CN1108864C - 用于转化气体混合物中所含有机化合物的催化剂 - Google Patents
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J23/20—Vanadium, niobium or tantalum
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Abstract
本催化剂适用于转化气体混合物中的有机化合物,如烃、卤化烃、醇和溶剂。为了使该催化剂特别具有热稳定性与耐酸性,本发明的催化剂(6、16、18、20)含有氧化钛,和至少一种催化活性组分。氧化钛主要是具有高于40m2/g的BET比表面积的金红石型二氧化钛TiO2。本发明催化剂可用于净化燃烧废气,以及各种工业废气。
Description
本发明涉及一种用于转化气体混合物中所含有机化合物的催化剂,它包含氧化钛和至少一种其它的催化活性组分。上述有机化合物通常包括烃、溶剂、一氧化碳、环状的和芳香的化合物、以及卤化烃,特别是二喔星和呋喃。上述气体混合物可以是汽车废气、工业废气、固定式内燃机的废气与燃烧装置的烟气,例如,发电厂与垃圾焚烧装置排放的废气。
德国专利文献DE-OS-3804722揭示了一种从废气中除去有机化合物的方法和催化剂。该方法提出把含有有机化合物的废气与氧气,特别是与空气,一起送入其反应温度为250-500℃的选择性催化剂中进行反应。经反应使上述有机化合物转化为可与环境保持相容的反应生成物,例如二氧化碳与水汽。其耐酸性直接受到二喔星/呋喃分解(转化成HCl、HF)的影响。较适用的催化剂是一种由氧化物混合物所组成的催化剂。其中,所考虑的催化剂中含有大量重量组分的二氧化钛,而且以晶体状的锐钛矿为宜。可用作催化活性组分的物质包括:二氧化钛化合物和/或过渡元素铬、锰、钴、镍、铜、钒、锌、钼、钨的氧化物和/或其混合氧化物,并以氧化铬为宜。
欧洲专利文献EP0290947B1介绍了一种用于氧化氨(NH3)的催化剂。这种催化剂也含有高重量组分的,直至50%的二氧化钛,它以锐钛矿的结晶改型存在。该锐钛矿改型通常比金红石改型具有更高的BET比表面积。由于具有较高的BET比表面积,使该催化剂具有较高的催化活性。
德国专利文献DE3804722A1,或欧洲专利文献EP0290947B1介绍了一种用于分解有机化合物的这种催化剂的制备方法。其中,把二氧化钛与活性组分一起进行粉碎,均匀混合,并加以过滤。然后,向形成的滤饼加入粘合剂,混合上述形成的物料,并制成预定的形状。例如,涂敷在板上、或挤压成蜂窝形、或丸粒状的物质。接着,使上述形成的物质进行干燥,并进行热处理或煅烧。
用上述催化剂所进行的化学反应是放热反应。因此,通过反应,有可能在催化剂中出现局部过热现象,即所谓的过热部位。由于这种催化剂大部分由锐钛矿型的二氧化钛构成。当锐钛矿型二氧化钛转变成金红石型二氧化钛时,粒径发生变化,受上述局部过热的限制,使催化剂的比表面积不可逆的降低。这就会导致,催化剂的活性随反应时间逐步减退。
众所周知,可以用其他物质代替作为催化剂基本材料的二氧化钛,例如氧化铝基的催化剂。这种含氧化铝的催化剂,只轻微遭受温度负荷的影响,特别是对于局部过热。然而,使用这种催化剂的结果表明,与含有锐钛矿变型的二氧化钛催化剂相反,它没有足够的耐酸性,特别是在分解卤化烃时。
本发明的目的在于,制备一种用于转化气体混合物中所含有机化合物的,特别是具有热稳定性与耐酸性的催化剂。
本发明的任务通过本文开始所述的根据本发明的方法加以完成,即作为二氧化钛大部分是具有BET比表面积高于40m2/g的金红石型二氧化钛。
用二氧化钛作为催化剂的基本材料,就可以使该催化剂具有特别好的耐酸性。其耐酸性优于锐钛矿变型二氧化钛作为催化剂基本材料的催化剂。采用金红石型二氧化钛的催化剂与锐钛矿型二氧化钛的催化剂相比较,前者在高温下没有或是很小地发生晶体增长现象。因此,也达到了较高的温度稳定性。上述温度稳定性的原因在于以下事实,金红石型二氧化钛本身在700~1000℃高温度条件下,仍表明完好,没有出现晶体增长现象。晶体增长会导致在锐钛矿型二氧化钛的情况那样使比表面积降低。本发明中采用金红石型二氧化钛的作法是值得令人注意的,这是由于本领域的技术人员通常是排斥使用金红石型二氧化钛。因为,金红石型二氧化钛通常只是用于制备白色颜料。通常市场上只能得到其比表面积较小的,即约10m2/g的金红石型二氧化钛。反之,市场上可以得到其比表面积较高的,如100m2/g的锐钛矿型的二氧化钛。
当锐钛矿型二氧化钛的部分少于所使用的二氧化钛总量的25%(重量)时,将特别有利于其温度稳定性。
当作为催化活性组分是选自元素钼、钨、钒、铜、铁、铬与锰中的一个或多个化合物时,该催化剂的催化活性将特别高。其中,特别适用的化合物是铜-锰-尖晶石,铜铬铁矿、氧化铬、锰铬铁矿,以及有五氧化二钒的氧化铁。
由于成本和根据工艺条件,催化剂中不应含有任意高含量的催化活性成分。催化活性组分含量以不超过20%(重量)为宜,并最好是2-10%(重量)。
催化剂宜加工制成蜂窝状或丸状和/或颗粒状则催化剂特别便于使用。
本发明的催化剂的制备原则上可以根据本文上面提及的方法,在相同条件下进行,该方法是通常制备用于由废气中除去有机化合物的现有技术已知催化剂的方法。
二氧化钛逐渐地并在提高温度时加速地由锐钛矿变型不可逆地转变成金红石变型。在提高温度的情况下,当然没有出现金红石型晶粒大小的变化。因此可以得知,在开始时所添加的原材料表明催化剂中的金红石变型二氧化钛相对于锐钛矿变型二氧化钛的比例是相等或更高些。
具有BET比表面积大于40m2/g的金红石变型二氧化钛,可以按基本上相同的众所周知的,用于制备具有BET比表面积约10m2/g的白色颜料的金红石型二氧化钛的方法制备。这种方法是经过硫酸钛的沉淀或四氯化钛的氧化燃烧而实施的。必要时它必须相应改变结晶速度,以便达到合适的结晶粒度。
参考附图进一步详述本发明的实施方案,其中:
图1,装有用于转化有机化合物的催化剂的废气管道的示意图,
图2,图1中所用的催化剂的可能的实施形式的示意图。
图1中,有一个图中未进一步详述的工业装置的废气管道2,其中在其扩张段4区域内装有使用的催化剂6。在扩张段4中沿废气8流动方向,在上述催化剂6之前,装有一个热交换器10和一个混合部件12。在上述催化剂6之后的废气8流动方向的扩张段4的区域内装有另一个热交换器14。后者与上述热交换器10共同构成回流换热交换器,如图中虚线所示。在转化卤化烃时,特别是转化垃圾焚烧所形成的二喔星和呋喃时,还可以添置一个图中未示出的用于酸性反应生成物,如HCl、HF的分离器。
在废气管道2内流动的废气8中含有有机化合物,它们是醇、溶剂、甲苯与二甲苯。该废气在通入扩张段4前的温度约为20℃,并此外含有通常的空气组分,而且其体积流量约为10,000Nm3/h。
如图2所示的,本发明实施方案的催化剂6是陶瓷蜂窝状物体16所组成的。这种蜂窝状物体16的规格通常是25-500蜂房/平方英寸。本发明实施方案的蜂窝状物体16是由约90%(重量)的二氧化钛所组成的。其中约95%(重量)的二氧化钛是金红石型,而约5%(重量)的二氧化钛是锐钛矿型。该蜂窝状物体16还含有约3%(重量)的纤维物质,例如玻璃纤维或氧化铝纤维和/或氧化硅纤维,以便增强其机械强度。
此外,该催化剂6中其余的约7%(重量)组分基本上是催化剂6的催化活性物质。它们包括2%(重量)的氧化铁Fe2O3,2%(重量)的五氧化二钒,以及各占1%(重量)的铜-锰尖晶石、铜-铬尖晶石、和锰-铬尖晶石,它们的化学式分别为CuMn2O4、CuCr2O4和MnCr2O4。
废气8通过热交换器10被加热到约200℃。通过位于热交换器10下游位置上的混合部件12,使得废气8均匀混合,从而导致废气8在扩张段4的总截面上的温度分布达到均匀。前述的废气中的有机化合物与催化剂6接触以后,就大致上转化成可与环境保护相容的物质,例如二氧化碳与水。
通过催化剂6处理后流出的废气流,在适应的催化剂6的设计参数下,基本上不含有害的有机化合物。为此,必须如下选定催化剂6的容积,即每小时流过催化剂6的废气8的容积,不能超过大约50,000的因数。也就是说,废气的体积流速最高是50,000/小时,其中废气体积流速以500-10,000/小时为宜。
通过热交换器14可以收回废气8在通过前面的热交换器10所供的热量。该热量还可以再次输送到热交换10中。或者也可以设计为回收式热交换器使废气管2从催化剂6出口后,直接通到热交换器10而进行。
当催化剂中的金红石型二氧化钛的比表面积,即所谓的BET比表面积,高于80m2/g时,则该催化剂6就具有特别高的耐酸性,温度稳定性与催化活性。因此,通过使用金红石型的二氧化钛可以进一步提高其酸稳定性;通过提高金红石型二氧化钛的含量,可以达到其温度稳定性。当一方面选定BET比表面积高于40m2/g和另一方面选定催化活性组分,就会达到高的催化活性。
图2中,除了蜂窝状催化剂16外,还图示其他两种催化剂型物体18与20。即催化剂颗粒18与催化剂丸状物20。催化剂颗粒18可以是其直径约为1~5mm的球状体,而丸状物20通常具有约1-5mm的直径与约5-30mm的长度。
Claims (6)
1.一种用于反应存在于气体混合物(8)中的有机化合物的催化剂(6、16、18、20),包括:
二氧化钛、氧化钒和至少一种其它的催化活性成分;其特征在于二氧化钛是以锐钛矿型和金红石型二氧化钛存在的二氧化钛,所述金红石型二氧化钛的BET表面积大于40m2/g,并且基于二氧化钛总量,锐钛矿型二氧化钛TiO2的含量低于25%重量;并且作为其它的催化活性成分,至少是选自元素钼、钨、钒、铜、铁、铬和锰的一种化合物。
2.根据权利要求1的催化剂(6、16、18、20),其特征是,上述至少一种其它的催化活性成分是选自铜-锰尖晶石,铜铬铁矿,氧化铬,锰铬铁矿,与具有五氧化二钒的氧化铁的至少一种化合物。
3.根据权利要求1或2的催化剂(6、16、18、20),其特征是,上述至少一种其它的催化活性成分的含量不超过20%重量。
4.根据权利要求1-3中任一项的催化剂(6、16、18、20),其特征是,上述至少一种其它的催化剂活性成分的含量为2-10%重量。
5.根据权利要求1-4中之一的催化剂(6、16、18、20),其特征是,该催化剂为蜂窝状物体。
6.根据权利要求1-5中之一的催化剂(6、16、18、20),其特征是,该催化剂为丸状物(20)或颗粒状物(18)。
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DE19509893A DE19509893C1 (de) | 1995-03-17 | 1995-03-17 | Katalysatorträger aus Titandioxid sowie seine Verwendung |
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EP2444150A1 (de) * | 2010-10-22 | 2012-04-25 | crenox GmbH | Trägerkatalysator aus Aufschlussrückständen der titanylsulfathaltigen Schwarzlösung |
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US3948807A (en) * | 1973-01-13 | 1976-04-06 | Kuraray Co., Ltd. | Oxide catalysts and process for preparation thereof |
US4870195A (en) * | 1986-10-20 | 1989-09-26 | Alusuisse Italia S.P.A. | Oxidation catalyst and process for its preparation |
US4962078A (en) * | 1987-05-07 | 1990-10-09 | Exxon Research And Engineering Company | Cobalt-titania catalysts, process utilizing these catalysts for the preparation of hydrocarbons from synthesis gas, and process for the preparation of said catalysts |
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DE3855942D1 (de) * | 1987-05-12 | 1997-07-17 | Siemens Ag | Katalytische Beseitigung von Ammoniak aus Abgasen. |
DE3804722A1 (de) * | 1988-02-15 | 1989-08-24 | Siemens Ag | Verfahren, vorrichtung und katalysator zur beseitigung einer organischen verbindung aus einem abgas |
DE3913938A1 (de) * | 1989-04-27 | 1990-10-31 | Degussa | Presslinge auf basis von pyrogen hergestelltem titandioxid, verfahren zu ihrer herstellung sowie ihre verwendung |
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US3948807A (en) * | 1973-01-13 | 1976-04-06 | Kuraray Co., Ltd. | Oxide catalysts and process for preparation thereof |
US4870195A (en) * | 1986-10-20 | 1989-09-26 | Alusuisse Italia S.P.A. | Oxidation catalyst and process for its preparation |
US4962078A (en) * | 1987-05-07 | 1990-10-09 | Exxon Research And Engineering Company | Cobalt-titania catalysts, process utilizing these catalysts for the preparation of hydrocarbons from synthesis gas, and process for the preparation of said catalysts |
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ATE203428T1 (de) | 2001-08-15 |
DE19509893C1 (de) | 1996-12-19 |
CN1178483A (zh) | 1998-04-08 |
EP0814904B1 (de) | 2001-07-25 |
WO1996029147A1 (de) | 1996-09-26 |
DK0814904T3 (da) | 2001-11-12 |
DE59607365D1 (de) | 2001-08-30 |
JP3920332B2 (ja) | 2007-05-30 |
EP0814904A1 (de) | 1998-01-07 |
JPH11502148A (ja) | 1999-02-23 |
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