异丙醇催化碱式碳酸镁晶体的合成
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摘要
以菱镁矿为原料、异丙醇为添加剂,采用水化碳酸化法-直接热解法合成了碱式碳酸镁晶体(4MgCO_3·Mg(OH)_2·4H_2O)。利用X射线衍射仪和扫描电子显微镜探究了热解温度、异丙醇添加量、热解时间对产物的物相组成和形貌的影响,并通过动力学分析计算了合成反应活化能。结果表明:当异丙醇与Mg(HCO_3)_2溶液的体积比为2:1,热解时间为120 min时,在50℃合成了平均直径为1.0μm,平均长度为10μm,表面带绒毛的棒状4MgCO_3·Mg(OH)_2·4H_2O晶体;4MgCO_3·Mg(OH)_2·4H_2O热分解温度范围为150～700℃,分3个阶段进行,分解产物为MgO、H_2O和CO_2;合成反应活化能为1.330 7 kJ/mol,异丙醇降低了亚稳相水合碳酸镁向稳定相4MgCO_3·Mg(OH)_2·4H_2O转变所需要的能量,加速了低温环境下的相转化进程。
Hydromagnesite(4 MgCO_3·Mg(OH)_2·4H_2O) crystals were synthesized via hydration and carbonation treatment and direct pyrolysis with magnesite as a raw material and isopropanol as an additive. The influences of the pyrolysis temperature, dosage of isopropanol and pyrolysis time on the phase composition and morphology of products were investigated. The structure and shape of the as-prepared samples were examined by X-ray diffraction and scanning electron microscopy. The activation energy of the reaction was calculated through the kinetic analysis. The results show that the rod-like hydromagnesite crystals with a fluff and average diameter of 1.0 μm and average length of 10 μm are obtained when the volume ratio of isopropanlo to Mg(HCO_3)_2 solution is 2:1,pyrolysis temperature is 50 ℃, and pyrolysis time is 120 min. The thermal decomposition of hydromagnesite is carried out through three processes within 150-700 ℃, and the decomposed products are MgO, H_2O and CO_2. The activation energy of pyrolysis process assisted with isopropanlo is 1.330 7 kJ/mol. Isopropanol reduces the energy required to covert the metastable hydrated magnesium carbonate to the stable hydromagnesite, and accelerates the phase transformation process at low temperatures.
Hydromagnesite(4 MgCO_3·Mg(OH)_2·4H_2O) crystals were synthesized via hydration and carbonation treatment and direct pyrolysis with magnesite as a raw material and isopropanol as an additive. The influences of the pyrolysis temperature, dosage of isopropanol and pyrolysis time on the phase composition and morphology of products were investigated. The structure and shape of the as-prepared samples were examined by X-ray diffraction and scanning electron microscopy. The activation energy of the reaction was calculated through the kinetic analysis. The results show that the rod-like hydromagnesite crystals with a fluff and average diameter of 1.0 μm and average length of 10 μm are obtained when the volume ratio of isopropanlo to Mg(HCO_3)_2 solution is 2:1,pyrolysis temperature is 50 ℃, and pyrolysis time is 120 min. The thermal decomposition of hydromagnesite is carried out through three processes within 150-700 ℃, and the decomposed products are MgO, H_2O and CO_2. The activation energy of pyrolysis process assisted with isopropanlo is 1.330 7 kJ/mol. Isopropanol reduces the energy required to covert the metastable hydrated magnesium carbonate to the stable hydromagnesite, and accelerates the phase transformation process at low temperatures.
引文
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[2]王余莲,印万忠,张夏翔,等.三水碳酸镁法制备碱式碳酸镁过程研究[J].矿产保护与利用,2017(4):81?86.WNAG Yulian,YIN Wanzhong,ZHANG Xiaxiang,et al.Conserv Util Miner Resour(in Chinese),2017(4):81?86.
[3]谢发之,胡婷婷,付浩瀚,等.碱式碳酸镁为新结合相的薄膜梯度扩散技术原位富集测定富营养水体中的磷[J].分析化学研究报告,2016,44(6):965?969.XIE Fazhi,HU Tingting,FU Haohan,et al.Chin J Anal Chem(in Chinese),2016,44(6):965?969.
[4]侯云峰,刘辉利,郑荷花,等.碳酸镁与镉离子的吸附和沉淀作用研究[J].工业安全与环保,2018,44(4):78?82.HOU Yunfeng,LIU Huili,ZHENG Hehua,et al.Ind Saf Environ Prot(in Chinese),2018,44(4):78?82.
[5]王国胜,王迪,张天天.利用硼酸母液制备碱式碳酸镁并用于母液除铁的研究[J].无机盐工业,2017,49(5):61?63.WANG Guosheng,WANG Di,ZHANG Tiantian.Inorg Chem Ind(in Chinese),2017,49(5):61?63.
[6]王秋雨,范智,付文斌,等.关于碱式碳酸镁在气体发生剂中的作用研究[J].当代化工,2015,44(9):2140?2142,2145.WANG Qiuyu,FAN Zhi,FU Wenbin,et al.Contemp Cheml Ind(in Chinese),2015,44(9):2140?2142,2145.
[7]HOLLINGBERY L A,HURRY T R.The thermal decomposition of hunite and hydromagnesite-A review[J].Thermo-chim Acta,2010,509:1?11.
[8]秦麟卿,刘以波,黄志雄,等.碱式碳酸镁阻燃环氧树脂的研究[J].武汉理工大学学报,2008,30(4):18?22,102.QIN Linqing,LIU Yibo,HUANG Zhixiong,et al,J Wuhan Univ Technol(in Chinese),2008,30(4):18?22,102.
[9]王余莲,印万忠,钟文兴,等.微纳米三水碳酸镁晶须的制备及性能[J].中南大学学报(自然科学版),2014,35(3):708?713.WANG Yulian,YIN Wanzhong,ZHONG Wenxing,et al.J Cent South Univ:Sci Technol(in Chinese),2014,35(3):708?713.
[10]孙龙艳,董立春,郑小刚,等.纳米花状氧化镁的乳液直接沉淀法制备与表征[J].硅酸盐学报,2015,43(7):941?945.SUN Longyan,DONG Lichun,ZHENG Xiaogang,et al,J Chin Ceram Soc,2015,43(7):941?945.
[11]王恩民,李文翠,雷成,等.碱式碳酸镁催化酚醛聚合制备多孔炭及其CO2吸附性能[J].化工学报,2016,66(7):2565?2572.WANG Enming,LI Wencui,LEI Cheng,et al,J Chem Ind Eng(in Chinese),2016,66(7):2565?2572.
[12]HARIHARAN S,MAZZOTTI M.Growth kinetics hydromagnesite at90℃[J].Cryst Growth Des,2017,17:317?327.
[13]BHATTACHARJVA D,SELVAMANI T,MUKHOPADHYAY I.Thernal decomposition of hydromagnesite[J].J Therm Anal Calorim,2012,107:439?445.
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[15]YANG C,SONG X F,HUANG S S,et al.Low-temperature synthesis of hydromagnesite microspheres by a sodium dodecyl sulfate-assisted process[J].J Chin Ceram Soc,2012,28(4):757?762.
[16]SONG X F,YANG C,WANG J,et al.Synthesis of porous hydromagnesite microspheres with rosette-like morphology[J].J Chin Ceram Soc,2011,27(5):1008?1014.
[17]田朋.碳酸镁模板化制备复杂微纳米结构及性能表征[D].大连:大连理工大学,2013.TIAN Peng.Magnesium carbonate templates to synthesize complex micro/nanostructures and characterization(in Chinese,dissertation),Dalian:Dalian University of Technology,2013.
[18]赵斌,马雪晴,白艳,等.硫酸镁与碳酸钠反应制备碱式碳酸镁的研究[J].无机盐工业,2017,49(9):23?27.ZHAO Bin,MA Xueqing,BAI Yan,et al.Inorg Chem Ind(in Chinese),2017,49(9):23?27.
[19]陈娟,黄志良,陈常连,等.碱式碳酸镁晶须的均相沉淀法制备及其生长机理研究[J].武汉工程大学学报,2015,37(12):16?20.CHEN Juan,HUANG Zhiliang,CHEN Changlian,et al.J Wuhan Inst Technol(in Chinese),2015,37(12):16?20.
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[22]阮恒,黄尚顺,桑艳霞,等.花状碱式碳酸镁的合成及其阻燃性能[J].化工技术与开发,2016,45(6):13?16.RUAN Heng,HUANG Shangshun,SANG Yanxia,et al.Technol Dev Chem Ind(in Chinese),2016,45(6):13?16.
[23]王余莲,印万忠,张夏翔,等.大长径比三水碳酸镁晶须的制备及晶体生长机理[J].硅酸盐学报,2018,46(7):938?945.WANG Yulian,YIN Wanzhong,ZHANG Xiaxiang,et al.J Chin Ceram Soc,2018,46(7):938?945.
[24]孙红娟,曾丽,彭同江.石棉尾矿硫酸铵焙烧法提取氧化镁制备碱式碳酸镁的实验研究[J].岩石矿物学杂志,2013,32(6):911?917.SUN Hongjuan,ZENG Li,PENG Tongjiang.Acta Petrol Miner(in Chinese),2013,32(6):911?917.
[25]王志强,刘家祥,饶发明.以轻烧白云石为原料二次碳化法制备高纯碱式碳酸镁[J].硅酸盐学报,2013,41(10):1437?1441.WANG Zhiqiang,LIU Jiaxiang,RAO Faming,et al.J Chin Ceram Soc,2013,41(10):1437?1441.
[26]郭毅夫,张瑶,郭日杰.均匀沉淀法制备碱式碳酸镁粉体工艺研究[J].内蒙古石油化工,2015,(20):38?39,154.GUO Yifu,ZHANG Yao,GUO Rijie.Inner Mongolia Petrochem Ind(in Chinese),2015,(20):38?39,154.
[27]王余莲.微/纳米水合碳酸镁的制备及应用研究[D].沈阳:东北大学,2015.WANG Yulian.preparation and application of micro/Nano hydrated magnesium carbonate(in Chinese,dissertation),Shenyang,:Northeastern University,2015.
[28]徐惠娟,袁海涛,高佳令.相转移催化技术在无机化工中的拓展[J].当代化工,2002,31(2):105?106.XU Huijuan,YUAN Haitao,GAO Jialing,Contemp Chem Ind(in Chinese),2002,31(2):105?106.
[29]陈敏,李月圆,王健东,等.利用菱镁矿制备碳酸镁晶须[J].硅酸盐学报,2009,37(10):1649?1653.CHEN Min,LI Yueyuan,WANG Jiandong,et al.J Chin Ceram Soc,2009,37(10):1649?1653.
[30]周相廷,刘丽艳,翟学良.碱式碳酸镁前驱状态的研究[J].化学试剂,1999,21(3):135?137.ZHOU Xiangting,LIU Liyan,ZHAI Xueliang.Chem Reagents(in Chinese),1999,21(3):135?137.
[31]董梅,程文婷,李志宝,等.三水碳酸镁(MgCO3·3H2O)在Na Cl-NH4Cl-H2O卤水体系中溶解度的研究[J].中国稀土学报(专辑),2008,26:759?763.DONG Mei,CHENG Wenting,LI Zhibao.J Chin Rare Earth Soc(Album,in Chinese),2008,26:759?763.