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 trying to find a carbon nanotube production method with large output, high purity, few defects, low cost, and industrialized preparation prospects. For now, 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：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。The object of the present invention is to provide a kind of catalyst that is used to prepare carbon nanotube, it is characterized in that: first adopt the co-precipitation reaction of metal salt solution and alkaline solution, prepare the multi-element hydrotalcite precursor that contains iron, cobalt, nickel, then through The composite oxide catalyst is obtained after high-temperature calcination.
所述金属盐溶液为镁、铝的硝酸盐或硫酸盐或盐酸盐和过渡金属硝酸盐或硫酸盐或盐酸盐的混合水溶液或醇溶液或以水和醇的混合溶剂溶解形成的溶液。所述过渡金属为铁、钴、镍或其混合物，其中过渡金属元素在催化剂所有金属元素中的摩尔百分含量为1.7-25％。The metal salt solution is a mixed aqueous solution or alcohol solution of magnesium, aluminum nitrate or sulfate or hydrochloride and transition metal nitrate or sulfate or hydrochloride or a solution formed by dissolving in a mixed solvent of water and alcohol. The transition metal is iron, cobalt, nickel or a mixture thereof, wherein the mole percentage of transition metal elements in all metal elements of the catalyst is 1.7-25%.
所述碱溶液为氢氧化钠或氨水和碳酸钠或碳酸铵的水溶液。The alkaline solution is an aqueous solution of sodium hydroxide or ammonia water and sodium carbonate or ammonium carbonate.
所述制备催化剂具体步骤为：将盐溶液和碱溶液在搅拌下混合，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。The specific steps for preparing the catalyst are: mixing the salt solution and the alkali solution under stirring, then crystallizing at 40-90°C for 0.5-6h, filtering, washing, and drying to obtain multi-component hydrotalcite, and then roasting at 500-700°C for 3- 5h, the prepared catalyst was obtained.
所述催化剂在制备碳纳米管中的应用，该工艺是在固定床反应器中进行；将一定量的催化剂在H2气氛下升温至500-950℃，通入碳源气体，反应20-120分钟停止，氩气保护下冷却，收集产物；产物纯化将产物浸泡在1.0N的硝酸溶液中，超声处理15分钟，过滤、洗涤、干燥后，制备得碳纳米管，并由透射电子显微镜观测形貌。The application of the catalyst in the preparation of carbon nanotubes is carried out in a fixed-bed reactor; a certain amount of catalyst is heated up to 500-950°C underH2 atmosphere, and carbon source gas is introduced to react for 20-120 Stop for 1 minute, cool under the protection of argon, and collect the product; product purification Soak the product in 1.0N nitric acid solution, ultrasonically treat it for 15 minutes, filter, wash, and dry to prepare carbon nanotubes, and observe the shape by transmission electron microscope appearance.
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
本发明为一种用于制备碳纳米管的催化剂。其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：将盐溶液和碱溶液在搅拌下混合，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。上述金属盐溶液为镁、铝硝酸盐或硫酸盐或盐酸盐和过渡金属硝酸盐或硫酸盐或盐酸盐的混合水溶液或醇溶液或以水和醇的混合溶剂溶解形成的溶液。上述碱溶液为氢氧化钠或氨水和碳酸钠或碳酸铵的水溶液。The invention is a catalyst for preparing carbon nanotubes. It first uses 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 obtains a composite oxide catalyst after high-temperature calcination. The specific steps for preparing the catalyst are: mix the salt solution and the 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, Then the prepared catalyst is obtained. The above-mentioned metal salt solution is a mixed aqueous or alcohol solution of magnesium, aluminum nitrate or sulfate or hydrochloride and transition metal nitrate or sulfate or hydrochloride or a solution formed by dissolving in a mixed solvent of water and alcohol. Above-mentioned alkaline solution is the aqueous solution of sodium hydroxide or ammoniacal liquor and sodium carbonate or ammonium carbonate.
下面再举实施例对本发明予以说明。The present invention will be described by giving examples again below.
实施例1Example 1
将18.92g(0.0767mol)的固体MgSO4·7H2O和3.73g(0.0133mol)的固体CoSO4·7H2O及14.99g(0.0225mol)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8.64g(0.216mol)NaOH和4.77g(0.045mol)Na2CO3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。18.92g (0.0767mol) of solid MgSO4 .7H2 O and 3.73g (0.0133mol) of solid CoSO4 .7H2 O and 14.99g (0.0225mol) of solid Al2 (SO4 )3 - 18H2 O (Mg:Co:Al=1.7:0.3:1 molar ratio) was dissolved in 100ml deionized water to form a mixed salt solution, and 8.64g (0.216mol) NaOH and 4.77g (0.045mol) Na2 CO3 Dissolve in 100ml deionized water to make 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 Mg3.4 Co0.6 Al2 (OH )12 CO3 ·4H2 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 underH2 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(0.081mol)的固体Mg(NO3)2·6H2O和2.62g(0.009mol)的固体Ni(NO3)2·6H2O及16.88g(0.045mol)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(0.08mol)(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。20.77g (0.081mol) of solid Mg(NO3 )2 6H2 O and 2.62g (0.009mol) of solid Ni(NO3 )2 6H2 O and 16.88g (0.045mol) of solid Al(NO3 )3 ·9H2 O (Mg:Ni:Al=1.8:0.2:1 molar ratio) was dissolved in 100ml ethanol to form a solution, and 90ml ammonia water and 7.68g (0.08mol) (NH4 )2 CO3 Dissolve 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 Mg3.6 Ni0.4 Al2 (OH )12 CO3 ·4H2 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 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(0.09mol)的固体Mg(NO3)2·6H2O和1.82g(0.0045mol)的固体Fe(NO3)3·9H2O及15.19g(0.0405mol)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8.64g(0.216mol)NaOH和4.77g(0.045mol)Na2CO3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。23.08g (0.09mol) of solid Mg(NO3 )2 6H2 O and 1.82g (0.0045mol) of solid Fe(NO3 )3 9H2 O and 15.19g (0.0405mol) of solid Al(NO3 )3 9H2 O whose Mg:Fe:Al=2:0.1:0.9 (molar ratio) was dissolved in a mixed solvent of 60ml ethanol and 60ml deionized water to form a solution, and another 8.64g (0.216mol) NaOH was weighed Dissolve 4.77g (0.045mol) Na2 CO3 in 120ml deionized water to form 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 Mg4 Fe0.2 Al1.9 ( OH)12 CO3 ·4H2 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. Heat 200mg of iron-magnesium-aluminum composite oxide catalyst to 500°C underH2 atmosphere, feed ethylene with a flow rate of 45ml/min and hydrogen with a flow rate of 205ml/min, stop the reaction for 120 minutes, cool under the protection of argon, and collect the product . 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(0.081mol)的固体MgCl2，1.17g(0.009mol)的固体NiCl2和0.73g(0.0045mol)的固体FeCl3及5.41g(0.0405mol)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8.64g(0.216mol)NaOH和4.77g(0.045mol)Na2CO3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。From the solid MgCl2 of 7.70g (0.081mol), the solid NiCl2 of 1.17g (0.009mol) and the solid FeCl3 of 0.73g (0.0045mol) and the aqueous solution of the solid AlCl3 of 5.41g (0.0405mol), wherein Mg: Ni: Fe: Al = 1.8: 0.2: 0.1: 0.9 (molar ratio) and 8.64g (0.216mol) NaOH and 4.77g (0.045mol) Na2 CO3 alkali solution reacted at 90°C for 6h to prepare nickel-iron-magnesium-aluminum water Talc precursor Mg3.6 Ni0.4 Fe0.2 Al1.8 (OH)12 CO3 4H2 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 of 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
由20.77g(0.081mol)的固体Mg(NO3)2·6H2O，2.62g(0.009mol)的固体Co(NO3)2·6H2O和1.21g(0.003mol)的固体Fe(NO3)3·9H2O及10.13g(0.027mol)的固体Al(NO3)3·9H2O其Mg∶Co∶Fe∶Al＝2.7∶0.3∶0.1∶0.9(摩尔比)的水溶液，与8.64g(0.216mol)NaOH和4.77g(0.045mol)Na2CO3碱溶液于80℃反应4h，制备钴铁镁铝水滑石前驱体Mg6.4Co0.6Fe0.2Al0.8(OH)16CO3 4H2O。600℃下焙烧3小时得纳米尺寸钴铁镁铝复合氧化物。From 20.77g (0.081mol) of solid Mg(NO3 )2 ·6H2 O, 2.62g (0.009mol) of solid Co(NO3 )2 ·6H2 O and 1.21g (0.003mol) of solid Fe(NO3) 3.9H2 O and 10.13g (0.027mol) of solid Al(NO3 ) 3 .9H2 O and its Mg:Co:Fe:Al=2.7: 0.3:0.1:0.9 (molar ratio) aqueous solution, and 8.64g (0.216mol) NaOH and 4.77g (0.045mol) Na2 CO3 alkaline solution were reacted at 80℃ for 4h to prepare cobalt iron magnesium aluminum hydrotalcite precursor Mg6.4 Co0.6 Fe0.2 Al0.8 (OH)16 CO3 4H2 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
由20.77g(0.081mol)的固体Mg(NO3)2·6H2O，2.62g(0.009mol)的固体Ni(NO3)2·6H2O和1.82g(0.0045mol)的固体Fe(NO3)3·9H2O及6.75g(0.018mol)的固体Al(NO3)3·9H2O其Mg∶Ni∶Fe∶Al＝3.6∶0.4∶0.2∶0.8(摩尔比)的水溶液，与8.64g(0.216mol)NaOH和4.77g(0.045mol)Na2CO3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。From 20.77g (0.081mol) of solid Mg(NO3 )2 ·6H2 O, 2.62g (0.009mol) of solid Ni(NO3 )2 ·6H2 O and 1.82g (0.0045mol) of solid Fe(NO3) 3.9H2 O and 6.75g (0.018mol) of solid Al(NO3 )3 .9H2 O and its Mg:Ni:Fe:Al=3.6:0.4:0.2:0.8 (molar ratio) aqueous solution, and 8.64g (0.216mol) NaOH and 4.77g (0.045mol) Na2 CO3 alkali solution were reacted at 70°C for 3h to prepare the precursor of nickel-iron-magnesium-aluminum hydrotalcite Mg7.2 Ni0.8 Fe0.4 Al1.6 (OH)20 CO3 4H2 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.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03105056CN1199727C (en) | 2003-03-03 | 2003-03-03 | Catayst for preparing carbon-nano tube |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03105056CN1199727C (en) | 2003-03-03 | 2003-03-03 | Catayst for preparing carbon-nano tube |
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| CN1438072Atrue CN1438072A (en) | 2003-08-27 |
| CN1199727C CN1199727C (en) | 2005-05-04 |
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| CN 03105056Expired - Fee RelatedCN1199727C (en) | 2003-03-03 | 2003-03-03 | Catayst for preparing carbon-nano tube |
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