丙二酸二乙酯在Cu∕SiO2催化剂上的加氢过程.pdf

石油化
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PETROCHEMICAL TECHNOLOGY
2(016年第45卷第6期
DOl:10.3969/iss.1000-8144,2016.06.004
研究与开发
丙二酸二乙酯在 Cu/Sio2催化剂上的加氢过程
丁同梅,吴文滨,田恒水
(华东理工大学化工学院,上海200237
摘要」在连续流动固定床反应器上,研究了 Cu/ Sio催化丙二酸二乙韩(D上M)加氢制备1,3-丙二醇(1,3-P1DO)的反应。采
用I1-PR、XRI、SIM、N2吸附-脱附等方法对催化剂进行表征。进一步优化了原料液含量、氢階摩尔比、液态空速、反应
温度、反应压力等因素对反应结果的影响。表征结果显示,不同还原条件会影响 Cu/Sio2还原后活性铜的量及其分散状态;于
300℃下还原41h时,Cu/SiO,催化剂的活性中心较多且分散均匀。实验结果表明,采用于300℃下还原4h的 Cu/Sio,催化剂,在
原料液含量7.5%(w)、氯酯摩尔比330、液态空速1.8h、反应温度200℃:、反应压力2.0MPa的反应条件下,DFM的转化率为
85.2受,产物1,3-PDO的收率为41.0%,副产物3-羟基丙酸乙的收率为32.9%。
关键词」C:uSi()2催化剂;内二酸二乙脂:;催化加氢;1,3-内二醇
文章编号]1000~8144(2016)06-0664-07
中图分类号」TQ032
[文献标志码]A
The hydrogenation process of diethyl malonate over Cu/Si0] catalyst
Ding Tongmei, Wu Wenbin, Tian lengshui
(Department of Chemical Enginccring, East China Univcrsity of Scicnce and Tcchnology, Shanghai 200237, China
Abstract The gas-phase hydrogenation of diethyl malonate to 1, 3-propanediol over Cu/Sio
catalysts was investigated in a continuous fixed-bed reactor. The catalysts were characterized by means
OTH2-TPR, XRD, SEM and N adsorption-desorption, which indicated that the active sites and
their dispersity wcrc aftcctcd by rcduction conditions. The catalyst rcduccd at 300 C for 4 h, which
possessed more active sites and better dispersion, showed the optimum catalytic performance. The
cffccts of raw matcrial conccntration, mole ratio of hydrogcn to diethyl malonate, LHSV, reaction
temperature and reaction pressure on the catalytic hydrogenation were investigated. The results showed
that, under the optimied conditions of raw material concentration 7. 5%(w), mole ratio of hydrogen
to diethyl malonate 330, LHSV 1.8 h", rcaction tcmperaturc 200C and rcaction prcssurc 2.0 Mpa
the diethyl malonate conversion, 1, 3-propanediol yield and 3-hydroxy ethyl propionate yield could
rcach 85. 2%, 41.0% and 32. 9%, rcspcctivcl
Keywords Cu/Sio catalyst; diethyl malonate; catalytic hydrogenation; 1, 3-propancdiol
1,3-丙二醇(1,3-PDO)是合成聚对本二甲酸点。采用丙二酸二乙酯(DEM)为原料催化加直
丙二醇酯的重要原料"2。目前,1,3-PDO的生产接合成1,3-PDO,避免了传统工艺中不稳定中间
方法包括环氧乙烷法3、丙烯矅法和微牛物发酵体醛的生成。
法,但上述方法存在反应温度和反应压力过高
采用蒸氨法制备 Cu/Sio2催化剂可获得较高的
原料不易获得、中间体不稳定及产品品质不高等缺铜负载量及分散度,在草酸二甲酯(DMO)加氡工
收稿日期」2015-11~-26;修改稿日期」2016-03-08
作者简介]丁同梅(1981ー),女,江苏省东台市人,博十.生,电话021-64251914,电邮dum116163.co0m。联系人:田恒水,电话
021-64252198,电邮 hetian( accust.cdu.cn