CN1433456A - 钴催化剂 - Google Patents

钴催化剂 Download PDF

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CN1433456A
CN1433456A CN01810773A CN01810773A CN1433456A CN 1433456 A CN1433456 A CN 1433456A CN 01810773 A CN01810773 A CN 01810773A CN 01810773 A CN01810773 A CN 01810773A CN 1433456 A CN1433456 A CN 1433456A
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cobalt
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彼得·雅各布斯·范伯奇
简·范德卢斯德奇
雅各布斯·卢卡斯·维萨吉
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Sastech Pty Ltd
Sasol Technology Pty Ltd
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Abstract

一种制备钴基催化剂前体的方法，该方法包括：在载体浸渍阶段，用钴盐浸渍含有用碳涂敷的多孔催化剂载体颗粒涂敷的催化剂载体，并部分干燥浸渍的载体。之后在焙烧阶段，焙烧部分干燥的载体以得到钴基催化剂前体。钴基催化剂前体于是在还原阶段进行还原以得到钴基F－T催化剂。

Description

钴催化剂
本发明涉及钴催化剂。具体地说，本发明涉及制备钴基Fischer-Tropsch(F-T)催化剂前体的方法，制备该钴催化剂的方法及使用该钴催化剂生产烃类的方法。
申请人注意到制备钴基催化剂前体熟知的方法包括用钴盐淤浆浸渍催化剂载体，干燥浸渍的催化剂载体，焙烧干燥浸渍的催化剂载体，以得到希望的钴负载量。于是通过对得到的前体还原使其活化，以得到钴基F-T催化剂。这些催化剂当用于F-T合成时表现出良好的固有活性，但是使用熟知的方法不容易得到具有增强或优异的固有活性。因此本发明的目的是提供一种具有增强的初始和/或稳定的固有F-T合成活性的钴基F-T催化剂，及制备该催化剂的方法。
根据本发明的第一方面，提供一种制备钴基催化剂前体的方法，该方法包括：
在载体浸渍阶段，用钴盐浸渍包括用碳涂敷的多孔催化剂载体颗粒的涂敷的催化剂载体，并部分干燥浸渍的载体；及
在焙烧阶段，焙烧部分干燥的载体以得到钴基催化剂前体。
得到的钴基催化剂前体在实际使用时要还原以得到钴基F-T催化剂。惊奇地发现该催化剂具有增强的或优异的初始及稳定的固有F-T合成活性。
因此根据本发明的第二方面，提供一种制备钴基F-T催化剂的方法，该方法包括：
在载体浸渍阶段，用钴盐浸渍包括用碳涂敷的多孔催化剂载体颗粒的涂敷的催化剂载体，并部分干燥浸渍的载体；
在焙烧阶段，焙烧部分干燥浸渍的载体以得到钴基催化剂前体；及
在还原阶段，还原钴基催化剂前体以得到钴基F-T催化剂。
如果需要较高的钴负载量，于是在以下描述的第一次浸渍、干燥和焙烧步骤后进行第二、甚至第三次浸渍、干燥和焙烧步骤。
在本发明说明书中，除非具体另外指出，均指催化剂的质量，给出的质量是相对于焙烧的催化剂的质量，即在任何的催化剂还原前的催化剂质量是有效的。
钴盐可以，特别是硝酸钴，Co(NO3)·6H2O。
碳涂敷的催化剂载体可以是任何的商业可获得的用碳涂敷的多孔氧化物催化剂载体例如氧化铝(Al2O3)、氧化硅(SiO2)、氧化硅氧化铝(SiO2·Al2O3)、氧化钛(TiO2)和氧化镁(MgO)，该载体用碳涂敷。
载体可以是被保护的修饰的催化剂载体，包括例如作为修饰组分的硅，如在WO 99/42214中的描述，在此引入作为参考。
根据第一和第二方面的方法可以，如果必要，包括制备碳涂敷的催化剂载体，即它们可包括使用碳通过涂敷而修饰多孔的催化剂载体。
一般地说，涂敷催化剂载体颗粒可以任何适合的方法完成。例如碳涂敷的催化剂载体可以通过EP 0681868中描述的方法，用均一的碳基层涂敷预成型的球形多孔催化剂载体颗粒而制备，在此引入作为参考。
应理解作为有效涂敷可使用的碳的最大量可以通过碳的涂敷对原始催化剂载体孔体积的影响来确定，因为催化剂载体的孔体积决定了有多少(碳)能够被浸渍到催化剂载体中。当需要具有相对高的钴负载量的催化剂时，这一点尤其重要。类似地，可以通过碳的最低水平来确定作为有效涂敷可使用的碳的最低量，所述的最低水平是指其仍然可以对得到的钴催化剂稳定的固有F-T合成性能产生积极的影响。因此最大的碳量为40g C/100g载体，优选为20g C/100g载体，更优选为10g C/100g，同时碳的最低水平为0.1g C/100g载体，优选为0.5gC/100载体，更优选为1.2g C/100g载体。
一般地说，载体用钴盐浸渍可以通过熟知的浸渍方法完成，例如初始湿法浸渍或淤浆浸渍。类似地，焙烧可以任何熟知的焙烧装置进行，如流化床、固定床、炉子、转窑和/或云母(torbed)锻烧炉，优选的温度为150°～300℃。具体地说，焙烧可以根据PCT/IB00/01745中描述的方法，在此引入作为参考。因此焙烧可包括PCT/IB00/01745中描述的流化床焙烧。
钴催化剂前体可以通过二步淤浆浸渍、干燥和焙烧方法而得到。二步法可包括，第一步，用钴盐浸渍碳涂敷的催化剂-载体，部分干燥浸渍的载体，焙烧部分干燥载体，以得到焙烧的材料，之后，在第二步，用钴盐浸渍焙烧的材料，部分干燥浸渍的材料，并焙烧部分干燥的材料以得到催化剂前体。
特别是可根据WO 00/20116中描述的方法用钴盐浸渍载体、干燥并焙烧，在此引入作为参考。
载体浸渍和干燥通常可以在配有旋转螺旋桨的圆锥形的真空干燥器中或转鼓真空干燥器中完成。
催化剂的前体可以含有5g Co/100g～70g Co/100g的载体，优选为20g Co/100g～50g Co/100g载体。
在淤浆浸渍步骤的任一步或两步期间，可以加入水溶性的前体钯(Pd)或铂(Pt)盐或该盐的混合物，作为具有增强钴还原能力的掺杂剂。优选加入的掺杂剂钯金属、铂金属或钯和铂金属混合物与钴金属的质量比例为0.01∶100到0.3∶100。
本发明也涉及通过本发明的第二方面的方法制备的钴催化剂，及通过本发明的第一方面的方法制备的钴催化剂前体。
根据本发明的第三方面，提供生产烃类的方法，其包括在180℃～250℃的高温下、1～40巴的高压下，使含有氢(H2)和一氧化碳(CO)的合成气与本发明的钴催化剂接触，由CO和H2淤浆F-T反应得到烃类。
本发明也涉及当用上述的方法生产的烃类。
参考附图和以下的非限制性实施例，将更详细地描述本发明。
附图简述
图1显示碳水平对碳涂敷催化剂的孔体积的影响。
实施例1催化剂B(30g Co/100g Al2O3)(与本发明的不一致)制备
Pt助催化的催化剂在SASOL德国GmbH的商标产品：PuraloxSCCa 5/150，作为选择的预成型Al2O3载体上制备，根据WO 00/20116的催化剂实施例1或PCT/IB00/01745的催化剂D、E、G或H中任一的方法，即水淤浆浸渍、真空干燥，之后直接进行流化床焙烧的方法制备。
在准备用于试验室规模的淤浆连续搅拌釜式反应器(CSTR)的F-T合成试验时，采用如下的步骤对焙烧的材料进行还原和蜡涂敷：
27.5g的催化剂在1巴纯氢(空速≥200mLn H2/g催化剂/h)下还原，同时使温度以1℃/min的速度从25℃升高到380°～425℃，之后将温度恒定在380°～425℃下保持16小时。
还原的催化剂冷却到室温，在该阶段用氩气代替氢气，在氩气层的保护下催化剂被卸载于熔融态的F-T蜡中。将该蜡涂敷的催化剂于是转移到淤浆反应器中。CSTR F-T合成反应试验
扩展的淤浆CSTR F-T合成试验(编号106F)在催化剂B上进行。试验持续进行约90天，期间保持如下的合成条件：
反应器温度：220.5℃
反应器压力：20.3巴
催化剂装填量：20.8g
(H2+CO)空速：2169 mLn/(g催化剂·h)
APG空速：2452 mLn/(g催化剂·h)
其中APG是Arge Pure Gas的首字母缩写，即根据碳的气化方法，由南非Sasolburg的SchümannSasol(Pty)有限公司生产的商业化的合成气，之后用Rectisol(商标)净化。
进料气的组成：
H2： 49.1vol％
CO： 25.9vol％
CH4：9.3vol％
CO2：0.5vol％
Ar： 15.2％
该次试验(即106F)得到的合成性能数据列于表1。
相对(F-T)固有活性因子(R.I.A.F.)定义如下：
考虑任意的淤浆钴F-T催化剂，在CSTR中显示了如下的观察到的合成性能：
τFT＝在T＝y开尔文时，每克催化剂每秒Z摩尔CO转换为F-T产品，在如下的一套反应器分压下下观察得到：
PH2＝v巴
PCO＝τ巴
于是R.I.A.F.定义如下：
R.I.A.F＝[Z(1+1.82τ)2]/[49480.9 e(-11113.4/y)vτ]
淤浆钴基催化剂的起始固有F-T活性(ai)定义如下：
ai＝连续置于如下一套梯度淤浆合成条件下操作时间为15小时(即，ti＝初始时间)后的R.I.A.F.：
220℃，20巴，(H2+CO)％的转化率大于50％，所用的进料气组成：约50vol％H2及约25vol％的CO，其余由Ar，N2、CH4和/或CO2组成。催化剂C(C239)(40g Co/100g Al2O3)(与本发明不一致)制备
催化剂C与类似催化剂B的方法制备。不同之处为：催化剂C通过三个连续的浸渍/干燥/焙烧步骤，而催化剂B通过二个这样的步骤。这样作可以将Co的负载量从30g/100gAl2O3提高到40g/100gAl2O3。
催化剂C也进行了F-T合成性能的试验(293F次试验)，并将结果列于表1。
    催化剂             C             D
催化剂特征：组成合成性能数据：试验分析数操作时间(小时)(H2+CO)％转化率反应器分压：H2(巴)CO(巴)H2O(巴)CO2(巴)起始相对固有(F-T)活性因子(即：ai＝在tj时的R.I.A.F.) 40gCo/0.100gPt/100gAl2O3293F15655.32.84.70.43.5 30gCo/0.075gPt/100gAl2O3106F15.5733.72.45.00.32.7
实施例2
与发明(催化剂E、K、L)一致的Al2O3负载的钴淤浆催化剂样品的实施例显示了增强的初始固有F-T活性。催化剂E(40gCo/0.100gPt/100gAl2O3)制备
在Kataleuna GmbH Catalysis(Amhaupttor；D-06236 Leuna；德国)用均一的碳基层涂敷SASOL德国GmbH的商标产品：Puralox SCCa5/150(即预成型的球形多孔Al2O3催化剂载体材料)，采用EP 0681868中描述的方法，在此引入作为参考。该试验结果得到了12.4gC/100gAl2O3修饰的载体。
根据US 5733839、WO 99/42214和WO 00/20116中公开的方法，采用水淤浆浸渍、真空干燥，之后直接流化床焙烧的方法，在已修饰的12.4gC/100gAl2O3预成型载体材料上制备40gCo/0.100gPt/100g Al2O3淤浆F-T催化剂，该方法在此引入作为参考。具体地讲，催化剂E的制备如下：
将34.1g Co(NO3)2·6H2O溶解在40ml蒸镏水中，及0.0185g(NH3)4Pt(NO3)2溶解于10ml蒸镏水中。该两种溶液在60℃、大气压下在旋转蒸发仪的500ml圆底球形烧瓶中混合，加入50g 12.4gC/100gAl2O3修饰的载体。水淤浆浸渍和真空干燥通过如下步骤完成。
    油浴的温度(℃) 旋转蒸发仪的压力(mbar)     时间(分钟)
    60     大气压     10
    60     240     30
    70     240     90
    85     240     60
    85     50     240
真空干燥的中间产品直接进行流化床焙烧步骤，其遵循如下的步骤：
-连续气流为1.7dm3 n/min
-温度程序：
50g中间焙烧的材料进行如下的第二次Co/Pt浸渍和焙烧步骤：
34.1g Co(NO3)2·6H2O溶解在40ml的蒸镏水中，及0.0189g(NH3)4Pt(NO3)2溶解于10ml蒸镏水中。该两种溶液在60℃、大气压下在旋转蒸发仪的500ml圆底球形烧瓶中混合，加入50g前面第一次(ex 1st)浸渍和焙烧的中间体，以第一次Co/Pt的浸渍步骤同样的方式完成水淤浆浸渍和真空干燥。真空干燥的中间产品直接进行流化床焙烧步骤，其遵循如下的步骤：
-连续流动的气流为1.7dm3/min
-温度程序：
50g中间焙烧的材料进行如下的第三次Co/Pt浸渍和焙烧步骤：
将25.4g Co(NO3)2·6H2O溶解在40ml蒸镏水中，及0.0446g(NH3)4Pt(NO3)2溶解于10ml蒸镏水中。该两种溶液在60℃、大气压下在旋转蒸发仪的500ml圆底球形烧瓶中混合，加入50g前面第二次(ex 2nd)浸渍和焙烧的中间体。以第一次Co/Pt的浸渍步骤同样的方式完成水淤浆浸渍和真空干燥。真空干燥的中间产品直接进行流化床焙烧步骤，其遵循如下的步骤：
-连续流动的气流为1.7dm3/min
-温度程序：
三个连续浸渍步骤的总(量)如其固体材料的孔空体积施加的限制所表示。
在准备用于试验室规模的淤浆连续搅拌釜式反应器CSTR的F-T合成试验时，焙烧催化剂的前体在外部350℃下还原。为此目的，22.8g催化剂在1巴纯氢下还原(空速为2000mln/g催化剂·h)，同时使温度以1℃/min的速度从25℃升高到350℃，之后将温度恒定在350℃下保持16小时。
还原的催化剂冷却到室温，其中用氩气代替氢气，在氩气层的保护下催化剂被卸载于熔融态的蜡中。将该蜡涂敷的催化剂于是转移到淤浆合成反应器中。催化剂K(C258)(30g Co/0.075gPt/1.5gSi/100gAl2O3)制备
在Kataleuna GmbH Catalysis(Am Haupttor；D-06236 Leuna；德国)用均一的碳基层涂敷SASOL德国GmbH的商标产品：Siralox 1.5(即预成型的球形多孔Al2O3催化剂载体材料，含有1.5m％SiO2)，采用EP 0681868中描述的方法，在此引入作为参考。该试验结果得到了12.4gC/100gAl2O3修饰的载体。
根据US 5733839、WO 99/42214和WO 00/20116中描述的方法，采用水淤浆浸渍、真空干燥，之后直接流化床焙烧的方法，在已修饰的12.4gC/1.5gSi/100gAl2O3预成型载体材料上制备30gCo/0.075gPt/1.5gSi/100g Al2O3淤浆F-T催化剂，所述的方法在此引入作为参考。
催化剂K因此以类似催化剂E的制备方式制备，仅有的区别为催化剂K的钴负载量较低，即为30gCo/100g Al2O3，相对于40gCo/100gAl2O3，该催化剂通过两步浸渍/干燥/焙烧步骤实现。催化剂L(C339)(30gCo/0.075gPt/1.5gSi/100gAl2O3)制备
在Kataleuna GmbH Catalysis(Am Haupttor；D-06236 Leuna；德国)用均一的碳基层涂敷SASOL德国GmbH的商标产品：Siralox 1.5(即预成型的球形多孔Al2O3催化剂载体材料，含有1.5m％SiO2)，采用EP 0681868中描述的方法，在此引入作为参考。该试验结果得到了1.2gC/100gAl2O3的修饰载体。
根据US 5733839、WO 99/42214和WO 00/20116中公开的方法，采用水淤浆浸渍、真空干燥，之后直接流化床焙烧的方法，在已修饰的1.2gC/1.5gSi/100gAl2O3预成型载体材料上制备3OgCo/0.075gPt/1.5gSi/100g Al2O3淤浆F-T催化剂，所述的方法在此引入作为参考。
催化剂L因此以类似催化剂K的制备方式制备，仅有的区别为催化剂L的碳负载量较低，即为1.2gC/100gAl2O3，相对于12.4gC/100gAl2O3。
用于制备催化剂B、C、E、K和L的(碳涂敷的)催化剂载体孔体积作为催化剂载体上碳量的函数示意于表1中。可见随碳量的增加催化剂载体的孔体积减少。
以类似实施例1描述的方式测试催化剂E、K和L的F-T合成试验性能。观察得到的结果列于表2中。
    催化剂催化剂特征组成合成性能数据：试验分析次数操作时间(小时)％(H2+CO)转化率反应器分压H2(bar)CO(bar)H2O(bar)CO2(bar)起始的相对固有(F-T)活性因子(即在ti时aI＝R.I.A.F.)          E40gCo/0.100gPt/100gAl2O345f15764.02.35.90.55.6          K30gCo/0.075gPt/1.5gSi/100g Al2O355f15546.53.53.80.34.3          L30gCo/0.075gPt/1.5gSi/100g Al2O397f15724.12.04.50.44.0
从表1和表2得到如下的推论：
在用碳涂敷的氧化铝上载体上制备的催化剂E即40gCo/0.100gPt/100gAl2O3，显示出起始RIAF为5.6，其明显高于催化剂C，即在用碳涂敷的氧化铝上载体上制备的40gCo/0.100gPt/100gAl2O3的起始RIAF3.5。
催化剂K和L即都是30gCo/0.075gPt/100g载体，都在用碳涂敷的氧化铝载体上制备，显示出明显高于催化剂B的起始RIAF，即起始RIAF分别为4.3和4.0，催化剂B为在用碳涂敷的氧化铝载体上制备的30gCo/0.075gPt/100g Al2O3，起始RIAF为2.7。
在本发明中，因此惊人地发现当钴基F-T合成催化剂在碳涂敷的载体上制备时，这些催化剂显示了增加的固有催化性能，所述的碳涂敷在浸渍/干燥步骤期间活性钴相沉积到载体上并进入其中之前进行。

Claims (8)

1.一种制备钴基催化剂前体的方法，该方法包括：
在载体浸渍阶段，用钴盐浸渍含有用碳涂敷的多孔催化剂载体颗粒的涂敷的催化剂载体，并部分干燥浸渍的载体；及
在焙烧阶段，焙烧部分干燥浸渍的载体以得到钴基催化剂前体。
2.一种制备钴基F-T催化剂的方法，该方法包括：
在载体浸渍阶段，用钴盐浸渍含有用碳涂敷的多孔催化剂载体颗粒的涂敷的催化剂载体，并部分干燥浸渍的载体；
在焙烧阶段，焙烧部分干燥浸渍的载体以得到钴基催化剂前体；及
在还原阶段，还原钴基催化剂前体以得到钴基F-T催化剂。
3.根据权利要求1或2的方法，其中载体上的碳量为0.1g C/100g载体～40g C/100g载体。
4.根据权利要求3的方法，其中载体上的碳量为0.5g C/100g载体～20g C/100g载体。
5.根据权利要求1-4的任一项的方法，其中钴盐是硝酸钴，且其中多孔催化剂载体颗粒是氧化铝、氧化硅、氧化硅-氧化铝、氧化钛或氧化镁颗粒。
6.根据权利要求1-5的任一项的方法，其中载体是含有修饰组分硅的被保护的修饰的催化剂载体。
7.根据权利要求1-6的任一项的方法，其中得到的钴催化剂前体是通过2-步淤浆浸渍、干燥和焙烧的方法得到的，所述的方法包括，在第一步中，用钴盐浸渍碳涂敷的催化剂载体，并部分干燥浸渍的载体，焙烧部分干燥的载体以得到焙烧的材料，之后，在第二步中，用钴盐浸渍焙烧的材料，部分干燥浸渍的材料，及焙烧部分干燥的材料以得到催化剂前体。
8.根据权利要求7的方法，在两步淤浆浸渍步骤中的任一步或两步期间，可加入水溶性的前体钯或铂盐或该盐的混合物，作为具有增强钴还原能力的掺杂剂。
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CN106000404A (zh) * 2016-05-24 2016-10-12 江南大学 一种用于费托合成的碳改性二氧化硅载体负载的铁基催化剂的制备及其应用
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