1、第 23 卷第 2 期2023年 2月过 程 工 程 学 报The Chinese Journal of Process EngineeringVol.23 No.2Feb.2023Preparation of chromic oxide green by thermal decomposition of CrOOH with base center orthorhombic structure and trigonal structurePanpan MU1,2,3,Hongling ZHANG2,3,4*,Taiping LOU1*,Peng ZHOU2,3,4,Haiqin SHI5,L
2、inming CHEN5,Hongbin XU2,3,41.School of Metallurgy,Northeastern University,Shenyang,Liaoning 110819,China2.CAS Key Laboratory of Green Process and Engineering,Institute of Process Engineering,Chinese Academy of Sciences,Beijing 100190,China3.National Engineering Research Center of Green Recycling fo
3、r Strategic Metal Resources,Institute of Process Engineering,Chinese Academy of Sciences,Beijing 100190,China4.University of Chinese Academy of Sciences,Beijing 100049,China5.Qinghai Provincial Bohong Chemical Technology Co.,Ltd.,Xining,Qinghai 810000,ChinaAbstract:Through hydrogen reduction of alka
4、li metal chromates,chromic oxide green can be prepared by the thermal decomposition of chromium oxyhydroxide(CrOOH).It was reported that the crystal structures of CrOOH have a significant effect on the color of the chromic oxide green obtained.However,the mechanisms remain unclear and need to be sys
5、tematically studied.In this work,two kinds of CrOOH with different crystal structures were prepared by aqueous hydrogen reduction of sodium chromate.The chemical composition,phase structure,and morphologies of the prepared CrOOH were characterized by chemical titration,FT-IR,XRD,and SEM.The thermal
6、decomposition processes were discussed according to the TG-DSC results.Subsequently,CrOOH with different crystal structures were used as the raw materials to prepare chromic oxide green with different color performance.The structure and morphologies of the chromic oxide green obtained were character
7、ized by XRD and SEM.The color performance data of chromic oxide green was reported by a Datacolor 110 colorimeter using the CIE L*a*b*(1976)colorimetric system according to the International Commission on Illumination.The results showed that the CrOOH samples prepared were of base center orthorhombi
8、c structure and trigonal structure,respectively.The morphology of the CrOOH samples was flaky and hexagonal sheet shape,respectively.Their compositions could be expressed as Cr2O31.49H2O and Cr2O31.12H2O,respectively.Compared with the chromic oxide green sample obtained by the thermal decomposition
9、of trigonal CrOOH,the chromic oxide green sample obtained by the thermal decomposition of CrOOH with base center orthorhombic structure yielded a smaller particle size,more uniform particle size distribution,and a brighter yellower color.Finally,chromic oxide green pigments with different color perf
10、ormances,such as bright yellow-green,blue-green,and dark green,were obtained using different ratios of CrOOH raw materials with base center orthorhombic and trigonal structures.Key words:chromium oxyhydroxide;thermal decomposition;chromic oxide green;crystal structure;color performance Thermal decom
11、position process CrOOH with center orthorhombic structure(S1)CrOOH with trigonal structure(S2)Chromium oxide obtained by thermal decomposition of CrOOH with trigonal structure(A5)Chromium oxide obtained by thermal decomposition of CrOOH with center orthorhombic structure(A1)研究论文DOI:10.12034/j.issn.1
12、009-606X.222052收稿：2022-02-15，修回：2022-04-12，网络发表：2022-04-20；Received:2022-02-15,Revised:2022-04-12,Published online:2022-04-20基金项目：国家自然科学基金资助项目(编号：52174282)作者简介：穆攀攀，硕士研究生，冶金工程专业，E-mail:；通讯联系人，张红玲，副研究员，从事化工冶金清洁生产工艺与产品工程研究，E-mail:；娄太平，教授，从事材料与资源有价元素提取研究，E-mail:引用格式引用格式：穆攀攀,张红玲,娄太平,等.底心正交和三方CrOOH热分解制备氧化
13、铬绿的研究.过程工程学报,2023,23(2):272279.Mu P P,Zhang H L,Lou T P,et al.Preparation of chromic oxide green by thermal decomposition of CrOOH with base center orthorhombic structure and trigonal structure(in Chinese).Chin.J.Process Eng.,2023,23(2):272279,DOI:10.12034/j.issn.1009-606X.222052.第 2 期穆攀攀等：底心正交和三方Cr
14、OOH热分解制备氧化铬绿的研究底心正交和三方CrOOH热分解制备氧化铬绿的研究穆攀攀1,2,3，张红玲2,3,4*，娄太平1*，周 鹏2,3,4，史海琴5，陈林明5，徐红彬2,3,41.东北大学冶金学院，辽宁 沈阳 1108192.中国科学院过程工程研究所，中国科学院绿色过程与工程重点实验室，北京 1001903.中国科学院过程工程研究所，战略金属资源绿色循环利用国家工程研究中心，北京 1001904.中国科学院大学，北京 1000495.青海省博鸿化工科技股份有限公司，青海 西宁 810000摘要：羟基氧化铬(CrOOH)热分解制备氧化铬绿颜料是铬酸盐氢还原法制备氧化铬绿清洁工艺的单元之一。
15、研究表明，CrOOH的结构对其热分解所得氧化铬绿的色度有显著影响，但CrOOH晶体结构对所得氧化铬绿色度的影响尚未有系统研究报道。本工作通过铬酸钠溶液氢还原制备得到了两种晶型的CrOOH并借助化学滴定、傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)、扫描电子显微镜(SEM)和热重-差示扫描量热分析(TG-DSC)对其组成、结构、形貌和热分解过程进行了研究。以两种不同晶型的CrOOH为原料调控制备得到了不同色度的氧化铬绿颜料，借助XRD和SEM对其物相和形貌进行了表征，并使用Datacolor110色度仪测定了其色度参数。结果表明，两种CrOOH的晶体结构分别为底心正交和三方，其形貌分别
16、呈现片状和六方片状，组成可分别写作Cr2O31.49H2O和Cr2O31.12H2O。与三方CrOOH相比，底心正交的CrOOH热分解得到的氧化铬绿颗粒尺寸更小、大小更均匀、颜色更亮更黄。最终，以不同比例的底心正交和三方CrOOH为原料，调控制备得到了多种色调的氧化铬绿颜料。关键词：羟基氧化铬；热分解；氧化铬绿；晶型；色度中图分类号：TQ622.21 文献标识码：A 文章编号：1009-606X(2023)020272081 前 言 氧化铬绿(Cr2O3)是常用的绿色颜料之一，因稳定性好、耐酸碱、耐候、耐高温，广泛应用于冶金原料、精细陶瓷、耐火材料、颜料、防蚀涂层、军工伪装材料和热喷涂材料等方面1,2。氧化铬绿的主要生产工艺包括重铬酸钠-硫酸铵热分解法和铬酸酐热分解法3。重铬酸钠-硫酸铵热分解法是国外主流生产工艺，该法生产的氧化铬绿颜料品种齐全，但该工艺对设备要求高，氧化铬绿产品含硫量高，且会产生含铬的硫酸钠副产物4。铬酸酐热分解法为国内主要的生产工艺，该法工艺简单，但重铬酸钠硫酸熔融法生产铬酸酐的过程不仅硫酸利用率低，同时还产生危害环境的含铬硫酸氢钠，铬酐分解过程中含六价铬黄烟的污染
