囊泡状二氧化硅的合成及油气吸附性能

doi:10.7503/cjcu20140750

摘要/Abstract

摘要：

以正硅酸四甲酯(TMOS)为硅源, P123(EO₂₀PO₇₀EO₂₀)为表面活性剂, 在pH=6的磷酸缓冲体系中制备了囊泡状二氧化硅材料. 利用乙醇萃取脱除模板剂P123, 电镜观测结果表明所得二氧化硅具有大孔囊泡结构, N₂吸附结果表明其具有高比表面积和大孔容. 通过Boehm滴定法确定了硅羟基数量与吸水率呈正相关. 用囊泡状二氧化硅材料与商业化活性炭(AC)和硅胶(SG)对水蒸气、正己烷和油气进行静态吸附. 在自建的动态正己烷吸附装置上用对囊泡状二氧化硅材料和商业化AC和SG对正己烷进行动态吸附. 吸附结果表明, 囊泡状二氧化硅材料的静/动态吸附容量和稳定性都远高于商业化活性炭和硅胶.

关键词: 囊泡状二氧化硅, 油气吸附, 吸水, 静/动态吸附

Abstract:

Vesicular silica was synthesized using tetramethylorthosilicate[Si(OCH₃)₄, TMOS] as silica source and P123(EO₂₀PO₇₀EO₂₀) as the structure-directing agent in phosphate buffer solution(pH=6). Then, P123 was removed by extraction with ethanol. The synthesized siliceous materials were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM) and N₂ sorption isotherm. The results indicated that all the samples have a good dispersibility and vesiclar structure with a high specific surface area and a large pore volume. The adsorption and desorption performance of vesicular silica under static(for water vapor, n-hexane and 93# gasoline) and dynamic(for n-hexane) conditions were investigated with commercial silica gel(SG) and activated carbon(AC) as reference. The densities of surface hydroxyl group were determined by Boehm titration, which are linear to the corresponding water vapor adsorption capacities. The synthesized vesicular silica showed higher static adsorption capacity for n-hexane and 93# gasoline with good stability, higher dynamic adsorption capacity and stable breakthrough time under dynamic adsorption conditions.

Key words: Vesicular silica, Oil vapor adsorption, Water vapor adsorption, Static/dynamic adsorption

中图分类号:

O613.7

TrendMD:

王红宁, 戎霄, 黄维秋, 韩路, 王涛, 陈若愚. 囊泡状二氧化硅的合成及油气吸附性能. 高等学校化学学报, 2014, 35(12): 2516.

WANG Hongning, RONG Xiao, HUANG Weiqiu, HAN Lu, WANG Tao, CHEN Ruoyu. Synthesis of Vesicular Silica and Its Application in Volatile Organic Compounds Adsorption^†. Chem. J. Chinese Universities, 2014, 35(12): 2516.

图/表 7

Fig.1 SEM(A—D) and TEM(E—H) images of N0(A,E), N1(B,F), N3(C,G) and N6(D,H)

Fig.2 N2 adsorption-desorption isotherms(A) and pore size distributions(B) for N0(a), N1(b), N3(c) and N6(d) (A) the Y-axes values of isotherms b, c, d are raised 300, 600, 1000 cm3/g, respectively.

Table 1 Structure parameters of N0, N1, N3, N6

Sample	Surface area/(m²·g^-1)	Micropore area/(m²·g^-1)	Pore volume/(cm³·g^-1)	Micropore volume/(cm³·g^-1)
N0	342	53	0.77	0.022
N1	358	63	0.94	0.024
N3	406	69	1.12	0.026
N6	365	61	1.10	0.025

Fig.3 Histograms of static adsorption capacity(A, B) and desorption efficiency(C, D) from triplicate measurements of different adsorbents for n-hexane(A, C) and 93# gasoline(B, D), respectively

Fig.4 Histograms of static water vapor adsorption capacity from triplicate measurements(A) and the linear relationship between water absorption capacities and the densities of surface hydroxyl(B) of different adsorbents

Fig.5 First breakthrough curves(A) and breakthrough time(B), equilibrium time(C), equilibrium adsorption capacity(D) for n-hexane of different adsorbents □ 1st; ○ 2nd; △ 3rd;▽ 4th.

Table 2 Dynamic equilibrium adsorption capacities and desorption efficiency of samples synthesized by different concentration of NaNO3, SG and AC

Sample	Adsorption cycle	Breakthrough time/min	Equilibrium adsorption time/min	Equilibrium adsorption capacity/(g·g^-1)	Desorption efficiency(%)
N0	1st	8	44	0.719	99.9
N0	4th	8	46	0.720	98.6
N1	1st	10	38	0.697	99.3
N1	4th	12	42	0.719	99.6
N3	1st	32	129	1.89	98.9
N3	4th	30	130	1.88	100.0
N6	1st	26	108	1.28	99.1
N6	4th	22	107	1.25	98.2
AC	1st	38	50	0.471	78.6
AC	4th	22	36	0.365	97.6
SG	1st	12	46	0.326	94.7
SG	4th	12	47	0.316	98.1

参考文献 38

[1]	Ramalingam S. G., Hamon L., Pré P., Giraudet S., Coq L.L., Cloirec P. L., J. Colloid Interface Sci., 2012, 377(1), 375—378
[2]	Liu B., Zhang W., Zhang Q. Y., Zhang H., Yu L., Yang X. L., J. Colloid Interface Sci., 2012, 375(1), 70—77
[3]	Al-Deen F. N., Selomulya C., Williams T., Colloids Surf. B, 2013, 102(1), 492—503
[4]	Long C., Yu W. H., Li A., Chem. Eng. J., 2013, 221(1), 105—110
[5]	Sui G. J., Li J. L., Ito A., Sep. Purif. Technol., 2009, 68(2), 283—287
[6]	Chiarotto I., Feroci M., Orisini M., Inesi A., Adv. Synth. Catal., 2010, 352(18), 3287—3292
[7]	He J. M., Ng K. C., Yap C., Saha B. B., J. Chem. Eng. Data, 2009, 54(5), 1504—1509
[8]	Dou B., Hu Q., Li J., Qiao S. Z., Hao Z. P., J. Hazard. Mater., 2011, 186(2), 1615—1624
[9]	Ramos M. E., Bonelli P. R., Cukierman A. L., Ribeiro C. M. L. L., Carrott P. J. M., J. Hazard. Mater., 2010, 177(1), 175—182
[10]	Hu X., Qiao S., Zhao X. S., Lu G. Q., Ind. Eng. Chem. Res., 2001, 40(3), 862—867
[11]	Serrano D. P., Calleja G., Botaset J. A., Gutierrez F. J., Ind. Eng. Chem. Res., 2004, 43(22), 7010—7018
[12]	Guillemot M., Mijoin J., Mignard S., Magnoux P., Ind. Eng. Chem. Res., 2007, 46(13), 4614—4620
[13]	Makowski W., Kus'trowski P., Microporous Mesoporous Mater., 2007, 102(1), 283—289
[14]	Christensen C. H., Johannsen K., Schmidt I., Christensen C. H., J. Am. Chem. Soc., 2003, 125(44), 13370—13371
[15]	Yu M., Zhang J., Yuan P., Wang H. N., Liu N., Wang Y. H., Yu C. Z., Chem. Lett., 2009, 38(5), 442—443
[16]	Kosuge K., Kubo S., Kikukawa N., Takemori M., Langmuir,2007, 23(6), 3095—3102
[17]	Qiao S. Z., Bhatia S. K., Nicholson D., Langmuir,2004, 20(2), 389—395
[18]	Zhang B. H., Fan H., Bian T., Wu L. Z., Tong Z. H., Zhang T. R., Chem. J. Chinese Universities, 2013, 34(1), 1—14
	(张百惠, 樊华, 卞僮, 吴骊珠, 佟振合, 张铁锐. 高等学校化学学报, 2013, 34(1), 1—14)
[19]	Stein A., Melde B. J., Schroden R. C., Adv. Mater., 2000, 12(19), 1403—1419
[20]	Vinh-Thang H., Huang Q. L., Eic M., Trong-On D., Kaliaguine S., Langmuir,2005, 21(11), 5094—5101
[21]	Schmidt-Winkel P., Lukens W. W., Zhao D., J. Am. Chem. Soc., 1999, 121(1), 254—255
[22]	Imhof A., Pine D., Nature,1997, 389(6654), 948—950
[23]	Norell M. A., Makovicky P., Clark J. M., Nature,1997, 389(2), 447—448
[24]	Wang H. N., Zhou X. F., Yu M. H., Han L., Zhang J., Yuan P., Auchterlonie G., Zhou J., Yu C. Z., J. Am. Chem. Soc., 2006, 128(50), 15992—15993
[25]	Yuan P., Zhou X F., Wang H. N., Small,2009, 5(3), 377—382
[26]	Barton T. J., Bull L. M., Klemperer W. G., Chem. Mater., 1999, 11(10), 2633—2656
[27]	Sumper M., Angew. Chem. Int. Ed, 2004, 43(17), 2251—2254
[28]	Zhao D. Y., Feng J. L., Huo Q. S., Melosh N., Fredrickson G. H., Chmelka B. F., Science,1998, 279(5350), 548—552
[29]	Wang H. N., Wang Y. H., Zhou X., Adv. Funct. Mater., 2007, 17(4), 613—617
[30]	Wang H. N., Tang M., Zhang K., Cai D. F., Huang W. Q., J. Hazard. Mater., 2014, 268(15), 115—123
[31]	Lloyd G. O., Steed J. W., Nat. Chem., 2009, 1(6), 437—442
[32]	Sun Q. Y., Kooyman P. J., Grossmann J. G., Bomans P. H. H., Frederik P. M., Magusin P. C. M. M., Beelen T. P. M., van Santen R. A., Sommerdijk N., Adv. Mater., 2003, 15(13), 1097
[33]	Djojoputro H., Zhou X. F., Qiao S. Z., Wang L. Z., Yu C. Z., Lu G. Q., J. Am. Chem. Soc., 2006, 128(19), 6320—6321
[34]	Xie Y., Lü Z. Y., Sun Z. Y., An L. J., Chem. J. Chinese Universities, 2013, 34(6), 1454—1459
	(谢宇, 吕中元, 孙昭艳, 安立佳. 高等学校化学学报, 2013, 34(6), 1454—1459)
[35]	Hang W. Q., Lü A. H., Zhong J., Chin. J. Envir. Eng., 2007, 1(2), 73—77
	(黄维秋, 吕爱华, 钟璟. 环境工程学报, 2007, 1(2), 73—77)
[36]	Hu Q., Li J. J., Qiao S. Z., Hao Z. P., Tian H., Ma C. Y., He C., J. Hazard. Mater., 2009, 164(2/3), 1205—1212
[37]	Sears G. W., Anal. Chem., 1956, 28(12), 1981—1983
[38]	Ouyang Z. H., Wu L., Li K. B., Cao S. C., Wang Y., Lian L., Yi D. L., Qin X. R., Chem. Ind. Eng. Prog., 2005, 24, 1265—1268