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第 35 卷第 10 期 精 细 化 工 Vol.35, No.10
2018 年 10 月 FINE CHEMICALS Oct. 2018
催化与分离提纯技术
Pd/SAPO-5 的制备及其在合成甲基正戊基酮中的应用
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王 强,王乃威,付睿峰,王忍青,江志东
(上海交通大学 化学化工学院,上海市绝缘与老化重点实验室,上海 200240)
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摘要:以三乙胺为模板剂,采用水热法制备了 Pd/SAPO-5 双功能催化剂,并用 H 2 -TPR,XRD,SEM,XRF, Si
MAS NMR 等手段对催化剂进行了表征。结果表明:钯的加入并不能改变分子筛的晶体结构;而不同的硅铝比
(SiO 2 与 Al 2 O 3 的物质的量比,下同)会导致 SAPO-5 分子筛晶体结构以及形貌上的差异。将所制备的催化剂用于
丙酮和丁醛气相一步法合成甲基正戊基酮(MAK)的反应中,考察了硅铝比、反应温度和金属负载量对催化活
性的影响,在 SAPO-5 分子筛结构完整的前提下,Pd/SAPO-5 催化活性随硅铝比的上升而增加。在硅铝比为 1.5、
反应温度 180 ℃、w(Pd)=0.25%时,MAK 的收率最高,可达 57.86%,并可运行 500 h 以上而不明显失活。
关键词:Pd/SAPO-5;双功能催化剂;硅铝比;一步合成;甲基正戊基酮;催化技术
中图分类号:TQ224.2 文献标识码:A 文章编号:1003-5214 (2018) 10-1667-06
Preparation of Pd/SAPO-5 Bifunctional Catalysts for One-step
Synthesis of Methyl Amyl Ketone
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WANG Qiang, WANG Nai-wei, FU Rui-feng, WANG Ren-qing, JIANG Zhi-dong
(Shanghai Key Laboratory of Electric Insulation and Thermal Aging, School of Chemistry and Chemical Engineering,
Shanghai Jiao Tong University, Shanghai 200240, China)
Abstract: A series of Pd/SAPO-5 bifunctional catalysts were prepared through hydrothermal method by
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using triethylamine as template and were characterized by H 2-TPR, XRD, SEM, XRF and Si MAS NMR.
The results revealed that the doping of Pd didn't change the molecular sieve crystalline structure of SAPO-5,
while the alteration of molar ratio of SiO 2 to Al 2O 3 could induce the changes in crystalline structure and
morphology of SAPO-5. Subsequently, the Pd/SAPO-5 bifunctional catalysts were applied for one-step
synthesis of methyl amyl ketone (MAK) from acetone and butyraldehyde. The influences of SiO 2/Al 2O 3
molar ratio, reaction temperature and amount of palladium loading on the catalytic activity of catalyst were
investigated. When the SAPO-5 crystalline structure kept intact, the activity of Pd/SAPO-5 increased with
increasing the SiO 2/Al 2O 3 molar ratio. When the SiO 2/Al 2O 3 molar ratio was 1.5, the reaction temperature
was 180 ℃, and the amount of Pd loading was 0.25%, the catalytic activity reached the best. The highest
yield of MAK was 57.86%. Moreover, the catalytic activity was rather stable under 500 h time-on-stream
test.
Key words: Pd/SAPO-5; bifunctional catalyst; SiO 2/Al 2O 3 molar ratio; one-step synthesis; methyl-amyl-
ketone; catalysis technology
甲基正戊基酮(methyl amyl ketone,MAK)又 应,生成中间产物羟酮;第二步是中间产物羟酮在
名 2-庚酮,是一种环保型有机溶剂,广泛用于工业 酸的催化下脱水生成 3-庚烯-2-酮;第三步是对烯酮
[1]
溶剂、医药、农药、香料和香精等领域 。目前国 的双键选择性加氢,一般选用 Pd/C 作为催化剂,得
[2]
内外现有 MAK 生产均采用液相反应体系,由丙酮 到甲基正戊基酮(MAK) 。多步液相反应使用一
和丁醛经过三步反应合成;第一步是丙酮和丁醛 次性的酸或碱作为催化剂,经历多个反应和分离步
[3]
(BD)在酸或碱的催化条件下发生羟醛交叉缩合反 骤,副反应多、得率低、污染重、成本高 。
收稿日期:2017-10-24; 定用日期:2018-02-26; DOI: 10.13550/j.jxhg.20170861
作者简介:王 强(1991—),男,硕士生。联系人:江志东(1967—),男,副教授,E-mail:zdjiang@sjtu.edu.cn,电话:021-34203107。