Determination of Cyclohexanone, Cyclohexanone Oxime and Nitrocyclohexane in Hydroxylamine Hydrochloride Oximation Reaction Solution by GC
摘 要
建立了气相色谱法(GC)同时测定盐酸羟胺肟化反应液中环己酮、环己酮肟和硝基环己烷含量的方法。称取盐酸羟胺肟化反应液0.1 g,加入5.0 mL环戊酮肟内标溶液,用无水乙醇稀释至100 mL。优化的GC条件为:以Kromat KB-624色谱柱(30 m×0.32 mm,1.8 μm)为分析柱,采用程序升温方式分离待测物和其他杂质组分,流量2.0 mL·min-1,分流比为100∶1。以环戊酮肟为内标物,内标法定量。结果表明:环己酮、环戊酮肟、环己酮肟、硝基环己烷色谱峰与相邻组分的分离度均大于2.0,3种待测物的标准曲线的线性范围均为1.0~1 000.0 mg·L-1,检出限(3S/N)均为0.02 mg·L-1;按标准加入法进行回收试验,3种待测物的回收率为97.5%~102%,测定值的相对标准偏差(n=6)为1.5%~4.5%。方法用于测定8批盐酸羟胺肟化反应液,测得环己酮、环己酮肟和硝基环己烷的质量分数为5.51%~55.32%,11.86%~88.52%和0.10%~80.62%。
Abstract
A method for simultaneous determination of cyclohexanone, cyclohexanone oxime and nitrocyclohexane in hydroxylamine hydrochloride oximation reaction solution by gas chromatography (GC) was developed. Hydroxylamine hydrochlonde oximation reaction solution of 0.1 g was added to 5.0 mL internal standard solution of cyclopentanone oxime, and diluted to 100 mL by anhydrous ethanol. The optimized conditions of GC were found. Kromat KB-624 chromatographic column (30 m×0.32 mm, 1.8 μm) was used to separate the targets and other impurities by temperature programmed method, with the flow rate of 2.0 mL·min-1 and the split ratio of 100∶1. Internal standard method was applied to quantification with cyclopentanone oxime as internal standard substance. As shown by the results, the resolutions of the chromatographic peaks of cyclohexanone, cyclopentanone oxime, cyclohexanone oxime and nitrocyclohexane with their adjacent components were all greater than 2.0. Linear ranges of the standard curves of 3 compounds were 1.0-1 000.0 mg·L-1, with detection limits (3S/N) of 0.02 mg·L-1. Recovery test was made by standard addition method, giving results of 3 compounds in the range of 97.5%-102%, with RSDs (n=6) of the determined values ranged from 1.5% to 4.5%. This method was used to determine 8 batches of hydroxylamine hydrochloride oximation reaction solution, and the mass fractions of cyclohexanone, cyclohexanone oxime and nitrocyclohexane were 5.51%-55.32%, 11.86%-88.52% and 0.10%-80.62%, respectively.
中图分类号 O656.3 DOI 10.11973/lhjy-hx202110007
所属栏目 工作简报
基金项目 山东省政府“泰山学者”建设工程资金项目(08190201)
收稿日期 2020/6/5
修改稿日期
网络出版日期
作者单位点击查看
备注邢伶,工程师,研究方向为精细化工产品的分析检测
引用该论文: XING Ling,WANG Ruifei,TANG Xiaochan,CHEN Guijun,YUE Tao,FENG Weichun. Determination of Cyclohexanone, Cyclohexanone Oxime and Nitrocyclohexane in Hydroxylamine Hydrochloride Oximation Reaction Solution by GC[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2021, 57(10): 898~902
邢伶,王瑞菲,唐晓婵,陈贵军,岳涛,冯维春. 气相色谱法测定盐酸羟胺肟化反应液中环己酮、环己酮肟和硝基环己烷的含量[J]. 理化检验-化学分册, 2021, 57(10): 898~902
共有人对该论文发表了看法,其中:
人认为该论文很差
人认为该论文较差
人认为该论文一般
人认为该论文较好
人认为该论文很好
参考文献
【1】陈武威.酮肟及其应用于盐酸羟胺的合成工艺研究[D].杭州:浙江大学, 2013.
【2】严生虎, 林春昕, 沈介发, 等.丙酮肟水解可逆反应的进程分析和过程工艺[J].化工进展, 2014, 33(12):3374-3378.
【3】杨龙.反应蒸馏耦合技术合成盐酸羟胺的工艺设计[D].北京:北京化工大学, 2008.
【4】刘光虎.反应-萃取耦合技术制备盐酸羟胺的研究[D].北京:北京化工大学, 2006.
【5】陈虹娅.二硫化碳溶剂解吸-气相色谱法同时测定工作场所空气中环己烷和环己酮[J].中国卫生检验杂志, 2017, 27(8):1098-1100.
【6】彭书萍, 鲍林, 蔡卓弟.毛细管柱气相色谱法同时测定工作场所空气中环己酮和异佛尔酮[J].广东化工, 2016, 43(15):289-290.
【7】项应龙, 胡清启.气相色谱法测定工作场所空气中丙酮、丁酮、甲基异丁酮及环己酮的含量[J].理化检验-化学分册, 2013, 49(10):1202-1204.
【8】姚坚, 顾咏红.气相色谱法同时测定乙酸乙酯、乙酸丁酯、环己酮和苯系物[J].光谱实验室, 2010, 27(5):2004-2008.
【9】李凌凌, 吕早生, 黄乐繁, 等.2, 4-二硝基苯肼显色法测定环己酮含量[J].化学与生物工程, 2010, 27(5):89-91.
【10】蒋文强, 吕霞, 邱光正, 等.一次性使用输液(血)器水浸液中环己酮的分光光度法测定[J].药物分析杂志, 1998, 18(3):52-53.
【11】左伟, 应卫.高效液相色谱分析测定环三甲撑三硝胺炸药中环己酮的残留量[J].甘肃科技, 2004, 20(8):31-32.
【12】吴素芳, 刘建青, 徐有田, 等.分光光度法测定转位酯中环己酮肟[J].分析化学, 2002, 30(7):891-891.
【13】陈萍, 王艳, 段青兵, 等.环己酮肟重排反应混合物中游离肟的测定[J].化工进展, 2004, 23(8):896-898.
【14】赵方方, 游奎一, 彭超, 等.一种同时测定环己酮肟水解反应中环己酮肟和硫酸羟胺含量的方法[J].应用化学, 2015, 32(11):1312-1318.
【15】ZHANG J S, WANG K, LU Y C, et al. Beckmann rearrangement of cyclohexanone oxime in a microchemical system:The role of SO3 and product inhibition[J]. AIChE Journal, 2012, 58(10):3156-3160.
【16】SOOKNOI T, CHITRANUWATKUL V. Ammoximation of cyclohexanone in acetic acid using titanium silicalite-1 catalys:Activity and reaction pathway[J]. Journal of Molecular Catalysis A:Chemical, 2005, 236(1):220-226.
【17】庄明晨.固体超强酸催化环己烷液相硝化制备硝基环己烷的研究[D].湘潭:湘潭大学, 2011.
【2】严生虎, 林春昕, 沈介发, 等.丙酮肟水解可逆反应的进程分析和过程工艺[J].化工进展, 2014, 33(12):3374-3378.
【3】杨龙.反应蒸馏耦合技术合成盐酸羟胺的工艺设计[D].北京:北京化工大学, 2008.
【4】刘光虎.反应-萃取耦合技术制备盐酸羟胺的研究[D].北京:北京化工大学, 2006.
【5】陈虹娅.二硫化碳溶剂解吸-气相色谱法同时测定工作场所空气中环己烷和环己酮[J].中国卫生检验杂志, 2017, 27(8):1098-1100.
【6】彭书萍, 鲍林, 蔡卓弟.毛细管柱气相色谱法同时测定工作场所空气中环己酮和异佛尔酮[J].广东化工, 2016, 43(15):289-290.
【7】项应龙, 胡清启.气相色谱法测定工作场所空气中丙酮、丁酮、甲基异丁酮及环己酮的含量[J].理化检验-化学分册, 2013, 49(10):1202-1204.
【8】姚坚, 顾咏红.气相色谱法同时测定乙酸乙酯、乙酸丁酯、环己酮和苯系物[J].光谱实验室, 2010, 27(5):2004-2008.
【9】李凌凌, 吕早生, 黄乐繁, 等.2, 4-二硝基苯肼显色法测定环己酮含量[J].化学与生物工程, 2010, 27(5):89-91.
【10】蒋文强, 吕霞, 邱光正, 等.一次性使用输液(血)器水浸液中环己酮的分光光度法测定[J].药物分析杂志, 1998, 18(3):52-53.
【11】左伟, 应卫.高效液相色谱分析测定环三甲撑三硝胺炸药中环己酮的残留量[J].甘肃科技, 2004, 20(8):31-32.
【12】吴素芳, 刘建青, 徐有田, 等.分光光度法测定转位酯中环己酮肟[J].分析化学, 2002, 30(7):891-891.
【13】陈萍, 王艳, 段青兵, 等.环己酮肟重排反应混合物中游离肟的测定[J].化工进展, 2004, 23(8):896-898.
【14】赵方方, 游奎一, 彭超, 等.一种同时测定环己酮肟水解反应中环己酮肟和硫酸羟胺含量的方法[J].应用化学, 2015, 32(11):1312-1318.
【15】ZHANG J S, WANG K, LU Y C, et al. Beckmann rearrangement of cyclohexanone oxime in a microchemical system:The role of SO3 and product inhibition[J]. AIChE Journal, 2012, 58(10):3156-3160.
【16】SOOKNOI T, CHITRANUWATKUL V. Ammoximation of cyclohexanone in acetic acid using titanium silicalite-1 catalys:Activity and reaction pathway[J]. Journal of Molecular Catalysis A:Chemical, 2005, 236(1):220-226.
【17】庄明晨.固体超强酸催化环己烷液相硝化制备硝基环己烷的研究[D].湘潭:湘潭大学, 2011.
相关信息