WO2023173352A1 - 一种催化裂解甲醇或丙烯制备碳纳米管的方法 - Google Patents

一种催化裂解甲醇或丙烯制备碳纳米管的方法 Download PDF

Info

Publication number
WO2023173352A1
WO2023173352A1 PCT/CN2022/081392 CN2022081392W WO2023173352A1 WO 2023173352 A1 WO2023173352 A1 WO 2023173352A1 CN 2022081392 W CN2022081392 W CN 2022081392W WO 2023173352 A1 WO2023173352 A1 WO 2023173352A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
nitrogen
propylene
carbon nanotubes
reaction
Prior art date
Application number
PCT/CN2022/081392
Other languages
English (en)
French (fr)
Inventor
沈宇栋
漆祯祯
Original Assignee
无锡东恒新能源科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 无锡东恒新能源科技有限公司 filed Critical 无锡东恒新能源科技有限公司
Priority to PCT/CN2022/081392 priority Critical patent/WO2023173352A1/zh
Publication of WO2023173352A1 publication Critical patent/WO2023173352A1/zh

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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

Definitions

  • the invention relates to a method for preparing carbon nanotubes by catalytically cracking methanol or propylene, and belongs to the field of chemical technology.
  • Carbon nanotubes are one-dimensional carbon nanomaterials with a hollow tubular structure and a high aspect ratio. They are composed of carbon atoms arranged in a hexagonal shape. Carbon nanotubes have super tensile strength, excellent thermal conductivity and excellent electrical conductivity. Carbon nanotubes have achieved commercial applications in conductive plastics and battery additives. In recent years, carbon nanotubes, as excellent conductive agents, have been widely used in the new energy vehicle lithium battery industry. Because of its ultra-high aspect ratio and high conductivity, compared with traditional conductive agents graphite and superP, a very small amount of addition can form an efficient three-dimensional conductive network structure in the electrode. The conductive efficiency is extremely high and it can also improve Battery energy density, service life and other key indicators.
  • carbon nanotubes are mainly prepared by chemical vapor precipitation, and the production cost is high.
  • the main reason is that carbon nanotubes have a hollow tubular structure and the particles and bulk density of the catalyst are relatively small, resulting in the bulk density of the growing carbon nanotubes (Apparent). Density) is relatively low, basically in the range of 0.01 to 0.1g/ml. The longer the length of the carbon nanotube, the more obvious the repulsion effect, and the smaller the density of the carbon nanotube.
  • the space utilization of the CVD cracking furnace can be effectively improved.
  • the present invention is a method of producing high-density carbon nanotubes by increasing the size of catalyst particles and bulk density, and loading the metal element cobalt through a uniform precipitation method to obtain a high-performance and high-activity catalyst.
  • the invention provides a method for preparing carbon nanotubes, which includes the following steps:
  • catalyst Dissolve soluble cobalt salt, urea, and ammonium heptamolybdate tetrahydrate in water and mix well to obtain a cobalt solution; disperse ammonium carbonate and hydrogen peroxide in water, then add titanium alumina and mix well to obtain water Talc suspension; mix the cobalt solution and the hydrotalcite suspension, and perform a hydrothermal reaction. After completion, the solid-liquid separation is performed, the solid is collected, washed, roasted, and sieved and crushed to obtain the catalyst;
  • step (2) The catalyst obtained in step (1) is subjected to reduction treatment, and then added to the fluidized bed reactor, and the carbon source reaction gas is introduced.
  • the catalyst catalyzes the cracking of the carbon source reaction gas, and the reaction produces carbon nanotubes.
  • the mass ratio of the soluble cobalt salt and urea in step (1) is 1: (8-10).
  • the mass ratio of the soluble cobalt salt in step (1) and ammonium heptamolybdate tetrahydrate is 1: (0.05-0.1).
  • the concentration of the soluble cobalt salt in the cobalt solution in step (1) is 0.02-0.03g/mL.
  • the soluble cobalt salt in step (1), may be cobalt nitrate hexahydrate.
  • the mass fraction of titanium alumina in the hydrotalcite suspension is 0.1-0.3g/mL. Specifically, 0.125g/mL can be selected.
  • step (1) the mass ratio of ammonium carbonate, hydrogen peroxide, and titanium alumina is 5:4:10.
  • step (1) the mass ratio of soluble cobalt salt and titanium alumina is (0.8-1.2):1.
  • the oil bath temperature of the hydrothermal reaction is 100-110°C; the time is 5-8 hours.
  • step (1) after the reaction is completed, the reaction mixture is kept incubated and left to stand for 6 hours; the precipitate is collected by suction filtration.
  • step (1) washing is performed until the pH value of the filtrate becomes neutral.
  • the calcining temperature is 350-450°C and the calcining time is 1-2 h.
  • the mesh number of sieving and crushing is 40-80 mesh.
  • the reduction treatment includes: placing the catalyst in a reducer, flowing in nitrogen and hydrogen, and performing reduction treatment on the catalyst.
  • the amount of nitrogen introduced in the reduction treatment is 5 slm; the amount of hydrogen introduced is 20 slm;
  • the treatment time in the reduction treatment is 10 minutes; the temperature is 500°C.
  • the carbon source in the carbon source reaction gas is methanol or propylene, and the carrier gas is nitrogen.
  • step (2) 9 slm of propylene and 10 slm of nitrogen are introduced to react for 15 minutes, and then 11.6 slm of propylene and 10 slm of nitrogen are introduced for 50 minutes.
  • the present invention prepares and provides a carbon nanotube based on the above method.
  • the invention also provides the application of the above-mentioned carbon nanotubes in the field of new energy vehicle lithium batteries.
  • This method uses an alumina titanium carrier ( ⁇ -Al 2 O 3 -TiO 2 ) to be activated by ammonium carbonate and hydrogen peroxide solutions, and then uses a uniform precipitation method to load the transition metal element cobalt, and the utilization rate of cobalt is improved.
  • alumina titanium carrier ⁇ -Al 2 O 3 -TiO 2
  • the present invention adopts the method of preparing a single crystal catalyst to improve the mechanical strength and bulk density of the catalyst, thereby reducing the crushing and powdering during the catalytic cracking reaction, and the catalyst has strong activity.
  • the present invention utilizes high-temperature catalytic cracking of methanol or propylene in a fluidized bed to prepare carbon nanotubes, and the process is simple and easy to operate.
  • the bulk density (Apparent Density) of the carbon nanotubes produced by the method of the present invention is increased by 20% (about 0.012g/ml), maintained at 0.01-0.025, and the purity is The change in specific surface area is small (preferably maintained at 250-300m2/g), the length of carbon nanotubes remains at 20-40 microns, and the resistivity does not exceed 43 ⁇ m.
  • Figure 1 is a scanning electron microscope image of the catalyst in Example 1 magnified 5000 times; Figures a and b were taken at different angles.
  • Figure 2 is a scanning electron microscope image of the catalyst in Example 1 magnified 3000 times.
  • Figure 3 is a scanning electron microscope image of the carbon nanotubes obtained in Example 1.
  • Figure 4 is a scanning electron microscope image of the carbon nanotubes obtained in Example 2.
  • Figure 5 is a scanning electron microscope image of the carbon nanotubes obtained in Example 3.
  • the small fluidized bed reactor with a diameter of 100mm and a height of 1200mm is heated to 660°C, and the matching small reducer is heated to 500°C.
  • the reducer added 5g of the above catalyst through the additive tank, introduced 5slm of nitrogen and 20slm of hydrogen for reduction for 10 minutes, and then transported the catalyst to the reactor through nitrogen.
  • the air inlet nozzle at the bottom of the reactor passes through the flow meter to 9slm propylene and 10slm nitrogen to react for 15 minutes, then 11.6slm propylene and 10slm nitrogen to react for 50 minutes.
  • the reaction gas is stopped, and the product is transported to the carbon nanotube storage through nitrogen. inside the tank.
  • FIG. 1 The scanning electron microscope image of the prepared catalyst is shown in Figure 1. It can be clearly seen from this figure that the particle size of the catalyst in the present invention has been significantly improved, and the catalyst has no fine differentiation, which lays the foundation for the efficient growth of carbon nanotubes.
  • Figure 2 is a scanning electron microscope image of the catalyst magnified 3000 times. From this figure, we can see that the catalyst particles do not have obvious agglomeration on a microscopic level, and each catalyst particle is uniform, which increases the bulk density of the catalyst and enhances the catalyst activity.
  • the scanning electron microscope image of the synthesized carbon nanotubes is shown in Figure 3.
  • the obtained carbon nanotube has a bulk density of 0.012g/ml, a yield of 26 times, a resistivity of 43 ⁇ m, a specific surface area of 272m2/g, an ash content of 3.0%, and a length of 20 ⁇ m.
  • the small fluidized bed reactor with a diameter of 100mm and a height of 1200mm is heated to 660°C, and the matching small reducer is heated to 500°C.
  • the reducer added 5g of the above catalyst through the additive tank, introduced 5slm of nitrogen and 20slm of hydrogen for reduction for 10 minutes, and then transported the catalyst to the reactor through nitrogen.
  • the air inlet nozzle at the bottom of the reactor passes through the flow meter to 9slm methanol and 10slm nitrogen to react for 15 minutes, then 11.6slm methanol and 10slm nitrogen to react for 50 minutes. After the reaction is completed, the reaction gas is stopped, and the product is transported to the carbon nanotube storage through nitrogen. inside the tank.
  • the scanning electron microscope image of the synthesized carbon nanotubes is shown in Figure 4.
  • the obtained carbon nanotube has a bulk density of 0.013g/ml, a yield of 25.6 times, a resistivity of 42 ⁇ m, a specific surface area of 272m2/g, an ash content of 3.0%, and a length of 20 ⁇ m.
  • the small fluidized bed reactor with a diameter of 100mm and a height of 1200mm is heated to 660°C, and the matching small reducer is heated to 500°C.
  • the reducer added 5g of the above catalyst through the additive tank, introduced 5slm of nitrogen and 20slm of hydrogen for reduction for 10 minutes, and then transported the catalyst to the reactor through nitrogen.
  • the air inlet nozzle at the bottom of the reactor passes through the flow meter to 9slm methanol and 10slm nitrogen to react for 15 minutes, then 11.6slm propylene and 10slm nitrogen to react for 50 minutes.
  • the reaction gas is stopped, and the product is transported to the carbon nanotube storage through nitrogen. inside the tank.
  • the scanning electron microscope image of the synthesized carbon nanotubes is shown in Figure 5.
  • the obtained carbon nanotube has a bulk density of 0.013g/ml, a yield of 26.2 times, a resistivity of 43 ⁇ m, a specific surface area of 269m2/g, an ash content of 3.0%, and a length of 20 ⁇ m.
  • a small fluidized bed reactor with a diameter of 100mm and a height of 1200mm is heated to 660°C, and the matching small reducer is heated to 500°C.
  • the reducer added 5g of the above catalyst through the additive tank, introduced 5slm of nitrogen and 20slm of hydrogen for reduction for 10 minutes, and then transported the catalyst to the reactor through nitrogen.
  • the air inlet nozzle at the bottom of the reactor passes through the flow meter to 9slm propylene and 10slm nitrogen to react for 15 minutes, then 11.6slm propylene and 10slm nitrogen to react for 50 minutes.
  • the reaction gas is stopped, and the product is transported to the carbon nanotube storage through nitrogen. inside the tank.
  • the synthesized carbon nanotubes have a bulk density of 0.053g/ml, a yield of 16 times, a resistivity of 63 ⁇ m, a specific surface area of 152m2/g, an ash content of 6.5%, and a length of 10 ⁇ m.
  • a small fluidized bed reactor with a diameter of 100mm and a height of 1200mm is heated to 660°C, and the matching small reducer is heated to 500°C.
  • the reducer added 5g of the above catalyst through the additive tank, introduced 5slm of nitrogen and 20slm of hydrogen for reduction for 10 minutes, and then transported the catalyst to the reactor through nitrogen.
  • the air inlet nozzle at the bottom of the reactor passes through the flow meter to 9slm propylene and 10slm nitrogen to react for 15 minutes, then 11.6slm propylene and 10slm nitrogen to react for 50 minutes.
  • the reaction gas is stopped, and the product is transported to the carbon nanotube storage through nitrogen. inside the tank.
  • the synthesized carbon nanotubes have a bulk density of 0.33g/ml, a yield of 3.6 times, a resistivity of 168 ⁇ m, a specific surface area of 232m2/g, an ash content of 7.6%, and a length of 13 ⁇ m.
  • a small fluidized bed reactor with a diameter of 100mm and a height of 1200mm is heated to 660°C, and the matching small reducer is heated to 500°C.
  • the reducer added 5g of the above catalyst through the additive tank, introduced 5slm of nitrogen and 20slm of hydrogen for reduction for 10 minutes, and then transported the catalyst to the reactor through nitrogen.
  • the air inlet nozzle at the bottom of the reactor passes through the flow meter to 9slm propylene and 10slm nitrogen to react for 15 minutes, then 11.6slm propylene and 10slm nitrogen to react for 50 minutes.
  • the reaction gas is stopped, and the product is transported to the carbon nanotube storage through nitrogen. inside the tank.
  • the synthesized carbon nanotubes have a bulk density of 0.009g/ml, a yield of 18 times, a resistivity of 68 ⁇ m, a specific surface area of 252m2/g, an ash content of 4.5%, and a length of 18 ⁇ m.
  • a small fluidized bed reactor with a diameter of 100mm and a height of 1200mm is heated to 660°C, and the matching small reducer is heated to 500°C.
  • the reducer added 5g of the above catalyst through the additive tank, introduced 5slm of nitrogen and 20slm of hydrogen for reduction for 10 minutes, and then transported the catalyst to the reactor through nitrogen.
  • the air inlet nozzle at the bottom of the reactor passes through the flow meter to 9slm propylene and 10slm nitrogen to react for 15 minutes, then 11.6slm propylene and 10slm nitrogen to react for 50 minutes.
  • the reaction gas is stopped, and the product is transported to the carbon nanotube storage through nitrogen. inside the tank.
  • the synthesized carbon nanotubes have a bulk density of 0.007g/ml, a yield of 24 times, a resistivity of 62 ⁇ m, a specific surface area of 242m2/g, an ash content of 5.2%, and a length of 12 ⁇ m.
  • a small fluidized bed reactor with a diameter of 100mm and a height of 1200mm is heated to 660°C, and the matching small reducer is heated to 500°C.
  • the reducer added 5g of the above catalyst through the additive tank, introduced 5slm of nitrogen and 20slm of hydrogen for reduction for 10 minutes, and then transported the catalyst to the reactor through nitrogen.
  • the air inlet nozzle at the bottom of the reactor is passed through the flow meter to pass 9slm cyclohexane and 10slm nitrogen for 15 minutes, and then 11.6slm cyclohexane and 10slm nitrogen are passed for 50 minutes.
  • the reaction gas is stopped, and the product is transported to Inside the carbon nanotube storage tank.
  • the synthesized carbon nanotubes have a bulk density of 0.13g/ml, a yield of 1.8 times, a resistivity of 222 ⁇ m, a specific surface area of 23m2/g, an ash content of 63%, and a length of 9 ⁇ m.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Catalysts (AREA)

Abstract

一种催化裂解甲醇或丙烯制备碳纳米管的方法，使用氧化铝钛载体(γ-Al 2O 3-TiO 2)经过碳酸铵和双氧水溶液活化后，采用均匀沉淀法负载过渡金属元素钴，钴的利用率得到了提高。采用制备单晶催化剂来提高催化剂的机械强度和堆密度，减少了催化裂解反应过程的破碎和粉化，催化剂的活性较强；利用流化床高温催化裂解甲醇和丙烯制备碳纳米管，工艺简单易操作。

Description

一种催化裂解甲醇或丙烯制备碳纳米管的方法 技术领域
本发明涉及一种催化裂解甲醇或丙烯制备碳纳米管的方法，属于化学技术领域。
背景技术
碳纳米管是一种具有中空管状结构和高的长径比的一维纳米碳材料，以六边形排列的碳原子构成。碳纳米管拥有超强的拉伸强度，卓越的导热性能和优异的导电性能，碳纳米管已在导电塑料和电池添加剂方面实现了商业应用。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行业得到广泛应用。因其具有超高长径比和高导电性，与传统导电剂石墨、superP相比，很少的添加量，便能在电极内组建高效的三维导电网络结构，导电效率极高，同时可提升电池能量密度、使用寿命等关键指标。因此，合成新型的碳纳米管导电剂取代传统导电剂已成为趋势。大吨位的碳纳米管可以通过化学气相沉淀的工艺实现，对于多壁碳纳米管，其问题在于，随着多壁碳纳米管数的增加，无序石墨的比例增加，从而导致多壁碳纳米管的品质降低，为此，工业界一直在努力减少多壁碳纳米管的壁数而不降低多壁碳纳米管的生产产量和生产品质。
目前碳纳米管的制备主要通过化学气相沉淀法，生产成本较高，其主要原因是碳纳米管属于中空管状结构及催化剂的颗粒和堆密度都比较小，导致生长的碳纳米管堆密度(Apparent Density)偏低，基本都在0.01～0.1g/ml这个范围，而碳纳米管的长度越长，排斥效应越明显，碳纳米管的堆密度就越小。在尽量不改变碳纳米管的性能和结构的基础上，通过提高载体表面的催化剂的有效负载量以提高碳纳米管产物的堆密度，可以有效提高CVD裂解炉的空间利用率。因此，为了生产出高性能高产率的碳纳米管，提高催化剂的堆密度和颗粒大小势在必行。基于此种情况，本发明就是一种通过提高催化剂颗粒和堆密度大小，通过均匀沉淀法负载金属元素钴，得到高性能高活性的催化剂，生产高堆密度的碳纳米管的方法。
发明内容
本发明提供一种制备碳纳米管的方法，包括如下步骤：
(1)制备催化剂：将可溶性钴盐、尿素、四水七钼酸铵溶解在水中，混匀，获得钴溶液；将碳酸铵、双氧水分散在水中，然后加入氧化铝钛，混匀，获得水滑石悬浊液；将钴溶液和水滑石悬浊液混合，并进行水热反应，结束后，固液分离、收集固体，洗涤，焙烧，过筛破 碎，得到催化剂；
(2)步骤(1)所得催化剂经过还原处理，然后加入到流化床反应器中，通入碳源反应气，催化剂催化碳源反应气裂解，反应得到碳纳米管。
在本发明的一种实施方式中，步骤(1)所述可溶性钴盐与尿素的质量比为1：(8-10)。
在本发明的一种实施方式中，步骤(1)所述可溶性钴盐与四水七钼酸铵的质量比为1：(0.05-0.1)。
在本发明的一种实施方式中，步骤(1)所述钴溶液中可溶性钴盐的浓度为0.02-0.03g/mL。
在本发明的一种实施方式中，步骤(1)中，可溶性钴盐可选六水硝酸钴。
在本发明的一种实施方式中，步骤(1)中，水滑石悬浊液中氧化铝钛的质量分数为0.1-0.3g/mL。具体可选0.125g/mL。
在本发明的一种实施方式中，步骤(1)中，碳酸铵、双氧水、氧化铝钛的质量比为5：4：10。
在本发明的一种实施方式中，步骤(1)中，可溶性钴盐、氧化铝钛的质量比为(0.8-1.2)：1。
在本发明的一种实施方式中，步骤(1)中，水热反应的油浴温度为100-110℃；时间为5-8h。
在本发明的一种实施方式中，步骤(1)中，反应结束后，保温静置6小时；抽滤、收集沉淀。
在本发明的一种实施方式中，步骤(1)中，洗涤至滤液pH值呈中性。
在本发明的一种实施方式中，焙烧的温度为350-450℃，时间为1-2h。
在本发明的一种实施方式中，过筛破碎的目数为40-80目。
在本发明的一种实施方式中，步骤(2)中，还原处理包括：将催化剂置于还原器，通入氮气和氢气，对催化剂进行还原处理。
在本发明的一种实施方式中，还原处理中的氮气通入量为5slm；氢气通入量为20slm；
在本发明的一种实施方式中，还原处理中通入处理的时间为10min；温度为500℃。
在本发明的一种实施方式中，步骤(2)中，碳源反应气中碳源为甲醇或者丙烯，载气为氮气。
在本发明的一种实施方式中，步骤(2)中，通入9slm丙烯、10slm氮气反应15min，然后通入11.6slm丙烯、10slm氮气反应50min。
本发明基于上述方法制备提供了一种碳纳米管。
本发明还提供了上述碳纳米管在新能源汽车锂电池领域中的应用。
有益效果
本方法使用氧化铝钛载体(γ-Al 2O 3-TiO 2)经过碳酸铵和双氧水溶液活化后，采用均匀沉淀法负载过渡金属元素钴，钴的利用率得到了提高。
本发明采用制备单晶催化剂来提高催化剂的机械强度和堆密度，减少了催化裂解反应过程的破碎和粉化，催化剂的活性较强。
本发明利用流化床高温催化裂解甲醇或丙烯制备碳纳米管，工艺简单易操作。
本发明方法生产的碳纳米管相比凝胶法或共沉淀CoMgAl催化剂合成的碳纳米管，堆密度(Apparent Density)增加了20％(大约0.012g/ml)、维持在0.01-0.025，且纯度和比表面积变化较小(较好维持在250-300㎡/g)，碳纳米管的长度依然保持在20-40微米，电阻率不超过43Ω·m。
附图说明
图1为实施例1中催化剂放大5000倍的扫描电镜图；图a、b分别是在不同角度拍摄得到。
图2为实施例1中催化剂放大3000倍的扫描电镜图。
图3是实施例1所得碳纳米管的扫描电镜图。
图4是实施例2所得碳纳米管的扫描电镜图。
图5是实施例3所得碳纳米管的扫描电镜图。
具体实施方式
以下结合具体实例，对本发明一种碳纳米管的合成方法行具体说明。
实施例1
(1)制备催化剂：
称取9.2g六水硝酸钴、90g尿素、0.7g四水七钼酸铵，加400g纯水，搅拌溶解，配制得到钴溶液；另外称取80g纯水、5g碳酸铵、4g双氧水，搅拌溶解后加入10g氧化铝钛载体，浸泡30min，得到水滑石悬浊液。然后将钴溶液和水滑石悬浊液倒入500mL圆底烧瓶中，105℃油浴加热、磁力搅拌反应6小时；反应结束停止搅拌，保温静置6小时；抽滤、收集沉淀，纯水洗涤至滤液pH值呈中性，置于马弗炉400℃焙烧1h，80目过筛破碎，得到催化剂。
(2)制备碳纳米管：
将直径100mm、高度1200mm的小型流化床反应器升温至660℃，配套的小型还原器升 温至500℃。还原器通过加剂罐加入5g上述催化剂，通入5slm氮气和20slm氢气还原10min，然后将催化剂通过氮气输送至反应器内。反应器底部的进气喷头通过流量计通入9slm丙烯、10slm氮气反应15min，然后通入11.6slm丙烯、10slm氮气反应50min，反应结束停止通入反应气体，将产物通过氮气输送至碳纳米管储罐内。
制备得到的催化剂的扫描电镜图如图1所示。从此图可以很明显的看到，本发明中催化剂的颗粒大小得到了明显的改善，催化剂没有细小分化，为碳纳米管的高效生长打下了基础。图2为催化剂放大3000倍的扫描电镜图。从此图中我们可以看到，催化剂的颗粒在微观上没有出现明显的团聚现象，每个催化剂颗粒均一，这使得催化剂的堆密度得到增大，催化剂活性增强。
合成的碳纳米管的扫描电镜图如图3所示。所得的碳纳米管堆密度为0.012g/ml，产率26倍，电阻率43Ω·m，比表面积272㎡/g、灰分3.0％，长度20μm。
实施例2
(1)制备催化剂：
称取9.2g六水硝酸钴、90g尿素、0.7g四水七钼酸铵，加400g纯水，搅拌溶解，配制得到钴溶液。另外称取80g纯水、5g碳酸铵、4g双氧水，搅拌溶解后加入10g氧化铝钛载体，浸泡30min，得到水滑石悬浊液。然后将钴溶液和水滑石悬浊液倒入500mL圆底烧瓶，105℃油浴加热、磁力搅拌反应6小时。反应结束停止搅拌，保温静置6小时；抽滤、收集沉淀，纯水洗涤至滤液pH值呈中性，置于马弗炉400℃焙烧1h，80目过筛破碎，得到催化剂。。
(2)制备碳纳米管：
直径100mm、高度1200mm的小型流化床反应器升温至660℃，配套的小型还原器升温至500℃。还原器通过加剂罐加入5g上述催化剂，通入5slm氮气和20slm氢气还原10min，然后将催化剂通过氮气输送至反应器内。反应器底部的进气喷头通过流量计通入9slm甲醇、10slm氮气反应15min，然后通入11.6slm甲醇、10slm氮气反应50min，反应结束停止通入反应气体，将产物通过氮气输送至碳纳米管储罐内。
合成的碳纳米管的扫描电镜图如图4所示。所得的碳纳米管堆密度为0.013g/ml，产率25.6倍，电阻率42Ω·m，比表面积272㎡/g、灰分3.0％，长度20μm。
实施例3
(1)制备催化剂：
称取9.2g六水硝酸钴、90g尿素、0.7g四水七钼酸铵，加400g纯水，搅拌溶解，配制得到钴溶液。另外称取80g纯水、5g碳酸铵、4g双氧水，搅拌溶解后加入12g氧化铝钛载体，浸泡30min，得到水滑石悬浊液。然后将钴溶液和水滑石悬浊液倒入500mL圆底烧瓶，105℃ 油浴加热、磁力搅拌反应6小时。反应结束停止搅拌，保温静置6小时；抽滤、收集沉淀，纯水洗涤至滤液pH值呈中性，置于马弗炉400℃焙烧1h，40目过筛破碎，得到催化剂。。
(2)制备碳纳米管：
直径100mm、高度1200mm的小型流化床反应器升温至660℃，配套的小型还原器升温至500℃。还原器通过加剂罐加入5g上述催化剂，通入5slm氮气和20slm氢气还原10min，然后将催化剂通过氮气输送至反应器内。反应器底部的进气喷头通过流量计通入9slm甲醇、10slm氮气反应15min，然后通入11.6slm丙烯、10slm氮气反应50min，反应结束停止通入反应气体，将产物通过氮气输送至碳纳米管储罐内。
合成的碳纳米管的扫描电镜图如图5所示。所得的碳纳米管堆密度为0.013g/ml，产率26.2倍，电阻率43Ω·m，比表面积269㎡/g、灰分3.0％，长度20μm。
对比例1 相比实施例1，仅替换钴为铁
(1)制备催化剂：
称取9.2g硝酸铁、90g尿素、0.7g四水七钼酸铵，加400g纯水，搅拌溶解，配制得到铁溶液；另外称取80g纯水、5g碳酸铵、4g双氧水，搅拌溶解后加入10g氧化铝钛载体，浸泡30min，得到水滑石悬浊液。然后将钴溶液和水滑石悬浊液倒入500mL圆底烧瓶中，105℃油浴加热、磁力搅拌反应6小时；反应结束停止搅拌，保温静置6小时；抽滤、收集沉淀，纯水洗涤至滤液pH值呈中性，置于马弗炉400℃焙烧1h，80目过筛破碎，得到催化剂。
(2)制备碳纳米管：
将直径100mm、高度1200mm的小型流化床反应器升温至660℃，配套的小型还原器升温至500℃。还原器通过加剂罐加入5g上述催化剂，通入5slm氮气和20slm氢气还原10min，然后将催化剂通过氮气输送至反应器内。反应器底部的进气喷头通过流量计通入9slm丙烯、10slm氮气反应15min，然后通入11.6slm丙烯、10slm氮气反应50min，反应结束停止通入反应气体，将产物通过氮气输送至碳纳米管储罐内。
合成的碳纳米管堆密度为0.053g/ml，产率16倍，电阻率63Ω·m，比表面积152㎡/g、灰分6.5％，长度10μm。
对比例2 相比实施例1，仅将氧化铝钛替换为氧化铝硅
(1)制备催化剂：
称取9.2g六水硝酸钴、90g尿素、0.7g四水七钼酸铵，加400g纯水，搅拌溶解，配制得到钴溶液；另外称取80g纯水、5g碳酸铵、4g双氧水，搅拌溶解后加入10g氧化铝硅载体，浸泡30min，得到水滑石悬浊液。然后将钴溶液和水滑石悬浊液倒入500mL圆底烧瓶中，105℃油浴加热、磁力搅拌反应6小时；反应结束停止搅拌，保温静置6小时；抽滤、收集沉淀， 纯水洗涤至滤液pH值呈中性，置于马弗炉400℃焙烧1h，80目过筛破碎，得到催化剂。
(2)制备碳纳米管：
将直径100mm、高度1200mm的小型流化床反应器升温至660℃，配套的小型还原器升温至500℃。还原器通过加剂罐加入5g上述催化剂，通入5slm氮气和20slm氢气还原10min，然后将催化剂通过氮气输送至反应器内。反应器底部的进气喷头通过流量计通入9slm丙烯、10slm氮气反应15min，然后通入11.6slm丙烯、10slm氮气反应50min，反应结束停止通入反应气体，将产物通过氮气输送至碳纳米管储罐内。
合成的碳纳米管堆密度为0.33g/ml，产率3.6倍，电阻率168Ω·m，比表面积232㎡/g、灰分7.6％，长度13μm。
对比例3 相比实施例1，仅改变钴源用量
(1)制备催化剂：
称取4.6g六水硝酸钴、90g尿素、0.7g四水七钼酸铵，加400g纯水，搅拌溶解，配制得到钴溶液；另外称取80g纯水、5g碳酸铵、4g双氧水，搅拌溶解后加入10g氧化铝钛载体，浸泡30min，得到水滑石悬浊液。然后将钴溶液和水滑石悬浊液倒入500mL圆底烧瓶中，105℃油浴加热、磁力搅拌反应6小时；反应结束停止搅拌，保温静置6小时；抽滤、收集沉淀，纯水洗涤至滤液pH值呈中性，置于马弗炉400℃焙烧1h，80目过筛破碎，得到催化剂。
(2)制备碳纳米管：
将直径100mm、高度1200mm的小型流化床反应器升温至660℃，配套的小型还原器升温至500℃。还原器通过加剂罐加入5g上述催化剂，通入5slm氮气和20slm氢气还原10min，然后将催化剂通过氮气输送至反应器内。反应器底部的进气喷头通过流量计通入9slm丙烯、10slm氮气反应15min，然后通入11.6slm丙烯、10slm氮气反应50min，反应结束停止通入反应气体，将产物通过氮气输送至碳纳米管储罐内。
合成的碳纳米管堆密度为0.009g/ml，产率18倍，电阻率68Ω·m，比表面积252㎡/g、灰分4.5％，长度18μm。
对比例4 相比实施例1，仅改变钴源用量
(1)制备催化剂：
称取18.4g六水硝酸钴、90g尿素、0.7g四水七钼酸铵，加400g纯水，搅拌溶解，配制得到钴溶液；另外称取80g纯水、5g碳酸铵、4g双氧水，搅拌溶解后加入10g氧化铝钛载体，浸泡30min，得到水滑石悬浊液。然后将钴溶液和水滑石悬浊液倒入500mL圆底烧瓶中，105℃油浴加热、磁力搅拌反应6小时；反应结束停止搅拌，保温静置6小时；抽滤、收集沉淀，纯水洗涤至滤液pH值呈中性，置于马弗炉400℃焙烧1h，80目过筛破碎，得到催化剂。
(2)制备碳纳米管：
将直径100mm、高度1200mm的小型流化床反应器升温至660℃，配套的小型还原器升温至500℃。还原器通过加剂罐加入5g上述催化剂，通入5slm氮气和20slm氢气还原10min，然后将催化剂通过氮气输送至反应器内。反应器底部的进气喷头通过流量计通入9slm丙烯、10slm氮气反应15min，然后通入11.6slm丙烯、10slm氮气反应50min，反应结束停止通入反应气体，将产物通过氮气输送至碳纳米管储罐内。
合成的碳纳米管堆密度为0.007g/ml，产率24倍，电阻率62Ω·m，比表面积242㎡/g、灰分5.2％，长度12μm。
对比例5 相比实施例1，仅替换碳源种类
(1)制备催化剂：
称取9.2g六水硝酸钴、90g尿素、0.7g四水七钼酸铵，加400g纯水，搅拌溶解，配制得到钴溶液；另外称取80g纯水、5g碳酸铵、4g双氧水，搅拌溶解后加入10g氧化铝钛载体，浸泡30min，得到水滑石悬浊液。然后将钴溶液和水滑石悬浊液倒入500mL圆底烧瓶中，105℃油浴加热、磁力搅拌反应6小时；反应结束停止搅拌，保温静置6小时；抽滤、收集沉淀，纯水洗涤至滤液pH值呈中性，置于马弗炉400℃焙烧1h，80目过筛破碎，得到催化剂。
(2)制备碳纳米管：
将直径100mm、高度1200mm的小型流化床反应器升温至660℃，配套的小型还原器升温至500℃。还原器通过加剂罐加入5g上述催化剂，通入5slm氮气和20slm氢气还原10min，然后将催化剂通过氮气输送至反应器内。反应器底部的进气喷头通过流量计通入9slm环己烷、10slm氮气反应15min，然后通入11.6slm环己烷、10slm氮气反应50min，反应结束停止通入反应气体，将产物通过氮气输送至碳纳米管储罐内。
合成的碳纳米管堆密度为0.13g/ml，产率1.8倍，电阻率222Ω·m，比表面积23㎡/g、灰分63％，长度9μm。

Claims (10)

  1. 一种制备碳纳米管的方法，其特征在于，包括如下步骤：
    (1)制备催化剂：将可溶性钴盐、尿素、四水七钼酸铵溶解在水中，混匀，获得钴溶液；将碳酸铵、双氧水分散在水中，然后加入氧化铝钛，混匀，获得水滑石悬浊液；将钴溶液和水滑石悬浊液混合，并进行水热反应，结束后，固液分离、收集固体，洗涤，焙烧，过筛破碎，得到催化剂；
    (2)步骤(1)所得催化剂经过还原处理，然后加入到流化床反应器中，通入碳源反应气，催化剂催化碳源反应气裂解，反应得到碳纳米管。
  2. 根据权利要求1所述的方法，其特征在于，步骤(1)所述可溶性钴盐、尿素、四水七钼酸铵的质量比为1：(8-10)：(0.05-0.1)。
  3. 根据权利要求1所述的方法，其特征在于，步骤(1)所述钴溶液中可溶性钴盐的浓度为0.02-0.03g/mL。
  4. 根据权利要求1所述的方法，其特征在于，步骤(1)中，水滑石悬浊液中氧化铝钛的质量分数为0.1-0.3g/mL。
  5. 根据权利要求1所述的方法，其特征在于，步骤(1)中，碳酸铵、双氧水、氧化铝钛的质量比为5：4：10。
  6. 根据权利要求1所述的方法，其特征在于，步骤(1)中，可溶性钴盐、氧化铝钛的质量比为(0.8-1.2)：1。
  7. 根据权利要求1所述的方法，其特征在于，步骤(2)中，碳源反应气中碳源为甲醇或者丙烯，载气为氮气。
  8. 根据权利要求1所述的方法，其特征在于，步骤(2)中，通入9slm丙烯、10slm氮气反应15min，然后通入11.6slm丙烯、10slm氮气反应50min。
  9. 权利要求1-8任一项所述方法制备得到的碳纳米管。
  10. 权利要求9所述的碳纳米管在新能源汽车锂电池领域中的应用。
PCT/CN2022/081392 2022-03-17 2022-03-17 一种催化裂解甲醇或丙烯制备碳纳米管的方法 WO2023173352A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2022/081392 WO2023173352A1 (zh) 2022-03-17 2022-03-17 一种催化裂解甲醇或丙烯制备碳纳米管的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2022/081392 WO2023173352A1 (zh) 2022-03-17 2022-03-17 一种催化裂解甲醇或丙烯制备碳纳米管的方法

Publications (1)

Publication Number Publication Date
WO2023173352A1 true WO2023173352A1 (zh) 2023-09-21

Family

ID=88021882

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/081392 WO2023173352A1 (zh) 2022-03-17 2022-03-17 一种催化裂解甲醇或丙烯制备碳纳米管的方法

Country Status (1)

Country Link
WO (1) WO2023173352A1 (zh)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1950144A (zh) * 2004-05-11 2007-04-18 约翰森·马瑟公开有限公司 催化剂
JP2015182908A (ja) * 2014-03-20 2015-10-22 公立大学法人大阪市立大学 球状ハイドロタルサイトとその製造方法
CN107454861A (zh) * 2015-01-21 2017-12-08 斯特拉斯堡大学 用于制备高度氮掺杂中孔碳复合材料的方法
CN108079999A (zh) * 2017-12-06 2018-05-29 山东大展纳米材料有限公司 一种连续制备碳纳米管用多金属氧化物孔洞结构催化剂的方法
CN109626357A (zh) * 2019-01-31 2019-04-16 新奥石墨烯技术有限公司 一种超细碳纳米管及其制备方法
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

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1950144A (zh) * 2004-05-11 2007-04-18 约翰森·马瑟公开有限公司 催化剂
JP2015182908A (ja) * 2014-03-20 2015-10-22 公立大学法人大阪市立大学 球状ハイドロタルサイトとその製造方法
CN107454861A (zh) * 2015-01-21 2017-12-08 斯特拉斯堡大学 用于制备高度氮掺杂中孔碳复合材料的方法
CN108079999A (zh) * 2017-12-06 2018-05-29 山东大展纳米材料有限公司 一种连续制备碳纳米管用多金属氧化物孔洞结构催化剂的方法
CN109626357A (zh) * 2019-01-31 2019-04-16 新奥石墨烯技术有限公司 一种超细碳纳米管及其制备方法
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

Similar Documents

Publication Publication Date Title
Wan et al. Defect engineered mesoporous graphitic carbon nitride modified with AgPd nanoparticles for enhanced photocatalytic hydrogen evolution from formic acid
KR101303061B1 (ko) 다중벽 탄소나노튜브 제조용 촉매조성물
Sunny et al. Synthesis and properties of highly stable nickel/carbon core/shell nanostructures
Mhlanga et al. The effect of synthesis parameters on the catalytic synthesis of multiwalled carbon nanotubes using Fe-Co/CaCO3 catalysts
CN103145199B (zh) 一种四氧化三钴/石墨烯复合纳米材料的制备方法
Hu et al. Mechanochemical preparation of single atom catalysts for versatile catalytic applications: A perspective review
Wang et al. A facile self-template and carbonization strategy to fabricate nickel nanoparticle supporting N-doped carbon microtubes
JP2010188337A (ja) 薄型多層カーボンナノチューブ製造用触媒組成物とその調製方法
CN109665512A (zh) 一种多壁碳纳米管的制备方法
Ping et al. Co-production of hydrogen and carbon nanotubes on nickel foam via methane catalytic decomposition
CN113058605B (zh) 碳纳米管用催化剂及其制备方法和应用
CN104640633A (zh) 制备碳纳米管制备用的金属催化剂的方法和使用该催化剂制备碳纳米管的方法
WO2019100949A1 (zh) 一种制备碳纳米管的方法及装置及制备的碳纳米管
CN111495381A (zh) 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
Yang et al. Synthesis of nano onion-like fullerenes by chemical vapor deposition using an iron catalyst supported on sodium chloride
Lv et al. Formation of carbon nanofibers/nanotubes by chemical vapor deposition using Al2O3/KOH
Wen et al. In situ preparation of magnetic nickel-containing functionalized carbon nanotubes to support palladium as a catalyst for the Heck reaction
KR101018660B1 (ko) 다중벽 탄소나노튜브 제조용 촉매조성물
Wang et al. Preparation of bimetallic catalysts Ni-Co and Ni-Fe supported on activated carbon for methane decomposition
Wang et al. Non‐noble metal‐based catalysts applied to hydrogen evolution from hydrolysis of boron hydrides
WO2007108455A1 (ja) カーボンナノコイル製造用触媒粒子およびその製造方法ならびにカーボンナノコイルの製造方法
CN110075899A (zh) 一种多孔氮化硼纳米纤维负载的双金属催化剂的制备方法
Li et al. Synthesis of supported Pd nanocluster catalyst by spontaneous reduction on layered double hydroxide
WO2023159698A1 (zh) 一种高活性催化剂的合成方法
Zhao et al. Enhanced spatial charge separation at surface & interface via GO/MoS2/Ag3PO4 ternary Z-scheme heterostructure for nitrogen photo-fixation

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22931389

Country of ref document: EP

Kind code of ref document: A1