色谱分析在化工过程中的研究与应用
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摘要
本文是湖南省科技重点攻关项目的部分工作。根据攻关项目试验的需要，研究了在攻关项目中涉及的医药、农药及石油化工生产过程中的色谱分析方法。
全文共分三章：
第一章详细地研究了环己烷氧化废液中的有机酸的分离和定量分析。环己烷氧化废液是在己内酰胺生产过程中环己烷液相氧化时产生的副产物，体系非常复杂。根据样品的特点采用毛细管气相色谱法测定了综合利用环己烷氧化产生的皂化废液过程中的多种一元有机酸和反相高效液相色谱法分离分析多种一元有机酸和二元有机酸。废碱液经过氧化、离心、酸化、抽滤等处理以后，采用强极性的聚乙二醇20M(PEG20M)毛细管柱，程序升温，用丙酸做内标，用丙酮做溶剂对每一步工艺过程中的产物采用毛细管气相色谱法进行了跟踪分析。实验结果表明，该方法中乙酸、丙酸、正戊酸、正己酸的线性范围分别为0.1～8，0.1～10，0.2～12，0.2～12g／L，相关系数分别为0.9992，0.9988，0.9986，0.9990。各酸的相对标准偏差小于2.2％(n=5)，测定各个样品中各有机酸的回收率在88.0％～105.0％之间。采用反相高效液相色谱法在YWG—C18色谱柱(25cm×4.6mm，i．d．，5μm)上以20 mmol／L磷酸盐缓冲溶液(pH=2.30)和甲醇的二元流动相分离测定了废碱液综合利用过程中的各种有机酸。流动相流速为1.0 mL／min，紫外检测波长为210nm。实验结果表明，该方法中正戊酸、正己酸，丁二酸、戊二酸、己二酸的线性范围分别为2.00～20.00，2.12～21.20，1.97～19.70，2.00～20.00，2.50～35.00g／L，相关系数分别为0.9986，0.9988，0.9992，0.9986，0.9988。该方法各酸的相对标准偏差小于1.5％，回收率在95.5～103.2％之间。
第二章详细地研究了反相高效液相色谱分离和检测合成医药
产品布替蔡芬过程中的复杂体系的色谱条件。采用甲醇一水一三乙
胺体系(85:13:2，v/v)作流动相，UV检测，检测波长254nm，
流速1.smL/min，分离分析了布替蔡芬。方法线性范围0.29/L一
2.09/L，相关系数为0.9986，相对标准偏差小于1.8%，平均回
收率为98.5%。该方法简便、准确、快速，己成功地应用于有机合
成过程中复杂体系中的布替蔡芬的测定。
第三章详细地研究了毛细管气相色谱法测定水溶液中仿生农
药N，N一二甲基一2，3一二氯丙胺盐酸盐含量的分析方法。该方法是
在国家标准方法(GB820O一87)存在准确度问题的情况下开展研究
的。样品经过氢氧化钠溶液中和，并用三氯甲烷溶剂萃取后，用甲
苯作内标，采用毛细管气相色谱法进行分析。采用ACI弹性石英毛
细管柱，30 mxO.32Inm i.d.，固定液:100%二甲基聚硅氧烷;柱
温1巧℃，汽化室温度160℃，检测室温度160℃;载气(高纯N2)
压力16psig;FID检测;Range20;衰减2;进样量1 pL;分流比
75:1。相对标准偏差RSD(n=5)小于2.0%，回收率在96.6%~103.6%
之间。该方法简单、快速、准确、重现性好，弥补了国家标准方法
的不足。方法已成功地应用于生产厂家不同批次的N，N一二甲基一2，
3一二氯丙胺盐酸盐的测定。
总之，本文通过大量深入、广泛的研究，建立了几种用色谱分
析化工过程中产品含量的分析方法。其方法简便、准确、颇有实用
价值，为完成湖南省科技重点攻关项目打下了良好的基础。
This paper is part of task of Hunan province science and technology tackling key project. According to the requirement of the trial, chromatographic analysis has been studied in the key project involved medicine, pesticide and petrochemical industry emphatically.
This paper consists of three chapters:
In Chapter 1 ,the separating and determining of organic acids from the process of waste alkali water from the oxidation of cyclohexane has been studied. Waste alkali water from the oxidation of cyclohexane is the side product of cyclohexane oxidating in the process of producing caprolactam, which is very complex. According to the properties of samples,a capillary gas chromatography is described for separating and determining various carboxylic acid .Waste lye is oxidized, centrifuged, acidified and pumping filtrated .The separating condition is strong polarity PEG(20M) capillary column treated by procedure temperature, acetone solvent, propanoic acid as internal material .The linear range of acetic acid, propanoic acid, pentanoic acid , hexanooic acid is 0.01~ 0.4, 0.02 ~ 0.8, 0.02 - 0.6, 0.02~0.5g/L respectively, correlation coefficient is 0.9992, 0.9988, 0.9986, 0.9990 respectively. The relative deviations are less than 2.2%(n=5),and in every sample the recoveries are85%~105%.
The separation and determination of organic acids from the process of cyclohexane oxidation in waste alkali water is described by reverse-phase high performance liquid chromatography. The operating conditions are: YWG-C18 column (10μm,4.6mm i.d. X 25cm) at 25℃, 20 mmol/L phosphoric acids buffer solution (pH=2.30)and methanol as mobile phase at a flow rate of 1 .0mL/min and UV detector at 210 nm. The linear range of pentanoic acid , hexanoic acid, succinic acid,
pentanedioic acid, hexanedioic acid is 2.00-20.00, 2.12-21.20, 1.97-19.70, 2.00~20.00, 2.50-35.00 g/L respectively, correlation coefficient is 0.9986,0.9988,0.9992,0.9986,0.9988 respectively. The relative standard deviations are less than 1.5% and the recoveries are 95.5%~103.2%.
In Chapter 2, the separation and determination of the synthesis product butenafine and related materials are investigated by reverse-phase high-performance liquid chromatography in detail .The separating conditions are: SS Exile ODS (150 X 4.6mm, 10m)as column, MeOH-H2O-(C2H5)3 N (85:13:2,V/V) as mobile phase ,UV detector (254nm)and a flow rate at 1.5mL/min.The linear range is from 0.2 g/L to 2.0 g/L, correlation coefficient is 0.9986.The average recovery of the method was 98.5% and the RSD is 1.8% (n=5).The coefficient of variation was less than 2%.The method is simple , rapid, accurate and has been successfully applied to determine butenafine of the complex system in the process of synthesis .
In Chapter 3, a method for determination of biotics pesticide 2,3-dichloro-N,N-dimethylpropyl-amine hydrochloride in aqueous has been developed by capillary gas chromatography in detail .The method has been brought forward under the condition of national standard method (GB8200-87) existing the problem of accuracy .The samples are neutralized by sodium hydroxide and extracted by trichloromethane. Toluene is used as the internal standard. The separating conditions are : column AC 1 fused silica capillary column(30mx0.32mm i.d.),consisted of 100% dimethyl-polysiloxane, the temperature of the column, injector and the detector are 115℃,160℃,and 160℃ respectively. Carrier gas (N2) pressure: 16 psig; range: 20; Attenuation: 2; injection volume: lL.The relative standard deviation was less than 2.0% and the recovery of the method is in the range of 96.6%~103.6%.The method is simple,
rapid, accurate and reproducible, making up the short of national standard method.
In a word, we have established several new systems for analyzing the samples of chemical process. The method was convenient ,simple and accurate which laid good foundation for finishing Hunan province science and technology tackling key project.
全文共分三章：
第一章详细地研究了环己烷氧化废液中的有机酸的分离和定量分析。环己烷氧化废液是在己内酰胺生产过程中环己烷液相氧化时产生的副产物，体系非常复杂。根据样品的特点采用毛细管气相色谱法测定了综合利用环己烷氧化产生的皂化废液过程中的多种一元有机酸和反相高效液相色谱法分离分析多种一元有机酸和二元有机酸。废碱液经过氧化、离心、酸化、抽滤等处理以后，采用强极性的聚乙二醇20M(PEG20M)毛细管柱，程序升温，用丙酸做内标，用丙酮做溶剂对每一步工艺过程中的产物采用毛细管气相色谱法进行了跟踪分析。实验结果表明，该方法中乙酸、丙酸、正戊酸、正己酸的线性范围分别为0.1～8，0.1～10，0.2～12，0.2～12g／L，相关系数分别为0.9992，0.9988，0.9986，0.9990。各酸的相对标准偏差小于2.2％(n=5)，测定各个样品中各有机酸的回收率在88.0％～105.0％之间。采用反相高效液相色谱法在YWG—C18色谱柱(25cm×4.6mm，i．d．，5μm)上以20 mmol／L磷酸盐缓冲溶液(pH=2.30)和甲醇的二元流动相分离测定了废碱液综合利用过程中的各种有机酸。流动相流速为1.0 mL／min，紫外检测波长为210nm。实验结果表明，该方法中正戊酸、正己酸，丁二酸、戊二酸、己二酸的线性范围分别为2.00～20.00，2.12～21.20，1.97～19.70，2.00～20.00，2.50～35.00g／L，相关系数分别为0.9986，0.9988，0.9992，0.9986，0.9988。该方法各酸的相对标准偏差小于1.5％，回收率在95.5～103.2％之间。
第二章详细地研究了反相高效液相色谱分离和检测合成医药
产品布替蔡芬过程中的复杂体系的色谱条件。采用甲醇一水一三乙
胺体系(85:13:2，v/v)作流动相，UV检测，检测波长254nm，
流速1.smL/min，分离分析了布替蔡芬。方法线性范围0.29/L一
2.09/L，相关系数为0.9986，相对标准偏差小于1.8%，平均回
收率为98.5%。该方法简便、准确、快速，己成功地应用于有机合
成过程中复杂体系中的布替蔡芬的测定。
第三章详细地研究了毛细管气相色谱法测定水溶液中仿生农
药N，N一二甲基一2，3一二氯丙胺盐酸盐含量的分析方法。该方法是
在国家标准方法(GB820O一87)存在准确度问题的情况下开展研究
的。样品经过氢氧化钠溶液中和，并用三氯甲烷溶剂萃取后，用甲
苯作内标，采用毛细管气相色谱法进行分析。采用ACI弹性石英毛
细管柱，30 mxO.32Inm i.d.，固定液:100%二甲基聚硅氧烷;柱
温1巧℃，汽化室温度160℃，检测室温度160℃;载气(高纯N2)
压力16psig;FID检测;Range20;衰减2;进样量1 pL;分流比
75:1。相对标准偏差RSD(n=5)小于2.0%，回收率在96.6%~103.6%
之间。该方法简单、快速、准确、重现性好，弥补了国家标准方法
的不足。方法已成功地应用于生产厂家不同批次的N，N一二甲基一2，
3一二氯丙胺盐酸盐的测定。
总之，本文通过大量深入、广泛的研究，建立了几种用色谱分
析化工过程中产品含量的分析方法。其方法简便、准确、颇有实用
价值，为完成湖南省科技重点攻关项目打下了良好的基础。
This paper is part of task of Hunan province science and technology tackling key project. According to the requirement of the trial, chromatographic analysis has been studied in the key project involved medicine, pesticide and petrochemical industry emphatically.
This paper consists of three chapters:
In Chapter 1 ,the separating and determining of organic acids from the process of waste alkali water from the oxidation of cyclohexane has been studied. Waste alkali water from the oxidation of cyclohexane is the side product of cyclohexane oxidating in the process of producing caprolactam, which is very complex. According to the properties of samples,a capillary gas chromatography is described for separating and determining various carboxylic acid .Waste lye is oxidized, centrifuged, acidified and pumping filtrated .The separating condition is strong polarity PEG(20M) capillary column treated by procedure temperature, acetone solvent, propanoic acid as internal material .The linear range of acetic acid, propanoic acid, pentanoic acid , hexanooic acid is 0.01~ 0.4, 0.02 ~ 0.8, 0.02 - 0.6, 0.02~0.5g/L respectively, correlation coefficient is 0.9992, 0.9988, 0.9986, 0.9990 respectively. The relative deviations are less than 2.2%(n=5),and in every sample the recoveries are85%~105%.
The separation and determination of organic acids from the process of cyclohexane oxidation in waste alkali water is described by reverse-phase high performance liquid chromatography. The operating conditions are: YWG-C18 column (10μm,4.6mm i.d. X 25cm) at 25℃, 20 mmol/L phosphoric acids buffer solution (pH=2.30)and methanol as mobile phase at a flow rate of 1 .0mL/min and UV detector at 210 nm. The linear range of pentanoic acid , hexanoic acid, succinic acid,
pentanedioic acid, hexanedioic acid is 2.00-20.00, 2.12-21.20, 1.97-19.70, 2.00~20.00, 2.50-35.00 g/L respectively, correlation coefficient is 0.9986,0.9988,0.9992,0.9986,0.9988 respectively. The relative standard deviations are less than 1.5% and the recoveries are 95.5%~103.2%.
In Chapter 2, the separation and determination of the synthesis product butenafine and related materials are investigated by reverse-phase high-performance liquid chromatography in detail .The separating conditions are: SS Exile ODS (150 X 4.6mm, 10m)as column, MeOH-H2O-(C2H5)3 N (85:13:2,V/V) as mobile phase ,UV detector (254nm)and a flow rate at 1.5mL/min.The linear range is from 0.2 g/L to 2.0 g/L, correlation coefficient is 0.9986.The average recovery of the method was 98.5% and the RSD is 1.8% (n=5).The coefficient of variation was less than 2%.The method is simple , rapid, accurate and has been successfully applied to determine butenafine of the complex system in the process of synthesis .
In Chapter 3, a method for determination of biotics pesticide 2,3-dichloro-N,N-dimethylpropyl-amine hydrochloride in aqueous has been developed by capillary gas chromatography in detail .The method has been brought forward under the condition of national standard method (GB8200-87) existing the problem of accuracy .The samples are neutralized by sodium hydroxide and extracted by trichloromethane. Toluene is used as the internal standard. The separating conditions are : column AC 1 fused silica capillary column(30mx0.32mm i.d.),consisted of 100% dimethyl-polysiloxane, the temperature of the column, injector and the detector are 115℃,160℃,and 160℃ respectively. Carrier gas (N2) pressure: 16 psig; range: 20; Attenuation: 2; injection volume: lL.The relative standard deviation was less than 2.0% and the recovery of the method is in the range of 96.6%~103.6%.The method is simple,
rapid, accurate and reproducible, making up the short of national standard method.
In a word, we have established several new systems for analyzing the samples of chemical process. The method was convenient ,simple and accurate which laid good foundation for finishing Hunan province science and technology tackling key project.
引文
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