有机空间位阻剂对NaP分子筛的调控作用

陈彦广; 康薇; 韩洪晶; 张亚男; 王海英; 徐婷婷; 杨秀琪; 宋华

有机空间位阻剂对NaP分子筛的调控作用

陈彦广^{1, 2, ,},
康薇^{1, 2},
韩洪晶^{1, 2},
张亚男^{1, 2},
王海英^{1, 2},
徐婷婷³,
杨秀琪^{1, 2},
宋华^{1, 2}

1.
东北石油大学化学化工学院, 黑龙江大庆 163318
2.
黑龙江省石油与天然气化工省重点实验室, 黑龙江大庆 163318
3.
中国石油大庆化工研究中心, 黑龙江大庆 163714

基金项目:

国家自然科学基金面上项目 51674089

黑龙江省新世纪优秀人才支持计划 1254-NCET-004

黑龙江省博士后科研启动项目 LHB-Q16037

黑龙江省研究生创新项目 YJSCX2017-014NEPU

黑龙江省研究生创新项目 YJSCX2015-022NEPU

详细信息

通讯作者:
陈彦广, Tel:0459-6507729, E-mail:ygchen79310@126.com

中图分类号: TQ534
计量
- 文章访问数: 85
- HTML全文浏览量: 27
- PDF下载量: 4
- 被引次数: 0
出版历程
- 收稿日期: 2017-04-17
- 修回日期: 2017-07-07
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-10-10

Regulation of the crystal growth of NaP zeolite with organic steric hindrance agents

CHEN Yan-guang^{1, 2
, ,},
KANG Wei^{1, 2},
HAN Hong-jing^{1, 2},
ZHANG Ya-nan^{1, 2},
WANG Hai-ying^{1, 2},
XU Ting-ting³,
YANG Xiu-qi^{1, 2},
SONG Hua^{1, 2}

1.
College of Chemistry and Chemical Engineering, Northeast Petroleum University, Daqing 163318, China
2.
Heilongjiang Provincial Key Laboratory of Oil and Gas Chemical Technology, Daqing 163318, China
3.
Daqing Petrochemical Research Center of CNPC, Daqing 163714, China

Funds:

The project was supported by the National Natural Science Foundation of China 51674089

the Program for New Century Excellent Talent in University of Heilongjiang Province 1254-NCET-004

Postdoctoral Scientific Research Developmental Fund LHB-Q16037

the Postgraduate Innovative Resative Research Projects of Northeast Petroleum University YJSCX2017-014NEPU

the Postgraduate Innovative Resative Research Projects of Northeast Petroleum University YJSCX2015-022NEPU

摘要

摘要: 以粉煤灰中提取出的硅酸钠和铝酸钠为原料，通过水热合成法制备NaP型分子筛。通过正交实验优化了晶化时间、晶化温度和溶液硅水比等工艺参数，提出了通过空间位阻效应调控晶粒生长过程的方法，探索了结构空间位阻作用对NaP型分子筛生长过程晶型、粒径的调控规律。采用XRD、FI-IR、SEM、BET等手段对产物的晶型、粒径和形貌进行表征，并对不同条件下制备的NaP型分子筛的吸附性能进行了评价。结果表明，水热反应体系中引入空间位阻效应能有效调控NaP型分子筛的形貌和粒径；空间位阻效应的影响规律为环状结构>链状结构，长链结构>短链结构。吸附性能测试表明，Zn²⁺有效吸附去除率可达99.8%。
- 粉煤灰 /
- 空间位阻调控 /
- NaP型分子筛 /
- Zn²⁺ /
- 吸附性能
Abstract: With sodium silicate and sodium aluminate extracted from fly ash as the raw materials, NaP zeolite was prepared by hydrothermal synthesis method; the synthesis parameters such as crystallization time, temperature and the ratio of silicon/H₂O were optimized via orthogonal tests. The method to regulate the crystal growth process was proposed through controlling the steric hindrance effect. The NaP zeolite was characterized by XRD, FT-IR, SEM and N₂ sorption; the effect of steric hindrance on the crystal phase and grain size was investigated. The results show that the morphology and grain size of NaP zeolite can be effectively regulated by introducing steric hindrance agents into the hydrothermal reaction system. The strength of steric hindrance effect of various agents follows the order of ring structure > linear structure, long chain structure > short chain structure. The adsorption test suggests that removal rate of Zn²⁺ exceeds 99.8% for NaP zeolite under the optimal adsorption conditions.
- fly ash /
- steric hindrance regulation /
- NaP zeolite /
- Zn²⁺ /
- adsorption performance

HTML全文

图 1 正交实验制备NaP型分子筛的XRD谱图

Figure 1 XRD patterns of the NaP zeolite prepared under different synthesis conditions

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图 2 正交实验分析

Figure 2 Analysis of orthogonal tests

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图 3 不同空间位阻剂制备NaP型分子筛的SEM照片

Figure 3 SEM images of the NaP zeolites prepared with different organic space-confined additives

(a): NaP-RAW; (b): NaP-TWEEN-20; (c): NaP-AMP; (d): NaP-ANOL

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图 4 空间位阻剂对晶体生长的影响过程

Figure 4 Effect of steric hindrance on the crystal growth process

(a): RAW; (b): organic space-confined additives

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图 5 不同比例AMP制备NaP型分子筛的XRD谱图

Figure 5 XRD patterns of the NaP zeolites prepared with different amounts of AMP

a: crystallinity=89.44% Al₂O₃:M=1:5;b: crystallinity=35.27% Al₂O₃:M=1:3;c: crystallinity=8.19% Al₂O₃:M=1:1

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图 6 不同比例AMP制备NaP型分子筛的SEM照片

Figure 6 SEM images of the NaP zeolites prepared with different amounts of AMP

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图 7 不同比例TWEEN-20制备NaP型分子筛的XRD谱图

Figure 7 XRD patterns of the NaP zeolites prepared with different amounts of TWEEN-20

a: crystallinity=12.26% Al₂O₃:M=500:1; b: crystallinity=96.66% Al₂O₃:M=1000:1; c: crystallinity=35.08% Al₂O₃:M=2000:1

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图 8 不同比例TWEEN-20制备NaP型分子筛SEM照片

Figure 8 SEM images of the NaP zeolites prepared with different amounts of TWEEN-20

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图 9 不同比例ANOL制备NaP型分子筛的XRD谱图

Figure 9 XRD patterns of the NaP zeolites prepared with different amounts of ANOL

a: crystallinity=52.57% Al₂O₃:M=1:5; b: crystallinity=85.15% Al₂O₃:M=1:3; c: crystallinity=73.3% Al₂O₃:M=1:1; d: crystallinity=23.69% Al₂O₃:M=2:1

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图 10 不同比例ANOL制备NaP型分子筛的SEM照片

Figure 10 SEM images of the NaP zeolites prepared with different amounts of ANOL

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图 11 不同有机空间位阻剂制备NaP型分子筛的FT-IR谱图

Figure 11 FI-IR spectra of the NaP zeolites prepared with different organic steric hindrance agents

a: NaP-AMP; b: NaP-ANOL; c: NaP-TWEEN-20; d: NaP-RAW

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图 12 添加不同空间位阻剂制备的NaP型分子筛对溶液中Zn²⁺的去除率

Figure 12 Removal rate of Zn²⁺ by the NaP zeolite prepared with different organic steric hindrance agents

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表 1 正交实验

Table 1 Results of the orthogonal tests for the synthesis of NaP zeolite

Entry		H₂O/Si	Crystallization temperature t/℃	Crystallization time t/h	Yield w/%
1		156	100	8	50.69
2		156	120	10	58.96
3		156	140	12	55.93
4		136	100	10	48.32
5		136	120	12	59.64
6		136	140	8	48.88
7		116	100	12	58.89
8		116	120	8	60.34
9		116	140	10	53.22
X	k1	55.19	52.63	53.30	—
	k2	52.28	59.65	53.50	—
	k3	57.48	52.68	58.15	—
	Error R	5.203	7.014	4.853	—

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表 2 不同条件下制备NaP型分子筛的氮吸附

Table 2 Textural properties of the NaP zeolites prepared under different conditions

Steric hindrance agent	Surface area A/(m²·g^-1)	Pore volume v/(cm³ g^-1)	Pore diameter d/nm
NaP-RAW	67.5	0.046	2.8
NaP-AMP	29.1	0.028	3.9
NaP-TWEEN-20	26.8	0.024	3.6
NaP-ANOL	82.1	0.056	2.8

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