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第 36 卷第 7 期                             精   细   化   工                                  Vol.36, No.7
             201 9 年 7 月                             FINE CHEMICALS                                 July    2019


              精细化工中间体
                      双氧水氧化乙二醛合成乙醛酸的连续流工艺



                                                        2
                  李钰欣      1,2 ,严生虎       1,2 ,张   跃 ,刘建武            1,2 ,沈介发      1,2* ,辜顺林      1,2 ,
                                                                        1
                                                                                     1
                                                                                                  4
                                                            3
                      马晓明      1,2 ,陈代祥      1,2 ,余   蕴 ,钱江浩 ,石一洲 ,朱子铭
                 (1.  常州大学  制药与生命科学学院,江苏  常州    213164;2.  石油和化工行业连续流技术工程实验室,
                 江苏  常州    213164;3.  常州大学  国际教育交流学院,江苏  常州    213164;4.  中国药科大学,江苏  南
                 京    210009)


                 摘要:以乙二醛和双氧水为原料,在微通道反应器中考察了液相氧化合成乙醛酸的连续流工艺。考察了物料比、
                 催化剂用量、双氧水浓度、停留时间、温度等对反应的影响。确定该法最佳工艺条件为,n(乙二醛)∶n(H 2 O 2 )∶
                 n(FeSO 4 )=1.0∶1.0∶0.13,双氧水浓度 1.67 mol/L,停留时间 10 min,反应温度 30  ℃。在该条件下,乙二醛转
                 化率达到 94.7%,乙醛酸选择性达到 85.4%。该工艺充分利用微通道反应器优良的传质传热特点,大大缩短了反
                 应时间,提高了反应速率,扩大了工艺条件选择区间,实现了对氧化反应过程的有效控制,增加了安全系数。
                 关键词:乙二醛;乙醛酸;氧化;微通道反应器;连续流工艺;精细化工中间体
                 中图分类号:TQ225.61      文献标识码:A      文章编号:1003-5214 (2019) 07-1483-05



                           Continuous Flow Synthesis Process of Glyoxylic Acid by
                                 Oxidation of Glyoxal with Hydrogen Peroxide


                                                                       1,2
                           1,2
                                            1,2
                                                                                                    1,2
                                                          2
                   LI Yu-xin , YAN Sheng-hu , ZHANG Yue , LIU Jian-wu , SHEN Jie-fa  1,2* , GU Shun-lin ,
                               1,2
                                                                                                       4
                                                 1,2
                                                                            1
                                                                                         1
                                                           3
                  MA Xiao-ming , CHEN Dai-xiang , YU Yun , QIAN Jiang-hao , SHI Yi-zhou , ZHU Zi-ming
                 (1. School of Pharmaceutical and Life Sciences, Changzhou University, Changzhou  213164,  Jiangsu, China;
                 2. Continuous Flow Engineering Laboratory of National Petroleum and Chemical Industry, Changzhou 213164, Jiangsu,
                 China;  3. School of International Education Exchange, Changzhou University, Changzhou  213164, Jiangsu, China;
                 4. China Pharmaceutical University, Nanjing 210009, Jiangsu, China)
                 Abstract:  The  continuous  flow  process  for  synthesis  of  glyoxylic  acid  by  liquid-phase  oxidation  in  a
                 microchannel  reactor  was  studied  using  glyoxal  and  hydrogen  peroxide  as  raw  materials.The  effects  of
                 material  ratio,  catalyst  dosage,  hydrogen  peroxide  concentration,  residence  time  and  temperature  on  the
                 reaction  were  investigated.The  optimized  reaction  conditions  were  determined  as  follows:  n(glyoxal)∶
                 n(H 2O 2)∶n(FeSO 4)=1.0∶1.0∶0.13, hydrogen peroxide concentration 1.67 mol/L, residence time 10 min,
                 and  reaction  temperature  30  ℃.  Under  the  above-mentioned  reaction  conditions,  the  conversion rate  of
                 glyoxal  reached  94.7%  and  the  selectivity  of  glyoxylic  acid  reached  85.4%.  This  process  takes  full
                 advantage  of  the  excellent  mass  and  heat  transfer  characteristics  of  the  microchannel  reactor,  greatly
                 shortens the reaction time, improves the reaction rate, expands the selection range of process conditions,
                 realizes the effective control of the oxidation reaction process, and increases the safety factor.
                 Key  words:  glyoxal;  glyoxylic  acid;  oxidation;  microchannel  reactor;  continuous  flow  process;  fine
                 chemical intermediates



                 乙醛酸由于兼有醛和酸的性质,可与很多化合                          药中间体,如香兰素、尿囊素、对羟基苯甘氨酸、
                                                                                                        [1]
            物发生缩合或成环缩合反应,工业上常用于合成医                             对羟基苯乙酸、2-羟基喹啉、2-羟基磷乙酸等 。


                 收稿日期:2018-12-04;  定用日期:2019-03-04; DOI: 10.13550/j.jxhg.20180882
                 作者简介:李钰欣(1994—),女,硕士生,E-mail:1225521412@qq.com。联系人:沈介发(1967—),男,高级工程师,E-mail:
                 shenjiefa@cczu.edu.cn。
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