磷矿和磷肥中微量元素Bi、Cd、Cr、Cu、Fe、Pb及常量元素Ca、P的测定研究
发布时间：2018-09-09 08:37
【摘要】：本文综述了国内外对磷矿和磷肥中微量元素和常量元素的测定方法,磷矿和磷肥中微量元素测定时基体干扰问题的处理,以及质量稀释法的研究进展。本文在此基础上研究了:1、以离子交换纤维为固相萃取剂分离富集待测元素后,用电感耦合等离子体发射光谱法(ICP-AES)测定磷矿和磷肥中微量元素Bi、Cd、Cr、Cu、Fe和Pb。2、对本课题所涉及固相萃取体系的热力学和动力学机理进行了研究。3、用质量稀释法稀释磷矿和磷肥样品溶液后,用ICP-AES同时测定磷矿和磷肥中常量元素Ca和P的含量。1、研究表明,当待测液中P和Ca的质量浓度分别大于Cd和Pb的10倍时,使用电感耦合等离子体发射光谱法(ICP-AES)直接测定Cd和Pb的结果其相对误差均大于5%,而磷矿及磷肥中P和Ca相对于Cd和Pb的含量远高于此倍数。在pH≈2并含有0.01g/mL抗坏血酸和0.20mol/LKI的试液中,强碱性阴离子交换纤维(SBAEF)能够定量萃取试液中的Cd(Ⅱ)和Pb(Ⅱ),而Ca2+、PO43-和其他共存的阳离子不被萃取;被SBAEF萃取的Cd(Ⅱ)和Pb(Ⅱ),能够通过0.070mol/L EDTA溶液定量洗脱后,用ICP-AES测定,消除了 P和Ca等共存组分对测定的干扰。方法中Cd和Pb的测定下限分别为1.0×10-2和3.3×10-2μg/g。将该方法应用于实际磷矿和磷肥样品中Cd和Pb的测定,结果的相对标准偏差(RSD,n=5)不超过4.4%,回收率在95.0%～107%之间。本分离方法也适用于火焰原子吸收光谱法(FAAS)测定磷矿和磷肥中Cd和Pb。2、研究表明,当Ca的共存质量浓度大于Bi、Cr、Cu和Fe的50倍,P的共存质量浓度大于Bi、Cr、Cu和Fe的1500倍,Fe的共存质量浓度大于Bi、Cr和Cu时,ICP-AES直接测定Bi、Cr、Cu和Fe的误差大于5%,而磷矿及磷肥中P和Ca相对于Bi、Cr、Cu、Fe以及Fe相对于Bi、Cr、Cu的含量远高于此倍数。本文用0.60g抗坏血酸先将样品溶液中的Fe3+还原为Fe2+,调节pH≈4,使Bi3+、Cr3+和Cu2+与0.01Omol/LEDTA形成不被强酸性阳离子纤维(SACEF)萃取的配阴离子BiY-、CrY-和CuY2-,而此时试液中的Ca2+、Mg2+和Fe2+不与EDTA络合,而被SACEF萃取;在萃取除去Ca2+、Mg2+和Fe2+的试液中,P对Bi、Cr和Cu的干扰可以通过往Bi、Cr和Cu的标准溶液中加入1.00×102μg/mL的P进行补偿,从而实现ICP-AES准确测定Bi、Cr和Cu。对于Fe的测定,直接调节pH≈4后,使Fe3+与O.O1Omol/L EDTA形成FeY-后进行萃取分离,并加入1.00×102μg/mL的P进行补偿,实现ICP-AES准确测定Fe。将该方法应用于实际磷矿和磷肥样品中Bi、Cr、Cu和Fe的测定,结果相对标准偏差(RSD,n=5)不超过3.4%,回收率在96.2%～107%之间。3、研究表明,用ICP-AES直接测定按照国家标准方法溶解磷矿和磷肥后的样品溶液时,Ca和P浓度高于ICP-AES测量线性范围,而将溶液中Ca和P的浓度稀释至1.00～10.0μg/mL后,Ca和P的浓度落在仪器测量线性范围内,且直接测定溶液中Ca和P的误差小于5%。本文选择Ca 315.887nm和P 214.914nm作为分析谱线,用质量稀释法将样品溶液中Ca和P浓度稀释至1.00～10.0μg/mL后,用ICP-AES同时测定Ca和P。将该方法应用于实际磷矿和磷肥样品中Ca和P的测定,结果相对标准偏差(RSD,n=5)不超过1.8%,回收率在98.6%～108%之间。将本文质量稀释法测定结果、体积稀释法测定结果和国家标准方法测定结果进行比较,结果表明,本文方法所测结果与国家标准方法所测结果更为接近,相对误差不超过2.5%。4、本文对本课题所涉及固相萃取体系(SACEF萃取Ca2+和Mg2+,SBAEF萃取CdI42-和PPbI42-)的热力学和动力学机理进行了研究。研究表明,SACEF萃取Ca2+和Mg2+的过程均能较好的符合Freundlich和Langmuir方程,其中Freundlich方程经验常数n分别为1.87和4.46,表明萃取过程较容易进行;热力学常数AH0,AS0,AG0,表示萃取为吸热过程,提高温度有利于萃取进行,萃取过程熵增大且自发进行;动力学研究表明,萃取符合Mckay准二级动力学过程,且主要控速步骤为化学反应。SBAEF萃取CdI42-和PbI42-的过程也均能较好符合Freundlich和Langmuir方程,其中其中Freundlich方程经验常数n为3.08和3.09,表明萃取过程较容易进行;热力学常数△H0,△S0,△G0,表示萃取为吸热过程,提高温度有利于萃取进行,萃取过程熵增大且自发进行;动力学研究表明,萃取也符合Mckay准二级动力学过程,但主要控速步骤为纤维内扩散。
[Abstract]:In this paper, the determination methods of trace elements and major elements in phosphate rock and phosphate fertilizer, the treatment of matrix interference in the determination of trace elements in phosphate rock and phosphate fertilizer, and the research progress of mass dilution method are reviewed. Determination of trace elements Bi, Cd, Cr, Cu, Fe and Pb.2 in phosphate rock and phosphate fertilizer by inductively coupled plasma-atomic emission spectrometry (ICP-AES). Thermodynamic and kinetic mechanism of the solid phase extraction system involved in this subject were studied. 3. After diluting phosphate rock and phosphate fertilizer sample solution by mass dilution method, the major elements Ca in phosphate rock and phosphate fertilizer were determined simultaneously by ICP-AES. The results show that the relative errors of direct determination of Cd and P B by inductively coupled plasma emission spectrometry (ICP-AES) are more than 5% when the mass concentrations of P and Ca in the solution are 10 times higher than those of Cd and P B respectively, while the contents of P and Ca in phosphate rock and phosphate fertilizer are much higher than those of Cd and P B. In the solution of ascorbic acid and 0.20mol/LKI, strong basic anion exchange fiber (SBAEF) can extract Cd (II) and P B (II) quantitatively, but Ca 2+, PO43 - and other coexisting cations can not be extracted; Cd (II) and P B (II) extracted by SBAEF can be quantitatively eluted by 0.070mol/L EDTA solution, and determined by ICP-AES, eliminating P and Ca. The method was applied to the determination of Cd and Pb in phosphate rock and phosphate fertilizer samples. The relative standard deviation (RSD, n=5) of the results was less than 4.4%, and the recovery was between 95.0% and 107%. The determination of Cd and P B.2 in phosphate rock and phosphate fertilizer by FAAS shows that when the coexistence mass concentration of Ca is 50 times higher than that of Bi, Cr, Cu and Fe, the coexistence mass concentration of P is 1500 times higher than that of Bi, Cr, Cu and Fe, and the coexistence mass concentration of Fe is higher than that of Bi, Cr, Cu and Cu, the error of ICP-AES in the direct determination of Bi, Cr, Cu and Fe in phosphate rock and phosphate fertilizer is greater than 5%. In this paper, 0.60g ascorbic acid was used to reduce Fe 3+ to Fe 2+, adjusting pH 4, so that Bi 3+, Cr3+ and Cu 2+ could form complex anions BiY-, CrY-and Cu 2-, which were not extracted by strong acid cationic fiber (SACEF), but Ca2+, Mg2+ and Fe 2+ in the test solution were not. The interference of P on Bi, Cr and Cu can be compensated by adding 1.00 6550 The method was applied to the determination of Bi, Cr, Cu and Fe in phosphate rock and fertilizer samples. The relative standard deviation (RSD, n=5) was less than 3.4%, and the recovery was between 96.2% and 107%. Methods When the solution of phosphate rock and phosphate fertilizer was dissolved, the concentration of Ca and P was higher than the linear range of ICP-AES. When the concentration of Ca and P in the solution was diluted to 1.00-10.0 ug/mL, the concentration of Ca and P fell within the linear range of instrumental measurement. The error of direct determination of Ca and P in the solution was less than 5%. Ca 315.887 nm and P 214.914 nm were selected as fractions. After diluting the concentration of Ca and P in the sample solution to 1.00-10.0 ug/mL by mass dilution method, Ca and P were simultaneously determined by ICP-AES. The method was applied to the determination of Ca and P in phosphate rock and fertilizer samples. The relative standard deviation (RSD, n=5) was less than 1.8% and the recovery was between 98.6% and 108%. The results of volumetric dilution method were compared with those of national standard method. The results showed that the results of this method were closer to those of national standard method, and the relative error was less than 2.5%. 4. The thermodynamics and kinetics of solid phase extraction system (SACEF extraction of Ca 2+ and Mg 2+, SBAEF extraction of CdI42 - and PPPI42 -) were studied in this paper. The results show that the process of extracting Ca 2+ and Mg 2+ by SACEF is in good agreement with Freundlich equation and Langmuir equation. The empirical constants n of Freundlich equation are 1.87 and 4.46 respectively, indicating that the extraction process is easy to proceed. The thermodynamic constants AH0, AS0 and AG0 indicate that the extraction is an endothermic process and the increase of temperature is beneficial to the extraction process. The extraction process of CdI42 - and PBI42 - by SBAEF was also in good agreement with Freundlich and Langmuir equations, in which the empirical constants n of Freundlich equation were 3.08 and 3.09, indicating the extraction process. The thermodynamic constants (?) H0, (?) S0, (?) G0) indicate that the extraction is an endothermic process, and the increase of temperature is conducive to the extraction, and the entropy of the extraction process increases and spontaneously proceeds.
【学位授予单位】：广西大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.31;TQ440.72
本文编号：2231872
[Abstract]:In this paper, the determination methods of trace elements and major elements in phosphate rock and phosphate fertilizer, the treatment of matrix interference in the determination of trace elements in phosphate rock and phosphate fertilizer, and the research progress of mass dilution method are reviewed. Determination of trace elements Bi, Cd, Cr, Cu, Fe and Pb.2 in phosphate rock and phosphate fertilizer by inductively coupled plasma-atomic emission spectrometry (ICP-AES). Thermodynamic and kinetic mechanism of the solid phase extraction system involved in this subject were studied. 3. After diluting phosphate rock and phosphate fertilizer sample solution by mass dilution method, the major elements Ca in phosphate rock and phosphate fertilizer were determined simultaneously by ICP-AES. The results show that the relative errors of direct determination of Cd and P B by inductively coupled plasma emission spectrometry (ICP-AES) are more than 5% when the mass concentrations of P and Ca in the solution are 10 times higher than those of Cd and P B respectively, while the contents of P and Ca in phosphate rock and phosphate fertilizer are much higher than those of Cd and P B. In the solution of ascorbic acid and 0.20mol/LKI, strong basic anion exchange fiber (SBAEF) can extract Cd (II) and P B (II) quantitatively, but Ca 2+, PO43 - and other coexisting cations can not be extracted; Cd (II) and P B (II) extracted by SBAEF can be quantitatively eluted by 0.070mol/L EDTA solution, and determined by ICP-AES, eliminating P and Ca. The method was applied to the determination of Cd and Pb in phosphate rock and phosphate fertilizer samples. The relative standard deviation (RSD, n=5) of the results was less than 4.4%, and the recovery was between 95.0% and 107%. The determination of Cd and P B.2 in phosphate rock and phosphate fertilizer by FAAS shows that when the coexistence mass concentration of Ca is 50 times higher than that of Bi, Cr, Cu and Fe, the coexistence mass concentration of P is 1500 times higher than that of Bi, Cr, Cu and Fe, and the coexistence mass concentration of Fe is higher than that of Bi, Cr, Cu and Cu, the error of ICP-AES in the direct determination of Bi, Cr, Cu and Fe in phosphate rock and phosphate fertilizer is greater than 5%. In this paper, 0.60g ascorbic acid was used to reduce Fe 3+ to Fe 2+, adjusting pH 4, so that Bi 3+, Cr3+ and Cu 2+ could form complex anions BiY-, CrY-and Cu 2-, which were not extracted by strong acid cationic fiber (SACEF), but Ca2+, Mg2+ and Fe 2+ in the test solution were not. The interference of P on Bi, Cr and Cu can be compensated by adding 1.00 6550 The method was applied to the determination of Bi, Cr, Cu and Fe in phosphate rock and fertilizer samples. The relative standard deviation (RSD, n=5) was less than 3.4%, and the recovery was between 96.2% and 107%. Methods When the solution of phosphate rock and phosphate fertilizer was dissolved, the concentration of Ca and P was higher than the linear range of ICP-AES. When the concentration of Ca and P in the solution was diluted to 1.00-10.0 ug/mL, the concentration of Ca and P fell within the linear range of instrumental measurement. The error of direct determination of Ca and P in the solution was less than 5%. Ca 315.887 nm and P 214.914 nm were selected as fractions. After diluting the concentration of Ca and P in the sample solution to 1.00-10.0 ug/mL by mass dilution method, Ca and P were simultaneously determined by ICP-AES. The method was applied to the determination of Ca and P in phosphate rock and fertilizer samples. The relative standard deviation (RSD, n=5) was less than 1.8% and the recovery was between 98.6% and 108%. The results of volumetric dilution method were compared with those of national standard method. The results showed that the results of this method were closer to those of national standard method, and the relative error was less than 2.5%. 4. The thermodynamics and kinetics of solid phase extraction system (SACEF extraction of Ca 2+ and Mg 2+, SBAEF extraction of CdI42 - and PPPI42 -) were studied in this paper. The results show that the process of extracting Ca 2+ and Mg 2+ by SACEF is in good agreement with Freundlich equation and Langmuir equation. The empirical constants n of Freundlich equation are 1.87 and 4.46 respectively, indicating that the extraction process is easy to proceed. The thermodynamic constants AH0, AS0 and AG0 indicate that the extraction is an endothermic process and the increase of temperature is beneficial to the extraction process. The extraction process of CdI42 - and PBI42 - by SBAEF was also in good agreement with Freundlich and Langmuir equations, in which the empirical constants n of Freundlich equation were 3.08 and 3.09, indicating the extraction process. The thermodynamic constants (?) H0, (?) S0, (?) G0) indicate that the extraction is an endothermic process, and the increase of temperature is conducive to the extraction, and the entropy of the extraction process increases and spontaneously proceeds.
【学位授予单位】：广西大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.31;TQ440.72
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