Cu-MgO催化剂的MOCVD法制备及其γ-戊内酯加氢制1,4-戊二醇性能

文章编号:0253?2409(2017)05?0537?10

　Received :2017?02?15;Revised :2017?04?06.　*Corresponding author.Tel :+86?0411?84986353,Fax :+86?0411?84986353,E?mail :changhai @https://www.wendangku.net/doc/a514238442.html,.

The project was supported by the National Natural Science Foundation of China (21573031,21428301),the Fundamental Research Funds for the Central Universities (DUT 15ZD 106)and Program for Excellent Talents in Dalian City (2016RD 09).

国家自然科学基金(21573031,21428301),中央高校基本科研业务费专项基金(DUT 15ZD 106)和大连市高层次人才创新支持计划(2016RD 09)资助　本文的英文电子版由Elsevier 出版社在ScienceDirect 上出版(http ://https://www.wendangku.net/doc/a514238442.html, /science /journal /18725813).Preparation of Cu /MgO catalysts for 酌?valerolactone hydrogenation to 1,4?pentanediol by MOCVD

ZHAI Xue?jiao ,LI Chuang ,DI Xin ,YIN Dong?dong ,LIANG Chang?hai *

(Laboratory of Advanced Materials and Catalytic Engineering ,School of Petroleum and Chemical Engineering ,Dalian University of Technology ,Panjin 124221,China )

Abstract :The laminar MgO with high specific area and the organometallic precursor Cu (acac )2were used for the successful synthesis of Cu /MgO catalysts by metal?organic chemical vapor deposition (MOCVD )method.The copper supported on MgO catalysts were characterized by means of X?ray diffraction ,Fourier?transform infrared (FT?IR )spectroscopy ,field emission scanning electron microscopy (FE?SEM ),transmission electron microscopy (TEM )and N 2?physisorption.Characterization results indicated that the organic precursor was successfully deposited onto MgO and the crystal structure of MgO remained intact after deposition.The hydrogenation of γ?valerolactone (γ?GVL )was employed to evaluate the catalytic performance of the Cu /MgO catalysts.It was found that the 18%Cu /MgO catalyst exhibited excellent catalytic activity (90.5%)and selectivity (94.4%)for 1,4?PDO at 473K and 10MPa ,and the catalytic activity of Cu /MgO did not diminish significantly after cycling for three times.Key words :Cu /MgO ;MOCVD ;γ?valerolactone ;hydrogenation ;1,4?PDO CLC number :O 643.36 Document code :A Most of the commonly used transportation fuels ,materials and chemicals are derived from fossil resources.As the global demand for energy is ever?increasing ,the fossil reserves are going to be depleted at a desperate pace.Together with the ever?deteriorating environment associated with the worldwide fuel?intensive industry ,considerable amount of efforts are being made to seek green alternatives to fossil resources [1-3].Renewable ,inexpensive and abundantly available biomass is the most promising sustainable resource for organic carbon on the earth [4,5].In this context ,the catalytic conversion of biomass and biomass?derived compounds to a wide variety of fuels and chemicals have attracted a great deal of energy researchers ’attention around the world.Conversion of biomass?derived compounds to fuels and value?added chemicals has immense potential to replace fossil fuel.One of the biomass?based platform molecules ,γ?valerolactone (γ?GVL ),has been identified as an important and promising sustainable intermediates which can be further converted into a variety of desired compounds [6,7],such as liquid fuels ,1,4?pentanediol (1,4?PDO )etc.(Figure 1).1,4?PDO along with

other diols is an important and valuable chemical intermediate and is also considered to be a potential monomer in the production of biodegradable polymers and other polymeric materials [8].2?methyltetrahydrofuran (2?MTHF )prepared from biomass?derived compounds can be used as an alternative solvent for many reactions and is also considered as a P?series fuel component for transportation infrastructure [9,10].Currently ,many studies have been devoted to the conversion of levulinic acid (LA )to various products ,γ?GVL ,2?MTHF and 1,4?PDO etc [11-16],and only a few reports has been found on the utilization of γ?GVL to produce high added value 1,4?PDO or 2?MTHF (Figure 1).Recently ,Buitrago et al [17]used carbon?supported Pd?NbCe catalysts to convert γ?GVL to pentanoic acid (PA ),and high conversion of γ?GVL (90%)and selectivity of PA (around 90%)were obtained.Li et al [18]performed the hydrogenation of γ?GVL over 4%Rh?MoO x /SiO 2catalyst at low temperature (353K )and 10MPa H 2,and obtained a conversion of 68.2%and selectivity of 61.8%to 1,4?PDO.According to the researches ,the production of 1,4?PDO from γ?GVL by ring opening and hydrogenation is one of the most 第45卷第5期2017年5月燃　料　化　学　学　报Journal of Fuel Chemistry and Technology Vol.45No.5May 2017万方数据