NH4MnPO4·H2O热分解动力学Kinetics of NH4MnPO4·H2O Thermal Decomposition
侯翠红,苗俊艳,王仁宗,王燕,王好斌
摘要(Abstract)：
以MnSO_4·H_2O、(NH_4)_2SO_4和H_3PO_4为原料,通过共沉淀法制备了NH_4MnPO_4·H_2O,并通过XRD、FTIR、激光粒度分析仪和SEM对产物晶型、化学结构、粒度大小及形貌进行表征。结果表明该产物为NH_4MnPO_4·H_2O,结晶度高,颗粒较细,呈短棒状。通过热分析法研究该产物的热分解过程,表明分解过程分为两个阶段,并对第一阶段分解过程进行了热分解动力学研究,用F1ynn-Wall-Ozawa法和Friedman法求得NH_4MnPO_4·H_2O第一阶段热分解活化能分别为93.201和88.681 kJ×mol~(-1);在以上方法基础上,通过Coats-Redfern法求得第一阶段热解活化能E_1=91.533 kJ×mol~(-1),指前因子A_1=3.846×107 s~(-1),并得到热分解动力学模型和动力学方程,为磷酸铵锰作为缓释氮磷锰肥的使用及其在复肥中的添加应用提供理论依据。
关键词(KeyWords)： NH_4MnPO_4·H_2O;沉淀;热分解动力学;活化能;粒度分布
基金项目(Foundation): “十三五”国家重点研发计划项目(2016YFD0200401)
作者(Author): 侯翠红,苗俊艳,王仁宗,王燕,王好斌
参考文献(References)：
- [1]LI P,DU Y M,HUANG L B,et al.Preparation and characterization of manganese and iron compounds as potential control-release foliar fertilizers[J].Open Access Journal,2014,4(3):746-753.
- [2]WANG Rui(王瑞),WANG Ren-zong(王仁宗),LIU Yu(刘裕),et al.A method for synthesis of slow-release manganese fertilizer(一种缓释锰肥的合成方法):CN201410268404.9[P].2014-06-17.
- [3]FAN Yan-jin(樊艳金).Synthesis of phosphates via solid-state reaction and study on their properties(低热固相法合成磷酸盐系列纳米材料及其性能研究)[D].Nanning(南宁):Guangxi University(广西大学),2008.
- [4]FENG De-xue(冯德学),CHANG Xing-hua(常兴华),WANG Jin-yun(王金云),et al.Manganese-containing phosphoric acid diamine fertilizer(含锰的磷酸二铵肥):CN103693999 A[P].2014-04-02.
- [5]Bridger G L,Salutsky M L,Starostka R W.Micronutrient sources,netal ammonium phosphates as fertilizers[J].Micronutrient sources,1962,10(3):181-188.
- [6]Natalia N B,Helmut E.Precursor-based synthesis and electrochemical performance of Li Mn PO4[J].Journal of Alloys and Compounds,2008,464(1-2):259-264.
- [7]SHEN Pan-wen(申泮文),WANG Ji-tao(王积涛).Compound dictionary(化合物词典)[M].Shanghai(上海):Shanghai Lexicographical(上海辞书出版社),2002:220-221.
- [8]HOU Cui-hong(侯翠红),WANG Yan(王燕),WANG Hao-bin(王好斌),et al.Preparation and property study of manganese ammonium phosphate(磷酸铵锰的制备及性能研究)[J].Industrial Minerals&Processing(化工矿物与加工),2017,46(1):19-22.
- [9]ZHOU Ze-guang(周泽广),YUAN Ai-qun(袁爱群),BAI Li-juan(白丽娟),et al.Influence of synthesis routes on particle morphology of NH4MPO4·H2O(M=Mn,Fe,Co,Ni,Cu)(合成方法对NH4MPO4·H2O(M=Mn,Fe,Co,Ni,Cu)颗粒形貌的影响)[J].Applied Chemical Industry(应用化工),2007,36(3):217-221.
- [10]Stefov V,Soptrajanov B,Kuzmanovski I,et al.Infrared and Raman spectra of magnesium ammonium phosphate hexahydrate(struvite)and its isomorphous analogues.III.Spectra of protiated and partially deuterated magnesium ammonium phosphate hexahydrate[J].Journal of Molecular Structure,2005,752(1/2/3):60-67.
- [11]Violeta G.K.Vibrational behavior of the phosphates ions in dittmarite-type compounds M"M""PO4·H2O(M"=K+,NH+4;M""=Mn2+,Co2+,Ni2+)[J].Spectrochimica Acta,Part A:2007,66(2):413-418.
- [12]SUI Xi-na(隋锡娜).Study of synthesis,structure and properties of iron,manganese and copper complexes containing nitrogen bidentate ligands(含氮双齿配体铁、锰、铜配合物的合成、结构和性能研究)[D].Beijing(北京):Capital Normal University(首都师范大学),2008:36-39.
- [13]Kissinger H E.Reaction kinetics in differential thermal analysis[J].Analytical Chemistry,1957,29(11):1702-1706.
- [14]Starink M J.A new method for the derivation of activation energies from experiments performed at constant heating rate[J].Thermochim Acta,1995,258(1):309-323.
- [15]Flynn J H,Wall L A.A quick,direct method for the determination of activation energy from thermogravimetric data[J].Journal of Polymer Science Part B:Polymer Letters,1966,4(5):323-328.
- [16]Chanaiporn D,Pittayagorn N,Sujittra Y.Some thermodynamic functions and kinetics of thermal decomposition of NH4Mn PO4·H2O in nitrogen atmosphere[J].Journal of Thermal Analysis and Calorimetry,2010,100(1):117-124.
- [17]HU Rong-zu(胡荣祖),SHI Qi-zhen(史启祯).Thermal analysis kinetics(热分析动力学)[M].Beijing(北京):Science Press(科学出版社),2001:100.
- [18]GUAN Chun-xiu(关春秀),CHEN Dong-hua(陈栋华).A description of thermal analysis kinetics of dehydration of ammonium oxalate monohydrate(一水合草酸铵脱水的热分析动力学)[J].Journal of South-Central University for Nationalities(Nature Science Edition)(中南民族大学学报:自然科学版),2004,23(1):14-17.
- [19]Coats A W,Redfern J P.Kinetic parameters from thermogravimetric data[J].Nature,1964,201(4914):68-69.
- [20]ZHOU Cai-rong(周彩荣),SHI Xiao-hua(石晓华),WANG Hai-feng(王海峰),et al.Thermal decomposition and the non-isothermal decomposition kinetic of DL-2-naproxen(DL-2-萘普生热分解过程和非等温热分解动力学研究)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2011,25(3):442-446.