CN1199727C - Catayst for preparing carbon-nano tube - Google Patents
Catayst for preparing carbon-nano tube Download PDFInfo
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- CN1199727C CN1199727C CN 03105056 CN03105056A CN1199727C CN 1199727 C CN1199727 C CN 1199727C CN 03105056 CN03105056 CN 03105056 CN 03105056 A CN03105056 A CN 03105056A CN 1199727 C CN1199727 C CN 1199727C
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 36
- 239000002041 carbon nanotube Substances 0.000 title abstract description 36
- 229910021393 carbon nanotube Inorganic materials 0.000 title abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011777 magnesium Substances 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 12
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 12
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims 4
- 238000005516 engineering process Methods 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 2
- 238000009938 salting Methods 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 235000012222 talc Nutrition 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- YPFNIPKMNMDDDB-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O YPFNIPKMNMDDDB-UHFFFAOYSA-K 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 150000007513 acids Chemical class 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- -1 cobalt-magnesium-aluminum Chemical compound 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 239000002105 nanoparticle Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000001241 arc-discharge method Methods 0.000 description 2
- 150000003840 hydrochlorides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
本发明公开了属于催化剂范围的一种用于制备碳纳米管的催化剂，该催化剂是由镁和铝与过渡金属铁、钴或镍的金属盐溶液与碱溶液的共沉淀反应，制备得到含有铁、钴、镍的多元水滑石前驱体，再经高温焙烧后得到复合氧化物催化剂。该复合氧化物合成方法简单，操作简便，成本低，广泛用于制备碳纳米管。该催化剂溶于常用酸，易与碳纳米管分离。本发明克服了现有技术中工艺复杂、能耗大的缺陷。是具大规模工业生产的一种方法。The invention discloses a catalyst for preparing carbon nanotubes, which belongs to the scope of catalysts. The catalyst is prepared by co-precipitation reaction of metal salt solution of magnesium and aluminum, transition metal iron, cobalt or nickel and alkali solution, and contains iron , cobalt, nickel multi-component hydrotalcite precursor, and then after high-temperature calcination, a composite oxide catalyst is obtained. The composite oxide has simple synthesis method, convenient operation and low cost, and is widely used for preparing carbon nanotubes. The catalyst is soluble in common acids and can be easily separated from carbon nanotubes. The invention overcomes the defects of complex process and high energy consumption in the prior art. It is a method of large-scale industrial production.
Description
技术领域technical field
本发明属于催化剂范围，特别涉及一种用于制备碳纳米管的催化剂。The invention belongs to the scope of catalysts, in particular to a catalyst for preparing carbon nanotubes.
背景技术Background technique
碳纳米管自1991年被Iijima发现以来，其特有的力学、电学和化学性质以及独特的准一维管状分子结构，在未来高科技领域中显示出许多潜在的应用价值，成为化学、物理及材料科学等领域的研究热点。人们正在努力寻找产量大、纯度高、缺陷少、成本低廉，具有工业化制备前景的碳纳米管生产方法。就目前来说，文献报道的制备方法主要有电弧放电法、等离子体法、激光法和化学气相沉积法。电弧放电法、等离子体法和激光法都存在设备及工艺过程复杂、能耗大、成本高的缺点；而化学气相沉积法具有设备简单、操作简便、产物纯度高等优点，是最具大规模工业生产的一种方法。化学气相沉积法生产碳纳米管的关键是催化剂，文献报道采用该法制备碳纳米管的催化剂一般为负载型，载体包括硅胶、分子筛、氧化铝等，也有以有机金属化合物或复合氧化物为催化剂的。负载型催化剂制备碳纳米管存在产物后处理复杂的弊病。Since carbon nanotubes were discovered by Iijima in 1991, their unique mechanical, electrical and chemical properties and unique quasi-one-dimensional tubular molecular structure have shown many potential application values in the future high-tech fields. Research hotspots in science and other fields. People are working hard to find a carbon nanotube production method with large output, high purity, few defects, low cost, and industrialized preparation prospects. At present, the preparation methods reported in the literature mainly include arc discharge method, plasma method, laser method and chemical vapor deposition method. The arc discharge method, plasma method and laser method all have the disadvantages of complex equipment and process, high energy consumption and high cost; while the chemical vapor deposition method has the advantages of simple equipment, easy operation and high product purity, and is the most large-scale industrial method. A method of production. The key to the production of carbon nanotubes by chemical vapor deposition is the catalyst. It is reported in the literature that the catalysts for the preparation of carbon nanotubes by this method are generally supported, and the carriers include silica gel, molecular sieve, alumina, etc. of. The preparation of carbon nanotubes by supported catalysts has the disadvantage of complex post-processing of the product.
CN1335257A和CN1170631A分别公开了一种制备碳纳米管的复合氧化物催化剂，催化剂采用柠檬酸络合法制备，原料价格较高，操作步骤繁琐，能耗大。CN1335257A and CN1170631A respectively disclose a composite oxide catalyst for preparing carbon nanotubes. The catalyst is prepared by a citric acid complexation method, and the raw material price is relatively high, the operation steps are cumbersome, and the energy consumption is large.
发明内容Contents of the invention
本发明的目的是提供一种用于制备碳纳米管的催化剂，其特征在于：所述制备碳纳米管的催化剂由镁和铝与过渡金属铁、钴或镍中的一种或两种组成，其中各成份按摩尔比为：镁∶铝∶铁∶钴∶镍＝(1.7～3.6)∶(0.8～1)∶(0.1～0.2)∶0.3∶(0.2～0.4)。The object of the present invention is to provide a catalyst for preparing carbon nanotubes, characterized in that: the catalyst for preparing carbon nanotubes is composed of one or both of magnesium and aluminum and transition metal iron, cobalt or nickel, The molar ratio of each component is: magnesium: aluminum: iron: cobalt: nickel = (1.7-3.6): (0.8-1): (0.1-0.2): 0.3: (0.2-0.4).
所述制备碳纳米管的催化剂的制备工艺是采用金属盐溶液与碱溶液的共沉淀反应，制备含有铁、钴、镍的多元水滑石前驱体，再经高温焙烧后得到复合氧化物催化剂；制备催化剂具体步骤为：The preparation process of the catalyst for preparing carbon nanotubes is to use the co-precipitation reaction of metal salt solution and alkali solution to prepare a multi-component hydrotalcite precursor containing iron, cobalt and nickel, and then obtain a composite oxide catalyst after high-temperature roasting; preparation Catalyst specific steps are:
1)将镁、铝以及过渡金属铁、钴、镍中的一种或两种的硝酸盐、硫酸盐或盐酸盐按比例溶解于水、醇或者水和醇的混合溶剂中形成盐溶液；1) Magnesium, aluminum, and one or two nitrates, sulfates, or hydrochlorides of transition metals iron, cobalt, and nickel are dissolved in water, alcohol, or a mixed solvent of water and alcohol in proportion to form a salt solution;
2)将氢氧化钠和碳酸钠按摩尔比4.8∶1混合溶于水中或90ml氨水和7.68g(NH4)2CO3溶于30ml的水中配成混合碱溶液；2) Mix and dissolve sodium hydroxide and sodium carbonate in water at a molar ratio of 4.8:1 or dissolve 90ml of ammonia water and 7.68g (NH 4 ) 2 CO 3 in 30ml of water to form a mixed alkali solution;
3)将盐溶液和碱溶液等体积在搅拌下混合，然后在40-90℃晶化0.5-6h，过滤、洗涤、干燥得到多元水滑石，再于500-700℃焙烧3-5h，则得到所制备的催化剂。3) Mix equal volumes of salt solution and alkali solution under stirring, then crystallize at 40-90°C for 0.5-6h, filter, wash, and dry to obtain multi-component hydrotalcite, and then roast at 500-700°C for 3-5h to obtain prepared catalyst.
本发明有益效果是提供的催化剂制备方法简单，成本低，应用该催化剂可制得大量管径均匀的碳纳米管。The beneficial effect of the invention is that the preparation method of the catalyst provided is simple and the cost is low, and a large amount of carbon nanotubes with uniform tube diameters can be prepared by using the catalyst.
具体实施方式Detailed ways
本发明提供一种用于制备碳纳米管的催化剂。所述制备碳纳米管的催化剂由镁和铝与过渡金属铁、钴或镍中的一种或两种组成，其中各成份按摩尔比为：镁∶铝∶铁∶钴∶镍＝(1.7～3.6)∶(0.8～1)∶(0.1～0.2)∶0.3∶(0.2～0.4)。The invention provides a catalyst for preparing carbon nanotubes. The catalyst for preparing carbon nanotubes is composed of one or both of magnesium and aluminum and transition metal iron, cobalt or nickel, wherein the molar ratio of each component is: magnesium: aluminum: iron: cobalt: nickel=(1.7～ 3.6): (0.8-1): (0.1-0.2): 0.3: (0.2-0.4).
所述制备碳纳米管的催化剂的制备工艺是先采用金属盐溶液与碱溶液的共沉淀反应，制备含有铁、钴、镍的多元水滑石前驱体，再经高温焙烧后得到复合氧化物催化剂；制备催化剂具体步骤为：The preparation process of the catalyst for preparing carbon nanotubes is to firstly adopt the co-precipitation reaction of metal salt solution and alkali solution to prepare a multi-component hydrotalcite precursor containing iron, cobalt and nickel, and then obtain a composite oxide catalyst after high-temperature roasting; The specific steps for preparing the catalyst are:
1)将镁、铝以及过渡金属铁、钴、镍中的一种或两种的硝酸盐、硫酸盐或盐酸盐按比例溶解于水、醇或者水和醇的混合溶剂中形成盐溶液；1) Magnesium, aluminum, and one or two nitrates, sulfates, or hydrochlorides of transition metals iron, cobalt, and nickel are dissolved in water, alcohol, or a mixed solvent of water and alcohol in proportion to form a salt solution;
2)将氢氧化钠和碳酸钠按摩尔比4.8∶1混合溶于水中或90ml氨水和7.68g(NH4)2CO3溶于30ml的水中配成混合碱溶液；2) Mix and dissolve sodium hydroxide and sodium carbonate in water at a molar ratio of 4.8:1 or dissolve 90ml of ammonia water and 7.68g (NH 4 ) 2 CO 3 in 30ml of water to form a mixed alkali solution;
3)将盐溶液和碱溶液等体积在搅拌下混合，然后在40-90℃晶化0.5-6h，过滤、洗涤、干燥得到多元水滑石，再于500-700℃焙烧3-5h，则得到所制备的催化剂。3) Mix equal volumes of salt solution and alkali solution under stirring, then crystallize at 40-90°C for 0.5-6h, filter, wash, and dry to obtain multi-component hydrotalcite, and then roast at 500-700°C for 3-5h to obtain prepared catalyst.
下面再举实施例对本发明予以具体说明。The following examples are given to illustrate the present invention in detail.
实施例1Example 1
将18.92g的固体MgSO4·7H2O和3.73g的固体CoSO4·7H2O及14.99g的固体Al2(SO4)3·18H2O(Mg∶Co∶Al＝1.7∶0.3∶1的摩尔比)溶于100ml去离子水中，配成混合盐溶液，另称取8.64gNaOH和4.77gNa2CO3溶于100ml去离子水中配成混合碱溶液。在剧烈搅拌下将盐溶液滴加到碱溶液中，升温至60℃，反应0.5h，生成粉色沉淀，经过滤、洗涤及干燥制得纳米尺寸钴镁铝水滑石Mg3.4Co0.6Al2(OH)12CO3·4H2O，于600℃下焙烧3小时得纳米尺寸钴镁铝复合氧化物。18.92 g of solid MgSO 4 ·7H 2 O and 3.73 g of solid CoSO 4 ·7H 2 O and 14.99 g of solid Al 2 (SO 4 ) 3 ·18H 2 O (Mg:Co:Al=1.7:0.3:1 molar ratio) was dissolved in 100ml of deionized water to form a mixed salt solution, and 8.64g of NaOH and 4.77g of Na 2 CO 3 were dissolved in 100ml of deionized water to form a mixed alkali solution. Add the salt solution dropwise to the alkali solution under vigorous stirring, raise the temperature to 60°C, and react for 0.5h to form a pink precipitate, which is filtered, washed and dried to obtain nano-sized cobalt-magnesium-aluminum hydrotalcite Mg 3.4 Co 0.6 Al 2 (OH ) 12 CO 3 ·4H 2 O, calcined at 600°C for 3 hours to obtain nano-sized cobalt-magnesium-aluminum composite oxide.
碳纳米管的制备在固定床反应器中进行。将200mg钴镁铝复合氧化物催化剂在H2气氛下升温至800℃，通入流量为52ml/min的丙烷及流量为200ml/min的氢气，反应90分钟停止，氩气保护下冷却，收集产物。产物经纯化、洗涤、干燥，得到纯碳纳米管530mg。由本方法制得的碳纳米管外径30-60nm。The preparation of carbon nanotubes is carried out in a fixed bed reactor. Heat 200mg of cobalt-magnesium-aluminum composite oxide catalyst to 800°C under H2 atmosphere, feed propane with a flow rate of 52ml/min and hydrogen with a flow rate of 200ml/min, stop the reaction for 90 minutes, cool under the protection of argon, and collect the product . The product was purified, washed and dried to obtain 530 mg of pure carbon nanotubes. The outer diameter of the carbon nanotubes prepared by the method is 30-60nm.
实施例2Example 2
将20.77g的固体Mg(NO3)2·6H2O和2.62g的固体Ni(NO3)2·6H2O及16.88g的固体Al(NO3)3·9H2O(Mg∶Ni∶Al＝1.8∶0.2∶1的摩尔比)溶于100ml乙醇中配成溶液，另称取90ml氨水和7.68g(NH4)2CO3溶于30ml去离子水中配成混合碱溶液。在剧烈搅拌下将盐溶液快速加到碱溶液中，升温至60℃，反应1.5h，生成绿色沉淀，经过滤、洗涤及干燥制得纳米尺寸镍镁铝水滑石Mg3.6Ni0.4Al2(OH)12CO3·4H2O，于500℃下焙烧5小时得纳米尺寸镍镁铝复合氧化物。20.77 g of solid Mg(NO 3 ) 2 .6H 2 O and 2.62 g of solid Ni(NO 3 ) 2 .6H 2 O and 16.88 g of solid Al(NO 3 ) 3 .9H 2 O (Mg:Ni: Al=1.8:0.2:1 molar ratio) was dissolved in 100ml ethanol to make a solution, and 90ml ammonia water and 7.68g (NH 4 ) 2 CO 3 were weighed and dissolved in 30ml deionized water to make a mixed alkali solution. Quickly add the salt solution to the alkali solution under vigorous stirring, raise the temperature to 60°C, and react for 1.5 hours to form a green precipitate, which is filtered, washed and dried to obtain nano-sized nickel-magnesium-aluminum hydrotalcite Mg 3.6 Ni 0.4 Al 2 (OH ) 12 CO 3 ·4H 2 O, calcined at 500°C for 5 hours to obtain nano-sized nickel-magnesium-aluminum composite oxide.
碳纳米管的制备在固定床反应器中进行。将200mg镍镁铝复合氧化物催化剂在H2气氛下升温至700℃，通入流量为45ml/min的甲烷及流量为200ml/min的氢气，反应60分钟停止，氩气保护下冷却，收集产物。产物经纯化、洗涤、干燥，得到纯碳纳米管300mg。由本方法制得的碳纳米管外径15-35nm。The preparation of carbon nanotubes is carried out in a fixed bed reactor. Heat 200mg of nickel-magnesium-aluminum composite oxide catalyst to 700°C under H2 atmosphere, feed methane with a flow rate of 45ml/min and hydrogen gas with a flow rate of 200ml/min, stop the reaction for 60 minutes, cool under the protection of argon, and collect the product . The product was purified, washed and dried to obtain 300 mg of pure carbon nanotubes. The outer diameter of the carbon nanotubes prepared by the method is 15-35nm.
实施例3Example 3
将23.08g的固体Mg(NO3)2·6H2O和1.82g的固体Fe(NO3)3·9H2O及15.19g的固体Al(NO3)3·9H2O其Mg∶Fe∶Al＝2∶0.1∶0.9(摩尔比)溶于60ml乙醇和60ml去离子水的混合溶剂中配成溶液，另称取8.64gNaOH和4.77gNa2CO3溶于120ml去离子水中配成混合碱溶液。在剧烈搅拌下将盐溶液快速加到碱溶液中，升温至40℃，反应0.5h，生成土黄色沉淀，经过滤、洗涤及干燥制得纳米尺寸铁镁铝水滑石Mg4Fe0.2Al1.9(OH)12CO3·4H2O，于700℃下焙烧4小时得纳米尺寸铁镁铝复合氧化物。23.08 g of solid Mg(NO 3 ) 2 .6H 2 O and 1.82 g of solid Fe(NO 3 ) 3 .9H 2 O and 15.19 g of solid Al(NO 3 ) 3 .9H 2 O were Mg:Fe: Al=2:0.1:0.9 (molar ratio) was dissolved in a mixed solvent of 60ml ethanol and 60ml deionized water to make a solution, and another 8.64gNaOH and 4.77gNa2CO3 were weighed and dissolved in 120ml deionized water to make a mixed alkali solution . Quickly add the salt solution to the alkali solution under vigorous stirring, raise the temperature to 40°C, and react for 0.5h to form a khaki-yellow precipitate, which is filtered, washed and dried to obtain nano-sized iron-magnesium-aluminum hydrotalcite Mg 4 Fe 0.2 Al 1.9 ( OH) 12 CO 3 ·4H 2 O, calcined at 700°C for 4 hours to obtain nano-sized iron-magnesium-aluminum composite oxide.
碳纳米管的制备在固定床反应器中进行，将200mg铁镁铝复合氧化物催化剂在H2气氛下升温至500℃，通入流量为45ml/min的乙烯及流量为205ml/min的氢气，反应120分钟停止，氩气保护下冷却，收集产物。产物经纯化、洗涤、干燥，得到纯碳纳米管380mg。由本方法制得的碳纳米管外径15-30nm。The preparation of carbon nanotubes is carried out in a fixed-bed reactor. 200mg of iron-magnesium-aluminum composite oxide catalyst is heated to 500°C under H2 atmosphere, and ethylene with a flow rate of 45ml/min and hydrogen with a flow rate of 205ml/min are introduced. The reaction was stopped after 120 minutes, cooled under the protection of argon, and the product was collected. The product was purified, washed and dried to obtain 380 mg of pure carbon nanotubes. The outer diameter of the carbon nanotubes prepared by the method is 15-30nm.
实施例4Example 4
由7.70g的固体MgCl2，1.17g的固体NiCl2和0.73g的固体FeCl3及5.41g的固体AlCl3的水溶液，其中Mg∶Ni∶Fe∶Al＝1.8∶0.2∶0.1∶0.9(摩尔比)与8.64gNaOH和4.77gNa2CO3碱溶液于90℃反应6h，制备镍铁镁铝水滑石前驱体Mg3.6Ni0.4Fe0.2Al1.8(OH)12CO3·4H2O。600℃下焙烧3小时得纳米尺寸镍铁镁铝复合氧化物。By the solid MgCl of 7.70g 2 , the solid NiCl of 1.17g 2 and the solid FeCl of 0.73g 3 and the solid AlCl of 5.41g The aqueous solution of 3 , wherein Mg: Ni: Fe: Al=1.8: 0.2: 0.1: 0.9 (molar ratio ) was reacted with 8.64g NaOH and 4.77g Na 2 CO 3 alkali solution at 90°C for 6h to prepare the precursor of nickel-iron-magnesium-aluminum hydrotalcite Mg 3.6 Ni 0.4 Fe 0.2 Al 1.8 (OH) 12 CO 3 ·4H 2 O. Calcined at 600°C for 3 hours to obtain nano-sized nickel-iron-magnesium-aluminum composite oxide.
碳纳米管的制备是在700℃下，将流量为75ml/min的乙炔及150ml/min的氢气通入200mg催化剂反应20分钟停止，收集产物，纯化后得到碳纳米管600mg。由本法制得的碳纳米管外径40-70nm。The preparation of carbon nanotubes is at 700°C, passing 75ml/min of acetylene and 150ml/min of hydrogen into 200mg catalyst to stop the reaction for 20 minutes, collecting the product, and obtaining 600mg of carbon nanotubes after purification. The outer diameter of the carbon nanotubes prepared by this method is 40-70nm.
实施例5Example 5
将固体的20.77g Mg(NO3)2·6H2O、2.62g Co(NO3)2·6H2O、1.21gFe(NO3)3·9H2O及10.13g Al(NO3)3·9H2O按Mg∶Co∶Fe∶Al＝2.7∶0.3∶0.1∶0.9(摩尔比)的水溶液，与8.64gNaOH和4.77gNa2CO3碱溶液于80℃反应4h，制备钴铁镁铝水滑石前驱体Mg5.4Co0.6Fe0.2Al1.8(OH)16CO3·4H2O。600℃下焙烧3小时得纳米尺寸钴铁镁铝复合氧化物。20.77g Mg(NO 3 ) 2 ·6H 2 O, 2.62g Co(NO 3 ) 2 ·6H 2 O, 1.21g Fe(NO 3 ) 3 ·9H 2 O and 10.13g Al(NO 3 ) 3 · According to the aqueous solution of Mg:Co:Fe:Al=2.7:0.3:0.1:0.9 (molar ratio), 9H 2 O reacted with 8.64g NaOH and 4.77g Na 2 CO 3 alkali solution at 80°C for 4h to prepare cobalt-iron-magnesium-aluminum hydrotalcite Precursor Mg 5.4 Co 0.6 Fe 0.2 Al 1.8 (OH) 16 CO 3 ·4H 2 O. Calcined at 600°C for 3 hours to obtain nanometer-sized cobalt-iron-magnesium-aluminum composite oxide.
碳纳米管的制备是在600℃下，将流量为100ml/min的丙烷及150ml/min的氢气通入200mg催化剂反应40分钟停止，收集产物，纯化后得到碳纳米管580mg。由本法制得的碳纳米管外径25-55nm。The preparation of carbon nanotubes is at 600°C, passing propane with a flow rate of 100ml/min and hydrogen at a flow rate of 150ml/min into 200mg catalyst for 40 minutes to stop the reaction, and the product is collected and purified to obtain 580mg of carbon nanotubes. The outer diameter of the carbon nanotubes prepared by this method is 25-55nm.
实施例6Example 6
将固体的20.77gMg(NO3)2·6H2O、2.62gNi(NO3)2·6H2、1.82gFe(NO3)3·9H2O及6.75g的固体Al(NO3)3·9H2O按Mg∶Ni∶Fe∶Al＝3.6∶0.4∶0.2∶0.8(摩尔比)的水溶液与8.64gNaOH和4.77gNa2CO3碱溶液于70℃反应3h，制备镍铁镁铝水滑石前驱体Mg7.2Ni0.8Fe0.4Al1.6(OH)20CO3·4H2O。600℃下焙烧3小时得纳米尺寸镍铁镁铝复合氧化物。20.77g of solid Mg(NO 3 ) 2 ·6H 2 O, 2.62g of Ni(NO 3 ) 2 ·6H 2 , 1.82g of Fe(NO 3 ) 3 ·9H 2 O and 6.75g of solid Al(NO 3 ) 3 ·9H 2 O according to Mg: Ni: Fe: Al = 3.6: 0.4: 0.2: 0.8 (molar ratio) aqueous solution and 8.64g NaOH and 4.77g Na 2 CO 3 alkali solution at 70 ° C for 3 hours to prepare the nickel-iron-magnesium-aluminum hydrotalcite precursor Mg 7.2 Ni 0.8 Fe 0.4 Al 1.6 (OH) 20 CO 3 ·4H 2 O. Calcined at 600°C for 3 hours to obtain nano-sized nickel-iron-magnesium-aluminum composite oxide.
碳纳米管的制备是在950℃下，将流量为200ml/min的丙烷及100ml/min的氢气通入200mg催化剂反应30分钟停止，收集产物，纯化后得到碳纳米管630mg。由本法制得的碳纳米管外径30-70nm。The preparation of carbon nanotubes is at 950°C, passing propane with a flow rate of 200ml/min and hydrogen at a flow rate of 100ml/min into 200mg catalyst for 30 minutes to stop the reaction, collecting the product, and obtaining 630mg of carbon nanotubes after purification. The outer diameter of the carbon nanotubes prepared by this method is 30-70nm.
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| CN102770206A (en) * | 2010-02-16 | 2012-11-07 | 拜耳知识产权有限责任公司 | Production of carbon nanotubes |
| WO2024096695A1 (en) * | 2022-11-03 | 2024-05-10 | 주식회사 엘지화학 | Catalyst for producing carbon nanotubes, and method for producing catalyst for producing carbon nanotubes |
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| WO2024096695A1 (en) * | 2022-11-03 | 2024-05-10 | 주식회사 엘지화학 | Catalyst for producing carbon nanotubes, and method for producing catalyst for producing carbon nanotubes |
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