萃取—反应制备高纯磷酸铵盐的过程
|
摘要
溶剂萃取是湿法磷酸净化的主流方法。湿法磷酸成本较热法磷酸低,但杂质含量较高,在用于制备纯度等级较高的磷酸盐产物时往往需要采用溶剂萃取等方法进行净化处理。现有溶剂萃取工艺通常包括：湿法磷酸浓缩、萃取、洗涤、反萃等步骤,再以所得的反萃磷酸作为制备磷酸盐的出发原料。从理论上分析,通过有机相中磷酸的直接反应制备磷酸盐产物,可以省去反萃取操作；通过对萃取相磷酸反应进程的分阶段控制,有可能得到不同纯度等级的磷酸盐产物。
本文以此为背景开展研究工作,以磷酸铵盐作为目的产物。采用的工艺流程包括湿法磷酸浓缩、多级萃取、多级洗涤、成盐反应,萃取中以甲基异丁基甲酮为萃取剂。通过该工艺流程,可以得到不同等级的磷酸铵盐,其中一部分是高纯度的铵盐。
为了建立分级反应制备高纯磷酸铵盐的方法,先考察目的产物磷酸铵盐和杂质盐在非水介质中溶解过程的热力学特性。研究了磷酸氢二铵、磷酸二氢铵、磷酸铁和硫酸铵在甲基异丁基甲酮中的溶解平衡特性,并且比较了不同温度下杂质盐的结晶析出的顺序与中和度之间的关系。由研究结果知,温度区间为25～35℃时,水饱和的甲基异丁基甲酮中溶解度大小排序为：磷酸二氢铵<硫酸铵<磷酸铁<磷酸氢二铵,温度35℃时有利于分级成盐反应的进行。
在此基础上,提出了分级反应制磷酸铵盐的初步流程,对提出的流程开展工艺学研究。为了提高分级反应制高纯度磷酸铵盐的需要,湿法磷酸的前端净化应该在较优化的条件下进行。考虑反应对净化酸纯度的要求,经实验验证,萃取净化的最佳条件：酸浓度为75%-79%,有机溶剂和酸的质量比为1.2：1,温度为30℃；洗涤净化的最佳条件：洗涤酸浓度为53%～54%,温度为30℃,萃取有机相与洗涤酸相的质量比为mO:mA=1:0.4。
在上述研究的基础上,用净化的湿法磷酸制备磷酸铵盐,在成盐反应过程中,通过控制反应中和度,在反应的各阶段分别制得工业级磷酸盐、食品级磷酸盐和高纯级磷酸盐。反应产物直接结晶析出,与传统方法中蒸发水得到磷酸盐产品的过程相比,省去了水的蒸发,存在节能的潜力。
Solvent extraction is the main method of purification of wet phosphoric acid, its costs are lower than thermal phosphoric acid, but its impurities level is higher, so wet phosphoric acid is required to be purified by solvent extraction or other methods in the preparation for the high purity grade phosphate products. Present solvent extraction process typically includes: concentration, extraction, scrubbing, back-extraction and so on, the back-extracted phosphoric acid is then used as the starting materials for preparation of phosphates. From the theoretical analysis, phosphoric acid in organic phase can directly react to prepare for phosphates, which can eliminate back-extracting operation. Through controling the neitralisation reaction degree of phosphoric acid, different purity level phosphates may be got by crystallisation from extract phase.
With ammonium phosphates as end products, a coupling process of extractive purification and stagewise reaction has been experimentally studied. The processes include: concentration, multi-stage extraction, multi-stage scrubbing and stagewise reaction, while methyl isobutyl ketone is used as extractant, through this process we can obtain different grades of ammonium phosphates (one part is high purity ammonium phosphates).
In order to establish the method for preparation of high purity ammonium phosphates through stagewise reaction, thermodynamic properties of end products and impurities salts were firstly researched. The solid liquid equilibrium properties of monoammonium phosphate, diammonium phosphate, ferric phosphate and ammonium sulphate in methyl isobutyl ketone were studied. Known from researching result, when temperature was ranged from 25℃to 35℃, the sequence of solubilities in water-saturated methyl isobutyl ketone is listed as follows:monoammonium phosphate On this basis, initial process of preparation of ammonium phosphate through grading reaction was proposed, and corresponding technological study was conducted. Studies indicated that the optimal conditions for extracting purification:acid concentration is from 75% to 79%, mass ratio between organic solvent and concentrated phosphoric acid is 1.2:1, the temperature is 30℃; the optimal conditions for scrubbing purification:the concentration of scrubbing acid is from 53% to 54%. mass ratio between organic extraction phase and scrubbing acid phase is 1:0.4. the temperature is 30℃.
Based on the above research, the extractive purified wet phosphoric acid is used for production of ammonium phosphate by stagewise reactive crystallizaion, by controlling the reaction degree industrial grade, food grade and high purity grade phosphates can be obtained in the reacting process. Reaction products can be crystallized directly from the extract phase, so the traditional process of evaporating water to get phosphate products can be eliminated.
本文以此为背景开展研究工作,以磷酸铵盐作为目的产物。采用的工艺流程包括湿法磷酸浓缩、多级萃取、多级洗涤、成盐反应,萃取中以甲基异丁基甲酮为萃取剂。通过该工艺流程,可以得到不同等级的磷酸铵盐,其中一部分是高纯度的铵盐。
为了建立分级反应制备高纯磷酸铵盐的方法,先考察目的产物磷酸铵盐和杂质盐在非水介质中溶解过程的热力学特性。研究了磷酸氢二铵、磷酸二氢铵、磷酸铁和硫酸铵在甲基异丁基甲酮中的溶解平衡特性,并且比较了不同温度下杂质盐的结晶析出的顺序与中和度之间的关系。由研究结果知,温度区间为25～35℃时,水饱和的甲基异丁基甲酮中溶解度大小排序为：磷酸二氢铵<硫酸铵<磷酸铁<磷酸氢二铵,温度35℃时有利于分级成盐反应的进行。
在此基础上,提出了分级反应制磷酸铵盐的初步流程,对提出的流程开展工艺学研究。为了提高分级反应制高纯度磷酸铵盐的需要,湿法磷酸的前端净化应该在较优化的条件下进行。考虑反应对净化酸纯度的要求,经实验验证,萃取净化的最佳条件：酸浓度为75%-79%,有机溶剂和酸的质量比为1.2：1,温度为30℃；洗涤净化的最佳条件：洗涤酸浓度为53%～54%,温度为30℃,萃取有机相与洗涤酸相的质量比为mO:mA=1:0.4。
在上述研究的基础上,用净化的湿法磷酸制备磷酸铵盐,在成盐反应过程中,通过控制反应中和度,在反应的各阶段分别制得工业级磷酸盐、食品级磷酸盐和高纯级磷酸盐。反应产物直接结晶析出,与传统方法中蒸发水得到磷酸盐产品的过程相比,省去了水的蒸发,存在节能的潜力。
Solvent extraction is the main method of purification of wet phosphoric acid, its costs are lower than thermal phosphoric acid, but its impurities level is higher, so wet phosphoric acid is required to be purified by solvent extraction or other methods in the preparation for the high purity grade phosphate products. Present solvent extraction process typically includes: concentration, extraction, scrubbing, back-extraction and so on, the back-extracted phosphoric acid is then used as the starting materials for preparation of phosphates. From the theoretical analysis, phosphoric acid in organic phase can directly react to prepare for phosphates, which can eliminate back-extracting operation. Through controling the neitralisation reaction degree of phosphoric acid, different purity level phosphates may be got by crystallisation from extract phase.
With ammonium phosphates as end products, a coupling process of extractive purification and stagewise reaction has been experimentally studied. The processes include: concentration, multi-stage extraction, multi-stage scrubbing and stagewise reaction, while methyl isobutyl ketone is used as extractant, through this process we can obtain different grades of ammonium phosphates (one part is high purity ammonium phosphates).
In order to establish the method for preparation of high purity ammonium phosphates through stagewise reaction, thermodynamic properties of end products and impurities salts were firstly researched. The solid liquid equilibrium properties of monoammonium phosphate, diammonium phosphate, ferric phosphate and ammonium sulphate in methyl isobutyl ketone were studied. Known from researching result, when temperature was ranged from 25℃to 35℃, the sequence of solubilities in water-saturated methyl isobutyl ketone is listed as follows:monoammonium phosphate
Based on the above research, the extractive purified wet phosphoric acid is used for production of ammonium phosphate by stagewise reactive crystallizaion, by controlling the reaction degree industrial grade, food grade and high purity grade phosphates can be obtained in the reacting process. Reaction products can be crystallized directly from the extract phase, so the traditional process of evaporating water to get phosphate products can be eliminated.
引文
[1]陈雪萍,蒋丽红.湿法磷酸净化技术进展[J].河北化工,2006,29(7)：7-10
[2]刘晶晶,毛常明,尹进华等.湿法磷酸的工艺研究进展[J].河北化工,2005,4：14-16
[3]A Marcilla, F Ruiz, D Martiez-Pons. Purification of wet process phosphoric acid by extraction[J]. Solvent extraction and ion exchange,1993,11(3):455
[4]金士威,欧阳贻德.磷酸生产技术及其发展方向[J].化工时刊,2003,17(2)：18-20
[5]许立信,尹进华,刘俊玲等.高品质磷石膏生产工艺研究[J].化工矿物与加工,2004,33(5)：28-30
[6]吴佩芝.湿法磷酸[M].北京：化学工业出版社,1987,1：6-8
[7]南京化学工业公司磷肥厂.萃取磷酸和磷酸铵的生产[M].燃料化学工业出版社,1974,1：11-15
[8]Liangshi Wang, Zhiqi Long, Xiaowei Huang, et al. Recovery of rare earths from wet-process phosphoric acid[J]. Hydrometallurgy,2010,101(1-2):41-47
[9]杨建中,李志祥.湿法磷酸净化技术[J].磷肥与复肥,2004,19(6)：13-17
[10]王辛龙,万先达.湿法磷酸净化的新进展[J].磷肥与复肥,2001,16(2)：32-33
[11]Y K Kim, H K Walters, J D Hatfield. Conditions affecting the purification of simulated wet-process phosphoric acids by solvent extraction [J]. Journal of Agricultural and Food Chemistry,1974,22(6):1099
[12]H Goreck, K Hoffmann, J Hoffmann. Special methods of purification of wet-process phosphoric acid[J]. Polish Journal of Applied Chemistry,1996,40(4):389-398
[13]骆广生,刘舜华,孙勇等.磷酸的溶剂萃取法净化[J].过程工程学报,2001,1(2)：211-213
[14]欧阳贻德,陈古圣,苏裕光.磷酸三丁酯萃取分离磷酸与盐酸的研究[J].汉化工学院学报,1998,20(1)：5-9
[15]R Dhouib-Sahnoun, M Feki, H F Ayedi. Extractive purification of wet phosphoric acid with tributyl-phosphate:study of the impurities distribution[J]. Journal chemical company Tunisia,2000,8:873-885
[16]吕中.磷酸三丁酯-水-磷酸体系液液相平衡研究[J].四川联合大学学报(工程科学版),1999,3(2)：54-59
[17]金士威,张中华,易琼.磷酸三丁酯萃取磷酸的动力学研究[J].化工时刊,2005,19(7)：17-19
[18]郭昌明,黎铉海.利用磷酸三丁酯在硫酸—磷酸体系中萃取净化低浓度湿法磷酸工艺的研究[J].磷肥与复肥,2009,24(5)：11-13
[19]F Ruiz, A Marcilla, A M Ancheta&Concepcionrico. Liquid-liquid equilibrium of the three liquid phases at equilibrium system water-phosphoric acid-di-isopropyl ether at 25 and 40℃[J]. Solvent Extraction and Ion Exchange,1986,4(4):789-802
[20]A Marcilla, F Ruiz, A M Ancheta. Purification of wet process phosphoric acid by solvent extraction with dibutyl ether. Part II. Study of the impurities distribution[J]. Solvent Extraction and Ion Exchange,1989,7(2):211-221
[21]A Marcilla, F Ruiz, A M Ancheta. Purification of wet process phosphoric acid by solvent extraction with propyl ether[J]. Solvent Extraction and Ion Exchange,1987,5(6): 1141-1150
[22]K Nazari, A Ghadiri, H Babaie. Elimination of cadmium from wet process phosphoric acid with Alamine 336[J]. Minerals Engineering,2005,18(13-14):1233-1238
[23]潘春升,钟耀荣,王和平等.湿法磷酸萃取法制取精细磷酸盐的研究[J].磷肥与复肥,2004,19(2)：15-17
[24]M Feki, H F Ayedi. Establishing models for wet process phosphoric acid purification with methyl isobutyl ketone[J]. Canadian Journal of Chemical Engineering,2000,78(3): 540-546
[25]K D Muldagaliev, M R Tanasheva, D Smagulova, et al. Extraction of phosphoric acid by cyclohexanone[J]. Izvestiya Akademii Nauk Kazakhskoi SSR, Seriya Khimicheskaya, 1970,20(3):74
[26]I L Krupatkin, T A Shcherbakova. Extraction systems of phosphoric acid with some ketones[J]. Zhurnal Prikladnoi Khimii,1970,43(6):1295-1298
[27]K Regina, K Zygmunt, P K Danuta. Purification of phosphoric acid by solvent extraction using methyl isobutyl ketone (MIBK). Technologia Chemiczna na Przelomie Wiekow, 2000,257-260
[28]Yuming Jiang, Yuanfu Su. Production of pure phosphoric acid and/or phosphorates from wet process phosphoric acid using an extractant[P]. US4781905A
[29]江玉明,李道纯,苏元复.萃取法净化磷酸工艺[J].化工学报,1982,(4)：310-318
[30]乐武阳,戢峻,丁一刚等.复合萃取剂萃取净化低浓度湿法磷酸工艺研究[J].化学与生物工程,2011,28(1)：67-69
[31]乐武阳,丁一刚,李攀等.复合萃取剂萃取湿法磷酸相平衡和动力学研究[J].武汉工程大学学报,2011,33(2)：31-33,37
[32]C D Gosling, F P Wilcher, L Sullivan, et al. Process LPG to BTX products[J]. Hydrocarbon Processing,1991,70(12):69-72
[33]尤彩霞,李军.甲醇沉淀法净化湿法稀磷酸制磷酸氢二铵[J].无机盐工业,2008,40(6)：27-29
[34]T Inui, Y Ishihara, K McKamachi, et al. Pt Loaded HIGH-Ga Silicates for Aromatization of Light Paraffins and Methane[J]. Studies in Surface Science and Catalysis,1989,49: 1183-1192
[35]Y Ono, H Nakatani, H Kitagawa, et al. The Role of Metal Cations in the Transformation of Lower Alkanes into Aromatic Hydrocarbons[J]. Studies in Surface Science and Catalysis,1989,44:279-290
[36]Y Ono, K Kanae. Transformation of butanes over ZSM-5 zeolites. Part 2.—Formation of aromatic hydrocarbons over Zn-ZSM-5 and Ga-ZSM-5[J]. Journal of the Chemical Society, Faraday Transactions,1991,87(4):669-675
[37]T Inui, Y Makino, F Okazumi, S Nagano, et al. Selective aromatization of light paraffins on platinum-ion-exchanged gallium-silicate bifunctional catalysts [J]. Industrial Engineering Chemistry Research,1987,26:647-652
[38]钟本和,陈亮,李军等.溶剂萃取法净化湿法磷酸的新进展[J].化工进展,2005,24(6)：596-602
[39]Yong Ma, Jiawen Zhu, Kui Chen, et al. Study on growth kinetics of phosphoric acid hemihydrate using FBRM[J]. Journal of Crystal Growth,2009, (312):109-113
[40]Leping Dang, Hongyuan Wei. Effects of ionic impurities on the crystal morphology of phosphoric acid hemihydrate[J]. Chemical Engineering Research and Design,2009:19
[41]Leping Dang, Hongyuan Wei, Zhen Zhu, et al. The influence of impurities on phosphoric acid hemihydrate crystallization[J]. Journal of Crystal Growth,2007,1(307):104-111
[42]Leping Dang, Hongyuan Wei, Jinkang Wang. Effects of Ionic Impurities (Fe2+ and SO42-) on the Crystal Growth and Morphology of Phosphoric Acid Hemihydrate during Batch Crystaltization[J]. Ind Eng Chem Res,2007,46 (10):3341-3347
[43]J P Smith, W E Brown, James R Lehr. Structure of crystalline phosphoric acid[J]. J Am Chem Soc,1955,77:2728-2730
[44]K Herzog, E Steger. Solid phases of phosphoric acid and phosphoric acid hemihydrate [J]. Journal of Inorganic and Nuclear Chemistry,1965,27(6):1429-1430
[45]黄斌,陈晓峰,程德军.湿法磷酸合成大颗粒磷酸脲的工艺研究[J].无机盐工业,2008,40(6)：32-33
[46]李云生.湿法磷酸制备磷酸脲的试验研究[J].硫磷设计与粉体工程,2000,(2)：30-31
[47]侯长军,霍丹群.磷酸三聚氰胺复盐结晶法净化湿法磷酸技术进展[J].化工进展,1996,(5)：32-35
[48]蒋丽红,赵声兰,赵榆林等.结晶法由湿法磷酸生产磷酸二氢钾结晶特性的研究[J].云南化工,2001,28(2)：1-3
[49]A N Baumann. Separation of dissolved substance from wet phosphoric acid[P]. US: 4640828A
[50]D H Michalski, V Srinivanan. Precipitation of aluminum, magnesium and iron impurities from wet process phosphoric acid[P]. US4639359A
[51]张允湘.钟本和,罗洪波.湿法磷酸的净化方法评述[J].磷酸盐工业,2001,(2)：21-25
[52]陈虎.黄海涛,柳丹.湿法磷酸净化预处理工艺研究[J].化工矿物与加工,2009,(2)：3-5
[53]王励生,胡文成.湿法磷酸浓缩特性及脱氟速率的研究[J].磷肥与复肥,1995,10(4)：5-7
[54]费德君,党洁修.共沸精馏法浓缩磷酸的研究[J].四川联合大学学报(工程科学版),1997,(1)：52-56
[55]A A El-Bayaa, N A Badawy, A M Gamal, et al. Purification of wet process phosphoric acid by decreasing iron and uranium using white silica sand[J]. Journal of Hazardous Materials,2011,190(1-3):324-329
[56]A A M Daifullah, N S Awwad, S A El-Reefy. Purification of wet phosphoric acid from ferric ions using modified rice husk[J]. Chemical Engineering and Processing:Process Intensification,2004,43(2):193-201
[57]谦培超,孟文杰,汤德元.离子交换技术净化湿法磷酸中的镁离子[J].贵州工业大学学报,2008,37(1)：36-39
[58]谦培超.湿法磷酸的离子交换法除镁研究[D].贵阳：贵州大学化工学院,2008
[59]高洁.浅谈湿法磷酸的净化[J].化工矿物与加工,2004,(7)：37-38
[60]熊祥祖,王威,李志保等.离子交换树脂脱除湿法磷酸中金属杂质的研究[J].武汉工程大学学报,2009,31(7)：26-29
[61]L Monser, M B Amor, M Ksibi. Purification of wet phosphoric acid using modified activated carbon[J]. Chemical Engineering and Processing:Process Intensification,1999, 38(3):267-271
[62]M B Chehida Elleuch, M B Amor, G Pourcelly. Phosphoric acid purification by a membrane process:Electrodeionization on ion-exchange textiles[J]. Separation and Purification Technology,2006,51(3):285-290
[63]M P Gonzalez, R Navarro, I Saucedo, et al. Purification of phosphoric acid solutions by reverse osmosis and nanofiltration[J]. Desalination,2002,147(1-3):315-320
[64]陈嘉甫,谭光薰.磷酸盐的生产及应用[M].成都科技大学出版社,1989：97-108
[65]杨兆麟.我国小磷铵技术现状与开发途径[J].化工设计,1998,(4)：45-47
[66]磷酸二氢铵生产的微反应器技术通过成果鉴定.企业科技与发展,2010,(1)：6-7
[67]刘妍.六氟磷酸锂制备方法的探讨[J].新疆有色金属,2009,A02：124-126
[68]N W Smith. Preparation of lithium hexafluorophosphate[P]. US3607020.1971
[69]周宁波,陈白珍,何新快等.有机溶剂法无水氯化镁的制备与表征[J].无机化学学报,2005,21(2)：286-290
[70]丛昱.液相沉淀法在有机溶剂中制备ZrO2超细粒子的研究[J].燃料化学学报,1998, 26(3):230-233
[71]Miyi Li. Lisheng Wang, Kunpeng Wang, et al. Experimental measurement and modeling of solubility of LiBr and LiNO3 in methanol, ethanol. 1-propanol,2-propanol and 1-butanol[J]. Fluid Phase Equilibria,2011,307:104-109
[72]Y P Jimenez, M E Taboada, Hector R Galleguillos. Solid-liquid equilibrium of K2SO4 in solvent mixtures at different temperatures [J]. Fluid Phase Equilibria,2009,284(2): 114-117
[73]GB2091-1992.工业磷酸[S]
[74]刑红伟.磷肥中有效磷含量的测定分析[M].科技信息,2008,(10)：247
[75]李耕.石墨炉原子吸收法测定铬[J].福建环境,2000,17(4)：11
[76]王玉英.用重量法分析硫酸根方法的讨论[J].纯碱工业,1992,(3)：30-31
[77]张乐.磷矿中氟含量的测定[J].磷肥与复肥,2007,22(1)：64-65
[78]GB7481-87.水质铵的测定水杨酸分光光度法[S]
[79]胡小玲,吴鹏.水杨酸-次氯酸盐测定水中氨氮方法的改进[J].干旱环境监测,2005,19(3)：184-185
[80]黄美英,杨三可,李军等.溶剂萃取法净化湿法磷酸的工艺研究[J].磷肥与复肥,2004,19(4)：9-11
[81]杨焕银.湿法磷酸溶剂萃取法工艺的研究[J].化肥工业,2001,28(4)：15-17
[82]M Feki, M Fourati, M M Chaabouni, et al. Purification of wet process phosphoric acid by solvent extraction liquid-liquid equilibrium at 25℃ and 40℃ of the system water-phosphoric acid-methylisobutylketone[J]. The Canadian Journal of Chemical Engineering,1994,72:939-944
[83]M Feki, M Fourati, D Pareau, et al. Study of the multicomponent system wet process phosphoric acid-methyl isobutyl ketone at 40℃ phase equilibria and extraction performances[J]. Chemical Engineering Journal,2002,88:71-80
[84]R Kijkowska, D Pawlowska-Kozinska, Z Kowalski, et al. Wet process phosphoric acid obtained from Kola apatite:Purification from sulphates, fluorine, and metals[J]. Separation and Purification Technology,2002,28(3):197-205
[85]R Kijkowska, Z Kowalski, D Pawlowska-Kozinska. Purification of phosphoric acid by solvent extraction using methyl isobutyl ketone (M1BK)[J]. Technologia Chemiczna na Przelomie Wiekow,2000,257-260
[86]刘光启等.化学化工物性数据手册无机卷[M].化学工业出版社,2002,370
[87]GB/T 2091-2008.工业磷酸[S]
[2]刘晶晶,毛常明,尹进华等.湿法磷酸的工艺研究进展[J].河北化工,2005,4：14-16
[3]A Marcilla, F Ruiz, D Martiez-Pons. Purification of wet process phosphoric acid by extraction[J]. Solvent extraction and ion exchange,1993,11(3):455
[4]金士威,欧阳贻德.磷酸生产技术及其发展方向[J].化工时刊,2003,17(2)：18-20
[5]许立信,尹进华,刘俊玲等.高品质磷石膏生产工艺研究[J].化工矿物与加工,2004,33(5)：28-30
[6]吴佩芝.湿法磷酸[M].北京：化学工业出版社,1987,1：6-8
[7]南京化学工业公司磷肥厂.萃取磷酸和磷酸铵的生产[M].燃料化学工业出版社,1974,1：11-15
[8]Liangshi Wang, Zhiqi Long, Xiaowei Huang, et al. Recovery of rare earths from wet-process phosphoric acid[J]. Hydrometallurgy,2010,101(1-2):41-47
[9]杨建中,李志祥.湿法磷酸净化技术[J].磷肥与复肥,2004,19(6)：13-17
[10]王辛龙,万先达.湿法磷酸净化的新进展[J].磷肥与复肥,2001,16(2)：32-33
[11]Y K Kim, H K Walters, J D Hatfield. Conditions affecting the purification of simulated wet-process phosphoric acids by solvent extraction [J]. Journal of Agricultural and Food Chemistry,1974,22(6):1099
[12]H Goreck, K Hoffmann, J Hoffmann. Special methods of purification of wet-process phosphoric acid[J]. Polish Journal of Applied Chemistry,1996,40(4):389-398
[13]骆广生,刘舜华,孙勇等.磷酸的溶剂萃取法净化[J].过程工程学报,2001,1(2)：211-213
[14]欧阳贻德,陈古圣,苏裕光.磷酸三丁酯萃取分离磷酸与盐酸的研究[J].汉化工学院学报,1998,20(1)：5-9
[15]R Dhouib-Sahnoun, M Feki, H F Ayedi. Extractive purification of wet phosphoric acid with tributyl-phosphate:study of the impurities distribution[J]. Journal chemical company Tunisia,2000,8:873-885
[16]吕中.磷酸三丁酯-水-磷酸体系液液相平衡研究[J].四川联合大学学报(工程科学版),1999,3(2)：54-59
[17]金士威,张中华,易琼.磷酸三丁酯萃取磷酸的动力学研究[J].化工时刊,2005,19(7)：17-19
[18]郭昌明,黎铉海.利用磷酸三丁酯在硫酸—磷酸体系中萃取净化低浓度湿法磷酸工艺的研究[J].磷肥与复肥,2009,24(5)：11-13
[19]F Ruiz, A Marcilla, A M Ancheta&Concepcionrico. Liquid-liquid equilibrium of the three liquid phases at equilibrium system water-phosphoric acid-di-isopropyl ether at 25 and 40℃[J]. Solvent Extraction and Ion Exchange,1986,4(4):789-802
[20]A Marcilla, F Ruiz, A M Ancheta. Purification of wet process phosphoric acid by solvent extraction with dibutyl ether. Part II. Study of the impurities distribution[J]. Solvent Extraction and Ion Exchange,1989,7(2):211-221
[21]A Marcilla, F Ruiz, A M Ancheta. Purification of wet process phosphoric acid by solvent extraction with propyl ether[J]. Solvent Extraction and Ion Exchange,1987,5(6): 1141-1150
[22]K Nazari, A Ghadiri, H Babaie. Elimination of cadmium from wet process phosphoric acid with Alamine 336[J]. Minerals Engineering,2005,18(13-14):1233-1238
[23]潘春升,钟耀荣,王和平等.湿法磷酸萃取法制取精细磷酸盐的研究[J].磷肥与复肥,2004,19(2)：15-17
[24]M Feki, H F Ayedi. Establishing models for wet process phosphoric acid purification with methyl isobutyl ketone[J]. Canadian Journal of Chemical Engineering,2000,78(3): 540-546
[25]K D Muldagaliev, M R Tanasheva, D Smagulova, et al. Extraction of phosphoric acid by cyclohexanone[J]. Izvestiya Akademii Nauk Kazakhskoi SSR, Seriya Khimicheskaya, 1970,20(3):74
[26]I L Krupatkin, T A Shcherbakova. Extraction systems of phosphoric acid with some ketones[J]. Zhurnal Prikladnoi Khimii,1970,43(6):1295-1298
[27]K Regina, K Zygmunt, P K Danuta. Purification of phosphoric acid by solvent extraction using methyl isobutyl ketone (MIBK). Technologia Chemiczna na Przelomie Wiekow, 2000,257-260
[28]Yuming Jiang, Yuanfu Su. Production of pure phosphoric acid and/or phosphorates from wet process phosphoric acid using an extractant[P]. US4781905A
[29]江玉明,李道纯,苏元复.萃取法净化磷酸工艺[J].化工学报,1982,(4)：310-318
[30]乐武阳,戢峻,丁一刚等.复合萃取剂萃取净化低浓度湿法磷酸工艺研究[J].化学与生物工程,2011,28(1)：67-69
[31]乐武阳,丁一刚,李攀等.复合萃取剂萃取湿法磷酸相平衡和动力学研究[J].武汉工程大学学报,2011,33(2)：31-33,37
[32]C D Gosling, F P Wilcher, L Sullivan, et al. Process LPG to BTX products[J]. Hydrocarbon Processing,1991,70(12):69-72
[33]尤彩霞,李军.甲醇沉淀法净化湿法稀磷酸制磷酸氢二铵[J].无机盐工业,2008,40(6)：27-29
[34]T Inui, Y Ishihara, K McKamachi, et al. Pt Loaded HIGH-Ga Silicates for Aromatization of Light Paraffins and Methane[J]. Studies in Surface Science and Catalysis,1989,49: 1183-1192
[35]Y Ono, H Nakatani, H Kitagawa, et al. The Role of Metal Cations in the Transformation of Lower Alkanes into Aromatic Hydrocarbons[J]. Studies in Surface Science and Catalysis,1989,44:279-290
[36]Y Ono, K Kanae. Transformation of butanes over ZSM-5 zeolites. Part 2.—Formation of aromatic hydrocarbons over Zn-ZSM-5 and Ga-ZSM-5[J]. Journal of the Chemical Society, Faraday Transactions,1991,87(4):669-675
[37]T Inui, Y Makino, F Okazumi, S Nagano, et al. Selective aromatization of light paraffins on platinum-ion-exchanged gallium-silicate bifunctional catalysts [J]. Industrial Engineering Chemistry Research,1987,26:647-652
[38]钟本和,陈亮,李军等.溶剂萃取法净化湿法磷酸的新进展[J].化工进展,2005,24(6)：596-602
[39]Yong Ma, Jiawen Zhu, Kui Chen, et al. Study on growth kinetics of phosphoric acid hemihydrate using FBRM[J]. Journal of Crystal Growth,2009, (312):109-113
[40]Leping Dang, Hongyuan Wei. Effects of ionic impurities on the crystal morphology of phosphoric acid hemihydrate[J]. Chemical Engineering Research and Design,2009:19
[41]Leping Dang, Hongyuan Wei, Zhen Zhu, et al. The influence of impurities on phosphoric acid hemihydrate crystallization[J]. Journal of Crystal Growth,2007,1(307):104-111
[42]Leping Dang, Hongyuan Wei, Jinkang Wang. Effects of Ionic Impurities (Fe2+ and SO42-) on the Crystal Growth and Morphology of Phosphoric Acid Hemihydrate during Batch Crystaltization[J]. Ind Eng Chem Res,2007,46 (10):3341-3347
[43]J P Smith, W E Brown, James R Lehr. Structure of crystalline phosphoric acid[J]. J Am Chem Soc,1955,77:2728-2730
[44]K Herzog, E Steger. Solid phases of phosphoric acid and phosphoric acid hemihydrate [J]. Journal of Inorganic and Nuclear Chemistry,1965,27(6):1429-1430
[45]黄斌,陈晓峰,程德军.湿法磷酸合成大颗粒磷酸脲的工艺研究[J].无机盐工业,2008,40(6)：32-33
[46]李云生.湿法磷酸制备磷酸脲的试验研究[J].硫磷设计与粉体工程,2000,(2)：30-31
[47]侯长军,霍丹群.磷酸三聚氰胺复盐结晶法净化湿法磷酸技术进展[J].化工进展,1996,(5)：32-35
[48]蒋丽红,赵声兰,赵榆林等.结晶法由湿法磷酸生产磷酸二氢钾结晶特性的研究[J].云南化工,2001,28(2)：1-3
[49]A N Baumann. Separation of dissolved substance from wet phosphoric acid[P]. US: 4640828A
[50]D H Michalski, V Srinivanan. Precipitation of aluminum, magnesium and iron impurities from wet process phosphoric acid[P]. US4639359A
[51]张允湘.钟本和,罗洪波.湿法磷酸的净化方法评述[J].磷酸盐工业,2001,(2)：21-25
[52]陈虎.黄海涛,柳丹.湿法磷酸净化预处理工艺研究[J].化工矿物与加工,2009,(2)：3-5
[53]王励生,胡文成.湿法磷酸浓缩特性及脱氟速率的研究[J].磷肥与复肥,1995,10(4)：5-7
[54]费德君,党洁修.共沸精馏法浓缩磷酸的研究[J].四川联合大学学报(工程科学版),1997,(1)：52-56
[55]A A El-Bayaa, N A Badawy, A M Gamal, et al. Purification of wet process phosphoric acid by decreasing iron and uranium using white silica sand[J]. Journal of Hazardous Materials,2011,190(1-3):324-329
[56]A A M Daifullah, N S Awwad, S A El-Reefy. Purification of wet phosphoric acid from ferric ions using modified rice husk[J]. Chemical Engineering and Processing:Process Intensification,2004,43(2):193-201
[57]谦培超,孟文杰,汤德元.离子交换技术净化湿法磷酸中的镁离子[J].贵州工业大学学报,2008,37(1)：36-39
[58]谦培超.湿法磷酸的离子交换法除镁研究[D].贵阳：贵州大学化工学院,2008
[59]高洁.浅谈湿法磷酸的净化[J].化工矿物与加工,2004,(7)：37-38
[60]熊祥祖,王威,李志保等.离子交换树脂脱除湿法磷酸中金属杂质的研究[J].武汉工程大学学报,2009,31(7)：26-29
[61]L Monser, M B Amor, M Ksibi. Purification of wet phosphoric acid using modified activated carbon[J]. Chemical Engineering and Processing:Process Intensification,1999, 38(3):267-271
[62]M B Chehida Elleuch, M B Amor, G Pourcelly. Phosphoric acid purification by a membrane process:Electrodeionization on ion-exchange textiles[J]. Separation and Purification Technology,2006,51(3):285-290
[63]M P Gonzalez, R Navarro, I Saucedo, et al. Purification of phosphoric acid solutions by reverse osmosis and nanofiltration[J]. Desalination,2002,147(1-3):315-320
[64]陈嘉甫,谭光薰.磷酸盐的生产及应用[M].成都科技大学出版社,1989：97-108
[65]杨兆麟.我国小磷铵技术现状与开发途径[J].化工设计,1998,(4)：45-47
[66]磷酸二氢铵生产的微反应器技术通过成果鉴定.企业科技与发展,2010,(1)：6-7
[67]刘妍.六氟磷酸锂制备方法的探讨[J].新疆有色金属,2009,A02：124-126
[68]N W Smith. Preparation of lithium hexafluorophosphate[P]. US3607020.1971
[69]周宁波,陈白珍,何新快等.有机溶剂法无水氯化镁的制备与表征[J].无机化学学报,2005,21(2)：286-290
[70]丛昱.液相沉淀法在有机溶剂中制备ZrO2超细粒子的研究[J].燃料化学学报,1998, 26(3):230-233
[71]Miyi Li. Lisheng Wang, Kunpeng Wang, et al. Experimental measurement and modeling of solubility of LiBr and LiNO3 in methanol, ethanol. 1-propanol,2-propanol and 1-butanol[J]. Fluid Phase Equilibria,2011,307:104-109
[72]Y P Jimenez, M E Taboada, Hector R Galleguillos. Solid-liquid equilibrium of K2SO4 in solvent mixtures at different temperatures [J]. Fluid Phase Equilibria,2009,284(2): 114-117
[73]GB2091-1992.工业磷酸[S]
[74]刑红伟.磷肥中有效磷含量的测定分析[M].科技信息,2008,(10)：247
[75]李耕.石墨炉原子吸收法测定铬[J].福建环境,2000,17(4)：11
[76]王玉英.用重量法分析硫酸根方法的讨论[J].纯碱工业,1992,(3)：30-31
[77]张乐.磷矿中氟含量的测定[J].磷肥与复肥,2007,22(1)：64-65
[78]GB7481-87.水质铵的测定水杨酸分光光度法[S]
[79]胡小玲,吴鹏.水杨酸-次氯酸盐测定水中氨氮方法的改进[J].干旱环境监测,2005,19(3)：184-185
[80]黄美英,杨三可,李军等.溶剂萃取法净化湿法磷酸的工艺研究[J].磷肥与复肥,2004,19(4)：9-11
[81]杨焕银.湿法磷酸溶剂萃取法工艺的研究[J].化肥工业,2001,28(4)：15-17
[82]M Feki, M Fourati, M M Chaabouni, et al. Purification of wet process phosphoric acid by solvent extraction liquid-liquid equilibrium at 25℃ and 40℃ of the system water-phosphoric acid-methylisobutylketone[J]. The Canadian Journal of Chemical Engineering,1994,72:939-944
[83]M Feki, M Fourati, D Pareau, et al. Study of the multicomponent system wet process phosphoric acid-methyl isobutyl ketone at 40℃ phase equilibria and extraction performances[J]. Chemical Engineering Journal,2002,88:71-80
[84]R Kijkowska, D Pawlowska-Kozinska, Z Kowalski, et al. Wet process phosphoric acid obtained from Kola apatite:Purification from sulphates, fluorine, and metals[J]. Separation and Purification Technology,2002,28(3):197-205
[85]R Kijkowska, Z Kowalski, D Pawlowska-Kozinska. Purification of phosphoric acid by solvent extraction using methyl isobutyl ketone (M1BK)[J]. Technologia Chemiczna na Przelomie Wiekow,2000,257-260
[86]刘光启等.化学化工物性数据手册无机卷[M].化学工业出版社,2002,370
[87]GB/T 2091-2008.工业磷酸[S]
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |