the separator may use a cyclone 40 and may additionally use a water trap 70.
  • cyclones can be used to capture unreacted nanodiamond aggregates or media particles, and purified nanodiamond aggregates can also be collected according to particle size.
  • the cyclone 40 and the water trap 70 may be referred to the above description.
  • the fluidized bed reactor 20 may be an oxidation reactor in which the oxidizing gas and the graphite layer surrounding the nanodiamond aggregates react.
  • Oxidation reaction in the fluidized bed reactor can be referred to the above-described details.
  • the apparatus of the present invention can more efficiently perform the oxidation reaction of the nanodiamond aggregates by flowing the media particles inside the fluidized bed reactor.
  • the above-mentioned contents may also be referred to the media particles and the media fluidized layer.
  • FIG. 2 is a device in which a vibrator 80 is added to the device of FIG. 1.
  • the apparatus of the present invention may further include a vibrator 80 at the bottom or the side of the oxidizing gas supply part of FIG. 1.
  • the vibrator 80 may increase fluidity of media particles having a relatively large particle size.
  • the intensity of the vibration applied to the vibrator 80 may be appropriately controlled according to the size of the refining apparatus or the size, density of particles to be injected.
  • the vibration unit may apply a vibration of 0.01 ⁇ 100 Hz to the purification apparatus.
  • the apparatus of the present invention may further include an air supply unit 80 that may periodically supply air to the oxidizing gas supply unit of FIG. 1.
  • Purification apparatus of the present invention can prevent the occurrence of abnormal operation by periodically injecting air into the medium fluidized bed 21 through the air supply unit (90).
  • the present invention can be used as a drug carrier by purifying the explosive nanodiamond.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)

Abstract

La présente invention concerne un procédé et un appareil de purification de nanodiamant, un agrégat de nanodiamant brut formé par un procédé d'explosion étant fluidisé pour éliminer sélectivement une couche de graphite (carbone amorphe). Le procédé et l'appareil de la présente invention utilisent un réacteur à lit fluidisé, ce qui permet d'assurer une température d'oxydation uniforme et d'augmenter l'efficacité de contact entre gaz oxydé et l'agrégat de nanodiamant brut. En outre, la présente invention peut augmenter les efficacités de mélange et de contact à l'aide d'un milieu fluidisé, tel que du diamant, permettant ainsi d'éliminer les impuretés, telles que la couche de graphite, plus rapidement.
PCT/KR2016/005279 2015-05-18 2016-05-18 Procédé et appareil de purification de nanodiamant à l'aide d'un lit fluidisé par un milieu WO2016186455A1 (fr)

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KR10-2015-0068953 2015-05-18
KR1020150068953A KR102329003B1 (ko) 2015-05-18 2015-05-18 매체유동층을 이용한 나노다이아몬드 정제 방법 및 장치

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JP2020089864A (ja) * 2018-12-07 2020-06-11 株式会社ダイセル ナノダイヤモンドの製造方法及びナノダイヤモンド

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RU2019502C1 (ru) * 1991-01-09 1994-09-15 Евгений Валерьевич Павлов Способ удаления примеси неалмазного углерода и устройство для его осуществления
US20100069567A1 (en) * 2007-05-21 2010-03-18 Igor Leonidovich Petrov Nanodiamond material, method and device for purifying and modifying a nanodiamond

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JP3546494B2 (ja) * 1994-10-27 2004-07-28 信越化学工業株式会社 微細シリカの精製法
KR100920145B1 (ko) * 2009-01-16 2009-10-08 권원현 응집 카본나노튜브 분말의 기계적 입자분리 방법 및 그로부터 구성되는 카본나노튜브 분말
KR101121852B1 (ko) * 2010-06-28 2012-03-21 현대제철 주식회사 용선 예비처리 부산물의 흑연 회수방법

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RU2019502C1 (ru) * 1991-01-09 1994-09-15 Евгений Валерьевич Павлов Способ удаления примеси неалмазного углерода и устройство для его осуществления
US20100069567A1 (en) * 2007-05-21 2010-03-18 Igor Leonidovich Petrov Nanodiamond material, method and device for purifying and modifying a nanodiamond

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PETROV, I. ET AL.: "Detonation Nanodiamonds Simultaneously Purified and Modified by Gas Treatment", DIAMOND & RELATED MATERIALS, vol. 16, no. 12, 2007, pages 2098 - 2103, XP022354283 *
SCHRAND, AMANDA M. ET AL.: "Nanodiamond Particles: Properties and Perspectives for Bioapplications", CRITICAL REVIEWS IN SOLID STATE AND MATERIALS SCIENCES, vol. 34, no. 1-2, 2009, pages 18 - 74, XP055064590 *

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KR20160135901A (ko) 2016-11-29

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