CN1304336A - 用于芳香烃的气相摧化氧化反应的涂层型催化剂的制备方法及由此方法得到的催化剂 - Google Patents
用于芳香烃的气相摧化氧化反应的涂层型催化剂的制备方法及由此方法得到的催化剂 Download PDFInfo
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- CN1304336A CN1304336A CN99806951A CN99806951A CN1304336A CN 1304336 A CN1304336 A CN 1304336A CN 99806951 A CN99806951 A CN 99806951A CN 99806951 A CN99806951 A CN 99806951A CN 1304336 A CN1304336 A CN 1304336A
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- 238000004519 manufacturing process Methods 0.000 title abstract description 4
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Abstract
一种从芳香烃制备羧酸和/或羧酸酐的气相催化氧化反应用的涂层型催化剂的制备方法,催化剂由一个载体芯和以层状形式涂于其上的催化活性金属氧化物组成,通过将含有活性金属氧化物的水性活性物质悬浮液在相对高的温度喷洒到50到450℃的下载体材料上而得到,其中基于活性物质悬浮液的固含量,水性活性物质悬浮液含有1到10wt%的粘合剂,组成为A)由自由基聚合得到的聚合物,含有5到100wt%的为烯属不饱和酸酐或其羧基能形成酐的烯属不饱和二羧酸形式的单体(a),以及0到95wt%的其它单烯属不饱和单体(b),附加条件为单体(a)和(b)平均最多6个没有被含氧的基团官能化的碳原子以及B)至少含有2个OH基团,最多2个氮原子和最多8个C原子的链烷醇胺,其中重量比A∶B为1∶0.05到1∶1。
Description
本发明涉及一种用于从芳香烃制备羧酸和/或羧酸酐的气相催化氧化反应的涂层型催化剂的制备方法,在该催化剂的载体材料上使用特定的粘合剂以层状形式涂上一层催化活性金属氧化物,涉及可由此方法得到的催化剂,并涉及在固定床中使用这些催化剂用含有氧分子的气体将芳香烃气相催化氧化成羧酸和/或羧酸酐的方法。
众所周知,大量的羧酸和/或羧酸酐在工业上都是通过芳香烃,如苯,二甲苯,萘,甲苯或均四甲苯的气相催化氧化反应,在固定床反应器,优选管束式反应器中来制备的。例如通过这种方法可以得到苯甲酸,马来酸酐,邻苯二甲酸酐,间苯二甲酸,对苯二甲酸或均苯四甲酸酐。为做到这一点,通常使一种含有氧分子的混合气体例如空气和待氧化的起始物质通过一组布置在反应器中的、至少填充一种催化剂的管子中。管子被包围在一种换热介质,例如一种盐浴中以进行温度控制。尽管有此恒温,在催化剂装填料中还会形成所谓的“热点”,这一点的温度比催化剂装填料中其它部分的温度高。这些热点会引起二级反应,例如起始物质的完全燃烧或导致形成不能从反应产物中分离出去或分离非常困难的非理想二级产物,例如在从邻二甲苯制备邻苯二甲酸酐过程中形成了邻羟甲基苯甲酸内酯或安息香酸。并且,一个显著的热点的形成会阻止反应器的快速开动, 因为从一个特定的热点温度,催化剂会不可逆的被破坏,因此装填提升只能一点一点进行,并且必须非常小心的控制。
为减少热点,在技术上已转而把不同活性的催化剂安排在催化剂装填料的各层中,一般是将活性较小的催化剂布置在固定床中能和反应气体混合物首先接触的部位,也就是装填料的气体入口处,而活性较大的催化剂布置在催化剂装填料的气体出口处。因此,催化剂装填料中每一种不同活性的催化剂可在相同的温度下与反应气体接触,或者不同活性的两层催化剂也可在恒温条到不同反应温度的条件下与反应气体接触,如DE-A 130 51中所述。
经证实合适的催化剂是所谓的涂层催化剂,其中催化活性物质以层状被涂到芯部的载体材料上,该载体材料一般在反应条件下是惰性的,例如石英(SiO2),陶瓷,氧化镁,二氧化锡,碳化硅,金红石,矾土,硅酸铝,硅酸镁(皂石),硅酸锆或硅酸铈或它们的混合物。通常,除了二氧化钛以其改性锐钛矿形式以外,五氧化二钒也用作这些涂层催化剂的催化活性物质的催化活性组分。另外,作为助催化剂的多种其它氧化物也可少量包含在催化活性物质中,它们可影响催化剂的活性和选择性,例如它们降低或增加其活性。对于这种类型的助催化剂,要提到的例子是碱金属氧化物,尤其是氧化锂,氧化钾,氧化铷和氧化铯,氧化铊(Ⅰ),氧化铝,氧化锆,氧化铁,氧化镍,氧化钴,氧化锰,氧化锡,氧化银,氧化铜,氧化铬,氧化钼,氧化钨,氧化铱,氧化钽,氧化铌,三氧化二砷,氧化锑,二氧化铈和五氧化二磷。例如碱金属氧化物作为助催化剂可降低活性而增加选择性,而磷氧化合物,尤其是五氧化二磷会增加催化剂的活性,但降低其选择性。这些组分可全部从相关技术文献中知道。例如,参考WO98/00778中的汇总性描述。
为制备这种涂层催化剂,例如根据DE-A16 42 938和DE-A17 69 998中的方法,活性物质组分和/或它们的前体化合物的水性的和/或含有一种有机溶剂的溶液或悬浮液(后面称之为“混合物”),在较高的温度下被喷洒到处于热的涂覆转筒中的载体材料上,直到达到在催化剂总量中理想的活性物质含量。根据DE21 06 796,涂覆也可在流化床涂覆器中进行,例如在DE12 80 756中所描述的。然而在涂覆转筒上喷洒和在流化床中涂覆都会有高的损失,因为相当量的混合物会雾化或者由于摩擦使部分已经成层的活性物质又被摩擦掉而被废气带走。由于通常总催化剂中活性物质含量仅与要求值有微量差别,并且活性物质涂覆量和壳层的厚度对催化剂的活性和选择性有强烈的影响,因此为了确定所涂的活性物质的量,在列出的制备过程中催化剂必须频繁地被冷却,从涂覆转筒或流化床上取出并称重。如果催化剂载体上沉积过多的活性物质,通常不可能在随后小心地去除过量涂上的活性物质时不对壳的稳定性有不利影响,尤其是在催化剂壳中形成裂缝。
为了减少这些问题,已有技术中通过向混合物中加入有机粘合剂来改进,优选醋酸乙烯酯/月桂酸乙烯酯,醋酸乙烯酯/丙烯酸酯,醋酸乙烯酯/马来酸酯和醋酸乙烯酯/乙烯共聚物,以水分散液的形式更有利,根据EP-A07 442 14,基于混合物的固体含量,采用10-20wt%的粘合剂。如果不加有机粘合剂时将混合物涂到载体上,高于150C的涂覆温度是有利的。根据DE210 67 96,在添加所指出的粘合剂的情况下,所用的涂覆温度明显地低,在70-130℃。填充催化剂及反应器投入使用之后,在很短时间内所涂覆的粘合剂就烧完了。而且添加粘合剂还有利于使活性物质很好的黏附在载体上,因此运输和装填催化剂都更便利。
然而在燃烧过程中,活性物质层在载体上的粘合会发生松散。这通常是不严格的,因为反应器管子中的催化剂不再暴露于强的机械应力下。然而不能排除由于活性物质层过多松散以至于它在反应条件下被气体混合物气流慢慢地带走,尤其在使用相对大量的粘合添加剂的情况下。这会导致催化剂的长期稳定性降低,并且为要求的PA质量所设定的反应器盐浴温度必须稳定地增加,这反过来对可得到的PA收率有不利影响。并且,对于粘合添加剂的燃烧,除了难闻的气味以及进一步的由于粘合添加剂的降解产物的点燃带来的对环境相容性的不利影响,还会发生危害反应器安全操作的爆炸。最后,使达到粘合添加剂的理想效果所必须的用量达到最小从成本方面考虑也是有用的。
因此本发明的目的就是找到一种用于从芳香烃制备羧酸和/或羧酸酐的气相催化氧化反应用的涂层型催化剂的制备方法,其中在保持通过添加粘合剂所获得的优点的同时,避免所列出的添加粘合剂的缺点。
我们已发现这一目标可以通过添加一种特殊的有机粘合剂来实现,它意外地导致上述的理想的优点,即使添加量小于混合物固含量的10wt%。详细地讲,根据本发明,通过一种用于芳香羧酸和/或羧酸酐的气相催化氧化反应的涂层型催化剂的制备方法实现了目标,催化剂由一个载体芯和以层状形式涂于其上的催化活性金属氧化物组成,这通过在相对高的温度下,将含有活性金属氧化物的水性活性物质悬浮液喷洒到50到450℃的载体材料上得到,其中基于活性物质悬浮液的固含量,水性活性物质悬浮液含有1到10%的粘合剂,组成为A)由自由基聚合得到的聚合物,含有5到100wt%的为烯属不饱和酸酐或其羧基能形成酐的烯属不饱和二羧酸形式的单体(a),以及0到95wt%的其它单烯属不饱和单体(b),附加条件为单体(a)和(b)平均最多有5个,优选2到4个没有被含氧的基团官能化的碳原子以及B)至少含有2个OH基团,最多2个氮原子,优选一个氮原子和最多8个C原子的烷醇胺,其中重量比A∶B为1∶0.05到1∶1。
这里的链烷醇具有一种通过形成酯基而作为交联剂的功能。此“固化”在高温下向载体上喷洒“混合物”时发生。
为了保持后来的在反应器中粘合剂燃烧过程中放出热量低,以及为避免催化剂过热的破坏,根据本发明使用的粘合剂链上应该含有尽可能少的碳原子,也就是尽可能少的不含氧的基团,例如没有被OH,COOH或COOR基团官能化的C原子。这些条件通过上面指出的单体中总的碳数目的特性来表示。
根据另一个表达同一种情形的定义,粘合剂中的原子比C∶O最大为3∶1,优选2.5∶1,尤其优选达到2∶1。
详细地,根据本发明的方法,合适的粘合剂是那些在WO97/31036中所描述的,它们完全满足上述的条件。关于所指出的选择标准,参考WO97/31036中给出的关于粘合剂的详细描述。
因此,马来酸,马来酸酐,衣康酸,1,2,3,6-四氢化邻苯二甲酸,1,2,3,6-四氢化邻苯二甲酸酐,其碱金属和铵盐或它们的混合物优选用作单体(a),尤其优选马来酸和马来酸酐。
可以使用的单体(b)为,例如:单烯属不饱和C3-到C6-单羧酸,如丙烯酸,甲基丙烯酸,乙基丙烯酸,烯丙基乙酸,丁烯酸,乙烯基乙酸,马来酸单酯如马来酸单甲酯,它们的混合物或它们的碱金属和铵盐,以及进一步的
乙烯基和烯丙基烷基醚,烷基上可能带有其它取代基,如一个羟基,或一个或多个烷氧基,如甲基乙烯基醚,乙基乙烯基醚,丙基乙烯基醚,异丁基乙烯基醚,乙烯基-4-羟基丁基醚和相应的烯丙基醚或它们的混合物,
丙烯酰胺和烷基-取代丙烯酰胺,例如,丙烯酰胺,甲基丙烯酰胺,N-叔丁基丙烯酰胺,N-甲基(甲基)丙烯酰胺,
含磺基单体,例如,烯丙基磺酸,甲代烯丙基磺酸,苯乙烯磺酸酯,乙烯基磺酸,烯丙氧基苯磺酸,2-丙烯酰胺基-2-甲基丙磺酸,它们相应的碱金属或铵盐或它们的混合物,
丙烯酸,甲基丙烯酸或马来酸的C1-到C4-烷基酯或C1-到C4-羟烷基酯,或者被2到50mol的氧化乙烯,氧化丙烯,氧化丁烯或其混合物烷氧基化了的C1-到C4-醇与丙烯酸,甲基丙烯酸或马来酸(单体b6)形成的酯,例如,(中基)丙烯酸甲酯,(甲基)丙烯酸乙酯,
C1-到C4-单羧酸的乙烯基和烯丙基酯,例如,甲酸乙烯酯,醋酸乙烯酯,丙酸乙烯酯或丁酸乙烯酯。另外可以提到的单体是:烷醇,丙烯醛,甲基丙烯醛或它们的混合物。
优选的单体(b)为丙烯酸,甲基丙烯酸,甲基乙烯基醚,乙基乙烯基醚,醋酸乙烯酯或它们的混合物。
尤其优选丙烯酸,甲基丙烯酸和它们的混合物。
聚合物优选含有20到90wt%,尤其是50到80wt%的单体(b)。
单体(a)和可选的(b)的聚合物可以通过通常的聚合工艺来制备,例如,通过本体,乳液,悬浮液,分散体,沉淀以及溶液聚合。所提到的聚合方法优选在排除氧的情况下进行,优选在氮气流中进行。通常的设备可以用于所有的聚合方法,比如搅拌釜,级联搅拌釜,高压反应釜,管式反应器和捏合机。聚合优选通过溶液,乳液,沉淀或悬浮液聚合方法进行。尤其优选溶液和乳液聚合法。聚合在溶剂或稀释剂中进行,例如,甲苯,邻二甲苯,对二甲苯,异丙基苯,氯苯,乙苯,烷基芳香族化合物的工业混合物,环己烷,脂肪族的工业混合物,丙酮,环己酮,四氢呋喃,二氧六环,二醇及二醇衍生物,聚亚烷基二醇及其衍生物,二乙基醚,叔丁基甲基醚,醋酸甲酯,异丙醇,乙醇,水或它们的混合物,例如,异丙醇/水混合物。优选使用的溶剂或稀释剂为水,可选择性的加入用量达60wt%的醇或二醇。尤其优选采用水。
聚合可以在从20到300C的温度下进行,优选从60到200℃。重均分子量的确定取决于选用的聚合条件,如从800到5000000,尤其从1000到1000000。优选重均分子量MW在15000以上。重均分子量尤其优选在15000到60000。MW由凝胶渗透色谱测定。
聚合优选在形成自由基的化合物存在下进行。这种化合物的需要量为最高30wt%,优选0.05-15wt%,特别优选0.2-8wt%,基于聚合时所用单体计。在多组分引发剂体系(氧化还原引发剂体系)中上述重量含量是基于各组分总量。
合适的聚合引发剂为,例如,过氧化物,氢过氧化物,过氧化二硫酸盐,过氧化碳酸盐,过氧化酯,过氧化氢以及偶氮化合物。可以是水溶性或者水不溶性的引发剂的实例为过氧化氢,过氧化二苯甲酰,过氧化二碳酸二环己酯,过氧化二月桂酰,甲基乙基酮过氧化物,二叔丁基过氧化物,乙酰丙酮过氧化物,叔丁基氢过氧化物,枯烯氢过氧化物,过新癸酸叔丁基酯,过氧化新戊酸叔戊酯,过氧化新戊酸叔丁基酯,过新己酸叔丁基酯,过-2-乙基己酸叔丁基酯,过苯甲酸叔丁基酯,锂,钠,钾和铵的过氧化二硫酸盐,偶氮二异丁腈,2,2’-偶氮二(2-脒基丙烷基)二氢氯化物,2-(氨基甲酰基偶氮)二异丁腈和4,4’-偶氮二(4-氰基戊酸)。
引发剂可以单独或者以它们的混合物形式使用,如过氧化氢和过氧化二硫酸钠的混合物。对于在水性介质中的聚合,优选使用水溶性引发剂。
已知的氧化还原引发剂体系也可以用作聚合引发剂。此类氧化还原引发剂体系包含至少一种含过氧化物的化合物与氧化还原共引发剂组合,例如,有还原作用的硫化物,如碱金属和铵化物的酸式亚硫酸盐,亚硫酸盐,硫代硫酸盐,连二亚硫酸盐,连四硫酸盐。因此可以采用过氧化二硫酸盐与碱金属或铵的亚硫酸氢盐的组合,例如过氧化二硫酸铵和亚硫酸氢铵的组合。含过氧化物的化合物与氧化还原共引发剂的相对用量比为30∶1到0.05∶1。
另外还可以采用过渡金属催化剂,如铁,钴,镍,铜,钒和锰盐与引发剂或氧化还原引发体系联合。例如合适的盐为硫酸亚铁(Ⅱ),氯化钴(Ⅱ),硫酸镍(Ⅱ),氯化亚铜(Ⅰ)。取决于单体,采用的有还原作用的过渡金属盐的浓度从0.1ppm到1000ppm。因此采用过氧化氢和亚铁盐的组合,例如过氧化氢为0.5到30%,莫尔盐为0.1到500ppm。
在有机溶剂中聚合时也可以将氧化还原共引发剂和/或过渡金属催化剂与上述引发剂结合使用,例如苯偶因、二甲基苯胺、抗坏血酸以及重金属例如铜、钴、铁、锰、镍和铬的有机溶性配合物。氧化还原共引发剂或过渡金属催化剂的通常用量一般大约为0.1-1000ppm,基于单体用量。
如果反应混合物的聚合在适合聚合的较低限的温度范围开始,然后在较高的温度完成,那么采用至少两种在不同温度下分解的不同的引发剂是方便的,这样在每个温度范围都可以得到合适的自由基浓度。
为了制备低平均分子量的聚合物,通常在调节剂的存在下进行共聚合是便利的。通常的调节剂都可以用于此目的,例如,含有有机SH基的化合物,如2-氢硫基乙醇,2-氢硫基丙醇,巯基乙酸,叔丁基硫醇,正辛基硫醇,正月桂基硫醇和叔月桂基硫醇,C1-到C4-醛,如甲醛,乙醛,丙醛,羟铵盐如硫酸羟铵盐,甲酸,酸式亚硫酸钠或异丙醇。通常使用的聚合调节剂用量为单体重量的0.1到10%。合适的溶剂的选择也可以对平均分子量产生影响。因此,在带有苄H的稀释剂的存在下的聚合会由于链转移的结果导致平均分子量的降低。
如果采用乳液,沉淀,悬浮液或分散体聚合法进行聚合,用表面活性的助剂来稳定聚合物液滴或聚合物粒子是有利的。特别的,乳化剂或保护胶体用于此目的。阴离子,非离子,阳离子和两性乳化剂是合适的。例如阴离子乳化剂为烷基苯磺酸,磺化脂肪酸,磺基琥珀酸酯,硫酸脂肪醇酯,硫酸烷基酚酯,硫酸脂肪醇醚酯。可用的非离子乳化剂为,如,烷基酚乙氧化物,伯醇乙氧化物,脂肪酸乙氧化物,链烷醇酰胺乙氧化物,脂肪胺乙氧化物,EO/PO嵌段共聚物以及烷基聚葡萄糖苷。可用的阳离子和两性乳化剂为,例如,季铵烷氧化物,烷基甜菜碱,烷基酰胺甜菜碱,磺基甜菜碱。
典型的保护胶体为,例如,纤维素衍生物,聚乙二醇,聚丙二醇,乙二醇和丙二醇的共聚物,聚醋酸乙烯,聚乙烯醇,聚乙烯醚,淀粉和淀粉衍生物,葡聚糖,聚乙烯吡咯烷酮,聚乙烯吡啶,聚乙烯亚胺,聚乙烯咪唑,聚乙烯丁二酰亚胺,聚乙烯-2-甲基丁二酰亚胺,聚乙烯-1,3-噁唑烷-2-酮,聚乙烯-2-甲基咪唑啉以及含有马来酸和马来酸酐的共聚物,例如在DE2 501 123中所描述的。
通常所用的乳化剂或保护胶体的浓度为单体重量的0.05到20%。
如果聚合在水性溶液或稀释液中进行,单体可在聚合前或聚合期间被碱完全地或部分地中和。合适的碱优选不含氮的碱,例如碱金属或碱土金属化合物如氢氧化钠,氢氧化钾,氢氧化钙,氢氧化镁和碳酸钠。
尤其优选,烯属不饱和羧酸在聚合前和聚合期间不被中和。优选除了链烷醇胺(B)之外,甚至在聚合之后也不加入任何中和试剂。聚合可按很多种变化连续或不连续地进行。通常,部分单体,如果恰当的话在乳化剂,保护胶体或另外的助剂存在下可选择性的加入到合适的稀释剂或溶剂中,惰性化并升温直到达到理想的聚合温度。然而,也可以只加入合适的稀释剂。在特定的时间内,自由基引发剂,其余的单体和其它助剂,如调节剂或交联剂,被分别选择性的计量加入稀释剂中。可选择不同的加料时间。例如,选择引发剂的加料时间比单体的加料时间长。
如果用溶液聚合法在水中得到聚合物,通常没有必要除去溶剂。然而如果希望分离出聚合物,可通过例如喷雾干燥法来实施。
如果按照溶液、沉淀或悬浮液聚合法在水蒸汽挥发性溶剂或溶剂混合物中制备聚合物,则通入水蒸汽来分离溶剂,以得到水溶液或水分散体。聚合物也可通过干燥工艺与有机稀释剂分离。
聚合物(A)可以优选以水性分散液或溶液的形式提供,其固含量优选10到80wt%,尤其从40到65wt%。
聚合物(A)也可以通过将马来酸或马来酸酐或含有马来酸或马来酸酐的单体混合物接枝到接枝基体上得到。合适的接枝基体为,如单糖,低聚糖,改性多糖,烷基聚乙二醇醚。这样的接枝聚合物如在DE4 003 172和EP116 930中所描述的。
对于组分B)采用至少带两个OH基团和最多两个氮原子,优选带一个氮原子的链烷醇胺。优选的链烷醇胺的分子式为其中R1是一个H原子,一个C1-到C4-烷基或一个C1-到C4-羟烷基,R2和R3都是一个C1-到C4-羟烷基。
尤其优选R2和R3相互独立地都是一个C2-到C4-羟烷基,R1是一个H原子,一个C1-到C3-烷基或一个C2-到C4-羟烷基。
提到的分子式Ⅰ的化合物为,如二乙醇胺,三乙醇胺,二异丙醇胺,三异丙醇胺,甲基二乙醇胺,丁基二乙醇胺,甲基二异丙醇胺。尤其优选三乙醇胺。
对于根据本发明所用的粘合剂的制备,聚合物(A)和链烷醇胺(B)优选以这样的相互比例使用,即组分(A)的羧基和组分(B)的羟基的摩尔比为20∶1到1∶1,优选8∶1到5∶1,尤其优选5∶1到1.7∶1(酸酐基被算作两个羧基)。
例如这里粘合剂可通过将链烷醇胺加入到聚合物(A)的水性分散液或溶液中来很简单的制备。
根据本发明所用的粘合剂优选含有基于(A)+(B)总量计的1.0wt%,尤其优选少于0.5wt%,更尤其优选少于0.3wt%,尤其少于0.1wt%的含磷反应加速剂。含磷反应加速剂为在EP-A651 088和EP-A583 086中所描述的。特别是碱金属次磷酸盐(hypophosphite),亚磷酸盐,多磷酸盐,磷酸二氢盐,多磷酸,次磷酸,磷酸,烷基次膦酸或这些盐和酸的齐聚物或高聚物。
然而,粘合剂优选不含任何含磷反应加速剂或任何量的对加速反应有效的含磷化合物。粘合剂可含有一种酯化催化剂,如硫酸或对甲苯磺酸。通常,根据本发明使用的粘合剂单独用作粘合剂来制备涂层催化剂。然而,它们也可以和其它粘合剂一起使用。
通过添加根据本发明采用的粘合剂所制备的催化剂大体上正是在开头所提专利文献中所述的那些,据此加以引用。通常,这些就是所谓的涂层催化剂,其中催化活性物质以层状形式涂到载体上,载体一般在反应条件下是惰性的,例如石英(SiO2),陶瓷,氧化镁,二氧化锡,碳化硅,金红石,矾土,硅酸铝,硅酸镁(皂石),硅酸锆或硅酸铈或这些载体材料的混合物。通常,除了二氧化钛以其改性锐钛矿形式以外,五氧化二钒用作这些涂层催化剂的催化活性物质的催化活性组分。另外,作为助催化剂的多种其它氧化物也可少量包含在催化活性物质中,它们可影响催化剂的活性和选择性,例如它们降低或增加其活性。对于这种类型的助催化剂,要提到的例子有碱金属氧化物,尤其是氧化锂,氧化钾,氧化铷和氧化铯,氧化铊(Ⅰ),氧化铝,氧化锆,氧化铁,氧化镍,氧化钴,氧化镁,氧化锡,氧化银,氧化铜,氧化铬,氧化钼,氧化钨,氧化铱,氧化钽,氧化铌,三氧化二砷,氧化锑,二氧化铈和五氧化二磷。例如碱金属氧化物作为助催化剂可降低活性而增加选择性,而磷氧化合物,尤其是五氧化二磷会增加催化剂的活性,但降低其选择性。
催化剂是通过将活性物质以一种已知方式涂覆到载体上,即将一种活性物质混合物例如在涂覆转筒或流化床涂覆器中喷洒到已预热到50-450℃的载体上来制备的,例如在DE21 06 796,DE17 69 998,DE16 42938或DE25 10 994中所描述的。在喷洒开始前,粘合剂被加入到混合物中。涂覆优选在100到250℃温度范围内进行,尤其优选在140到200℃,因为在这些温度范围内可进行粘合添加剂的最佳固化。
在涂覆期间的这一固化过程的结果是添加极少量的,即混合物固含量的1到10wt%的粘合剂就会足以明显提高活性物质与载体的黏附以及明显地降低涂覆过程中混合物的损失。粘合添加剂增加到10wt%以上虽然还会额外导致粘合性的进一步的轻微的改善;然而这一相对大量的粘合添加剂也将导致在催化剂经400℃煅烧之后活性物质的粘合性会大大降低,而含有少于10wt%的粘合添加剂的催化剂即使在煅烧之后仍然有很好的摩损值。
另外,在装填催化剂和反应器投入使用之后在必需的少量的新型粘合添加剂的燃烧中既没有难闻的气味也没有进一步的对环境相容性的不利影响。也没有观察到粘合剂的分解产物的燃烧,这会导致爆炸并因此会危及反应器的安全运行。
羧酸和羧酸酐,尤其是邻苯二甲酸酐通过已知的方式制备,即通过芳香烃,特别是邻二甲苯,在使用根据本发明制备的催化剂条件下的气相催化氧化法制备,这些在乌尔曼化学工业百科全书1992年卷A20第181页的K.Towae,W.Enke,R.Jackh,N.Bhargawa的“邻苯二甲酸及其衍生物”中总结性给出。这种情况下,优选采用2层或多层催化剂,其中优选在气体出口侧只布置一层本发明中的催化剂,因为在气体出口侧催化剂装填较低,因此一种标准的催化剂就足够了。详细地讲,例如当使用新的催化剂时,要采用一个步骤,即首先将催化剂装填到反应器的反应管中,反应管从外侧,例如通过盐浴被恒定在反应温度。反应气体在一般在从300到450℃,优选320到420℃并尤其优选340到400℃的温度下,并在一般从0.1到2.5巴,优选0.3到1.5巴的超压力下,以及在一般为750到5000h-1的空间速度下通过用这种方法制备的催化剂装填料中。
加入到的反应气体一般由含有氧分子的气体和要被氧化的芳香烃混合形成,含氧分子的气体除了氧气之外另外会含有合适的反应缓和剂和/或稀释剂,比如蒸汽,二氧化碳和/或氮气,其中含氧分子的气体中一般含有1到100mol%,优选2到50mol%并尤其优选10到30mol%的氧气,0到30mol%,优选0到10mol%的水蒸汽以及0到50mol%,优选0到1mol%的二氧化碳,其余为氮气。为制备反应气体,一般向含氧分子气体中加入30到150g/Nm3气体的将被氧化的芳香烃。
实施例1:不添加粘合剂的标准催化剂Ⅰ的制备(对比例)
50.0kg外径为8mm,长度为6mm,壁厚为1.5mm的皂石(硅酸镁)环在涂覆转筒上被加热到160℃并被喷洒上25.0kg BET表面积为20m2/g的锐钛矿(分析:0.18%S;0.08%P;0.24%Nb;0.01[sic]Na;0.01[sic]K;0.004%Zr;0.004%Pb),1.81kg草酸氧钒,0.143kg的硫酸铯,38kg水和9.85kg甲酰胺的悬浮液直到用这种方法涂覆的这一层的重量达到最终涂层催化剂总重量(在450℃煅烧之后)的10.0%。用此方法涂覆的催化活性物质,即催化剂壳,由O.40wt%的铯(计算作Cs)、4.0wt%的钒(计算作V2O5)和95.6wt%的二氧化钛组成。涂覆需要17.8kg的混合物,即约12%的喷洒的混合物在涂覆期间由于排出而损失。根据三次下落试验*磨损为14.4%,在400℃煅烧后磨损为23.7%。
*下落试验:让约50G[sic]的催化剂在长3m,内径为25mm的长管中下落。将落到管子下面的盘中的催化剂与撞击时形成的尘土分离开后再次通过管子落下。相对所涂的活性物质的用量(=100%),将三次下落试验后总的质量损失作为催化剂抗摩擦能力的度量。在煅烧后,即50g催化剂在400℃加热1h后的下落试验中,程序同上。
实施例2a)粘合剂的制备(根据WO97/31036)根据EP-A75 820中的细节,重量比为75∶25的丙烯酸/马来酸的共聚物用过氧化氢作为自由基引发剂,在110℃聚合得到。得到的聚合物的固含量为44.6%,PH值为0.7且Mw为90000。882.0g含聚合物的聚合物溶液与118.0g三乙醇胺混合。因此得到的粘合剂固含量为49.4wt%,PH值为2.9且粘度为3700mPas。b)根据本发明加入粘合剂的催化剂A-C的制备步骤如实施例1中所指出的,再附加上在喷洒到催化剂上之前,每一例中17.0kg的混合物用400g,800g或1050g的(a)中的水性粘合剂处理。皂石环被喷洒上以这种方法改性的混合物直到用此法涂覆的这一层的重量达到最终涂层催化剂总重量(在450℃煅烧之后)的10.0%。必需的混合物量,混合物损失和磨损值列于下面的表1中。
表1:
磨损1:初始样品的下落试验;磨损2:煅烧后样品的下落试验(400℃)粘合添加剂的燃烧
催化剂 | 49.4%浓度的粘合剂溶液 | 混合物消耗量 | 混合物损失 | 活性物质中的粘合剂含量 | 磨损1 | 磨损2 |
A | 400g | 16.2kg | 2% | 3.6% | 8.2% | 11.4% |
B | 800g | 16.5kg | 4% | 7.2% | 3.2% | 12.9% |
C | 1050g | 16.3kg | 3% | 9.5% | 2.3% | 20.1% |
为检验在粘合添加剂在燃烧期间是否有气味难闻的或对环境不利影响的物质释放出来,催化剂C在通空气条件下被从30℃加热到610℃(升温速度:5℃/min)。质量的降低以及产生的气态(分解)产物用偶合差示热重量分析法/FTIR光谱在线分析。发现所有的挥发性组分在达到400℃时已被除去;并且,在气相中只有H2O,CO和CO2被检测出来。未能够检测出任何难闻气味的,对环境有不利影响的或易燃的分解产物。实施例3:不添加粘合剂的标准催化剂Ⅱ的制备
50.0kg外径为8mm,长度为6mm,壁厚为1.5mm的皂石(硅酸镁)环在涂覆转筒上被加热到160℃并被喷洒上28.6kg BET表面积为20m2/g的锐钛矿,4.11kg草酸氧钒,1.03kg的三氧化二锑,0.179kg的磷酸氢铵,0.046kg的硫酸铯,44.1kg水和9.14kg甲酰胺的悬浮液直到用这种方法涂覆的这一层的重量达到最终涂层催化剂总重量(在450℃煅烧之后)的10.5%。用此方法涂覆的催化活性物质,即催化剂壳,由0.15wt%的磷(计算作P),7.5wt%的钒(计算作V2O5),3.3wt%的锑(计算作Sb2O3),0.1wt%的铯(计算作Cs)和89.05wt%的二氧化钛组成。涂覆需要17.2kg的混合物,即约6%的喷洒的混合物在涂覆期间由于排出而损失。根据三次下落试验*磨损为8.0%。实施例4:根据本发明催化剂D的制备及添加粘合剂超过10%的对比催化剂E的制备步骤如实施例1中所指出的,再附加上在喷洒到催化剂上之前,每一例中17.0kg的混合物用700g,1500g的实施例2a中的水性粘合剂处理。皂石被喷洒上以这种方法改性的混合物直到用此法涂覆的层的重量达到最终涂层催化剂总重量(在450℃煅烧之后)的10.5%。必需的混合物量,混合物损失和磨损值列于下面的表2中。
表2:
磨损1:初始样品的下落试验;磨损2:煅烧后样品的下落试验(400℃)实施例5:邻苯二甲酸酐的制备
催化剂 | 粘合剂溶液 | 混合物消耗量 | 混合物损失 | 活性物质中的粘合剂含量 | 磨损1 | 磨损2 |
D | 400g | 16.4kg | 2% | 6.3% | 5.2% | 19.6% |
E | 1500g | 16.3kg | 1% | 13.4% | 3.3% | 51.3% |
每一例中1.30m的催化剂Ⅱ,然后是1.60m的催化剂Ⅰ(对比)或催化剂C(本发明)被从低部向上装填入内径为25mm的3.85m长的铁管中。铁管被盐浴包围以调节温度。每小时4.0Nm3载量为40到约80g/Nm3空气的浓度为98.5wt%邻二甲苯的空气不断地从上向下通过管子。在这一步骤中,装填量75-85g时得到的结果总结在下表3中(产量指的是基于100%的邻二甲苯的邻苯二甲酸酐(PA)的重量百分比;提升时间是指载量从40到80g/Nm3所需要的天数)。
表3:
实施例6-15
实施例催化剂组合 | 盐浴温度(℃) | PA平均产量(wt%) | 提升时间(天) |
I/Ⅱ(对比) | 352 | 113.3 | 36 |
C/Ⅱ | 354 | 113.5 | 25 |
如果将下面表4中粘合剂用于催化剂的制备中,得到关于磨损1,磨损2,PA产率和提升时间基本上完全相同的结果。
表4:
MA 马来酸 MDA甲基二乙醇胺MAN 马来酸酐 Mw重均分子量THP 1,2,3,6-四氢化邻苯二甲酸三乙醇胺AA 丙烯酸MAA 甲基丙烯酸MVE 甲基乙烯基醚TEA 三乙醇胺
聚合物A | 由A+B得到的粘合剂 | |||||||||
实施例 | 单体a | 单体b | 固含量 | pH | Mw | 聚合物A | 单体B | 固含量, | pH | 粘度 |
类型/(%) | 类型/(%) | (%) | (g) | 类型/(g) | (%) | (mPas) | ||||
6 | MA/60 | AA/60 | 40.3 | 1.3 | 125000 | 810 | TEA/190 | 46.3 | 2.9 | 1000 |
7 | MA/25 | MAA/75 | 42.7 | 0.9 | 90000 | 913 | TEA/87 | 48.5 | 3.4 | 3500 |
8 | MA/20 | MVE/80 | 41.5 | 1.5 | 75000 | 788 | TEA/212 | 46.5 | 3.7 | 14000 |
9 | MA/20 | AA/80 | 43.3 | 0.8 | 150000 | 825 | MDA/175 | 47.3 | 3.4 | 7000 |
10 | MA/40 | AA/60 | 40.7 | 1.2 | 60000 | 899 | MDA/101 | 45.3 | 3.1 | 950 |
11 | MAN/30 | AA/70 | 42.8 | 1.9 | 200000 | 773 | TEA/227 | 48.5 | 2.9 | 2600 |
12 | MAN/20 | MAA/80 | 43.6 | 1.4 | 80000 | 812 | TEA/188 | 48.9 | 3.4 | 4900 |
13 | MAN/20 | MVE/80 | 41.9 | 0.7 | 60000 | 900 | TEA/100 | 46.8 | 3.6 | 11200 |
14 | MAN/30 | AA/70 | 44.0 | 1.0 | 25000 | 801 | TEA/199 | 50.1 | 3 2 | 2500 |
15 | MAN/40 | AA/60 | 42.0 | 1.9 | 20000 | 875 | MDA/125 | 47.1 | 2.8 | 6700 |
Claims (11)
1.一种从芳香烃制备羧酸和/或羧酸酐的气相催化氧化反应用的涂层型催化剂的制备方法,该催化剂由一个载体芯和以层状形式涂于其上的催化活性金属氧化物组成,通过将含有活性金属氧化物的水性活性物质悬浮液在相对高的温度喷洒到50到450℃的载体材料上而得到,其中基于活性物质悬浮液的固含量,水性活性物质悬浮液含有1到10wt%的粘合剂,组成为
A)由自由基聚合得到的聚合物,含有5到100wt%的为烯属不饱和酸酐或其羧基能形成酐的烯属不饱和二羧酸形式的单体(a),以及0到95wt%的其它单烯属不饱和单体(b),附加条件为单体(a)和(b)平均最多有5个没有被含氧的基团官能化的碳原子以及
B)至少含有2个OH基团,最多2个氮原子和最多8个C原子的链烷醇胺,
其中重量比A∶B为1∶0.05到1∶1。
2.权利要求1中的方法,其中单体(a)和(b)含有2到4个C原子且链烷醇胺含有一个氮原子。
3.权利要求1中的方法,其中在(A)和(B)形成的粘合剂中,原子比C∶O最多为3∶1。
4.权利要求1中的方法,其中待涂载体材料的温度为100到250℃。
5.权利要求1中的方法,其中待涂载体材料的温度为140到200℃。
6.权利要求1到3中任一项的方法,其中基于活性物质悬浮液的固含量,粘合添加剂的有机组分为4-8wt%。
7.一种用于将芳香烃气相催化氧化成羧酸和/或羧酸酐的涂层型催化剂,在由石英,陶瓷,氧化镁,碳化硅,二氧化锡,金红石,矾土,硅酸铝,硅酸镁,硅酸锆和/或硅酸铈形成的该催化剂的载体材料上以层状形式涂上一层催化活性金属氧化物,除了锐钛矿形式的二氧化钛和五氧化二钒以外还包括碱金属,碱土金属,铊,铝,锆,铁,镍,钴,锰,锡,银,铜,铬,钼,钨,铱,钽,铌,砷,锑,铈和/或磷的氧化物,其中这些涂层催化剂通过权利要求书1中的方法制备。
8.一种用于将芳香烃气相催化氧化成羧酸和/或羧酸酐的涂层型催化剂,包括一个由石英,陶瓷,氧化镁,碳化硅,二氧化锡,金红石,矾土,硅酸铝,硅酸镁,硅酸锆和/或硅酸铈形成的基本上为惰性的载体芯和一层以基于载体计为5到20wt%的量以层状形式而涂于载体芯上的催化活性金属氧化物,这种金属氧化物其重要组成为锐钛矿形式的二氧化钛和五氧化二钒以及粘合剂,其中粘合剂基本组成为:
A)一种由自由基聚合得到的聚合物,含有5到100wt%的为烯属不饱和酸酐或其羧基能形成酐的烯属不饱和二羧酸形式的单体(a),以及0到95wt%的其它单烯属不饱和单体(b),附加条件为单体(a)和(b)平均最多有6个碳原子以及
B)一种烷醇胺,至少含有2个OH基团,最多2个氮原子和最多6个C原子,其中粘合剂的含量为活性金属氧化物量的1到10wt%。
9.权利要求8中催化剂的应用,用于在固定床中于较高温度下使用一种含有氧分子的气体将芳香烃气相催化氧化成羧酸和/或羧酸酐。
10.权利要求8中催化剂的应用,用于在固定床中于较高温度下使用一种含有氧分子的气体将甲苯和/或萘气相催化氧化成邻苯二甲酸酐。
11.一种将芳香烃气相催化氧化成羧酸和/或羧酸酐的方法,是在固定床中于较高温度下使用一种含有氧分子的气体,依靠一种或多种以层的形式布置在反应器中的涂层型催化剂,一层催化活性金属氧化物以层状形式涂于载体材料上,此方法包括至少使用一种权利要求8中的涂层型催化剂。
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CN100377785C (zh) * | 2003-08-01 | 2008-04-02 | 巴斯福股份公司 | 用于气相氧化的催化剂 |
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CN1938086B (zh) * | 2004-03-26 | 2011-07-13 | 巴斯福股份公司 | 具有银-钒氧化物相和助催化剂相的催化剂 |
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CN105073259A (zh) * | 2013-03-22 | 2015-11-18 | 克拉里安特国际有限公司 | 用于容纳无尘催化剂的可移除保护性涂层 |
CN105339338A (zh) * | 2013-06-26 | 2016-02-17 | 巴斯夫欧洲公司 | 起动气相氧化反应器的方法 |
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-
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- 1998-06-03 DE DE19824532A patent/DE19824532A1/de not_active Withdrawn
-
1999
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- 1999-06-02 CN CNB998069515A patent/CN1134302C/zh not_active Expired - Fee Related
- 1999-06-02 KR KR1020007013665A patent/KR20010052523A/ko not_active Application Discontinuation
- 1999-06-02 JP JP2000551886A patent/JP2002516751A/ja not_active Withdrawn
- 1999-06-02 DE DE59902418T patent/DE59902418D1/de not_active Expired - Lifetime
- 1999-06-02 ID IDW20002517A patent/ID28000A/id unknown
- 1999-06-02 WO PCT/EP1999/003828 patent/WO1999062637A1/de not_active Application Discontinuation
- 1999-06-03 TW TW088109212A patent/TW443944B/zh not_active IP Right Cessation
- 1999-06-09 US US09/701,517 patent/US6528683B1/en not_active Expired - Fee Related
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100377785C (zh) * | 2003-08-01 | 2008-04-02 | 巴斯福股份公司 | 用于气相氧化的催化剂 |
CN1938086B (zh) * | 2004-03-26 | 2011-07-13 | 巴斯福股份公司 | 具有银-钒氧化物相和助催化剂相的催化剂 |
US8163954B2 (en) | 2006-05-08 | 2012-04-24 | Bp Corporation North America Inc. | Process and catalyst for oxidizing aromatic compounds |
CN101983104A (zh) * | 2008-09-26 | 2011-03-02 | 田中贵金属工业株式会社 | 改进修补基面涂层和罩面层的粘合性和涂层完整性 |
CN105073259A (zh) * | 2013-03-22 | 2015-11-18 | 克拉里安特国际有限公司 | 用于容纳无尘催化剂的可移除保护性涂层 |
US10252254B2 (en) | 2013-03-22 | 2019-04-09 | Clariant International Ltd. | Removable protective coating for the receipt of a dust free catalyst |
CN105339338A (zh) * | 2013-06-26 | 2016-02-17 | 巴斯夫欧洲公司 | 起动气相氧化反应器的方法 |
CN105339338B (zh) * | 2013-06-26 | 2017-11-21 | 巴斯夫欧洲公司 | 起动气相氧化反应器的方法 |
Also Published As
Publication number | Publication date |
---|---|
WO1999062637A1 (de) | 1999-12-09 |
CN1134302C (zh) | 2004-01-14 |
EP1091806B1 (de) | 2002-08-21 |
TW443944B (en) | 2001-07-01 |
KR20010052523A (ko) | 2001-06-25 |
EP1091806A1 (de) | 2001-04-18 |
US6528683B1 (en) | 2003-03-04 |
DE19824532A1 (de) | 1999-12-09 |
DE59902418D1 (de) | 2002-09-26 |
JP2002516751A (ja) | 2002-06-11 |
ID28000A (id) | 2001-05-03 |
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