CN1934030B - 具有改进的抗机械性的活性炭、及其用途、特别是作为催化剂载体 - Google Patents

具有改进的抗机械性的活性炭、及其用途、特别是作为催化剂载体 Download PDF

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CN1934030B
CN1934030B CN2005800088647A CN200580008864A CN1934030B CN 1934030 B CN1934030 B CN 1934030B CN 2005800088647 A CN2005800088647 A CN 2005800088647A CN 200580008864 A CN200580008864 A CN 200580008864A CN 1934030 B CN1934030 B CN 1934030B
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gac
equal
less
phthalocyanine
gross weight
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CN1934030A (zh
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雷米·利贝克
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Carbonisation et Charbons Actifs CECA SA
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Abstract

本发明涉及具有改进机械性能的活性炭。这些碳可有利地用于石油馏分的软化，作为硫醇氧化转化为二硫化物的催化剂载体，也用于任何其它类型反应，例如水中存在的氰化物的氧化或草甘膦的合成，和用于由液相中和/或气相中的选择性吸附的提纯和/或分离方法(液体食品的脱色，水处理，空气处理，溶剂回收等)。

Description

具有改进的抗机械性的活性炭、及其用途、特别是作为催化剂载体
技术领域
本发明涉及一种活性炭，它特别是作为催化剂载体用于在液相中进行的反应，特别是用于在液体烃中存在的硫醇的氧化反应。 
背景技术
液体烃中存在的硫醇的氧化反应是由沉积在多孔固体载体上的催化剂的作用，通常是磺化酞菁钴的作用，使烃中存在的硫醇氧化为二硫化物。 
2RSH+1/2O2→RSSR+H2O     
此反应在碱性介质(氢氧化钠)中使用基于酞菁钴的催化剂而催化。 
对于重石油进料(FCC汽油，煤油，瓦斯油)，使用催化剂的固体载体以促进RSH化合物的反应，该RSH化合物比轻RSH化合物重和因此反应较少。 
此外，由于这些硫醇较重，所以它们不是从有机相萃取。在此情况下，硫的含量不改变；使用的术语是进料的“脱硫”：转化成二硫化物，它们的腐蚀性不如硫醇。主要应用是生产喷气燃料。 
题目为“Merox和相关金属酞菁催化的氧化方法”，Basu等人，Catal.，Rev.Sci.Eng.35(4)，571-609(1993)的文章，从载体、催化剂、掺杂添加剂、反应机理等方面特别详尽地汇集了在此主题下的公开文献。其中描述了许多类型的载体：粘土、氧化铝、活性炭、或任何其它固体载体，但发现通常优选是由碳质材料组成的载体。文献指出，从反应催化动力学的观点来看，活性炭通常比其它载体更有效：参照乙基硫醇在酞菁钴上的氧化，Huendorf U.等人，Heterog.Catal.，6(2)，73(1987)；矿物质载体上的酞菁，4a)，作为2-巯基乙醇氧化催化剂的在SiO2和Al2O3和活性炭上的低分子量和聚合物酞菁，Wohrle D.等人，Markromol.Chem.，190，961-974(1989)。 
在US4248694中，UOP教导了堆积密度为0.25-0.5g/cm3的密集木炭的使用使其可以达到比不密集活性炭更好的催化动力学。在实施例中，UOP显示密度为0.44g/cm3的木炭Darco MRX是比堆积密度为0.15g/cm3的木炭 Nuchar WA好的候选物。 
在烃脱硫的目前工业实践中，仅活性炭用作催化剂载体。 
名称为Merox(UOP技术)，Mericat(Merichem技术)和Sulfrex(IFP技术)的石油原料或工业烃脱硫的主要方法是已知的： 
◆由UOP开发的Merox技术，该技术的原理详细描述于US3371031，涉及最老和最通常的方法：它包括由从顶部向下的渗透而操作的简单固定床，随后为烃/氢氧化钠分离鼓， 
◆更近来由Merichem开发的Mericat技术。它的原理说明于EP203574，该系统包括纤维预接触器和然后采用底部向上模式操作的活性炭床；分离器与塔成为整体(使此单元更紧凑)， 
◆由IFP开发的Sulfrex技术，它的原理说明于专利FR2560889。 
在这些各种不同的脱硫方法中，将活性炭放入塔中之后在水下润湿。然后通过塔的循环浸透，使它浸渍催化剂的稀溶液(直到所需的浸渍程度)，该催化剂基本基于磺化酞菁钴。此操作通常在精炼厂的塔中原位进行。然而，它也可以离位进行，例如在如下文献中所示：腐蚀性最小化和管理的Merox方法，Holbrook等人(UOP)，NPRA 1993年度会议1993。 
随后，将活性炭的床层用氢氧化钠溶液(氢氧化钠浓度：5-20wt％)完全浸渍。最后，通过同时渗滤被处理的烃原料和循环的氢氧化钠溶液，才能真实地使反应开始，为了进行该反应，在该溶液中加入少量的空气。反应在适中的温度和适中的压力，即大约20-80℃和0.1-1MPa(1-10巴)和优选大约35-50℃和0.4-0.6MPa(4-6巴)下操作。接触时间从几分钟到几小时变化，优选从30到60分钟变化。硫醇浓度在入口为几百ppm在这样单元的出口变成小于30ppm。 
工业上可能遇到的问题很少是由于催化不良(即RSH化合物转化到二硫化物的转化程度不足)，而是由于活性炭的机械强度引起的，在催化不良的情况下，通常用催化剂充分再浸渍载体可以恢复好的效力。这是由于后者受机械应力，特别是当水力条件极端时(高通过率，大流量等)，当加工要求在活性炭层以下有陶瓷珠粒层时(Mericat工艺)导致后者必须经受的另外机械应力等。这些条件可破坏活性炭的颗粒而形成细粒，该细粒如果积聚，就造成工业装置的压降显著增加，该压降的显著增加可发展到强制工业装置停工以清除这些细粒，甚至完全改变活性炭的装料，即使催化剂仍然有效。 
由于精炼厂中长期停工昂贵，显然必须尽可能多地限制这些。清除细粒和改变木炭的装料都是非生产性操作，最好避免该操作。用催化剂润湿而又浸渍木炭的操作也是非生产性操作，它们必须尽可能快速地进行。从此观点甚至更快速润湿和浸渍的碳也更为有利。 
最后在一些情况下，处理过的烃原料变成有颜色，着色可能是由于存在杂质如氧化铁而催化的副反应。因此希望载体含杂质尽可能少，特别是金属杂质。 
发明内容
本发明涉及活性炭，当它们用作液相中进行的反应的催化剂载体时，特别是用于液体烃中存在的硫醇的氧化反应时，该活性炭不显示以上缺点。 
根据本发明的活性炭特征为： 
ο总孔体积为大于或等于1.00ml/g，优选大于或等于1.20ml/g， 
ο床层强度(BS)根据壳牌公司(Shell)的本体破碎测试测量的为大于或等于1MPa(10巴)和优选大于或等于1.5MPa(15巴)和有利地大于或等于1.7MPa(17巴)，和 
οBET比表面为大于或等于500m2/g，优选大于或等于700m2/g， 
和优选， 
ο微孔体积，由氮吸附测量的为大于或等于0.20ml/g，优选大于或等于0.30ml/g， 
ο中孔体积，由氮吸附和汞侵入测量的为大于或等于0.15ml/g，优选大于或等于0.20ml/g和 
ο大孔体积，由汞侵入测量的为大于或等于0.40ml/g，优选大于或等于0.50ml/g。 
在本文中，微孔、中孔和大孔体积的定义是根据IUPAC标准。 
有利的是，本发明活性炭中铁的重量含量为小于或等于2000ppm(重量)，优选小于或等于1000ppm，有利地小于或等于500ppm和更有利地小于或等于300ppm。 
在根据本发明的活性炭中，堆密度为0.20-0.50，优选0.3-0.4的那些也是优选的。 
在根据本发明的活性炭中，灰分含量(根据CEFIC方法测量)为在650℃ 下燃烧之前活性炭总重量的10％或更小，优选7％或更小。 
根据本发明的活性炭的粒度通常应使得这些炭粒被筛孔尺寸为0.2mm，优选0.4mm和有利地0.6mm的筛网保留，并通过筛孔尺寸为5mm，优选2mm的筛网。 
根据本发明的活性炭可以具有各种形状，如： 
-条形，例如由粉末状的开始碳质原材料与焦油或沥青类型粘结剂等的凝聚而得，然后活化， 
-颗粒，例如由破碎和筛分到活化活性炭的所需粒度而获得， 
-珠粒或任何其它形状的粒子，它的粒度优选如上所述。 
优选使用形式为颗粒或珠粒的活性炭。 
从充分活化的果核制造的活性炭，特别是基于橄榄榨渣的那些显示本发明的优选特性：它们在力学上是特别坚固的，是被氧化催化剂快速浸渍的并具有低含量的无机杂质和它们因此特别适合于作为特别长时间的氧化催化剂的载体。 
以果核为基料，最好是以橄榄榨渣为基料的活性炭可以根据常规方法制造，即可通过物理活化或化学活化来制备。术语“物理活化”理解为表示碳化第一阶段，其通常在大约500℃，随后为用水蒸气的活化阶段，通常在大约900℃下进行；术语“化学活化”理解为表示碳质原材料用化学试剂，如磷酸或氯化锌的浸渍，随后活化，通常在大约500℃下进行，随后进行洗涤操作以回收使用的化学试剂。 
本发明也涉及采用氧化催化剂浸渍这些活性炭的方法和涉及这些载体催化剂用于硫醇液相氧化的用途。 
采用金属配合物充当氧化催化剂浸渍活性炭；在金属配合物中可以提及酞菁钴、酞菁镍、酞菁铜、酞菁锌和酞菁钒、多氨基烷基多羧酸的金属配合物，如EDTA或其一种盐的配合物，例如公开于FR2560889，或任何其它金属配合物，特别优选是酞菁钴。 
酞菁通常不直接溶于水溶液和由此原因优选使用一种它们的水溶性衍生物，如磺化和羧基化衍生物，优选是磺化衍生物，其中特别优选的是二磺化衍生物。 
也可以加入文献中公开的一种或多种促进剂或掺杂添加剂，例如乙酸或甲醇(US4087378)，脲(US4098681)，羧酸(US4107078)，乙醇三甲基氯化铵 或氢氧化物(US4121997和US4124494)，多核芳族磺酸(US4121998)，季铵(US4157312)，链烷醇胺氢氧化物(US4159964)，吗啉(US4168245)或单乙醇胺(US5956325)。 
此浸渍可以在硫醇氧化反应成二硫化物的工业单元中放置炭之前或之后进行。 
随后，将活性炭的床层采用碱性溶液，通常氢氧化钠溶液(5-20wt％氢氧化钠)、氢氧化钾或氨水溶液完全浸渍，如在US4502949或US4913802中公开的那样。 
最后，例如通过同时渗透待处理的烃原料和循环的碱性溶液(氢氧化钠溶液，氢氧化钾溶液，氨溶液等)能使硫醇的氧化反应真正开始，为了进行该反应，已向其中加入少量空气。反应在适当温度和适当压力，即大约20-80℃和0.1-1MPa和优选大约35-50℃和0.4-0.6MPa下操作。接触时间通常从几分钟到几小时变化，优选30-60min。在这样单元中的硫醇浓度在入口为几百ppm在出口变成小于30ppm。 
由申请人公司优选的基于果核的活性炭具有非常良好的浸渍动力学和因此很快占据了应有的地位；它们的催化性能等同于工业上使用的已知载体的那些性能；由于它们具有优异的机械强度，所以这种载体催化剂的寿命相对于工业上已经使用的载体的寿命而言是增加了；最后，由于它们的铁含量非常低，副反应非常有限。 
根据本发明的活性炭也可以用作任何其它类型反应中催化剂的载体，例如用于水中存在的氰化物的氧化，如在化学氧化：九十年代的技术，Kurek PR等人(UOP)，Proceedings First International Symposium，Nashville，1993中所述，或用于草甘膦的合成，例如在FR2269533中所公开，作为催化剂和用于由液相中和/或气相中的选择性吸附的提纯和/或分离方法(液体食品的脱色，水处理，空气处理，溶剂回收等)。 
具体实施方式
比较不同量和来源的几种活性炭在表1中列出它们的主要特性。 
炭的特性根据标准方法，特别是CEFIC(Conseil Européen des Fédérations de 1’Industries Chimique[欧洲化学工业协会])方法测定。 
工业上通常用作烃脱硫的金属氧化催化剂载体的商品炭所选用的牌号为：由Ceca销售的BGP MX，和由Norit销售的Darco MRX，选择它们作为参照。
表1 
Figure DEST_PATH_GSB00000615614700021
开发了特定的测试方法以展示受试活性炭作为氧化催化剂载体的性能。 
实施例1：床层强度测试
此测试能测量固体粒子床层的机械强度，该粒子受到均匀分布的压力。它从壳牌公司的本体破碎强度测试获得启示。将20cm3吸附剂放入内径为27.6mm的金属圆筒中。通过活塞将静止期增加的压力施加到床层的顶部。在每个静止期之间，通过筛分和称重确定形成的细粒(＜0.2mm)的水平。随后从其由内插法推导获得0.5wt％细粒必须的压力。 
结果见下表2： 
表2.活性炭的床层强度 
清楚地看出，本发明以橄榄榨渣为基料的活性炭机械性能最强，且显著高于在此应用中工业上所用的那两种活性炭。 
实施例2：催化剂浸渍动力学的测试
使用由Europhtal以名称802销售的含30％磺化酞菁钴的催化剂溶液。 
将320ml活性炭引入烧杯中的1升水中。加入少量氨水溶液，使得在加入该氨水溶液之后此最终溶液的pH大于或等于9。将一剂量的Europhtal 802催化剂随后引入使得最终产物的剂量精确为2g催化剂每升活性炭。将混合物轻微搅拌和随时间间隔取样。测定溶液中仍然存在的催化剂数量。此测定可以在设备的预校准之后，由660nm波长下的光学密度测量进行。 
结果见下图1。 
看出基于橄榄榨渣的根据本发明的活性炭和Darco MRX比其它更快速浸渍。基于木材和基于椰子的那些是最慢的，它们的浸渍在500min之后仍然没有完成。 
实施例3：硫醇氧化的催化测试
此测试是从著作如：乙基硫醇通过酞菁钴的氧化，Huendorf U.等人，Heterog.Catal.，6(2)，73(1987)获得启发。 
用根据实施例2测试的催化剂预浸渍的0.5ml活性炭(即2g催化剂/升炭)，50ml氢氧化钠溶液(浓度：7wt％)和包括2.81g叔丁基硫醇的140g正庚烷连续引入由夹套保持在环境温度的0.5升玻璃反应器。开始搅拌调节到500转/min和通过喷入溶液引入控制在1升/h的空气流。 
随时间间隔从有机相取样以监测残余硫醇浓度。由色谱测定硫醇。 
RSH的初始含量是按重量20000ppm。 
结果见下表3： 
表3：硫醇氧化的动力学 
Figure GSB00000605756200081
注意到三种炭(BGP MX，Darco MRX和本发明基于橄榄榨渣的活性炭)显示或多或少的同等催化性能。此外，其它两种炭(GAC 10-30和NC 35)，它们显示可观的机械强度，与这些相比催化动力学显著缓慢。 
显然，只有从橄榄榨渣制造的活性炭才显示最优的特性，即：特别强的机械性能、快速浸渍、优异的催化性能和低含量的无机杂质，特别是铁。 

Claims (28)

1.一种通过物理活化制得的活性炭，其特征为：
ο总孔体积为大于或等于1.00ml/g，
ο床层强度，根据壳牌公司的本体破碎测试测量为大于或等于1MPa，
οBET比表面积为大于或等于700m2/g，和
ο大孔体积，由汞侵入测量，为大于或等于0.50ml/g。
2.根据权利要求1的活性炭，其特征在于它显示：
ο微孔体积，由氮吸附测量为大于或等于0.30ml/g，
ο中孔体积，由氮吸附和汞侵入测量为大于或等于0.15ml/g。
3.根据权利要求1的活性炭，其特征在于它的铁含量按重量计为小于或等于1000ppm。
4.根据权利要求2的活性炭，其特征在于它的铁含量按重量计为小于或等于1000ppm。
5.根据权利要求1的活性炭，其特征在于它的堆密度为0.20-0.50。
6.根据权利要求2的活性炭，其特征在于它的堆密度为0.20-0.50。
7.根据权利要求3的活性炭，其特征在于它的堆密度为0.20-0.50。
8.根据权利要求4的活性炭，其特征在于它的堆密度为0.20-0.50。
9.根据权利要求1的活性炭，其特征在于它的灰分含量小于或等于10％的活性炭总重量。
10.根据权利要求2的活性炭，其特征在于它的灰分含量小于或等于10％的活性炭总重量。
11.根据权利要求3的活性炭，其特征在于它的灰分含量小于或等于10％的活性炭总重量。
12.根据权利要求4的活性炭，其特征在于它的灰分含量小于或等于10％的活性炭总重量。
13.根据权利要求5的活性炭，其特征在于它的灰分含量小于或等于10％的活性炭总重量。
14.根据权利要求6的活性炭，其特征在于它的灰分含量小于或等于10％的活性炭总重量。
15.根据权利要求7的活性炭，其特征在于它的灰分含量小于或等于10％的活性炭总重量。
16.根据权利要求8的活性炭，其特征在于它的灰分含量小于或等于10％的活性炭总重量。
17.根据权利要求1-16任意一项的活性炭，其特征在于它的粒度使得炭粒被筛孔尺寸为0.2mm的筛网保留，和通过筛孔尺寸为5mm的筛网，并以条形、颗粒或珠粒的形状提供。
18.根据权利要求1-16任意一项的活性炭，其特征在于它是以果核为基料。
19.根据权利要求18的活性炭，其特征在于它是以橄榄榨渣为基料。
20.权利要求1-19任意一项的活性炭的浸渍方法，
a)用以下金属配合物的水溶液浸渍，其选自酞菁钴、酞菁镍、酞菁铜、酞菁锌和酞菁钒的金属配合物、多氨基烷基多羧酸的金属配合物，和任选地一种或多种促进或掺杂添加剂，和
b)碱性溶液浸渍。
21.硫醇氧化为二硫化物的催化剂，其特征在于它由如下物质组成：连接到权利要求1-19任意一项的活性炭上的至少一种金属配合物。
22.根据权利要求21的硫醇氧化为二硫化物的催化剂，其特征在于所述金属配合物为酞菁钴、酞菁镍、酞菁铜、酞菁锌或酞菁钒，或多氨基烷基多羧酸的一种金属配合物。
23.根据权利要求21的硫醇氧化为二硫化物的催化剂，其特征在于它能够根据权利要求20的浸渍方法获得，该浸渍阶段b)可以在硫醇氧化反应期间进行。
24.根据权利要求22的硫醇氧化为二硫化物的催化剂，其特征在于它能够根据权利要求20的浸渍方法获得，该浸渍阶段b)可以在硫醇氧化反应期间进行。
25.权利要求1-19任意一项的活性炭作为催化剂载体的用途。
26.权利要求25的用途，其中，活性炭作为用于水中存在的氰化物的氧化或草甘膦的合成的催化剂载体。
27.权利要求1-19任意一项的活性炭作为催化剂的用途。
28.权利要求1-19任意一项的活性炭在由液相中和/或气相中的选择性吸附的纯化和/或分离方法中的用途。
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