CN114524466A - Synthesis method of high-activity catalyst - Google Patents
Synthesis method of high-activity catalystDownload PDFInfo
- Publication number
- CN114524466A CN114524466ACN202210171373.XACN202210171373ACN114524466ACN 114524466 ACN114524466 ACN 114524466ACN 202210171373 ACN202210171373 ACN 202210171373ACN 114524466 ACN114524466 ACN 114524466A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carbon nanotubes
- edta
- solution
- temperature
- 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.)
- Granted
Links
Images
Classifications
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/80—Compounds containing cobalt, with or without oxygen or hydrogen, and containing one or more other elements
- C01G51/82—Compounds containing cobalt, with or without oxygen or hydrogen, and containing two or more other elements
- 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
- 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
- B01J21/10—Magnesium; 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
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
- 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
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
- B01J2523/22—Magnesium
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
- B01J2523/31—Aluminium
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
- B01J2523/68—Molybdenum
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/842—Iron
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/845—Cobalt
- 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
- C01B2202/30—Purity
- 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
- 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
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
Description
Translated fromChinese技术领域technical field
本发明涉及一种高活性催化剂的合成方法，属于催化剂技术领域。The invention relates to a method for synthesizing a high-activity catalyst, and belongs to the technical field of catalysts.
背景技术Background technique
近年来，碳纳米管作为优良的导电剂，已在新能源汽车锂电池等行业得到广泛应用。这是由于其具有优异的导热、导电性及较好的机械强度等优点。此外碳纳米管的一维结构可以增强活性材料的粘结的同时还可以改善极片的性能。因此被用于新能源电池方面有很大的应用前景。当前合成碳纳米管的方法主要有电弧放电法、热分解法、化学气相沉积法等。相较于其它制备方法，化学气相沉积法表现出较好的优越性，已实现大规模的工业化应用。这归因于采用此法碳纳米管的生长温度较低、易于调控及优化反应条件等优点。In recent years, carbon nanotubes have been widely used in industries such as lithium batteries for new energy vehicles as excellent conductive agents. This is due to its excellent thermal conductivity, electrical conductivity and good mechanical strength. In addition, the one-dimensional structure of carbon nanotubes can enhance the bonding of active materials and improve the performance of the pole pieces. Therefore, it has great application prospects for use in new energy batteries. The current methods for synthesizing carbon nanotubes mainly include arc discharge method, thermal decomposition method, chemical vapor deposition method, etc. Compared with other preparation methods, chemical vapor deposition method shows better advantages, and has achieved large-scale industrial application. This is attributed to the advantages of low growth temperature, easy control and optimized reaction conditions of carbon nanotubes using this method.
化学气相沉积法制备碳纳米管需要在催化剂的作用下完成，当前用于此法的催化剂主要有铁系催化剂及其他过渡金属催化剂，但是现有报道的催化剂存在合成碳纳米管的产率较低、制得的碳纳米管中金属残留较高，后续还需要酸洗提纯等过程，导致制备成本高昂的技术缺陷。The preparation of carbon nanotubes by chemical vapor deposition needs to be completed under the action of a catalyst. Currently, the catalysts used for this method mainly include iron-based catalysts and other transition metal catalysts, but the reported catalysts have low yields for synthesizing carbon nanotubes. , The metal residues in the prepared carbon nanotubes are relatively high, and subsequent processes such as acid washing and purification are required, resulting in the technical defect of high preparation cost.
发明内容SUMMARY OF THE INVENTION
[技术问题][technical problem]
现有报道的催化剂存在合成碳纳米管的产率较低、制得的碳纳米管中金属残留较高，后续还需要酸洗提纯等过程，导致制备成本高昂的技术缺陷。The catalysts reported in the prior art have the disadvantages of low yield of synthesizing carbon nanotubes, high metal residues in the prepared carbon nanotubes, and subsequent processes such as acid washing and purification, resulting in high production costs.
此外，现有报道合成的碳纳米管的长度较短，大多是5～30微米；而数百微米甚至毫米级长度的碳纳米管的报道很少，并且合成比较困难。In addition, the lengths of carbon nanotubes synthesized by existing reports are relatively short, mostly 5-30 micrometers; however, there are few reports on carbon nanotubes with lengths of hundreds of micrometers or even millimeters, and the synthesis is relatively difficult.
[技术方案][Technical solutions]
本发明的第一目的在于提供一种具有高活性的碳纳米管催化剂的制备方法，采用柠檬酸-乙二胺四乙酸络合法，所述方法包括如下步骤：The first object of the present invention is to provide a method for preparing a carbon nanotube catalyst with high activity, which adopts a citric acid-ethylenediaminetetraacetic acid complex method, and the method comprises the following steps:
(1)将金属前驱体盐、纯水、柠檬酸混合，制备得到混合溶液，然后向其中加入七钼酸铵，搅拌溶解，得到柠檬酸盐混合液；将所述柠檬酸盐混合液于水浴搅拌浓缩，冷却得到溶液A；其中，柠檬酸与金属前驱体盐的摩尔比为(1～1.5)：1；(1) mixing metal precursor salt, pure water and citric acid to prepare a mixed solution, then adding ammonium heptamolybdate thereto, stirring and dissolving to obtain a citrate mixed solution; the citrate mixed solution is placed in a water bath Stir and concentrate, and cool to obtain solution A; wherein, the molar ratio of citric acid to metal precursor salt is (1-1.5): 1;
(2)将EDTA溶解于氨水中，得到EDTA氨溶液；将溶液A与EDTA氨溶液混合，得到混合液B；然后，将混合液B置于敞口瓷元皿内，于马弗炉中500℃碳化30min；之后，于马弗炉中450℃焙烧240min，经过筛网过筛破碎形成粉末状催化剂；其中，EDTA与金属前驱体盐的摩尔比为(0.35～0.75):1。(2) EDTA is dissolved in ammonia water to obtain EDTA ammonia solution; solution A is mixed with EDTA ammonia solution to obtain mixed solution B; then, mixed solution B is placed in an open porcelain dish, and placed in a muffle furnace for 500 ℃ Carbonized at ℃ for 30 min; after that, calcined in a muffle furnace at 450 ℃ for 240 min, and sieved through a sieve to form a powder catalyst; wherein, the molar ratio of EDTA to metal precursor salt is (0.35～0.75):1.
作为本发明的一种实施方式，步骤(1)中的所述金属前驱体盐为Mg2+盐、Al3+盐、Fe3+盐、Co2+盐的混合物。As an embodiment of the present invention, the metal precursor salt in step (1) is a mixture of Mg2+ salt, Al3+ salt, Fe3+ salt, and Co2+ salt.
作为本发明的一种实施方式，氨水的质量分数为25wt％；氨水与EDTA质量比为(4～7):1。As an embodiment of the present invention, the mass fraction of ammonia water is 25wt%; the mass ratio of ammonia water to EDTA is (4-7):1.
作为本发明的一种实施方式，步骤(1)具体为：将102.6g六水硝酸镁、30g九水硝酸铝、8.9g九水硝酸铁、5.2g六水硝酸钴、585g纯水、100g柠檬酸混合，于92℃恒温水浴搅拌溶解，得到混合溶液；然后向其中加入0.71g七钼酸铵，搅拌溶解，继续搅拌加热浓缩至溶液体积为500mL，冷却至常温，得到溶液A。As an embodiment of the present invention, step (1) is specifically as follows: 102.6g magnesium nitrate hexahydrate, 30g aluminum nitrate nonahydrate, 8.9g ferric nitrate nonahydrate, 5.2g cobalt nitrate hexahydrate, 585g pure water, 100g lemon Acid mixing, stirring and dissolving in a 92°C constant temperature water bath to obtain a mixed solution; then adding 0.71 g of ammonium heptamolybdate to it, stirring and dissolving, continuing to stir and heating and concentrating until the solution volume is 500 mL, and cooling to room temperature to obtain solution A.
作为本发明的一种实施方式，步骤(2)具体为：将83.6g EDTA溶解于493.1g的质量分数为25wt％的氨水中，得到EDTA氨溶液；将溶液A与EDTA氨溶液混合，得到混合液B。As an embodiment of the present invention, step (2) is specifically as follows: dissolving 83.6 g of EDTA in 493.1 g of ammonia water with a mass fraction of 25 wt % to obtain an EDTA ammonia solution; mixing solution A with an EDTA ammonia solution to obtain a mixed solution Liquid B.
本发明的第二目的在于提供前述的方法制得的具有高活性的碳纳米管催化剂。The second object of the present invention is to provide a carbon nanotube catalyst with high activity prepared by the aforementioned method.
本发明的第三目的在于提供前述的具有高活性的碳纳米管催化剂在烯烃类气体裂解制备碳纳米管中的应用。The third object of the present invention is to provide the application of the aforementioned carbon nanotube catalyst with high activity in the preparation of carbon nanotubes by the cracking of olefin-based gases.
本发明的第四目的在于提供一种提高烯烃类气体裂解制备碳纳米管的产率的方法，其应用前述的具有高活性的碳纳米管催化剂，所述方法包括如下步骤：The fourth object of the present invention is to provide a method for improving the yield of olefin gas cracking to prepare carbon nanotubes, which uses the aforementioned carbon nanotube catalyst with high activity, and the method includes the following steps:
将前述的具有高活性的碳纳米管催化剂置于管式炉中，惰性气体保护下升温至300℃；待温度达到300℃后，持续通入1000sccm氢气，并以10℃/min升温至700℃；待温度达到700℃后，持续通入300sccm乙烯、300sccm氮气、100sccm氢气的混合气，恒温反应60min，然后降温，即可制得碳纳米管。The aforementioned carbon nanotube catalyst with high activity was placed in a tube furnace, and the temperature was raised to 300°C under the protection of inert gas; after the temperature reached 300°C, 1000sccm of hydrogen was continuously fed, and the temperature was raised to 700°C at 10°C/min ; After the temperature reaches 700 ℃, continue to feed a mixture of 300 sccm ethylene, 300 sccm nitrogen, and 100 sccm hydrogen, react at a constant temperature for 60 minutes, and then cool down to obtain carbon nanotubes.
本发明的第五目的在于提供一种碳纳米管，其中金属元素残留不高于0.6％，其结构为超长束状结构。The fifth object of the present invention is to provide a carbon nanotube, wherein the residual metal element is not higher than 0.6%, and its structure is an ultra-long bundle structure.
有益效果：Beneficial effects:
(1)本发明使用柠檬酸(CA)和乙二胺四乙酸(EDTA)氨溶液两步络合法，合成高活性的金属氧化物催化剂，用于合成碳纳米管。本发明的单位催化剂金属元素重量的高效催化剂所获得的碳纳米管产率不低于169g/g，最高可达246g/g，即碳纳米管中金属残留大约0.4％，可以减少甚至避免碳纳米管的提纯处理，降低了碳纳米管生产成本。(1) The present invention uses a two-step complexation method of citric acid (CA) and ethylenediaminetetraacetic acid (EDTA) ammonia solution to synthesize highly active metal oxide catalysts for synthesizing carbon nanotubes. The yield of carbon nanotubes obtained by the high-efficiency catalyst per unit catalyst metal element weight of the present invention is not less than 169 g/g, and the highest can reach 246 g/g, that is, the metal residue in the carbon nanotubes is about 0.4%, which can reduce or even avoid carbon nanotubes. The purification treatment of the tube reduces the production cost of carbon nanotubes.
(2)本发明基于CA-EDTA氨溶液两步络合法制备的催化剂呈现出松散片状堆积模式，使得其生长的碳纳米管呈超长束状，大大提高了催化剂的利用效率；较均匀的活性中心分布，使得其可以被充分利用，得到较高产率的碳纳米管。(2) The catalyst prepared by the two-step complexation method of CA-EDTA ammonia solution in the present invention exhibits a loose sheet-like accumulation pattern, so that the grown carbon nanotubes are in the form of ultra-long bundles, which greatly improves the utilization efficiency of the catalyst; The distribution of active centers can be fully utilized to obtain carbon nanotubes with higher yields.
(3)本发明基于CA-EDTA氨溶液两步络合法制备催化剂工艺简单，大大降低了生产成本，提高了企业生产利润。(3) The present invention has a simple process for preparing the catalyst based on the CA-EDTA ammonia solution two-step complexation method, greatly reduces the production cost, and improves the production profit of the enterprise.
(4)本发明制备得到的碳纳米管的特征结构为超长束状，碳纳米管的长度可达50微米以上，长径比大、导电、导热且机械性能良好，可以被使用作为碳纤维以及锂电池负极材料及导电剂。(4) The characteristic structure of the carbon nanotubes prepared by the present invention is an ultra-long bundle, the length of the carbon nanotubes can reach more than 50 microns, the aspect ratio is large, the electrical conductivity, thermal conductivity and mechanical properties are good, and can be used as carbon fibers and Lithium battery anode material and conductive agent.
附图说明Description of drawings
图1为本发明实施例2制备的催化剂的扫描电镜图，标尺为1μm。FIG. 1 is a scanning electron microscope image of the catalyst prepared in Example 2 of the present invention, and the scale is 1 μm.
图2为本发明实施例2制备的催化剂的扫描电镜图，标尺为5μm。FIG. 2 is a scanning electron microscope image of the catalyst prepared in Example 2 of the present invention, and the scale is 5 μm.
图3为应用本发明实施例2制得的催化剂合成的碳纳米管的扫描电镜图，标尺为2μm。3 is a scanning electron microscope image of carbon nanotubes synthesized by applying the catalyst prepared in Example 2 of the present invention, and the scale is 2 μm.
图4为应用本发明实施例2制得的催化剂合成的碳纳米管的扫描电镜图，标尺为10μm。4 is a scanning electron microscope image of carbon nanotubes synthesized by using the catalyst prepared in Example 2 of the present invention, and the scale is 10 μm.
图5为应用本发明实施例2制得的催化剂合成的碳纳米管的扫描电镜图，标尺为20μm。5 is a scanning electron microscope image of carbon nanotubes synthesized by using the catalyst prepared in Example 2 of the present invention, and the scale is 20 μm.
图6为应用本发明实施例2制得的催化剂合成的碳纳米管的扫描电镜图，标尺为50μm。6 is a scanning electron microscope image of carbon nanotubes synthesized by applying the catalyst prepared in Example 2 of the present invention, and the scale is 50 μm.
具体实施方式Detailed ways
各实施例与对比例中的氨水的质量分数为25wt％、试剂级的氨水溶液。The mass fraction of ammonia water in each embodiment and comparative example is 25wt%, reagent grade ammonia water solution.
碳纳米管的产率＝碳纳米管重量/催化剂金属元素重量；Yield of carbon nanotubes=carbon nanotube weight/catalyst metal element weight;
催化剂金属元素重量＝催化剂重量*铁钴元素/所有元素＝0.13*催化剂重量。Catalyst metal element weight=catalyst weight*iron cobalt element/all elements=0.13*catalyst weight.
实施例1Example 1
一种合成碳纳米管催化剂的制备方法，包括如下步骤：A preparation method for synthesizing carbon nanotube catalyst, comprising the following steps:
(1)向1L烧杯内依次加入102.6g六水硝酸镁、30g九水硝酸铝、8.9g九水硝酸铁、5.2g六水硝酸钴、585g纯水、100g柠檬酸，放入92℃恒温水浴锅内，四氟桨叶以400rpm机械搅拌溶解原料，然后加入0.71g七钼酸铵，搅拌溶解，继续搅拌加热浓缩至溶液液位为500mL。取出烧杯冷却至常温，得到溶液A。(1) Add 102.6g magnesium nitrate hexahydrate, 30g aluminum nitrate nonahydrate, 8.9g ferric nitrate nonahydrate, 5.2g cobalt nitrate hexahydrate, 585g pure water, 100g citric acid successively into a 1L beaker, put into a 92°C constant temperature water bath In the pot, the tetrafluoro blade mechanically stirs and dissolves the raw materials at 400 rpm, and then adds 0.71 g of ammonium heptamolybdate, stirs and dissolves, and continues to stir and heat to concentrate until the solution level is 500 mL. The beaker was taken out and cooled to room temperature to obtain solution A.
(2)向1L烧杯内依次加入60.8g EDTA、359g氨水，常温搅拌溶解形成EDTA氨溶液。(2) 60.8g of EDTA and 359g of ammonia water were sequentially added to the 1L beaker, and stirred and dissolved at room temperature to form an EDTA ammonia solution.
(3)将溶液A倒入EDTA氨溶液中，继续搅拌30min，然后称取30g溶液装入敞口瓷元皿内。马弗炉升温至500℃恒温后，将上述装有溶液的瓷元皿放入马弗炉内碳化30min以形成疏松多孔的催化剂前驱体，碳化完成后将马弗炉的温度设置为450℃，恒温焙烧240min。产物经过80目筛网过筛破碎形成粉末状催化剂。(3) Pour solution A into EDTA ammonia solution, continue stirring for 30min, then weigh 30g of solution and put it into an open porcelain dish. After the muffle furnace is heated to a constant temperature of 500 °C, the above-mentioned porcelain dish containing the solution is placed in the muffle furnace for carbonization for 30 minutes to form a loose and porous catalyst precursor. After the carbonization is completed, the temperature of the muffle furnace is set to 450 °C, Constant temperature roasting for 240min. The product is sieved through an 80-mesh sieve and crushed to form a powdered catalyst.
应用实施例1制得的催化剂制备碳纳米管的方法如下：The method for preparing carbon nanotubes using the catalyst prepared in Example 1 is as follows:
称取0.3g制备得到的粉末状催化剂置于φ60mm管式炉中间区域，1000sccm氮气保护以升温速率为10℃/min升温至300℃，开始持续通入1000sccm氢气，继续以升温速率为10℃/min升温至700℃，待达到700℃后，开始通入300sccm乙烯、300sccm氮气、100sccm氢气的混合气，恒温反应60分钟。降温然后取出产物——碳纳米管。Weigh 0.3 g of the prepared powdered catalyst and place it in the middle area of a φ60mm tube furnace. Under 1000sccm nitrogen protection, the temperature is raised to 300°C at a heating rate of 10°C/min, and 1000sccm of hydrogen is continuously fed in. The heating rate is 10°C/min. The temperature was raised to 700 ℃ for min. After reaching 700 ℃, a mixture of 300 sccm ethylene, 300 sccm nitrogen, and 100 sccm hydrogen was introduced, and the reaction was performed at a constant temperature for 60 minutes. Cool down and take out the product - carbon nanotubes.
结果表明，实施例1的催化剂能够成功制备得到产物碳纳米管，所得碳纳米管产物的重量为6.6g、堆密度为0.006g/ml。由单位催化剂金属元素重量的实施例1的催化剂所获得的碳纳米管产率为169g/g。碳纳米管中铁钴金属元素残留约为0.6％。The results show that the catalyst of Example 1 can successfully prepare the product carbon nanotubes, and the obtained carbon nanotube product has a weight of 6.6 g and a bulk density of 0.006 g/ml. The yield of carbon nanotubes obtained from the catalyst of Example 1 per weight of catalyst metal element was 169 g/g. The residual iron and cobalt metal elements in the carbon nanotubes are about 0.6%.
实施例2Example 2
一种合成碳纳米管催化剂的制备方法，参照实施例1，区别仅在于，调整EDTA与氨水的用量，具体地：A preparation method for synthesizing carbon nanotube catalyst, with reference to Example 1, the difference is only that the consumption of EDTA and ammonia water is adjusted, specifically:
(1)向1L烧杯内依次加入102.6g六水硝酸镁、30g九水硝酸铝、8.9g九水硝酸铁、5.2g六水硝酸钴、585g纯水、100g柠檬酸，放入92℃恒温水浴锅内，四氟桨叶以400rpm机械搅拌溶解原料，然后加入0.71g七钼酸铵，搅拌溶解，继续搅拌加热浓缩至溶液液位为500mL。取出烧杯冷却至常温，得到溶液A。(1) Add 102.6g magnesium nitrate hexahydrate, 30g aluminum nitrate nonahydrate, 8.9g ferric nitrate nonahydrate, 5.2g cobalt nitrate hexahydrate, 585g pure water, 100g citric acid successively into a 1L beaker, put into a 92°C constant temperature water bath In the pot, the tetrafluoro blade mechanically stirs and dissolves the raw materials at 400 rpm, and then adds 0.71 g of ammonium heptamolybdate, stirs and dissolves, and continues to stir and heat to concentrate until the solution level is 500 mL. The beaker was taken out and cooled to room temperature to obtain solution A.
(2)向1L烧杯内依次加入83.6g EDTA、493.1g氨水，常温搅拌溶解形成EDTA氨溶液。(2) 83.6g of EDTA and 493.1g of ammonia water were sequentially added into the 1L beaker, and stirred and dissolved at room temperature to form an EDTA ammonia solution.
(3)将溶液A倒入EDTA氨溶液中，继续搅拌30min，然后称取30g溶液装入敞口瓷元皿内。马弗炉升温至500℃恒温后，将上述装有溶液的瓷元皿放入马弗炉内碳化以形成疏松多孔的催化剂前驱体，500℃碳化30min完成后将马弗炉的温度设置为450℃，恒温焙烧240min。产物经过80目筛网过筛破碎形成粉末状催化剂。(3) Pour solution A into EDTA ammonia solution, continue stirring for 30min, then weigh 30g of solution and put it into an open porcelain dish. After the muffle furnace is heated to a constant temperature of 500 °C, the above-mentioned porcelain dish containing the solution is put into the muffle furnace for carbonization to form a loose and porous catalyst precursor. After the carbonization at 500 °C for 30 min is completed, the temperature of the muffle furnace is set to 450 ℃, constant temperature roasting for 240min. The product is sieved through an 80-mesh sieve and crushed to form a powdered catalyst.
应用实施例2制得的催化剂制备碳纳米管的方法同实施例1。The method for preparing carbon nanotubes using the catalyst prepared in Example 2 is the same as that in Example 1.
实施例2的粉末状催化剂及其制备的产物碳纳米管的扫描电镜图分别如图1-2和图3-4所示。如图1-2所示，本发明的催化剂呈现出松散片状堆积模式，较均匀的活性中心分布，该结构具有的作用：片状结构使得生长的碳纳米管成超长束状；较均匀的活性中心分布，使得催化剂的活性提升，得到较高产率的碳纳米管，大大提高了催化剂的利用效率。本发明制备得到的碳纳米管导电、导热且机械性能良好，可以被使用作为锂电池负极材料及导电剂。The scanning electron microscope images of the powdered catalyst of Example 2 and its prepared product carbon nanotubes are shown in Figures 1-2 and 3-4, respectively. As shown in Figures 1-2, the catalyst of the present invention exhibits a loose sheet-like accumulation pattern with a relatively uniform distribution of active centers. The structure has the following functions: the sheet-like structure makes the grown carbon nanotubes into ultra-long bundles; more uniform The distribution of active centers increases the activity of the catalyst and obtains carbon nanotubes with higher yields, which greatly improves the utilization efficiency of the catalyst. The carbon nanotubes prepared by the invention have good electrical conductivity, thermal conductivity and good mechanical properties, and can be used as negative electrode materials and conductive agents for lithium batteries.
结果表明，实施例2的催化剂能够成功制备得到产物碳纳米管，实施例2所得碳纳米管产物的重量为9.6g、堆密度为0.006g/ml。由单位催化剂金属元素重量的实施例2的催化剂所获得的碳纳米管产率为246g/g。碳纳米管中铁钴金属元素残留约为0.4％。The results show that the catalyst of Example 2 can successfully prepare the product carbon nanotubes, and the weight of the carbon nanotube product obtained in Example 2 is 9.6 g and the bulk density is 0.006 g/ml. The yield of carbon nanotubes obtained from the catalyst of Example 2 per weight of catalyst metal element was 246 g/g. The residual iron and cobalt metal elements in the carbon nanotubes are about 0.4%.
实施例3Example 3
一种合成碳纳米管催化剂的制备方法，参照实施例1，区别仅在于，调整EDTA与氨水的用量，具体地：A preparation method for synthesizing carbon nanotube catalyst, with reference to Example 1, the difference is only that the consumption of EDTA and ammonia water is adjusted, specifically:
(1)向1L烧杯内依次加入102.6g六水硝酸镁、30g九水硝酸铝、8.9g九水硝酸铁、5.2g六水硝酸钴、585g纯水、100g柠檬酸，放入92℃恒温水浴锅内，四氟桨叶以400rpm机械搅拌溶解原料，然后加入0.71g七钼酸铵，搅拌溶解，继续搅拌加热浓缩至溶液液位为500mL。取出烧杯冷却至常温，得到溶液A。(1) Add 102.6g magnesium nitrate hexahydrate, 30g aluminum nitrate nonahydrate, 8.9g ferric nitrate nonahydrate, 5.2g cobalt nitrate hexahydrate, 585g pure water, 100g citric acid successively into a 1L beaker, put into a 92°C constant temperature water bath In the pot, the tetrafluoro blade mechanically stirs and dissolves the raw materials at 400 rpm, and then adds 0.71 g of ammonium heptamolybdate, stirs and dissolves, and continues to stir and heat to concentrate until the solution level is 500 mL. The beaker was taken out and cooled to room temperature to obtain solution A.
(2)向1L烧杯内依次加入98.78g EDTA、582.8g氨水，常温搅拌溶解形成EDTA氨溶液。(2) 98.78g of EDTA and 582.8g of ammonia water were sequentially added into the 1L beaker, and stirred and dissolved at room temperature to form an EDTA ammonia solution.
(3)将溶液A倒入EDTA氨溶液中，继续搅拌30min，然后称取30g溶液装入敞口瓷元皿内。马弗炉升温至500℃恒温后，将上述装有溶液的瓷元皿放入马弗炉内碳化30min以形成疏松多孔的催化剂前驱体，碳化完成后将马弗炉的温度设置为450℃，恒温焙烧240min。产物经过80目筛网过筛破碎形成粉末状催化剂。(3) Pour solution A into EDTA ammonia solution, continue stirring for 30min, then weigh 30g of solution and put it into an open porcelain dish. After the muffle furnace is heated to a constant temperature of 500 °C, the above-mentioned porcelain dish containing the solution is placed in the muffle furnace for carbonization for 30 minutes to form a loose and porous catalyst precursor. After the carbonization is completed, the temperature of the muffle furnace is set to 450 °C, Constant temperature roasting for 240min. The product is sieved through an 80-mesh sieve and crushed to form a powdered catalyst.
应用实施例3制得的催化剂制备碳纳米管的方法同实施例1。The method for preparing carbon nanotubes using the catalyst prepared in Example 3 is the same as that in Example 1.
结果表明，实施例3的催化剂能够成功制备得到产物碳纳米管，实施例3所得碳纳米管产物的重量为7.8g、堆密度为0.006g/ml。由单位催化剂金属元素重量的实施例3的催化剂所获得的碳纳米管产率为200g/g。碳纳米管中铁钴金属元素残留约为0.5％。The results show that the catalyst of Example 3 can successfully prepare the product carbon nanotubes. The weight of the carbon nanotube product obtained in Example 3 is 7.8 g and the bulk density is 0.006 g/ml. The yield of carbon nanotubes obtained from the catalyst of Example 3 per weight of catalyst metal element was 200 g/g. The residual iron and cobalt metal elements in the carbon nanotubes are about 0.5%.
从实施例1-3可以分析出，实施例2制得的碳纳米管的产率最高，高达246g/g，表明实施例2的EDTA与氨水的含量最优，过高或过低可能导致催化剂的结构发生变化，从而影响其催化合成碳纳米管的活性。It can be analyzed from Examples 1-3 that the yield of carbon nanotubes prepared in Example 2 is the highest, up to 246 g/g, indicating that the content of EDTA and ammonia water in Example 2 is the best, and too high or too low may lead to catalysts. The structure of CNTs changes, which affects its catalytic activity for synthesizing carbon nanotubes.
对比例1Comparative Example 1
一种合成碳纳米管催化剂的制备方法，参照实施例2，区别仅在于，仅调整EDTA的用量，使得EDTA与金属前驱体盐摩尔比低于0.35:1。例如，EDTA与金属前驱体盐摩尔比为0.3:1。For a preparation method of a catalyst for synthesizing carbon nanotubes, refer to Example 2, the difference is only that the amount of EDTA is adjusted so that the molar ratio of EDTA to metal precursor salt is lower than 0.35:1. For example, the molar ratio of EDTA to metal precursor salt is 0.3:1.
按照与实施例2相同的方法利用对比例1的催化剂制备碳纳米管，结果表明，对比例1所得产物碳纳米管的重量为3.3g。由单位催化剂金属元素重量的对比例1的催化剂所获得的碳纳米管产率为85g/g。According to the same method as in Example 2, carbon nanotubes were prepared by using the catalyst of Comparative Example 1, and the results showed that the weight of the carbon nanotubes obtained in Comparative Example 1 was 3.3 g. The yield of carbon nanotubes obtained from the catalyst of Comparative Example 1 per weight of catalyst metal element was 85 g/g.
对比例2Comparative Example 2
一种合成碳纳米管催化剂的制备方法，参照实施例2，区别仅在于，仅调整EDTA的用量，使得EDTA与金属前驱体盐摩尔比高于0.75:1。例如，EDTA与金属前驱体盐摩尔比为0.8:1。For a preparation method of a catalyst for synthesizing carbon nanotubes, refer to Example 2, the difference is only that the amount of EDTA is adjusted so that the molar ratio of EDTA to metal precursor salt is higher than 0.75:1. For example, the molar ratio of EDTA to metal precursor salt is 0.8:1.
按照与实施例2相同的方法利用对比例2的催化剂制备碳纳米管，结果表明，对比例2所得产物碳纳米管的重量为5.1g。由单位催化剂金属元素重量的对比例2的催化剂所获得的碳纳米管产率为131g/g。According to the same method as in Example 2, carbon nanotubes were prepared by using the catalyst of Comparative Example 2. The results showed that the weight of the carbon nanotubes obtained in Comparative Example 2 was 5.1 g. The yield of carbon nanotubes obtained from the catalyst of Comparative Example 2 per weight of catalyst metal element was 131 g/g.
从实施例1-3、对比例1-2对比分析可见，EDTA与金属前驱体盐摩尔比的最优范围为0.35～0.75:1，在此范围之内，可成功制备得到6.6g～9.6g产物碳纳米管，单位催化剂金属元素重量的高效催化剂所获得的碳纳米管产率不低于169g/g；超出该范围之外，则无法实现前述效果。From the comparative analysis of Example 1-3 and Comparative Example 1-2, it can be seen that the optimal range of the molar ratio of EDTA to metal precursor salt is 0.35～0.75:1, within this range, 6.6g～9.6g can be successfully prepared Product carbon nanotubes, the yield of carbon nanotubes obtained by a high-efficiency catalyst per unit of catalyst metal element weight is not less than 169 g/g; beyond this range, the aforementioned effects cannot be achieved.
对比例3Comparative Example 3
一种合成碳纳米管催化剂的制备方法，参照实施例2，区别仅在于，仅调整氨水的用量，使得氨水与EDTA质量比低于4:1，例如使氨水与EDTA质量比为3:1。A preparation method for synthesizing a carbon nanotube catalyst, with reference to Example 2, the difference is only that the consumption of ammonia water is adjusted so that the mass ratio of ammonia water and EDTA is lower than 4:1, for example, the mass ratio of ammonia water and EDTA is 3:1.
按照与实施例2相同的方法利用对比例3的催化剂制备碳纳米管，结果表明，对比例3所得产物碳纳米管的重量为5.4g。由单位催化剂金属元素重量的对比例3的催化剂所获得的碳纳米管产率仅为138g/g。According to the same method as in Example 2, carbon nanotubes were prepared by using the catalyst of Comparative Example 3. The results showed that the weight of the carbon nanotubes obtained in Comparative Example 3 was 5.4 g. The yield of carbon nanotubes obtained from the catalyst of Comparative Example 3 per weight of catalyst metal element was only 138 g/g.
对比例4Comparative Example 4
一种合成碳纳米管催化剂的制备方法，参照实施例2，区别仅在于，仅调整氨水的用量，使得氨水与EDTA质量比高于7:1，例如使氨水与EDTA质量比为8:1。A preparation method for synthesizing carbon nanotube catalyst, with reference to Example 2, the difference is only that the consumption of ammonia water is adjusted so that the mass ratio of ammonia water and EDTA is higher than 7:1, for example, the mass ratio of ammonia water and EDTA is 8:1.
按照与实施例2相同的方法利用对比例4的催化剂制备碳纳米管，结果表明，对比例4所得产物碳纳米管的重量为6.0g。由单位催化剂金属元素重量的对比例4的催化剂所获得的碳纳米管产率为153.8g/g。According to the same method as in Example 2, carbon nanotubes were prepared by using the catalyst of Comparative Example 4, and the results showed that the weight of the carbon nanotubes obtained in Comparative Example 4 was 6.0 g. The yield of carbon nanotubes obtained from the catalyst of Comparative Example 4 per weight of catalyst metal element was 153.8 g/g.
从实施例1-3、对比例3-4对比分析可见，氨水与EDTA质量比最优范围为4～7:1，可成功制备得到6.6g～9.6g碳纳米管，单位催化剂金属元素重量的催化剂所获得的碳纳米管产率不低于169g/g；超出该范围之外，则无法实现前述效果。From the comparative analysis of Example 1-3 and Comparative Example 3-4, it can be seen that the optimal range of the mass ratio of ammonia water to EDTA is 4-7:1, and 6.6g-9.6g of carbon nanotubes can be successfully prepared. The yield of carbon nanotubes obtained by the catalyst is not less than 169 g/g; beyond this range, the aforementioned effects cannot be achieved.
对比例5Comparative Example 5
一种合成碳纳米管催化剂的制备方法，参照实施例2，区别仅在于，仅调整柠檬酸的用量，使得柠檬酸与金属前驱体盐的摩尔比低于1:1，例如使柠檬酸与金属前驱体盐的摩尔比为0.7:1。A preparation method for synthesizing a carbon nanotube catalyst, referring to Example 2, the difference is only that the amount of citric acid is adjusted so that the molar ratio of citric acid and metal precursor salt is lower than 1:1, for example, citric acid and metal The molar ratio of the precursor salts was 0.7:1.
按照与实施例2相同的方法利用对比例5的催化剂制备碳纳米管，结果表明，对比例5所得产物碳纳米管的重量为2.6g。由单位催化剂金属元素重量的对比例5的催化剂所获得的碳纳米管产率仅为66.7g/g。According to the same method as in Example 2, carbon nanotubes were prepared by using the catalyst of Comparative Example 5. The results showed that the weight of the carbon nanotubes obtained in Comparative Example 5 was 2.6 g. The yield of carbon nanotubes obtained from the catalyst of Comparative Example 5 per weight of catalyst metal element was only 66.7 g/g.
对比例6Comparative Example 6
一种合成碳纳米管催化剂的制备方法，参照实施例2，区别仅在于，仅调整柠檬酸的用量，使得柠檬酸与金属前驱体盐的摩尔比高于1.5:1，例如使柠檬酸与金属前驱体盐的摩尔比为2:1。A preparation method for synthesizing a carbon nanotube catalyst, referring to Example 2, the difference is only that the amount of citric acid is adjusted so that the molar ratio of citric acid to metal precursor salt is higher than 1.5:1, for example, citric acid and metal The molar ratio of the precursor salts was 2:1.
按照与实施例2相同的方法利用对比例6的催化剂制备碳纳米管，结果表明，对比例6所得产物碳纳米管的重量为4.6g。由单位催化剂金属元素重量的对比例6的催化剂所获得的碳纳米管产率仅为118g/g。According to the same method as in Example 2, carbon nanotubes were prepared by using the catalyst of Comparative Example 6, and the results showed that the weight of the carbon nanotubes obtained in Comparative Example 6 was 4.6 g. The yield of carbon nanotubes obtained from the catalyst of Comparative Example 6 per weight of catalyst metal element was only 118 g/g.
对比例7单独柠檬酸络合法Comparative Example 7 Alone Citric Acid Complexation
一种合成碳纳米管催化剂的制备方法，参照实施例2，区别仅在于，省略EDTA的添加，调整柠檬酸的用量为最优用量149.9g(根据单位催化剂金属元素重量的催化剂所获得的碳纳米管产率最高来确定)。A preparation method of synthesizing carbon nanotube catalyst, with reference to Example 2, the difference is only that the addition of EDTA is omitted, and the consumption of citric acid is adjusted to be an optimal consumption of 149.9g (according to the carbon nanometer obtained by the catalyst of unit catalyst metal element weight). to determine the highest tube yield).
按照与实施例2相同的方法利用对比例7的催化剂制备碳纳米管，结果表明，对比例7所得产物碳纳米管的重量为1.8g。由单位催化剂金属元素重量的对比例7的催化剂所获得的碳纳米管产率仅为46g/g。According to the same method as in Example 2, carbon nanotubes were prepared by using the catalyst of Comparative Example 7. The results showed that the weight of the carbon nanotubes obtained in Comparative Example 7 was 1.8 g. The yield of carbon nanotubes obtained from the catalyst of Comparative Example 7 per weight of catalyst metal element was only 46 g/g.
分析实施例2与对比例7可以发现，省略EDTA络合剂后，制备得到的催化剂的催化活性(单位催化剂金属元素重量的催化剂所获得的碳纳米管产率)显著降低，表明EDTA的添加对于本发明的催化剂活性的提升产生了预料不到的影响。From the analysis of Example 2 and Comparative Example 7, it can be found that after omitting the EDTA complexing agent, the catalytic activity of the prepared catalyst (the yield of carbon nanotubes obtained by the catalyst per the weight of the catalyst metal element) is significantly reduced, indicating that the addition of EDTA is effective for The increase in catalyst activity of the present invention has unexpected effects.
对比例8单独EDTA络合法Comparative Example 8 Alone EDTA network method
一种合成碳纳米管催化剂的制备方法，参照实施例2，区别仅在于，省略柠檬酸的添加，调整EDTA的用量为最优用量98.78g。For a preparation method of a catalyst for synthesizing carbon nanotubes, refer to Example 2, the difference is only that the addition of citric acid is omitted, and the amount of EDTA is adjusted to an optimal amount of 98.78g.
按照与实施例2相同的方法利用对比例8的催化剂制备碳纳米管，结果表明，对比例8所得产物碳纳米管的重量为0.90g。由单位催化剂金属元素重量的对比例8的催化剂所获得的碳纳米管产率仅为23g/g。According to the same method as in Example 2, carbon nanotubes were prepared by using the catalyst of Comparative Example 8. The results showed that the weight of the carbon nanotubes obtained in Comparative Example 8 was 0.90 g. The yield of carbon nanotubes obtained from the catalyst of Comparative Example 8 per weight of catalyst metal element was only 23 g/g.
分析实施例2与对比例8可以发现，省略柠檬酸后，制备得到的催化剂的催化活性(单位单位催化剂金属元素重量的催化剂所获得的碳纳米管产率)显著降低，表明柠檬酸的添加对于本发明的催化剂活性的提升产生了预料不到的影响。Analyzing Example 2 and Comparative Example 8, it can be found that after omitting citric acid, the catalytic activity of the prepared catalyst (the yield of carbon nanotubes obtained by the catalyst per unit weight of catalyst metal element) is significantly reduced, indicating that the addition of citric acid is effective for The increase in catalyst activity of the present invention has unexpected effects.
对比例9Comparative Example 9
一种合成碳纳米管催化剂的制备方法，参照实施例2，区别仅在于，先使用EDTA氨溶液络合，然后加入柠檬酸络合，具体地：A preparation method for synthesizing carbon nanotube catalyst, with reference to Example 2, the difference is only that, first use EDTA ammonia solution for complexation, then add citric acid for complexation, specifically:
(1)向1L烧杯内依次加入称取102.6g六水硝酸镁、30g九水硝酸铝、8.9g九水硝酸铁、5.2g六水硝酸钴、585g纯水，然后加入83.6g EDTA、493.1g氨水，搅拌溶解，加入0.71g七钼酸铵，常温搅拌30min以充分溶解，得到溶液B。(1) in the 1L beaker, add and weigh 102.6g magnesium nitrate hexahydrate, 30g aluminum nitrate nonahydrate, 8.9g ferric nitrate nonahydrate, 5.2g cobalt nitrate hexahydrate, 585g pure water successively, then add 83.6g EDTA, 493.1g Ammonia water, stir to dissolve, add 0.71 g of ammonium heptamolybdate, stir at room temperature for 30 minutes to fully dissolve, and obtain solution B.
(2)称取100g柠檬酸配置成水溶液；(2) take by weighing 100g of citric acid and configure it into an aqueous solution;
(3)将步骤(1)所得溶液B倒入柠檬酸水溶液中，放入92℃恒温水浴锅内，四氟桨叶以400rpm机械搅拌，加热浓缩至溶液体积与实施例1中步骤(3)得到的混合液等体积。取出烧杯冷却至常温后，称取30g溶液装入敞口瓷元皿内。马弗炉升温至500℃恒温后，将上述装有溶液的瓷元皿放入马弗炉内碳化30min以形成疏松多孔的催化剂前驱体，碳化完成后将马弗炉的温度设置为450℃，恒温焙烧240min。产物经过80目筛网过筛破碎形成粉末状催化剂。(3) Pour the solution B obtained in step (1) into the citric acid aqueous solution, put it into a 92 ° C constant temperature water bath, and mechanically stir the tetrafluoro paddle at 400 rpm, heat and concentrate to the solution volume and step (3) in Example 1. The resulting mixture was equal in volume. After the beaker was taken out and cooled to room temperature, 30 g of the solution was weighed and put into an open porcelain dish. After the muffle furnace is heated to a constant temperature of 500 °C, the above-mentioned porcelain dish containing the solution is placed in the muffle furnace for carbonization for 30 minutes to form a loose and porous catalyst precursor. After the carbonization is completed, the temperature of the muffle furnace is set to 450 °C, Constant temperature roasting for 240min. The product is sieved through an 80-mesh sieve and crushed to form a powdered catalyst.
按照与实施例2相同的方法利用对比例9的催化剂制备碳纳米管，结果表明，对比例9所得产物碳纳米管的重量仅为0.3g，几乎未见碳纳米管产物生成。According to the same method as Example 2, carbon nanotubes were prepared by using the catalyst of Comparative Example 9. The results showed that the weight of carbon nanotubes obtained in Comparative Example 9 was only 0.3 g, and almost no carbon nanotubes were produced.
Claims (9)
Translated fromChinesePriority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210171373.XACN114524466B (en) | 2022-02-24 | 2022-02-24 | A kind of synthetic method of highly active catalyst |
| PCT/CN2022/081355WO2023159698A1 (en) | 2022-02-24 | 2022-03-17 | Method for synthesizing highly active catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210171373.XACN114524466B (en) | 2022-02-24 | 2022-02-24 | A kind of synthetic method of highly active catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114524466Atrue CN114524466A (en) | 2022-05-24 |
| CN114524466B CN114524466B (en) | 2023-04-28 |
Family
ID=81625627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210171373.XAActiveCN114524466B (en) | 2022-02-24 | 2022-02-24 | A kind of synthetic method of highly active catalyst |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114524466B (en) |
| WO (1) | WO2023159698A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115414937A (en)* | 2022-08-17 | 2022-12-02 | 华东理工大学 | Catalyst for preparing carbon nanotube by microwave catalytic pyrolysis of waste plastics and preparation method and application thereof |
| CN115672327A (en)* | 2022-11-10 | 2023-02-03 | 无锡碳谷科技有限公司 | High specific surface area superfine nano catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1663681A (en)* | 2004-03-02 | 2005-09-07 | 广东工业大学 | Catalyst for preparing carbon nanotubes |
| CN103721750A (en)* | 2014-01-09 | 2014-04-16 | 深圳市三顺中科新材料有限公司 | Catalyst for preparing long-pipe-diameter carbon nano tubes and preparation method of catalyst |
| CN110801843A (en)* | 2019-11-11 | 2020-02-18 | 内蒙古骏成新能源科技有限公司 | Two-stage method for preparing high-magnification carbon nano tube with superfine tube diameter, catalyst and preparation method thereof |
| CN110961115A (en)* | 2019-11-26 | 2020-04-07 | 厦门大学 | Catalyst for preparing multi-walled carbon nanotube and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009078235A (en)* | 2007-09-26 | 2009-04-16 | Toray Ind Inc | Manufacturing method of catalyst body for carbon nanotube synthesis |
| JP2017196579A (en)* | 2016-04-28 | 2017-11-02 | 東洋インキＳｃホールディングス株式会社 | Production method of catalyst precursor for production of carbon nanotube |
| CN110339842A (en)* | 2019-06-26 | 2019-10-18 | 江西铜业技术研究院有限公司 | A kind of composite catalyst and preparation method thereof growing carbon nanotube |
| CN110586115B (en)* | 2019-09-29 | 2022-08-12 | 成都科汇机电技术有限公司 | High-rate carbon nanotube catalyst, carbon nanotube and preparation method thereof |
- 2022
- 2022-02-24CNCN202210171373.XApatent/CN114524466B/enactiveActive
- 2022-03-17WOPCT/CN2022/081355patent/WO2023159698A1/ennot_activeCeased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1663681A (en)* | 2004-03-02 | 2005-09-07 | 广东工业大学 | Catalyst for preparing carbon nanotubes |
| CN103721750A (en)* | 2014-01-09 | 2014-04-16 | 深圳市三顺中科新材料有限公司 | Catalyst for preparing long-pipe-diameter carbon nano tubes and preparation method of catalyst |
| CN110801843A (en)* | 2019-11-11 | 2020-02-18 | 内蒙古骏成新能源科技有限公司 | Two-stage method for preparing high-magnification carbon nano tube with superfine tube diameter, catalyst and preparation method thereof |
| CN110961115A (en)* | 2019-11-26 | 2020-04-07 | 厦门大学 | Catalyst for preparing multi-walled carbon nanotube and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115414937A (en)* | 2022-08-17 | 2022-12-02 | 华东理工大学 | Catalyst for preparing carbon nanotube by microwave catalytic pyrolysis of waste plastics and preparation method and application thereof |
| CN115414937B (en)* | 2022-08-17 | 2024-04-16 | 华东理工大学 | Catalyst for preparing carbon nano tube by microwave catalytic pyrolysis of waste plastics and preparation method and application thereof |
| CN115672327A (en)* | 2022-11-10 | 2023-02-03 | 无锡碳谷科技有限公司 | High specific surface area superfine nano catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114524466B (en) | 2023-04-28 |
| WO2023159698A1 (en) | 2023-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110694616B (en) | A universal method for preparing supported metal single atoms/metal nanoparticles | |
| CN106925314B (en) | A nickel-assisted low-temperature synthesis of molybdenum carbide electrocatalysts | |
| CN104549242B (en) | Preparation method of nanometer palladium-graphene three-dimensional porous composite electrocatalyst | |
| CN108837838B (en) | A kind of ultra-small vanadium carbide embedded carbon nanotube material, preparation method and its application in water splitting hydrogen production | |
| CN109675603A (en) | A kind of carbon-supported catalysts and its preparation method and application of silica protection | |
| CN111167495B (en) | A kind of catalyst Ni2-xFex@CN-G for hydrogen production from ammonia borane and preparation method thereof | |
| CN113151856B (en) | Preparation of high-entropy alloy phosphide nanoparticle catalyst and application of high-entropy alloy phosphide nanoparticle catalyst in hydrogen production by water electrolysis | |
| Sun et al. | In situ confined vertical growth of a 1D-CuCo 2 S 4 nanoarray on Ni foam covered by a 3D-PANI mesh layer to form a self-supporting hierarchical structure for high-efficiency oxygen evolution catalysis | |
| CN114524466B (en) | A kind of synthetic method of highly active catalyst | |
| CN108101111A (en) | A kind of molybdenum carbide/molybdenum dioxide composite nano-line and preparation method and application | |
| CN115896848A (en) | Nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst and preparation method and application thereof | |
| Zheng et al. | Emerging electrospinning platform toward nanoparticle to single atom transformation for steering selectivity in ammonia synthesis | |
| CN111013619B (en) | Molybdenum carbide nanorod for catalyst and preparation method and application thereof | |
| CN105964260A (en) | Preparation method for metal catalyst and preparation method for carbon nano tube prepared by metal catalyst | |
| CN109772411B (en) | A kind of non-precious metal double-atom electrocatalyst and preparation method and application thereof | |
| CN110961101A (en) | Platinum-based catalyst, preparation method and application thereof | |
| CN108654660A (en) | A kind of vanadium carbide/carbon nano tube compound material, preparation method and its application in terms of hydrogen is produced in water-splitting | |
| CN105081347B (en) | A kind of normal-pressure production method of low pine than high-purity spherical ultra-fine nickel powder | |
| CN114645284A (en) | A kind of three-phase system vanadium trioxide/vanadium nitride/molybdenum carbide nano-electrode material and its preparation method and application | |
| CN117512672A (en) | A nitrogen-phosphorus-doped carbon nanosheet loaded with iron-cobalt bimetallic phosphide and its preparation method and application | |
| CN115491696B (en) | Monoatomic catalyst for electrocatalytic carbon dioxide reduction and preparation method thereof | |
| WO2023173352A1 (en) | Method for preparing carbon nanotube by catalytic cracking of methanol or propylene | |
| CN113101981B (en) | Preparation method of catalyst for preparing carbon nanotube | |
| CN112458483B (en) | A kind of preparation method of NiFe LDH@Super-P composite electrocatalytic material | |
| CN112877730B (en) | Electro-catalytic oxygen evolution material with shuttle-shaped structure and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |