化工进展
化工進展
화공진전
CHEMICAL INDUSTRY AND ENGINEERING PROGRESS
2014年
10期
2711-2715,2721
,共6页
刘芝平%张嫱嫱%赵贺%马静红%李瑞丰
劉芝平%張嬙嬙%趙賀%馬靜紅%李瑞豐
류지평%장장장%조하%마정홍%리서봉
沸石ZSM-5%动力学%纳米粒子%扩散%活化能%零长柱法(ZLC)
沸石ZSM-5%動力學%納米粒子%擴散%活化能%零長柱法(ZLC)
비석ZSM-5%동역학%납미입자%확산%활화능%령장주법(ZLC)
zeolite ZSM-5%kinetics%nanoparticles%diffusion%activation energy%zero-length column
实验选取了碳原子数相同、结构和分子动力学直径不同的正庚烷和甲苯作为探针分子,通过零长柱法(zero-length column,ZLC)考察了纳米级介孔 ZSM-5沸石的孔结构对探针分子扩散性能的影响。采用 Crank扩散模型计算了有效扩散时间常数,并估算了扩散活化能。实验结果表明,由于甲苯比庚烷分子结构复杂、分子动力学直径大,因此甲苯在ZSM-5样品中的扩散活化能约为庚烷的1.5倍,有效扩散时间常数远小于庚烷。庚烷和甲苯在纳米级介孔ZSM-5沸石中的扩散速率取决于粒径的大小,两者在纳米级介孔ZSM-5中的有效扩散时间常数是微米级纯微孔ZSM-5的两倍,然而两者在微米级纯微孔ZSM-5中的活化能为纳米级介孔ZSM-5中的两倍,说明对于纳米级介孔ZSM-5,微粒粒径减小、扩散路径缩短,对扩散起到了极大的促进作用。
實驗選取瞭碳原子數相同、結構和分子動力學直徑不同的正庚烷和甲苯作為探針分子,通過零長柱法(zero-length column,ZLC)攷察瞭納米級介孔 ZSM-5沸石的孔結構對探針分子擴散性能的影響。採用 Crank擴散模型計算瞭有效擴散時間常數,併估算瞭擴散活化能。實驗結果錶明,由于甲苯比庚烷分子結構複雜、分子動力學直徑大,因此甲苯在ZSM-5樣品中的擴散活化能約為庚烷的1.5倍,有效擴散時間常數遠小于庚烷。庚烷和甲苯在納米級介孔ZSM-5沸石中的擴散速率取決于粒徑的大小,兩者在納米級介孔ZSM-5中的有效擴散時間常數是微米級純微孔ZSM-5的兩倍,然而兩者在微米級純微孔ZSM-5中的活化能為納米級介孔ZSM-5中的兩倍,說明對于納米級介孔ZSM-5,微粒粒徑減小、擴散路徑縮短,對擴散起到瞭極大的促進作用。
실험선취료탄원자수상동、결구화분자동역학직경불동적정경완화갑분작위탐침분자,통과령장주법(zero-length column,ZLC)고찰료납미급개공 ZSM-5비석적공결구대탐침분자확산성능적영향。채용 Crank확산모형계산료유효확산시간상수,병고산료확산활화능。실험결과표명,유우갑분비경완분자결구복잡、분자동역학직경대,인차갑분재ZSM-5양품중적확산활화능약위경완적1.5배,유효확산시간상수원소우경완。경완화갑분재납미급개공ZSM-5비석중적확산속솔취결우립경적대소,량자재납미급개공ZSM-5중적유효확산시간상수시미미급순미공ZSM-5적량배,연이량자재미미급순미공ZSM-5중적활화능위납미급개공ZSM-5중적량배,설명대우납미급개공ZSM-5,미립립경감소、확산로경축단,대확산기도료겁대적촉진작용。
In this study,the effect of pore structure on diffusion of two C7 hydrocarbons,n-heptane and toluene,which have the same number of carbon atoms and different diameters of molecular dynamics and structures,in nano-ZSM-5 materials were investigated using the zero-length column (ZLC) method. Furthermore,the corresponding MFI zeolite sample was also investigated using the same technique. The effective diffusion time constants of these two sorbates on ZSM-5 materials were evaluated by the Crank model,and the diffusion activation energies were estimated. The values of activation energy of diffusion of toluene were about 1.5 times higher than those of n-heptane,whereas the effective diffusion time constants of toluene were much smaller than those of heptane,which could be attributed to more complex structure and larger kinetic diameter of toluene. Diffusion rates of heptane and toluene depended on particle size of the nano-ZSM-5 crystal. Diffusion time constants of heptane and toluene in nano-ZSM-5 zeolite were found about 2 times higher in comparison to the corresponding MFI zeolite sample. However,diffusion activation energies for both C7 hydrocarbons in the MFI zeolite were about 2 times higher than those in the corresponding nano-ZSM-5 zeolite sample, which suggested that decrease of the diffusion path length within the microporous crystals by reducing the particle size could promote the process of diffusion.