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

doi:10.11949/0438-1157.20220150

Abstract

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

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

CLC Number:

TQ 426

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.

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.

Figures/Tables 10

Fig.1 Evaluation device of propane dehydrogenation reaction

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

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

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)

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

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

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

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

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

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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