红辉沸石两步水热法合成A型分子筛机理研究

doi:10.19964/j.issn.1006-4990.2022-0436

无机盐工业 ›› 2022, Vol. 54 ›› Issue (11): 59-64.doi: 10.19964/j.issn.1006-4990.2022-0436

红辉沸石两步水热法合成A型分子筛机理研究

裴胤昌¹(),莫胜鹏¹,解庆林^1,²(),陈南春^3,⁴

1.桂林理工大学环境科学与工程学院，广西桂林 541006
2.桂林理工大学广西岩溶地区水污染控制与用水安全保障协同创新中心
3.桂林理工大学材料科学与工程学院
4.桂林理工大学有色金属矿产勘查与资源高效利用省部共建协同创新中心

收稿日期:2022-08-15 出版日期:2022-11-10 发布日期:2022-11-23
作者简介:裴胤昌（1992─ ），男，博士研究生，主要从事矿物环境材料制备及其处理重金属离子废水的研究；E-mail：peiyinchang@glut.edu.cn。
基金资助:
国家自然科学基金(41662005)

Study on mechanism of zeolite A synthesized from stellerite zeolite by two-step hydrothermal method

PEI Yinchang¹(),MO Shengpeng¹,XIE Qinglin^1,²(),CHEN Nanchun^3,⁴

1. Guilin University of Technology，College of Environmental Science and Engineering，Guilin 541006，China
2. Guilin University of Technology，Collaborative Innovation Center for Water Pollution Control and Water Safety in Karst Area
3. Guilin University of Technology，College of Materials Science and Engineering
4. Guilin University of Technology，Collaborative Innovation Center for Exploration of Nonferrous Metal Deposits and Efficient Utilization of Resources in Guangxi

Received:2022-08-15 Published:2022-11-10 Online:2022-11-23

摘要/Abstract

摘要：

以红辉沸石为原料，采用两步水热法将其转化为A型分子筛，系统地探讨A型分子筛的转化机理。对不同晶化时间的样品进行系统表征，深入解析天然红辉沸石转化A型分子筛的成核机制、生长控制、晶型稳定转化等结构基础问题。研究表明，A型分子筛的生长可分为3个阶段：在成核诱导期（晶化时间≤0.5 h），凝胶中的β笼通过双四元环构筑成α笼，生成较多晶核及少量1 μm小晶体；此后为快速生长期（晶化时间1~4 h），大量晶核通过聚集生长形成2 μm大晶体；在生长稳定期（晶化时间5~8 h），通过二次成核凝胶将会转化为更多的分子筛晶体。A型分子筛的形成遵循：铝硅酸盐凝胶→四元环、六元环→双四元环、β笼→α笼的晶化过程，因而其转化过程符合液相转化机理。

关键词: 红辉沸石, A型分子筛, 两步水热法, 转化机理

Abstract:

Stellerite zeolite was used as raw material to convert into zeolite A by the two-step hydrothermal method，and the conversion mechanism of zeolite A was systematically investigated.The samples with different crystallization times were systematically characterized.The basic structural problems such as the nucleation mechanism，growth control and stable conversion of crystal form of natural stellerite zeolite into zeolite A were analyzed in depth.The results indicated that the growth process of zeolite A could be divided into three stages.When it was in the nucleation induction stage（crystallition time≤0.5 h），the β cages in gel was constructed by double four-membered rings to form α cages and many crystal nuclei and a few 1 μm small crystal were formed.When it was in the rapid growth（crystallition time of 1~4 h），a large number of nuclei were grown by aggregation to form large crystals with 2 μm.Finally，when it was in the stable growth（crystallition time of 5~8 h），the gel was converted into more zeolite crystals by secondary nucleation.The formation of zeolite A was followed：aluminosilicate gel→four-membered rings and six-membered rings→double four-membered rings and β cages→α cages.Therefore，the process of stellerite zeolite conversion to zeolite A was belonged to a liquid phase conversion mechanism.

Key words: stellerite zeolite, zeolite A, two-step hydrothermal method, conversion mechanism

中图分类号:

TQ426.95

裴胤昌,莫胜鹏,解庆林,陈南春. 红辉沸石两步水热法合成A型分子筛机理研究[J]. 无机盐工业, 2022, 54(11): 59-64.

PEI Yinchang,MO Shengpeng,XIE Qinglin,CHEN Nanchun. Study on mechanism of zeolite A synthesized from stellerite zeolite by two-step hydrothermal method[J]. Inorganic Chemicals Industry, 2022, 54(11): 59-64.

图/表 7

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参考文献 20

1	张椿英,陈南春,张小虎,等.A，X，P型分子筛的原位制备与结构控制[J].硅酸盐学报,2014,42(10):1332-1336.
	ZHANG Chunying, CHEN Nanchun, ZHANG Xiaohu, et al.In situ preparation and structure of zeolites A，X and P[J].Journal of the Chinese Ceramic Society,2014,42(10):1332-1336.
2	KUMAR M M, IRSHAD K A, JENA H.Removal of Cs⁺ and Sr²⁺ ions from simulated radioactive waste solutions using Zeolite-A synthesized from Kaolin and their structural stability at high pressures[J].Microporous and Mesoporous Materials,2021,312.Doi:10.1016/j.micromeso.2020.110773. doi: 10.1016/j.micromeso.2020.110773
3	PANGAN N, GALLARDO S, GASPILLO P A, et al.Hydrothermal synthesis and characterization of zeolite A from corn（Zea mays） stover ash[J].Materials（Basel，Switzerland）,2021,14(17).Doi:10.3390/ma14174915. doi: 10.3390/ma14174915
4	SAMANTA N S, BANERJEE S, MONDAL P, et al.Preparation and characterization of zeolite from waste Linz-Donawitz（LD） process slag of steel industry for removal of Fe³⁺ from drinking water[J].Advanced Powder Technology,2021,32(9):3372-3387.
5	崔家新,王连勇,李尧,等.水淬渣-粉煤灰基4A沸石的制备及性能表征[J].无机盐工业,2022,54(4):135-140.
	CUI Jiaxin, WANG Lianyong, LI Yao, et al.Preparation and properties characterization of water quenching slag-fly ash based 4A zeolite[J].Inorganic Chemicals Industry,2022,54(4):135-140.
6	WANG Binyu, LI Jing, ZHOU Xue, et al.Facile activation of lithium slag for the hydrothermal synthesis of zeolite A with commercial quality and high removal efficiency for the isotope of radioactive ⁹⁰Sr[J].Inorganic Chemistry Frontiers,2022,9(3):468-477.
7	SU Shuangqing, MA Hongwen, CHUAN Xiuyun.Hydrothermal synthesis of zeolite A from K-feldspar and its crystallization mechanism[J].Advanced Powder Technology,2016,27(1):139-144.
8	KUMAR A, NASKAR M K.Single-step process without organic template for the formation of zeolite A from RHA[J].International Journal of Applied Ceramic Technology,2019,16(4):1525-1532.
9	KUMAR A, NASKAR M K.Custard apple-shaped NaX zeolite with a large surface area derived from rice husk ash by a single-step template-free process[J].Journal of Asian Ceramic Societies,2019,7(3):355-360.
10	REN Limin, LI Caijin, FAN Fengtao, et al.UV-Raman and NMR spectroscopic studies on the crystallization of Zeolite A and a new synthetic route[J].Chemistry-A European Journal,2011,17(22):6162-6169.
11	黄志良,张联盟,刘羽,等.水热法合成4A沸石的相变/纳米聚合生长过程及其机理研究[J].无机材料学报,2005,20(2):401-406.
	HUANG Zhiliang, ZHANG Lianmeng, LIU Yu, et al.Phase transition/nano aggregation growth process of zeolite 4A prepared by hydrothermal synthesis and its mechanism[J].Journal of Inorganic Materials,2005,20(2):401-406.
12	李酽.天然红辉沸石合成A型分子筛（英文）[J].中国民航学院学报,2002(6):30-33.
	LI Yan.Synthesis of zeolite A from natural stellerite[J].Journal of Civil Aviation University of China,2002(6):30-33.
13	申少华,方克明,张术根,等.酸处理红辉沸石-氢氧化钠-铝酸钠-水的水热反应体系A型沸石的形成机理[J].北京科技大学学报,2003,25(6):489-494.
	SHEN Shaohua, FANG Keming, ZHANG Shugen, et al.Formation mechanism of zeolite A in the hydrothermal reaction system of acid-treated stellerite-NaOH-NaAlO₂-H₂O[J].Journal of University of Science and Technology Beijing,2003,25(6):489-494.
14	高沙沙,陈南春,裴胤昌,等.天然辉沸石为原料制备P型沸石的水热反应条件研究[J].人工晶体学报,2018,47(6):1096-1101.
	GAO Shasha, CHEN Nanchun, PEI Yinchang, et al.Hydrothermal reaction conditions for praparation of zeolite P from natural stilbite as raw material[J].Journal of Synthetic Crystals,2018,47(6):1096-1101.
15	贾敏,杨磊,王永旺.体型化NaA分子筛的制备研究[J].无机盐工业,2021,53(10):98-103.
	JIA Min, YANG Lei, WANG Yongwang.Study on preparation of body-shaped NaA Zeolite[J].Inorganic Chemicals Industry, 2021,53(10):98-103.
16	任英杰,赵永红,张广良.煤矸石两步除铁合成低铁杂质4A沸石[J].无机盐工业,2017,49(1):42-45.
	REN Yingjie, ZHAO Yonghong, ZHANG Guangliang.Synthesis of 4A zeolites with less Fe impurity from gangue after two removaliron stages[J].Inorganic Chemicals Industry,2017,49(1):42-45.
17	PEI Yinchang, ZHONG Yijian, XIE Qinglin, et al.Two-step hydrothermal synthesis and conversion mechanism of zeolite X from stellerite zeolite[J].RSC Advances,2022,12(6):3313-3321.
18	XIAO Yuchen, SHENG Na, CHU Yueying, et al.Mechanism on solvent-free crystallization of NaA zeolite[J].Microporous and Mesoporous Materials,2017,237: 201-209.
19	马淑杰,刘孔凡,崔美珍,等.A型沸石的生成机理[J].高等学校化学学报,1984,5(2):158-162.
	MA Shujie, LIU Kongfan, CUI Meizhen, et al.The machanism of formation of zeolite A[J].Chemical Research in Chinese Universities,1984,5(2):158-162.
20	YANG C S, MORA-FONZ J M, CATLOW C R A.Modeling the nucleation of zeolite A[J].The Journal of Physical Chemistry C,2013,117(47):24796-24803.

时间/h	w（SiO₂）%	w（Al₂O₃）%	w（Na₂O）%
0.5	48.50	32.50	18.49
1	48.36	32.95	18.56
2	48.08	32.99	18.81
3	47.39	33.30	19.20
4	47.05	33.81	19.00

时间/h	m（SiO₂）/g	m（Al₂O₃）/g	m（Na₂O）/g
0.5	0.054 2	0.082 6	1.841 1
1.0	0.037 7	0.028 8	1.742 6
2.0	0.031 8	0.019 7	1.650 7
3.0	0.025 2	0.024 7	1.533 3
4.0	0.029 9	0.020 1	1.637 2

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