摘要
乙酰丙酸乙酯(EL)加氢制1,4-戊二醇(1,4-PDO)和2-甲基四氢呋喃(2-MTHF)普遍采用极低的反应物浓度,以间歇釜式反应为主,不利于连续的规模化生产。为了提高生产效率,在固定床反应器上采用Cu基催化剂进行EL无溶剂加氢制1,4-PDO,并在HZSM-5分子筛作用下将后者原位脱水转化为2-MTHF。通过双固体催化剂分段组装可以在更低的反应温度下获得更优越的反应性能,较文献釜式反应器的温度低40℃及以上,EL转化率和2-MTHF选择性分别可达99.9%和97.8%。同时考察了绿铜锌矿、锌孔雀石和类水滑石等CuZn(Al)催化剂不同前体对EL加氢制1,4-PDO的影响,采用N2物理吸附、XRD、FTIR、H_(2)-TPR、NH_(3)-TPD、CO_(2)-TPD和原位XPS等表征技术对CuZn(Al)催化剂进行了系统的分析。结果表明,绿铜锌矿衍生的45CZ催化剂具有更高比例的Cu+位点,能更好地吸附和活化中间产物γ-戊内酯(GVL),同时具有适量的酸碱性位点,Cu+位点和酸碱性位点协同作用使得该催化剂表现出最佳的1,4-PDO选择性。本研究可为2-MTHF的规模化生产提供参考。
The hydrogenation of ethyl levulinate(EL)to 1,4-pentanediol(1,4-PDO)and 2-methyltetrahydrofuran(2-MTHF)commonly uses extremely low reactant concentrations and is mainly performed in the batch reactors,which is not conducive to the continuous large-scale production.To improve production efficiency,this paper describes solventless hydrogenation of EL to 1,4-PDO using a Cu-based catalyst in a fixed-bed reactor,followed by in-situ dehydration of the latter to 2-MTHF using HZSM-5 zeolite.Segmented assembly of dual solid catalysts can achieve superior reaction performance at more 40℃lower than the temperature of the batch reactors in literature,with EL conversion and 2-MTHF selectivity reached 99.9% and 97.8% respectively.The effects of different precursors(including aurichalcite,zincian malachite and hydrotalcite-like)of the CuZn(Al)catalysts on EL hydrogenation to 1,4-PDO was investigated.The catalysts were systematically analyzed by various characterization techniques such as N2 physical adsorption,XRD,FTIR,H_(2)-TPR,NH_(3)-TPD,CO_(2)-TPD,and in-situ XPS.The results showed that 45CZ catalyst derived from aurichalcite had a higher proportion of Cu+sites,which can improve the adsorption and activation of intermediate product γ-valerolactone(GVL).Moreover,this catalyst had an appropriate amount of acidic and alkaline sites.The synergistic effect between Cu+sites and acidic/basic sites made the catalyst exhibit the best 1,4-PDO selectivity.The insight shown in the research should be meaningful for the large-scale production of 2-MTHF.
作者
王洪星
于富红
张帅
李宁宁
田野
李新刚
WANG Hongxing;YU Fuhong;ZHANG Shuai;LI Ningning;TIAN Ye;LI Xingang(State Key Laboratory of Chemical Engineering and Low-carbon Technology,School of Chemical Engineering and Technology,Tianjin University,Tianjin 300354,China;Shandong Hualu Hengsheng Chemical Co.,Ltd.,Dezhou 253024,Shandong,China)
出处
《化工学报》
北大核心
2026年第1期356-365,共10页
CIESC Journal
基金
国家重点研发计划项目(2022YFB4101800)
山东省重点研发计划项目(2024CXGC010410)。
