新型硫化矿捕收剂的合成及其浮选性能研究
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摘要
硫化矿是有色金属的主要矿床资源,捕收剂是硫化矿综合回收的技术核心。在已有的研究基础上,以N-烃氧羰基异硫氰酸酯为中间体,合成了具有新结构的N-烃氧羰基硫氨酯、N-烃氧羰基硫脲以及N-烃氧羰基硫氮酯捕收剂,并由此研制出了新结构的二烃氧羰基双硫氨酯、二烃氧羰基双硫脲捕收剂。通过一类希夫碱相转移催化剂的制备,实现了有机相中N-烃氧羰基异硫氰酸酯及其衍生物的一锅法高效合成。考察了新型捕收剂对硫化矿单矿物和实际矿石的捕收性能,研究了捕收剂与矿物之间的作用机理。
采用异硫氰酸酯为中间体,分别与醇、胺以及硫醇反应,制备出三类新结构的捕收剂。以氯甲酸乙酯和硫氰酸钠为原料,于3-8℃的低温水相中在双(4-N,N-二甲基氨基苯基)甲烷的相转移催化作用下,反应4h合成了N-乙氧羰基异硫氰酸酯中间体,基于氯甲酸乙酯的收率为96.2%。将N-乙氧羰基异硫氰酸酯与乙醇在45℃下反应3h合成了O-乙基-N-乙氧羰基硫氨酯,基于异硫氰酸酯的收率为95.3%。将N-乙氧羰基异硫氰酸酯和丙胺在0-5℃下反应1h合成了N-丙基-N-乙氧羰基硫脲,基于异硫氰酸酯的收率为98.2%。将N-乙氧羰基异硫氰酸酯和苄硫醇在20℃下反应4h合成了S-苄基-N-乙氧羰基硫氮酯(BITCM),基于异硫氰酸酯的产率为92.53%。根据相同条件,合成了多种N-乙氧羰基硫氨酯和N-乙氧羰基硫脲。采用熔点测试、元素分析、紫外光谱分析、红外光谱分析、核磁共振波谱分析、质谱分析等手段对捕收剂进行了结构和性能表征。
设计出异硫氰酸酯分别与二元醇、二元胺经亲核加成反应制备浮选捕收剂的合成路线,制备了两类新型双配体捕收剂二乙氧羰基双硫氨酯(DTC)和二乙氧羰基双硫脲(DTU)。通过合成工艺条件的系统实验研究,得到了优化工艺条件与制备方法：制备DTC时反应温度为50℃,反应时间为4h；制备DTU时反应温度为20℃,反应时间为1h。制备出N,N’-二乙氧羰基-O,O’-(1,2-亚乙基)双硫氨酯(DTC-2)、N,N’-二乙氧羰基-O,O'-(1,4-亚丁基)双硫氨酯(DTC-4)、N,N’-二乙氧羰基-O,O’-(1,6-亚已基)双硫氨酯(DTC-6)、N,N’-二乙氧羰基-N",N’”-(1,2-亚乙基)双硫脲(DTU-2)、N,N’-二乙氧羰基-N”,N’”-(1,2-异丙基)双硫脲(DTU-3)、N,N’-二乙氧羰基-N”,N’”-(1,6-亚已基)双硫脲(DTU-6)两个系列共六种捕收剂。DTC系列捕收剂的产率均在95%以上,DTU系列捕收剂的产率均在83%以上。采用元素分析、紫外光谱、红外光谱、核磁共振氢谱和碳谱、质谱等分析手段,对产物进行了结构和性能表征,并测定了熔点等物理性质。
发明了以硫氰酸盐和氯甲酸酯为原料、在希夫碱类相转移催化剂的作用下于有机相中一锅法合成异硫氰酸酯及其衍生物的路线。设计出在催化剂对甲苯磺酸的作用下经酮(醛)胺缩聚反应制备希夫碱类催化剂的合成路线,制备了三种新型希夫碱类相转移催化剂：N-(N’,N’-二甲氨基丙基)甲基异丁基亚胺(PMIA)、N-苯基甲基异丁基亚胺(BMIA)、N-(N’,N’-二甲氨基丙基)苯甲亚胺(APPA)。再以硫氰酸钠和氯甲酸乙酯为原料,在新型希夫碱的催化作用下于有机溶剂中合成N-乙氧羰基异硫氰酸酯。通过合成工艺条件的系统实验研究,得到了优化工艺条件与制备方法：制备希夫碱时胺与酮(醛)的摩尔比为1：1.10,对甲苯磺酸与胺的摩尔比为2.5%：1,反应温度为110～120℃,反应时间为2h；制备N-乙氧羰基异硫氰酸酯时在邻苯二甲酸二乙酯体系中以PMIA为催化剂,原料的物质的量之比为硫氰酸钠：氯甲酸乙酯=1.10：1,反应时间为2h、反应温度为35℃,PMIA的最佳用量为硫氰酸钠摩尔用量的1.5%,产率为97.7%。由有机相中合成的异硫氰酸酯中间体,制备了复配捕收剂DT。
系统地研究了新型捕收剂对硫化矿中典型的两种单矿物和实际矿石的捕收性能。考察了几种硫氨酯捕收剂对黄铜矿和黄铁矿的捕收性能,得到有效分离黄铜矿和黄铁矿的最佳pH值为9.5～10,最佳捕收剂用量为60.24mg/L,得出上述捕收剂中性能最好的是O-异辛基-N-乙氧羰基硫氨酯(IOECTC)。将IOECTC和BITCM.DTC-4.DTU-3分别复配,考察了这三种复配捕收剂在不同配比下对黄铜矿和黄铁矿的捕收性能,并与单独使用IOECTC捕收剂时的效果进行了比较。试验结果表明,复配捕收剂的浓度越大,捕收能力越强,且在这三种复配捕收剂中,BITCM-IOECTC捕收剂的捕收能力优于另外两种复配捕收剂。对分别与IOECTC、BITCM-IOECTC、(DTC-4)-IOECTC和(DTU-3)-IOECTC作用前后的黄铜矿和黄铁矿进行了红外光谱表征,分析结果表明,捕收剂与黄铜矿之间发生的是化学作用,而与黄铁矿之间发生的是物理作用。对江西德兴铜矿的硫化铜矿石,在捕收剂用量非常小的条件下,新型捕收剂的捕收性能、黄铁矿选择性优于现有捕收剂丁基黄药,对铜有良好的捕收能力,而对钼的捕收能力远远高于Mac-12。对四川呷村的多金属硫化矿,新型捕收剂对硫化铜矿的捕收能力都很强,一段选铜所获得的回收率都比现场使用药剂BK905高,其中性能最优的是DTC-6。二段选铅结果表明DTU-6和BITCM对硫化铅的捕收能力都很强,优于现场使用药剂BK906,其中性能最优的是BITCM。秘鲁铜矿石浮选结果显示,复配捕收剂DT不但表现出对铜的强捕收能力,而且对砷具有很好的选择性,浮选性能优于Mac-12和Z-200。
研究了新型捕收剂与硫化矿的作用机理。通过紫外光谱考察了BITCM、DTC和DTU三类捕收剂与Cu2+、Fe3+、Ni2+、Pb2+、Zn2+、Ag+、Co2+之间作用的强弱,发现这些捕收剂最容易与Cu2+发生络合,可与Ni2+、Pb2+、Zn2+、Ag+、Co2+发生一定的络合,几乎不与Fe3+发生络合。且DTC与铜离子发生络合的能力随碳链的增长而减小,DTU与之相反。分别制备了BITCM、DTC-4、DTU-6与铜离子形成的络合物,对它们进行了红外光谱的表征,分析结果表明,C=S中的硫原子可能参与和铜的成键。量子化学计算结果表明,新型捕收剂BITCM、DTC-4、DTU-6的捕收性能优于传统的捕收剂丁基黄药等,具有广阔的应用前景。
Sulfide ores are main mineral resource of non-ferrous metals, collectors are the technical core. N-ethoxycarbonyl thiocarbamates, N-ethoxycarbonyl thioureas and N-ethoxycarbonyl dithiocarbamate with new structures were synthesized using N-ethoxycarbonyl isothiocyanate as intermediate based on the past research, diethoxycarbonyl dithionocarbamates and diethoxycarbonyl dithioureas were developed, either."One-pot" synthesis of N-ethoxycarbonyl isothiocyanate and its derivatives in organic phase was achieved via the preparation of schiff base phase transfer catalysts. The flotation performance of the novel collectors to monominerals and sulfide ores were investigated, the interactions between collectors and ores were studied.
Three types of novel collectors were prepared using isothiocyanate as intermediate and react with alchhol, amine or mercaptan. Isothiocyanate was synthesized with chloroformic ester and thiocyanate as raw materials, catalyzed by bis(4-N,N-dimethyl amino phenyl) methane in water in3～8℃for4h, and the yield was96.2%. O-ethyl-N-ethoxycarbonyl thiocarbamate was synthesized with N-ethoxycarbonyl isothiocyanate and ethanol in45℃for3h, the yield was95.3%. N-propyl-N-ethoxycarbonyl thiourea was synthesized with N-ethoxycarbonyl isothiocyanate and propylamine in0～5℃for1h, the yield was98.2%. S-benzyl-N-ethoxycarbonyl thiocarbamate was synthesized with N-ethoxycarbonyl isothiocyanate and benzyl mercaptan in20℃for4h, the yield was92.53%. With the same condition, several N-ethoxycarbonyl thiocarbamates and N-ethoxycarbonyl thioureas were prepared. Meltingtest, elemental analysis, UV spectrum, infrared spectrum,1H NMR,13C NMR and mass spectrum were adopted to characterize their structures and properties.
Addition reaction of isothiocyanate with dihydric alcohol or diamine as raw materials were employed to design the synthesis route of flotation collectors, two novel types of flotation collectors dithiocarbamate(DTC) and dithiourea(DTU) were invented. Synthetic processes were studied systematically by experimental research, and optimal conditions were as follows:reaction temperature50℃and reaction time4h for preparation of DTC; reaction temperature20℃and reaction time1h for preparation of DTU. Two series and six kinds of collectors N,N'-diethoxycarbonyl-0,0'-(1,2-ethylidene) dithionocarbamate(DTC-2), N,N'-diethoxycarbon-yl-O,O'-(1,4-butylidene) dithionocarbamate(DTC-4), N,N'-diethoxycar-bonyl-O,O'-(1,6-hexylidene) dithionocarbamate(DTC-6), N,N'-diethoxy-carbonyl-N",N'"-(1,2-ethylidene) dithiourea(DTU-2), N,N'-diethoxycar-bonyl-N",N"'-(1,2-isopropyl) dithiourea(DTU-3), N,N'-diethoxycarbon-yl-N",N'"-(1,6-hexylidene) dithiourea (DTU-6) were prepared. Yields of DTC are all above95%, yields of DTU are all above83%. Elemental analysis, UV spectrum, infrared spectrum,1H NMR,13C NMR and mass spectrum were adopted to characterize their structures and properties, physical properties such as melting point were also assayed.
"One-pot" synthesis route of isothiocyanate and its derivatives in organic phase catalyzed by schiff base phasetransfer catalyst with thiocyanate and chloroformic ester as raw materials was designed. Condensation polymerization with ketone (aldehyde) and amine was used to design the synthesis route of schiff base catalyst, and three new schiff based phasetransfer catalysts were developed, they are N-(N',N'-dimethyl amino propyl) methyl isobutyl imine (PMIA), N-phenyl methyl isobutyl imine (BMIA) and N-(N',N'-dimethyl amino propyl) phenyl methyl imine (APPA). N-ethoxylcarbonyl isothiocyanate was prepared with schiff base as catalyst, sodium thiocyanate and ethyl chloroformate as raw materials in organic solvent. Synthetic processes were studied systematically by experimental research, and optimal conditions were as follows:molar ratio of amine to methyl ketone(aldehyde)1:1.10, molar ratio of p-toluenesulfonic acid to amine2.5%:1, reaction temperature110～120℃, and reaction time2h for preparation of schiff base; use PMIA as catalyst, molar ratio of sodium thiocyanate to ethyl chloroformate1.10:1, molar ratio of PMIA to sodium thiocyanate1.5%:1, in diethyl phthaltate, reaction temperature35℃and reaction time2h for preparation of N-ethoxylcarbonyl isothiocyanate. Associative collector DT was prepared, too.
Flotation properties of new collectors for monominerals and actual ores of sulfide ore were investigated systematically. Flotation properties of some thiocarbamate collectors for chalcopyrite and pyrite were discussed first, the optimal pH value to efficiently separate them was9.5～10, the optimal dosage of collectors was60.24mg/L. In those collectors, the best one was O-isooctyl-N-ethoxycarbonyl thiocarbamate (IOECTC). Mix IOECTC with BITCM, DTC-4and DTU-3separately in different ratios, the flotation performances of chalcopyrite and pyrite were studied. The results showed that the thicker the collector was, the better the collecting ability was. And among those mixed collectors, BITCM-IOECTC performed best. Chalcopyrite and pyrite before and after complexed with IOECTC or (DTC-4)-IOECTC or (DTU-3)-IOECTC or BITCM-IOECTC were characterized by infrared spectrum, the result indicated that adsorption of collectors on chalcopyrite surface was chemical adsorption and on pyrite surface was physical adsorption. For copper sulfide ore from Dexing copper mine, those novel collectors showed superior flotation properties and selectivity for pyrite with less dosage compared with butyl xanthate. They displayed good collecting ability for copper, and their collecting ability for molybdenum were better than Mac-12. For polymetallic sulfide ore from Gacun, those collectors all performed strong collecting ability for copper sulfide ore, the recoveries were high than BK905in first section to select copper from ores, and the best one was DTC-6. DTC-6and BITCM showed excellent collecting ability for lead sulfide ore compared with BK906, the optimal was BITCM. Flotation performance of copper ores form Peru indicated that, DT showed excellent collecting ability for copper and selectivity for arsenic, and are better than Mac-12and Z-200.
The interaction mechanism of new collectors with sulfide ores was discussed. The intensity of interactions between BITCM, DTC, DTU and Cu2+, Fe3+, Ni2+, Pb2+, Zn2+, Ag+, Co2+were examined by ultraviolet spectrum. The results showed that, these collectors could complex with Cu2+easily, could complex with Ni2、Pb2+、Zn2+、Ag+、Co2+, and could hardly complex with Fe3+. The complexing abilities of DTC to Cu2+were weakened with the increase of the chain length, the condition of DTU was opposite. The complexes of DTC-4or DTU-6or BITCM with Cu2+was prepared, they were characterized by infrared spectrum and it was indicated that sulfur atom in C=S may bond with copper. The quantum chemistry calculation results demonstrated that BITCM, DTC-4and DTU-6have better flotation properties compared with now available collectors for sulfide ore such as butyl xanthate, and are hopeful to be put into practice.
采用异硫氰酸酯为中间体,分别与醇、胺以及硫醇反应,制备出三类新结构的捕收剂。以氯甲酸乙酯和硫氰酸钠为原料,于3-8℃的低温水相中在双(4-N,N-二甲基氨基苯基)甲烷的相转移催化作用下,反应4h合成了N-乙氧羰基异硫氰酸酯中间体,基于氯甲酸乙酯的收率为96.2%。将N-乙氧羰基异硫氰酸酯与乙醇在45℃下反应3h合成了O-乙基-N-乙氧羰基硫氨酯,基于异硫氰酸酯的收率为95.3%。将N-乙氧羰基异硫氰酸酯和丙胺在0-5℃下反应1h合成了N-丙基-N-乙氧羰基硫脲,基于异硫氰酸酯的收率为98.2%。将N-乙氧羰基异硫氰酸酯和苄硫醇在20℃下反应4h合成了S-苄基-N-乙氧羰基硫氮酯(BITCM),基于异硫氰酸酯的产率为92.53%。根据相同条件,合成了多种N-乙氧羰基硫氨酯和N-乙氧羰基硫脲。采用熔点测试、元素分析、紫外光谱分析、红外光谱分析、核磁共振波谱分析、质谱分析等手段对捕收剂进行了结构和性能表征。
设计出异硫氰酸酯分别与二元醇、二元胺经亲核加成反应制备浮选捕收剂的合成路线,制备了两类新型双配体捕收剂二乙氧羰基双硫氨酯(DTC)和二乙氧羰基双硫脲(DTU)。通过合成工艺条件的系统实验研究,得到了优化工艺条件与制备方法：制备DTC时反应温度为50℃,反应时间为4h；制备DTU时反应温度为20℃,反应时间为1h。制备出N,N’-二乙氧羰基-O,O’-(1,2-亚乙基)双硫氨酯(DTC-2)、N,N’-二乙氧羰基-O,O'-(1,4-亚丁基)双硫氨酯(DTC-4)、N,N’-二乙氧羰基-O,O’-(1,6-亚已基)双硫氨酯(DTC-6)、N,N’-二乙氧羰基-N",N’”-(1,2-亚乙基)双硫脲(DTU-2)、N,N’-二乙氧羰基-N”,N’”-(1,2-异丙基)双硫脲(DTU-3)、N,N’-二乙氧羰基-N”,N’”-(1,6-亚已基)双硫脲(DTU-6)两个系列共六种捕收剂。DTC系列捕收剂的产率均在95%以上,DTU系列捕收剂的产率均在83%以上。采用元素分析、紫外光谱、红外光谱、核磁共振氢谱和碳谱、质谱等分析手段,对产物进行了结构和性能表征,并测定了熔点等物理性质。
发明了以硫氰酸盐和氯甲酸酯为原料、在希夫碱类相转移催化剂的作用下于有机相中一锅法合成异硫氰酸酯及其衍生物的路线。设计出在催化剂对甲苯磺酸的作用下经酮(醛)胺缩聚反应制备希夫碱类催化剂的合成路线,制备了三种新型希夫碱类相转移催化剂：N-(N’,N’-二甲氨基丙基)甲基异丁基亚胺(PMIA)、N-苯基甲基异丁基亚胺(BMIA)、N-(N’,N’-二甲氨基丙基)苯甲亚胺(APPA)。再以硫氰酸钠和氯甲酸乙酯为原料,在新型希夫碱的催化作用下于有机溶剂中合成N-乙氧羰基异硫氰酸酯。通过合成工艺条件的系统实验研究,得到了优化工艺条件与制备方法：制备希夫碱时胺与酮(醛)的摩尔比为1：1.10,对甲苯磺酸与胺的摩尔比为2.5%：1,反应温度为110～120℃,反应时间为2h；制备N-乙氧羰基异硫氰酸酯时在邻苯二甲酸二乙酯体系中以PMIA为催化剂,原料的物质的量之比为硫氰酸钠：氯甲酸乙酯=1.10：1,反应时间为2h、反应温度为35℃,PMIA的最佳用量为硫氰酸钠摩尔用量的1.5%,产率为97.7%。由有机相中合成的异硫氰酸酯中间体,制备了复配捕收剂DT。
系统地研究了新型捕收剂对硫化矿中典型的两种单矿物和实际矿石的捕收性能。考察了几种硫氨酯捕收剂对黄铜矿和黄铁矿的捕收性能,得到有效分离黄铜矿和黄铁矿的最佳pH值为9.5～10,最佳捕收剂用量为60.24mg/L,得出上述捕收剂中性能最好的是O-异辛基-N-乙氧羰基硫氨酯(IOECTC)。将IOECTC和BITCM.DTC-4.DTU-3分别复配,考察了这三种复配捕收剂在不同配比下对黄铜矿和黄铁矿的捕收性能,并与单独使用IOECTC捕收剂时的效果进行了比较。试验结果表明,复配捕收剂的浓度越大,捕收能力越强,且在这三种复配捕收剂中,BITCM-IOECTC捕收剂的捕收能力优于另外两种复配捕收剂。对分别与IOECTC、BITCM-IOECTC、(DTC-4)-IOECTC和(DTU-3)-IOECTC作用前后的黄铜矿和黄铁矿进行了红外光谱表征,分析结果表明,捕收剂与黄铜矿之间发生的是化学作用,而与黄铁矿之间发生的是物理作用。对江西德兴铜矿的硫化铜矿石,在捕收剂用量非常小的条件下,新型捕收剂的捕收性能、黄铁矿选择性优于现有捕收剂丁基黄药,对铜有良好的捕收能力,而对钼的捕收能力远远高于Mac-12。对四川呷村的多金属硫化矿,新型捕收剂对硫化铜矿的捕收能力都很强,一段选铜所获得的回收率都比现场使用药剂BK905高,其中性能最优的是DTC-6。二段选铅结果表明DTU-6和BITCM对硫化铅的捕收能力都很强,优于现场使用药剂BK906,其中性能最优的是BITCM。秘鲁铜矿石浮选结果显示,复配捕收剂DT不但表现出对铜的强捕收能力,而且对砷具有很好的选择性,浮选性能优于Mac-12和Z-200。
研究了新型捕收剂与硫化矿的作用机理。通过紫外光谱考察了BITCM、DTC和DTU三类捕收剂与Cu2+、Fe3+、Ni2+、Pb2+、Zn2+、Ag+、Co2+之间作用的强弱,发现这些捕收剂最容易与Cu2+发生络合,可与Ni2+、Pb2+、Zn2+、Ag+、Co2+发生一定的络合,几乎不与Fe3+发生络合。且DTC与铜离子发生络合的能力随碳链的增长而减小,DTU与之相反。分别制备了BITCM、DTC-4、DTU-6与铜离子形成的络合物,对它们进行了红外光谱的表征,分析结果表明,C=S中的硫原子可能参与和铜的成键。量子化学计算结果表明,新型捕收剂BITCM、DTC-4、DTU-6的捕收性能优于传统的捕收剂丁基黄药等,具有广阔的应用前景。
Sulfide ores are main mineral resource of non-ferrous metals, collectors are the technical core. N-ethoxycarbonyl thiocarbamates, N-ethoxycarbonyl thioureas and N-ethoxycarbonyl dithiocarbamate with new structures were synthesized using N-ethoxycarbonyl isothiocyanate as intermediate based on the past research, diethoxycarbonyl dithionocarbamates and diethoxycarbonyl dithioureas were developed, either."One-pot" synthesis of N-ethoxycarbonyl isothiocyanate and its derivatives in organic phase was achieved via the preparation of schiff base phase transfer catalysts. The flotation performance of the novel collectors to monominerals and sulfide ores were investigated, the interactions between collectors and ores were studied.
Three types of novel collectors were prepared using isothiocyanate as intermediate and react with alchhol, amine or mercaptan. Isothiocyanate was synthesized with chloroformic ester and thiocyanate as raw materials, catalyzed by bis(4-N,N-dimethyl amino phenyl) methane in water in3～8℃for4h, and the yield was96.2%. O-ethyl-N-ethoxycarbonyl thiocarbamate was synthesized with N-ethoxycarbonyl isothiocyanate and ethanol in45℃for3h, the yield was95.3%. N-propyl-N-ethoxycarbonyl thiourea was synthesized with N-ethoxycarbonyl isothiocyanate and propylamine in0～5℃for1h, the yield was98.2%. S-benzyl-N-ethoxycarbonyl thiocarbamate was synthesized with N-ethoxycarbonyl isothiocyanate and benzyl mercaptan in20℃for4h, the yield was92.53%. With the same condition, several N-ethoxycarbonyl thiocarbamates and N-ethoxycarbonyl thioureas were prepared. Meltingtest, elemental analysis, UV spectrum, infrared spectrum,1H NMR,13C NMR and mass spectrum were adopted to characterize their structures and properties.
Addition reaction of isothiocyanate with dihydric alcohol or diamine as raw materials were employed to design the synthesis route of flotation collectors, two novel types of flotation collectors dithiocarbamate(DTC) and dithiourea(DTU) were invented. Synthetic processes were studied systematically by experimental research, and optimal conditions were as follows:reaction temperature50℃and reaction time4h for preparation of DTC; reaction temperature20℃and reaction time1h for preparation of DTU. Two series and six kinds of collectors N,N'-diethoxycarbonyl-0,0'-(1,2-ethylidene) dithionocarbamate(DTC-2), N,N'-diethoxycarbon-yl-O,O'-(1,4-butylidene) dithionocarbamate(DTC-4), N,N'-diethoxycar-bonyl-O,O'-(1,6-hexylidene) dithionocarbamate(DTC-6), N,N'-diethoxy-carbonyl-N",N'"-(1,2-ethylidene) dithiourea(DTU-2), N,N'-diethoxycar-bonyl-N",N"'-(1,2-isopropyl) dithiourea(DTU-3), N,N'-diethoxycarbon-yl-N",N'"-(1,6-hexylidene) dithiourea (DTU-6) were prepared. Yields of DTC are all above95%, yields of DTU are all above83%. Elemental analysis, UV spectrum, infrared spectrum,1H NMR,13C NMR and mass spectrum were adopted to characterize their structures and properties, physical properties such as melting point were also assayed.
"One-pot" synthesis route of isothiocyanate and its derivatives in organic phase catalyzed by schiff base phasetransfer catalyst with thiocyanate and chloroformic ester as raw materials was designed. Condensation polymerization with ketone (aldehyde) and amine was used to design the synthesis route of schiff base catalyst, and three new schiff based phasetransfer catalysts were developed, they are N-(N',N'-dimethyl amino propyl) methyl isobutyl imine (PMIA), N-phenyl methyl isobutyl imine (BMIA) and N-(N',N'-dimethyl amino propyl) phenyl methyl imine (APPA). N-ethoxylcarbonyl isothiocyanate was prepared with schiff base as catalyst, sodium thiocyanate and ethyl chloroformate as raw materials in organic solvent. Synthetic processes were studied systematically by experimental research, and optimal conditions were as follows:molar ratio of amine to methyl ketone(aldehyde)1:1.10, molar ratio of p-toluenesulfonic acid to amine2.5%:1, reaction temperature110～120℃, and reaction time2h for preparation of schiff base; use PMIA as catalyst, molar ratio of sodium thiocyanate to ethyl chloroformate1.10:1, molar ratio of PMIA to sodium thiocyanate1.5%:1, in diethyl phthaltate, reaction temperature35℃and reaction time2h for preparation of N-ethoxylcarbonyl isothiocyanate. Associative collector DT was prepared, too.
Flotation properties of new collectors for monominerals and actual ores of sulfide ore were investigated systematically. Flotation properties of some thiocarbamate collectors for chalcopyrite and pyrite were discussed first, the optimal pH value to efficiently separate them was9.5～10, the optimal dosage of collectors was60.24mg/L. In those collectors, the best one was O-isooctyl-N-ethoxycarbonyl thiocarbamate (IOECTC). Mix IOECTC with BITCM, DTC-4and DTU-3separately in different ratios, the flotation performances of chalcopyrite and pyrite were studied. The results showed that the thicker the collector was, the better the collecting ability was. And among those mixed collectors, BITCM-IOECTC performed best. Chalcopyrite and pyrite before and after complexed with IOECTC or (DTC-4)-IOECTC or (DTU-3)-IOECTC or BITCM-IOECTC were characterized by infrared spectrum, the result indicated that adsorption of collectors on chalcopyrite surface was chemical adsorption and on pyrite surface was physical adsorption. For copper sulfide ore from Dexing copper mine, those novel collectors showed superior flotation properties and selectivity for pyrite with less dosage compared with butyl xanthate. They displayed good collecting ability for copper, and their collecting ability for molybdenum were better than Mac-12. For polymetallic sulfide ore from Gacun, those collectors all performed strong collecting ability for copper sulfide ore, the recoveries were high than BK905in first section to select copper from ores, and the best one was DTC-6. DTC-6and BITCM showed excellent collecting ability for lead sulfide ore compared with BK906, the optimal was BITCM. Flotation performance of copper ores form Peru indicated that, DT showed excellent collecting ability for copper and selectivity for arsenic, and are better than Mac-12and Z-200.
The interaction mechanism of new collectors with sulfide ores was discussed. The intensity of interactions between BITCM, DTC, DTU and Cu2+, Fe3+, Ni2+, Pb2+, Zn2+, Ag+, Co2+were examined by ultraviolet spectrum. The results showed that, these collectors could complex with Cu2+easily, could complex with Ni2、Pb2+、Zn2+、Ag+、Co2+, and could hardly complex with Fe3+. The complexing abilities of DTC to Cu2+were weakened with the increase of the chain length, the condition of DTU was opposite. The complexes of DTC-4or DTU-6or BITCM with Cu2+was prepared, they were characterized by infrared spectrum and it was indicated that sulfur atom in C=S may bond with copper. The quantum chemistry calculation results demonstrated that BITCM, DTC-4and DTU-6have better flotation properties compared with now available collectors for sulfide ore such as butyl xanthate, and are hopeful to be put into practice.
引文
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