酸处理对斜发沸石结构影响的研究

许静; 王森; 王鹏飞; 闫文付; 魏渝伟; 李俊汾; 董梅; 王建国; 樊卫斌

酸处理对斜发沸石结构影响的研究

许静^{1, 2},
王森¹,
王鹏飞¹,
闫文付³,
魏渝伟⁴,
李俊汾^1, ,,
董梅¹,
王建国¹,
樊卫斌^1, ,

1.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001
2.
中国科学院大学, 北京 100049
3.
吉林大学, 吉林长春 130000
4.
洛阳建龙微纳新材料股份有限公司, 河南洛阳 471000

基金项目:

国家自然科学基金 21227002

国家自然科学基金 20143268

国家自然科学基金 21273264

国家自然科学基金 21273263

国家重点基础研究发展规划 973 program

国家重点基础研究发展规划 2011CB201400

山西省自然科学基金 2013021007-3

山西省自然科学基金 2012011005-2

详细信息

中图分类号: O643
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出版历程
- 收稿日期: 2018-03-30
- 修回日期: 2018-05-14
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-08-10

The effect of acid treatment on the structure of clinoptilolite

XU Jing^{1, 2},
WANG Sen¹,
WANG Peng-fei¹,
YAN Wen-fu³,
WEI Yu-wei⁴,
LI Jun-fen^{1
, ,},
DONG Mei¹,
WANG Jian-guo¹,
FAN Wei-bin^{1
, ,}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
Jilin University, Changchun 130000, China
4.
Luoyang Janlong Micro-Nano New Materials CO., LTD., Luoyang 471000, China

Funds:

the National Natural Science Foundation of China 21227002

the National Natural Science Foundation of China 20143268

the National Natural Science Foundation of China 21273264

the National Natural Science Foundation of China 21273263

National Basic Research Program of China 973 program

National Basic Research Program of China 2011CB201400

Natural Science Foundation Shanxi Province of China 2013021007-3

Natural Science Foundation Shanxi Province of China 2012011005-2

More Information

Corresponding author: LI Jun-fen, Tel:(0351) 4199009, E-mails:lijunfen@sxicc.ac.cn; FAN Wei-bin, Fax:(0351) 4050320, E-mails:fanwb@sxicc.ac.cn

摘要

摘要: 采用不同浓度硝酸对斜发沸石(HEU)进行改性处理, 结合元素分析(ICP-AES)、N₂物理吸附、X射线粉末衍射(XRD)、魔角旋转固体核磁(MAS NMR)等测试手段及DFT理论计算, 研究了酸处理对斜发沸石结构的影响。结果表明, 硝酸处理对不同平衡阳离子的HEU(Na-K-HEU、NH₄-HEU、H-HEU)具有不同的脱铝效果。酸处理后Na-K-HEU和NH₄-HEU的硅铝比、比表面积均显著升高。随硝酸浓度增大两个沸石样品的脱铝程度逐渐增加, 同时骨架结构也逐渐破坏, 硝酸浓度达到4 mol/L时其相对结晶度已低于50%。而H-HEU样品的骨架结构稳定, 随硝酸浓度的增大铝含量轻微降低, 硝酸浓度达到6 mol/L时相对结晶度仍高达94.8%。阳离子反交换实验结果证明, 平衡阳离子的类型不是影响HEU骨架稳定性的主要因素。Na-K-HEU和经硝酸铵交换后的NH₄-HEU中铝都以骨架铝的形式存在, 而在后者焙烧成为H-HEU时出现部分非骨架铝, 伴随了骨架的稳定化过程。
- 斜发沸石 /
- 硝酸处理 /
- 脱铝 /
- 骨架结构
Abstract: The influence of nitric acid treatment on the composition and structure of clinoptilolite (HEU) was analyzed by various characterization techniques, such as element analysis (ICP-AES), N₂ physical adsorption, X-ray powder diffraction (XRD), ²⁷Al/²⁹Si MAS NMR and DFT calculation.The Si/Al ratio and BET surface area of Na-K-HEU and NH₄-HEU were significantly increased after nitric acid treatment, and meanwhile, their relative crystallinity decreased to below 50% when the concentration of nitric acid reached 4 mol/L, illustrating the severe distortion of zeolite framework.However, the structure of H-HEU was more stable and it could maintain a high relative crystallinity of 94.8% even the concentration of nitric acid reached 6 mol/L.The results of ²⁷Al/²⁹Si MAS NMR indicated that some extra-framework aluminum species appeared in H-HEU and they could protect the framework aluminum from further distortion, whereas this protective effect did not exist on Na-K-HEU and NH₄-HEU, as they have little extra-framework aluminum species.It can be further proved that through back-exchanging the H-HEU to Na-HEU and K-HEU, their resistance to nitric acid treatment could be markedly improved.
- clinoptilolite /
- nitric acid treatment /
- dealumination /
- framework structure

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图 1 硝酸处理前后不同HEU样品的XRD谱图

Figure 1 XRD patterns of HEU samples before and after nitric acid treatment

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图 2 4 mol/L硝酸处理前后不同HEU样品的²⁹Si MAS NMR谱图

Figure 2 ²⁹Si MAS NMR spectra of HEU samples before and after treatment with 4 mol/L nitric acid

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图 3 4 mol/L硝酸处理前后不同HEU样品的²⁷Al MAS NMR谱图

Figure 3 ²⁷Al MAS NMR spectra of various HEU samples and their analogues treated with 4 mol/L nitric acid

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图 4 Al落位在HEU不同晶格T位点的取代能和占据概率

Figure 4 Substitution energy and occupation probability of Al siting in different lattice T sites of HEU

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图 5 4 mol/L硝酸处理前后的Na-HEU和K-HEUXRD谱图

Figure 5 XRD patterns of Na-HEU and K-HEU before and after treatment with 4 mol/L nitric acid

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图 6 Na-HEU和K-HEU的²⁷Al MAS NMR谱图

Figure 6 ²⁷Al MAS NMR spectra of Na-HEU and K-HEU

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图 7 H⁺和Na⁺分别作为平衡阳离子时不同非骨架铝结构的相对稳定能

Figure 7 Relative stability energy of different extra-framework Al structures when H⁺or Na⁺ as equilibrium cations

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表 1 硝酸处理前后不同HEU样品的结构性质和化学组成

Table 1 The textural properties and chemical composition morphological of the samples

Sample	Si/Al^a	A_BET/(m²·g^-1)^b	v_micropore /(cm³·g^-1)^b	Relative crystallinity/%^c
Na-K-HEU	4.86	7.3	0.00050	100
Na-K-HEU-0.5	6.25	229.8	0.091	90.4
Na-K-HEU-1	7.83	205.9	0.083	88.5
Na-K-HEU-2	8.72	186.5	0.076	87.7
Na-K-HEU-4	11.33	126.7	0.046	44.7
Na-K-HEU-6	13.82	82.6	0.025	30.3
NH₄-HEU	5.02	8.7	0.005	100
NH₄-HEU-0.5	6.87	250.6	0.099	72.6
NH₄-HEU-1	7.23	229.9	0.095	65.2
NH₄-HEU-2	8.54	198.0	0.079	58.0
NH₄-HEU-4	10.9	191.9	0.072	42.6
NH₄-HEU-6	14.39	168.4	0.061	27.4
H-HEU	5.07	309.1	0.13	100
H-HEU-0.5	5.44	303.6	0.13	98.3
H-HEU-1	5.53	297.5	0.12	97.8
H-HEU-2	5.66	294.5	0.12	96.8
H-HEU-4	5.70	293.2	0.12	96.7
H-HEU-6	5.92	288.6	0.12	94.8
^a:the Si/Al molar ratios were measured by ICP-AES; ^b:the surface area were calculated by BET method, and the micropore volume were determined by t-plot; ^c:the relative crystallinity determined by XRD was comparing the sum of diffraction peak area of a zeolite sample with 2θ of 9.9° and 22.5° to that of the reference samples (Na-K-HEU, NH₄-HEU, H-HEU, assuming that it had a crystallinity of 100%, respectively)

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表 2 4 mol/L硝酸处理前后不同HEU样品的²⁹Si MAS NMR谱图拟合结果

Table 2 ²⁹Si chemical shifts and intensity of HEU samples before and after treatment with 4 mol/L nitric acid

Sample	(Si/Al)_F^a (molar ratio)	W/I_Si(nAl)/%
		Si(2Al)		Si(1Al)		Si(0Al)
		-95	-99	-101.5	-106	-108	-112
Na-K-HEU	4.86	6.5	8.4	16.7	36.6	16.3	15.5
Na-K-HEU-4	7.61	1.1	0.0	29.1	21.3	8.3	40.2
NH₄-HEU	5.06	1.1	8.7	20.0	39.4	16.6	14.2
NH₄-HEU-4	7.75	3.9	0.0	23.8	20.0	11.3	41.0
H-HEU	8.30	2.1	2.9	17.1	17.7	28.6	31.6
H-HEU-4	8.94	4.4	2.5	15.2	15.7	28.9	33.3
^a:the (Si/Al)_F molar ratios were obtained from ²⁹Si MAS NMR spectra

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表 3 不同HEU样品的²⁷Al MAS NMR谱图拟合结果

Table 3 Al distribution of various HEU samples determined from ²⁷Al MAS NMR

Sample	4-fold FAl/%	5-fold EFAl/%	6-fold EFAl/%	FAl/%^a	EFAl/%^b
Na-K-HEU	100.0	0.0	0.0	100.0	0.0
Na-K-HEU-4	69.1	15.5	15.4	69.1	30.9
NH₄-HEU	100.0	0.0	0.0	100.0	0.0
NH₄-HEU-4	63.7	14.9	21.4	63.7	36.3
H-HEU	64.2	17.1	18.7	64.2	35.8
H-HEU-4	59.3	15.9	24.8	59.3	40.7
Na-HEU	60.1	36.9	3.0	60.1	39.9
K-HEU	68.1	29.9	2.0	68.1	31.9
^a:framework Al content; ^b:etraframework Al content

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表 4 不同HEU样品的T位骨架铝分布结果

Table 4 Al distribution at different T sites in various HEU samples

Sample	60/% ^a	56/% ^a	53/% ^a	47/% ^a
Theoretical HEU	26.2	59.8	14.0
Na-K-HEU	24.6	62.2	13.2	0.0
NH₄-HEU	23.1	66.6	10.3	0.0
H-HEU	4.1	50.3	8.1	37.5
Na-K-HEU-4	13.3	47.7	18.0	21.0
NH₄-HEU-4	17.5	41.5	26.8	14.2
H-HEU-4	3.7	50.2	8.0	38.1
^a:the ²⁷Al chemical shifts of various HEU samples

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表 5 4 mol/L硝酸处理前后Na-HEU和K-HEU的硅铝比和相对结晶度

Table 5 Si/Al molar rations and relative crystallinity of Na-HEU and K-HEU before and after treatment with 4 mol/L acid

Sample	Si/Al^a (molar ratio)	Relative crystallinity/%^b
Na-HEU	4.95	100.0
Na-HEU-4	5.77	99.9
K-HEU	5.02	100.0
K-HEU-4	5.82	99.5
^a:the Si/Al molar ratios were measured by ICP-AES; ^b:the relative crystallinity determined by XRD was comparing the sum of diffraction peak area of a zeolite sample with 2θ of 9.9° and 22.5° to that of the reference samples (Na-K-HEU, NH₄-HEU, H-HEU, assuming that it had a crystallinity of 100%, respectively)

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