Comparison on stability of sulfated solid superacid with water pretreatment

doi:10.11949/j.issn.0438-1157.20151173

Abstract

Abstract:

In order to conveniently and rapidly evaluate the stability of the sulfated solid superacid against the water, the TiO₂-supported and the ZrO₂-supported solid superacid were used as the objects to study the influence of support and preparation process on the stability of solid superacid under different temperature water pretreatment. The physical structure of solid superacid was characterized by means of XRD and BET. It was found that there were no significant changes in crystallite and pore structure of the solid superacid with water pretreatment. FTIR and NH₃-TPD results showed that the catalytic activity of all the solid superacid decreased a lot after water pretreatment. When the temperature of water pretreatment was rising, the amount of SO₄^2- further dropped so that the acid amount fell and the catalytic activity of solid superacid decreased significantly. Moreover, the present work showed that the stability of ZrO₂-supported sulfated solid superacid was better than that of TiO₂-supported sulfated solid superacid but the initial activity was worse than the TiO₂-supported superacid. In addition, the loss of SO₄^2- of solid superacid prepared by calcination before SO₄^2- acidification was less than that by SO₄^2- acidification before calcination, which indicated that the preparation process had influence on the stability of solid superacid.

Key words: solid superacid, water, esterification, stability, catalyst

摘要：

以TiO₂和ZrO₂为载体的固体超强酸作为考察对象,重点对比研究了载体与酸化方式不同的固体超强酸在两种不同温度水预处理条件下的催化稳定性。XRD和BET表征结果显示在经过水预处理之后,各组固体超强酸的晶型和孔结构没有发生变化。结合FTIR、NH₃-TPD对比研究发现,各组固体超强酸的催化活性在经过水预处理后均出现下降,水预处理温度越高,固体超强酸的酸量下降越多,酸强度减弱幅度越大,最终表现出催化活性明显下降;相比之下,硫酸促进型TiO₂固体超强酸的初始活性优于以ZrO₂为载体的固体超强酸,但稳定性较差;另外,对制备方式的研究发现,先焙烧再酸化所制得的固体超强酸其SO₄^2-在水预处理过程中损失相对较少,表现出了较好的稳定性。

关键词: 固体超强酸, 水, 酯化, 稳定性, 催化剂

CLC Number:

TQ032.4

QIAN Qi, WANG Danya, WANG Lei, ZHANG Xue, HU Di, ZHAO Xuejuan, LI Xiaobao, LI Licheng. Comparison on stability of sulfated solid superacid with water pretreatment[J]. CIESC Journal, 2016, 67(4): 1610-1617.

钱祺, 王丹雅, 王磊, 张雪, 扈翟, 赵学娟, 李小保, 李力成. 硫酸促进型固体超强酸在水预处理条件下的稳定性对比[J]. 化工学报, 2016, 67(4): 1610-1617.

References 26

[1]	沈翔, 魏小容, 王焰新, 等.SO42--TiO2/MOR新型固体酸催化果糖制备5-羟甲基糠醛[J]. 化工学报, 2011, 62 (12): 3411-3418. DOI: 10.3969/j.issn.0438-1157.2011.12.016. SHEN X, WEI X R, WANG Y X, et al. SO42--TiO2/MOR as novel solid acid catalyst for dehydration of fructose to 5-hydroxymethylfurfural[J]. CIESC Journal, 2011. 62 (12): 3411-3418. DOI: 10.3969/j.issn.0438-1157.2011.12.016.
[2]	李忠, 刘媛媛, 郑华, 等. 固体酸负载CuI催化剂表征及催化甲醇氧化羰基化[J]. 化工学报, 2010, 61 (6): 1443-1449. LI Z, LIU Y Y, ZHENG H, et al. Characterization and catalytic performance of Cu2-/solid acids catalysts in oxidative carbonylation of methanol[J].CIESC Journal, 2010, 61 (6): 1443-1449.
[3]	SUN Y Y, YUAN L, MA S Q, et al. Improved catalytic activity and stability of mesostructured sulfated zirconia by Al promoter[J]. Applied Catalysis, 2004, 268 (1/2): 17-24. DOI: 10.1016/j.apcata.2004.03.014.
[4]	MARTINS R L, SCHMAL M. Methane activation on superacidic catalystsbased on oxoanion modified zirconium oxide[J]. Applied Catalysis, 2006, 308 (10): 143-152. DOI: 10.1016/j.apcata.2006.04.018.
[5]	YU G X, Zhou X L, Li C L. et al. Gonzalez, esterification over rare earth oxide and alumina promoted SO42-/ZrO2[J]. Catal. Today, 2009, 148 (1/2): 169-173. DOI: 10.1016/j.cattod.2009.03.006.
[6]	WULFERS M J, TZOLOVA-MULLER G, VILLEGAS J I, et al. Deactivation of sulfated-zirconia and H-mordenite catalysts during n-butane and isobutane isomerization[J]. Journal of Catalysis, 2012, 296 (1): 132-142. DOI: 10.1016/j.jcat.2012.09.015.
[7]	张萍, 刘占荣, 张艳峰, 等. 纳米级SO42-/TiO2固体超强酸储存稳定性研究[J]. 河北师范大学学报, 2007, 31 (1): 81-84. ZHANG P, LIU Z R, ZHANG Y F, et al. Studies on the storge stability of the nano-sized SO42-/TiO2 solid super acid[J]. Journal of Hebei Normal University, 2007, 31 (1): 81-84.
[8]	黄海凤, 张峰, 卢晗锋, 等. 制备方法对低温NH3-SCR脱硝催化剂MnOx/TiO2结构与性能的影响[J]. 化工学报, 2010, 61 (1): 80-85. HUANG H F, ZHANG F, LU H F, et al. Effect of preparation methods on structures and performance of MnOx/TiO2 catalyst for low-temperature NH3-SCR[J]. CIESC Journal, 2010, 61 (1): 80-85.
[9]	孙红旗, 程友萍, 金万勤, 等. 镧、碳共掺杂TiO2的制备及其可见光催化性能[J]. 化工学报, 2006, 57 (7): 1570-1574. SUN H Q, CHEN Y P, JIN W Q, et al. Preparation of lanthanum and carbon co-doped TiO2 and photocatalysis under visible irradiation[J]. Journal of Chemical Industry and Engineering (China), 2006, 57 (7): 1570-1574.
[10]	Shi W P. A new deactivation mechanism of sulfate-promoted iron oxide[J]. Catal. Leter, 2013, 143 (12): 1285-1293. DOI: 10.1007/s10562-013-1016-4.
[11]	LI X B, NAGAOKA K, LERCHER J A. Labile sulfates as key components in active sulfated zirconia for n-butane isomerization at low temperatures[J]. Journal of Catalysis, 2004, 227 (1): 130-137. DOI: 10.1016/j.jcat.2004.07.003.
[12]	陈建民, 缪长喜, 华伟明, 等.SO42-/ZrO2固体超强酸储存稳定性研究[J]. 高等学校化学学报, 1996, 5 (7): 797-799. CHEN J M, MIAO C X, HUA W M, et al. Studies on the storage stability of SO42-/ZrO2 solid superacid[J]. Chemical Journal of Chinese Universities, 1996, 5 (7): 797-799.
[13]	SUWANNAKARN K, LOTERO E, GOODWIN J G, et al. Stability of sulfated zirconia and the nature of the catalytically active species in the transesterification of triglycerides[J]. Journal of Catalysis, 2008, 225 (2): 279-286. DOI: 10.1016/j.jcat.2008.02.014.
[14]	MAO W, MA H Z, WANG B. Mild ring-opening coupling of liquid-phase cyclohexane to diesel components using sulfated metal oxides[J]. Journal of Hazardous Materials, 2010, 176 (1/2/3): 361-366. DOI: 10.1016/j.jhazmat.2009.11.036.
[15]	LI Z L, WNETRZAK R, KWAPINSKI W, et al. Synthesis and characterization of sulfated TiO2 nanorods and ZrO2/TiO2 nanocomposites for the esterification of biobased organic acid[J]. American Chemical Society, 2012, 4 (9): 4499-4505. DOI: 10.1021/am300510u.
[16]	HINOA M, TAKASAKI S, FURUTA S, et al. Meta-stannic acid as an effective support for the preparation of sulfated and tungstated stannias[J]. Applied Catalysis A, 2007, 321 (2): 147-154. DOI: 10.1016/j.apcata.2007.01.044.
[17]	马中义, 徐润, 杨成, 等. 不同形态ZrO2的制备及其表面性质研究[J]. 物理化学学报, 2004, 20 (10): 1221-1225. MA Z Y, XU R, YANG C, et al. Preparation and surface properties of different zirconia polymorphs[J]. Acta Physcio-Chimica Sinica, 2004, 20 (10): 1221-1225.
[18]	JOZWIAK W K, NOWOSIELSKA M, RYNKOWSKI J. Reforming of methane with carbon dioxide over supported bimetallic catalysts containing Ni and noble metal(I):Characterization and activity of SiO2 supported Ni-Rh catalysts.[J]. Applied Catalysis A, 2005, 280 (2): 233-244. DOI: 10.1016/j.apcata.2004.11.003.
[19]	BARAN E J. Infrared and Raman spectra of inorganic and coordination compounds[J]. Journal of Coordination Chemistry, 2001, 54 (3/4): 215-238. DOI: 10.1080/00958970108022636.
[20]	NODA L K, DE ALMEIDA R M, PROBST L F D, et al. Characterization of sulfated TiO2 prepared by the sol-gel method and its catalytic activity in the n-hexane isomerization reaction[J]. Journal of Molecular Catalysis A: Chemical, 2005, 225 (1): 39-46. DOI: 10.1016/j.molcata.2004.08.025.
[21]	WANG P, YANG S W, KONDO J N, et al. Spectroscopic study of H2 and CO adsorption on platinum-promoted sulfated zirconia catalysts[J]. Journal of Physical Chemistry B, 2003, 107 (43): 11951-11959. DOI: 10.1021/jp030607c.
[22]	SU W, FU X, WEI K. Raman and infrared spectroscopic investigation of SO42-/ZrO2 solid acids[J]. Spectroscopy and Spectral Analysis, 2000, 20 (6): 840-841.
[23]	QI F, XU B B, CHEN Z L, et al. Influence of aluminum oxides surface properties on catalyzed ozonation of 2,4,6-trichloroanisole[J]. Separation and Purification Technology, 2009, 66 (2): 405-410. DOI: 10.1016/j.seppur.2009.01.013.
[24]	WEI Y B, ZONG Z M, XIE R L, et al. Solid superacid-catalyzed hydroconversion of demineralized Shengli coal liquefaction residue under microwave irradiation[J]. Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 2010, 32 (6): 551-558. DOI: 10.1080/15567030802564765.
[25]	于荟, 朱银华, 刘畅, 等. 新型介孔SO42-/TiO2固体酸的制备及其催化酯化性能[J] 催化学报, 2009, 30 (3): 265-271. YU H, ZHU Y H, LIU C, et al. Preparation of novel mesoporous SO42-/ZrO2 solid acid catalyst and its catalytic activity for esterification[J]. Chinese Journal of Catalysis, 2009, 30 (3): 265-271.
[26]	汪颖军, 孙博, 张海菊, 等. SO42-/MxOy型固体超强酸研究进展[J]. 工业催化, 2008, 16 (2): 12-17. WANG Y J, SUN B, ZHANG H J. Advances in SO42-/MxOy solid superacid catalysts[J]. Industrial Catalysis, 2008, 16 (2): 12-17.