用等离子体合成的H_2O_2和改性TS-1催化丙烯气相环氧化
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摘要
环氧丙烷(PO)是一种重要的丙烯衍生物。近年来出现的以钛硅沸石(TS-1)为催化剂,以稀H202溶液为氧化剂的丙烯液相环氧化工艺(HPPO),因为环境友好和原子利用率高的绿色化学优点受到广泛关注。相对于液相HPPO工艺而言,在气相中进行丙烯环氧化可以克服溶剂带来的问题,因此更具吸引力。本文利用前期建立的等离子体法“原位”合成H202与TS-1催化丙烯气相环氧化耦合方法(G-HPPO),着重研究了耦合反应条件、廉价法合成TS-1的后改性及TS-1中不同钛物种对G-HPPO反应的影响,并针对非骨架Ti-O-Ti物种的改性进行了深入研究,得到以下结论：
1.在优化条件下,即耦合反应器的上部H2/O2双介质阻挡放电等离子体反应段的输入功率为3.5W,H2和O2进料分别为170ml/min和8ml/min,接地电极循环水温度为5-25℃,下部丙烯气相环氧化反应段的反应温度110℃,改性TS-1(TPAOH水热处理)用量0.2g,丙烯气体进料18ml/min (质量空速10h-1,H2/O2/C3=170/8/18)的条件下,等离子体段H202时空产率为5.7g/(L×h), G-HPPO反应段的丙烯转化率、PO选择性、PO产率和H202有效利用率分别达到13%、97%、1.9kg/(kg×h)和74%。当丙烯进料量增至54ml/min时,PO产率和H202有效利用率可达到2.4kg/(kg×h)和98.4%,比前期研究结果分别提高了10倍和2倍。此外,结合600h连续反应实验和预失活催化剂的原位反应再生实验首次发现,H202在G-HPPO反应条件下对催化剂表面具有自清洁作用,可实时地氧化清除催化剂表面结焦物,从而避免了催化剂失活。
2.结合紫外拉曼光谱(UV Raman)和紫外可见吸收光谱(UV Vis)表征,首次归属了廉价TS-1中存在的无定型Ti-O-Ti物种,其在UV Raman光谱中的吸收峰位于700cm-1处,与UV Vis光谱260-280nm吸收带相对应。无定型Ti-O-Ti物种是导致H202分解和PO酸式副反应、制约廉价TS-1催化性能的主要原因。
3.用少量含硫碱金属盐浸渍并在高温下焙烧处理廉价TS-1,可消除无定型Ti-O-Ti物种的酸性和H202分解活性,有效地改善廉价TS-1的性能。含硫碱金属盐的改性作用与碱金属阳离子的酸性中和作用及硫酸根阴离子与Ti-O-Ti物种形成S-O-Ti物种有关。
4.用TPAOH稀溶液水热处理廉价TS-1也能显著地消除无定型Ti-O-Ti物种的副作用。用扫描透射电镜(STEM/EDX), FT-IR, UV Vis和UV Raman等表征发现,水热处理引起了廉价TS-1晶体形貌、钛物种分布以及骨架钛微环境等变化,表现在晶体内部溶解产生空腔,外部重结晶生长,无定型非骨架钛在重结晶中进入骨架,晶体表面出现骨架钛富集。同时,FT-IR和UV Raman光谱出现850cm-1吸收,而960cm-1吸收峰和1125cm-1吸收峰(拉曼)分别向高波数和低波数位移。
Propylene oxide(PO) is an important propylene derivatives. Recently, a new process HPPO, which shows high environmental benefits and atom utilization, has been commercialized. But HPPO process need large amount of solvent, which causes PO solvolysis and large energy consumption for separation. Gas-phase epoxidation method can effectively avoid liquid solvent problems. Therefore, a gas-phase propylene epoxidation process G-HPPO was reported. In G-HPPO gaseous plasma H2O2directly react with propylene on the surface ofTS-1catalyst to produce PO. In this work, the influences of reaction conditions and catalytic activity on reaction efficiency were studied by optimizing reaction conditions and modifying TS-1catalyst. At the same time, the catalytic performance of TS-1involving different Ti species was also investigated.
1, When the input power of the plasma unit reaches3.5W, the flow rates of H2, O2and propylene are170ml/min,8ml/min and18ml/min (the gaseous H2O2output in plasma unit is308mg/h), the epoxidation temperature is110℃and catalyst loading is0.2g, the propylene conversion and PO selectivity are13%and97%. PO productivity and H2O2utilization arel.9kg/(kg·h) and74%, respectively. When propylene flow rate is54ml/min, PO productivity and H2O2utilization can improved to2.4kg/(kg·h) and98.4%. More importantly, the activity of catalyst remains stable for more than600h. And the catalyst regeneration indicates that the absorption species could be burned by gaseous H2O2, which effectively avoids the inactivity of catalyst in G-HPPO process.
2, Amorphous Ti species in titanium silicalite-1(TS-1) was investigated by UV Raman spectroscopy (UV Raman), UV-Vis diffuse reflectance spectroscopy (UV Vis). A peak at700cm-1in UV Raman, which is corresponding to the UV Vis band at260-280nm, is first assigned to symmetric vibration of hexacoordinated Ti-O-Ti linkages of amorphous Ti species. The existence of amorphous Ti species is the main reason to cause enhanced acidity and H2O2decomposition inTS-1.
3, In order to improve the catalytic performance of TS-1, a small amount of sulfosalt impregnation can effectively reduce the negative effect of amorphous Ti species because of two reasons:(1) inhibiting the acidity of TS-1by metal cations, such as Na+or K+etc;(2) inactivating the ability of H2O2decomposition by formation of the Ti-O-S with anions SO42-.
4, Hydrothermal treatment with TPAOH dilute solution can also reduce the negative effectof amorphous Ti species, then improve the catalytic performance of TS-1. The results of STEM, FT-IR, UV Vis and UV Raman show that TPAOH treatment could change TS-1crystal morphology, redistribute the Ti species in TS-1and modify the chemical micro- environmen of framework Ti. It showed that, TPAOH activation caused many intracrystalline voids, new crystal growth on the top of TS-1and the framework Ti enriched on the surface of TS-1. TPAOH activation also caused the blue shifting of peak at960cm-1(FT-IR and UV Raman spectrum), the red shifting of peak1125cm-1(UV Raman spectrum), as well as, new peak at850cm-1appearing in FT-IR and UV Raman spectrum of treatment TS-1.
1.在优化条件下,即耦合反应器的上部H2/O2双介质阻挡放电等离子体反应段的输入功率为3.5W,H2和O2进料分别为170ml/min和8ml/min,接地电极循环水温度为5-25℃,下部丙烯气相环氧化反应段的反应温度110℃,改性TS-1(TPAOH水热处理)用量0.2g,丙烯气体进料18ml/min (质量空速10h-1,H2/O2/C3=170/8/18)的条件下,等离子体段H202时空产率为5.7g/(L×h), G-HPPO反应段的丙烯转化率、PO选择性、PO产率和H202有效利用率分别达到13%、97%、1.9kg/(kg×h)和74%。当丙烯进料量增至54ml/min时,PO产率和H202有效利用率可达到2.4kg/(kg×h)和98.4%,比前期研究结果分别提高了10倍和2倍。此外,结合600h连续反应实验和预失活催化剂的原位反应再生实验首次发现,H202在G-HPPO反应条件下对催化剂表面具有自清洁作用,可实时地氧化清除催化剂表面结焦物,从而避免了催化剂失活。
2.结合紫外拉曼光谱(UV Raman)和紫外可见吸收光谱(UV Vis)表征,首次归属了廉价TS-1中存在的无定型Ti-O-Ti物种,其在UV Raman光谱中的吸收峰位于700cm-1处,与UV Vis光谱260-280nm吸收带相对应。无定型Ti-O-Ti物种是导致H202分解和PO酸式副反应、制约廉价TS-1催化性能的主要原因。
3.用少量含硫碱金属盐浸渍并在高温下焙烧处理廉价TS-1,可消除无定型Ti-O-Ti物种的酸性和H202分解活性,有效地改善廉价TS-1的性能。含硫碱金属盐的改性作用与碱金属阳离子的酸性中和作用及硫酸根阴离子与Ti-O-Ti物种形成S-O-Ti物种有关。
4.用TPAOH稀溶液水热处理廉价TS-1也能显著地消除无定型Ti-O-Ti物种的副作用。用扫描透射电镜(STEM/EDX), FT-IR, UV Vis和UV Raman等表征发现,水热处理引起了廉价TS-1晶体形貌、钛物种分布以及骨架钛微环境等变化,表现在晶体内部溶解产生空腔,外部重结晶生长,无定型非骨架钛在重结晶中进入骨架,晶体表面出现骨架钛富集。同时,FT-IR和UV Raman光谱出现850cm-1吸收,而960cm-1吸收峰和1125cm-1吸收峰(拉曼)分别向高波数和低波数位移。
Propylene oxide(PO) is an important propylene derivatives. Recently, a new process HPPO, which shows high environmental benefits and atom utilization, has been commercialized. But HPPO process need large amount of solvent, which causes PO solvolysis and large energy consumption for separation. Gas-phase epoxidation method can effectively avoid liquid solvent problems. Therefore, a gas-phase propylene epoxidation process G-HPPO was reported. In G-HPPO gaseous plasma H2O2directly react with propylene on the surface ofTS-1catalyst to produce PO. In this work, the influences of reaction conditions and catalytic activity on reaction efficiency were studied by optimizing reaction conditions and modifying TS-1catalyst. At the same time, the catalytic performance of TS-1involving different Ti species was also investigated.
1, When the input power of the plasma unit reaches3.5W, the flow rates of H2, O2and propylene are170ml/min,8ml/min and18ml/min (the gaseous H2O2output in plasma unit is308mg/h), the epoxidation temperature is110℃and catalyst loading is0.2g, the propylene conversion and PO selectivity are13%and97%. PO productivity and H2O2utilization arel.9kg/(kg·h) and74%, respectively. When propylene flow rate is54ml/min, PO productivity and H2O2utilization can improved to2.4kg/(kg·h) and98.4%. More importantly, the activity of catalyst remains stable for more than600h. And the catalyst regeneration indicates that the absorption species could be burned by gaseous H2O2, which effectively avoids the inactivity of catalyst in G-HPPO process.
2, Amorphous Ti species in titanium silicalite-1(TS-1) was investigated by UV Raman spectroscopy (UV Raman), UV-Vis diffuse reflectance spectroscopy (UV Vis). A peak at700cm-1in UV Raman, which is corresponding to the UV Vis band at260-280nm, is first assigned to symmetric vibration of hexacoordinated Ti-O-Ti linkages of amorphous Ti species. The existence of amorphous Ti species is the main reason to cause enhanced acidity and H2O2decomposition inTS-1.
3, In order to improve the catalytic performance of TS-1, a small amount of sulfosalt impregnation can effectively reduce the negative effect of amorphous Ti species because of two reasons:(1) inhibiting the acidity of TS-1by metal cations, such as Na+or K+etc;(2) inactivating the ability of H2O2decomposition by formation of the Ti-O-S with anions SO42-.
4, Hydrothermal treatment with TPAOH dilute solution can also reduce the negative effectof amorphous Ti species, then improve the catalytic performance of TS-1. The results of STEM, FT-IR, UV Vis and UV Raman show that TPAOH treatment could change TS-1crystal morphology, redistribute the Ti species in TS-1and modify the chemical micro- environmen of framework Ti. It showed that, TPAOH activation caused many intracrystalline voids, new crystal growth on the top of TS-1and the framework Ti enriched on the surface of TS-1. TPAOH activation also caused the blue shifting of peak at960cm-1(FT-IR and UV Raman spectrum), the red shifting of peak1125cm-1(UV Raman spectrum), as well as, new peak at850cm-1appearing in FT-IR and UV Raman spectrum of treatment TS-1.
引文
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