磷礦和磷肥中微量元素Bi、Cd、Cr、Cu、Fe、Pb及常量元素Ca、P的測定研究
發(fā)布時(shí)間：2018-09-09 08:37
【摘要】：本文綜述了國內(nèi)外對磷礦和磷肥中微量元素和常量元素的測定方法,磷礦和磷肥中微量元素測定時(shí)基體干擾問題的處理,以及質(zhì)量稀釋法的研究進(jìn)展。本文在此基礎(chǔ)上研究了:1、以離子交換纖維為固相萃取劑分離富集待測元素后,用電感耦合等離子體發(fā)射光譜法(ICP-AES)測定磷礦和磷肥中微量元素Bi、Cd、Cr、Cu、Fe和Pb。2、對本課題所涉及固相萃取體系的熱力學(xué)和動(dòng)力學(xué)機(jī)理進(jìn)行了研究。3、用質(zhì)量稀釋法稀釋磷礦和磷肥樣品溶液后,用ICP-AES同時(shí)測定磷礦和磷肥中常量元素Ca和P的含量。1、研究表明,當(dāng)待測液中P和Ca的質(zhì)量濃度分別大于Cd和Pb的10倍時(shí),使用電感耦合等離子體發(fā)射光譜法(ICP-AES)直接測定Cd和Pb的結(jié)果其相對誤差均大于5%,而磷礦及磷肥中P和Ca相對于Cd和Pb的含量遠(yuǎn)高于此倍數(shù)。在pH≈2并含有0.01g/mL抗壞血酸和0.20mol/LKI的試液中,強(qiáng)堿性陰離子交換纖維(SBAEF)能夠定量萃取試液中的Cd(Ⅱ)和Pb(Ⅱ),而Ca2+、PO43-和其他共存的陽離子不被萃取;被SBAEF萃取的Cd(Ⅱ)和Pb(Ⅱ),能夠通過0.070mol/L EDTA溶液定量洗脫后,用ICP-AES測定,消除了 P和Ca等共存組分對測定的干擾。方法中Cd和Pb的測定下限分別為1.0×10-2和3.3×10-2μg/g。將該方法應(yīng)用于實(shí)際磷礦和磷肥樣品中Cd和Pb的測定,結(jié)果的相對標(biāo)準(zhǔn)偏差(RSD,n=5)不超過4.4%,回收率在95.0%～107%之間。本分離方法也適用于火焰原子吸收光譜法(FAAS)測定磷礦和磷肥中Cd和Pb。2、研究表明,當(dāng)Ca的共存質(zhì)量濃度大于Bi、Cr、Cu和Fe的50倍,P的共存質(zhì)量濃度大于Bi、Cr、Cu和Fe的1500倍,Fe的共存質(zhì)量濃度大于Bi、Cr和Cu時(shí),ICP-AES直接測定Bi、Cr、Cu和Fe的誤差大于5%,而磷礦及磷肥中P和Ca相對于Bi、Cr、Cu、Fe以及Fe相對于Bi、Cr、Cu的含量遠(yuǎn)高于此倍數(shù)。本文用0.60g抗壞血酸先將樣品溶液中的Fe3+還原為Fe2+,調(diào)節(jié)pH≈4,使Bi3+、Cr3+和Cu2+與0.01Omol/LEDTA形成不被強(qiáng)酸性陽離子纖維(SACEF)萃取的配陰離子BiY-、CrY-和CuY2-,而此時(shí)試液中的Ca2+、Mg2+和Fe2+不與EDTA絡(luò)合,而被SACEF萃取;在萃取除去Ca2+、Mg2+和Fe2+的試液中,P對Bi、Cr和Cu的干擾可以通過往Bi、Cr和Cu的標(biāo)準(zhǔn)溶液中加入1.00×102μg/mL的P進(jìn)行補(bǔ)償,從而實(shí)現(xiàn)ICP-AES準(zhǔn)確測定Bi、Cr和Cu。對于Fe的測定,直接調(diào)節(jié)pH≈4后,使Fe3+與O.O1Omol/L EDTA形成FeY-后進(jìn)行萃取分離,并加入1.00×102μg/mL的P進(jìn)行補(bǔ)償,實(shí)現(xiàn)ICP-AES準(zhǔn)確測定Fe。將該方法應(yīng)用于實(shí)際磷礦和磷肥樣品中Bi、Cr、Cu和Fe的測定,結(jié)果相對標(biāo)準(zhǔn)偏差(RSD,n=5)不超過3.4%,回收率在96.2%～107%之間。3、研究表明,用ICP-AES直接測定按照國家標(biāo)準(zhǔn)方法溶解磷礦和磷肥后的樣品溶液時(shí),Ca和P濃度高于ICP-AES測量線性范圍,而將溶液中Ca和P的濃度稀釋至1.00～10.0μg/mL后,Ca和P的濃度落在儀器測量線性范圍內(nèi),且直接測定溶液中Ca和P的誤差小于5%。本文選擇Ca 315.887nm和P 214.914nm作為分析譜線,用質(zhì)量稀釋法將樣品溶液中Ca和P濃度稀釋至1.00～10.0μg/mL后,用ICP-AES同時(shí)測定Ca和P。將該方法應(yīng)用于實(shí)際磷礦和磷肥樣品中Ca和P的測定,結(jié)果相對標(biāo)準(zhǔn)偏差(RSD,n=5)不超過1.8%,回收率在98.6%～108%之間。將本文質(zhì)量稀釋法測定結(jié)果、體積稀釋法測定結(jié)果和國家標(biāo)準(zhǔn)方法測定結(jié)果進(jìn)行比較,結(jié)果表明,本文方法所測結(jié)果與國家標(biāo)準(zhǔn)方法所測結(jié)果更為接近,相對誤差不超過2.5%。4、本文對本課題所涉及固相萃取體系(SACEF萃取Ca2+和Mg2+,SBAEF萃取CdI42-和PPbI42-)的熱力學(xué)和動(dòng)力學(xué)機(jī)理進(jìn)行了研究。研究表明,SACEF萃取Ca2+和Mg2+的過程均能較好的符合Freundlich和Langmuir方程,其中Freundlich方程經(jīng)驗(yàn)常數(shù)n分別為1.87和4.46,表明萃取過程較容易進(jìn)行;熱力學(xué)常數(shù)AH0,AS0,AG0,表示萃取為吸熱過程,提高溫度有利于萃取進(jìn)行,萃取過程熵增大且自發(fā)進(jìn)行;動(dòng)力學(xué)研究表明,萃取符合Mckay準(zhǔn)二級動(dòng)力學(xué)過程,且主要控速步驟為化學(xué)反應(yīng)。SBAEF萃取CdI42-和PbI42-的過程也均能較好符合Freundlich和Langmuir方程,其中其中Freundlich方程經(jīng)驗(yàn)常數(shù)n為3.08和3.09,表明萃取過程較容易進(jìn)行;熱力學(xué)常數(shù)△H0,△S0,△G0,表示萃取為吸熱過程,提高溫度有利于萃取進(jìn)行,萃取過程熵增大且自發(fā)進(jìn)行;動(dòng)力學(xué)研究表明,萃取也符合Mckay準(zhǔn)二級動(dòng)力學(xué)過程,但主要控速步驟為纖維內(nèi)擴(kuò)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.
【學(xué)位授予單位】：廣西大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.31;TQ440.72
本文編號：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.
【學(xué)位授予單位】：廣西大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.31;TQ440.72
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