并流滴加法制备大孔容纤维状γ-氧化铝

doi:10.11949/j.issn.0438-1157.20180609

摘要/Abstract

摘要：

以偏铝酸钠（NaAlO₂）-硫酸铝（Al₂（SO₄）₃）为原料，利用并流滴加法控制沉淀过程的反应pH，并通过调节原料浓度、老化pH和加入表面活性剂十二烷基苯磺酸钠（SDBS）等方法，成功制备得到了大孔容纤维状的γ-氧化铝。实验发现，不同的原料浓度会影响成核-生长过程，得到不规则片状、纤维状或颗粒状等不同形貌的γ-氧化铝，其中纤维状可形成大孔容。当NaAlO₂浓度为0.5~0.75 mol/L，反应pH控制在8~9.5，老化pH控制在9左右时，得到的γ-氧化铝呈纤维状，孔容较大；此外，在老化过程中添加SDBS可进一步提高孔容，并改善孔径分布。本方法成功制备出孔容为1.35~2.19 ml/g、比表面积为300~500 m²/g、平均孔径为14~21 nm的纤维状γ-氧化铝，纤维长度为50~60 nm，纤维宽度约5 nm，可为渣油加氢过程提供一种性能良好的催化剂载体。

关键词: 偏铝酸钠-硫酸铝, 沉淀法, γ-氧化铝, 并流滴加, 成核-生长, 表面活性剂

Abstract:

A co-current dropwise addition method was employed to prepare γ-alumina with a large pore volume with sodium aluminate (NaAlO₂) and aluminum sulfate (Al₂(SO₄)₃) used as raw materials. The effects of the reaction pH during the precipitation process, raw material concentration, aging pH and adding surfactant sodium dodecyl benzene sulfonate (SDBS) were investigated. It was found that raw material concentration could affect the nucleation-growth process and result in different morphologies, such as irregular sheets, fibers or granules, in which fibers could form the largest pore volume. When the NaAlO₂ concentration was 0.5-0.75 mol/L, the reaction pH was controlled at 8-9.5 and the aging pH was controlled at about 9, the obtained γ-alumina is fibrous. Besides, adding SDBS during the aging process could further improve the pore volume and pore size distribution. The method successfully prepared fibrous γ-alumina with a pore volume of 1.35-2.19 ml/g, a specific surface area of 300-500 m²/g and an average pore diameter of 14-21 nm, a fiber length of 50-60 nm and diameter about 5 nm. It can provide a good catalyst carrier for the residue hydrogenation process.

Key words: NaAlO₂-Al₂(SO₄)₃, precipitation method, γ-alumina, co-current dropwise addition, nucleation-growth, surfactant

中图分类号:

TQ133.1

万艳春, 王玉军, 骆广生. 并流滴加法制备大孔容纤维状γ-氧化铝[J]. 化工学报, 2018, 69(11): 4840-4847.

WAN Yanchun, WANG Yujun, LUO Guangsheng. Preparation of fibrous γ-alumina with large pore volume via co-current dropwise addition method[J]. CIESC Journal, 2018, 69(11): 4840-4847.

参考文献 31

[1]	李慧韫, 张天胜, 杨南. 纳米氧化铝的制备方法及应用[J]. 天津科技大学学报, 2003, 18(4):34-37. LI H Y, ZHANG T S, YANG N. The preparation and application of nanometer-Al2O3[J]. Journal of Tianjin University of Light Industry, 2003, 18(4):34-37.
[2]	周克刚, 李玉平, 李骏驰, 等. 直接沉淀法制备纤维状纳米Al2O3[J]. 湖南大学学报(自然科学版), 2009, 36(8):59-63. ZHOU K G, LI Y P, LI J C, et al. Preparation of fibrous nano-alumina by direct precipitation[J]. Journal of Hunan University (Natural Sciences), 2009, 36(8):59-63.
[3]	ZOU S, YANG Q, ZENG S, et al. The form of sulfate in pseudo-boehmite and its effect on properties of pseudo-boehmite[J]. China Petroleum Processing & Petrochemical Technology, 2014, 16(4):1-6.
[4]	陈玮, 尹周澜, 陈玮, 等. 氧化铝在汽车尾气催化剂载体中的应用研究[J]. 新技术新工艺, 2006, (2):98-99. CHEN W, YIN Z L, CHEN W, et al. Studying on alumina of catalyst substrate in automobile exhaust cleaning[J]. New Technology & New Process, 2006, (2):98-99.
[5]	王鼎聪, 刘纪端. 贯穿性框架式渣油脱金属催化剂氧化铝载体的研究[J]. 石油炼制与化工, 2010, 41(1):31-35. WANG D C, LIU J D. Study on the hydrodemetallization catalyst using alumina support with build-up framework pore structure[J]. Petroleum Processing and Petrochemicals, 2010, 41(1):31-35.
[6]	王楚. 裂解汽油加氢催化剂氧化铝载体的制备方法及其负载催化性能研究[D]. 兰州:兰州理工大学, 2015. WANG C. The research on preparation method and loading catalytic performance of pyrolysis gasoline hydrogenation catalyst alumina supporter[D]. Lanzhou:Lanzhou University of Technology, 2015.
[7]	曾双亲, 杨清河, 肖成武, 等. 干燥方式及老化条件对拟薄水铝石性质的影响[J]. 石油炼制与化工, 2012, 43(6):53-57. ZENG S Q, YANG Q H, XIAO C W, et al. Effect of drying and aging conditions on the properties of pseudo-boehmite[J]. Petroleum Processing and Petrochemicals, 2012, 43(6):53-57.
[8]	张李锋, 石悠, 赵斌元, 等. γ-Al2O3载体研究进展[J]. 材料导报, 2007, 21(2):67-71. ZHANG L F, SHI Y, ZHAO B Y, et al. Progress in research on γ-alumina catalyst carrier[J]. Materials Review, 2007, 21(2):67-71.
[9]	佟佳, 吕振辉, 张学辉. 大孔容孔径氧化铝的合成研究[J]. 当代化工, 2016, 45(6):1104-1107. TONG J, LYU Z H, ZHANG X H. Study on synthesis of alumina with large pore volume and pore size[J]. Contemporary Chemical Industry, 2016, 45(6):1104-1107.
[10]	饶拴民, 朱建军, 杜海荣. 大孔容活性氧化铝的用途和制备方法[J]. 轻金属, 2002, (3):17-18. RAO S M, ZHU J J, DU H R. Application and preparation of activated alumina with large pore volume[J]. Light Metals, 2002, (3):17-18.
[11]	杜淼, 孙中溪. 纳米氧化铝制备方法研究进展[J]. 无机盐工业, 2005, 37(12):9-11. DU M, SUN Z X. Recent development in the preparation of nano-alumina[J]. Inorganic Chemicals Industry, 2005, 37(12):9-11.
[12]	THIRUCHITRAMBALAM M, PALKAR V R, GOPINATHAN V. Hydrolysis of aluminium metal and sol-gel processing of nano alumina[J]. Materials Letters, 2004, 58(24):3063-3066.
[13]	杜善国, 刘勇. 碳化法制备超细氢氧化铝微粉晶种的研究[J]. 中国粉体技术, 2011, 17(4):80-82. DU S G, LIU Y. Preparation of seed crystals for superfine aluminum hydroxide powders by carbonization process[J]. China Powder Science and Technology, 2011, 17(4):80-82.
[14]	王玉. 铝酸钠溶液中和法制取拟薄水铝石[J]. 轻金属, 2010, (4):19-20. WANG Y. Preparation of psedo-boehmite from sodium aluminate solution[J]. Light Metals, 2010, (4):19-20
[15]	YOLDAS B E. Transparent porous alumina[J]. American Ceramic Society Bulletin, 1975, 54(3):286-288.
[16]	KOBAYASHI Y, ISHIZAKA T, KUROKAWA Y. Preparation of alumina films by the sol-gel method[J]. Journal of Materials Science, 2005, 40(2):263-283.
[17]	周峰, 张艳, 樊慧芳. 关于用偏铝酸钠——二氧化碳法制备拟薄水铝石的研究[J]. 世界有色金属, 2008, (5):31-33. ZHOU F, ZHANG Y, FAN H F. Researches on the preparation of pseudo-boemite with sodium aluminate-carbon dioxide process[J]. World Nonferrous Metals, 2008, (5):31-33.
[18]	曹效珍, 贾传宝. 影响拟薄水铝石胶溶指数的因素[J]. 有色冶金节能, 2008, 24(3):30-33. CAO X Z, JIA C B. Discussion on the factors to impact dispersion index of pseudo boehmite[J]. Energy Saving of Non-Ferrous Metallurgy, 2008, 24(3):30-33.
[19]	商连弟, 王惠惠. 活性氧化铝的生产及其改性[J]. 无机盐工业, 2012, 44(1):1-6. SHANG L D, WANG H H. Production and modification of activated alumina[J]. Inorganic Chemicals Industry, 2012, 44(1):1-6.
[20]	WANG Y J, XU D Q, SUN H T, et al. Preparation of pseudoboehmite with a large pore volume and a large pore size by using a membrane-dispersion microstructured reactor through the reaction of CO2 and a NaAlO2 solution[J]. Industrial & Engineering Chemistry Research, 2011, 50(7):3889-3894.
[21]	孙韵, 叶颖, 金江. 沉淀法制备低成本纳米氧化铝粉体[J]. 材料导报, 2007, 21(S1):150-152. SUN Y, YE Y, JIN J. Preparation of nanosized alumina with low cost by precipitation method[J]. Materials Review, 2007, 21(S1):150-152.
[22]	孟卫松. 沉淀法制备纳米氧化铝粉体的研究[D]. 武汉:武汉科技大学, 2004. MENG W S. Study on preparation of nano-Al2O3 powder by precipitation methods[D]. Wuhan:Wuhan University of Science and Technology, 2004.
[23]	杨岳洋, 江书安, 李建军, 等. pH对氢氧化铝晶型影响分析[J]. 无机盐工业, 2017, 49(11):41-43. YANG Y Y, JIANG S A, LI J J, et al. Influence of pH on crystal form of aluminum hydroxide[J]. Inorganic Chemicals Industry, 2017, 49(11):41-43.
[24]	LIPPENS B C. Structure and texture of aluminas[D]. USA:Waltman, 1961.
[25]	PENG L, XU X, LV Z, et al. Thermal and morphological study of Al2O3 nanofibers derived from boehmite precursor[J]. Journal of Thermal Analysis and Calorimetry, 2012, 110(2):749-754.
[26]	李少伟, 徐建鸿, 骆广生. 过饱和度和混合性能对晶体形貌的影响[C]//中国颗粒学会2006年年会暨海峡两岸颗粒技术研讨会. 北京:中国颗粒学会, 2006:173-177. LI S W, XU J H, LUO G S. The effect of oversaturation and mixing properties on crystal morphology[C]//2006 Annual Conference of Chinese Society of Particuology cum Symposium on Particle Technology across Taiwan Straits. Beijing:Chinese Society of Particuology, 2006:173-177.
[27]	MANTZARIS N V. Liquid-phase synthesis of nanoparticles:particle size distribution dynamics and control[J]. Chemical Engineering Science, 2005, 60(17):4749-4770.
[28]	JUDAT B, RACINA A, KIND M. Macro-and micromixing in a Taylor-Couette reactor with axial flow and their influence on the precipitation of barium sulfate[J]. Chemical Engineering & Technology, 2004, 27(3):287-292.
[30]	卢少元, 贺蕴秋. 表面活性剂在纳米氧化铝制备中的应用研究[J]. 材料导报, 2006, 20(S1):149-152. LU S Y, HE Y Q. Application of surfactant to synthesis of nano-alumina[J]. Materials Review, 2006, 20(S1):149-152.
	孙秀君. 表面活性剂在超细氧化铝制备和分散中的应用研究[J]. 粉末冶金技术, 2015, 33(4):254-258. SUN X J. Study on the application of surfactants in preparation and dispersion of ultra-fine alumina[J]. Powder Metallurgy Technology, 2015, 33(4):254-258.
[31]	蔡卫权, 李会泉, 张懿. 表面活性剂辅助水热合成异形薄水铝石[J]. 材料科学与工艺, 2008, 16(2):207-210. CAI W Q, LI H Q, ZHANG Y. Preparation of boehmites with novel morphologies via surfactants assisted hydrothermal synthesis[J]. Materials Science and Technology, 2008, 16(2):207-210.