工业铜萃取剂分子设计、合成及其萃取性能研究
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摘要
目前,铜萃取剂在分子结构上无新突破。本研究旨在寻找对铜具有特定螯合能力的新型化合物结构,为开发新型铜萃取剂探索新途径。研究的主要内容为:
1以配位化学理论和现有铜萃取剂的结构特征为依据,设计了8种供进行萃铜试验的新型化合物:4-特辛基-2-(苯偶氮)苯酚(简称TPP)、4-特辛基-2-[2-(羟基)苯偶氮]苯酚(简称THP)、4-特辛基-2-[2-(甲氧基)苯偶氮]苯酚(简称TMP)、4-特辛基-2-硝基苯酚(简称NTP)、4-特辛基-2-氨基苯酚(简称ATP)、5-特辛基-2-羟基苯肼(简称HTHB)、甲醛缩4-特辛基-2-氨基苯酚Schiff Bases(简称NFATP)和甲醛缩5-特辛基-2羟基苯肼Schiff Bases(简称NFHTHB)。
2以4-特辛基苯酚、苯胺、邻氨基苯酚和邻甲氧基苯胺等为原料合成了所设计的8种新型化合物,并用乙醇——水重结晶法对产物进行提纯。对除NTP以外的其它7种产物进行液相色谱检测、质谱检测、红外光谱检测和紫外光谱检测。液相色谱检测证明所得各产物纯度较高。质谱检测出了各产物的分子离子峰,红外光谱和紫外光谱检测出了各产物的特征官能团,以上表征证明合成得到了目标产物TPP、THP、TMP、ATP、HTHB、NFATP和NFHTHB。
3对合成的8种新型化合物进行了萃铜性能的初步探索,试验结果表明,甲醛缩4-特辛基-2-氨基苯酚Schiff Bases即NFATP对铜有较好的萃取性能:铜饱和容量为10.5g/mol,净传递量3.3g/L,萃取和反萃分相时间＜60s,铜铁选择系数＞2000,一级萃取60s以上时萃取率＞51%,一级反萃15s以上时反萃率＞95%,25℃时萃取等温点为:有机相铜离子浓度＞3.1g/L、水相铜离子浓度＜2.9g/L,萃合物在24h内无沉淀生成。
NFATF的萃铜性能良好、合成工艺简单,具有开发为工业铜萃取剂的应用前景。NFATP的萃铜性能证明—N=CH_2与酚羟基搭配时可以作为一种新型的萃铜官能团。
No big progress has been made in the molecular structure of copper extractant presently.In order to explore new ways for searching new copper extractant,we synthesized a serial of copper extractants with the especially capacity of chelating copper.The main contents of this study are shown as follows:
1 Based on theoretical of coordination compound chemistry and the structural features of the existing copper extractant,we designed eight new compounds to be tested on extraction capacity of copper,these are 4-tertoctyl-2-(phenylazo) phenol(Shortened form TPP)、4-tertoctyl-2-[2-(hydroxyl)phenylazo]phenol(Shortened form THP)、4-tertoctyl-2-[2-(methoxy)phenylazo]phenol (Shortened form TMP)、2-nitro-4-tertoctylphenol(Shortened form NTP)、2-amino-4-tertoctylphenol (Shor-tened form ATP)、2-hydroxyl-5-tertoctylhydrazinobenzene(Shortened form HTHB)、N-formaldehyde-2-amino-4-tertoctylphenol schiff bases(Shortened form NFATP) and N-form-aldehyde-2-hydroxyl-5-tertoctylhydrazinobenzene schiff bases(Shortened form NFHTHB).
2 We have synthesized eight new compounds with 4-tert-octylphenol、phenylamine、2-aminophenol and 2-methoxyaniline as raw materials,and purified them by the method of ethanol-water recrystallization.Seven of the compounds except NTP have been detected by high pressure liquid chromatography、mass spectrometer、infrared spectrometer and ultraviolet spectrometer respectively.The result of the detection by liquid chromatography proved that all products had high purity.The data of detection by mass spectrum showed that each product had its molecular ion peak.IR and UV spectrum showed the characteristic functional group for the corresponding product.The above characterizations proved that our products has been the target products,that are TPP、THP、TMP、ATP、HTHB、NFATP and NFHTHB.
3 The initial test of eight compounds on extraction of copper showed that N-formaldehyde-2- amino-4-tertoctylphenol schiff bases(NFATP) had the best performance on extraction of copper.The extraction parameter of NFATP are as follows:saturation capacity of copper is 10.5 g/mol,net amount of transfer is 3.3 g/L,time of extraction and stripping phase is less 60 s,β_(Cu/Fe) is more than 2000,first extraction rate is more than 51%when time of extraction more than 60 s, first stripping rate is more than 95%when time of stripping more than 15 s,[Cu]_o＞3.1 g/L、[Cu]_(aq)＜2.9 g/L at 25℃,extraction complex has no precipitation within 24 h.
NFATP has a good performance on extraction of copper,and the synthesizing technology is simple,which indicates that it has a good prospect of application.NFATP' s performance on extraction of copper proves that -N=CH_2 combined with phenolic hydroxyl group can be treated as a new functional group of copper extractant.
1以配位化学理论和现有铜萃取剂的结构特征为依据,设计了8种供进行萃铜试验的新型化合物:4-特辛基-2-(苯偶氮)苯酚(简称TPP)、4-特辛基-2-[2-(羟基)苯偶氮]苯酚(简称THP)、4-特辛基-2-[2-(甲氧基)苯偶氮]苯酚(简称TMP)、4-特辛基-2-硝基苯酚(简称NTP)、4-特辛基-2-氨基苯酚(简称ATP)、5-特辛基-2-羟基苯肼(简称HTHB)、甲醛缩4-特辛基-2-氨基苯酚Schiff Bases(简称NFATP)和甲醛缩5-特辛基-2羟基苯肼Schiff Bases(简称NFHTHB)。
2以4-特辛基苯酚、苯胺、邻氨基苯酚和邻甲氧基苯胺等为原料合成了所设计的8种新型化合物,并用乙醇——水重结晶法对产物进行提纯。对除NTP以外的其它7种产物进行液相色谱检测、质谱检测、红外光谱检测和紫外光谱检测。液相色谱检测证明所得各产物纯度较高。质谱检测出了各产物的分子离子峰,红外光谱和紫外光谱检测出了各产物的特征官能团,以上表征证明合成得到了目标产物TPP、THP、TMP、ATP、HTHB、NFATP和NFHTHB。
3对合成的8种新型化合物进行了萃铜性能的初步探索,试验结果表明,甲醛缩4-特辛基-2-氨基苯酚Schiff Bases即NFATP对铜有较好的萃取性能:铜饱和容量为10.5g/mol,净传递量3.3g/L,萃取和反萃分相时间＜60s,铜铁选择系数＞2000,一级萃取60s以上时萃取率＞51%,一级反萃15s以上时反萃率＞95%,25℃时萃取等温点为:有机相铜离子浓度＞3.1g/L、水相铜离子浓度＜2.9g/L,萃合物在24h内无沉淀生成。
NFATF的萃铜性能良好、合成工艺简单,具有开发为工业铜萃取剂的应用前景。NFATP的萃铜性能证明—N=CH_2与酚羟基搭配时可以作为一种新型的萃铜官能团。
No big progress has been made in the molecular structure of copper extractant presently.In order to explore new ways for searching new copper extractant,we synthesized a serial of copper extractants with the especially capacity of chelating copper.The main contents of this study are shown as follows:
1 Based on theoretical of coordination compound chemistry and the structural features of the existing copper extractant,we designed eight new compounds to be tested on extraction capacity of copper,these are 4-tertoctyl-2-(phenylazo) phenol(Shortened form TPP)、4-tertoctyl-2-[2-(hydroxyl)phenylazo]phenol(Shortened form THP)、4-tertoctyl-2-[2-(methoxy)phenylazo]phenol (Shortened form TMP)、2-nitro-4-tertoctylphenol(Shortened form NTP)、2-amino-4-tertoctylphenol (Shor-tened form ATP)、2-hydroxyl-5-tertoctylhydrazinobenzene(Shortened form HTHB)、N-formaldehyde-2-amino-4-tertoctylphenol schiff bases(Shortened form NFATP) and N-form-aldehyde-2-hydroxyl-5-tertoctylhydrazinobenzene schiff bases(Shortened form NFHTHB).
2 We have synthesized eight new compounds with 4-tert-octylphenol、phenylamine、2-aminophenol and 2-methoxyaniline as raw materials,and purified them by the method of ethanol-water recrystallization.Seven of the compounds except NTP have been detected by high pressure liquid chromatography、mass spectrometer、infrared spectrometer and ultraviolet spectrometer respectively.The result of the detection by liquid chromatography proved that all products had high purity.The data of detection by mass spectrum showed that each product had its molecular ion peak.IR and UV spectrum showed the characteristic functional group for the corresponding product.The above characterizations proved that our products has been the target products,that are TPP、THP、TMP、ATP、HTHB、NFATP and NFHTHB.
3 The initial test of eight compounds on extraction of copper showed that N-formaldehyde-2- amino-4-tertoctylphenol schiff bases(NFATP) had the best performance on extraction of copper.The extraction parameter of NFATP are as follows:saturation capacity of copper is 10.5 g/mol,net amount of transfer is 3.3 g/L,time of extraction and stripping phase is less 60 s,β_(Cu/Fe) is more than 2000,first extraction rate is more than 51%when time of extraction more than 60 s, first stripping rate is more than 95%when time of stripping more than 15 s,[Cu]_o＞3.1 g/L、[Cu]_(aq)＜2.9 g/L at 25℃,extraction complex has no precipitation within 24 h.
NFATP has a good performance on extraction of copper,and the synthesizing technology is simple,which indicates that it has a good prospect of application.NFATP' s performance on extraction of copper proves that -N=CH_2 combined with phenolic hydroxyl group can be treated as a new functional group of copper extractant.
引文
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