六甲基二硅氧烷裂解去除F_(22)副产盐酸中的氟离子
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摘要
利用六甲基二硅氧烷的裂解反应,去除二氟—氯甲烷(F_(22))副产盐酸中的氟离子;将裂解生成的三甲基氟硅烷通过碱金属盐进行缩合反应生成六甲基二硅氧烷进行回收。考察了六甲基二硅氧烷实际用量与理论用量的比对氟离子去除率的影响,并对回收产物的结构进行了表征。结果表明,当六甲基二硅氧烷的实际用量与理论用量的比超过5时,副产盐酸中氟离子的去除率≥90%,处理后残余的氟离子含量一般小于30.0×10~(-6)。GC测试表明,在碱液存在下,通过缩合生成的六甲基二硅氧烷纯度达到99.13%,核磁共振仪测定其~1H NMR、~(13)C NMR及~(29)Si NMR的化学位移均与文献值一致。
A new process for removing fluoride ion in by-product hydrochloric acid of chlorodifluoromethane was designed by cracking reaction of hexamethyldisiloxane. The trimethylfluorosilane generated by the cracking was to produce hexamethyldisiloxane to recovery by the condensation reaction with alkali metal salt. Influence of the ratio of actual dosage and theoretical dosage of hexamethyldisiloxane on the removal rate of fluoride ion was investigated and the structure of the recycled product was characterized. Results showed that when the ratio of the actual and theoretical dosage of hexamethyldisiloxane was over 5,the removal rate of the fluoride ion was equal or greater than 90% and the treated residual content of fluoride ion reduced to below30 ppm in hydrochloric acid. GC test showed that the purity of the hexamethyldisiloxane by condensation with alkali liquor was 99. 13%. The chemical shifts of H NMR,C NMR and Si NMR measured by nuclear magnetic resonance were agreeable with the literature value.
A new process for removing fluoride ion in by-product hydrochloric acid of chlorodifluoromethane was designed by cracking reaction of hexamethyldisiloxane. The trimethylfluorosilane generated by the cracking was to produce hexamethyldisiloxane to recovery by the condensation reaction with alkali metal salt. Influence of the ratio of actual dosage and theoretical dosage of hexamethyldisiloxane on the removal rate of fluoride ion was investigated and the structure of the recycled product was characterized. Results showed that when the ratio of the actual and theoretical dosage of hexamethyldisiloxane was over 5,the removal rate of the fluoride ion was equal or greater than 90% and the treated residual content of fluoride ion reduced to below30 ppm in hydrochloric acid. GC test showed that the purity of the hexamethyldisiloxane by condensation with alkali liquor was 99. 13%. The chemical shifts of H NMR,C NMR and Si NMR measured by nuclear magnetic resonance were agreeable with the literature value.
引文
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[3]姚鼎文,姚宁,黄华璋.盐酸分解中低品位磷矿制造饲料磷酸氢钙的方法:CN,101380062[P].2009-03-11.
[4]来国桥,幸松民.有机硅产品合成工艺及应用[M].北京:化学工业出版社,2010.
[5]OKUI N,MAGILL J H,GARDNER K H.A selective surface degradation study of polysiloxane homopolymers and randomblock copolymers with hydrofluoric acid solution[J].J Appl Phy,1977,48(10):4116-4121.
[6]OKUI N,MAGILL J H.Studies of the chemical degradation of polysiloxanes by hydrofluoric acid:1.poly(tetra methyl-p-silphenylene siloxane)[J].Polymer,1976,17(12):1086-1090.
[7]李培,王旭,高林.六甲基二硅氧烷的合成研究[J].化工新型材料.2016,44(3):132-134.
[8]朱淮军,廖洪流,李凤仪.三氟丙基甲基二氯硅烷的水解及一步法裂解制备环体[J].精细化工,2006,23(10):1027-1031.
[9]郭鼎力,聂峰.用HMDSA作氟的分离浓缩试剂-氟电极法测铝中的微量氟[J].化学试剂,1988(5):158.
[10]叶丽云,李维诸.氟电极测定水中氟的试验小结[J].净水技术,198(4):35-38.
[11]邱竹贤,张金生,孙挺.工业铝电解质分子比测定方法研究与应用[J].轻金属,1993(6):26-30.
[12]高德池.氟离子选择电极法测定磷酸中氟含量[J].磷肥与复肥,2010,25(5):82.
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