无模板剂ZSM-5沸石分子筛的合成研究
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摘要
ZSM-5沸石由于具有规整的孔道结构,好的热稳定性及较好的水热稳定性,广泛应用于催化材料和吸附材料。以ZSM-5沸石作为催化剂,以甲醇为原料合成汽油的科研成果曾经引起了世界同行的高度评价。此外作为催化剂,ZSM-5沸石在环己烯水合制环己醇方面也展现优良的性能,虽然转化率偏低,但环己醇的选择性达到99%以上,基本没有副产物。然而,ZSM-5沸石的传统合成方法要采用价格昂贵的有机模板剂(TPA+)来制得,成本高,需要高温焙烧脱除,脱除不完全容易造成孔道堵塞,同时造成环境污染。高温焙烧还容易引起沸石小颗粒烧结,不易分散。20世纪80年代Flanigen等报道了无模板剂法合成ZSM-5沸石以来,无模板剂法已经得到了工业化生产。无模板剂法合成ZSM-5沸石时需要严格控制合成液组成和合成条件,否则会产生杂晶或共生。小颗粒沸石晶体有很多优势,采用无模板剂法合成时条件的控制更重要。因此,无模板剂法合成ZSM-5沸石的研究仍然具有重要的学术价值和现实意义。
本文在无有机模板剂条件下采用不同合成方法合成ZSM-5沸石,研究其合成规律。考察了两步变温法中高温预晶化时间和低温晶化时间等因素的影响,研究了预晶化液添加法中预晶化液添加量和组成等对形成的沸石结构与晶型的影响,提出了分步加碱法合成ZSM-5沸石亚微米分散颗粒的新方法。对合成后得到的ZSM-5沸石分子筛做了各种结构性能的表征,并评价了环己烯水合反应性能。主要研究内容和结果如下：
(1)变温两步法合成小颗粒ZSM-5沸石：主要研究了无模板剂转动条件下变温两步法中晶化温度、晶化时间以及高温预晶化时间等因素对合成ZSM-5沸石的影响。在无模板剂存在下,以硅酸钠为硅源采用简单的变温两步法,通过控制高温预晶化时间,在转动烘箱中成功合成了小颗粒ZSM-5沸石团聚体。高温预晶化(190℃)是为了加快反应液的成核,而低温晶化(150℃)是为了获得小的分子筛晶体。采用X射线衍射(XRD),扫描电镜(SEM), NH3程序升温脱附(NH3-TPD)和N2吸附-脱附等技术对合成的ZSM-5沸石进行了表征。与一步法合成的微米级颗粒相比较,两步法合成的小颗粒团聚体ZSM-5沸石具有较高比表面积和相同酸量。得到的沸石的质子酸位占主要部分,路易斯酸位很少,也说明A1基本进入沸石骨架中。
(2)预晶化液添加法合成ZSM-5沸石：主要研究了旋转烘箱中无模板剂条件下预晶化液添加法中预晶化液添加量等因素对合成ZSM-5沸石的影响以及预晶化液和母液组成中Na2O:SiO2比对ZSM-5沸石与MOR沸石转晶的影响。预晶化液由高温(190℃)短时间处理而得,系统研究了预晶化液处理时间和加入量对合成分子筛晶化速率及颗粒大小的影响。采用XRD、SEM、N2吸附-脱附和激光粒度分布(LLS)等分析方法对合成的ZSM-5沸石样品的物化性能进行了表征。研究表明,预晶化液的添加可以明显加快分子筛的晶化速率,预晶化液添加量为33.3wt%时达到最大结晶度的合成时间由未添加时的48h减少到24h。添加预晶化液的母液在150℃晶化24h时所得ZSM-5沸石分子筛团聚体的颗粒大小随着预晶化液加入量的增大而增大,由5.5μM增大到26.3μM。团聚体颗粒的比表面积比未添加预晶化液得到的分子筛(292m2/g)有了不同程度的提高,如添加量为33.3wt%时为394m2/g。对预晶化液添加法合成ZSM-5沸石分子筛团聚体颗粒的生长机理进行了讨论。
(3)ZSM-5与丝光沸石之间的可控转晶：在无模板剂存在下,由于合成ZSM-5沸石的操作范围变窄,晶体很容易发生转晶和共生。本文主要研究在无模板剂的条件下ZSM-5与丝光沸石之间的转晶规律,考察了高温预晶化液的Na2O:SiO2比和预晶化时间以及低温晶化母液的Na2O:SiO2比对于ZSM-5与丝光沸石之间转晶的影响。采用XRD和SEM对合成的产物进行了表征。研究发现,通过改变整体合成液的Na2O:SiO2比,可以有效控制ZSM-5沸石与丝光沸石之间的转晶。当整体反应液的组成为100SiO2:2.5Al2O3:4000H2O时,Na2O:SiO2=0.18是ZSM-5沸石和丝光沸石的一个分界线。通过调节母液的Na2O:SiO2比,使Na2O:SiO2>0.18时,可以使高温预晶化过程中产生的MFI结构的晶体在低温晶化时向丝光沸石发生转晶；使Na2O:SiO2<0.18时,具有MFI和丝光沸石结构共生的晶体在低温晶化时向MFI结构的ZSM-5沸石发生转晶。ZSM-5与丝光沸石之间转晶的前提条件是高温预晶化所形成的晶体的结晶度不能太高(≤30%)。
(4)分步加碱法合成高分散亚微米ZSM-5沸石：报道了在无模板剂存在下,采用分步加碱法合成高分散亚微米ZSM-5沸石。采用XRD、SEM、N2吸附-脱附、固体NMR和粒度分布(DLS)等分析方法对合成的ZSM-5沸石样品的结构性能进行了表征。考察了碱加入量和双氧水加入量等对形成的沸石颗粒的影响。研究表明,采用两次加碱可以得到高分散亚微米ZSM-5沸石。该沸石颗粒大小主要集中在400-500nm之间,具有较高的结晶度。比表面积达到396m2/g。A1基本进入分子筛骨架。
(5)合成ZSM-5沸石环己烯水合催化反应性能研究：考察了自制纳米团簇ZSM-5催化剂与市售催化剂(CBV8014, Zeolyst和NH4-ZSM-5,上海石化研究院)的环己烯水合催化活性。将ZSM-5沸石经过不同后处理条件(酸处理和水热处理)后,考察了其环己烯水合反应的催化性能。研究发现质子酸量与催化活性有关。
Due to unique pore structure, good thermal stability and hydrothermal stability, ZSM-5zeolites were widely used in catalytic materials and adsorption materials. As a catalyst, the gas synthesized by ZSM-5zeolites with methanol as raw materials had caused a highly evaluation of the world scientific research. Moreover as a catalyst, the hydration of cyclohexene catalyzed by ZSM-5zeolites also showed good performance. Although the conversion was low, the selectivity of cyclohexanol was above99%, basically without by-products. However, for synthesis of ZSM-5zeolites, the traditional synthesis methods are to make use of the expensive structure directing agent (SDA). Despite the excellent template effect of TPA+cations, it causes many adverse problems such as high production cost, organic species contained in channel system due to incomplete decomposition and environment problems from thermal decomposition of organic species. Unfortunately, SDA removal to open the zeolite micropores, commonly done through high temperature calcination, has proved unsuitable for colloidal nanocrystals because it leads to significant irreversible aggregation. Since the synthesis of ZSM-5zeolites with the SDA was reported by Flanigen in1980s, the synthesis of ZSM-5zeolites in the absence of SDA for industrial application has been implemented and this method has been reported. From the point of industrial application and environment benign, the synthesis method of ZSM-5zeolite in the absence of SDA still has the important practical significance.
In this paper, the synthesis of ZSM-5zeolites in the absence of SDA with different methods was reported. The factors such as crystallized temperature and time were studied with two-step method. The various factors with nucleation solution method were mainly reported. The crystal transformation between ZSM-5and MOR was studied also. The dispersive and sub-micro ZSM-5zeolites were captured by base source step-feeding method. The physical and chemical properties of ZSM-5zeolites were characterized by various methods. The acquired ZSM-5zeolites were used as catalysts for catalytic reation. This paper is focused on the following several aspects:
(1) Zeolite ZSM-5small particle aggregates were synthesized with two-step method:The factors such as crystallized temperature and time with two-step method were discussed. Zeolite ZSM-5small particle aggregates were synthesized in the absence of template using sodium silicate as silica source by controlling nucleation time at high temperature with a simple two-step method by rotating autoclaves. The first stage at higher temperature is to accelerate the nucleation and the second stage at lower temperature is to obtain the small crystal size the absence of template. The resulting zeolites were characterized by X-Ray Powder Diffraction (XRD), scanning electron microscope (SEM), ammonia temperature-programmed desorption (NH3-TPD) and N2adsorption. Compared with micron-sized zeolite crystals synthesized by a one-step method, zeolite ZSM-5small particle aggregates prepared by the two-step method had higher specific surface area and equivalent acid amount. It is clear that the sample synthesized with the two-step method mainly had Br(?)nsted acid sites and less Lewis acid sites, indicating that the Al atom was incorporated into the framework of zeolite essentially.
(2) ZSM-5zeolite synthesized with nucleation solution method:The effect of adding nucleation solution on the preparation of aggregate ZSM-5zeolite was studied by rotating autoclaves, completely without organic structure-directing agent. The influence on the crystallization rate and particle size was systematically investigated. Physicochemical characteristics derived from XRD, SEM, and N2adsorption. It is indicated that the crystallization rate of the ZSM-5zeolite was increased by the addition of nucleation solution. The crystallization time with adding33.3wt%nucleation solution is24h while without adding nucleation solution is48h. Adding33.3wt%nucleation solution, after crystallization at150℃for24h, the average size of aggregate was increased from5.5μm to26.3μm, the specific surface from292m2/g to394m2/g. The mechanism of the crystal growth of aggregate zeolite ZSM-5 without organic template by nucleation solution method was also discussed in this work.
(3) The crystal transformation of zeolite ZSM-5and mordenite in the absence of organic structure-directing agent was studied in this paper. Zeolite crystals were synthesized at the lower temperature (150℃) by adding nucleation solution prepared at the higher temperature (190℃) into the mother solution. The effects of the ratio and the nucleation time of the nucleation solution, and the ratio of the mother solution on crystal transformation between ZSM-5and mordenite were investigated. By changing the overall SiO2:Al2O3ratio of the whole synthesis solution, the transformation between zeolite ZSM-5and mordenite could be controlled effectively. The Na2O:SiO2ratio of0.18was a boundary between the ZSM-5phase and mordenite phase when the composition of the whole synthesis solution was100SiO2:2.5Al2O3:4000H2O. Let Na2O:SiO2>0.18by altering the composition of the mother solution, the ZSM-5product formed at the higher temperature nucleation stage could be transformed into mordenite crystals at the lower temperature (150℃) crystallization stage; Let Na2O:SiO2<0.18, co-crystalline of ZSM-5and mordenite product obtained at the higher temperature nucleation stage could be transformed into ZSM-5crystals at the lower temperature crystallization stage. The precondition of crystal transformation between ZSM-5and mordenite was that the crystallinity of crystals formed at the higher temperature nucleation stage must be<30%. The crystal morphology of products changed with increasing the Na2O:SiO2ratio in the whole solution.
(4) Dispersive and sub-micro ZSM-5zeolites were prepared with a new base source step-feeding method. It was reported a new base source step-feeding method for obtaining dispersive and sub-micro ZSM-5zeolites. Physicochemical characteristics derived from XRD, NMR, SEM/TEM, DLS and N2adsorption. The effects of addition of H2O2and NaOH during the synthesis process were studied. It indicated that highly dispersed ZSM-5zeolites with400-500run and high crystallinity were aqcuired with alkalinity control method. The specific surface is396m2/g. The Al atom was incorporated into the framework of zeolite essentially.
(5) Hydration of cyclohexene catalyzed by ZSM-5zeolites:The effect of acid properties and acid amount on catalytic activity for hydration of cyclohexene were also investigated. It is found that hydration of cyclohexene was mainly depended on the Bronsted acid sites.
本文在无有机模板剂条件下采用不同合成方法合成ZSM-5沸石,研究其合成规律。考察了两步变温法中高温预晶化时间和低温晶化时间等因素的影响,研究了预晶化液添加法中预晶化液添加量和组成等对形成的沸石结构与晶型的影响,提出了分步加碱法合成ZSM-5沸石亚微米分散颗粒的新方法。对合成后得到的ZSM-5沸石分子筛做了各种结构性能的表征,并评价了环己烯水合反应性能。主要研究内容和结果如下：
(1)变温两步法合成小颗粒ZSM-5沸石：主要研究了无模板剂转动条件下变温两步法中晶化温度、晶化时间以及高温预晶化时间等因素对合成ZSM-5沸石的影响。在无模板剂存在下,以硅酸钠为硅源采用简单的变温两步法,通过控制高温预晶化时间,在转动烘箱中成功合成了小颗粒ZSM-5沸石团聚体。高温预晶化(190℃)是为了加快反应液的成核,而低温晶化(150℃)是为了获得小的分子筛晶体。采用X射线衍射(XRD),扫描电镜(SEM), NH3程序升温脱附(NH3-TPD)和N2吸附-脱附等技术对合成的ZSM-5沸石进行了表征。与一步法合成的微米级颗粒相比较,两步法合成的小颗粒团聚体ZSM-5沸石具有较高比表面积和相同酸量。得到的沸石的质子酸位占主要部分,路易斯酸位很少,也说明A1基本进入沸石骨架中。
(2)预晶化液添加法合成ZSM-5沸石：主要研究了旋转烘箱中无模板剂条件下预晶化液添加法中预晶化液添加量等因素对合成ZSM-5沸石的影响以及预晶化液和母液组成中Na2O:SiO2比对ZSM-5沸石与MOR沸石转晶的影响。预晶化液由高温(190℃)短时间处理而得,系统研究了预晶化液处理时间和加入量对合成分子筛晶化速率及颗粒大小的影响。采用XRD、SEM、N2吸附-脱附和激光粒度分布(LLS)等分析方法对合成的ZSM-5沸石样品的物化性能进行了表征。研究表明,预晶化液的添加可以明显加快分子筛的晶化速率,预晶化液添加量为33.3wt%时达到最大结晶度的合成时间由未添加时的48h减少到24h。添加预晶化液的母液在150℃晶化24h时所得ZSM-5沸石分子筛团聚体的颗粒大小随着预晶化液加入量的增大而增大,由5.5μM增大到26.3μM。团聚体颗粒的比表面积比未添加预晶化液得到的分子筛(292m2/g)有了不同程度的提高,如添加量为33.3wt%时为394m2/g。对预晶化液添加法合成ZSM-5沸石分子筛团聚体颗粒的生长机理进行了讨论。
(3)ZSM-5与丝光沸石之间的可控转晶：在无模板剂存在下,由于合成ZSM-5沸石的操作范围变窄,晶体很容易发生转晶和共生。本文主要研究在无模板剂的条件下ZSM-5与丝光沸石之间的转晶规律,考察了高温预晶化液的Na2O:SiO2比和预晶化时间以及低温晶化母液的Na2O:SiO2比对于ZSM-5与丝光沸石之间转晶的影响。采用XRD和SEM对合成的产物进行了表征。研究发现,通过改变整体合成液的Na2O:SiO2比,可以有效控制ZSM-5沸石与丝光沸石之间的转晶。当整体反应液的组成为100SiO2:2.5Al2O3:4000H2O时,Na2O:SiO2=0.18是ZSM-5沸石和丝光沸石的一个分界线。通过调节母液的Na2O:SiO2比,使Na2O:SiO2>0.18时,可以使高温预晶化过程中产生的MFI结构的晶体在低温晶化时向丝光沸石发生转晶；使Na2O:SiO2<0.18时,具有MFI和丝光沸石结构共生的晶体在低温晶化时向MFI结构的ZSM-5沸石发生转晶。ZSM-5与丝光沸石之间转晶的前提条件是高温预晶化所形成的晶体的结晶度不能太高(≤30%)。
(4)分步加碱法合成高分散亚微米ZSM-5沸石：报道了在无模板剂存在下,采用分步加碱法合成高分散亚微米ZSM-5沸石。采用XRD、SEM、N2吸附-脱附、固体NMR和粒度分布(DLS)等分析方法对合成的ZSM-5沸石样品的结构性能进行了表征。考察了碱加入量和双氧水加入量等对形成的沸石颗粒的影响。研究表明,采用两次加碱可以得到高分散亚微米ZSM-5沸石。该沸石颗粒大小主要集中在400-500nm之间,具有较高的结晶度。比表面积达到396m2/g。A1基本进入分子筛骨架。
(5)合成ZSM-5沸石环己烯水合催化反应性能研究：考察了自制纳米团簇ZSM-5催化剂与市售催化剂(CBV8014, Zeolyst和NH4-ZSM-5,上海石化研究院)的环己烯水合催化活性。将ZSM-5沸石经过不同后处理条件(酸处理和水热处理)后,考察了其环己烯水合反应的催化性能。研究发现质子酸量与催化活性有关。
Due to unique pore structure, good thermal stability and hydrothermal stability, ZSM-5zeolites were widely used in catalytic materials and adsorption materials. As a catalyst, the gas synthesized by ZSM-5zeolites with methanol as raw materials had caused a highly evaluation of the world scientific research. Moreover as a catalyst, the hydration of cyclohexene catalyzed by ZSM-5zeolites also showed good performance. Although the conversion was low, the selectivity of cyclohexanol was above99%, basically without by-products. However, for synthesis of ZSM-5zeolites, the traditional synthesis methods are to make use of the expensive structure directing agent (SDA). Despite the excellent template effect of TPA+cations, it causes many adverse problems such as high production cost, organic species contained in channel system due to incomplete decomposition and environment problems from thermal decomposition of organic species. Unfortunately, SDA removal to open the zeolite micropores, commonly done through high temperature calcination, has proved unsuitable for colloidal nanocrystals because it leads to significant irreversible aggregation. Since the synthesis of ZSM-5zeolites with the SDA was reported by Flanigen in1980s, the synthesis of ZSM-5zeolites in the absence of SDA for industrial application has been implemented and this method has been reported. From the point of industrial application and environment benign, the synthesis method of ZSM-5zeolite in the absence of SDA still has the important practical significance.
In this paper, the synthesis of ZSM-5zeolites in the absence of SDA with different methods was reported. The factors such as crystallized temperature and time were studied with two-step method. The various factors with nucleation solution method were mainly reported. The crystal transformation between ZSM-5and MOR was studied also. The dispersive and sub-micro ZSM-5zeolites were captured by base source step-feeding method. The physical and chemical properties of ZSM-5zeolites were characterized by various methods. The acquired ZSM-5zeolites were used as catalysts for catalytic reation. This paper is focused on the following several aspects:
(1) Zeolite ZSM-5small particle aggregates were synthesized with two-step method:The factors such as crystallized temperature and time with two-step method were discussed. Zeolite ZSM-5small particle aggregates were synthesized in the absence of template using sodium silicate as silica source by controlling nucleation time at high temperature with a simple two-step method by rotating autoclaves. The first stage at higher temperature is to accelerate the nucleation and the second stage at lower temperature is to obtain the small crystal size the absence of template. The resulting zeolites were characterized by X-Ray Powder Diffraction (XRD), scanning electron microscope (SEM), ammonia temperature-programmed desorption (NH3-TPD) and N2adsorption. Compared with micron-sized zeolite crystals synthesized by a one-step method, zeolite ZSM-5small particle aggregates prepared by the two-step method had higher specific surface area and equivalent acid amount. It is clear that the sample synthesized with the two-step method mainly had Br(?)nsted acid sites and less Lewis acid sites, indicating that the Al atom was incorporated into the framework of zeolite essentially.
(2) ZSM-5zeolite synthesized with nucleation solution method:The effect of adding nucleation solution on the preparation of aggregate ZSM-5zeolite was studied by rotating autoclaves, completely without organic structure-directing agent. The influence on the crystallization rate and particle size was systematically investigated. Physicochemical characteristics derived from XRD, SEM, and N2adsorption. It is indicated that the crystallization rate of the ZSM-5zeolite was increased by the addition of nucleation solution. The crystallization time with adding33.3wt%nucleation solution is24h while without adding nucleation solution is48h. Adding33.3wt%nucleation solution, after crystallization at150℃for24h, the average size of aggregate was increased from5.5μm to26.3μm, the specific surface from292m2/g to394m2/g. The mechanism of the crystal growth of aggregate zeolite ZSM-5 without organic template by nucleation solution method was also discussed in this work.
(3) The crystal transformation of zeolite ZSM-5and mordenite in the absence of organic structure-directing agent was studied in this paper. Zeolite crystals were synthesized at the lower temperature (150℃) by adding nucleation solution prepared at the higher temperature (190℃) into the mother solution. The effects of the ratio and the nucleation time of the nucleation solution, and the ratio of the mother solution on crystal transformation between ZSM-5and mordenite were investigated. By changing the overall SiO2:Al2O3ratio of the whole synthesis solution, the transformation between zeolite ZSM-5and mordenite could be controlled effectively. The Na2O:SiO2ratio of0.18was a boundary between the ZSM-5phase and mordenite phase when the composition of the whole synthesis solution was100SiO2:2.5Al2O3:4000H2O. Let Na2O:SiO2>0.18by altering the composition of the mother solution, the ZSM-5product formed at the higher temperature nucleation stage could be transformed into mordenite crystals at the lower temperature (150℃) crystallization stage; Let Na2O:SiO2<0.18, co-crystalline of ZSM-5and mordenite product obtained at the higher temperature nucleation stage could be transformed into ZSM-5crystals at the lower temperature crystallization stage. The precondition of crystal transformation between ZSM-5and mordenite was that the crystallinity of crystals formed at the higher temperature nucleation stage must be<30%. The crystal morphology of products changed with increasing the Na2O:SiO2ratio in the whole solution.
(4) Dispersive and sub-micro ZSM-5zeolites were prepared with a new base source step-feeding method. It was reported a new base source step-feeding method for obtaining dispersive and sub-micro ZSM-5zeolites. Physicochemical characteristics derived from XRD, NMR, SEM/TEM, DLS and N2adsorption. The effects of addition of H2O2and NaOH during the synthesis process were studied. It indicated that highly dispersed ZSM-5zeolites with400-500run and high crystallinity were aqcuired with alkalinity control method. The specific surface is396m2/g. The Al atom was incorporated into the framework of zeolite essentially.
(5) Hydration of cyclohexene catalyzed by ZSM-5zeolites:The effect of acid properties and acid amount on catalytic activity for hydration of cyclohexene were also investigated. It is found that hydration of cyclohexene was mainly depended on the Bronsted acid sites.
引文
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