高硅MFI分子筛孔道调控及其乙烷/乙烯吸附分离性能研究

熊峰; 柯权力; 卢梅; 方国楠; 潘鹏云; 牛晓坡; 崔国凯; 卢晗锋

doi:10.12434/j.issn.2097-2547.20240243

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高硅MFI分子筛孔道调控及其乙烷/乙烯吸附分离性能研究

分离材料与净化技术

- 高硅MFI分子筛孔道调控及其乙烷/乙烯吸附分离性能研究
- Study on pore regulation of high-silica MFI zeolites and their ethane/ethylene adsorption separation performances
- 低碳化学与化工 2024, 49(11): 97-103.
- 作者机构：
  
  1.浙江工业大学化学工程学院催化反应工程研究所，浙江杭州 310014
  2.浙江环境科技有限公司，浙江杭州 311121
- 作者简介：
  
  熊峰（1999—），硕士研究生，研究方向为分子筛活性位调控及其低浓度气体捕集性能，E-mail：2112101504@zjut.edu.cn。
  柯权力（1990—），博士，讲师，研究方向为分子筛合成和气体分离技术，E-mail：quanlike@zjut.edu.cn；
  卢晗锋（1977—），博士，教授，研究方向为环境催化和大气污染催化控制技术，E-mail：luhf@zjut.edu.cn。
- 基金信息：
  
  国家自然科学基金(22208300);浙江省自然科学基金(LQ23B060007);浙江省教育厅科研基金(Y202352744);浙江省“尖兵”“领雁”研发攻关计划(2023C03127;2024C03114;2024C03108);浙江省属高校基本科研业务费专项资金(RF-A2023004);浙江省博士后科研择优资助项目(ZJ2023145)
- DOI：10.12434/j.issn.2097-2547.20240243
  中图分类号： TQ424.23
- 纸质出版日期：2024-11-25，
  
  收稿日期：2024-06-01，
  
  修回日期：2024-07-15，
- 稿件说明：
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熊峰,柯权力,卢梅等.高硅MFI分子筛孔道调控及其乙烷/乙烯吸附分离性能研究[J].低碳化学与化工,2024,49(11):97-103.

XIONG Feng,KE Quanli,LU Mei,et al.Study on pore regulation of high-silica MFI zeolites and their ethane/ethylene adsorption separation performances[J].Low-carbon Chemistry and Chemical Engineering,2024,49(11):97-103.
熊峰,柯权力,卢梅等.高硅MFI分子筛孔道调控及其乙烷/乙烯吸附分离性能研究[J].低碳化学与化工,2024,49(11):97-103. DOI： 10.12434/j.issn.2097-2547.20240243.

XIONG Feng,KE Quanli,LU Mei,et al.Study on pore regulation of high-silica MFI zeolites and their ethane/ethylene adsorption separation performances[J].Low-carbon Chemistry and Chemical Engineering,2024,49(11):97-103. DOI： 10.12434/j.issn.2097-2547.20240243.

摘要

借助固体吸附分离技术可获得高纯度乙烯，对提高乙烯产品质量有重要意义。采用表面修饰策略对Mn掺杂高硅MFI分子筛（H-MFI-Mn）进行修饰分别制得P修饰H-MFI-Mn（H-MFI-Mn-P）和HCOOH修饰H-MFI-Mn（H-MFI-Mn-COOH和H-MFI-Mn-P-COOH）。采用XRD、SEM和N

吸/脱附等对所得分子筛进行了表征。在混合气体中（

(乙烯):

(乙烷) = 50:50）对所得分子筛的乙烷/乙烯吸附分离性能进行了评价，并采用UV-Vis和XPS对所得分子筛的乙烷/乙烯吸附分离机理进行了分析。结果表明，H-MFI-Mn-P-COOH的微孔孔径（0.68 nm）和平均孔径（2.70 nm）较H-MFI-Mn的孔径（0.55 nm）和平均孔径（1.61 nm）明显增大。与H-MFI-Mn的比表面积（446 m

/g）相比，H-MFI-Mn-P、H-MFI-Mn-COOH和H-MFI-Mn-P-COOH的比表面积（400 m

/g左右）均有所减小。H-MFI-Mn-P-COOH表现出较好的乙烷/乙烯吸附分离性能，其乙烷动态平衡吸附容量为1 mmol/g，乙烷/乙烯动态分离选择性为2.08。与H-MFI-Mn相比，H-MFI-Mn-P-COOH中Mn

和Mn

在总Mn离子中的占比较高，说明P修饰+ HCOOH修饰可削弱分子筛结构中Mn

物种的电子转移性能，进而抑制H-MFI-Mn-P-COOH的乙烯吸附性能。

Abstract

High purity ethylene can be obtained by the solid adsorption separation technology

which is of great significance to improve the quality of ethylene products. Mn-doped high-silica MFI zeolite (H-MFI-Mn) were modified by surface modification strategy to obtain P-modified H-MFI-Mn (H-MFI-Mn-P) and HCOOH-modified H-MFI-Mn (H-MFI-Mn-COOH and H-MFI-Mn-P-COOH)

respectively. The prepared zeolites were characterized by XRD

SEM and N

adsorption/desorption

etc. The ethane/ethylene adsorption separation performances of prepar

ed zeolites were evaluated in mixed gas (

(ethane):

(ethylene) = 50:50). And the ethane/ethylene adsorption separation mechanisms of prepared zeolites were analyzed by UV-Vis and XPS. The results show that the micropore size (0.68 nm) and average pore size (2.70 nm) of H-MFI-Mn-P-COOH are significantly larger than the micropore size (0.55 nm) and average pore size (1.61 nm) of H-MFI-Mn. Compared with the specific surface area of H-MFI-Mn (446 m

/g)

the specific surface areas (about 400 m

/g) of H-MFI-Mn-P

H-MFI-Mn-COOH and H-MFI-Mn-P-COOH decrease. H-MFI-Mn-P-COOH shows better ethane/ethylene adsorption separation performance with ethane dynamic equilibrium adsorption capacity of 1 mmol/g and ethane/ethylene dynamic separation selectivity of 2.08. Compared with H-MFI-Mn

and Mn

in H-MFI-Mn-P-COOH accounted for higher proportions in total Mn ions

indicating that P-modification + HCOOH-modification can weaken the electron transfer performance of Mn

species in the zeolite structure

and then inhibit the ethylene adsorption performance of H-MFI-Mn-P-COOH.

关键词

高硅MFI分子筛乙烷/乙烯吸附分离表面修饰

Keywords

high-silica MFI zeolitesethane/ethylene adsorption separationsurface modification

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