一维中孔分子筛的合成及其对烷烃临氢异构性能的影响
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摘要
长链正构烷烃临氢异构催化剂可以将影响柴油和润滑油低温流动性能的正构烷烃支链化,并将其转化为油品中的有效成份,所以研究和开发长链正构烷烃临氢异构催化剂,对提高柴油和润滑油品质及增加油品收率有重要意义。通常认为烷烃临氢异构所用的双功能催化剂采用中等强度酸性、一维中孔分子筛作为酸性载体,贵金属Pt或Pd作为金属组分,对长链正构烷烃具有高异构选择性。一维中孔分子筛的研究通常集中在比较其与有交叉孔道或大孔分子筛对正构烷烃临氢异构的影响,而对一维中孔分子筛之间临氢异构性能差别的研究较少。因此,研究一维中孔分子筛的合成及其载Pt催化剂的正构烷烃临氢异构性能,对开发高性能长链烷烃临氢异构催化剂,具有重要的现实意义。
本论文采用水热法合成了四种典型的一维中孔分子筛SAPO-41、SAPO-11、ZSM-12和ZSM-22,利用XRD、SEM、N2吸附脱附、XRF、MAS NMR、TG等手段表征了分子筛样品的晶相、相对结晶度、形貌、孔性质、元素组成、原子环境和孔内包含物等性质。合成的四种一维中孔分子筛结晶度均较高,热稳定性好。对合成SAPO-41和ZSM-12的影响因素进行了系统研究,确定了合成纯相SAPO-41和ZSM-12的参数范围。采用逐步升温法改进了SAPO-41分子筛合成方法,该法可以将晶化时间由50h缩短到35h,并且能够引入较多的Si,提高了SAPO-41分子筛酸性位数量。当采用高孔容拟薄水铝石作为铝源合成SAPO-41时,发现首先生成大量SAPO-11,然后完全转化为SAPO-41。同时为了降低ZSM-12的酸强度,合成了富铝的ZSM-12分子筛。
对一维中孔分子筛SAPO-41、SAPO-11、ZSM-12和ZSM-22的孔道性质和酸性进行了讨论。利用微反装置研究了一维中孔分子筛载铂催化剂上正十二烷的临氢异构性能,催化评价结果表明,Pt/ZSM-12和Pt/ZSM-22活性高于Pt/SAPO-11和Pt/SAPO-41,Pt/SAPO-11、Pt/SAPO-41和Pt/ZSM-22催化剂的异构选择性较高, n-C_(12)转化率为85%-90%时,异构收率达到最大值70%-78%。Pt/SAPO-11、Pt/SAPO-41和Pt/ZSM-22上目的产物-端甲基十二烷异构体选择性较Pt/ZSM-12高,并且只有Pt/ZSM-12的产物中包含具有大孔分子筛特征产物的乙基十二烷异构体。Pt/SAPO-11、Pt/SAPO-41和Pt/ZSM-22上的裂化产物随碳数变化基本呈对称分布,而Pt/ZSM-12催化剂上的裂化产物由于二次裂化随碳数变化呈现不对称的分布。
探讨了烷烃临氢异构的反应机理,以及一维中孔分子筛的酸性和孔道结构对其载铂催化剂上正十二烷临氢异构性能的影响。一维中孔分子筛的酸性主要影响正十二烷临氢异构的反应活性,特别是较低温度时的反应活性。正十二烷临氢异构反应的异构选择性主要由孔道结构决定,十二元环的Pt/ZSM-12上各种单甲基十二烷异构体的含量与PCP假说相近,而十元环的Pt/SAPO-11、Pt/SAPO-41和Pt/ZSM-22上端甲基十二烷异构体含量相比PCP假说较多。
根据一维中孔分子筛载铂催化剂上正十二烷的临氢异构结果和正碳离子机理,建立了一维中孔分子筛载铂催化剂上烷烃临氢异构反应网络,并给出了各反应的动力学方程,分子筛酸性和孔道结构分别影响反应速率方程中的本征速率常数和吸附平衡常数,从而造成催化反应速率不同。
为增强烷烃吸附性能,在制备SAPO-11分子筛的反应混合物中,引入碳黑作为介孔模板剂,制备了含有10nm-30nm直径介孔的中孔与介孔复合SAPO-11。该中孔与介孔复合SAPO-11的结晶度较高,具有和常规SAPO-11相近的酸性。载Pt中孔与介孔复合SAPO-11催化剂上的正十二烷临氢异构反应表明,与常规SAPO-11制备的催化剂相比,该催化剂在563K的较低反应温度下,具有较高的异构选择性和异构收率,分别达到92.6%和83.1%。在与工业相近的操作条件下,研究了操作条件对Pt/中孔与介孔复合SAPO-11催化剂上烷烃临氢异构化性能的影响,并对Pt/中孔与介孔复合SAPO-11催化剂寿命进行了评价。实验结果表明,Pt/中孔与介孔复合SAPO-11催化剂在与工业相近的反应条件下,同样具有良好的反应活性和异构选择性,分别达到36.7%和95%,并且在与工业相近的反应压力和氢烷摩尔比条件下,该催化剂具有较好的稳定性。
The removal of long chain normal paraffins from diesel and lubricating oils is essential to produce oils with acceptable cold flow property. Long-chain n-alkane hydroisomerization catalysts can isomerize normal paraffins to isoparaffins which are efficient parts in the oils. Therefore, it is significant to develop high quality long-chain n-alkane hydroisomerization catalysts for excellent properties of diesel or lubricating oils and more oils yield. Bifunctional catalysts with mild strength acid, monodimentional medium-pore molecular sieve as acid function and Pt or Pd as metal function are generally found to be high isomers selective. Otherwise the monodimentional medium-pore molecular sieves are of different types and properties, and n-alkane hydroisomerization porformances of monodimentional medium-pore molecular sieves were seldom researched. Thus it is of actual benefit to research synthesis of monodimentional medium-pore molecular sieves and their effects on n-alkane hydroisomerization porformances.
In this paper, four typical monodimentional medium-pore molecular sieves SAPO-41, SAPO-11, ZSM-12 and ZSM-22 were synthesized with hydrothermal method and characterized by XRD, SEM, N2 adsorption desorption, XRF, MAS NMR, TG for crystalline phase, crystallinity, morphology, pore properties, elemental composition, atom environment, embraced materials. The samples of SAPO-41, SAPO-11, ZSM-12 and ZSM-22 obtained were highly crystallized and thermally stablized. The influencing factors of SAPO-41 and ZSM-12 syntheses were sysmetically researched, and the condition regions of pure SAPO-41 and ZSM-12 were determined. Gradual Heating was used to synthesize SAPO-41, the crystallization time was reduced from 50h to 35h, and more Si was induced resulting in more acid sites with this method. When the pseudo-boehmite with higher pore volume was used, a large amount of SAPO-11 was occured and then thansformed to SAPO-41 completely. Al-rich ZSM-12 was synthesized in order to reduce its acid strength.
The pore channel structute and acidity of SAPO-41, SAPO-11, ZSM-12 and ZSM-22 were discussed. The hydroisomerization performances of n-dodecane over Pt/monodimentional medium-pore molecular sieves were tested. The catalytic performances indicate that the activities of n-dodecane over Pt/ZSM-12 and Pt/ZSM-22 are higher than that over Pt/SAPO-11 and Pt/SAPO-41, in the meantime Pt/SAPO-11, Pt/SAPO-41 and Pt/ZSM-22 show higher isomers selectivity which reaches 70~80% under 85%-90% n-C_(12) conversion. The selectivity of objective products namely end-methyl-C_(11) over Pt/SAPO-11, Pt/SAPO-41 and Pt/ZSM-22 is higher than that over Pt/ZSM-12, and only Pt/ZSM-12 produces ethyl-C_(10) which is usually occurred over large-pore molecular sieves. The cracked products are symmetrical with carben number over Pt/SAPO-11, Pt/SAPO-41 and Pt/ZSM-22, and they are asymmetrical over Pt/ZSM-12 due to secondary cracking.
The n-alkane hydroisomerization mechanisms and the effects of acdity and pore channel structure on n-dodecane hydroisomerization were discussed. The conversion activity of n-dodecane is dependent on the acidity of molecular sieves, especially at low temperature. And the selectivity to isomers in hydroisomerization of n-dodecane is highly influenced by the pore channel structure of molecular sieves. The contents of methyl isomers over 12-ring Pt/ZSM-12 are close to that of PCP hypothesis, and 10-ring Pt/SAPO-11, Pt/SAPO-41 and Pt/ZSM-22 produce more end-methyl-C11.
The reaction scheme of n-alkane hydroisomerization over monodimentional medium-pore molecular sieves loaded with Pt was established according to the catalytic results and n-alkane carboncation mechanism, and the kinetic equations were provided. The intrinsic rate constant and physisorption equilibrium contant are determined by the acidity or pore channel structure, respectively, and then lead to the diffences of n-alkane hydroisomerization rate.
Mesoporous SAPO-11 was synthesized hydrothermally by using carbon black and di-n-propylamime (DPA) as templates for the expected mesopores and micropores, respectively. Mesoporous SAPO-11 was highly crystallized and the mesopore diameters are in range of 10nm-30nm. Mesoporous SAPO-11 has the same acidity with conventional one. The mesoporous SAPO-11 exhibited higher isomers selectivity (92.6%) and yield (83.1%) compared with conventional one at low reaction temperature 563K. The performance of n-dodecane hydroisomerization over Pt/mesoporous SAPO-11 was examined under industrial conditions. And the long term property was also evaluated. The results indicate that Pt/mesoporous SAPO-11 showed good reaction activity (36.7%) and isomers slectivity (95%). And that catalyst shows good stability under industrial reaction pressure and H_2/n-C_(12) ratio.
本论文采用水热法合成了四种典型的一维中孔分子筛SAPO-41、SAPO-11、ZSM-12和ZSM-22,利用XRD、SEM、N2吸附脱附、XRF、MAS NMR、TG等手段表征了分子筛样品的晶相、相对结晶度、形貌、孔性质、元素组成、原子环境和孔内包含物等性质。合成的四种一维中孔分子筛结晶度均较高,热稳定性好。对合成SAPO-41和ZSM-12的影响因素进行了系统研究,确定了合成纯相SAPO-41和ZSM-12的参数范围。采用逐步升温法改进了SAPO-41分子筛合成方法,该法可以将晶化时间由50h缩短到35h,并且能够引入较多的Si,提高了SAPO-41分子筛酸性位数量。当采用高孔容拟薄水铝石作为铝源合成SAPO-41时,发现首先生成大量SAPO-11,然后完全转化为SAPO-41。同时为了降低ZSM-12的酸强度,合成了富铝的ZSM-12分子筛。
对一维中孔分子筛SAPO-41、SAPO-11、ZSM-12和ZSM-22的孔道性质和酸性进行了讨论。利用微反装置研究了一维中孔分子筛载铂催化剂上正十二烷的临氢异构性能,催化评价结果表明,Pt/ZSM-12和Pt/ZSM-22活性高于Pt/SAPO-11和Pt/SAPO-41,Pt/SAPO-11、Pt/SAPO-41和Pt/ZSM-22催化剂的异构选择性较高, n-C_(12)转化率为85%-90%时,异构收率达到最大值70%-78%。Pt/SAPO-11、Pt/SAPO-41和Pt/ZSM-22上目的产物-端甲基十二烷异构体选择性较Pt/ZSM-12高,并且只有Pt/ZSM-12的产物中包含具有大孔分子筛特征产物的乙基十二烷异构体。Pt/SAPO-11、Pt/SAPO-41和Pt/ZSM-22上的裂化产物随碳数变化基本呈对称分布,而Pt/ZSM-12催化剂上的裂化产物由于二次裂化随碳数变化呈现不对称的分布。
探讨了烷烃临氢异构的反应机理,以及一维中孔分子筛的酸性和孔道结构对其载铂催化剂上正十二烷临氢异构性能的影响。一维中孔分子筛的酸性主要影响正十二烷临氢异构的反应活性,特别是较低温度时的反应活性。正十二烷临氢异构反应的异构选择性主要由孔道结构决定,十二元环的Pt/ZSM-12上各种单甲基十二烷异构体的含量与PCP假说相近,而十元环的Pt/SAPO-11、Pt/SAPO-41和Pt/ZSM-22上端甲基十二烷异构体含量相比PCP假说较多。
根据一维中孔分子筛载铂催化剂上正十二烷的临氢异构结果和正碳离子机理,建立了一维中孔分子筛载铂催化剂上烷烃临氢异构反应网络,并给出了各反应的动力学方程,分子筛酸性和孔道结构分别影响反应速率方程中的本征速率常数和吸附平衡常数,从而造成催化反应速率不同。
为增强烷烃吸附性能,在制备SAPO-11分子筛的反应混合物中,引入碳黑作为介孔模板剂,制备了含有10nm-30nm直径介孔的中孔与介孔复合SAPO-11。该中孔与介孔复合SAPO-11的结晶度较高,具有和常规SAPO-11相近的酸性。载Pt中孔与介孔复合SAPO-11催化剂上的正十二烷临氢异构反应表明,与常规SAPO-11制备的催化剂相比,该催化剂在563K的较低反应温度下,具有较高的异构选择性和异构收率,分别达到92.6%和83.1%。在与工业相近的操作条件下,研究了操作条件对Pt/中孔与介孔复合SAPO-11催化剂上烷烃临氢异构化性能的影响,并对Pt/中孔与介孔复合SAPO-11催化剂寿命进行了评价。实验结果表明,Pt/中孔与介孔复合SAPO-11催化剂在与工业相近的反应条件下,同样具有良好的反应活性和异构选择性,分别达到36.7%和95%,并且在与工业相近的反应压力和氢烷摩尔比条件下,该催化剂具有较好的稳定性。
The removal of long chain normal paraffins from diesel and lubricating oils is essential to produce oils with acceptable cold flow property. Long-chain n-alkane hydroisomerization catalysts can isomerize normal paraffins to isoparaffins which are efficient parts in the oils. Therefore, it is significant to develop high quality long-chain n-alkane hydroisomerization catalysts for excellent properties of diesel or lubricating oils and more oils yield. Bifunctional catalysts with mild strength acid, monodimentional medium-pore molecular sieve as acid function and Pt or Pd as metal function are generally found to be high isomers selective. Otherwise the monodimentional medium-pore molecular sieves are of different types and properties, and n-alkane hydroisomerization porformances of monodimentional medium-pore molecular sieves were seldom researched. Thus it is of actual benefit to research synthesis of monodimentional medium-pore molecular sieves and their effects on n-alkane hydroisomerization porformances.
In this paper, four typical monodimentional medium-pore molecular sieves SAPO-41, SAPO-11, ZSM-12 and ZSM-22 were synthesized with hydrothermal method and characterized by XRD, SEM, N2 adsorption desorption, XRF, MAS NMR, TG for crystalline phase, crystallinity, morphology, pore properties, elemental composition, atom environment, embraced materials. The samples of SAPO-41, SAPO-11, ZSM-12 and ZSM-22 obtained were highly crystallized and thermally stablized. The influencing factors of SAPO-41 and ZSM-12 syntheses were sysmetically researched, and the condition regions of pure SAPO-41 and ZSM-12 were determined. Gradual Heating was used to synthesize SAPO-41, the crystallization time was reduced from 50h to 35h, and more Si was induced resulting in more acid sites with this method. When the pseudo-boehmite with higher pore volume was used, a large amount of SAPO-11 was occured and then thansformed to SAPO-41 completely. Al-rich ZSM-12 was synthesized in order to reduce its acid strength.
The pore channel structute and acidity of SAPO-41, SAPO-11, ZSM-12 and ZSM-22 were discussed. The hydroisomerization performances of n-dodecane over Pt/monodimentional medium-pore molecular sieves were tested. The catalytic performances indicate that the activities of n-dodecane over Pt/ZSM-12 and Pt/ZSM-22 are higher than that over Pt/SAPO-11 and Pt/SAPO-41, in the meantime Pt/SAPO-11, Pt/SAPO-41 and Pt/ZSM-22 show higher isomers selectivity which reaches 70~80% under 85%-90% n-C_(12) conversion. The selectivity of objective products namely end-methyl-C_(11) over Pt/SAPO-11, Pt/SAPO-41 and Pt/ZSM-22 is higher than that over Pt/ZSM-12, and only Pt/ZSM-12 produces ethyl-C_(10) which is usually occurred over large-pore molecular sieves. The cracked products are symmetrical with carben number over Pt/SAPO-11, Pt/SAPO-41 and Pt/ZSM-22, and they are asymmetrical over Pt/ZSM-12 due to secondary cracking.
The n-alkane hydroisomerization mechanisms and the effects of acdity and pore channel structure on n-dodecane hydroisomerization were discussed. The conversion activity of n-dodecane is dependent on the acidity of molecular sieves, especially at low temperature. And the selectivity to isomers in hydroisomerization of n-dodecane is highly influenced by the pore channel structure of molecular sieves. The contents of methyl isomers over 12-ring Pt/ZSM-12 are close to that of PCP hypothesis, and 10-ring Pt/SAPO-11, Pt/SAPO-41 and Pt/ZSM-22 produce more end-methyl-C11.
The reaction scheme of n-alkane hydroisomerization over monodimentional medium-pore molecular sieves loaded with Pt was established according to the catalytic results and n-alkane carboncation mechanism, and the kinetic equations were provided. The intrinsic rate constant and physisorption equilibrium contant are determined by the acidity or pore channel structure, respectively, and then lead to the diffences of n-alkane hydroisomerization rate.
Mesoporous SAPO-11 was synthesized hydrothermally by using carbon black and di-n-propylamime (DPA) as templates for the expected mesopores and micropores, respectively. Mesoporous SAPO-11 was highly crystallized and the mesopore diameters are in range of 10nm-30nm. Mesoporous SAPO-11 has the same acidity with conventional one. The mesoporous SAPO-11 exhibited higher isomers selectivity (92.6%) and yield (83.1%) compared with conventional one at low reaction temperature 563K. The performance of n-dodecane hydroisomerization over Pt/mesoporous SAPO-11 was examined under industrial conditions. And the long term property was also evaluated. The results indicate that Pt/mesoporous SAPO-11 showed good reaction activity (36.7%) and isomers slectivity (95%). And that catalyst shows good stability under industrial reaction pressure and H_2/n-C_(12) ratio.
引文
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