CN106000409B - 用于co2氧化乙苯脱氢制苯乙烯的铁基复合氧化物催化剂 - Google Patents
用于co2氧化乙苯脱氢制苯乙烯的铁基复合氧化物催化剂 Download PDFInfo
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 5
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Abstract
本发明公开了一种用于CO2氧化乙苯脱氢制苯乙烯的铁基复合氧化物催化剂,该催化剂载体为γ‑Al2O3,活性组分为FeOx,助剂为TiO2、PdO、ZnO、V2O5中的任意一种,其采用原子层沉积法制备而成。本发明催化剂用于CO2氧化乙苯脱氢制苯乙烯,苯乙烯的选择性均可达到95%以上,且乙苯的转化率可达到65%以上,最高可达到85%左右。另外,采用本发明方法制备催化剂时,不涉及前驱体的溶解、沉淀等液相过程,直接将前驱体分散在载体表面和孔道中,获得的催化剂活性组分分散度较高,且制备方法简单、周期短、条件温和。
Description
技术领域
本发明属于催化剂技术领域,具体涉及到一种用于CO2氧化乙苯脱氢制苯乙烯催化剂的制备和对其反应活性的评价。
背景技术
苯乙烯是石油化工产品中最重要的单体之一,主要用作生产塑料、树脂和合成橡胶的生产原料。目前,市场上大约90%的苯乙烯通过乙苯直接脱氢制得。该方法存在反应温度高、水蒸气潜热难以回收和耗能大等问题。因此在新世纪能源短缺的条件下,迫切需要开发一种新工艺,能够打破热力学平衡限制、解决自供热问题并且降低反应温度。但是,空气或氧气氧化乙苯制苯乙烯伴有深度氧化和氧分子插入等副反应,使苯乙烯的选择性降低,除此以外还伴有大量的热量生成,使反应温度难以控制。因此,此方法也难以实现工业化。为了克服传统乙苯脱氢的不足,研究者提出了CO2氧化乙苯脱氢制苯乙烯,从而提高了苯乙烯的选择性和日益增多的温室气体CO2的活化转化。
CO2氧化乙苯脱氢制苯乙烯的反应中,使用最多的是铁基催化剂和钒基催化剂。现有文献报道的催化剂的制备方法主要有:(1)采用水热法一步制备而成,该方法操作简单,但反应需要的时间比较长,催化活性一般,乙苯转化率最高在70%左右。 (2)采用共沉淀法或溶胶凝胶法先制备复合氧化物,然后负责活性成分。其中,共沉淀法很难让所有的金属阳离子同时沉淀,造成组成成分的分离,而溶胶凝胶法需使用价格比较高的醇盐,并且凝胶比较容易板结。另外,所负载的活性组分分散度低,从而其乙苯转化率仅为60%左右。(3)采用浸渍法制备,该方法操作简便,但耗时长,催化剂活性组分分散度一般,故乙苯转化率较低,一般不会超过60%。 (4)采用燃烧分解法,该方法操作简单,反应时间短,合成温度低,乙苯转化率可达到65%,苯乙烯选择性较高。
发明内容
本发明所要解决的技术问题在于提供一种采用原子层沉积法制备的用于CO2氧化乙苯脱氢制苯乙烯铁基复合氧化物催化剂。
解决上述技术问题所采用的技术方案是:该催化剂的载体为γ-Al2O3,活性组分为FeOx,助剂为TiO2、PdO、ZnO、V2O5中的任意一种,其采用原子层沉积法按下述步骤制备而成:
1、将γ-Al2O3粉末加入原子层沉积系统的反应腔内,密封反应腔,将原子层沉积系统内抽真空后通入惰性气体,调节反应腔出口阀门使腔内压力处于负压,反应腔温度维持在300~400℃。
2、向反应腔内注入铁的前驱体,时间为1000~3000s,然后通入惰性气体冲洗,时间为1000~2000s;向反应腔内注入第二种反应前驱体,时间为1000~3000s,再通入惰性气体冲洗,时间为1000~2000s。
3、重复步骤2一至四次;
4、将原子层沉积系统内抽真空后通入惰性气体,调节反应腔出口阀门使腔内压力处于负压,反应腔温度维持在100~200℃,向反应腔内注入助剂的前驱体,时间为50~300s,然后通入惰性气体冲洗,时间为100~200s;向反应腔内注入第二种反应前驱体,时间为50~300s,再通入惰性气体冲洗,时间为100~200s,得到铁基复合氧化物催化剂。
上述步骤2中,优选向反应腔内注入铁的前驱体,时间为1500~2000s,然后通入惰性气体冲洗,时间为1000~2000s;向反应腔内注入第二种反应前驱体,时间为1500~2000s,再通入惰性气体冲洗,时间为1000~2000s,其中所述的铁前驱体为二茂铁或(2,2,6,6-四甲基-3,5-庚二酮)化铁,第二种反应前驱体为去离子水、双氧水、氧气、臭氧中的任意一种。
上述步骤3中,进一步优选重复步骤2两次。
本发明催化剂中,所述的助剂为TiO2时,在步骤4中,优选将原子层沉积系统内抽真空后通入惰性气体,调节反应腔出口阀门使腔内压力处于负压,反应腔温度维持在150℃,向反应腔内注入TiO2的前驱体,时间为50~200s,然后通入惰性气体冲洗,时间为100~200s;向反应腔内注入第二种反应前驱体,时间为50~200s,再通入惰性气体冲洗,时间为100~200s,其中所述的TiO2的前驱体为异丙醇钛、叔丁醇钛、氯化钛、四(二甲基胺基)钛、四(乙基甲基胺基)钛中的任意一种。
本发明催化剂中,所述的助剂为PdO时,在步骤4中,优选将原子层沉积系统内抽真空后通入惰性气体,调节反应腔出口阀门使腔内压力处于负压,反应腔温度维持在200℃,向反应腔内注入PdO的前驱体,时间为100~200s,然后通入惰性气体冲洗,时间为100~200s;向反应腔内注入第二种反应前驱体,时间为100~200s,再通入惰性气体冲洗,时间为100~200s,其中所述的PdO的前驱体为六氟乙酰丙酮钯、乙酰丙酮钯、二(2,2,6,6-四甲基-3,5-庚二酮酸)钯、(η3-烯丙基)(六氟乙酰丙酮)钯、(η3-烯丙基)(乙酰丙酮)钯、(η3-烯丙基)(环戊二烯基)钯、二甲基双(三甲基膦)钯、二甲基双(三乙基膦)钯中的任意一种。
本发明催化剂中,所述的助剂为ZnO时,在步骤4中,优选将原子层沉积系统内抽真空后通入惰性气体,调节反应腔出口阀门使腔内压力处于负压,反应腔温度维持在100℃,向反应腔内注入ZnO的前驱体,时间为50~100s,然后通入惰性气体冲洗,时间为100~200s;向反应腔内注入第二种反应前驱体,时间为50~ 100s;再通入惰性气体冲洗,时间为100~200s,其中所述的ZnO的前驱体为二乙基锌。
本发明催化剂中,所述的助剂为V2O5时,在步骤4中,优选将原子层沉积系统内抽真空后通入惰性气体,调节反应腔出口阀门使腔内压力处于负压,反应腔温度维持在100℃,向反应腔内注入V2O5的前驱体,时间为150~250s,然后通入惰性气体冲洗,时间为100~200s;向反应腔内注入第二种反应前驱体,时间为150~ 250s,再通入惰性气体冲洗,时间为100~200s,其中所述的V2O5的前驱体为三异丙氧醇钒、异丙醇钒、乙酰丙酮氧化钒中的任意一种。
本发明采用原子层沉积法制备成用于CO2氧化乙苯脱氢制苯乙烯铁基复合氧化物催化剂,该催化剂用于CO2氧化乙苯脱氢制苯乙烯,苯乙烯的选择性均可达到 95%以上,且乙苯的转化率可达到65%以上,最高可达到85%左右。另外,采用本发明方法制备催化剂时,不涉及前驱体的溶解、沉淀等液相过程,直接将前驱体分散在载体表面和孔道中,获得的催化剂活性组分分散度较高,且制备方法简单、周期短、条件温和。
具体实施方式
下面结合实施例对本发明进一步详细说明,但本发明的保护范围不仅限于这些实施例。
实施例1
1、将130mg粒径为20~30μm的γ-Al2O3放入原子层沉积系统的反应腔内,密封反应腔,将原子层沉积系统内抽真空后通入氮气,调节反应腔出口阀门使腔内压力为100Pa,加热反应腔使反应腔温度维持在350℃。
2、将二茂铁加热到90℃,将产生的二茂铁蒸汽注入原子层沉积系统的反应腔内与γ-Al2O3发生气-固界面反应,反应时间为1800s,然后向反应腔内通入氮气冲洗过量二茂铁和副产物,时间为1800s;向反应腔内注入氧气,反应时间为1800s,再通入氮气冲洗过量氧气和副产物,时间为1800s。
3、重复步骤2两次,得到FeOx/Al2O3粉体。
4、将原子层沉积系统内抽真空后通入氮气,调节反应腔出口阀门使腔内压力为130Pa,使反应腔温度维持在100℃,常温状态下将二乙基锌由氮气带入反应腔内,与FeOx/Al2O3粉体发生反应,反应时间为100s,然后向反应腔内通入氮气冲洗过量二乙基锌和副产物,时间为100s;向反应腔内通入由氮气携带的水蒸气,反应时间为100s,再向反应腔内通入氮气冲洗,时间为100s,得到铁基复合氧化物催化剂ZnO-FeOx/Al2O3。所制备的催化剂用Micromeritics AutoChemⅡ-2920型物理吸附仪进行测试,其比表面积为166m2/g、孔容为0.48cm3/g、平均孔径为11.5nm。
实施例2
在实施例1的步骤4中,将原子层沉积系统内抽真空后通入氮气,调节反应腔出口阀门使腔内压力为130Pa,使反应腔温度维持在200℃,将六氟乙酰丙酮钯加热到60℃,将产生的六氟乙酰丙酮钯蒸汽由氮气带入原子层沉积系统的反应腔内,与FeOx/Al2O3粉体发生反应,反应时间为150s,然后向反应腔内通入氮气冲洗过量六氟乙酰丙酮钯和副产物,时间为100s;向反应腔内通入由氮气携带的水蒸气,反应时间为150s,再向反应腔内通入氮气冲洗,时间为100s,其他步骤与实施例 1相同,得到铁基复合氧化物催化剂PdO-FeOx/Al2O3。所制备的催化剂用 Micromeritics AutoChemⅡ-2920型物理吸附仪进行测试,其比表面积为139m2/g、孔容为0.41cm3/g、平均孔径为11.7nm。
实施例3
在实施例1的步骤4中,将原子层沉积系统内抽真空后通入氮气,调节反应腔出口阀门使腔内压力为80Pa,使反应腔温度维持在150℃,将钛酸四异丙酯加热到60℃,将产生的钛酸四异丙酯蒸汽由氮气带入原子层沉积系统的反应腔内,与 FeOx/Al2O3粉体发生反应,反应时间为100s,然后向反应腔内通入氮气冲洗过量钛酸四异丙酯和副产物,时间为100s;向反应腔内通入由氮气携带的双氧水,反应时间为100s,然后向反应腔内通入氮气冲洗,时间为100s,其他步骤与实施例1 相同,得到铁基复合氧化物催化剂TiO2-FeOx/Al2O3。所制备的催化剂用Micromeritics AutoChemⅡ-2920型物理吸附仪进行测试,其比表面积为186m2/g、孔容为0.66 cm3/g、平均孔径为10.3nm。
实施例4
在实施例1的步骤4中,将原子层沉积系统内抽真空后通入氮气,调节反应腔出口阀门使腔内压力为100Pa,使反应腔温度维持在100℃,将三异丙氧醇钒加热到50℃,将产生的三异丙氧醇钒蒸汽由氮气带入原子层沉积系统的反应腔内,与 FeOx/Al2O3粉体发生反应,反应时间为200s,然后向反应腔内通入氮气冲洗过量三异丙氧醇钒和副产物,时间为100s;向反应腔内通入由氮气携带的水蒸气,反应时间为200s,然后向反应腔内通入氮气冲洗,时间为100s,其他步骤与实施例1 相同,得到铁基复合氧化物催化剂V2O5-FeOx/Al2O3。所制备的催化剂用Micromeritics AutoChemⅡ-2920型物理吸附仪进行测试,其比表面积为156m2/g、孔容为0.57cm3/g、平均孔径为10.8nm。
实施例5
在实施例1的步骤3中,重复步骤2一次,得到FeOx/Al2O3粉体。其他步骤与实施例1相同,得到铁基复合氧化物催化剂ZnO-FeOx/Al2O3。所制备的催化剂用 MicromeriticsAutoChemⅡ-2920型物理吸附仪进行测试,其比表面积为167m2/g、孔容为0.4cm3/g、平均孔径为11.2nm。
实施例6
在实施例3的步骤3中,重复步骤2四次,得到FeOx/Al2O3粉体。其他步骤与实施例3相同,得到铁基复合氧化物催化剂TiO2-FeOx/Al2O3。所制备的催化剂用 MicromeriticsAutoChemⅡ-2920型物理吸附仪进行测试,其比表面积为103m2/g、孔容为0.32cm3/g、平均孔径为8.7nm。
为了证明本发明的有益效果,发明人将实施例1~6制备的催化剂用于CO2氧化乙苯脱氢制苯乙烯,具体试验方法如下:
将400mg催化剂装填到固定床反应器内,反应器内径为4mm,反应温度为 550℃,反应气体总空速(以标准状态计)为6000h-1,反应在常压条件下进行,反应6小时,反应产物用冷浴捕集,气相色谱分析,结果见表1。
表1本发明催化剂催化CO2氧化乙苯脱氢制苯乙烯反应结果
催化剂 | 乙苯转化率 | 苯乙烯选择性 |
实施例1 | 75.31% | 95.18% |
实施例2 | 77.61% | 95.63% |
实施例3 | 85.88% | 96.89% |
实施例4 | 82.33% | 95.56% |
实施例5 | 67.98% | 96.23% |
实施例6 | 68.15% | 95.60% |
由表1可见,本发明采用原子层沉积法制备的铁基复合氧化物催化剂用于CO2氧化乙苯脱氢制苯乙烯,苯乙烯的选择性均可达到95%以上,且乙苯的转化率可达到65%以上,最高可达到85%左右,说明本发明铁基复合氧化物催化剂活性较好,且助剂为TiO2时所得铁基复合氧化物催化剂的活性最佳。
Claims (6)
1.一种用于CO2氧化乙苯脱氢制苯乙烯的铁基复合氧化物催化剂,其特征在于:该催化剂的载体为γ-Al2O3,活性组分为FeOx,助剂为TiO2、PdO、ZnO、V2O5中的任意一种,其采用原子层沉积法按下述步骤制备而成:
(1)将γ-Al2O3粉末加入原子层沉积系统的反应腔内,密封反应腔,将原子层沉积系统内抽真空后通入惰性气体,调节反应腔出口阀门使腔内压力处于负压,反应腔温度维持在300~400 ℃;
(2)向反应腔内注入铁的前驱体,时间为1000~3000 s,然后通入惰性气体冲洗,时间为1000~2000 s;向反应腔内注入第二种反应前驱体,时间为1000~3000 s,再通入惰性气体冲洗,时间为1000~2000 s;
(3)重复步骤(2)一至四次;
(4)将原子层沉积系统内抽真空后通入惰性气体,调节反应腔出口阀门使腔内压力处于负压,反应腔温度维持在100~200 ℃,向反应腔内注入助剂的前驱体,时间为50~300s,然后通入惰性气体冲洗,时间为100~200 s;向反应腔内注入第二种反应前驱体,时间为50~300 s,再通入惰性气体冲洗,时间为100~200 s,得到铁基复合氧化物催化剂;
上述的铁的 前驱体为二茂铁或(2,2,6,6-四甲基-3,5-庚二酮)化铁;
上述的第二种反应前驱体为去离子水、双氧水、氧气、臭氧中的任意一种。
2.根据权利要求1所述的用于CO2氧化乙苯脱氢制苯乙烯的铁基复合氧化物催化剂,其特征在于:在步骤(2)中,向反应腔内注入铁的前驱体,时间为1500~2000 s,然后通入惰性气体冲洗,时间为1000~2000 s;向反应腔内注入第二种反应前驱体,时间为1500~2000s,再通入惰性气体冲洗,时间为1000~2000 s;在步骤(3)中,重复步骤(2)两次。
3.根据权利要求1所述的用于CO2氧化乙苯脱氢制苯乙烯的铁基复合氧化物催化剂,其特征在于:在步骤(4)中,将原子层沉积系统内抽真空后通入惰性气体,调节反应腔出口阀门使腔内压力处于负压,反应腔温度维持在150 ℃,向反应腔内注入TiO2的前驱体,时间为50~200 s,然后通入惰性气体冲洗,时间为100~200 s;向反应腔内注入第二种反应前驱体,时间为50~200 s,再通入惰性气体冲洗,时间为100~200 s,其中所述的TiO2的前驱体为异丙醇钛、叔丁醇钛、氯化钛、四(二甲基氨 基)钛、四(乙基甲基氨 基) 钛中的任意一种。
4.根据权利要求1所述的用于CO2氧化乙苯脱氢制苯乙烯的铁基复合氧化物催化剂,其特征在于:在步骤(4)中,将原子层沉积系统内抽真空后通入惰性气体,调节反应腔出口阀门使腔内压力处于负压,反应腔温度维持在200 ℃,向反应腔内注入PdO的前驱体,时间为100~200 s,然后通入惰性气体冲洗,时间为100~200 s;向反应腔内注入第二种反应前驱体,时间为100~200 s,再通入惰性气体冲洗,时间为100~200 s,其中所述的PdO的前驱体为六氟乙酰丙酮钯、乙酰丙酮钯、二(2,2,6,6-四甲基-3,5-庚二酮酸)钯、(η3-烯丙基)(六氟乙酰丙酮)钯、(η3-烯丙基)(乙酰丙酮)钯、(η3-烯丙基)(环戊二烯基)钯、二甲基双(三甲基膦)钯、二甲基双(三乙基膦)钯中的任意一种。
5.根据权利要求1所述的用于CO2氧化乙苯脱氢制苯乙烯的铁基复合氧化物催化剂,其特征在于:在步骤(4)中,将原子层沉积系统内抽真空后通入惰性气体,调节反应腔出口阀门使腔内压力处于负压,反应腔温度维持在100 ℃,向反应腔内注入ZnO的前驱体,时间为50~100 s,然后通入惰性气体冲洗,时间为100~200 s;向反应腔内注入第二种反应前驱体,时间为50~100 s;再通入惰性气体冲洗,时间为100~200 s,其中所述的ZnO的前驱体为二乙基锌。
6.根据权利要求1所述的用于CO2氧化乙苯脱氢制苯乙烯的铁基复合氧化物催化剂,其特征在于:在步骤(4)中,将原子层沉积系统内抽真空后通入惰性气体,调节反应腔出口阀门使腔内压力处于负压,反应腔温度维持在100 ℃,向反应腔内注入V2O5的前驱体,时间为150~250 s,然后通入惰性气体冲洗,时间为100~200 s;向反应腔内注入第二种反应前驱体,时间为150~250 s,再通入惰性气体冲洗,时间为100~200 s,其中所述的V2O5的前驱体为三异丙氧醇钒、异丙醇钒、乙酰丙酮氧化钒中的任意一种。
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