基于介尺度结构解聚-重组装的Beta分子筛的绿色合成及应用

doi:10.11949/0438-1157.20220150

化工学报 ›› 2022, Vol. 73 ›› Issue (6): 2690-2697.DOI: 10.11949/0438-1157.20220150

• 催化、动力学与反应器 • 上一篇下一篇

基于介尺度结构解聚-重组装的Beta分子筛的绿色合成及应用

王婵^1,²(),肖国锡¹,郭小雪¹,徐人威³,岳源源^1,²(),鲍晓军^1,²

^1.福州大学石油化工学院化肥催化剂国家工程研究中心，福建福州 350002
^2.清源创新实验室，福建泉州 362801
^3.中化泉州能源科技有限责任公司，福建泉州 362000

收稿日期:2022-01-25 修回日期:2022-04-08 出版日期:2022-06-05 发布日期:2022-06-30
通讯作者: 岳源源
作者简介:王婵（1987—），女，博士，讲师，chan.wang@fzu.edu.cn
基金资助:
国家自然科学基金重大研究计划集成项目(91934301);面上项目(22178059);福建省自然科学基金面上项目(2020J01513)

Green synthesis and application of Beta zeolite prepared via mesoscale depolymerization-reorganization strategy

Chan WANG^1,²(),Guoxi XIAO¹,Xiaoxue GUO¹,Renwei XU³,Yuanyuan YUE^1,²(),Xiaojun BAO^1,²

^1.National Engineering Research Center of Chemical Fertilizer Catalyst, College of Chemical Engineering, Fuzhou University, Fuzhou 350002, Fujian, China
^2.Qingyuan Innovation Laboratory, Quanzhou 362801, Fujian, China
^3.Sinochem Quanzhou Energy Technology Co. , Ltd. , Quanzhou 362000, Fujian, China

Received:2022-01-25 Revised:2022-04-08 Online:2022-06-05 Published:2022-06-30
Contact: Yuanyuan YUE

摘要/Abstract

摘要：

Beta分子筛作为一种重要的催化材料，被广泛应用于石油化工、煤化工及环境保护等领域，但其常规的水热合成过程存在成本高、单釜产率低和废水排放量大等问题。本研究提出了一条基于天然矿物介尺度结构解聚-重组装的无溶剂绿色合成Beta分子筛的新路线，采用该路线所合成的Beta分子筛（Beta-Anhyd）含有丰富的介孔和大孔结构，且具有较商业Beta分子筛（Beta-Ref）更高的比表面积和更低的酸量，以其为载体，通过脱Al补Sn制备的Sn-Beta催化剂（Beta-Anhyd-Deal）在丙烷脱氢反应中表现出较参比催化剂（Beta-Ref-Deal）更加优异的催化性能。

关键词: 分子筛, 载体, 催化剂, 介尺度, 绿色合成, 丙烷脱氢

Abstract:

As an important catalytic material, Beta zeolite is widely used in petrochemical, coal chemical and environmental protection fields, but its conventional hydrothermal synthesis process has problems such as high cost, low yield per kettle and large waste water discharge. This article presents a green and economic strategy to synthesize Beta zeolite from natural mineral via a mesoscale depolymerization-reorganization approach. The proposed methodology results in a Beta zeolite (denoted as Beta-Anhyd) owning abundant meso- and macro-pores, larger specific surface area and lower acid amount than a commercial sample (Beta-Ref). The Beta-Anhyd derived catalyst (Beta-Anhyd-Deal) that was prepared by a two-step post-synthesis method consisting of the dealumination of Beta-Anhyd and the incorporation of tin shows much better catalytic performance in the propane dehydrogenation reaction than the reference one (Beta-Ref-Deal).

Key words: molecular sieves, support, catalyst, mesoscale, green synthesis, propane dehydrogenation

中图分类号:

TQ 426

王婵, 肖国锡, 郭小雪, 徐人威, 岳源源, 鲍晓军. 基于介尺度结构解聚-重组装的Beta分子筛的绿色合成及应用[J]. 化工学报, 2022, 73(6): 2690-2697.

Chan WANG, Guoxi XIAO, Xiaoxue GUO, Renwei XU, Yuanyuan YUE, Xiaojun BAO. Green synthesis and application of Beta zeolite prepared via mesoscale depolymerization-reorganization strategy[J]. CIESC Journal, 2022, 73(6): 2690-2697.

图/表 10

图1 丙烷脱氢反应性能测试装置

Fig.1 Evaluation device of propane dehydrogenation reaction

图2 Na-Beta-Anhyd、Beta-Anhyd和Beta-Ref的XRD谱图

Fig.2 XRD patterns of Na-Beta-Anhyd, Beta-Anhyd and Beta-Ref

图3 Beta-Anhyd和Beta-Ref的N2吸附-脱附等温线和BJH孔径分布

Fig.3 N2 adsorption-desorption isotherms and BJH pore size distributions of Beta-Anhyd and Beta-Ref

表1 Beta-Anhyd和Beta-Ref的孔结构参数

Table 1 Textural characteristics of Beta-Anhyd and Beta-Ref

Sample

S_BET^①/

(m²/g)

S_micro^②/

(m²/g)

S_ext^②/

(m²/g)

V_total^①/

(cm³/g)

V_micro^②/

(cm³/g)

V_meso^③/

(cm³/g)

图4 Beta-Anhyd和Beta-Ref的27Al MAS NMR谱图

Fig.4 27Al MAS NMR spectra of Beta-Anhyd and Beta-Ref

图5 Beta-Anhyd-Deal和Beta-Ref-Deal的XPS谱图

Fig.5 XPS spectra of Beta-Anhyd-Deal and Beta-Ref-Deal

图6 Beta分子筛和Sn-Beta催化剂的NH3-TPD曲线

Fig.6 NH3-TPD curves of the Beta zeolites and Sn-Beta catalysts

图7 Beta-Anhyd、Beta-Ref、Beta-Anhyd-Deal和Beta-Ref-Deal的Py-IR谱图

Fig.7 Py-IR spectra of Beta-Anhyd, Beta-Ref, Beta-Anhyd-Deal and Beta-Ref-Deal

表2 Beta-Anhyd-Deal和Beta-Ref-Deal的酸量

Table 2 Acid sites amount of Beta-Anhyd-Deal and Beta-Ref-Deal

Samples	Amount of acid sites/(μmol/g)
	200℃			350℃
	B	L	Total	B	L	Total
Beta-Ref	182.37	176.01	358.38	84.73	112.56	197.28
Beta-Anhyd	143.76	87.57	231.34	97.29	62.92	160.24
Beta-Ref-Deal	31.94	175.84	207.78	15.37	8.59	23.96
Beta-Anhyd-Deal	22.74	153.06	175.80	6.97	45.04	52.00

图8 Beta-Anhyd-Deal和Beta-Ref-Deal在常压、630℃、质量空速为3.02 h-1下的丙烷脱氢催化性能

Fig.8 The catalytic performance of Beta-Anhyd-Deal and Beta-Ref-Deal in propylene dehydrogenation at atmospheric pressure, 630℃ and WHSV of 3.02 h-1

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基于介尺度结构解聚-重组装的Beta分子筛的绿色合成及应用

Green synthesis and application of Beta zeolite prepared via mesoscale depolymerization-reorganization strategy

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