MCM-49和MCM-22分子筛催化剂上1-丁烯骨架异构化反应的研究
摘要
将MCM-49 和MCM-22 分子筛用于1-丁烯的骨架异构化反应,系统地研究了合成方法、反应温度、1-丁烯空速和分压、Si/Al 比以及反应时间对两种分子筛催化剂性能的影响,发现两种分子筛均适宜在高空速条件下使用,且都具有较高的催化活性。两种分子筛催化剂的适宜反应条件为:T=450℃,WHSV = 42 h-1,P(1-C4=)=0.01 MPa。异丁烯主要通过单分子这一优势机理生成,而副产物则通过双分子二聚(齐聚)-裂解途径生成。
使用硼酸和磷酸对MCM-49 分子筛进行修饰,或采用正硅酸乙酯CVD及碳酸锶对MCM-22 分子筛进行了外表面修饰,结果表明上述方法可以有效消除或钝化分子筛外表面引发副反应的非选择性活性中心,降低分子筛表面酸中心的强度和浓度,改善分子筛的1-丁烯骨架异构化催化性能。位于内表面的中等强度的B 酸中心为丁烯骨架异构化的有效活性中心,而L 酸中心对该反应几乎没有作用。MCM-49和MCM-22分子筛上的丁烯骨架异构化反应,不仅受分子筛的表面酸性影响,还与分子筛的孔道结构有关。
MCM-22 分子筛上积炭的SEM 测试和TG-DTA 分析结果表明,反应后催化剂表面有薄片状或絮状的积炭物质形成;在反应初催化剂的积炭速率较大,且主要在分子筛的外表面形成,之后随反应时间的增加催化剂的积炭量缓慢增加。随反应时间的延长,催化剂表面的强酸中心的强度逐渐降低、数量逐渐减少、比表面逐渐下降,由此导致催化剂的1-丁烯转化率降低,异丁烯的选择性明显提高,并缓慢失活。催化剂表面可溶性积炭主要包含长链的脂肪烃和多环芳烃。随反应时间的增长,MCM-22 分子筛表面形成的不可溶性积炭的H/C 比逐渐降低。催化剂表面形成的积炭的质量、性质、种类主要受催化剂酸性的影响。
The demand of isobutene is continually increased every year because it is widely used in many chemistry industry processes as chemical raw material or reaction intermediates. Skeletal isomerization of 1-butene is of considerable interest as an alternative route to produce isobutene because of the cheapness of raw material and its simple technique. So far, various proton-form zeolites, including ZSM-22, ZSM-23, SAPO-11, and ferrierite (FER) were found to be active catalysts for the selective skeletal isomerization of 1-butene. However, a common problem is that most of the studied catalysts exhibited unsatisfactory selectivity and/or poor stability. Besides, many questions such as the nature of active sites, the role of coke, the reason of deactivation and the reaction mechanism are still unclear. Therefore, it is a highly attractive and challenging research subject to search new and effective catalysts and to solve the basic problems for the skeletal isomerization of 1-butene.
In this work, MCM-49 and MCM-22, two new members of 10-member-ring zeolites, were selected as novel catalysts for the skeletal isomerization of 1-butene. The structure and the physiochemical properties of the zeolites catalysts were
characterized by various characterization means. The relationship between the acidic properties of the catalysts and the catalytic performance was systematically studied. Moreover, the nature of active centers, role of surface acidity and the isomerization mechanism were discussed. The main experimental results and conclusions are list below:
1. Highly crystalline and pure MCM-49 and MCM-22 with high Si/Al ratio are synthesized by improved dynamic and static hydrothermal methods. Compared with the static method, the samples synthesized by dynamic method show higher crystalline level and larger specific surface area. The results of NH3-TPD and FT-IR suggest that the strength and the concentration of Bronsted and Lewis acidity in the sample synthesized by dynamic method were slightly higher than those synthesized by static method.
2. Both MCM-49 and MCM-22 are active for the skeletal isomerization of 1-butene to isobutene. The main side-product is propene, and other side-products like C6 (or above) are undetectable. The catalytic performance of the catalysts can be considerable influenced by various factors, such as preparation method, Si/Al ratio, reaction conditions (temperature, space velocity) etc. Under an optimized reaction conditions (i.e. T = 450oC, WHSV = 42 h-1, P1-C4== 0.01 Mpa, reaction-time = 1 h), the MCM-49 sample (Si/Al=15, dynamic method) shows a 56.5% conversion of 1-butene, and 51.4% selectivity of isobutene, while the MCM-22 sample (Si/Al=15, static method) exhibits a relatively high catalytic performances with 47.9% conversion of 1-butene and 68.3% selectivity of isobutene, which is comparable with the previously reported FER and SAPO-11 zeolites. By the analysis of the reaction data and related references, we believe that the
formation of isobutene is mainly followed a mono-molecule mechanism, while the side-products are formed via a bi-molecule mechanism over the MCM-49 and MCM-22 catalysts.
3. The catalytic performance especially the selectivity to isobutene of MCM-49 can be considerably improved by the controlled treatment with phosphorous acid or boric acid. For example, the isobutene selectivity on the MCM-49 sample (Si/Al = 15, dynamic method) increase from 51.4% to 79.6%, together with a slightly decrease of n-butane conversion after the treatment with 2.5% phosphorous acid. Modification of MCM-22 zeolites (Si/Al = 30, static method) with different deposition agent, such as tetraethoxysilane (TEOS), silicon tetrachloride (SiCl4) etc., can also improve the selectivity of isobutene (i.e. from 67.2% to 82.3%).
4. The results of NH3-TPD, FT-IR and MAS-NMR suggest that the modification of MCM-49 and MCM-22 with different agents could mainly diminish the Br?nsted acidic sites located on the external surface of zeolites, which is believed non-shape selective to isomerization of 1-butene, thus increasing the selectivity to the main product of isobutene. Therefore, the isomerization of 1-butene mainly occurs inside of the microporous channel the zeolites. The Br?nsted acidic sites located on the internal surface of the zeolites are proved to be the main active centers for the selective skeletal isomerization of 1-butene to isobutene. And no obvious role of Lewis sites on the isomerization reaction is detectable over these catalysts. It can be conclude that the catalytic performance of both MCM-49 and MCM-22 could be influenced by the acidic types (L or B acid), acidic strength, acidic density and by the location of the acidic sites (related with the size and space microporous channel).
使用硼酸和磷酸对MCM-49 分子筛进行修饰,或采用正硅酸乙酯CVD及碳酸锶对MCM-22 分子筛进行了外表面修饰,结果表明上述方法可以有效消除或钝化分子筛外表面引发副反应的非选择性活性中心,降低分子筛表面酸中心的强度和浓度,改善分子筛的1-丁烯骨架异构化催化性能。位于内表面的中等强度的B 酸中心为丁烯骨架异构化的有效活性中心,而L 酸中心对该反应几乎没有作用。MCM-49和MCM-22分子筛上的丁烯骨架异构化反应,不仅受分子筛的表面酸性影响,还与分子筛的孔道结构有关。
MCM-22 分子筛上积炭的SEM 测试和TG-DTA 分析结果表明,反应后催化剂表面有薄片状或絮状的积炭物质形成;在反应初催化剂的积炭速率较大,且主要在分子筛的外表面形成,之后随反应时间的增加催化剂的积炭量缓慢增加。随反应时间的延长,催化剂表面的强酸中心的强度逐渐降低、数量逐渐减少、比表面逐渐下降,由此导致催化剂的1-丁烯转化率降低,异丁烯的选择性明显提高,并缓慢失活。催化剂表面可溶性积炭主要包含长链的脂肪烃和多环芳烃。随反应时间的增长,MCM-22 分子筛表面形成的不可溶性积炭的H/C 比逐渐降低。催化剂表面形成的积炭的质量、性质、种类主要受催化剂酸性的影响。
The demand of isobutene is continually increased every year because it is widely used in many chemistry industry processes as chemical raw material or reaction intermediates. Skeletal isomerization of 1-butene is of considerable interest as an alternative route to produce isobutene because of the cheapness of raw material and its simple technique. So far, various proton-form zeolites, including ZSM-22, ZSM-23, SAPO-11, and ferrierite (FER) were found to be active catalysts for the selective skeletal isomerization of 1-butene. However, a common problem is that most of the studied catalysts exhibited unsatisfactory selectivity and/or poor stability. Besides, many questions such as the nature of active sites, the role of coke, the reason of deactivation and the reaction mechanism are still unclear. Therefore, it is a highly attractive and challenging research subject to search new and effective catalysts and to solve the basic problems for the skeletal isomerization of 1-butene.
In this work, MCM-49 and MCM-22, two new members of 10-member-ring zeolites, were selected as novel catalysts for the skeletal isomerization of 1-butene. The structure and the physiochemical properties of the zeolites catalysts were
characterized by various characterization means. The relationship between the acidic properties of the catalysts and the catalytic performance was systematically studied. Moreover, the nature of active centers, role of surface acidity and the isomerization mechanism were discussed. The main experimental results and conclusions are list below:
1. Highly crystalline and pure MCM-49 and MCM-22 with high Si/Al ratio are synthesized by improved dynamic and static hydrothermal methods. Compared with the static method, the samples synthesized by dynamic method show higher crystalline level and larger specific surface area. The results of NH3-TPD and FT-IR suggest that the strength and the concentration of Bronsted and Lewis acidity in the sample synthesized by dynamic method were slightly higher than those synthesized by static method.
2. Both MCM-49 and MCM-22 are active for the skeletal isomerization of 1-butene to isobutene. The main side-product is propene, and other side-products like C6 (or above) are undetectable. The catalytic performance of the catalysts can be considerable influenced by various factors, such as preparation method, Si/Al ratio, reaction conditions (temperature, space velocity) etc. Under an optimized reaction conditions (i.e. T = 450oC, WHSV = 42 h-1, P1-C4== 0.01 Mpa, reaction-time = 1 h), the MCM-49 sample (Si/Al=15, dynamic method) shows a 56.5% conversion of 1-butene, and 51.4% selectivity of isobutene, while the MCM-22 sample (Si/Al=15, static method) exhibits a relatively high catalytic performances with 47.9% conversion of 1-butene and 68.3% selectivity of isobutene, which is comparable with the previously reported FER and SAPO-11 zeolites. By the analysis of the reaction data and related references, we believe that the
formation of isobutene is mainly followed a mono-molecule mechanism, while the side-products are formed via a bi-molecule mechanism over the MCM-49 and MCM-22 catalysts.
3. The catalytic performance especially the selectivity to isobutene of MCM-49 can be considerably improved by the controlled treatment with phosphorous acid or boric acid. For example, the isobutene selectivity on the MCM-49 sample (Si/Al = 15, dynamic method) increase from 51.4% to 79.6%, together with a slightly decrease of n-butane conversion after the treatment with 2.5% phosphorous acid. Modification of MCM-22 zeolites (Si/Al = 30, static method) with different deposition agent, such as tetraethoxysilane (TEOS), silicon tetrachloride (SiCl4) etc., can also improve the selectivity of isobutene (i.e. from 67.2% to 82.3%).
4. The results of NH3-TPD, FT-IR and MAS-NMR suggest that the modification of MCM-49 and MCM-22 with different agents could mainly diminish the Br?nsted acidic sites located on the external surface of zeolites, which is believed non-shape selective to isomerization of 1-butene, thus increasing the selectivity to the main product of isobutene. Therefore, the isomerization of 1-butene mainly occurs inside of the microporous channel the zeolites. The Br?nsted acidic sites located on the internal surface of the zeolites are proved to be the main active centers for the selective skeletal isomerization of 1-butene to isobutene. And no obvious role of Lewis sites on the isomerization reaction is detectable over these catalysts. It can be conclude that the catalytic performance of both MCM-49 and MCM-22 could be influenced by the acidic types (L or B acid), acidic strength, acidic density and by the location of the acidic sites (related with the size and space microporous channel).
引文
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