酸改性SBA-15介孔材料制备、表征及催化性能
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摘要
利用介孔材料的大比表面和丰富的硅羟基，采用后合成法对SBA-15进行有机或无机改性，制备了不同种类的酸改性介孔材料，以合成乙酸正丁酯的固液相催化反应为考察对象，研究了改性介孔材料的活性组分构成、制备方法和制备条件对反应收率的影响：通过X射线多晶衍射、N_2吸附-脱附、红外光谱、热重分析、NH_3-TPD吸附脱附、透射电子显微镜等分析方法对催化剂进行了表征；并将合成的催化剂应用于脂肪酸酯合成反应中，探索了改性材料的催化性能，结果表明：
1、催化剂的制备
以三嵌段共聚物P123(聚氧乙烯-聚氧丙烯-聚氧乙烯)为模板剂、正硅酸乙酯(TEOS)为硅源，在强酸性和水热条件下合成介孔分子筛SBA-15。以SBA-15作为载体，分别采用室温浸渍法和固体研磨法制备了SBA-15的酸性改性材料。通过单因素实验对负载型介孔分子筛的制备工艺条件进行优化，确定催化剂较佳的制备条件。
采用浸渍法制备的镧改性SBA-15催化剂La-SO_4~(2-)／SBA-15，制备条件为：以2mol／L硫酸溶解氧化镧，配成浓度为0．03mol／L的La_2(SO_4)_3溶液浸渍SBA-15，在300℃温度下焙烧4h；采用浸渍法制备的铈改性SBA-15催化剂Ce-SO_4~(2-)/SBA-15，制备条件为：将硫酸高铈溶于0．5mol／L的硫酸中，配成0．1mol／L的Ce~(4+)溶液浸渍SBA-15，在300℃温度下焙烧3h；采用浸渍法制备的对甲苯磺酸改性SBA-15催化剂TsOH／SBA-15，制备条件为：配制0．5mol／L对甲苯磺酸乙醇溶液浸渍煅烧的主体材料SBA-15，在300℃温度下焙烧4h。
采用固相研磨法制备镧改性SBA-15催化剂La-S_2O_8~(2-)／SBA-15和La-SO_4~(2-)／SBA-15，制备条件为：以SBA-15为载体，将活性成分La_2O_3与(NH_4)_2S_2O_8或(NH_4)_2SO_4，分别按物质量1：7或1：6的比例固相混合研磨，在300℃温度下焙烧3h；采用固相研磨法制备铈改性SBA-15催化剂Ce-S_2O_8~(2-)／SBA-15和Ce-SO_4~(2-)／SBA-15，制备条件为：以SBA-15为载体，将活性成分Ce(SO_4)_2与(NH_4)_2S_2O_8或(NH_4)_2SO_4分别按物质量1：7或1：6的比例固相混合研磨，在300℃温度下焙烧3h。实验表明，在催化剂制备过程中焙烧温度对催化剂表面酸中心的形成起到重要作用。
2、催化剂的表征
通过X射线多晶衍射、N_2吸附-脱附、红外光谱、热重分析、NH_3-TPD吸附脱附、透射电子显微镜等方法对合成材料的晶体结构、孔结构、骨架结构、热稳定性等进行表征。实验结果表明，所合成的固体酸催化剂具有与SBA-15相同的高度有序的介孔一维六方结构。采用浸渍法制备的改性介孔材料的BJH孔径均小于载体SBA-15的孔径，说明活性物质在载体表面负载的同时，有部分活性组分进入了孔道中；用固体研磨法制备的改性材料的BJH孔径，与载体SBA-15的孔径基本相同，说明活性组分只是对介孔材料的表面进行了修饰。采用Hammett指示剂法测定表面酸强度，结果表明，所制的改性材料的酸强度均H_0在-4．44-3．33之间，属于固体酸。NH_3-TPD测定表明，在制备的固体酸表面具有弱酸中心和中强酸中心。
3、催化酯化反应
将改性的酸性介孔材料应用于乙酸正丁酯和棕榈酸甲酯的酯化反应中，重点研究了酸醇物质的量比、催化剂用量和反应时间等因素对酯化反应的影响，采用正交实验确定酯化反应较优的工艺条件。实验表明所合成的固体酸催化剂具有良好的催化性能，催化剂的催化活性与固体酸表面的总酸量具有良好的对应关系，即表面酸量越大，催化剂的催化活性越高。将制备的催化剂进行5次循环重复使用，表现出较好的重复使用性能。
As a newly reported silica mesoporous material, SBA-15 has regular pore array with uniform pore diameter, high surface area and pore volume. It is chemically inert but allow irreversible surface modification by reaction of the surface silanol groups. Herein, we report the preparation of acid-modified SBA-15 mesoporous molecular sieves by post systhesis methods. Esterification of acetic acid with n-butanol was carried out over the acid-modified SBA-15 catalysts in liquid phase conditions.The effects of the factors involved in catalysts compose, catalysts preparation methods and preparation conditions had been investigated. Characterization was done by powder X-ray diffraction (XRD),transmission electron micrographs (TEM), N_2 adsorption desorption, IR, thermogravimetry analysis.The total amount of acidity on loaded catalysts was estimated by NH3-TPD. The catalytic activity of this family of mesoporous solids had been studied by catalytic tests of esterification.The results show that :
1. The preparation of acid-modified SBA-15s
SBA-15 mesoporous molecular sieves were prepared by hydrothermal method using triblock copolymer Pluronic P123 (EO_(20)PO_(70)EO_(20)) as templating agent and tetraethoxysilane (TEOS) as silicon source under a strong acidic condition. Mesoporous silica materials were used as a solid support. The solid acid was prepared by impregnation or solid state grinding in absence of solvent respectively. The optimum conditions of the preparation by single factors are studied.
La-SO_4~(2-)/SBA-15 and Ce-SO_4~(2-)/SBA-15 composite materials were prepared by incipient -wetness impregnation using the calcined host material SBA-15 molecular sieve and oxidation lanthanum and sulfuric cerium in sulfuric acid media respectively. The best conditions for preparation of La-SO_4~(2-)/SBA-15 were that the concentration of impregnation La_2(SO_4)_3 0.03mol/L, calcination temperature 300℃, calcination time 4h. The best conditions for preparation of Ce-SO_4~(2-)/SBA-15 were that the concentration of impregnation Ce(SO_4)_2 0.1mol/L, calcination temperature 300℃, calcination time 3h. TsOH/SBA-15 composite materials were prepared by impregnation using the calcined host material SBA-15 molecular sieve and TsOH in alcohol media. The best conditions were that the concentration of impregnation TsOH alcohol solution 0.5mol/L, calcination temperature 300℃, calcination time 4h.
La-S_2O_8~(2-)/SBA-15, La-SO_4~(2-)/ SBA-15, Ce-S_2O_8~(2-)/SBA-15 and Ce-SO_4~(2-)/SBA-15 composite materials were prepared by solid state grinding in absence of solvent. The best conditions for preparation of La-S_2O_8~(2-)/SBA-15 and La-SO_4~(2-)/SBA-15 were that the mole ratio of La_2O_3 to (NH_4)_2S_2O_8 or (NH_4)_2SO_4 is 1 : 7 or 1 : 6 by manually grinding the corresponding the host SBA-15,calcination temperature 300℃, calcination time 3h.The best conditions for preparation of Ce-S_2O_8~(2-)/SBA-15 and Ce-SO_4~(2-)/SBA-15 were that the mole ratio of Ce(SO_4)_2 to (NH_4)_2S_2O_8 or (NH_4)_2SO_4 is 1 : 7 or 1 : 6 by manually grinding the corresponding the host SBA-15,calcination temperature 300℃, calcination time 3h.It can be concluded that calcination temperature play an important role in the form of acid sites on the surface of catalyst during the preparation of catalysts.
2. The characterization of acid-modified SBA-15s
The properties of modified SBA-15 mesoporous molecular sieves were characterized by powder X-ray diffraction (XRD), transmission electron micrographs (TEM), N_2 adsorption desorption, IR, thermogravimetry analysis. The total amount of acidity of loaded catalysts was estimated by NH3-TPD. Results show that the active components have been incorporated into SBA-15 molecular sieve. The prepared catalysts keep highly ordered mesoporous two-dimensional hexagonal structure and do not change mesoporous channel structure of SBA-15 molecular sieve. The Acid strength on catalyst surface was determined by mean of Hammett indication method (-4.44 3. The catalysis performance for esterification
The modified mesporous materials is an excellent catalyst to synthesize n-butyl acetate and methyl palmitate. Optimum conditions of esterification such as mole ratio of acid to alcohol, amount of catalyst and reaction time were studied by orthogonal experiments, it is observed that the straight correlation of the esterification behavior with the acidic properties of the catalysts. The catalytic activity increases with the rise of acid amount on the surface of catalysts.The results show that the catalysts can be recovered or regenerated for reuse.
1、催化剂的制备
以三嵌段共聚物P123(聚氧乙烯-聚氧丙烯-聚氧乙烯)为模板剂、正硅酸乙酯(TEOS)为硅源，在强酸性和水热条件下合成介孔分子筛SBA-15。以SBA-15作为载体，分别采用室温浸渍法和固体研磨法制备了SBA-15的酸性改性材料。通过单因素实验对负载型介孔分子筛的制备工艺条件进行优化，确定催化剂较佳的制备条件。
采用浸渍法制备的镧改性SBA-15催化剂La-SO_4~(2-)／SBA-15，制备条件为：以2mol／L硫酸溶解氧化镧，配成浓度为0．03mol／L的La_2(SO_4)_3溶液浸渍SBA-15，在300℃温度下焙烧4h；采用浸渍法制备的铈改性SBA-15催化剂Ce-SO_4~(2-)/SBA-15，制备条件为：将硫酸高铈溶于0．5mol／L的硫酸中，配成0．1mol／L的Ce~(4+)溶液浸渍SBA-15，在300℃温度下焙烧3h；采用浸渍法制备的对甲苯磺酸改性SBA-15催化剂TsOH／SBA-15，制备条件为：配制0．5mol／L对甲苯磺酸乙醇溶液浸渍煅烧的主体材料SBA-15，在300℃温度下焙烧4h。
采用固相研磨法制备镧改性SBA-15催化剂La-S_2O_8~(2-)／SBA-15和La-SO_4~(2-)／SBA-15，制备条件为：以SBA-15为载体，将活性成分La_2O_3与(NH_4)_2S_2O_8或(NH_4)_2SO_4，分别按物质量1：7或1：6的比例固相混合研磨，在300℃温度下焙烧3h；采用固相研磨法制备铈改性SBA-15催化剂Ce-S_2O_8~(2-)／SBA-15和Ce-SO_4~(2-)／SBA-15，制备条件为：以SBA-15为载体，将活性成分Ce(SO_4)_2与(NH_4)_2S_2O_8或(NH_4)_2SO_4分别按物质量1：7或1：6的比例固相混合研磨，在300℃温度下焙烧3h。实验表明，在催化剂制备过程中焙烧温度对催化剂表面酸中心的形成起到重要作用。
2、催化剂的表征
通过X射线多晶衍射、N_2吸附-脱附、红外光谱、热重分析、NH_3-TPD吸附脱附、透射电子显微镜等方法对合成材料的晶体结构、孔结构、骨架结构、热稳定性等进行表征。实验结果表明，所合成的固体酸催化剂具有与SBA-15相同的高度有序的介孔一维六方结构。采用浸渍法制备的改性介孔材料的BJH孔径均小于载体SBA-15的孔径，说明活性物质在载体表面负载的同时，有部分活性组分进入了孔道中；用固体研磨法制备的改性材料的BJH孔径，与载体SBA-15的孔径基本相同，说明活性组分只是对介孔材料的表面进行了修饰。采用Hammett指示剂法测定表面酸强度，结果表明，所制的改性材料的酸强度均H_0在-4．44-3．33之间，属于固体酸。NH_3-TPD测定表明，在制备的固体酸表面具有弱酸中心和中强酸中心。
3、催化酯化反应
将改性的酸性介孔材料应用于乙酸正丁酯和棕榈酸甲酯的酯化反应中，重点研究了酸醇物质的量比、催化剂用量和反应时间等因素对酯化反应的影响，采用正交实验确定酯化反应较优的工艺条件。实验表明所合成的固体酸催化剂具有良好的催化性能，催化剂的催化活性与固体酸表面的总酸量具有良好的对应关系，即表面酸量越大，催化剂的催化活性越高。将制备的催化剂进行5次循环重复使用，表现出较好的重复使用性能。
As a newly reported silica mesoporous material, SBA-15 has regular pore array with uniform pore diameter, high surface area and pore volume. It is chemically inert but allow irreversible surface modification by reaction of the surface silanol groups. Herein, we report the preparation of acid-modified SBA-15 mesoporous molecular sieves by post systhesis methods. Esterification of acetic acid with n-butanol was carried out over the acid-modified SBA-15 catalysts in liquid phase conditions.The effects of the factors involved in catalysts compose, catalysts preparation methods and preparation conditions had been investigated. Characterization was done by powder X-ray diffraction (XRD),transmission electron micrographs (TEM), N_2 adsorption desorption, IR, thermogravimetry analysis.The total amount of acidity on loaded catalysts was estimated by NH3-TPD. The catalytic activity of this family of mesoporous solids had been studied by catalytic tests of esterification.The results show that :
1. The preparation of acid-modified SBA-15s
SBA-15 mesoporous molecular sieves were prepared by hydrothermal method using triblock copolymer Pluronic P123 (EO_(20)PO_(70)EO_(20)) as templating agent and tetraethoxysilane (TEOS) as silicon source under a strong acidic condition. Mesoporous silica materials were used as a solid support. The solid acid was prepared by impregnation or solid state grinding in absence of solvent respectively. The optimum conditions of the preparation by single factors are studied.
La-SO_4~(2-)/SBA-15 and Ce-SO_4~(2-)/SBA-15 composite materials were prepared by incipient -wetness impregnation using the calcined host material SBA-15 molecular sieve and oxidation lanthanum and sulfuric cerium in sulfuric acid media respectively. The best conditions for preparation of La-SO_4~(2-)/SBA-15 were that the concentration of impregnation La_2(SO_4)_3 0.03mol/L, calcination temperature 300℃, calcination time 4h. The best conditions for preparation of Ce-SO_4~(2-)/SBA-15 were that the concentration of impregnation Ce(SO_4)_2 0.1mol/L, calcination temperature 300℃, calcination time 3h. TsOH/SBA-15 composite materials were prepared by impregnation using the calcined host material SBA-15 molecular sieve and TsOH in alcohol media. The best conditions were that the concentration of impregnation TsOH alcohol solution 0.5mol/L, calcination temperature 300℃, calcination time 4h.
La-S_2O_8~(2-)/SBA-15, La-SO_4~(2-)/ SBA-15, Ce-S_2O_8~(2-)/SBA-15 and Ce-SO_4~(2-)/SBA-15 composite materials were prepared by solid state grinding in absence of solvent. The best conditions for preparation of La-S_2O_8~(2-)/SBA-15 and La-SO_4~(2-)/SBA-15 were that the mole ratio of La_2O_3 to (NH_4)_2S_2O_8 or (NH_4)_2SO_4 is 1 : 7 or 1 : 6 by manually grinding the corresponding the host SBA-15,calcination temperature 300℃, calcination time 3h.The best conditions for preparation of Ce-S_2O_8~(2-)/SBA-15 and Ce-SO_4~(2-)/SBA-15 were that the mole ratio of Ce(SO_4)_2 to (NH_4)_2S_2O_8 or (NH_4)_2SO_4 is 1 : 7 or 1 : 6 by manually grinding the corresponding the host SBA-15,calcination temperature 300℃, calcination time 3h.It can be concluded that calcination temperature play an important role in the form of acid sites on the surface of catalyst during the preparation of catalysts.
2. The characterization of acid-modified SBA-15s
The properties of modified SBA-15 mesoporous molecular sieves were characterized by powder X-ray diffraction (XRD), transmission electron micrographs (TEM), N_2 adsorption desorption, IR, thermogravimetry analysis. The total amount of acidity of loaded catalysts was estimated by NH3-TPD. Results show that the active components have been incorporated into SBA-15 molecular sieve. The prepared catalysts keep highly ordered mesoporous two-dimensional hexagonal structure and do not change mesoporous channel structure of SBA-15 molecular sieve. The Acid strength on catalyst surface was determined by mean of Hammett indication method (-4.44
The modified mesporous materials is an excellent catalyst to synthesize n-butyl acetate and methyl palmitate. Optimum conditions of esterification such as mole ratio of acid to alcohol, amount of catalyst and reaction time were studied by orthogonal experiments, it is observed that the straight correlation of the esterification behavior with the acidic properties of the catalysts. The catalytic activity increases with the rise of acid amount on the surface of catalysts.The results show that the catalysts can be recovered or regenerated for reuse.
引文
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