微通道中R23资源化转化合成R14的连续工艺
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摘要
研究在微通道反应器中氟气氟化CHF_3制备CF_4的工艺,考察原料配比、反应温度、停留时间、氟氮混合气的比例对反应的转化率和选择性的影响。结果表明,较优工艺参数为:氟氮混合比20%,氟气与CHF_3摩尔比1.1∶1,常压反应,温度40℃,停留时间6 s。在此条件下,CHF_3的转化率100%,CF_4的选择性>99%。实现了连续化操作,提高了生产安全性。此外,对该工艺路线反应机理进行了推测。
In a microl reactor the CF_4 was synthesized with F_2 and CHF_3 as raw material. The effects of material ration,reaction temperature,reaction residence time and the concentration of fluorine in nitrogen on the conversion ratio and selectivity were evaluated. The result showed that the suitable operation parameters were selected as follows:the concentration of fluorine in nitrogen of 20%,n( F_2)∶ n(CHF_3) =1. 1∶ 1,the reaction temperature at 40 ℃,residence time of 6 s,pressure of 0 MPa. Under these conditions,the conversion of CHF_3 reached 100% and selectivity of CF_4 reached more than 99%,and process continuity ensured higher operation safety. Moreover the experiment of the continuous stabilization in the microreactor was studied and the possible reaction mechanism was proposed.
In a microl reactor the CF_4 was synthesized with F_2 and CHF_3 as raw material. The effects of material ration,reaction temperature,reaction residence time and the concentration of fluorine in nitrogen on the conversion ratio and selectivity were evaluated. The result showed that the suitable operation parameters were selected as follows:the concentration of fluorine in nitrogen of 20%,n( F_2)∶ n(CHF_3) =1. 1∶ 1,the reaction temperature at 40 ℃,residence time of 6 s,pressure of 0 MPa. Under these conditions,the conversion of CHF_3 reached 100% and selectivity of CF_4 reached more than 99%,and process continuity ensured higher operation safety. Moreover the experiment of the continuous stabilization in the microreactor was studied and the possible reaction mechanism was proposed.
引文
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[2]杨虹,张剑波,冯金敏.中国HCFC-22的消费与排放清单及预测[J].北京大学学报:自然科学版,2010,46(2):251-257.
[3]Mc Culloch A,Lindley A A.Global emissions of HFC-23estimated to year 2015[J].Atmos Environ,2007,41(7):1560-1566.
[4]Deam R T,Dayal A R,Mc Allister T,et al.Interconversion of chlorofluorocarbons in plasmas[J].J Chem Soc Chem Commun,1995,3(3):347-348.
[5]林慧,崔永丽,肖学智,等.三氟甲烷减排可行性分析[J].中国人口资源与环境,2014,24(11):13-15.
[6]宋淑伟,史阿莹.二氟一氯甲烷副产氯化氢的精制及三氟甲烷回收的方法与装置:CN,102101651A[P].2011-10-12.
[7]韩文峰,靳碧波,周强,等.三氟甲烷(HFC-23)的资源化转化利用[J].化工进展,2014,33(2):483-492.
[8]席盂斯.氟化学[M].路之康,译.北京:科学出版社,1961.
[9]Bruce E Smart,Richard E Fernandez.Fluorine compounds,organic(aliphatic)[J].Kirk-Othmer Encyclopedia of Chemical Technology,1993,11:499-521.
[10]Ohno H,Nakajo T,Arai T,et a1.Process for producing tetrafluoromethane:US,5714648[P].1997-02-03.
[11]张彦,陈科峰.四氟甲烷的合成与开发[J].化工生产与技术,2008,15(2):1-4.
[12]Ohsaka Y,Sonoyama H.Process for preparing high purity tetrafluoromethane:US,4264530[P].1981-04-28.
[13]Foulletier L.Catalysts for gaseous phase fluorination of aliphatic chlorinated and chlorofluorinated hydrocarbons:US,4474895[P].1984-10-02.
[14]Mae K.Advanced chemical processing using microspace[J].Chemical Engineering Science,2007,62(18/19/20):4842-4851.
[15]骆广生,王凯,吕阳成,等.微尺度下非均相反应的研究进展[J].化工学报,2013,64(1):165-172.
[16]Wiles C,Watts P.Recent advances in micro reaction technology[J].Chemical Communications,2011,47(23):6512-6535.
[17]Mason B P,Price K E,Steinbacher J L,et al.Greener approaches to organic synthesis using microreactor technology[J].Chemical Reviews,2007,107(6):2301-2307.
[18]赵玉潮,陈光文.微化工系统的并行放大研究进展[J].中国科学(化学),2015,45(1):16-23.
[19]赵玉潮,张好翠,沈佳妮,等.微化工技术在化学反应中的应用进展[J].中国科技论文,2008,3(3):157-169.
[20]Roberge D M,Gottsponer M,Eyholzer M,et al.Industrial design,scale-up,and use of microreactors[J].Chemistry Today,2009,7:8-11.
[21]Usutani H,Tomida Y,Nagaki A,et al.Generation and reactions of o-bromophenyllithium without benzyne formation using a microreactor[J].Journal of the American Chemical Society,2007,129(11):3046-3047.
[22]Zhang X,Stefanick S,Villani F J.Application of microreactor technology in process development[J].Organic Process Research&Development,2004,8(3):455-460.
[23]Newman S G,Gu L,Lesniak C,et al.Rapid Wolff-Kishner reductions in a silicon carbide microreactor[J].Green Chemistry,2014,16(1):176-180.
[24]Haswells J,Watts P.Green chemistry:synthesis in microreactors[J].Green Chemistry,2003,5(2):240-249.
[25]Yoshida J,Kim H,Nagaki A.Green and sustainable chemical synthesis using flow microreactors[J].Chem Sus Chem,2011,4(3):331-340.
[26]Navarrp-Brull F J,Poveda P,Ruiz-Femenia R,et al.Guidelines for the design of efficient microreactors[J].Green Processing and Synthesis,2014,3(5):311-320.