AHT型磷酸铝分子筛的合成及表征

doi:10.16085/j.issn.1000-6613.2020-2323

化工进展 ›› 2021, Vol. 40 ›› Issue (11): 6219-6227.DOI: 10.16085/j.issn.1000-6613.2020-2323

AHT型磷酸铝分子筛的合成及表征

王晓天¹^,²(), 罗海燕¹, 徐俊波¹, 杨超¹, 刘会洲¹(), 李英波¹^,³()

^1.中国科学院绿色过程与工程重点实验室(中国科学院过程工程研究所)，北京 100190
^2.中国科学院大学化学工程学院，北京 100049
^3.雅邦绿色过程与新材料研究院，江苏南京 210047

收稿日期:2020-11-20 修回日期:2021-04-15 出版日期:2021-11-05 发布日期:2021-11-19
通讯作者: 刘会洲,李英波
作者简介:王晓天（1996—），男，博士研究生，研究方向为多孔材料的合成与应用。E-mail：wangxiaotian18@mails.ucas.edu.cn。
基金资助:
国家重点研发计划重点专项(2016YFB0301702);中国科学院科技服务网络计划（STS计划）区域重点项目(KFJ-STS-QYZD-2021-14-002)

Synthesis of AHT aluminophosphate molecular sieve and its characterization

WANG Xiaotian¹^,²(), LUO Haiyan¹, XU Junbo¹, YANG Chao¹, LIU Huizhou¹(), LI Yingbo¹^,³()

^1.CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^2.College of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
^3.Yabang Institute of Green Process and Advanced Materials, Nanjing 210047, Jiangsu, China

Received:2020-11-20 Revised:2021-04-15 Online:2021-11-05 Published:2021-11-19
Contact: LIU Huizhou,LI Yingbo

摘要/Abstract

摘要：

以不同链长的有机胺为模板，选用不同的铝源，采用水热法合成AHT型分子筛。考察铝源、原料摩尔比和有机模板剂对AHT型磷酸铝分子筛（AlPO₄-H2）合成的影响，并利用XRD、SEM、BET、TG/DTG等技术对合成的AHT构型磷酸铝分子筛进行表征。结果表明，在所测试的4种铝源中，只有以拟薄水铝石为铝源时才能获得AHT型分子筛；反应混合物中水的含量对AHT型磷酸铝分子筛的合成具有显著的影响，当n(H₂O)/n(Al₂O₃)大于或小于20时，均有杂相生成；在优化的条件下，以烷基链长度大于4的有机胺为模板剂，均能获得纯相的AHT型磷酸铝分子筛。当有机胺烷基链长度小于或等于4时，有机胺的最大伸展长度达不到AHT型磷酸铝分子筛的晶胞参数c值，无法合成纯相AHT型磷酸铝分子筛。合成的AHT型磷酸铝分子筛形貌为针状或棒状，结构骨架中磷铝摩尔比为1，是一种典型的磷酸铝分子筛。该分子筛具有良好的酸碱稳定性，但高温容易导致其结构转变。

关键词: 分子筛, 有机胺, AHT, 磷酸铝, 合成

Abstract:

AHT aluminophosphate molecular sieves (AlPO₄-H2) were synthesized by hydrothermal method using different chain-length organic amines as templates and different aluminum sources. The effects of aluminum sources, substrate molar ratio, and organic template on the synthesis of AHT aluminophosphate molecular sieves were investigated. Multiple analytical techniques, including XRD, SEM, BET, and TG/DTG, were employed to characterize the AlPO₄-H2. The results showed that only pseudo-boehmite can be used to synthesize AlPO₄-H2 among the four tested aluminum sources. The water content in the reaction mixture has a remarkable impact. When n(H₂O)/n(Al₂O₃) was over or less than 20, impurities were formed. When the length of the alkyl chain of the organic amines was larger than 4, pure AlPO₄-H2 can be obtained under optimized conditions. While the alkyl chain length of organic amine was smaller than or equal to 4, pure AlPO₄-H2 cannot be obtained, because the stretching extends of these amines are smaller than the value of crystal cell parameter c. The morphology of the synthesized AlPO₄-H2 was needle-like or rod-like, with a n(Al)/n(P) of 1 in its structural skeleton. This molecular sieve has good chemical stability although it is unstable at high temperature.

Key words: molecular sieves, organic amine, AHT, aluminophosphate, synthesis

中图分类号:

TQ424.29

王晓天, 罗海燕, 徐俊波, 杨超, 刘会洲, 李英波. AHT型磷酸铝分子筛的合成及表征[J]. 化工进展, 2021, 40(11): 6219-6227.

WANG Xiaotian, LUO Haiyan, XU Junbo, YANG Chao, LIU Huizhou, LI Yingbo. Synthesis of AHT aluminophosphate molecular sieve and its characterization[J]. Chemical Industry and Engineering Progress, 2021, 40(11): 6219-6227.

图/表 13

参考文献 23

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编号	原料摩尔比				铝源	温度/℃	时间/h	产物
编号	二正戊胺	Al₂O₃	P₂O₅	H₂O	铝源	温度/℃	时间/h	产物
1	1	1	1	50	氢氧化铝	120	24	Al(OH)₃
2	1	1	1	50	勃姆石	120	24	勃姆石、Variscite-20
3	1	1	1	50	无定形氢氧化铝	120	24	Metavariscite
4	1	1	1	50	拟薄水铝石	120	24	AHT分子筛、AlPO₄-H3

编号	原料摩尔比				铝源	温度/℃	时间/h	产物
编号	二正戊胺	Al₂O₃	P₂O₅	H₂O	铝源	温度/℃	时间/h	产物
1	1	1	1	50	氢氧化铝	120	24	Al(OH)₃
2	1	1	1	50	勃姆石	120	24	勃姆石、Variscite-20
3	1	1	1	50	无定形氢氧化铝	120	24	Metavariscite
4	1	1	1	50	拟薄水铝石	120	24	AHT分子筛、AlPO₄-H3

编号	原料摩尔比				铝源	有机模板	温度/℃	时间/h	产物
编号	有机模板	Al₂O₃	P₂O₅	H₂O	铝源	有机模板	温度/℃	时间/h	产物
1	1	1	1	20	拟薄水铝石	二正丙胺	120	24	VPI-5、AlPO₄-tridymite
2	1	1	1	20	拟薄水铝石	二正丁胺	120	24	VPI-5、AHT分子筛
3	1	1	1	20	拟薄水铝石	二正戊胺	120	24	AHT分子筛
4	1	1	0.8	20	拟薄水铝石	二正己胺	120	24	AHT分子筛
5	1	1	1	20	拟薄水铝石	二正己胺	120	24	AHT分子筛、AlPO₄-H3
6	1	1	1.25	20	拟薄水铝石	二正己胺	120	24	AHT分子筛、AlPO₄-H3
7	1	1	1	20	拟薄水铝石	二正庚胺	120	24	AHT分子筛
8	1	1	1	20	拟薄水铝石	二正辛胺	120	24	AHT分子筛

编号	原料摩尔比				铝源	有机模板	温度/℃	时间/h	产物
编号	有机模板	Al₂O₃	P₂O₅	H₂O	铝源	有机模板	温度/℃	时间/h	产物
1	1	1	1	20	拟薄水铝石	二正丙胺	120	24	VPI-5、AlPO₄-tridymite
2	1	1	1	20	拟薄水铝石	二正丁胺	120	24	VPI-5、AHT分子筛
3	1	1	1	20	拟薄水铝石	二正戊胺	120	24	AHT分子筛
4	1	1	0.8	20	拟薄水铝石	二正己胺	120	24	AHT分子筛
5	1	1	1	20	拟薄水铝石	二正己胺	120	24	AHT分子筛、AlPO₄-H3
6	1	1	1.25	20	拟薄水铝石	二正己胺	120	24	AHT分子筛、AlPO₄-H3
7	1	1	1	20	拟薄水铝石	二正庚胺	120	24	AHT分子筛
8	1	1	1	20	拟薄水铝石	二正辛胺	120	24	AHT分子筛

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AHT型磷酸铝分子筛的合成及表征

Synthesis of AHT aluminophosphate molecular sieve and its characterization

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