双氧水氧化乙二醛合成乙醛酸的连续流工艺
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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_2O_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。
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.
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.
引文
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[13]Liu Chunxiu(刘春秀),Wang Jiang(王奖),Sa Gala(萨嘎拉).The research of oxidation of glyoxal to glyoxylic acid over gold catalyst[J].Journal of Molecular Catalysis(分子催化),2012,26(4):322-327.
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[16]Wang Qihua(王奇华),Hu Zhengzhong(胡郑重),Yan Changyu(颜昌玉),et al.Synthesis of glyoxylic acid by oxidation of glyoxal with H2O2[J].Chemistry&Bioengineering(化学与生物工程),2007,(3):70-71.
[2]Yadav G D,GuptaV R.Synthesis of glyoxalic acid from glyoxal[J].Process Biochemistry(Oxford),2000,36(1/2):73-78.
[3]Xia Ning(夏宁),Zheng Xi(郑曦),Chen Riyao(陈日耀),et al.Electro-oxidation of glyoxal to glyoxalic acid[J].Journal of Fujian Normal University(Natural Science Edition)(福建师范大学学:自然科学版),2007,23(6):60-62,67.
[4]Sun Lida,Liu Wei,Li Zijing,et al.Oxidation of glyoxal to glyoxalic acid by prepared nano-Au/C catalysts[J].Current Nanoscience,2012,8(1):26-28.
[5]Xu Qingchai,Kit S Lam.An efficient approach to prepare glyoxylyl functionality onsolid-support[J].Tetrahedron Letters,2002,43:4435-4437.
[6]Zhang Yougong(张友恭),Zhang Shao(张昭),Peng Li(彭莉),et al.Study of trial production for synthesis of glyoxylic acid by oxygen method[J].Fine Chemicals(精细化工),2008,19(8):479-481.
[7]Zhu Yamei(朱鸭梅),Jiang Yaming(蒋亚明),Chen Dan(陈丹).Improvement of feed way and conditions optimization of preparation of glyoxal from acetaldehyde and nitric acid[J].Chemical Reaction Engineering and Technology(化学反应工程与工艺),2009,25(2):175-179.
[8]Pei Lei(裴蕾),Wang Qingjun(王庆军),Liu Fusheng(刘福胜),et al.Cleaner productin process for preparation of crystalline glyoxylic acid by ozone oxidation process[J].Environmental Protection of Chemical Industry(化工环保),2007,27(6):559-562.
[9]Liu Tianxing(刘天星),Zhang Chaoli(张朝立),Pan Sujuan(潘素娟),et al.Study on the glyoxylic acid content of glyoxal for preparing glyoxylic acid[J].Journal of Dalian Polytechnic University(大连工业大学学报),2008,27(3):235-237.
[10]Wang Chao(王超),Deng Qiulin(邓秋林),Chen Chao(陈超),et al.Preparation of glyoxylic acid through oxidation ofglyoxal with HNO3in a microreactor[J].Journal of Nanjing Tech University(Natural Science Edition)(南京工业大学学报:自然科学版),2018,40(1):66-73.
[11]Akanksha Sinhaa,Chandra Kumar.Kinetic studies of Os(Ⅷ)promoted oxidation of maleic acid by chloramine-T in alkaline medium[J].Journal Chemtracks,2015,17(2):391-396.
[12]Zhu Shuguang(朱曙光),Zhang Ning(张宁),Chen Xiang(陈翔),et al.Study on the mechanism of fenton reagent catalytic oxidation of glyoxal to glyoxylic acid[C]//Proceedings of the 7th National Symposium on Catalyst Preparation Science and Technology(第七届全国催化剂制备科学与技术研讨会论文集),Proceedings of the Chinese Chemical Society Conference(中国化学会会议):Taiyuan,2010.
[13]Liu Chunxiu(刘春秀),Wang Jiang(王奖),Sa Gala(萨嘎拉).The research of oxidation of glyoxal to glyoxylic acid over gold catalyst[J].Journal of Molecular Catalysis(分子催化),2012,26(4):322-327.
[14]Fan Chunzhen(范春贞),Li Caiting(李彩亭),Lu Pei(路培),et al.Experimental research of purification NO-containing gas by aqueous oxidation with fenton-like agent[J].China Environmental Science(中国环境科学),2012,32(6):988-993.
[15]Hermans S.Molybdenum oxoanions as dispersing agents in the preparation of Pd/C catalysts for the selective oxidation of glyoxal[J].Catalysis Letters,2012,142(5):521-530.
[16]Wang Qihua(王奇华),Hu Zhengzhong(胡郑重),Yan Changyu(颜昌玉),et al.Synthesis of glyoxylic acid by oxidation of glyoxal with H2O2[J].Chemistry&Bioengineering(化学与生物工程),2007,(3):70-71.