胺类捕收剂可生物降解性能研究
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摘要
随着矿业的发展,由浮选药剂引起的环境污染越来越严重。为了控制和防治浮选药剂污染问题,以及为选矿药剂的合成和科学合理使用提供理论依据,本研究选取六种典型的胺类捕收剂作为研究对象,运用BOD5/CODCr法、振荡培养法和CO2生成量法等三种评价方法,对典型胺类捕收剂在好氧条件下的生物降解性能进行研究,并初步探讨了典型胺类捕收剂的生物降解动力学模型。运用多元线性回归,对典型胺类捕收剂的生物降解性能与分子结构之间的关系模型进行了研究,并通过红外光谱分析,对胺类捕收剂的可能生物降解途径进行了探讨。
运用BOD5/CODCr法、振荡培养法和CO2生成量法等三种评价方法,研究了典型胺类捕收剂十二胺、十八胺、醚胺609、醚胺601、十二烷基三甲基氯化铵和十二烷基三甲基溴化铵在好氧条件下的生物降解性能,综合分析三种评价结果,六种药剂均为可生物降解有机物。其中,十二胺、十二烷基三甲基氯化铵、十二烷基三甲基溴化铵、十八胺的降解性能较好,而醚胺609、醚胺601的生物降解性能相对较差。
通过分析有关生物降解性与化学结构定量关系模型的研究现状,分析了有关的分子结构参数以及模型建立方法,选取EHOMO、ELUMO、Vm、Clog P、μ以及分子二阶连接性指数2X作为药剂分子的结构性参数,通过回归分析,建立了胺类捕收剂的定量结构——生物降解性能关系模型(QSBR),并进行了预测。ClogP、EHOMO(疏水性大小和电性参数)对胺类捕收剂的生物降解性能有显著影响。
利用红外光谱分析,对胺类捕收剂的生物降解途径进行了探讨。醚胺类捕收剂的降解可能存在两种途径,一种途径是首先C-N键断裂,然后经ω、β氧化,生成代谢产物。另一种可能的途径是C-O键断裂,生成丙胺和脂肪酸,然后进一步被氧化；脂肪伯胺可能的降解途径是,首先C-N键断裂,生成NH3和脂肪醇,脂肪醇进一步经微生物氧化生成最终产物；季铵盐阳离子捕收剂可能的降解途径是,首先C-N键断裂,生成(CH3)3N和脂肪醇,脂肪醇进一步经微生物的氧化作用生成最终代谢产物。
With the development of mineral industries, the pollution caused by flotation agents is more and more serious. In order to control and prevent the pollution of agents, and provide the theory for the synthesis and reasonable application of flotation agent, six kinds of amine collectors were selected as objects of study. The aerobic biodegradability of amine collectors has been evaluated by the methods of BOD5/CODCr, shaking cultivation and the amount of CO2 produced, and their kinetics models of biodegradability were investigated preliminarily. Making use of multiple linear regression, the relationship between the biodegradability of typical amine collectors and their chemical structure were discusssed. The degradation pathway of amine collectors were analysized by use of infrared spectroscopic analysis.
Utilizing the methods of BOD5/CODCr, shaking cultivation and the amount of CO2 produced, the aerobic biodegradability of lauryl amine, octadecylamine, laurtrimonium chloride, lauryl trimethyl ammonium bromide, decane-propyl ether amine and dodecyl propyl ether amine were studied. By means of analyzing the evaluation results synthetically, all of these test substances are biodegradable. Among of them, lauryl amine, laurtrimonium chloride, lauryl trimethyl ammonium bromide and octadecylamine is more easy to be degradated than decane-propyl ether amine and dodecyl propyl ether amine.
According to analyzing the situation of study on the relationship between the biodegradability of compounds and their chemical structure, and comparing the parameters of chemical structure and the methods of building model, these parameters, such as EHOMO, ELUMO, Vm, ClogP,μ, and 2X, were selected as the ones of amine collectors. Through the regression analysis, the quantitative structure biodegradability relationships (QSBR) on amine collectors was created, and the biodegradability of amine collectors were predicted. The biodegradability of amine collectors are affected by ClogP and EHOMO markedly.
By use of infrared spectroscopic analysis, the biodegradation pathway of amine collectors were analysized. There are two kinds of potential biodegradation pathway for ether amine, the one is the rupture of C-N firstly, and via the oxidation ofωandβ, the ultima metabolites are produced, the another one is the rupture of C-O firstly, and the products are propylamine and fatty acid which is oxidized furthermore. The possible biodegradation pathway for primary amine is the rupture of C-N firstly, the the products are NH3 and aliphatic alcohol which is oxidized furthermore. And quaternary ammonium salt is biodegradated as a result of the rupture of C-N firstly, (CH3)3N and aliphatic alcohol are produced, and aliphatic alcohol is degradated to finalproducts.
运用BOD5/CODCr法、振荡培养法和CO2生成量法等三种评价方法,研究了典型胺类捕收剂十二胺、十八胺、醚胺609、醚胺601、十二烷基三甲基氯化铵和十二烷基三甲基溴化铵在好氧条件下的生物降解性能,综合分析三种评价结果,六种药剂均为可生物降解有机物。其中,十二胺、十二烷基三甲基氯化铵、十二烷基三甲基溴化铵、十八胺的降解性能较好,而醚胺609、醚胺601的生物降解性能相对较差。
通过分析有关生物降解性与化学结构定量关系模型的研究现状,分析了有关的分子结构参数以及模型建立方法,选取EHOMO、ELUMO、Vm、Clog P、μ以及分子二阶连接性指数2X作为药剂分子的结构性参数,通过回归分析,建立了胺类捕收剂的定量结构——生物降解性能关系模型(QSBR),并进行了预测。ClogP、EHOMO(疏水性大小和电性参数)对胺类捕收剂的生物降解性能有显著影响。
利用红外光谱分析,对胺类捕收剂的生物降解途径进行了探讨。醚胺类捕收剂的降解可能存在两种途径,一种途径是首先C-N键断裂,然后经ω、β氧化,生成代谢产物。另一种可能的途径是C-O键断裂,生成丙胺和脂肪酸,然后进一步被氧化；脂肪伯胺可能的降解途径是,首先C-N键断裂,生成NH3和脂肪醇,脂肪醇进一步经微生物氧化生成最终产物；季铵盐阳离子捕收剂可能的降解途径是,首先C-N键断裂,生成(CH3)3N和脂肪醇,脂肪醇进一步经微生物的氧化作用生成最终代谢产物。
With the development of mineral industries, the pollution caused by flotation agents is more and more serious. In order to control and prevent the pollution of agents, and provide the theory for the synthesis and reasonable application of flotation agent, six kinds of amine collectors were selected as objects of study. The aerobic biodegradability of amine collectors has been evaluated by the methods of BOD5/CODCr, shaking cultivation and the amount of CO2 produced, and their kinetics models of biodegradability were investigated preliminarily. Making use of multiple linear regression, the relationship between the biodegradability of typical amine collectors and their chemical structure were discusssed. The degradation pathway of amine collectors were analysized by use of infrared spectroscopic analysis.
Utilizing the methods of BOD5/CODCr, shaking cultivation and the amount of CO2 produced, the aerobic biodegradability of lauryl amine, octadecylamine, laurtrimonium chloride, lauryl trimethyl ammonium bromide, decane-propyl ether amine and dodecyl propyl ether amine were studied. By means of analyzing the evaluation results synthetically, all of these test substances are biodegradable. Among of them, lauryl amine, laurtrimonium chloride, lauryl trimethyl ammonium bromide and octadecylamine is more easy to be degradated than decane-propyl ether amine and dodecyl propyl ether amine.
According to analyzing the situation of study on the relationship between the biodegradability of compounds and their chemical structure, and comparing the parameters of chemical structure and the methods of building model, these parameters, such as EHOMO, ELUMO, Vm, ClogP,μ, and 2X, were selected as the ones of amine collectors. Through the regression analysis, the quantitative structure biodegradability relationships (QSBR) on amine collectors was created, and the biodegradability of amine collectors were predicted. The biodegradability of amine collectors are affected by ClogP and EHOMO markedly.
By use of infrared spectroscopic analysis, the biodegradation pathway of amine collectors were analysized. There are two kinds of potential biodegradation pathway for ether amine, the one is the rupture of C-N firstly, and via the oxidation ofωandβ, the ultima metabolites are produced, the another one is the rupture of C-O firstly, and the products are propylamine and fatty acid which is oxidized furthermore. The possible biodegradation pathway for primary amine is the rupture of C-N firstly, the the products are NH3 and aliphatic alcohol which is oxidized furthermore. And quaternary ammonium salt is biodegradated as a result of the rupture of C-N firstly, (CH3)3N and aliphatic alcohol are produced, and aliphatic alcohol is degradated to finalproducts.
引文
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