CN103379958A - 通过火焰喷射热解制备的用于自热丙烷脱氢的催化剂 - Google Patents
通过火焰喷射热解制备的用于自热丙烷脱氢的催化剂 Download PDFInfo
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- CN103379958A CN103379958A CN2012800086590A CN201280008659A CN103379958A CN 103379958 A CN103379958 A CN 103379958A CN 2012800086590 A CN2012800086590 A CN 2012800086590A CN 201280008659 A CN201280008659 A CN 201280008659A CN 103379958 A CN103379958 A CN 103379958A
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Abstract
本发明涉及一种制备催化剂粒子的方法,其含有在二氧化锆载体上的铂和锡以及至少一种选自镧和铯的其它元素,所述方法包括以下步骤:制备一种或多种溶液,其含有Pt、Sn和至少一种选自镧和铯的其它元素和ZrO2的前体化合物;将所述溶液转化成气溶胶,将气溶胶加入直接或间接加热的热解区中;进行热解,和从热解气体分离出所形成的粒子。合适的前体化合物包含乙酰丙酮酸锆(IV)、乙酰丙酮酸镧(II)、乙酸铯、六甲基二硅氧烷、2-乙基己酸锡、乙酰丙酮酸铂、在正丙醇中的丙氧化锆(IV)和乙酰丙酮酸镧(II)。本发明还涉及可使用本发明方法获得的催化剂粒子,以及所述粒子作为脱氢催化剂的用途。
Description
描述
本发明涉及催化剂粒子、其制备方法以及所述催化剂粒子用作脱氢催化剂的用途。
通过浸渍工艺或喷雾干燥制备脱氢催化剂的方法是已知的。在这些方法中,通过浸渍工艺将催化活性金属施用到氧化物载体或硅酸盐载体上,或者通过将共沉淀的氧化物前体进行喷雾干燥来制备催化剂。
DE-A 196 54 391描述了制备脱氢催化剂的方法,其中用Pt(NO3)2和Sn(OAc)2的溶液浸渍基本上单斜的ZrO2,或者用Pt(NO3)2的第一溶液浸渍ZrO2,然后用La(NO3)3的第二溶液浸渍。浸渍的载体进行干燥,然后煅烧。如此获得的催化剂作为脱氢催化剂用于丙烷向丙烯的脱氢反应。
一种已知的通过火焰喷射热解制备金属催化剂的方法描述在Pisduangnawakij等,Applied Catalysis A:General 370 1-6,2009中。其中,含有铂和锡的前体化合物和载体氧化铝在二甲苯中的溶液被转化成气溶胶,将其在惰性载气中在热解反应器中在比前体化合物的分解温度更高的温度下处理,然后将所形成的细碎金属从载气分离出来。
已知的通过湿化学制备方式合成贵金属粉末催化剂的方法是耗时和昂贵的。
所以,仍然需要制备脱氢催化剂的方法,其在所涉及的时间和成本方面得到改进。
本发明要解决的技术问题是提供一种便宜且省时的制备脱氢催化剂的方法,其中所得的脱氢催化剂应当在活性和选择性方面与在现有技术中通过浸渍工艺或喷雾干燥制得的催化剂相当。
此问题通过一种制备催化剂粒子的方法实现,所述催化剂粒子含有在含二氧化锆的载体上的铂和锡以及至少一种选自镧和铯的其它元素,所述方法包括以下步骤:
(i)制备一种或多种溶液,其含有铂、锡和至少一种选自镧和铯的其它元素的前体化合物以及二氧化锆的前体化合物,
(ii)将所述溶液转化成气溶胶,
(iii)将气溶胶加入直接或间接加热的热解区中,
(iv)进行热解,和
(v)从热解气体分离出所形成的粒子。
金属化合物和能形成氧化物的前体化合物是作为气溶胶加入热解区的。优选的是,加入热解区的气溶胶是通过仅仅一种溶液的雾化获得的,所述溶液含有全部金属化合物和能形成氧化物的前体化合物。以此方式,总是确保所制得的粒子的组成是均匀和恒定的。在制备要被转化成气溶胶的溶液期间,各个组分因此优选选择使得在溶液中所含的能形成氧化物的前体以及贵金属化合物能彼此均匀地溶解,直到溶液进行雾化。或者,也可以使用几种不同的溶液,其在一方面含有能形成氧化物的前体,另一方面含有活性或促进剂金属化合物。所述一种或多种溶液可以同时含有极性和非极性的溶剂或溶剂混合物。
在热解区中,贵金属化合物分解形成贵金属,并且所述氧化物前体进行分解和/或氧化,同时形成氧化物。一部分贵金属也可以蒸发,然后在较冷的区域中再沉积在已形成的载体粒子上。热解一般导致具有不同比表面的球形粒子。
在热解区中的温度高于贵金属化合物在足够形成氧化物的温度下的分解温度,通常是500-2000℃。热解优选在900-1500℃的温度下进行。
热解反应器可以从外部间接地加热,例如通过电炉加热。由于在间接加热中需要从外部向内部的温度梯度,电炉必须比热解所需的温度显著更热。间接加热需要热稳定性炉材料和昂贵的反应器构造,但是所需的气体总量小于在火焰反应器情况下的气体总量。
在一个优选实施方案中,热解区通过火焰加热(火焰喷射热解)。热解区则包含点燃装置。对于直接加热,使用常规的可燃气体,但是优选使用氢气、甲烷或乙烯。在热解区中的温度可以通过可燃气体的量与气体总量之间的比率而按照需要调节。为了保持气体总量低、但能达到尽可能高的温度,也可以向热解区供应纯氧气来代替空气作为用于可燃气体的燃烧的氧气源。气体的总量也包含用于气溶胶的载气和气溶胶的已蒸发的溶剂。向热解区供应的一种或多种气溶胶优选直接加入火焰中。虽然空气一般优选作为用于气溶胶的载气,但是也可以使用氮气、CO2、O2或可燃气体,例如氢气、甲烷、乙烯、丙烷或丁烷。
在本发明方法的另一个实施方案中,热解区通过电子等离子体或感应等离子体加热。在此实施方案中,催化活性的贵金属粒子沉积在载体粒子的表面上,并牢固地固定在所述表面上。
火焰喷射热解设备通常包含用于要雾化的液体的储存容器,用于载气、可燃气体和含氧气体的进料管线,中心气溶胶喷嘴以及布置在其周围的环形燃烧器,用于气体-固体分离的装置,其包含过滤元件和用于固体的排料装置,以及用于废气的出口。这些粒子用骤冷气体冷却,例如用氮气或空气。
热解区优选包含所谓的预干燥器,其用于使气溶胶在进入热解反应器之前进行初期干燥,这种初期干燥例如在流动管中进行,在流动管周围具有加热组件。在不进行初期干燥的情况下,存在的风险是获得具有较宽粒径分布的产物,更尤其存在过量的细级分。预干燥器的温度取决于被溶解的前体的性质及其浓度。在预干燥器中的温度通常高于溶剂的沸点,至多为250℃;在水用作溶剂的情况下,预干燥器中的温度优选是120-250℃,更尤其是150-200℃。预干燥的气溶胶经由管线供应到热解反应器,然后经由出口喷嘴浸入所述反应器。
为了产生平衡的温度分布,燃烧空间是隔热的,所述燃烧空间优选是管形的。
由于热解,获得热解气体,其含有具有不同比表面的球形粒子。所得颜料粒子的尺寸分布基本上直接来自被加入热解区的气溶胶的液滴谱和所用的一种或多种溶液的浓度。
优选,在从热解气体分离所形成的粒子之前,将热解气体冷却,从而排除烧结在一起的粒子。因此,热解区优选含有冷却区,其与热解反应器的燃烧空间邻接。通常需要将热解气体和在其中所含的催化剂粒子冷却到约100-500℃的温度,这取决于所用的过滤元件。优选冷却到约100-150℃。在离开热解区之后,含有催化剂粒子且被部分冷却的热解气体进入用于从热解气体分离粒子的装置,此装置包含过滤元件。为了冷却,加入骤冷气体,例如氮气、空气或被水润湿的空气。
合适的能形成二氧化锆的前体化合物是醇盐,例如乙氧化锆(IV)、正丙氧化锆(IV)、异丙氧化锆(IV)、正丁氧化锆(IV)和叔丁氧化锆(IV)。在本发明方法的一个优选实施方案中,丙氧化锆(IV),优选作为在正丙醇中的溶液形式,用作ZrO2前体化合物。
其它合适的能形成二氧化锆的前体化合物是羧酸盐,例如乙酸锆、丙酸锆、草酸锆、辛酸锆、2-乙基己酸锆、乙酸锆、丙酸锆、草酸锆、辛酸锆、2-乙基己酸锆、新癸酸锆、硬脂酸锆和丙酸锆。在本发明方法的另一个优选实施方案中,乙酰丙酮酸锆(IV)用作前体化合物。
在一个实施方案中,前体化合物另外含有二氧化硅前体化合物。用于二氧化硅的可能前体是有机硅烷,以及SiCl4与低级醇或低级羧酸的反应产物。也可以使用上述有机硅烷和/或有机硅烷醇的具有Si-O-Si单元的缩合物。优选使用硅氧烷。也可以使用SiO2。在本发明方法的一个优选实施方案中,前体化合物含有六甲基二硅氧烷作为能形成二氧化硅的前体化合物。
除了二氧化锆和任选地二氧化硅作为载体之外,本发明的催化剂粒子还含有铂和锡以及至少一种选自镧和铯的其它元素。
在本发明的一个优选实施方案中,Pt载荷是0.05-1重量%,Sn载荷是0.05-2重量%。
优选的用于镧和铯的前体化合物分别是羧酸盐和硝酸盐,例如对应于上述关于锆所定义的羧酸盐。在本发明方法的一个优选实施方案中,前体化合物含有乙酰丙酮酸镧(III)和/或乙酸铯。
在本发明方法的另一个优选实施方案中,前体化合物含有2-乙基己酸镧(III)。
优选的用于锡的前体化合物是羧酸盐和硝酸盐,例如对应于上述关于锆所定义的羧酸盐。在本发明方法的另一个优选实施方案中,前体化合物含有2-乙基己酸锡。
优选的用于铂的前体化合物是羧酸盐和硝酸盐,例如对应于上述关于锆所定义的羧酸盐,以及铂酸铵。在本发明方法的一个优选实施方案中,前体化合物含有乙酰丙酮酸铂。
极性和非极性的溶剂或溶剂混合物可以用于制备用于形成气溶胶的一种或多种溶液。
优选的极性溶剂是水、甲醇、乙醇、正丙醇、异丙醇、正丁醇、叔丁醇、正丙醇、正丁醇、乙醚、叔丁基甲基醚、四氢呋喃、C1-C8羧酸、乙酸乙酯以及它们的混合物。
在本发明方法的一个优选实施方案中,一种或多种前体化合物、优选全部的前体化合物溶解在乙酸、乙醇和水的混合物中。优选,此混合物含有30-75重量%的乙酸、30-75重量%的乙醇和0-20重量%的水。尤其是,乙酰丙酮酸锆(IV)、六甲基二硅氧烷、2-乙基己酸锡、乙酰丙酮酸铂、乙酰丙酮酸镧(II)和乙酸铯溶解在乙酸、乙醇和水的混合物中。
优选的非极性溶剂是甲苯、二甲苯、正庚烷、正戊烷、辛烷、异辛烷、环己烷、乙酸甲酯、乙酸乙酯或乙酸丁酯,或它们的混合物。具有5-15个碳原子的烃或烃混合物也是合适的。二甲苯是尤其优选的。
尤其是,丙氧化Zr(IV)、六甲基二硅氧烷、2-乙基己酸锡、乙酰丙酮酸铂和乙酰丙酮酸镧(III)溶解在二甲苯中。
本发明还涉及可通过本发明方法获得的载体和催化剂粒子。它们优选具有20-70m2/g的比表面。
在一个优选实施方案中,催化剂粒子具有以下百分比组成:作为载体的30-99.5重量%的ZrO2和0.5-25重量%的SiO2,0.1-1重量%的Pt,0.1-10重量%的Sn、La和/或Cs,基于载体的质量计,其中含有至少Sn和La或Cs。
本发明还涉及催化剂粒子作为氢化催化剂或脱氢催化剂的用途。链烷、例如丁烷和丙烷、以及乙基苯优选进行脱氢。
本发明催化剂用于将丙烷脱氢成丙烯的用途是尤其优选的。
通过以下实施例更详细地说明本发明。
实施例
所用的化学品:
乙酰丙酮酸锆Zr(acac)2(98%)
丙氧化锆(IV)Zr(OPr)4(70%在1-丙醇中)
六甲基二硅氧烷(HMDSO)(98%)
2-乙基己酸锡(II)(约95%)
乙酰基乙酸铂(II)(98%)
2-乙基己酸镧(III)(10%w/v)
乙酰丙酮酸镧(III)(99.99%)
乙酸铯(99.99%)
乙酸(100%)、乙醇(96%)和水(去离子)的混合物
二甲苯(BASF,异构体的混合物)
制备前体化合物的溶液
溶剂是HoAc:EtOH:H2O,其重量比为4.6:4.6:1。乙酸-乙醇混合物是新鲜制备的。用于Sn、Cs、La、Si、Pt和Zr的前体化合物溶解在所述溶剂中。
实施例1、2、3、9和10中的前体化合物的极性溶液的组成列在表1中。
表1:用于极性混合物(EtOH:HoAc:H2O)的前体化合物溶液的组成
[g] | 物质 | 纯度[重量%] |
99.52 | 乙酰丙酮酸锆(IV) | 98 |
1.77 | 六甲基二硅氧烷 | 99 |
0.93 | 2-乙基己酸锡 | 95 |
0.27 | 乙酰丙酮酸铂 | 98 |
2.45 | 乙酰丙酮酸镧(III) | 99.9 |
0.38 | 乙酸铯 | 99.99 |
为了制备用于实施例4的前体化合物的溶液,将以下物质溶解在二甲苯中。组成显示在表2中。
表2:用于非极性混合物(二甲苯)的前体化合物溶液的组成
[g]物质 | 纯度[重量%] |
374.40在正丙醇中的丙氧化Zr(IV) | 70 |
10.11六甲基二硅氧烷 | 99 |
5.322-乙基己酸锡 | 95 |
1.52乙酰丙酮酸铂 | 98 |
103.472-乙基己酸镧(III) | 10 |
在制备用于实施例5、6和8的前体化合物溶液的情况下,另外使用2.24g的乙酸铯。
实施例1-10
通过火焰喷射热解制备催化剂粒子
含有前体化合物的溶液是通过活塞泵经由双组分喷嘴供应的,并用相应量的空气雾化。为了达到相应的温度,有时使用来自乙烯-空气混合物的支持火焰,其是经由位于喷嘴周围的环形燃烧器提供的。压降保持恒定为1.1巴。
火焰合成条件总结在表3中。
表3:关于火焰喷射热解制备催化剂的试验参数
不含铯前体化合物的溶液
**仅仅存在Si和Zr前体
1GLMR=气体:液体的质量比。
袋式过滤器用于分离这些粒子。这些过滤器可以通过向滤袋施加5巴压力的氮气吹扫来清洁。
粒子表征使用X-射线衍射(XRD)和BET检测进行,也进行元素分析。使用前体化合物3和4的溶液所形成的催化剂粒子的微晶尺寸如表4所示。
表4:用于表征ZrO2的X-射线粉末衍射
从上述含有特定前体化合物的溶液合成催化剂,获得了具有比表面积为36-70m2/g的粒子(参见表5)。
在另一个实验中,研究BET表面积随着燃烧室温度的变化。这涉及在其溶剂方面(乙酸对于二甲苯)比较含有前体化合物的溶液。在乙酸混合物的情况下,没有明显的倾向。
二甲苯混合物显示出BET表面积随着温度的升高而增加,这可以归因于较短的停留时间,从而限制了粒子的生长。
实施例11-17
催化检测
丙烷脱氢反应是在约600℃下进行(在20ml催化剂体积下流动,质量参见表5):21Nl/h总气体(20Nl/h丙烷,1Nl/h氮气作为内标),5g/h水。再生在400℃下如下进行:2小时21Nl/h N2+4Nl/h空气;2小时25Nl/h空气;1小时25Nl/h氢气。
来自水热合成以及随后喷雾干燥的参比催化剂的载体(ZrO2)是由95%ZrO2和5%SiO2组成的。活性/促进剂金属是0.5%Pt,1%Sn,3%La,0.5%Cs和0.2%K,将它们根据EP 1 074 301中的实施例4所述按照湿化学方式通过浸渍施用到载体上。
在催化试验中研究了转化率、长期稳定性和对形成丙烯的选择性。结果列在表5中。活性和选择性涉及最佳的操作状态。
表5:火焰合成的催化剂粒子在自热丙烷脱氢反应中的催化剂结果
图1显示了火焰合成的催化剂(▲实施例13,■实施例17)和参比催化剂(-)在丙烷向丙烯的自热脱氢反应中的活性和选择性。在催化剂(■)的情况下,仅仅载体通过热解制备,并且载体随后进行如对于参比实施例所述的湿化学浸渍。在横轴上绘制单位为小时的时间,在纵轴上绘制转化率(40-50%)和选择性(>80%)。
可见,三种催化剂具有相当的性能。参比催化剂具有较低的初始选择性。但是,在数星期的试验周期中,其等同于本发明的催化剂。因此,火焰合成的催化剂的性能就象老化的催化剂那样,后者是通过常规湿化学工艺制备的。
Claims (19)
1.一种制备催化剂粒子的方法,其含有在含二氧化锆和任选二氧化硅的载体上的铂和锡以及至少一种选自镧和铯的其它元素,所述方法包括以下步骤:
(i)制备一种或多种溶液,其含有铂、锡和至少一种选自镧和铯的其它元素的前体化合物以及二氧化锆的前体化合物,
(ii)将所述溶液转化成气溶胶,
(iii)将气溶胶加入直接或间接加热的热解区中,
(iv)进行热解,和
(v)从热解气体分离出所形成的催化剂粒子。
2.权利要求1的方法,其中前体化合物另外含有二氧化硅前体化合物。
3.权利要求1或2的方法,其中热解区用火焰加热。
4.权利要求1的方法,其中所形成的催化剂粒子含有0.05-1重量%和0.05-2重量%的Sn。
5.权利要求1-4中任一项的方法,其中前体化合物含有乙酰丙酮酸锆(IV)。
6.权利要求1-5中任一项的方法,其中前体化合物含有乙酰丙酮酸镧(III)和/或乙酸铯。
7.权利要求1-6中任一项的方法,其中前体化合物含有六甲基二硅氧烷。
8.权利要求1-7中任一项的方法,其中前体化合物含有2-乙基己酸锡。
9.权利要求1-4中任一项的方法,其中前体化合物含有乙酰丙酮酸铂。
10.权利要求1-4中任一项的方法,其中前体化合物含有丙氧基化锆(IV)。
11.权利要求1-4中任一项的方法,其中前体化合物含有2-乙基己酸镧(III)。
12.权利要求1-9中任一项的方法,其中一种或多种前体化合物溶解在乙酸、乙醇和水的混合物中。
13.权利要求7-11中任一项的方法,其中一种或多种前体化合物溶解在二甲苯中。
14.权利要求1-13中任一项的方法,其中热解在900-1500℃的温度下进行。
15.催化剂粒子,其可以通过根据权利要求1-14中任一项所述的方法获得。
16.权利要求15的催化剂粒子,其具有比表面积为36-70m2/g。
17.权利要求15或16的催化剂粒子,其含有作为载体的30-99.5重量%的ZrO2和0.5-25重量%的SiO2,0.1-1重量%的Pt,0.1-10重量%的Sn、La和/或Cs,基于载体的质量计,其中含有至少Sn和至少La或Cs。
18.权利要求15-17中任一项的催化剂粒子作为脱氢催化剂的用途。
19.权利要求18的用途,所述催化剂粒子用于丙烷向丙烯的脱氢反应或丁烷向丁烯的脱氢反应。
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