Preparation of NaP Zeolite with Low Si/Al Molar Ratio from Flying Ash†

doi:10.7503/cjcu20140845

Abstract

Abstract:

Taking Na₂SiO₃ and NaAlO₂ obtained from flying ash by staged treatment as raw material, NaP zeolite was prepared via hydrothermal method. The influences of organic steric agents and sodium salts with different anions on the preparation of NaP zeolite were investigated. The synthetic parameters of the hydrothermal system for NaP zeolite were optimized. The crystal form, morphology and pore volume of the NaP zeolite were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and Brunauer-Emmett-Teller(BET) surface analysis, respectively. The adsorption performance of the NaP zeolite in Ni²⁺-containing solution was evaluated. The results show that the optimal parameters for the preparation NaP zeolite are as following: n(Na₂O)∶n(SiO₂)∶n(Al₂O₃)∶n(H₂O)=1.66∶1∶0.51∶116, the reaction temperature is 120 ℃, crystalization time is 8 h. Br^- is in favor of improving the purity and increasing the yield of NaP zeolite. With the addition of triethylolamine(TEA), the grain size of NaP zeolite becomes smaller and the pore volume is enlarged. The maximum removal rate for Ni²⁺ is about 96.2%.

Key words: Flying ash, NaP zeolite, Hydrothermal synthesis, Organic steric agent, Anion, Ni2+

CLC Number:

O611.4
X773

TrendMD:

CHEN Yanguang, XIE Conghao, HAN Hongjing, ZHAO Fajun, WANG Baohui. Preparation of NaP Zeolite with Low Si/Al Molar Ratio from Flying Ash^†[J]. Chem. J. Chinese Universities, 2015, 36(2): 229.

Figures/Tables 16

Fig.1 Structure of P zeolite framework

Fig.2 Synthetic routes of NaP zeolite from flying ash

Fig.3 XRD patterns of products prepared with different molar ratios of H2O/SiO2 n(H2O)/n(SiO2): a. 96; b. 116; c. 136; d. 156. X, P and S represent X-type, P-type zeolites and SOD, respectively.

Fig.4 XRD patterns of products prepared with different reaction temperature X, P and S represent X-type, P-type zeolites and SOD, respectively. Reaction temperature/℃: a. 90; b. 105; c. 120; d. 135.

Fig.5 XRD patterns of products prepared at different reaction time Reaction time/h: a. 2; b. 4; c. 6; d. 8.

Fig.6 SEM images of products prepared for different reaction time Reaction time/h: (A) 2; (B) 4; (C) 6; (D) 8.

Fig.7 XRD patterns of products prepared with different additives a. TEA; b. MEA; c. DEA.

Fig.8 SEM images of products prepared with different additives

Table 1 Yield and average diameter of NaP with different additives

Organic steric agent	Yield(%)	Average diameter/μm
	87.8	2.78
TEA	80.2	1.64
MEA	81.8	2.25
DEA	78.4	2.65

Fig.9 Yield of NaP prepared with different n(TEA)/n(Al2O3) ratios

Fig.10 SEM image of NaP prepared at n(TEA)/n(Al2O3)=1

Fig.11 XRD patterns of products prepared with NaCl(a), NaBr(b), NaNO3(c) and NaOH(d)

Fig.12 SEM(A) and EDS(B) results of NaP prepared with the addition of NaBr

Table 2 Variation of pH value of solution and yield of product

NaX	pH(before reaction)	pH(after reaction)	Yield(%)
NaOH	14.38	14.47	87.8
NaCl	14.22	14.11	89.7
NaBr	14.22	14.26	94.2
NaNO₃	14.23	14.19	90.1

Fig.13 Result of Ni2+ removed by NaP zeolite prepared with different treatment method

Table 3 Pore volume and diameter of zeolites

Treatment method	Pore volume/(cm³·g^-1)	Average diameter/nm
Raw	0.026456	22.00225
NaBr addition	0.043124	7.59387
TEA addition^*	0.046964	4.31398

References 24

[1]	Yao Z. T., Xia M. S., Sarkerd P. K., Chen T., Fuel, 2014, 120(3), 74—85
[2]	Musyoka N. M., Petrik L. F., Hums E., Baser H., Schwieger W., Catal. Today, 2012, 190(1), 38—46
[3]	Zhong S. L., Zhang M. S., Su Q., Chem. J. Chinese Universities, 2005, 26(9), 1603—1606
	(钟声亮, 张迈生, 苏锵. 高等学校化学学报, 2005, 26(9), 1603—1606)
[4]	Bohra S., Kundu D., Naskar M. K., Mater. Lett., 2013, 106(1), 182—185
[5]	Kong D. S., Li Z., Li L., Fan J. X., J. Synth. Cryst., 2013, 42(4), 772—777
	(孔德顺, 李志, 李琳, 范佳鑫. 人工晶体学报, 2013, 42(4), 772—777)
[6]	Kong D. S., Ji Y. H., Qin B. K., Fan J. X., Wu H., China Ceram., 2013, 49(3), 24—27
	(孔德顺, 籍永华, 秦丙克, 范佳鑫, 吴红. 中国陶瓷, 2013, 49(3), 24—27)
[7]	Liu Z. L., Cao J. L., Liu X. W., Gao C. H., J. Synth. Cryst., 2009, 38(5), 1128—1133
	(刘振路, 曹吉林, 刘秀伍, 高长虹. 人工晶体学报, 2009, 38(5), 1128—1133)
[8]	Du Y. C., Shi S. L., Dai H. X., Particuology, 2011, 9(2), 174—178
[9]	Samadi-Maybodi A., Pourali S. M., Microporous Mesoporous Mater., 2013, 167(4), 127—132
[10]	Zhang Q., Li C. Y., Shan H. H., Yang Z. H., Chem. J. Chinese Universities, 2011, 32(12), 2721—2726
	(张强, 李春义, 山红红, 杨朝合. 高等学校化学学报, 2011, 32(12), 2721—2726)
[11]	Zhang Q., Xu S. J., Meng X. J., Yang W. H., Li C. Y., Shan H. H., Yang Z. H., Chem. J. Chinese Universities, 2013, 34(4), 782—787
	(张强, 徐少军, 孟晓静, 杨文慧, 李春义, 山红红, 杨朝合. 高等学校化学学报, 2013, 34(4), 782—787)
[12]	Azizi S. N., Ghasemi S., Amiripour F., Electrochim. Acta, 2014, 137(8), 395—403
[13]	Bohra S., Kundu D., Naskar M. K., Ceram. Int., 2014, 40(1), 1229—1234
[14]	Chen Y. G., Xie C. H., Li Z. M., Han H. J., Li F., Song J., A Method of Using Fly Ash to Prepare P Zeolite, 201410501187.3, 2014-09-26
	(陈彦广, 解骢浩, 李治淼, 韩洪晶, 李锋, 宋军. 一种以粉煤灰为原料制备P型分子筛的方法, 201410501187.3, 2014-09-26)
[15]	Zhang Q., Chen C. Y., Ding S., Zhang W. T., Xu D. O., Tang X. J., Wang R. W., Jiang R. H., Zhang Z. T., Qiu S. L., Chem. J. Chinese Universities, 2012, 33(3), 453—457
	(张前, 陈春影, 丁双, 张文婷, 许迪欧, 唐晓建, 王润伟, 姜日花, 张宗弢, 裘式纶. 高等学校化学学报, 2012, 33(3), 453—457)
[16]	Lang W. Z., Ouyang J. X., Guo Y. J., East China University Sci. Technol.(Nat. Sci. Edition), 2010, 36(3), 334—339
	(郎万中, 欧阳洁霞, 郭亚军. 华东理工大学学报(自然科学版), 2010, 36(3), 334—339)
[17]	Kim J. K., Lee H. D., J. Ind. Eng. Chem., 2009, 15(5), 736—742
[18]	Hollman G.G.Steenbruggen G.Jurkoviěová J. M., Fuel, 1999, 78(10), 1225—1230
[19]	Bonaccorsi L., Proverbio E., Microporous Mesoporous Mater., 2004, 74(1—3), 221—229
[20]	Sun H., Shen B. X., Liu J. C., Dong J. H., East China University Sci. Technol.(Nat. Sci. Edition), 2008, 34(2), 172—177
	(孙辉, 沈本贤, 刘纪昌, 董霁虹. 华东理工大学学报(自然科学版), 2008, 34(2), 172—177)
[21]	Bosnar S.,B., J. Cryst. Growth, 2004, 267(1/2), 270—282
[22]	Bosnar S., ., Microporous Mesoporous Mater., 2011, 142(1), 389—397
[23]	Li M., Fu J. Q., Beijing Institute Clothing Technol.(Nat. Sci. Edition), 2012, 32(4), 51—58
	(李猛, 傅吉全. 北京服装学院学报(自然科学版), 2012, 32(4), 51—58)
[24]	GB 11910-89, Standards Press of China, Beijing, 1990(GB11910-89, 北京: 中国标准出版社, 1990)
	(Ed.: F, K, M)