CN1114485C - 二氧化钛催化剂和制备方法及在费－托合成中的应用 - Google Patents

二氧化钛催化剂和制备方法及在费－托合成中的应用 Download PDF

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CN1114485C
CN1114485C CN99802856A CN99802856A CN1114485C CN 1114485 C CN1114485 C CN 1114485C CN 99802856 A CN99802856 A CN 99802856A CN 99802856 A CN99802856 A CN 99802856A CN 1114485 C CN1114485 C CN 1114485C
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S·普莱查
C·H·毛尔丁
L·E·派德里克
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Abstract

本发明公开了通过把二氧化硅和三氧化二铝加入主要由二氧化钛组成的载体，制成了提高强度和耐磨性的费-托催化剂载体；因此，费-托活性金属可以与载体组合；在淤浆反应中该催化剂特别有用。

Description

二氧化钛催化剂和制备方法 及在费-托合成中的应用
本发明的领域
本发明涉及含二氧化钛的催化剂载体，它的制备方法和在费-托烃合成中作为催化剂(与添加的一种或多种金属一起)的应用。更具体地说，本发明涉及可以经得起在烃合成过程中例如淤浆合成过程中常常遇到的高水分压的材料。
本发明的技术背景
美国专利5140050号公开了费-托催化剂制备中载体制备的改进和这些催化剂在费-托过程中得到了出乎预料的结果。虽然这些改进的催化剂和载体有用，但是，在费-托合成的条件下，特别是由于费-托反应的结果产生较高的水分压导至催化剂减活和反应混合物中过细物料的形成。这些过细物料有严重的破坏作用，例如使管道堵塞、降低催化剂的效率、催化剂通过过滤器损失和堵塞过滤器。因此，要求开发象在费-托过程中存在的汽蒸条件下，能够保持完整性和保持催化剂的效率的催化剂。特别是，淤浆操作与汽蒸条件的严酷性要求高耐磨的催化剂。
本发明的概述
按照本发明，为实现在费-托过程中使用的催化剂所要求的完整性，采用二氧化硅和三氧化二铝作含二氧化钛的载体粘合剂。通过把一种或几种费-托合成活性金属，例如钴或钌之类的VIII族金属分散在载体的表面上制成催化剂。因此，制成的高强度(通过耐磨试验测量)催化剂在升高温度的较高水分压的条件下，例如在费-托过程中所使用的175-400℃温度的较高水蒸汽压的条件下保持其完整性。
美国专利5140050和4992406号公开了借助于使用三氧化二铝或氧化锆或二氧化硅粘合剂物料(按所列顺序优选)，改进含二氧化钛载体孔隙率的方法。但是，本申请中公开了比用作为粘合剂的三氧化二铝不优选的物料二氧化硅，与三氧化二铝一起，比只用三氧化二铝或二氧化硅生产干态或在汽蒸条件下更耐磨的含二氧化钛的物料。因此，似乎反常的事实是，把不优选的物料加入含二氧化钛和三氧化二铝的组合物中甚至制备出了更强的载体材料。
三氧化二铝和二氧化硅的协同作用生产更强含二氧化钛物料的机理不清楚。然而，尽管不希望受某一具体机理约束，但是，我们推理认为，在成品催化剂中，煅烧载体小的二氧化硅颗粒占据三氧化二铝大颗粒和更大的二氧化钛颗粒之间界面的位置，且用作化学粘合剂。因此，二氧化硅微晶与三氧化二铝微晶和二氧化钛微晶两者可能部分结合，生成基本上连续的微晶相。二氧化硅用作三氧化二铝和二氧化钛之间的粘合剂，和在煅烧或费-托合成过程汽蒸期间，可以进一步生成二氧化硅与三氧化二铝和二氧化硅与二氧化钛的混合边界相。而且，三氧化二铝本身不与二氧化钛很好混合，只是依靠物理力粘合颗粒。汽蒸可能破坏了这些物理力，可能使三氧化二铝烧结并生成大颗粒的三氧化二铝，这些大颗粒不能够提供粘合质量。由于二氧化硅对二氧化钛的亲合力，使二氧化硅失去了独立的性质，因此，二氧化硅本身不是优良的粘合剂。
附图的描述
图1是不同样品的声波磨损图，其中，纵轴表示小于25微米细粒的重量％，横轴表示超声波浴的时间(分)。曲线A、B、C和D分别表示二氧化钛与汽蒸三氧化二铝载体、二氧化钛与新鲜三氧化二铝载体、二氧化钛与汽蒸二氧化硅-三氧化二铝载体和二氧化钛与新鲜二氧化硅-三氧化二铝载体。
优选实施方案的描述
含二氧化钛载体是颗粒状物料，优选含50重量％二氧化钛，更优选含至少80重量％二氧化钛和优选金红石∶锐钛矿为至少约1∶9。这种物料与用作粘合剂物料的二氧化硅和三氧化二铝适量掺合，以载体的总重量计，其中粘合剂占约小于30重量％，优选小于约20重量％，更优选约3-20重量％，最优选约4-15重量％，特别优选5-10重量％。二氧化硅和三氧化二铝粘合剂混合物可以含50重量％或50重量％以下的二氧化硅，优选为约3-50重量％二氧化硅，更优选为5-35重量％二氧化硅。
载体用如挤出、制丸、压片、喷雾干燥等众所周知的方法，一般制成多孔的基本上为球形或圆柱形状。优选的方法是喷雾干燥的方法，在该方法中，二氧化钛和粘合剂物料的适宜淤浆进入一个用加热空气吹扫的室雾化。喷雾干燥产生的球形载体的粒径范围为20-120微米，该载体非常适合在淤浆费-托过程中使用。
为了得到孔隙率和强度的双重优点，粘合剂组分与二氧化钛原料在成型操作之前进行混合。它们可以不同的形态如盐或优选胶体悬浮液或溶胶形态添加。例如，从三氯化铝、醋酸铝或硝酸铝制备的三氧化二铝溶胶是优选的三氧化二铝组分源。易购的硅溶胶是优选的硅组分源。但是，在每种情况下，为避免这些粘合剂溶胶被对费-托活性金属有害的元素污染必须特别小心。例如，碱金属和碱土金属和含硫的阴离子如硫酸盐在费-托条件下是强有力的毒物，因此，在制备钴催化剂的载体时必须将其量减至最小。
在成形之后，二氧化钛载体通常进行煅烧，以便锻烧粘合剂和供选择地使二氧化钛的锐钛矿晶型转化成金红石晶型。这样的煅烧通常在500-1000℃温度下进行。
当从这种载体制备费-托催化剂时，用于费-托合成的催化活性金属与载体组合。优选的金属是元素周期表VIII族元素的金属，特别是铁、钴和钌，优选钴和钌，更优选钴。促进剂也可以采用，例如锆、钛、铼、铪、铈、钍和铀，和本领域内的技术人员众所周知的其它的促进剂。在费-托合成中，存在的一种或一种以上催化活性金属的量将随所选择的金属而变化。例如，在这种情况下，钌比钴活性高，因此，其用量为0.5-3.0重量％，而钴的用量优选为2-40重量％，更优选为5-30重量％最优选为10-25重量％。
当采用促进剂时，它们的用量比催化活性金属少例如，以催化活性金属为基准，其重量比为1/20-1/10。(本发明也考虑使用钌作促进剂和用钴作为主要的活性金属。)最优选的催化剂是含钴和铼、钴和钌和钴和钍的催化剂，特别是含钴和铼的催化剂。催化剂可以通过本技术领域技术人员众所周知的各种各样的技术制备，例如浸渍(或与促进剂共浸渍或系列浸渍—或通过干浸或通过起始润湿浸渍技术)。由于费-托过程的优选催化剂是催化活性金属存在于催化剂颗粒外部，即催化活性金属在一层中，深度不大于250微米，优选不大于200微米，所以制备催化剂的优选方法是美国专利5140050所述的喷雾干燥法(该专利的相关内容引入本中请供参考)或EP0266898所述的方法(该专利的相关内容引入本申请供参考)。对淤浆费-托过程来说，催化剂优选通过喷雾干燥的载体用起始润湿浸渍的方法制备。
含二氧化钛颗粒强度的测量是一项艰巨的任务，因为高度分散的磨损产物易粘附到原来的颗粒上，且通过传统的方法，如众所周知的Davison磨损试验，Microtrac or Malven光衍射仪都不可检测。所以，开发新的加速磨损试验，在该试验中，结果是可再现的，并根据磨损产物的SEM低倍放大照片认为，在侵蚀性或研磨环境下操作与在浓淤浆、鼓泡塔中的环境相似。
测试由下述试验组成：少量样品即悬浮在丙酮中的催化剂或载体如约0.5-约3克，进行预定时间期间的超声波浴，随后过滤定量产生的细颗粒即粒径小于25微米的颗粒的量。这样，筛分到+45微米尺寸并悬浮在12亳升丙酮中的2.5克样品加入0.5盎司(OZ.)瓶中。在Branson2200型超声波浴中进行超声波处理30分钟或30分钟以上的时间后，混合物通过500目筛网(25微米孔)在0.02微米过滤膜上(WhatmanAnodisc)过滤。然后，用丙酮洗涤固体物，干燥和称重，测量产生的小于25微米的颗粒的百分率(重量％)。
费-托合成是众所周知的方法，反应条件在现有文献中已经描述。例如，温度可以为约175℃-约400℃，优选为约180-250℃，而压力为1-100巴，优选为15-40巴。H2/CO可以为0.5/1-4/1，优选为1.7/1-2.5/1更优选为化学计算量约正负3％。从本发明的粘合剂制备的催化剂优选以淤浆使用，例如，在淤浆鼓泡塔中使用，反应器的气时空速为4000-20000h-1。优选的淤浆鼓泡塔的操作如美国专利5348982所述，其内容引入本文参考。
实施例
通过不同的粘合剂与Degussa P-25TiO2的混合物的喷雾干燥制备12种二氧化钛载体。干燥后的载体在一旋转煅烧炉中在700℃和1000℃之间的温度煅烧。这12种载体的每一种所使用的三氧化二铝粘合剂的量和源、二氧化硅粘合剂的量和源、喷雾干燥加料的固体重量％和煅烧温度总结在表1中。氯化铝水溶胶(alumina chlorhydrol sol)是GRACE Davison制造，命名为CX-100，含三氧化二铝为约23.5重量％。分析检测结果，包括30分钟的声波磨损试验的数据也示于表1。金红石含量指的是二氧化钛中金红石晶型的重量％，而平衡量的锐钛矿晶型是通过X-射线衍射(ASTMD 3720-78)测量。SA表示BET表面积，PV表示直径小于5000埃孔的孔体积，通过汞孔隙计(利用汞接触角为125度)测量。
实施例1&2表示三氧化二铝粘合剂的基本情况和合理地具有良好强度，但是，如下文所表明的，当汽蒸时强度降低。实施例3-5是用不同销售商的二氧化钛溶胶生产的在煅烧后大部分以细粒状存在的质量很差的颗粒，表明只用二氧化硅粘合剂的选择是不可行的。实施例6说明本发明加入由三氧化二铝和二氧化硅溶胶的混合物组成，其重量比为9∶1-1∶1的粘合剂。已经证实，在这些末汽蒸的实施例中，这种载体具有最低的声波磨损值，因此强度最高。
表1中的实施例7-12是在700℃温度下进行煅烧，因此，与实施例1-6相比，在二氧化钛中含较低的金红石，较高的表面和较高的孔体积。由于起始润温浸渍时因为孔体积的增加可以沉积较多的活性金属，因此较大的孔体积是一重要的特征。与实施例6使用相同三氧化二铝和二氧化硅粘合剂混合物的实施例7说明在较低温度煅烧，颗粒的强度不仅损失很小，而且在孔体积方面可实现明显地提高。对比例8和7表明在组合物中总粘合剂的含量为常量6重量％的情况下，三氧化二铝与二氧化硅的比例从9∶1改变到2∶1，得到了优良的孔体积。但是，总粘合剂的浓度升高，从6重量％升高到12重量％，如实施例8、9和12所示得到低孔体积。实施11和12说明，使用硝酸铝水溶胶代替氯化铝水溶胶作为粘合剂的三氧化二铝源，得到非常相似的结果。
表2总结了当二氧化硅加入三氧化二铝粘合的载体时，在喷雾-干燥后得到了下述结果。二氧化硅是通过浸渍硅酸四乙酯的甲醇溶液，随后干燥并在实验室用的炉内在800℃温度下煅烧3小时加入的。如表中所表明的那样，加入的大部分硅酸盐在干燥和煅烧过程中挥发损失，这是这种方法的一个严重问题。更重要地是，保留在载体上的二氧化硅对提高颗粒的强度不起什么作用。在实施例13中，加入实施例1载体中的二氧化硅末能明显地提高强度。实施例14所使用的载体与实施例1中的相同，但是，原料差得多，因此在一静电炉内在850℃再煅烧。实施例15使用二氧化钛沉淀物通过喷雾干燥实验制备的很差的载体代替Degussa P-25。在实施例14和15中，在加入二氧化硅后，载体甚至变得更差，这也许是由于在煅烧步骤中汽蒸使三氧化二铝粘合剂进一步变质的缘故。从这些实施例中可以清楚地看出，二氧化硅与三氧化二铝作为改进粘合剂所起的作用，两者必须是在起始的喷雾干燥步骤中存在。
为了进一步确定对二氧化硅-三氧化二铝粘合剂的认可，制备Co-Re催化剂：基本情况二氧化钛载体含6重量％三氧化二铝粘合剂，而本发明的实施例包括总粘合剂量为6重量％，其中三氧化二铝∶二氧化硅为9∶1的二氧化钛载体。喷雾干燥的载体是与实施例1和6相似的方法制备，但规模更大。然后，每种催化剂是用硝酸钴和高铼酸的水溶液起始润湿浸渍法、接着在旋转煅烧炉内在400℃煅烧制备。应用重复浸渍/煅烧达到最终的金属负载量。该催化剂在温度降低到375℃时，用H2/CO为2/1的合成气在一小固定床反应器中进行测试。两种催化剂生成烃的活性和选择性非常高，如表3所示。
最后，当催化剂在中等温度进行高水蒸汽分压处理时，例如象在烃合成时产生的高压水蒸汽那样，进行最关键的强度试验。为模拟这种环境，每种催化剂的一部分加入流化床反应器，并用纯水蒸汽在250℃温度，6.8大气压下处理6天。然后，对新鲜催化剂和汽蒸的催化剂利用声波磨损试验在不同的声波作用时间下进行耐磨试验。其结果如表4的实施例16-19并绘制在图1。参考图1，图1清楚表明，对全部物料来说，在耐磨试验中所产生的细颗粒的量随声波作用的时间而增加。汽蒸三氧化二铝粘合剂变差的情况的数据由线A表示。本发明的二氧化硅三氧化二铝粘合剂(线C)当汽蒸时，只很轻微地变弱，仍保持在末汽蒸的三氧化二铝的情况内(线B)。用本发明的改进粘合剂起始强度和对水蒸汽的稳定性都显著地提高。
              表1喷雾的二氧化钛载体
实施例 三氧化二铝重量％ 三氧化二铝源 二氧化硅重量％ 二氧化硅源 在喷雾干燥器中加料的固含量重量％ 煅烧温度℃ 金红石 SA  PV 声波磨损
1 6 氯水溶胶 0 无 36 800 94 17  0.36 3.9
2 6 氯水溶胶 0 无 36 800 95 14  0.34 3.6
3 0 无 6 Nyacol2034D.I. 23 83 20  0.28 -
4 0 无 6 Nalco2327 20 87 17  0.30 -
5 0 无 6 Nalcol034A 20 92 17  0.30 10.5
6 5.4 氯水溶胶 0.6 Nyaco12034D.I. 36 1000 93 17  0.33 1.1
7 5.4 氯水溶胶 0.6 Nyacol2034D.I. 36 700 16 44  0.54 3.2
8 4 氯水溶胶 2 Nyacol2034D.I. 36 700 14 51  0.50 -
9 10.8 氯水溶胶 1.2 Nyacol2034D.I. 700 14 52  0.37 -
10 8 氯水溶胶 4 Nyacol2034D.I. 700 15 55  0.38 -
11 5.4 硝酸铝 0.6 Nyacol2034D.I. 700 14 50  0.47 -
12 10.8 硝酸铝 1.2 Nyacol2034D.I. 700 13 55  0.35 -
      表2：加入二氧化硅到带三氧化二铝粘合剂的载体
实施例 加入的二氧化硅重量％ 测得的二氧化硅重量％ 在加入二氧化硅前声波磨损 在加入二氧化硅后声波磨损
13 0.6 0.13 3.9 3.2
14 0.6 0.13 14.7 30.4
15 0.6 0.21 37.6 46.1
 表3：用二氧化硅和三氧化二铝粘合载体的HCS试验
    200℃，280psig，64％H2-32％CO-4％He
粘合剂   三氧化二铝 9∶1三氧化二铝-二氧化硅
重量％Co   12.0 10.6
重量％Re   1.0 0.9
松密度，g/cc   1.33 1.47
GHSV(h-1)   3000 3000
CO转化率％   66 77
 Mol％CH4   6.6 5.6
       表4：汽蒸对催化剂磨损的影响
  实施例 粘合剂   处理       声波磨损试验
    分 重量％25-
  16 三氧化二铝   新鲜     0     0.2
    10     0.4
    20     0.7
    20     0.9
    30     3.6
    40     3.8
    60     8.5
    90     7.0
    90     6.3
  17 三氧化二铝   汽蒸6天     0     0.7
    10     5.0
    20     5.4
    20     6.2
    30     7.4
    30     12.0
    40     11.6
    60     18.5
    90     22.1
    120     28.4
  18 二氧化硅-三氧化二铝   新鲜     30     0.4
    30     0.5
    60     1.3
    120     1.1
    120     1.9
  19 二氧化硅-三氧化二铝   汽蒸6天     30     1.1
    30     1.4
    30     2.3
    60     2.7
    60     4.5
    120     6.6
    120     8.8

Claims (21)

1.一种催化剂载体组合物，该组合物主要包括二氧化钛和在其中加入由二氧化硅和三氧化二铝组成的粘合剂，其中粘合剂的量小于载体重量的30重量％，二氧化硅的量小于粘合剂重量的50重量％。
2.按权利要求1的载体，其中载体含至少80重量％二氧化钛。
3.按权利要求1的载体，其中粘合剂的量为载体重量的3-20重量％，二氧化硅的量为粘合剂重量的3-50重量％。
4.一种催化剂组合物，包括按照权利要求1的载体和一种有效量的沉积在所述载体上的促进费-托反应的活性金属。
5.按权利要求4的组合物，其中金属是VIII族金属。
6.按权利要求5的组合物，其中金属是选自由钴、钌和其混合物组成的组。
7.按权利要求6的组合物，其中金属用有效量的选自由铼、铪、锆、铈、钍和铀组成组的一种金属来促进。
8.一种费-托方法，该方法包括氢气与一氧化碳在权利要求4的组合物上反应和回收C5+的烃。
9.权利要求8的方法是在权利要求7的组合物上进行。
10.权利要求8的方法以淤浆形式进行。
11.权利要求3的载体，其中二氧化硅为粘合剂的量的约5-35％。
12.制备权利要求1，2，3或11任一项的载体的方法，包括形成含有效量的二氧化钛和氧化铝的盐或溶胶和二氧化硅的盐或溶胶的水淤浆，喷雾干燥淤桨并形成载体。
13.权利要求12的方法，其中载体在500-1000℃下煅烧。
14.权利要求13的方法，其中喷雾干燥后的载体在700-1000℃下煅烧。
15.制备权利要求4或5的组合物的方法，包括形成含有效量的二氧化钛和氧化铝的盐或溶胶和二氧化硅的盐或溶胶，喷雾干燥淤桨以形成载体，在500-1000℃下煅烧载体，并将载体与费-托法活性VIII族金属复合。
16.权利要求15的方法，其中活性金属用一种选自铼、铪、锆、铈、钍和铀的金属促进。
17.权利要求15的方法，其中VIII族金属是钴。
18.权利要求15的方法，其中煅烧温度为700-1000℃。
19.一种费-托催化剂，它含在一种载体上的有效量的选自钴、钌及它们的混合物的金属，该载体主要包括二氧化钛及加入其中的粘合剂，粘合剂由二氧化硅和氧化铝组成，其中粘合剂小于载体重量的30重量％且二氧化硅小于粘合剂重量的50重量％。
20.权利要求19的催化剂，其粒径范围为20-120微米。
21.权利要求20的催化剂，其中催化剂有至少80重量％的二氧化钛。
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