铝酸钾溶液自发分解过程中的氢氧化铝晶型转变
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摘要
氢氧化铝作为生产金属铝的前驱体,其产品的多晶型控制对于下游操作以及产品性质存在至关重要的影响。考察了温度和苛性碱浓度对过饱和铝酸钾溶液自发分解产物及其晶型转化的影响。结果表明:温度对于溶液析出的初始晶相影响显著,在低温(30℃和40℃)下,主要晶型为拜耳石;高温(60℃和80℃)下,主要晶型为三水铝石和拜耳石的混合物;苛性碱浓度对初始晶相的类型影响并不显著。通过对三水铝石和拜耳石饱和浓度与溶液浓度的比较,结合低温下拜耳石作为主要晶相析出的现象,可知拜耳石的形成在动力学上要优于三水铝石。通过SEM像观测到了拜耳石的溶解,说明由拜耳石向三水铝石的晶型转变过程应为SMPT(以溶液为介质的晶型转化)过程,同时温度的提高与苛性碱浓度的增加均能加快晶型从拜耳石向三水铝石的转化,更验证这是一个溶解-再结晶过程。
As the precursor for production of aluminum, aluminum trihydroxide has four polymorphs and the control of polymorphism of crystal product is vital for downstream operation and product quality. The effects of temperature and caustic concentration on the initial crystalline product and polymorphism transformation were investigated during spontaneous decomposition of supersaturated potassium aluminate solution. The results show that the initial crystalline product under relatively lower temperature(30 ℃, 40 ℃) is bayerite and that under relatively higher temperature(60 ℃,80 ℃) is a mixture of gibbsite and bayerite. The influence of alkaline concentration on the initial products is not significant. By comparison between the saturation concentration of the polymorphs and the solution concentration, it is concluded that the formation of bayerite is kinetically favored according to a predominance of the initial crystalline products under low temperature. The dissolution of bayerite was detected by SEM, which infers that the transformation of bayerite to gibbsite is attributed to the solvent-mediated polymorphic transformation(SMPT) process. The polymorphic transformation is promoted with the increase of temperature and caustic concentration, which further indicates a dissolution-recrystallization process.
As the precursor for production of aluminum, aluminum trihydroxide has four polymorphs and the control of polymorphism of crystal product is vital for downstream operation and product quality. The effects of temperature and caustic concentration on the initial crystalline product and polymorphism transformation were investigated during spontaneous decomposition of supersaturated potassium aluminate solution. The results show that the initial crystalline product under relatively lower temperature(30 ℃, 40 ℃) is bayerite and that under relatively higher temperature(60 ℃,80 ℃) is a mixture of gibbsite and bayerite. The influence of alkaline concentration on the initial products is not significant. By comparison between the saturation concentration of the polymorphs and the solution concentration, it is concluded that the formation of bayerite is kinetically favored according to a predominance of the initial crystalline products under low temperature. The dissolution of bayerite was detected by SEM, which infers that the transformation of bayerite to gibbsite is attributed to the solvent-mediated polymorphic transformation(SMPT) process. The polymorphic transformation is promoted with the increase of temperature and caustic concentration, which further indicates a dissolution-recrystallization process.
引文
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[8]常志宏,郭奋,陈建峰,王国全,李振刚,赵超凡.纳米氢氧化铝填充LDPE/EVA的力学和阻燃性能[J].化工学报,2005,56(9):1771-1776.CHANG Zhi-hong,GUO Fen,CHEN Jian-feng,WANGGuo-quan,LI Zhen-gang,ZHAO Chao-fan.Mechanical properties and flame retardancy of CG-ATH/LDPE/EVA[J].Journal of Chemical Industry and Engineering(China),2005,56(9):1771-1776.
[9]YOU S W,LI Y,ZHANG Y F,YANG C,ZHANG Y.Synthesis of uniformly spherical bayerite from a sodium aluminate solution reacted with sodium bicarbonate[J].Industrial&Engineering Chemistry Research,2013,52(36):12710-12716.
[10]王熙慧,于海燕,吴玉胜,毕诗文,陈玉国.添加剂对铝酸钠溶液种分产物质量的影响[J].化工学报,2007,58(8):2120-2124.WANG Xi-hui,YU Hai-yan,WU Yu-sheng,BI Shi-wen,CHEN Yu-guo.Effects of additive on product quality of seed precipitation in sodium aluminate solution[J].Journal of Chemical Industry and Engineering(China),2007,58(8):2120-2124.
[11]王子云,邵磊,郭奋,陈建峰,赵瑞红,王东光.超重力碳分法制备六角片状纳米级氢氧化铝[J].化工学报,2006,57(7):1699-1703.WANG Zi-yun,SHAO Lei,GUO Fen,CHEN Jian-feng,ZHAO Rui-hong,WANG Dong-guang.Preparation of hexagonal plate nano-aluminum trihydrate by hypergravitycarbonation[J].Journal of Chemical Industry and Engineering(China),2006,57(7):1699-1703.
[12]KOGA N,FUKAGAWA T,TANAKA H.Preparation and thermal decomposition of synthetic bayerite[J].Journal of Thermal Analysis and Calorimetry,2001,64(3):965-972.
[13]ADDAI M J.Surface and structural characteristics of gibbsite precipitated from pure,synthetic Bayer liquor[J].Minerals Engineering,1997,10(1):81-96.
[14]LI Y,ZHANG Y F,CHEN F F,YANG C,ZHANG Y.Polymorphic transformation of aluminum hydroxide precipitated from reactive NaAl(OH)4-NaHCO3 solution[J].Crystal Growth&Design,2011,11(4):1208-1214.
[15]KOCJAN A,DAKSKOBLER A,KOSMA?T.Evolution of aluminum hydroxides in diluted aqueous aluminum nitride powder suspensions[J].Crystal Growth&Design,2012,12(3):1299-1307.
[16]LEE M Y,PARKINSON G M,SMITH P G,LINCOLN F J,REYHANI M M.Characterization of aluminum trihydroxide crystals precipitated from caustic solutions[C]//ACSsymposium Series.Washington,DC,America:American Chemical Society,1997:123-135.
[17]LI H X,ADDAI-MENSAH J,THOMAS J C,GERSON A R.The crystallization mechanism of Al(OH)3 from sodium aluminate solutions[J].Journal of Crystal Growth,2005,279(3/4):508-520.
[18]LEE Y P,LIU Y H,YEH C S.Formation of bayerite,gibbsite and boehmite particles by laser ablation[J].Physical Chemistry Chemical Physics,1999,1(19):4681-4686.
[19]WANG H Q,WANG Z,LIU L,GONG X Z,WANG M Y.Alumina hydrate polymorphism control in Al-water reaction crystallization by seeding to change the metastable zone width[J].Crystal Growth&Design,2016,16(2):1056-1062.
[20]COUNTER J,GERSON A,RALSTON J.Caustic aluminate liquors:Preparation and characterisation using static light scattering and in situ X-ray diffraction[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,1997,126(2/3):103-112.
[21]GERSON A R,COUNTER J A,COOKSON D J.Influence of solution constituents,solution conditioning and seeding on the crystalline phase of aluminium hydroxide using in situ X-ray diffraction[J].Journal of Crystal Growth,1996,160(3/4):346-354.
[22]SATO T.Preparation of gelatinous aluminium hydroxide[J].Journal of Inorganic General Chemistry,1972,391(1):69-78.(in German)
[23]李小斌,赵东峰,王丹琴,阎丽.铝酸钠溶液分解过程的理论及技术研究进展[J].中国有色金属学报,2011,21(10):2577-2593.LI Xiao-bin,ZHAO Dong-feng,YU Dan-qin,YAN Li.Research progress in theory and technology of gibbsite precipitation from sodium aluminate solution[J].The Chinese Journal of Nonferrous Metals,2011,21(10):2577-2593.
[24]LI Y,ZHANG Y F,YANG C,ZHANG Y.Precipitating sandy aluminium hydroxide from sodium aluminate solution by the neutralization of sodium bicarbonate[J].Hydrometallurgy,2009,98(1/2):52-57.
[25]LEFEVRE G,PICHOT V,FéDOROFF M.Controlling particle morphology during growth of bayerite in aluminate solutions[J].Chemistry of Materials,2003,15(13):2584-2592.
[26]VAN STRATEN H A,DE B P L.Precipitation from supersaturated aluminate solutions.Ⅱ.Role of temperature[J].Journal of Colloid and Interface Science,1984,102(1):260-277.
[27]SIPOS P.The structure of Al(Ⅲ)in strongly alkaline aluminate solutions-A review[J].Journal of Molecular Liquids,2009,146(1):1-14.
[28]WEI D,YIN Q X,HAO H X,YING B,XIA Z,HUANG J T,XIANG L,XIE C,GONG J B.Solution-mediated polymorphic transformation of prasugrel hydrochloride from formⅡto formⅠ[J].Industrial&Engineering Chemistry Research,2014,53(14):5652-5659.
[29]O’BRIEN L E,TIMMINS P,WILLIAMS A C,YORK P.Use of in situ FT-Raman spectroscopy to study the kinetics of the transformation of carbamazepine polymorphs[J].Journal of Pharmaceutical and Biomedical Analysis,2004,36(2):335-340.
[30]TONG Y,WANG ZZ,YANG E,PAN B C,DANG L P,WEIH Y.Insights into cocrystal polymorphic transformation mechanism of ethenzamide-saccharin:A combined experimental and simulative study[J].Crystal Growth&Design,2016,16(9):5118-5126.
[31]ROSALES G D,RUIZ M D C,RODRIGUEZ M H.Novel process for the extraction of lithium fromβ-spodumene by leaching with HF[J].Hydrometallurgy,2014,147/148:1-6.
[32]CHEN Y,TIAN Q Q,CHEN B Z,SHI X C,LIAO T.Preparation of lithium carbonate from spodumene by a sodium carbonate autoclave process[J].Hydrometallurgy,2011,109(1/2):43-46.
[33]LI J,PRESTIDGE C A,ADDAI-MENSAH J A.The influence of alkali metal ions on homogeneous nucleation of Al(OH)3 crystals from supersaturated caustic aluminate solutions[J].Journal of Colloid and Interface Science,2000,224(2):317-324.
[34]LI H X,ADDAI M J,THOMAS J C,GERSON A R.A study of colloidal Al(Ⅲ)-containing species in fresh/caustic aluminate solutions[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2003,223(1/3):83-94.
[35]LI X B,ZHAO D F,YANG S S,WANG D Q,ZHOU Q S,LIU G H.Influence of thermal history on conversion of aluminate species in sodium aluminate solution[J].Transactions of Nonferrous Metals Society of China,2014,10:3348-3355.
[36]戴国亮,解莹,康琦,胡文瑞.溶液热历史对蛋白质晶体生长影响的内在原因研究[J].化学学报,2007,65(13):1202-1206.DAI Guo-liang,XIE Ying,KANG Qi,HU Wen-rui.Study of intrinsic reason of effect of solution thermal history on protein crystal growth[J].Acta Chemica Sinica,2007,65(13):1202-1206.
[37]APPS J A,NEILL JM,JUN C H.Thermochemical properties of gibbsite,bayerite,boehmite,diaspore,and the aluminate ion between 0 and 350℃[J].Lawrence Berkeley National Laboratory,1988.
[38]MULLIN J W.Crystallization[M].4th ed.Oxford:Butterworth-Heinemann,2001.
[39]JIANG Y F,LIU C L,XUE J,LI P,YU J G.Insights into the polymorphic transformation mechanism of aluminum hydroxide during carbonation of potassium aluminate solution[J].Crystengcomm,2018,20:1431-1442.
[40]SWEEGERS C,van ENCKEVORT W J P,MEEKES H,BENNEMA P,HIRALAL I D K,RIJKEBOER A.The impact of twinning on the morphology ofγ-Al(OH)3crystals[J].Journal of Crystal Growth,1999,197:244-253.
[41]SONTHALIA R,BEHARA P,KUMARESAN T,THAKRES.Review on alumina trihydrate precipitation mechanisms and effect of Bayer impurities on hydrate particle growth rate[J].International Journal of Mineral Processing,2013,125:137-148.
[42]GALE J D,ROHL A L,MILMAN V,WARREN M C.An ab initio study of the structure and properties of aluminum hydroxide:Gibbsite and bayerite[J].The Journal of Physical Chemistry B,2001,105(42):10236-10242.
[2]SVERDRUP H U,RAGNARSDOTTIR K V,KOCA D.Aluminium for the future:Modelling the global production,market supply,demand,price and long term development of the global reserves[J].Resources,Conservation and Recycling,2015,103:139-154.
[3]聂玉娟,王二东,王许云.制备高纯超细氧化铝粉体新方法[J].化工学报,2017,68(9):3616-3622.NIE Yu-juan,WANG Er-dong,WANG Xu-yun.New approach to prepare high purity and superfine alumina powder[J].New Journal of Chemical Industry and Engineering,2017:68(9):3616-3622.
[4]SASANI G M,ABDUL-HAMID M A,RADIMAN S,SASANI G A,RAHMANI S H.Carbonation effect on the synthesis of highly crystallineγ-alumina nanopowders[J].Materials Letters,2013,106:439-442.
[5]DEMICHELIS R,NO?L Y,UGLIENGO P,EICOVICH C,DOVESI R.Physico-chemical features of aluminum hydroxides as modeled with the hybrid B3LYP functional and localized basis functions[J].The Journal of Physical Chemistry C,2011,115(27):13107-13134.
[6]GALE J D,ROHL A L,MILMAN V,WARREN M C.An ab initio study of the structure and properties of aluminum hydroxide:gibbsite and bayerite[J].The Journal of Physical Chemistry B,2001,105(42):10236-10242.
[7]KLOPROGGE J T,DUONG L V,WOOD B J,FROST R.XPS study of the major minerals in bauxite:Gibbsite,bayerite and(pseudo-)boehmite[J].Journal of Colloid and Interface Science,2006,296(2):572-576.
[8]常志宏,郭奋,陈建峰,王国全,李振刚,赵超凡.纳米氢氧化铝填充LDPE/EVA的力学和阻燃性能[J].化工学报,2005,56(9):1771-1776.CHANG Zhi-hong,GUO Fen,CHEN Jian-feng,WANGGuo-quan,LI Zhen-gang,ZHAO Chao-fan.Mechanical properties and flame retardancy of CG-ATH/LDPE/EVA[J].Journal of Chemical Industry and Engineering(China),2005,56(9):1771-1776.
[9]YOU S W,LI Y,ZHANG Y F,YANG C,ZHANG Y.Synthesis of uniformly spherical bayerite from a sodium aluminate solution reacted with sodium bicarbonate[J].Industrial&Engineering Chemistry Research,2013,52(36):12710-12716.
[10]王熙慧,于海燕,吴玉胜,毕诗文,陈玉国.添加剂对铝酸钠溶液种分产物质量的影响[J].化工学报,2007,58(8):2120-2124.WANG Xi-hui,YU Hai-yan,WU Yu-sheng,BI Shi-wen,CHEN Yu-guo.Effects of additive on product quality of seed precipitation in sodium aluminate solution[J].Journal of Chemical Industry and Engineering(China),2007,58(8):2120-2124.
[11]王子云,邵磊,郭奋,陈建峰,赵瑞红,王东光.超重力碳分法制备六角片状纳米级氢氧化铝[J].化工学报,2006,57(7):1699-1703.WANG Zi-yun,SHAO Lei,GUO Fen,CHEN Jian-feng,ZHAO Rui-hong,WANG Dong-guang.Preparation of hexagonal plate nano-aluminum trihydrate by hypergravitycarbonation[J].Journal of Chemical Industry and Engineering(China),2006,57(7):1699-1703.
[12]KOGA N,FUKAGAWA T,TANAKA H.Preparation and thermal decomposition of synthetic bayerite[J].Journal of Thermal Analysis and Calorimetry,2001,64(3):965-972.
[13]ADDAI M J.Surface and structural characteristics of gibbsite precipitated from pure,synthetic Bayer liquor[J].Minerals Engineering,1997,10(1):81-96.
[14]LI Y,ZHANG Y F,CHEN F F,YANG C,ZHANG Y.Polymorphic transformation of aluminum hydroxide precipitated from reactive NaAl(OH)4-NaHCO3 solution[J].Crystal Growth&Design,2011,11(4):1208-1214.
[15]KOCJAN A,DAKSKOBLER A,KOSMA?T.Evolution of aluminum hydroxides in diluted aqueous aluminum nitride powder suspensions[J].Crystal Growth&Design,2012,12(3):1299-1307.
[16]LEE M Y,PARKINSON G M,SMITH P G,LINCOLN F J,REYHANI M M.Characterization of aluminum trihydroxide crystals precipitated from caustic solutions[C]//ACSsymposium Series.Washington,DC,America:American Chemical Society,1997:123-135.
[17]LI H X,ADDAI-MENSAH J,THOMAS J C,GERSON A R.The crystallization mechanism of Al(OH)3 from sodium aluminate solutions[J].Journal of Crystal Growth,2005,279(3/4):508-520.
[18]LEE Y P,LIU Y H,YEH C S.Formation of bayerite,gibbsite and boehmite particles by laser ablation[J].Physical Chemistry Chemical Physics,1999,1(19):4681-4686.
[19]WANG H Q,WANG Z,LIU L,GONG X Z,WANG M Y.Alumina hydrate polymorphism control in Al-water reaction crystallization by seeding to change the metastable zone width[J].Crystal Growth&Design,2016,16(2):1056-1062.
[20]COUNTER J,GERSON A,RALSTON J.Caustic aluminate liquors:Preparation and characterisation using static light scattering and in situ X-ray diffraction[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,1997,126(2/3):103-112.
[21]GERSON A R,COUNTER J A,COOKSON D J.Influence of solution constituents,solution conditioning and seeding on the crystalline phase of aluminium hydroxide using in situ X-ray diffraction[J].Journal of Crystal Growth,1996,160(3/4):346-354.
[22]SATO T.Preparation of gelatinous aluminium hydroxide[J].Journal of Inorganic General Chemistry,1972,391(1):69-78.(in German)
[23]李小斌,赵东峰,王丹琴,阎丽.铝酸钠溶液分解过程的理论及技术研究进展[J].中国有色金属学报,2011,21(10):2577-2593.LI Xiao-bin,ZHAO Dong-feng,YU Dan-qin,YAN Li.Research progress in theory and technology of gibbsite precipitation from sodium aluminate solution[J].The Chinese Journal of Nonferrous Metals,2011,21(10):2577-2593.
[24]LI Y,ZHANG Y F,YANG C,ZHANG Y.Precipitating sandy aluminium hydroxide from sodium aluminate solution by the neutralization of sodium bicarbonate[J].Hydrometallurgy,2009,98(1/2):52-57.
[25]LEFEVRE G,PICHOT V,FéDOROFF M.Controlling particle morphology during growth of bayerite in aluminate solutions[J].Chemistry of Materials,2003,15(13):2584-2592.
[26]VAN STRATEN H A,DE B P L.Precipitation from supersaturated aluminate solutions.Ⅱ.Role of temperature[J].Journal of Colloid and Interface Science,1984,102(1):260-277.
[27]SIPOS P.The structure of Al(Ⅲ)in strongly alkaline aluminate solutions-A review[J].Journal of Molecular Liquids,2009,146(1):1-14.
[28]WEI D,YIN Q X,HAO H X,YING B,XIA Z,HUANG J T,XIANG L,XIE C,GONG J B.Solution-mediated polymorphic transformation of prasugrel hydrochloride from formⅡto formⅠ[J].Industrial&Engineering Chemistry Research,2014,53(14):5652-5659.
[29]O’BRIEN L E,TIMMINS P,WILLIAMS A C,YORK P.Use of in situ FT-Raman spectroscopy to study the kinetics of the transformation of carbamazepine polymorphs[J].Journal of Pharmaceutical and Biomedical Analysis,2004,36(2):335-340.
[30]TONG Y,WANG ZZ,YANG E,PAN B C,DANG L P,WEIH Y.Insights into cocrystal polymorphic transformation mechanism of ethenzamide-saccharin:A combined experimental and simulative study[J].Crystal Growth&Design,2016,16(9):5118-5126.
[31]ROSALES G D,RUIZ M D C,RODRIGUEZ M H.Novel process for the extraction of lithium fromβ-spodumene by leaching with HF[J].Hydrometallurgy,2014,147/148:1-6.
[32]CHEN Y,TIAN Q Q,CHEN B Z,SHI X C,LIAO T.Preparation of lithium carbonate from spodumene by a sodium carbonate autoclave process[J].Hydrometallurgy,2011,109(1/2):43-46.
[33]LI J,PRESTIDGE C A,ADDAI-MENSAH J A.The influence of alkali metal ions on homogeneous nucleation of Al(OH)3 crystals from supersaturated caustic aluminate solutions[J].Journal of Colloid and Interface Science,2000,224(2):317-324.
[34]LI H X,ADDAI M J,THOMAS J C,GERSON A R.A study of colloidal Al(Ⅲ)-containing species in fresh/caustic aluminate solutions[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2003,223(1/3):83-94.
[35]LI X B,ZHAO D F,YANG S S,WANG D Q,ZHOU Q S,LIU G H.Influence of thermal history on conversion of aluminate species in sodium aluminate solution[J].Transactions of Nonferrous Metals Society of China,2014,10:3348-3355.
[36]戴国亮,解莹,康琦,胡文瑞.溶液热历史对蛋白质晶体生长影响的内在原因研究[J].化学学报,2007,65(13):1202-1206.DAI Guo-liang,XIE Ying,KANG Qi,HU Wen-rui.Study of intrinsic reason of effect of solution thermal history on protein crystal growth[J].Acta Chemica Sinica,2007,65(13):1202-1206.
[37]APPS J A,NEILL JM,JUN C H.Thermochemical properties of gibbsite,bayerite,boehmite,diaspore,and the aluminate ion between 0 and 350℃[J].Lawrence Berkeley National Laboratory,1988.
[38]MULLIN J W.Crystallization[M].4th ed.Oxford:Butterworth-Heinemann,2001.
[39]JIANG Y F,LIU C L,XUE J,LI P,YU J G.Insights into the polymorphic transformation mechanism of aluminum hydroxide during carbonation of potassium aluminate solution[J].Crystengcomm,2018,20:1431-1442.
[40]SWEEGERS C,van ENCKEVORT W J P,MEEKES H,BENNEMA P,HIRALAL I D K,RIJKEBOER A.The impact of twinning on the morphology ofγ-Al(OH)3crystals[J].Journal of Crystal Growth,1999,197:244-253.
[41]SONTHALIA R,BEHARA P,KUMARESAN T,THAKRES.Review on alumina trihydrate precipitation mechanisms and effect of Bayer impurities on hydrate particle growth rate[J].International Journal of Mineral Processing,2013,125:137-148.
[42]GALE J D,ROHL A L,MILMAN V,WARREN M C.An ab initio study of the structure and properties of aluminum hydroxide:Gibbsite and bayerite[J].The Journal of Physical Chemistry B,2001,105(42):10236-10242.
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