CN103492074B - 具有优良传热能力的用于费-托合成的催化剂 - Google Patents
具有优良传热能力的用于费-托合成的催化剂 Download PDFInfo
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Abstract
本发明涉及一种具有优良传热能力的用于费-托合成的催化剂。本发明的催化剂包括（1）一种或多种由传热材料（HTM）制成的中央核心颗粒，所述传热材料选自由金属、金属氧化物、陶瓷及其混合物组成的群组；和（2）外部颗粒层，其包围中央核心颗粒并通过粘合剂材料层粘附至所述中央核心颗粒的表面。所述外部颗粒层含有载体和负载在该载体上的含金属颗粒的粉末形式的催化剂颗粒。本发明的具有上述双颗粒结构的催化剂具有优良的传热能力，并由此对目标烃表现出高选择性。因此，本发明的催化剂可有效用在通过费-托合成由合成气生产烃的固定床反应器中。
Description
技术领域
本发明涉及具有优良传热能力的用于费-托(Fischer-Tropsch)合成的催化剂，用于由合成气生产烃类。
背景技术
所述费-托法(F-T合成)由德国化学家FranzFischer和HansTropsch在1923首次开发，并且该方法能够通过来自煤、天然气、生物质等的合成气生产液态烃。由煤炭生产液态燃料的工艺称为“煤制液(coal-to-liquids,CTL)工艺”；由天然气生产液态燃料的工艺称为“气制液(gas-to-liquids,GTL)工艺”；由生物质生产液态燃料的工艺称为“生物质液化(biomass-to-liquids，BTL)工艺”；最近，术语“XTL”(“X”资源制液)经常被用作类似工艺的总称。
这些工艺首先将每种原料如煤、天然气、生物质等通过气化、重整等转化成合成气；为了生产液态燃料，适合XTL工艺的合成气的组成优选为氢气：一氧化碳＝2:1，如以下反应式I所示，其中CO,H2,-[CH2]-n和H2O分别代表一氧化碳、氢气、链长为n(n表示碳的数目)的烃，和水。
反应式I
CO+2H2+-[CH2]-n→-[CH2]-n+1+H2O
当氢气的比例超过2时，这会增加甲烷的选择性并相对地抑制C5+(具有五个或更多个碳原子的烃类)的选择性，因此这是不希望的。除了反应式I的直链烃外，还可以生产其他烃，例如石蜡、含氧化合物(oxygenate)(含有氧原子的分子，包括醇、醛、酮等)等。
XTL工艺的主要目的之一是获得液态燃料，因此，目前的趋势是优化催化反应、合成气的比例、温度、压力等，来增加直链烃的选择性，更特别是C5+的选择性。在催化反应中，经常使用钴或铁基催化剂，这些金属催化剂均匀地分散或沉积在诸如氧化铝、二氧化硅、二氧化钛等的载体上。可以使用诸如钌、铂、铼等贵金属作为助催化剂来提高催化性能。
同时，多种类型的反应器均可用于F-T合成，例如，管式固定床反应器、流化床反应器、浆液反应器(slurryphasereactor)和装配有热交换器的微通道反应器或多通道反应器。然而，最终产品的响应特性和分布可能会因所用反应器的类型而变化，因此，应根据最终目标产品选择合适的反应器。管式固定床反应器、流化床反应器和浆液反应器就它们的输出而言占用太多空间。因此，近来更优选的是多通道反应器(涵盖“微通道反应器”)，其对于输出而言占用相对小的空间(其他类型反应器大小的1/5至1/2)。多通道反应器被设计为使传热效率最大化，以使其可以在高空间速度(spacevelocity)下使反应运行，其优点包括，设备和安装的成本相对较低，由于能够调节系统至任何所需的容量因而能方便容易地扩大规模，并且当设备移动时可能造成的以下损失均是微不足道的：由于摩擦或碰撞引起的机械损失，以及由于反应器性能的变化或催化剂的振荡引起的损失。
多通道反应器具有为交替层状结构的催化床和具有热交换器，对于F-T合成，可通过将催化剂插入反应器(即固定床反应器)内部而将该催化剂负载到反应器中，或通过将催化剂涂覆在反应器的内壁上而使该催化剂贴附至反应器上。在催化剂涂覆至反应器内壁上的情况下，负载容量(即，可以装载在反应器中的催化剂的量)是相当小的，因此对生产量有限制，更换催化剂非常困难或者几乎是不可能的。因此，更优选的是负载催化剂颗粒的固定床反应器。对于固定床反应器，催化剂的负载容量高，并且更换催化剂相对容易。然而，该类型反应器的传热效率差，而且它也会形成热点(hotspot)或使失控(run-away)，使得反应无法控制。
在F-T合成过程中，即时地从催化剂颗粒中除去反应热是非常重要的，因为捕获的反应热可能会降低目标烃的选择性并造成催化剂的劣化。因此，在常规方法中，已尝试通过使用一定量的惰性载体制备固定床催化剂层(见美国专利No.4,075,231)或混合惰性颗粒与催化剂颗粒以形成催化剂层从而适当地控制反应来克服这些问题。但是，在使用惰性载体的情况下，所述惰性载体本身是多孔材料，因此催化剂材料吸入该载体中并且催化反应也发生在该载体内，这使得很难控制该放热反应。在物理混合惰性颗粒与催化剂颗粒的情况下，难以均匀地混合这些颗粒，导致催化剂材料的聚集，从而防止了均匀的催化反应。
因此，对具有良好传热能力的催化剂进行了综合深入研究，以减少所述与控制反应热以及提高生产率相关的问题。例如，美国专利申请公开文本No.2004/0251001公开了一种用于F-T合成的薄箔型催化剂，KR特开专利公开文本No.2007-0010190公开了一种具有氧化性核心材料、氧化锌壳和负载或涂覆在该壳上的催化活性材料(其中基础材料含有一种或多种选自钴、铁、钌和镍的元素)的催化剂。
然而，这些用于F-T合成的常规催化剂在传热性能方面无法获得理想的物理性能。
发明内容
因此，本发明的一个目的是提供一种具有优良传热能力的用于由合成气生产烃的费-托合成的催化剂，以改善多通道固定床反应器的传热性能。
根据本发明的一个方面，提供了一种具有双颗粒结构的催化剂，其包括：
(1)一种或多种由传热材料(HTM)制成的中央核心颗粒，所述传热材料选自由金属、金属氧化物、陶瓷及其混合物组成的群组；和
(2)外部颗粒层，其包围所述一种或多种中央核心颗粒并通过粘合剂材料层粘附至所述一种或多种中央核心颗粒的表面，并且所述外部颗粒层包含具有载体和置于所述载体上的金属颗粒的粉末形式的催化剂颗粒。
本发明的双颗粒结构的催化剂具有优良传热能力，使得对目标烃、特别是C5+(具有五个或更多碳原子的烃)具有高选择性，因此可在用于由合成气生产烃的费托合成中。本发明的催化剂还有效地在常规的固定床反应器(管壳式热交换器)以及在以高空速发生反应的多通道反应器中用作催化剂。
附图说明
图1是说明本发明具有双颗粒结构的催化剂的示意图(1：由HTM制成的中央核心颗粒，2：由粉末形式的催化剂颗粒制成的外部颗粒层，3：粘合剂材料层)。
图2(a)和2(b)是装配有固定床热交换器的多通道反应器的示意图，示出了热交换部分，在该部分中，催化剂被负载到反应器中；和热交换器板，其分别包围所述热交换部分的前面部分和后面部分。
具体实施方式
本发明的具有双颗粒结构的催化剂包含(1)一种或多种由传热材料(HTM)制成的中央核心颗粒，所述传热材料选自由金属、金属氧化物、陶瓷及其混合物组成的群组；和(2)外部颗粒层，其包围所述中央核心颗粒并通过粘合剂材料层粘附至所述中央核心颗粒的表面。所述外部颗粒层包含具有载体和置于所述载体上的金属颗粒的粉末形式的催化剂颗粒。本文所用的术语“双颗粒结构”是指所述中央核心颗粒和所述外部颗粒层的组合结构。发明的用于热交换器的具有双颗粒结构的催化剂示于图1中(1：由HTM制成的中央核心颗粒，2：由粉末形式的催化剂颗粒制成的外部颗粒层，3：粘合剂材料层)。
本发明催化剂的中央核心颗粒由选自金属、金属氧化物、陶瓷及其混合物的HTM制成。HTM的具体例子包括：碳化硅(SiC)、氧化铝、铝氧粉、二氧化硅、铝、不锈钢、铜及其混合物。为了负载到反应器的固定床中，所述中央核心颗粒的尺寸优选为约0.5-20mm。但是，如果需要，该尺寸可以调节。此外，所述颗粒可以使用任何合适的形状，并且所述颗粒可以具有不规则的形状。所述颗粒的形状的例子包括球体、多面体、空心圆筒、拉西环(Raschigring)和鲍尔环(pallring)。
本发明催化剂的外部颗粒层包含具有载体和置于所述载体上的金属颗粒的粉末形式的催化剂颗粒。所述载体可以由氧化铝、二氧化硅、氧化锆、二氧化钛或其混合物构成。所述金属颗粒可以是Co、Fe、Ru、Re、Rh、Ni、Pd、Pt、Os、Ir、其合金或其混合物。所述载体的尺寸优选在约10-200μm范围内。具有所述载体和负载在所述载体中的金属颗粒的粉末形式的催化剂颗粒可以通过常规方法制备。
本发明的催化剂包含一个粘合剂材料层，以将中央核心颗粒粘合至包围所述中央核心颗粒的外部颗粒层。所述粘合剂材料层优选由陶瓷材料构成，所述陶瓷材料如二氧化硅、勃姆石(boehmite)及其混合物，或含有Si、Al或其混合物和氧的氧化物。
当所述粘合剂材料层是由陶瓷材料构成时，在所述中央核心颗粒的表面上涂覆陶瓷溶胶，如二氧化硅溶胶、勃姆石溶胶及其混合物，将所述粉末形式的催化剂颗粒粘附至涂覆有陶瓷材料的中央核心颗粒，然后将得到的材料在400-500℃的温度范围内烧结1-4小时，以形成粘合剂材料层。由此形成的经烧结的粘合剂材料层将中央核心颗粒完全粘合至含粉末形式的催化剂颗粒的外部颗粒层。例如，将粉末形式的催化剂颗粒放在板等的上面，添加合适量的涂覆有陶瓷材料的中央核心颗粒，然后可通过使用适当的方法，例如通过移动或摇动所述板，将该粉末形式的催化剂颗粒粘合至涂覆有陶瓷溶胶的中央核心颗粒的粘合表面。
由此得到的具有双颗粒结构的催化剂包含作为中央核心颗粒的具有优良传热能力的HTM，其中没有任何催化剂材料。因此，反应热可以迅速地扩散而不是被困在催化剂内部，这可防止催化剂由于热而劣化，并且其还会减少在高温下目标烃的选择性降低的问题。KR特开专利公开文本No.2007-0010190公开的用于F-T合成的催化剂为核壳型催化剂，具有氧化性核材料、氧化锌壳和负载在该壳中或涂覆在该壳上的催化活性材料。与本发明不同的是，这类催化剂仅能通过将金属催化剂材料放置或涂覆在壳上而使用该金属催化剂材料(而本发明的催化剂具有含中央核心颗粒和外部颗粒层的双颗粒结构进行热交换)。如韩国特开专利公开文本No.2007-0010190中所公开，在用催化材料涂覆或浸渍所述表面同时使用多孔颗粒作为中央核心的情况下，催化材料移至核心颗粒，催化反应发生，由此导致与本发明催化剂相比较差的可控性。
因此，本发明的具有双颗粒结构的催化剂具有优良的传热能力，使得对目标烃、特别是C5+具有高的选择性，因此可在费托合成中用于由合成气生产烃。因此本发明的催化剂可有效地在常规的固定床反应器(管壳式热交换器)中用作固定床反应器的催化剂，以及在以高空速发生反应的多通道反应器中用作催化剂。
下文将更详细地描述本发明。给出以下实施例的目的仅是为了说明，并不意在限制本发明的范围。
实施例
为了测试本发明的具有双颗粒结构的催化剂的催化性能，分别制备了两种不同类型的催化剂。然后，将由此得到的催化剂负载到多通道反应器中进行费-托合成，并观察反应器的反应。使用如图2所示的装配有固定床型热交换器的反应器作为该实验中的多通道反应器。在图2中，(a)代表热交换部分，在其中催化剂被负载到反应器中，(b)代表热交换器板，其包围所述热交换部分的前面部分和后面部分。
实施例1和比较例1：催化剂的制备
将23wt％的钴和0.05wt％的铂浸渍在粒径分布为50-120μm的γ-氧化铝粉末中，在110℃干燥，并在500℃烧结5小时，得到粉末形式的催化剂颗粒，在该颗粒中，钴和铂颗粒被负载到γ-氧化铝上。将足够量的由此得到的催化剂颗粒放置在一个板上，然后将适当量的大小约1mm且涂覆有勃姆石溶胶粘合剂的不规则形状的氧化铝颗粒(HTM)放置在该粉末形式的催化剂颗粒上。摇动该板，使得所述粉末形式的催化剂颗粒均匀地粘附至涂覆有勃姆石溶胶的HTM(中央核心颗粒)。然后，将所得颗粒在400℃烧结1小时，以将它们粘合从而防止它们彼此分离。将得到的催化剂命名为“催化剂A”，说明该具有双颗粒结构的催化剂的示意图示于图1中(实施例1)。
同时，将23wt％的钴和0.05％的铂浸渍在一个圆筒状的γ-氧化铝载体中，在110℃干燥，并在500℃烧结5小时。将由此形成的催化剂粉碎成大小约1mm的颗粒。将得到的该催化剂命名为“催化剂B”(比较例1)。
实施例2:使用催化剂A的费-托合成反应
将实施例1中的1g催化剂A负载到一个如图2所示的通道型反应器(约0.0001桶每天(BPD))中，然后，对合成气实施费-托合成。负载有催化剂的该反应器的内部空间的体积为2cm3，在该反应器的热交换部分的每一侧上装配一个固定床热交换器。在实施费-托合成之前，使用混合气体(H2:He＝5:95)在约400℃活化该催化剂。反应条件如下：
反应温度：220℃，
压力：20巴
空速：2,000mL/g催化剂/小时
合成气组成：H/CO/Ar＝63/31.5/5.5mol％，
其中在所述组成中，氢气与一氧化碳的比例为约2:1，并且当计算空速时，排除HTM的重量。
费-托合成的结果是，CO转化率是18.63％；甲烷的选择性和C5+烃的选择性分别为10.19％和87.32％。
比较例2:使用催化剂B的费-托合成反应
重复实施例2的过程，不同之处在于，使用实施例1中获得的催化剂B来对合成气实施费-托合成。
费-托合成的结果是，CO转化率是13.04％；甲烷的选择性和C5+烃的选择性分别为12.85％和83.06％。
从上述合成反应的结果明显可知，与使用催化剂B相比，当使用本发明的具有双颗粒结构的催化剂A时，CO转化率(其表示反应的程度)和C5+烃的选择性更高。
Claims (8)
1.一种用于费-托合成的具有双颗粒结构的催化剂，包括：
(1)一种或多种由传热材料(HTM)制成的中央核心颗粒，所述传热材料选自由金属、金属氧化物、陶瓷及其混合物组成的群组；和
(2)外部颗粒层，其包围中央核心颗粒并通过粘合剂材料层粘附至所述中央核心颗粒的表面，
其中所述外部颗粒层由粉末形式的催化剂颗粒制成，所述催化剂颗粒包含置于载体上的金属颗粒，并且其中所述粘合剂材料层在粘附至所述外部颗粒层之后进行烧结。
2.权利要求1所述的催化剂，其中所述HTM选自由碳化硅(SiC)、氧化铝、铝氧粉、二氧化硅、铝、不锈钢、铜及其混合物组成的群组。
3.权利要求1所述的催化剂，其中所述载体选自由氧化铝、二氧化硅、氧化锆、二氧化钛及其混合物组成的群组。
4.权利要求1所述的催化剂，其中所述载体的尺寸在10-200μm范围内。
5.权利要求1所述的催化剂，其中所述粉末形式的催化剂颗粒的金属颗粒选自由Co、Fe、Ru、Re、Rh、Ni、Pd、Pt、Os、Ir、其合金及其混合物组成的群组。
6.权利要求1所述的催化剂，其中所述粘合剂材料层由陶瓷材料构成，所述陶瓷材料选自由二氧化硅、勃姆石及其混合物组成的群组。
7.权利要求6所述的催化剂，其中所述粘合剂材料层通过在400-500℃的温度范围内烧结陶瓷溶胶而形成，所述陶瓷溶胶选自由二氧化硅溶胶、勃姆石溶胶及其混合物组成的群组。
8.权利要求1所述的催化剂，其中所述粘合剂材料层由含有Si、Al或其混合物以及氧的氧化物材料构成。
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| CN104162430A (zh) * | 2014-09-09 | 2014-11-26 | 安徽工程大学 | 一种蛋壳型的催化剂 |
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| EP2703082A4 (en) | 2014-11-19 |
| WO2012148165A2 (ko) | 2012-11-01 |
| KR101297599B1 (ko) | 2013-08-19 |
| WO2012148165A3 (ko) | 2012-12-27 |
| AU2012248972B2 (en) | 2016-02-04 |
| EP2703082A2 (en) | 2014-03-05 |
| CN103492074A (zh) | 2014-01-01 |
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| US9012352B2 (en) | 2015-04-21 |
| US20140038813A1 (en) | 2014-02-06 |
| KR20120121071A (ko) | 2012-11-05 |
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