CN1141250C - 一种流化床连续化制备碳纳米管的方法及其反应装置 - Google Patents
一种流化床连续化制备碳纳米管的方法及其反应装置 Download PDFInfo
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Abstract
本发明涉及一种流化床连续化制备碳纳米管的方法，首先将过渡金属的氧化物催化剂载于担体上，然后将其放在催化剂活化反应器内，通入流动的氢气或一氧化碳与氮气的混合气体进行还原反应，最后将催化剂送至流化床中，通入反应混合气体，流化床的下部则得到碳纳米管。本发明的方法和装置，在流化床中经过化学气相沉积，在催化剂载体上生长出碳纳米管。该方法的装置结构简单，方法易操作，适于连续化千吨./年级工业规模化生产。
Description
本发明涉及一种流化床连续化制备碳纳米管的方法及其反应装置，属化工设备技术领域。
传统气固流化床仅能用于直径大于30微米的非C类颗粒的流化过程，对于催化裂解制备碳纳米管这类固体气相沉积过程，由于会出现一维纳米材料并易产生粘结，极易造成生产过程中的流化困难，从而使床内出现结块、局部温度、浓度不均匀或因碳在颗粒间沉积而无法正常操作。因此，至今尚未见有关利用流化床进行连续化大批量生产碳纳米材料的文献报道。
纳米颗粒聚团流态化技术由于充分考虑到了纳米颗粒的聚集及粘结行为，通过对催化裂解化学气相沉积过程中的生长行为、纳米颗粒团聚状态及流态化状态的全面分析，控制合理的一维纳米材料生长结构及状态来达到使反应过程中始终处于正常流态化甚至散式流态化的状态。因而合理的反应速度、操作条件以及与床内结构的合理组合，确保床层处于纳米颗粒聚团流化状态，是进行流化床碳纳米管连续化生产的核心技术。
本发明的目的是提出一种流化床连续化制备碳纳米管的方法及其反应装置，通过控制催化剂及生成碳纳米材料在气流作用下的流化状态，实现碳纳米材料的连续化、大批量生产，得到晶化程度高、纯度高和产量高的碳纳米管。
本发明提出的流化床连续化制备碳纳米管的方法，包括下列步骤：
(1)将过渡金属的氧化物催化剂载于担体上；
(2)将上述负载催化剂放在催化剂活化反应器内，于500～900℃温度下，通入流动的氢气或一氧化碳与氮气的混合气体进行还原反应，使过渡金属氧化物纳米颗粒还原为单质金属纳米颗粒，氢气或一氧化碳与氮气按体积比1∶0.3～1混合，还原时间为0.3～3小时；
(3)将催化剂送至流化床中，流化床的温度为500～900℃，通入一氧化碳及7碳以下低碳烃与氢气、氮气的混合气体至反应器内，气体配比为氢气∶碳源气体∶氮气＝0.4～1∶1∶0.1～2，反应过程的空速为5～10000小时-1，气体的空塔流速为0.08～2米/秒，流化床的下部得到碳纳米管。
本发明设计的流化床连续化制备碳纳米管的反应装置，包括主反应器、催化剂活化器、气体分布器、气固分离器和产品脱气段。催化剂活化器与主反应器相通，气体分布器置于主反应器内的下部，气固分离器置于主反应器内的顶部，主反应器壁上设有换热管，主反应器底部设有气体入口，产品脱气段与主反应器下部相联。
本发明的方法和装置，在氢气和氮气中还原制成纳米金属催化剂，利用过渡金属纳米颗粒的催化效应和载体的模板效应，在流化床中经过化学气相沉积，在催化剂载体上生长出直径为4～80纳米，长度为0.5～200微米的碳纳米管。该方法的装置)结构简单，方法易操作，适于连续化千吨/年级工业规模化生产。
本发明设计的装置还具有以下几个明显的特点：
1、综合利用了流化床反应器的特点，设计结构紧凑，实用性强
2、反应器系统可调性强，操作弹性大。反应器的进料及出料位置可根据对反应停留时间的要求、产品结构的要求进行调整。
3、可连续地将催化剂及反应所产碳纳米材料移入、移出，实现连续化、大批量生产。
4、可实现床内温度、浓度均匀地进行碳纳米材料的生长，无局部过热及粘结现象发生。
5、可在大规模装置上实现反应器的移热/供热，对放热或吸热的催化裂解过程均适合。
附图说明：
图1是本发明设计的反应装置的结构示意图。
图1中，1是反应器，2是气体分布器，3是移热/供热器，4是催化剂入口，5是产品出口，6是催化剂活化器，7是气固分离器，8是进气装置，9是产品脱气段。
如图1所示，本发明设计的流化床连续化制备碳纳米管的反应装置，包括主反应器1、催化剂活化器6、气体分布器2、气固分离器7和产品脱气段9。催化剂活化器6与主反应器1相通，气体分布器2置于主反应器1内的下部，气固分离器7置于主反应器内的顶部，主反应器壁上设有换热管3，主反应器底部设有气体入口，产品脱气段9通过产品出口5与主反应器1的下部相联。产品出料口5可用以调节流化床内物料高度。出料口处设有脱气段9，以脱除产品吸附的有机物。反应器顶部设有气固分离器7。根据不同工艺要求，该装置可用于烃类催化裂解制碳纳米管、纤维，制氢以及合成其它纳米材料的过程。
下面介绍本发明的实施例：
实施例一：
(1)将过渡金属Ni-Cu氧化物载于担体玻璃珠上；
(2)将上述负载催化剂放在催化剂活化反应器内于520℃下通入氢气与氮气混合气体进行还原反应，氢气与氮气按体积比1∶1混合，还原时间为2小时；
(3)将催化剂送至流化床中，温度为520℃，通入氢气、丙烯与氮气的混合气体至反应器内，配比为H2∶C＝ 3∶N2＝1∶1∶1，反应过程的空速为5小时-1，气体的空塔流速为0.09米/秒。
实施例二：
(1)将过渡金属Fe-Cu氧化物载于担体SiO2上；
(2)将上述负载催化剂放在催化剂活化反应器内于650℃下通入氢气与氮气混合气体进行还原反应，氢气与氮气按体积比1∶0.5混合，还原时间为0.5小时；
(3)将催化剂送至流化床中，温度为700℃，通入氢气、乙烯与氮气的混合气体至反应器内，配比为H2∶C＝ 3∶N2＝1∶1∶1，反应过程的空速为10000小时-1，气体的空塔流速为0.5米/秒。
实施例三：
(1)将过渡金属Co-Mn氧化物载于担体Al2O3上；
(2)将上述负载催化剂放在催化剂活化反应器内于800℃下通入氢气与氮气混合气体进行还原反应，氢气与氮气按体积比1∶0.5混合，还原时间为0.3小时；
(3)将催化剂送至流化床中，温度为870℃，通入氢气、甲烷与氮气的混合气体至反应器内，配比为H2∶CH1∶N2＝0.5∶1∶0.1，反应过程的空速为5000小时-1，气体的空塔流速为0.8米/秒。
实施例四：
(1)将过渡金属Xi氧化物载于担体Al2O3上；
(2)将上述负载催化剂放在催化剂活化反应器内于870℃下通入一氧化碳与氮气混合气体进行还原反应，一氧化碳与氮气按体积比1∶0.5混合，还原时间为3小时；
(3)将催化剂送至流化床中，温度为870℃，通入氢气、乙烯与氮气的混合气体至反应器内，配比为H2∶C＝ 3∶N2＝1∶1∶0.5，反应过程的空速为8000小时-1，气体的空塔流速为1.3米/秒。
实施例五：
(1)将过渡金属Xi-Cu氧化物载于担体Al203上；
(2)将上述负载催化剂放在催化剂活化反应器内于870℃下通入氢气与氮气混合气体进行还原反应，氢气与氮气按体积比1∶0.5混合，还原时间为0.5小时；
(3)将催化剂送至流化床中，温度为870℃，通入氢气、甲烷与氮气的混合气体至反应器内，配比为H2∶CH1∶N2＝1∶1∶0.5，反应过程的空速为9000小时-1，气体的空塔流速为1.7米/秒。
Claims (2)
1、一种流化床连续化制备碳纳米管的方法，其特征在于该方法包括下列各步骤：
(1)将过渡金属的氧化物催化剂载于担体上；
(2)将上述负载催化剂放在催化剂活化反应器内，于500～900℃温度下，通入流动的氢气或一氧化碳与氮气的混合气体进行还原反应，使过渡金属氧化物纳米颗粒还原为单质金属纳米颗粒，氢气或一氧化碳与氮气按体积比1∶0.3～1混合，还原时间为0.3～3小时；
(3)将催化剂送至流化床中，流化床的温度为500～900℃，通入一氧化碳及7碳以下低碳烃与氢气、氮气的混合气体至反应器内，气体配比为氢气∶碳源气体∶氮气＝0.4～1∶1∶0.1～2，反应过程的空速为5～10000小时-1，气体的空塔流速为0.08～2米/秒，流化床的下部得到直径为4～80纳米、长度为0.5～200微米的碳纳米管。
2、一种用于如权利要求1所述的方法的反应装置，其特征在于碳纳米管的直径为4～80纳米、长度为0.5～200微米，反应装置包括主反应器、催化剂活化器、气体分布器、气固分离器和产品脱气段；所述的催化剂活化器与主反应器相通，气体分布器置于主反应器内的下部，气固分离器置于主反应器内的顶部，主反应器壁上设有换热管，主反应器底部设有气体入口，产品脱气段与主反应器下部相联。
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| CNB011183497A CN1141250C (zh) | 2001-05-25 | 2001-05-25 | 一种流化床连续化制备碳纳米管的方法及其反应装置 |
| JP2002591391A JP3878555B2 (ja) | 2001-05-25 | 2002-01-29 | ナノ凝集体流動層を用いたカーボンナノチューブの連続製造方法及びその反応装置 |
| DE60237361T DE60237361D1 (de) | 2001-05-25 | 2002-01-29 | Kontinuierliche massenproduktion von kohlenstoffnanoröhren in einer nanoagglomerat-wirbelschicht |
| US10/478,512 US7563427B2 (en) | 2001-05-25 | 2002-01-29 | Continuous mass production of carbon nanotubes in a nano-agglomerate fluidized-bed and the reactor |
| PCT/CN2002/000044 WO2002094713A1 (fr) | 2001-05-25 | 2002-01-29 | Production de nanotubes de carbone a grande echelle dans un reacteur a lit fluidise a base de nano-agglomerats |
| EP02700107A EP1391425B1 (en) | 2001-05-25 | 2002-01-29 | Continuous mass production of carbon nanotubes in a nano-agglomerate fluidized-bed |
| AT02700107T ATE478031T1 (de) | 2001-05-25 | 2002-01-29 | Kontinuierliche massenproduktion von kohlenstoffnanoröhren in einer nanoagglomerat- wirbelschicht |
| US12/400,713 US20090286675A1 (en) | 2001-05-25 | 2009-03-09 | Continuous mass production of carbon nanotubes in a nano-agglomerate fluidized-bed and the reactor |
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| CN (1) | CN1141250C (zh) |
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| CN113336283B (zh) * | 2021-05-31 | 2022-07-12 | 清华大学 | 将含氰有机废液转化为氮掺杂碳纳米材料的装置及方法 |
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| US4650657A (en) * | 1982-01-15 | 1987-03-17 | Trw Inc. | Method for making carbonaceous materials |
| DE3347677A1 (de) * | 1983-12-31 | 1985-07-11 | VEG-Gasinstituut N.V., Apeldoorn | Verfahren zur herstellung eines katalysators |
| US4663230A (en) | 1984-12-06 | 1987-05-05 | Hyperion Catalysis International, Inc. | Carbon fibrils, method for producing same and compositions containing same |
| US6375917B1 (en) | 1984-12-06 | 2002-04-23 | Hyperion Catalysis International, Inc. | Apparatus for the production of carbon fibrils by catalysis and methods thereof |
| US5458784A (en) * | 1990-10-23 | 1995-10-17 | Catalytic Materials Limited | Removal of contaminants from aqueous and gaseous streams using graphic filaments |
| JPH11310407A (ja) | 1998-04-30 | 1999-11-09 | Osaka Gas Co Ltd | 機能性炭素材料の製造法 |
| JP2000203819A (ja) | 1999-01-14 | 2000-07-25 | Osaka Gas Co Ltd | 直線状カ―ボンナノチュ―ブの製造方法 |
| EP1059266A3 (en) * | 1999-06-11 | 2000-12-20 | Iljin Nanotech Co., Ltd. | Mass synthesis method of high purity carbon nanotubes vertically aligned over large-size substrate using thermal chemical vapor deposition |
| CN1140448C (zh) * | 2000-03-07 | 2004-03-03 | 天津大学 | 镍催化裂解甲烷制备碳纳米管的方法 |
| CN1183031C (zh) * | 2000-03-23 | 2005-01-05 | 中国科学院成都有机化学研究所 | 一种制备碳纳米管的方法 |
| US6413487B1 (en) * | 2000-06-02 | 2002-07-02 | The Board Of Regents Of The University Of Oklahoma | Method and apparatus for producing carbon nanotubes |
| US6919064B2 (en) * | 2000-06-02 | 2005-07-19 | The Board Of Regents Of The University Of Oklahoma | Process and apparatus for producing single-walled carbon nanotubes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI807169B (zh) * | 2019-02-28 | 2023-07-01 | 南韓商Ｌｇ化學股份有限公司 | 流化床反應器 |
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|---|---|
| WO2002094713A1 (fr) | 2002-11-28 |
| JP3878555B2 (ja) | 2007-02-07 |
| EP1391425A1 (en) | 2004-02-25 |
| EP1391425A4 (en) | 2005-08-03 |
| CN1327943A (zh) | 2001-12-26 |
| US7563427B2 (en) | 2009-07-21 |
| EP1391425B1 (en) | 2010-08-18 |
| JP2004526660A (ja) | 2004-09-02 |
| DE60237361D1 (de) | 2010-09-30 |
| US20040151654A1 (en) | 2004-08-05 |
| ATE478031T1 (de) | 2010-09-15 |
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