WO2016140443A1 - Catalyseur produit à l'aide de technique de coprécipitation par synthèse hydrothermique, et nanotube de carbone fabriqué à l'aide de ce dernier - Google Patents

Catalyseur produit à l'aide de technique de coprécipitation par synthèse hydrothermique, et nanotube de carbone fabriqué à l'aide de ce dernier Download PDF

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WO2016140443A1
WO2016140443A1 PCT/KR2016/001262 KR2016001262W WO2016140443A1 WO 2016140443 A1 WO2016140443 A1 WO 2016140443A1 KR 2016001262 W KR2016001262 W KR 2016001262W WO 2016140443 A1 WO2016140443 A1 WO 2016140443A1
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catalyst
coprecipitation
producing
precipitation
carbon nanotubes
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Korean (ko)
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강경연
조동현
김성진
우지희
이승용
차진명
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주식회사 엘지화학
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Priority to CN201680000716.9A priority Critical patent/CN106132537B/zh
Publication of WO2016140443A1 publication Critical patent/WO2016140443A1/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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/32—Specific surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/34—Length
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/36—Diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • C01P2006/10—Solid density

Definitions

  • the present invention relates to a catalyst using a hydrothermal synthesis coprecipitation method and a carbon nanotube obtained therefrom, which can produce a low diameter carbon nanotube without a sintering step and can shorten the production time and a carbon nanotube obtained therefrom. It is about.
  • carbon nanotubes are cylindrical carbon tubes having a diameter of about 3 to 150 nm, specifically about 3 to 100 nm, and having a length several times the diameter, for example, 100 times or more. Refers to. These CNTs consist of layers of aligned carbon atoms and have different types of cores. Such CNTs are also called, for example, carbon fibrils or hollow carbon fibers.
  • CNTs are of industrial importance in the manufacture of composites due to their excellent electrical and conductivity and physical strength, and have high utility in the field of electronic materials, energy materials and many other fields.
  • CNTs do not exist as strands, but as CNTs grow through the reduction of metals based on high van der Waals interactions and catalyst supports due to nanometer-level small diameters, CNTs form aggregates around the support.
  • CNTs in order to express excellent properties of CNTs, it is necessary to disperse the strands of CNTs, and the biggest obstacle to the current CNT-related applications is the dispersion of CNTs.
  • the dispersibility of CNTs is related to the structure of aggregates of CNTs.
  • the structure of aggregates is largely divided into entangle type and bundle type.
  • the entangled form has a high bulk density with CNTs twisted without orientation and having a spherical or potato shape.
  • the entangled type can produce high yield CNTs and can be produced with low cost CNTs due to its simple fluidized bed process, while the CNTs are severely twisted and thus have poor dispersion.
  • the CNTs have a directivity to form an aggregate and have a pupa form or a rod form, and have a low bulk density.
  • low CNT productivity is low due to low bulk density, and inexpensive CNT production is difficult due to unstable process conditions.
  • the remaining length of CNTs is long, so the CNTs have excellent characteristics when used as conductive additives in polymers.
  • CNTs Another important property of CNTs is the diameter and length of the CNTs. In order to have a high effect on the product, the diameter of the CNTs must be small. This is advantageous for the formation of a one-dimensional strand network because the number of CNT strands per mass of CNTs is large, and the contact area with a matrix of a polymer or a metal is larger, which results in a higher CNT effect.
  • the length of CNT the residual length after CNT dispersion in a polymer of CNT polymer or metal is important. The longer the length of CNT, the longer the residual length after CNT dispersion.
  • CNTs are advantageous in that the CNTs have small diameters and long lengths in the form of uniform bundles.
  • the present invention to solve the above problems,
  • Separating and drying the slurry provides a method for producing a catalyst comprising a.
  • the present invention to solve the other problem
  • the present invention to solve the above another problem
  • It provides a method of producing a CNT comprising a; growing the CNT through decomposition of the carbon source on the surface of the supported catalyst.
  • the present invention provides a CNT obtained by the production method.
  • the method of preparing the catalyst using the hydrothermal synthesis method according to the present invention does not include a calcination step, and thus is useful for the preparation of low-diameter CNTs.
  • a uniform bundle is formed by controlling CNT reaction conditions and the like, and the CNTs have a small diameter and a long length. It is possible to get In addition, it can be manufactured in a short time to provide the effect of improved economic efficiency.
  • FIG. 4 to 7 show SEM images of the coprecipitation catalyst obtained in Example 1.
  • FIG. 8 to 11 show SEM images of the coprecipitation catalyst obtained in Example 2.
  • FIG. 17 to 19 show SEM images of CNTs obtained in Example 4.
  • the aggregate form of the CNTs is determined according to the bulk form of the catalyst.
  • the CNTs have a plate-like catalyst structure, the CNTs grow in a direction perpendicular to the plate to form a bundle of CNTs. It is therefore an object of the present invention to provide a catalyst for the production of bundled CNTs having a well-defined plate shape.
  • a method for preparing a catalyst for producing CNTs is known in various ways, but in the case of using chemical vapor deposition, coprecipitation and impregnation are representatively known.
  • the impregnation method refers to a method of obtaining a catalyst precursor in powder form by mixing a metal salt aqueous solution with a support that can be used as a support having micropores, followed by filtration or spray drying.
  • the catalyst precursor in powder form obtained by the impregnation method is also obtained as a catalyst for producing CNT through thermal oxidation or reduction.
  • the coprecipitation method dissolves the metal salt in an aqueous solution state, and induces precipitation between the metal salts by various changes such as pH or temperature, and the precipitate obtained is subjected to filtration drying or spray drying to obtain a catalyst precursor in powder form. Tell how to get.
  • the catalyst precursor in powder form thus obtained is obtained as a catalyst for producing CNTs through a process such as thermal oxidation or reduction.
  • the primary particle form of the coprecipitation catalyst varies according to the type of the coprecipitation agent, and when the coprecipitation agent is, for example, sodium hydroxide, a precipitate is formed due to rapid pH change. Form agglomerates of, and have a plate-like form when, for example, urea is used as a coprecipitation agent.
  • the catalyst according to one aspect of the present invention may be prepared by the following method using hydrothermal synthesis coprecipitation method:
  • the method of preparing the coprecipitation catalyst according to the present invention is characterized by using a hydrothermal synthesis coprecipitation method, unlike the conventional coprecipitation method. That is, in the conventional coprecipitation method, a step of forming a slurry-like precipitate by heating a metal aqueous solution and then adding a coprecipitation agent, in the present invention, a coprecipitation agent is simultaneously added to an aqueous solvent together with a metal component serving as a catalyst. After that, it is heated at a higher temperature to form a slurry-like precipitate.
  • the hydrothermal coprecipitation process is a coprecipitation-containing metal aqueous solution at a temperature of 120 °C to 200 °C, or 120 °C to 180 °C about 1 hour to about 10 hours, or about 1 hour to It is made by heating for about 5 hours, or about 2 to 4 hours, it is possible to form a more efficient coprecipitation catalyst for the production of CNT in the above range, if the reaction time is too long the thickness of the catalyst increases There is a fear that the number of catalysts produced is reduced, and if too short, sufficient catalyst yield cannot be obtained.
  • the coprecipitation agent used in the coprecipitation catalyst can be used without limitation as long as it is used in the art, for example, ammonium hydroxide (NH 4 OH), ammonium carbonate ((NH 4 ) 2 CO 3 ), ammonium bicarbonate (NH 4 HCO 3 ), Urea, etc. can be used 1 or more types, Preferably, urea can be used. By these, coprecipitation of the metal salt can be induced.
  • the coprecipitation may be performed batchwise or continuously. It is also possible to add surface-active substances, for example ionic or nonionic emulsifiers or carboxylic acids, for improving the coprecipitation properties and for surface modification of the catalysts produced.
  • surface-active substances for example ionic or nonionic emulsifiers or carboxylic acids
  • the coprecipitation-containing metal salt aqueous solution may be formed by adding a coprecipitation agent and a metal salt to an aqueous solvent, wherein the aqueous solvent may include water or a mixed solvent of water and a lower alcohol. Water is preferable as the aqueous solvent.
  • a metal salt of the catalyst component and a metal salt of the active component can be used, and examples of the form of acetate, nitrate, halide (for example chloride or bromide) or other soluble compounds.
  • At least one selected from iron (Fe), nickel (Ni), cobalt (Co), and the like may be used, and iron and cobalt are preferable. They remain in the co-precipitation catalyst to serve as the main catalyst.
  • At least one or more selected from magnesium (Mg), aluminum (Al), molybdenum (Mo), manganese (Mn), chromium (Cr), vanadium (V) and the like may be used, and aluminum and magnesium are preferable. . They serve as carriers and promoters.
  • the catalyst component and the active ingredient may be used in a weight ratio of 1 to 0.5 to 10, and can exhibit better CNT production activity in this content range.
  • the metal salts of the catalyst component and the active ingredient are not limited thereto, and the precursor concentration may be included in an amount of 0.05 g / ml to 0.5 g / ml in the aqueous metal solution.
  • the co-precipitation agent may be used in the range of about 0.3 to 2 equivalents relative to the content of the metal element in the co-precipitation-containing metal aqueous solution. In such a range, sufficient co-precipitation can be induced.
  • the co-precipitation-containing metal aqueous solution as described above may be hydrothermally synthesized coprecipitation treatment to obtain a co-precipitated slurry, which is separated and dried to prepare a co-precipitation catalyst.
  • the separation process of the slurry can be separated by known methods, such as filtration, centrifugation, evaporation and concentration, of which centrifugation and filtration processes are preferred.
  • the separated coprecipitation catalyst may be further washed or used as is in a separated state.
  • the step of drying it After the drying process, the step of pulverizing the dry matter into smaller particles may also be included.
  • the coprecipitation catalyst obtained by the above production method may further include a conditioning step if necessary.
  • a conditioning process is intended to improve catalytic properties, and may include, in addition to firing and heat treatment, steam treatment.
  • the coprecipitation catalyst obtained in the above process may be heat treated at a temperature of 300 ° C to 1200 ° C and an oxidizing atmosphere. This conditioning process may be performed before or after shaping and / or grading the co-catalyst.
  • the coprecipitation catalyst obtained by the above production method may have various forms, for example, may have a plate-like structure.
  • the term "plate-like" means a small piece of planar structure with a predetermined thickness.
  • the co-catalyst of the plate structure may have a thickness of 1 to 20 nm
  • the plate diameter is generally 0.5 to 5 ⁇ m It may have a range of, and may have a somewhat irregular shape, for example, crushed square or circle shape. In the case of square or irregular shapes, the diameter means the diameter of the circumscribed circle.
  • the size of the plate-like structure shows a tendency to decrease, and thus the number of catalysts is increased so that the yield is used when the coprecipitation catalyst for CNT synthesis is used. It is possible to increase the specific surface area and to reduce the size of the bundle shape.
  • Such a coprecipitation catalyst of the present invention can be used for the synthesis of carbon nanostructures, for example CNTs.
  • the process for preparing CNTs from the coprecipitation catalysts obtained by the above method includes, but is not limited to:
  • the reactor may be a fixed bed reactor or a fluidized bed reactor without limitation.
  • the reaction temperature of the reactor in the CNT manufacturing process may be used in the range of about 500 to 900 °C, or about 600 °C to 800 °C, it is preferable to use the range of about 600 °C to 700 °C in terms of CNT production yield. Can be. As shown in the following examples, as the reaction temperature increases, the yield of CNTs increases, and the specific surface area decreases, thereby increasing the diameter of the CNTs.
  • reaction time in the reactor in the CNT manufacturing process may be used in the range of 0.5 to 10 hours, or 1 hour to 5 hours.
  • the CNT specific surface area at reaction times of 1 to 2 hours is similar but decreases beyond 4 hours. Therefore, when the reaction time increases as the reaction temperature increases, coating of amorphous carbon occurs, which may increase the diameter of the CNT.
  • the CNT of the present invention obtained according to the manufacturing method may be, for example, a bundle type of bulk density of 10 to 50 kg / m 3 .
  • the term "bulk density” used in the present invention is defined by Equation 1 below, and as the coprecipitation catalyst produced by hydrothermal synthesis is used, the density distribution of CNTs grown therefrom may also have a specific range.
  • the CNT obtained by the above production method may have a particle size or an average particle diameter of 50 to 800 ⁇ m and a strand diameter of the CNTs of 1 to 50 nm.
  • the CNT of the present invention can be used as a raw material in the electric field, the electronic field, the energy field, etc., and can also be used as the reinforcing material in the plastic field.
  • the precipitate was stirred at a temperature of 80 ° C. for 18 hours. After completion of the reaction, the mixture was cooled to room temperature, and the obtained precipitate was filtered and dried in an oven at 120 ° C. for 24 hours to obtain a catalyst powder.
  • Comparative Example 1 NaHCO 3 was used instead of NaOH, and the coprecipitation catalyst was obtained by performing the same process as in Comparative Example 1 except that the heating temperature was changed from 80 ° C. to 110 ° C.
  • Comparative Example 1 a co-precipitation catalyst was carried out in the same manner as in Comparative Example 1 except that urea was used instead of NaOH such that the equivalent ratio was 0.87, and the heating temperature was changed from 80 ° C to 110 ° C. Obtained.
  • FIGS. 1 to 3 SEM images of the coprecipitation catalysts obtained in Comparative Examples 1 to 3 are shown in FIGS. 1 to 3, respectively.
  • the shape of the primary particles of the co-precipitation catalyst is different depending on the type of the co-precipitation agent. That is, when NaOH was used as a coprecipitation agent, it had a rounded aggregate shape, and in the case of urea, it showed a plate shape but did not show a perfect plate shape.
  • a coprecipitation catalyst was prepared in the same manner as in Example 1-1 (hydrothermal synthesis time 3 hours) except that the content of urea in Example 1-1 was variously changed as shown in Table 2 below. .
  • Example 2-1 0.47 Flower-like shape -
  • Example 2-2 0.63 Flower-like shape + plate > 3
  • Example 2-3 0.87 Plate 2 ⁇ 0.5
  • Example 2-4 1.11 Plate 1.3 ⁇ 0.3
  • Example 2-5 1.34 Plate 1.1 ⁇ 0.3
  • Example 2-6 1.66 Plate 1 ⁇ 0.3
  • FIGS. 8, 9, 10, and 11 SEM images of the coprecipitation catalysts obtained in Examples 2-1, 2-2, 2-3, and 2-5 are shown in FIGS. 8, 9, 10, and 11, respectively.
  • the amount of urea is 0.47
  • the catalyst is present in a plate-like agglomerate in a flower-like shape instead of an independent plate-like form.
  • 0.63 is a mixture of flower-like and independent plate shapes. Looking at the tendency of the size of the catalyst plate diameter according to the content of urea, it can be seen that as the content of the urea increases, the plate size of the co-precipitation catalyst decreases, thereby increasing the number of catalysts.
  • FIGS. 12, 13 and 14 SEM images of the CNTs obtained in Comparative Examples 4, 5 and 6 are shown in FIGS. 12, 13 and 14.
  • the CNT is manufactured using the coprecipitation catalysts obtained in Comparative Examples 1 to 3, the produced CNTs mostly have an entangled shape, and the coprecipitation catalysts obtained in Comparative Example 3 have some plate-like shapes. Therefore, it can be seen that the CNTs obtained therefrom are mixed in some bundle shapes.
  • Example 4-1 1.34 1.5 hours 15.8 267.0
  • Example 4-2 1.34 2 hours 23.3 297.0
  • Example 4-3 1.34 3 hours 27.2 320.0
  • Example 4-4 1.34 6 hours 15.5 295.0
  • Example 4-5 1.34 10 hours 14.1 284.6
  • Example 4-6 1.34 60 hours 5.2 120.0
  • the hydrothermal reaction time of the coprecipitation catalyst is preferably about 3 hours.
  • Example 4-1 0.63 19.6 230.5
  • Example 4-2 0.87 21.4 256.8
  • Example 4-3 1.34 27.2 320.0
  • Example 4-4 1.66 30.3 261.4

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Abstract

La présente invention concerne : un procédé de production d'un catalyseur à l'aide d'une technique de coprécipitation par synthèse hydrothermique, et un catalyseur pour la synthèse de nanotubes de carbone obtenus à l'aide de ce dernier ; et un procédé de production d'un catalyseur à l'aide d'une technique de coprécipitation par synthèse hydrothermique, qui peut produire des nanotubes de carbone ayant de petits diamètres, sans processus de calcination, et qui peut réduire le temps de production, et un catalyseur pour la synthèse de nanotubes de carbone obtenus à l'aide de ce dernier.
PCT/KR2016/001262 2015-03-04 2016-02-04 Catalyseur produit à l'aide de technique de coprécipitation par synthèse hydrothermique, et nanotube de carbone fabriqué à l'aide de ce dernier WO2016140443A1 (fr)

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CN108821267B (zh) * 2018-09-12 2021-09-07 芦露华 一种基于真菌制备石墨烯的方法
CN111495381A (zh) * 2019-01-31 2020-08-07 新奥石墨烯技术有限公司 一种片状催化剂的制备方法、片状催化剂及其在制备超细碳纳米管中的应用
KR102307637B1 (ko) * 2019-06-11 2021-09-30 전남대학교산학협력단 탄소나노튜브 번들 합성용 촉매의 제조 방법 및 이를 이용한 탄소나노튜브 번들의 제조 방법
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CN114229833B (zh) * 2020-09-09 2023-04-07 哈尔滨金纳科技有限公司 一种易分散、高导电碳纳米管材料的制备方法
CN113603548B (zh) * 2021-08-17 2022-11-04 华中农业大学 一种锰元素叶面喷施肥及制备方法
CN115155507B (zh) * 2022-07-07 2023-07-07 浙江大学 一种碳酸氧镁负载绿绣的纳米复合材料、制备方法及其应用
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