SAPO-34催化剂的制备及在甲醇制烯烃反应中的应用
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摘要
全球石油资源的日益匮乏,加上乙烯、丙烯等下游化工产品需求量的不断增大,极大地推动了非石油路线制备低碳烯烃工艺的发展。煤炭、天然气或生物质经由甲醇制取烯烃工艺是目前认为最具应用前景的路线。其中,制约这一工艺路线的关键是甲醇制低碳烯烃(Methanol-to-Olefin,简称MTO)过程中的催化剂。
由于孔径较小(0.43-0.50nm)、酸性适中、水热稳定性较强,SAPO-34分子筛被认为是MTO工艺的最佳催化剂。然而,由于MTO反应的强放热和传统SAPO-34分子筛表面过高的酸密度导致催化剂快速失活,加上较低的烯烃选择性和较差的耐磨性能,使得SAPO-34难以满足工业流化床工艺的要求。本研究从硅源、模板剂、催化剂的粒径等方面对水热晶化合成法制备SAPO-34的工艺进行了系统的研究,并对过程的主要影响因素进行了优化；同时以煅烧高岭土为载体,发展了原位水热合成工艺；探索了适合流化床工艺的、高活性、长寿命的工业催化剂的制备方法,取得了如下主要研究成果。
研究了硅源分散性对合成SAPO-34分子筛性能的影响。以盐酸为调节剂,氟化铵为分散剂有效地提高了硅源的分散性。以此为硅源,在相同硅铝比的条件下合成SAPO-34分子筛,可有效地抑制SAPO-5杂晶生成,减小其晶粒尺寸,从而提高催化剂在MTO反应中对低碳烯烃(C2=-C4=)的选择性,显著延长了其单程反应寿命。Ni改性高分散硅源后,会引起大量SAPO-5晶粒的产生和SAPO-34酸中心性能的变化,最终导致烯烃选择性的显著下降。
采用TEA/TEAOH混合模板剂合成了SAPO-34分子筛。研究了混合模板剂的组成对SAPO-34分子筛的化学组成、形貌、晶粒尺寸、Si嵌入方式以及对MTO反应催化性能的影响。结果表明,合成的SAPO-34分子筛催化的MTO反应具有相似的活性和产物分布。当模板剂TEAOH/TEA在0.05～0.1时,可合成出具有大量弱酸中心、适宜酸强度和纯的SAPO-34分子筛。当TEAOH/TEA等于0.1时合成的SAPO-34分子筛对MTO反应的C2=-C4=选择性达到95.9%,催化剂单程寿命达到430min,优于使用单一TEA或TEAOH为模板剂合成的SAPO-34催化剂。
采用两步水热晶化工艺,结合H202脱除模板法成功制备了粒径为160～550nm的SAPO-34分子筛。合成的SAPO-34具有相似的CHA结构、类立方体形貌和Si/(AL+P+Si)比。随着SAPO-34催化剂粒径的减小,对MTO反应的催化活性明显增强、催化剂寿命明显延长。采用粒径为160nm的SAPO-34催化MTO反应时,低碳烯烃选择性可达94.8%,单程寿命延长至596min。
以TEAOH和TEA为模板剂,平均粒径60μm的煅烧高岭土微球(CKM)为载体,采用原位水热晶化工艺在CKM表面合成了SAPO-34分子筛。考察了不同的预处理条件对合成SAPO-34/CKM催化剂性能的影响。结果表明,经过NaOH溶液处理,可显著改善在CKM表面上SAPO-34晶粒的生长。通过调整NaOH溶液的浓度(4-14%),可有效调控高岭土微球的化学组成和结构,进而影响合成催化剂的性能。随着NaOH溶液浓度的增加,CKM载体表面的Si2p/Al2p的比例降低,表面的粗糙程度增加。用4%NaOH处理的CKM为载体原位合成的SAPO-34/4-CKM催化剂用于MTO反应时具有高的甲醇转化率(100%)和低碳烯烃选择性(90%)、长寿命(964min)以及较高的耐磨性能。
以硅溶胶和磷酸铝溶胶为主胶粘剂和粘结助剂,采用喷雾成型工艺制备出SAPO-34基高岭土微球催化剂。采用碱处理-酸交换工艺处理的高岭土微球为载体原位水热法合成了SAPO-34/高岭土负载型催化剂。对于流化床MTO反应,使用所制备的SAPO-34基高岭土微球催化剂和SAPO-34/高岭土负载型催化剂,低碳烯烃选择性可分别达到94.8%和93.1%,磨耗率分别为1.28%/h和0.72%/h。
The increasing shortage of the crude oil and the growing need of light olefins, such as ethylene and propylene, have greatly stimulated the development of the alternative non-oil routes for light olefins production. Up to date, methanol to olefins (MTO) coupled with transformation of coal or natural gas to methanol has been considered as the most promising route with an economic advantage. However, the catalyst for MTO is still a challenge.
SAPO-34, a silicoaluminophosphate molecular sieve with CHA structure, due to the moderate acid strength, relatively small pores (0.43nm) and hydrothermal stability, appears to be most attractive and many research works have been reported relating to its synthesis and crystallization mechanism, catalytic properties and catalytic reaction mechanisms for MTO reaction. However, as a microporous zeolite material, the traditional SAPO-34catalyst with the high density of strong acid sites and poor abrasive resistance is known to suffer rapid deactivation easily by carbon deposition in the strong exothermic MTO reaction, thereby leading to a rapid decrease of the catalytic performance and short lifetime.
In this dissertation, the SAPO-34catalyst was prepared hydro thermally and optimizedly and the effects of dispersity of silica source, mixed templates etc on the particles size and properties of SAPO-34samples were studied in detail. SAPO-34on the calcined kaolin microspheres was in-situ hydrothermal synthesized successfully. The spherical SAPO-34catalyst used in fluidic bed reactor with high catalytic activity and long lifetime was explored. The main results obtained are as follows.
The effect of the dispersity of silica source on the properties of SAPO-34was investigated. It is found that the dispersity of silica source after adding HCl as modifier and NH4F as dispersant could be obviously enhanced. When this high-dispersity silica was used as a precursor, is it in favor of preparing the sample with very low SAPO-5content and small size. As a result, the catalytic selectivity in MTO reaction can be improved and the single-pass lifetime can be prolonged. The incorporation of Ni in the preparation process of SAPO-34leads to an increase of the SAPO-5and a change of the acidic site in the samples, resulting in a decrease of the selectivity to olefins.
The effect of the mixed template of TEA and TEAOH on the properties of SAPO-34molecular sieve was studied. The results show that, the chemical composition, morphology. crystal size and Si incorporation and the catalytic activity and single-pass lifetime in MTO reaction of SAPO-34can be influenced by the ratio of TEAOH/TEA. When the TEAOH/TEA ratio of0.05-0.1was used, the SAPO-34molecular sieves dominated by weak acid sites with moderate acid strength can be prepared. Using the SAPO-34catalyst prepared with the mixed complete of TEAOH/TEA=0.1, the C2--C4-selectivity and lifetime of the catalyst reached the maximum of95.9%and430min, respectively, which is obviously superior to that SAPO-34prepared by single TEA or TEAOH template.
SAPO-34molecular sieve with crystalline size of160～550nm were synthesized by a two-step varying-temperature hydrothermal crystallization and H2O2solution de-template method. The obtained SAPO-34exhibits the similar CHA structure, cubic-like morphology and ratio of Si/(Al+P+Si) to traditional SAPO-34. With the reduction in the crystalline size of SAPO-34catalyst, its conversion of methanol to olefins, the catalytic activity and single-pass lifetime obviously increase. When the160nm SAPO-34prepared was used as the catalyst for MTO, the olefins selectivity and single-pass lifetime can reach over94.8%and596min, respectively.
Supported SAPO-34catalyst on the fully calcined kaolin particles (CKMs) with the average size of60μm was synthesized in situ successfully, in which CKMs were pretreated by NaOH solution and the mixture of TEAOH and TEA was used as a template. The chemical composition and the morphology of the kaolin microsphere and supported SAPO-34catalyst prepared can be modulated by the concentration of NaOH of4-14%. With the increasing of the concentration of the NaOH solution, the Si2p/Al2p ratio on the surface of CKMs decreases and the surface roughness of CKMs increases. Using CKMs pretreated by4%NaOH solution as the support, SAPO-34in situ grown on CKMs exhibits the high methanol conversion (100%), longest single-pass lifetime (964min) and strongest abrasive resistance.
Using silica gel and aluminium phosphate as the main adhesive and auxiliary agent, SAPO-34-based kaolin microspheres were prepared by a spray-drying method. SAPO-34/kaolin supported catalyst was prepared by in situ hydrothermal process onto the surface of the calcined kaolin microspheres pretreated by alkali solution treatment and subsequent acid exchange. In the testing with fluid-bed MTO reactor system, the selectivities of the olefins over the prepared SAPO-34-based kaolin microspheres and SAPO-34/kaolin supported catalyst can reach94.8%and93.1%, respectively. And the attrition rates of two catalysts are1.28%/h and0.72%/h, respectively.
由于孔径较小(0.43-0.50nm)、酸性适中、水热稳定性较强,SAPO-34分子筛被认为是MTO工艺的最佳催化剂。然而,由于MTO反应的强放热和传统SAPO-34分子筛表面过高的酸密度导致催化剂快速失活,加上较低的烯烃选择性和较差的耐磨性能,使得SAPO-34难以满足工业流化床工艺的要求。本研究从硅源、模板剂、催化剂的粒径等方面对水热晶化合成法制备SAPO-34的工艺进行了系统的研究,并对过程的主要影响因素进行了优化；同时以煅烧高岭土为载体,发展了原位水热合成工艺；探索了适合流化床工艺的、高活性、长寿命的工业催化剂的制备方法,取得了如下主要研究成果。
研究了硅源分散性对合成SAPO-34分子筛性能的影响。以盐酸为调节剂,氟化铵为分散剂有效地提高了硅源的分散性。以此为硅源,在相同硅铝比的条件下合成SAPO-34分子筛,可有效地抑制SAPO-5杂晶生成,减小其晶粒尺寸,从而提高催化剂在MTO反应中对低碳烯烃(C2=-C4=)的选择性,显著延长了其单程反应寿命。Ni改性高分散硅源后,会引起大量SAPO-5晶粒的产生和SAPO-34酸中心性能的变化,最终导致烯烃选择性的显著下降。
采用TEA/TEAOH混合模板剂合成了SAPO-34分子筛。研究了混合模板剂的组成对SAPO-34分子筛的化学组成、形貌、晶粒尺寸、Si嵌入方式以及对MTO反应催化性能的影响。结果表明,合成的SAPO-34分子筛催化的MTO反应具有相似的活性和产物分布。当模板剂TEAOH/TEA在0.05～0.1时,可合成出具有大量弱酸中心、适宜酸强度和纯的SAPO-34分子筛。当TEAOH/TEA等于0.1时合成的SAPO-34分子筛对MTO反应的C2=-C4=选择性达到95.9%,催化剂单程寿命达到430min,优于使用单一TEA或TEAOH为模板剂合成的SAPO-34催化剂。
采用两步水热晶化工艺,结合H202脱除模板法成功制备了粒径为160～550nm的SAPO-34分子筛。合成的SAPO-34具有相似的CHA结构、类立方体形貌和Si/(AL+P+Si)比。随着SAPO-34催化剂粒径的减小,对MTO反应的催化活性明显增强、催化剂寿命明显延长。采用粒径为160nm的SAPO-34催化MTO反应时,低碳烯烃选择性可达94.8%,单程寿命延长至596min。
以TEAOH和TEA为模板剂,平均粒径60μm的煅烧高岭土微球(CKM)为载体,采用原位水热晶化工艺在CKM表面合成了SAPO-34分子筛。考察了不同的预处理条件对合成SAPO-34/CKM催化剂性能的影响。结果表明,经过NaOH溶液处理,可显著改善在CKM表面上SAPO-34晶粒的生长。通过调整NaOH溶液的浓度(4-14%),可有效调控高岭土微球的化学组成和结构,进而影响合成催化剂的性能。随着NaOH溶液浓度的增加,CKM载体表面的Si2p/Al2p的比例降低,表面的粗糙程度增加。用4%NaOH处理的CKM为载体原位合成的SAPO-34/4-CKM催化剂用于MTO反应时具有高的甲醇转化率(100%)和低碳烯烃选择性(90%)、长寿命(964min)以及较高的耐磨性能。
以硅溶胶和磷酸铝溶胶为主胶粘剂和粘结助剂,采用喷雾成型工艺制备出SAPO-34基高岭土微球催化剂。采用碱处理-酸交换工艺处理的高岭土微球为载体原位水热法合成了SAPO-34/高岭土负载型催化剂。对于流化床MTO反应,使用所制备的SAPO-34基高岭土微球催化剂和SAPO-34/高岭土负载型催化剂,低碳烯烃选择性可分别达到94.8%和93.1%,磨耗率分别为1.28%/h和0.72%/h。
The increasing shortage of the crude oil and the growing need of light olefins, such as ethylene and propylene, have greatly stimulated the development of the alternative non-oil routes for light olefins production. Up to date, methanol to olefins (MTO) coupled with transformation of coal or natural gas to methanol has been considered as the most promising route with an economic advantage. However, the catalyst for MTO is still a challenge.
SAPO-34, a silicoaluminophosphate molecular sieve with CHA structure, due to the moderate acid strength, relatively small pores (0.43nm) and hydrothermal stability, appears to be most attractive and many research works have been reported relating to its synthesis and crystallization mechanism, catalytic properties and catalytic reaction mechanisms for MTO reaction. However, as a microporous zeolite material, the traditional SAPO-34catalyst with the high density of strong acid sites and poor abrasive resistance is known to suffer rapid deactivation easily by carbon deposition in the strong exothermic MTO reaction, thereby leading to a rapid decrease of the catalytic performance and short lifetime.
In this dissertation, the SAPO-34catalyst was prepared hydro thermally and optimizedly and the effects of dispersity of silica source, mixed templates etc on the particles size and properties of SAPO-34samples were studied in detail. SAPO-34on the calcined kaolin microspheres was in-situ hydrothermal synthesized successfully. The spherical SAPO-34catalyst used in fluidic bed reactor with high catalytic activity and long lifetime was explored. The main results obtained are as follows.
The effect of the dispersity of silica source on the properties of SAPO-34was investigated. It is found that the dispersity of silica source after adding HCl as modifier and NH4F as dispersant could be obviously enhanced. When this high-dispersity silica was used as a precursor, is it in favor of preparing the sample with very low SAPO-5content and small size. As a result, the catalytic selectivity in MTO reaction can be improved and the single-pass lifetime can be prolonged. The incorporation of Ni in the preparation process of SAPO-34leads to an increase of the SAPO-5and a change of the acidic site in the samples, resulting in a decrease of the selectivity to olefins.
The effect of the mixed template of TEA and TEAOH on the properties of SAPO-34molecular sieve was studied. The results show that, the chemical composition, morphology. crystal size and Si incorporation and the catalytic activity and single-pass lifetime in MTO reaction of SAPO-34can be influenced by the ratio of TEAOH/TEA. When the TEAOH/TEA ratio of0.05-0.1was used, the SAPO-34molecular sieves dominated by weak acid sites with moderate acid strength can be prepared. Using the SAPO-34catalyst prepared with the mixed complete of TEAOH/TEA=0.1, the C2--C4-selectivity and lifetime of the catalyst reached the maximum of95.9%and430min, respectively, which is obviously superior to that SAPO-34prepared by single TEA or TEAOH template.
SAPO-34molecular sieve with crystalline size of160～550nm were synthesized by a two-step varying-temperature hydrothermal crystallization and H2O2solution de-template method. The obtained SAPO-34exhibits the similar CHA structure, cubic-like morphology and ratio of Si/(Al+P+Si) to traditional SAPO-34. With the reduction in the crystalline size of SAPO-34catalyst, its conversion of methanol to olefins, the catalytic activity and single-pass lifetime obviously increase. When the160nm SAPO-34prepared was used as the catalyst for MTO, the olefins selectivity and single-pass lifetime can reach over94.8%and596min, respectively.
Supported SAPO-34catalyst on the fully calcined kaolin particles (CKMs) with the average size of60μm was synthesized in situ successfully, in which CKMs were pretreated by NaOH solution and the mixture of TEAOH and TEA was used as a template. The chemical composition and the morphology of the kaolin microsphere and supported SAPO-34catalyst prepared can be modulated by the concentration of NaOH of4-14%. With the increasing of the concentration of the NaOH solution, the Si2p/Al2p ratio on the surface of CKMs decreases and the surface roughness of CKMs increases. Using CKMs pretreated by4%NaOH solution as the support, SAPO-34in situ grown on CKMs exhibits the high methanol conversion (100%), longest single-pass lifetime (964min) and strongest abrasive resistance.
Using silica gel and aluminium phosphate as the main adhesive and auxiliary agent, SAPO-34-based kaolin microspheres were prepared by a spray-drying method. SAPO-34/kaolin supported catalyst was prepared by in situ hydrothermal process onto the surface of the calcined kaolin microspheres pretreated by alkali solution treatment and subsequent acid exchange. In the testing with fluid-bed MTO reactor system, the selectivities of the olefins over the prepared SAPO-34-based kaolin microspheres and SAPO-34/kaolin supported catalyst can reach94.8%and93.1%, respectively. And the attrition rates of two catalysts are1.28%/h and0.72%/h, respectively.
引文
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