CN102753265A - 二氧化钛-氧化铝负载钯催化剂 - Google Patents

二氧化钛-氧化铝负载钯催化剂 Download PDF

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CN102753265A
CN102753265A CN2010800640741A CN201080064074A CN102753265A CN 102753265 A CN102753265 A CN 102753265A CN 2010800640741 A CN2010800640741 A CN 2010800640741A CN 201080064074 A CN201080064074 A CN 201080064074A CN 102753265 A CN102753265 A CN 102753265A
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D.T.谢
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Lyondell Chemical Technology LP
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Abstract

本发明公开一种包含负载于二氧化钛-氧化铝挤出物上的钯的催化剂。挤出物包含至少80%重量二氧化钛和0.1至15%重量氧化铝。从二氧化钛-氧化铝挤出物制备的钯催化剂具有显著较高的抗碎强度。本发明也改进其在乙酸乙烯酯制造中的催化性能。

Description

二氧化钛-氧化铝负载钯催化剂
发明领域
本发明涉及包含负载于二氧化钛-氧化铝载体上的钯的催化剂。
发明背景
包含负载于二氧化钛的钯和第11族金属的催化剂可用于催化烯烃的乙酰氧基化，参见例如美国专利6,022,823、美国专利申请公布2008/0146721和2008/0281122。然而，从二氧化钛挤出物制备的催化剂一般具有低抗碎强度。具有低抗碎强度的催化剂倾向于在反应器中磨碎，导致在反应器中压力下降，并堵塞工艺管道。因此，需要研发具有高抗碎强度的催化剂。
发明概述
本发明为一种包含负载于挤出物上的钯的催化剂。挤出物包含至少80%重量二氧化钛和0.1至15%重量氧化铝。从二氧化钛-氧化铝挤出物制备的钯催化剂具有显著较高的抗碎强度和良好的活性。
附图简述
图1显示负载于二氧化钛-氧化铝挤出物上的催化剂的抗碎强度和其氧化铝含量的相关性。
发明详述
本发明为一种包含负载于二氧化钛-氧化铝挤出物上的钯的催化剂，所述挤出物包含至少80%重量二氧化钛和0.1至15%重量氧化铝。它优选包含至少85%重量(更优选至少90%重量)二氧化钛和0.2至10%重量(更优选0.5至5%重量)氧化铝。
为了制备挤出物，将二氧化钛或二氧化钛前体和氧化铝或氧化铝前体用任何适合方法(例如，研磨或捏和)混合成糊。工业上，可通过氯化物法、硫酸盐法、水热法或四氯化钛的高温水解制备二氧化钛。适合二氧化钛的实例包括Millennium Inorganic Chemicals的TiONA® DT-51、DT-52、DT-51D、DT-40和DT-20。适合二氧化钛前体包括钛盐、卤化钛、烷氧基钛、卤氧化钛等。适合氧化铝的实例包括Sasol的DISPERAL®、PURAL®、PURALOX®。适合氧化铝前体包括烷氧基铝和铝盐。
用溶剂形成糊。适合溶剂的实例包括水、醇、酯、酰胺等及其混合物。优选的溶剂为水和醇。水是最优选的。
可用挤出助剂形成糊。适合的挤出助剂包括羧酸、烷基铵化合物、氨基醇、纤维素、纤维素衍生物、淀粉、聚丙烯酸酯、聚甲基丙烯酸酯、聚(乙烯醇)、聚(乙烯基吡咯烷酮)、聚(氨基酸)、聚醚、聚(四氢呋喃)、金属羧酸盐等及其混合物。纤维素衍生物的实例包括羧烷基纤维素钠、羟烷基纤维素和甲基纤维素。优选挤出助剂包括羧烷基纤维素钠和羟烷基纤维素的组合。3:1至1:1的羧烷基纤维素与羟烷基纤维素重量比更优选。
羧烷基纤维素为具有结合到组成纤维素主链的吡喃葡萄糖单体的一些羟基的羧烷基的纤维素衍生物。它通常作为其钠盐-羧烷基纤维素钠使用。优选使用羧甲基纤维素的钠盐。
羟烷基纤维素为其中重复葡萄糖单元中的一些羟基已羟烷基化的纤维素的衍生物。优选羟烷基为2-羟基乙基或2-羟基丙基。
糊的挤出产生包含溶剂和可能的挤出助剂的挤出物。挤出是其中糊挤过模或孔以产生固定横截面的长物体的制造过程。一般用挤出处理塑料或食品，和形成吸附剂或催化剂。可使用任何常规挤出机。挤出物通常具有0.5至10mm的直径，具体1至5mm。适合的螺杆型挤出机描述于“Particle Size Enlargement”(粒径增大)，Handbook of Powder Technology，vol. 1(1980)pp.112-22。
煅烧挤出物。优选煅烧在含氧气氛中进行，以烧尽挤出物中包含的有机物质(例如，残余溶剂、挤出助剂等)。煅烧可在400至1000℃进行，更优选450至700℃。有时，有益初始在惰性气氛(例如，氮，氦)中煅烧挤出物，以热分解挤出物中包含的有机化合物，然后烧尽含氧气氛中的有机物质。
催化剂一般包含0.05至3%重量钯和任选0.05至1.5%重量的第11族金属。更优选催化剂包含0.5至1.5%重量钯和0.25至0.75%重量金。
为了制备催化剂，煅烧的挤出物一般用钯盐的水溶液处理。所用溶液的浓度和量取决于最终催化剂中钯的所需浓度。然后去除水，留下在挤出物上沉积的钯盐。适合的钯盐包括氯化钯、氯亚钯酸钠、硝酸钯和硫酸钯。第11族金属盐可随同加钯或在单独的步骤加入到挤出物。例如，可使用氯化金、四氯金酸、四氯金酸钠等的水溶液。
浸渍的挤出物在100℃至600℃的温度在惰性或氧化气体中煅烧，例如氦、氮、氩、氖、氮氧化物、氧、空气、二氧化碳等。也可使用上述气体的混合物。优选煅烧在氮、氧或空气或其混合物中进行一般0.1和5小时。
在煅烧后，使所得产物还原，以转化至少部分钯和第11族金属(如果使用)，以制备还原的催化剂。通常可用任何已知方法使用常规还原剂，例如氨、一氧化碳、氢、烃、烯烃、醛、醇、肼、伯胺、羧酸、羧酸盐和羧酸酯。氢、乙烯、丙烯、碱性肼和碱性甲醛为非常有用的还原剂，乙烯和氢是特别优选的。虽然可使用纯氢，但更一般使用氢和惰性气体(例如氮、氦、氩等)的混合物。这些混合物一般包含最高约50%体积(vol.%)氢，更一般包含约5至25%体积氢和75至95%体积惰性气体。还原时间一般为0.1至5小时。还原所用温度可以为20至600℃。
催化剂可用于烯烃(例如乙烯或丙烯)的乙酰氧基化，以产生乙酰氧基化烯烃，例如乙酸乙烯酯或乙酸烯丙酯。优选在乙酰氧基化反应中使用强化的催化剂，强化的催化剂可通过活化剂加入到还原的催化剂制备。活化剂为碱或碱土金属化合物，其实例为钾、钠、铯、镁、钡等的氢氧化物、乙酸盐、硝酸盐、碳酸盐和碳酸氢盐。钾盐是优选的活化剂。活化剂含量可以为催化剂的0.1至15%重量，优选0.5至10%重量。
本发明还包括制备乙酸乙烯酯的方法，所述方法包括使包含乙烯、氧和乙酸的进料在催化剂存在下反应。
进料一般包含20至70%摩尔乙烯、2至8%摩尔氧和2至20%摩尔乙酸。进料可包含稀释剂。适合稀释剂的实例包括丙烷、氮、氦、氩、二氧化碳等及其混合物。
反应一般在固定床反应器中在100至250℃(优选125至200℃)的温度并在15至500psig的压力下进行。
实施例 1
挤出物制备和表征：
将D-T51二氧化钛(178.2g)、氧化铝(DISPERAL® P2，购自Sasol，1.8g)、高纯度WALOCELTM C 羧甲基纤维素钠(The Dow Chemical Company，3.8g)、聚(氧化乙烯)(MW=100,000，3.4g)和纤维素衍生物(METHOCELTM K4M，购自The Dow Chemical Company，1.8g)混合5分钟。将水(100g)、氢氧化铵水溶液(14.8M，10.5g)和苄醇(1.3g)加入到混合物，并进一步混合产生糊。将糊放入装配有直径1/8英寸的2个孔的模面的Bonnot 1-英寸挤出机(The Bonnot Company)的料斗中。
收集挤出物，并在空气中在80℃干燥12小时，然后在空气中煅烧。使煅烧温度以2℃/分钟的速率从室温升高到500℃，在500℃保持2小时，以10℃/分钟的速率从500℃升高到700℃，在700℃保持3小时，然后降低至室温。
Pd-Au催化剂
将NaHCO3粉末(2.7g)缓慢加入到包含Na2PdCl4·3H2O(3.1g)、NaAuCl4·2H2O(1.1g)和水(23.5g)的水溶液。在室温搅拌混合物10分钟。溶液用吸移管喷到经煅烧的挤出物(100g)上，同时使它们在旋转烧瓶中滚动。一旦完成浸渍，用加热枪将旋转的烧瓶加热到约100℃。使经浸渍的挤出物在100℃滚动另外30分钟，然后放入烘箱中在80℃经历2小时，随后冷却到室温。
用温水(50至80℃)洗涤经干燥的挤出物，直到可通过使洗涤滤出液与1%重量硝酸银溶液混合观察沉淀，检测没有氯化物。洗涤完成后，在80至100℃干燥催化剂，以去除水。然后将它们在230℃在空气中加热3小时，在氮流下在230℃加热30分钟。在氮气中10%摩尔氢的流下使温度升高到500℃，保持3小时，随后冷却到室温。
挤出物用包含10%重量乙酸钾和1%重量氢氧化钾的水溶液(1L)洗涤。经洗涤的挤出物在氮下在125℃干燥2小时。得到钯-金催化剂。催化剂包含0.93%重量Pd、0.54%重量Au和1.5%重量K。
催化剂的一些物理性质列于表1中。催化剂的抗碎强度用Chatillon抗碎强度分析仪(Model DPP 50)测量。将25次测量1/8英寸长挤出物断裂所需的力取平均，得到报告值。通过将40g催化剂放入100mL量筒(1"公称外径)测量堆积密度。轻敲量筒，直到表观体积不再变化，然后用质量除以此值，计算堆积密度。通过在第二量筒中向50mL水加入粒料，然后轻敲到填充所有空隙，测定空隙度。从水和粒料单独所占的总体积减去所得水量，以测定水占据的空隙体积。由混合物倾倒通过筛篮，摇动去除过量水，然后将湿挤出物称重，测定总孔体积。将超过初始40g催化剂的质量增加除以水的密度作为孔体积的量度。
乙酸乙烯酯制备：
在固定床反应器(不锈钢，1英寸O.D.)中试验钯-金催化剂用于乙酸乙烯酯制备。将反应器用催化剂(10g)和惰性α-氧化铝圆柱形粒料(1/8"直径，表面积4m2/g，孔体积0.25mL/g，25g)的混合物填充。进料包含46.1%摩尔氦、33.9%摩尔乙烯、11.48%摩尔乙酸、4.2%摩尔氧和4.2%摩尔氮。反应器压力为80psig，在标准温度和压力相对于催化剂体积的空间速度为3050h-1。反应器用流化砂浴冷却，温度设定在130℃。产物流通过气相色谱(GC)分析。在流上40至50h之间的氧转化率、氧选择性、生成乙酸乙烯酯的氧产率(yield)和生成乙酸乙烯酯的乙烯选择性从GC结果计算，并列于表1中。通过消耗的氧量除以送到反应器的总氧量，计算氧转化率。生成乙酸乙烯酯的氧选择性为在制备乙酸乙烯酯中消耗的氧量除以消耗的总氧量。生成乙酸乙烯酯的氧产率为氧转化率乘以氧选择性的乘积。生成乙酸乙烯酯的乙烯选择性为在制备乙酸乙烯酯中消耗的乙烯量除以消耗的总乙烯量。催化剂生产能力为制备的乙酸乙烯酯克数/升催化剂·小时。
实施例 2 和比较性实施例 3,4
用表1中所示的配方重复实施例1的方法。
表1和图1显示，负载于具有1和10%重量氧化铝的二氧化钛-氧化铝挤出物的钯-金催化剂具有与负载于二氧化钛挤出物的催化剂相似的孔隙率，但具有增加的表面积和改善的活性，并且具有比从二氧化钛挤出物制备的催化剂(比较性实施例4)显著更高的抗碎强度。然而，从包含20%重量氧化铝和80%重量二氧化钛的挤出物制备的催化剂得到比从二氧化钛挤出物制备的催化剂更低的乙酸乙烯酯生产能力，即使它具有较大表面积。在比较性实施例3得到的低活性可能是由于较小孔的形成，如其较大表面积所示
表1
Figure 2010800640741100002DEST_PATH_IMAGE002
。

Claims (15)

1. 一种包含负载于挤出物上的钯的催化剂，所述挤出物包含至少80%重量二氧化钛和0.1至15%重量氧化铝。
2. 权利要求1的催化剂，其中挤出物包含0.2至10%重量氧化铝。
3. 权利要求1的催化剂，其中挤出物包含0.5至5%重量氧化铝。
4. 权利要求1的催化剂，所述催化剂进一步包含第11族金属。
5. 权利要求4的催化剂，其中第11族金属为金。
6. 权利要求1的催化剂，其中钯的量为催化剂的0.05至3%重量。
7. 权利要求1的催化剂，其中挤出物通过使用包含羧烷基纤维素和羟烷基纤维素的挤出助剂制备。
8. 权利要求7的方法，其中羧烷基纤维素与羟烷基纤维素的重量比为3:1至1:1。
9. 权利要求7的方法，其中羟烷基纤维素选自甲基2-羟基丙基纤维素、甲基2-羟基乙基纤维素及其混合物。
10. 权利要求1的方法，其中挤出物在650至750℃的温度煅烧。
11. 一种制备乙酸乙烯酯的方法，所述方法包括使乙烯、氧和乙酸在权利要求1的催化剂存在下反应。
12. 权利要求11的方法，其中挤出物包含0.2至10%重量氧化铝。
13. 权利要求11的方法，其中挤出物包含0.5至5%重量氧化铝。
14. 权利要求11的方法，其中权利要求1的催化剂进一步包含第11族金属。
15. 权利要求14的方法，其中第11族金属为金。
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