氧化铬绿性状特征及生产工艺改进研究
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摘要
氧化铬绿是重要的无机颜料。刚玉晶体结构型氧化铬有高的着色力、高热稳定性及耐化学腐蚀等特点。目前我国颜料级铬绿的生产已具备一定规模，但生产工艺和产品质量距国际先进水平均有不少差距，对于导致这种差距的本质原因的研究也少见报道。民丰农化是氧化铬绿的主要厂家之一，改善我厂氧化铬绿产品质量，尽快提高企业的经济效益和环境效益，关系着企业的发展和前途。因此，本课题的研究具有明显的应用价值和理论意义。
氧化铬绿的颜料特征与粒子的结构特别是晶体结构和正负离子配位结构有很大关系，其中起主导作用的是Cr3+及其周围作八面体配位的O2-的影响。考察这一基本单元的构造特征及其电子分布状态，将有利于深入了解氧化铬绿的构效关系，为提高该类产品的颜料性能提供帮助。为此，本文选取德国Bayer公司的标准氧化铬绿样品和民丰农化集团生产的几种有代表性的铬绿样品，采用多种仪器进行了性质状态和结构分析，包括X射线衍射，红外、紫外可见光谱，原子吸收，能谱分析，电子显微分析，热重分析和差热分析，激光粒度分析，色度、色差分析，液相色谱和BEF表面分析等，相互映证，相互配合，全方位多层次获取铬绿颜料的信息。同时用量子化学从头计算方法进行了理论计算，并对有关结果进行了比较研究。结果表明，民丰铬绿颜料与Bayer样品在着色性质上的差别，主要来自二者晶体结构的差异，特别是晶胞在a向线度的微小变化，将使铬离子周围的配体场强弱发生变化，导致Fermi能级附近量子跃迁的明显改变，从而影响铬离子的呈色功能。此外，某些杂质（如六价铬）的存在，以及粒度和表面特征，也会对氧化铬绿的颜料性质产生影响。
在工艺方面，本文根据上述分析，对氧化铬绿的生产过程提出了改进意见，如通过控制焙烧温度范围和升温程序、添加整形剂、改进粉碎方法等措施控制和稳定晶型，以及降低有害杂质（如六价铬）的含量，实施合理的后处理方案等。同时重点讨论了铬酐生产车间的固体废料回收利用问题，通过实验，本文提出可以通过碱中和、过滤、水洗、分离除杂、焙烧、粉碎等工序从废弃物中回收氧化铬绿，不仅可以提高铬资源的综合利用水平，而且还能减少环境污染，产生一定的经济效益。
Chromium oxide green is a kind of important inorganic pigment. Chromium oxide green with corundum crystal structure has such characteristics as high thermal stability, high painted capacity, chemical corrosion-resisting capacity, etc. At present, in China, the produce of chromium oxide green has reached a certain scale, but there are still some disparities in the producing technology and product quality between home and abroad chromium oxide green. However, the essential factors which result in the disparities are reported scarcely. MinFeng Agricultural and Chemical Factory is one of the main manufacturers producing chromium oxide greens. How to improve the quality of chromium oxide greens and increase economic and environmental benefits as quickly as possible are the keys to our factory's development and prospect. So the researches have some apparent application values and theoretical significance.
The pigmental properties of chromium oxide green have much relationship with its particles' structures, especially the crystal structures and cation-anion coordination structures, in which trivalent chrome(Cr3+) and the O2- ligands bonded to Cr3+ play main roles. Considering the structural properties of this basic unit and the electron distributing states is helpful to deeply identify the relation between it's structure and it's effect, and we can get beneficial information on how to improve the pigments' properties from it. To get full information about chromium oxide green we analyzed the properties, state and structure of standard chromium oxide green and several representative chromium oxide green samples from MFACF co. ltd. with several apparatus analysis such as X-ray diffraction analysis, IR spectrum analysis, UV-analysis, Atomic Absorption, EDS(energy dispersive spectroscope), Electron Microscope, TG and DTA analysis，laser partial size analysis, chroma and chromatism analysis, Liquid Chromatography and BET analysis, etc. At the same time, we calculated theoretically with ab initio calculation and compared some related results. It shows that the color property difference between the MFACF and Bayer samples mainly comes from the difference of its structures, especially the subtle changes of the parameter a direction , which will change the intensity of ligand field around chromium ion and lead to apparent changes of quantum transition around Fermi energy level consequently affects the hue-showing function of chromic ion. In addition, the impurities(such as Cr6+), granularity and the surface properties will also affect the
properties of chromium oxide green .
On the basis of previous analysis, some advices are given to improve producing technics about chromium oxide green. For example, the crystal shape can be controlled and stabilized by controlling baked temperature scope and stabilizing heating-up program, adding plastic reagent, improving smashed method etc. We can also reduce the content of some bad impurities (such as Cr6+), adopt some after-processing working procedure, etc. At the same time we discussed the recycling of solid scrap produced by chromic acid anhydride workshop. From our experiments, we put forward a procedure that can reclaim chromium oxide green from the scrap. This procedure includes alkaline neutralization, filtration, water-washing, baking, smashing, etc. The procedure not only can improve the whole application of chrome resource but also can greatly alleviate environment pollutions and bring certain economic benefits.
氧化铬绿的颜料特征与粒子的结构特别是晶体结构和正负离子配位结构有很大关系，其中起主导作用的是Cr3+及其周围作八面体配位的O2-的影响。考察这一基本单元的构造特征及其电子分布状态，将有利于深入了解氧化铬绿的构效关系，为提高该类产品的颜料性能提供帮助。为此，本文选取德国Bayer公司的标准氧化铬绿样品和民丰农化集团生产的几种有代表性的铬绿样品，采用多种仪器进行了性质状态和结构分析，包括X射线衍射，红外、紫外可见光谱，原子吸收，能谱分析，电子显微分析，热重分析和差热分析，激光粒度分析，色度、色差分析，液相色谱和BEF表面分析等，相互映证，相互配合，全方位多层次获取铬绿颜料的信息。同时用量子化学从头计算方法进行了理论计算，并对有关结果进行了比较研究。结果表明，民丰铬绿颜料与Bayer样品在着色性质上的差别，主要来自二者晶体结构的差异，特别是晶胞在a向线度的微小变化，将使铬离子周围的配体场强弱发生变化，导致Fermi能级附近量子跃迁的明显改变，从而影响铬离子的呈色功能。此外，某些杂质（如六价铬）的存在，以及粒度和表面特征，也会对氧化铬绿的颜料性质产生影响。
在工艺方面，本文根据上述分析，对氧化铬绿的生产过程提出了改进意见，如通过控制焙烧温度范围和升温程序、添加整形剂、改进粉碎方法等措施控制和稳定晶型，以及降低有害杂质（如六价铬）的含量，实施合理的后处理方案等。同时重点讨论了铬酐生产车间的固体废料回收利用问题，通过实验，本文提出可以通过碱中和、过滤、水洗、分离除杂、焙烧、粉碎等工序从废弃物中回收氧化铬绿，不仅可以提高铬资源的综合利用水平，而且还能减少环境污染，产生一定的经济效益。
Chromium oxide green is a kind of important inorganic pigment. Chromium oxide green with corundum crystal structure has such characteristics as high thermal stability, high painted capacity, chemical corrosion-resisting capacity, etc. At present, in China, the produce of chromium oxide green has reached a certain scale, but there are still some disparities in the producing technology and product quality between home and abroad chromium oxide green. However, the essential factors which result in the disparities are reported scarcely. MinFeng Agricultural and Chemical Factory is one of the main manufacturers producing chromium oxide greens. How to improve the quality of chromium oxide greens and increase economic and environmental benefits as quickly as possible are the keys to our factory's development and prospect. So the researches have some apparent application values and theoretical significance.
The pigmental properties of chromium oxide green have much relationship with its particles' structures, especially the crystal structures and cation-anion coordination structures, in which trivalent chrome(Cr3+) and the O2- ligands bonded to Cr3+ play main roles. Considering the structural properties of this basic unit and the electron distributing states is helpful to deeply identify the relation between it's structure and it's effect, and we can get beneficial information on how to improve the pigments' properties from it. To get full information about chromium oxide green we analyzed the properties, state and structure of standard chromium oxide green and several representative chromium oxide green samples from MFACF co. ltd. with several apparatus analysis such as X-ray diffraction analysis, IR spectrum analysis, UV-analysis, Atomic Absorption, EDS(energy dispersive spectroscope), Electron Microscope, TG and DTA analysis，laser partial size analysis, chroma and chromatism analysis, Liquid Chromatography and BET analysis, etc. At the same time, we calculated theoretically with ab initio calculation and compared some related results. It shows that the color property difference between the MFACF and Bayer samples mainly comes from the difference of its structures, especially the subtle changes of the parameter a direction , which will change the intensity of ligand field around chromium ion and lead to apparent changes of quantum transition around Fermi energy level consequently affects the hue-showing function of chromic ion. In addition, the impurities(such as Cr6+), granularity and the surface properties will also affect the
properties of chromium oxide green .
On the basis of previous analysis, some advices are given to improve producing technics about chromium oxide green. For example, the crystal shape can be controlled and stabilized by controlling baked temperature scope and stabilizing heating-up program, adding plastic reagent, improving smashed method etc. We can also reduce the content of some bad impurities (such as Cr6+), adopt some after-processing working procedure, etc. At the same time we discussed the recycling of solid scrap produced by chromic acid anhydride workshop. From our experiments, we put forward a procedure that can reclaim chromium oxide green from the scrap. This procedure includes alkaline neutralization, filtration, water-washing, baking, smashing, etc. The procedure not only can improve the whole application of chrome resource but also can greatly alleviate environment pollutions and bring certain economic benefits.
引文
[1] 朱骥良等. 颜料工艺学. 北京:化学工业出版社,1989, 12-18
[2] Mznsmann等.由红矾钠同铵盐制氧化铬绿.US 4040860(1977)
[3] 李托文,韩绍娟,张立健等. 电熔淬冷制备工艺对氧化铬粉末和涂层性能的影响. 硅酸盐通报.1996. 第1期.27～30
[4] 麻鋶璜. 贾永昌. 刘维祥译. 热喷涂原理与应用技术. 美国焊接协会编.成都:四川科学技术出版社. 1987.3
[5] 李玉衡,朱冗民,梁绵长等. 中国热喷涂技术经验交流会论文集. 桂林:1988. 164—166，138.
[6] Ding C X,et al Thin solid Films,1984,118:485—493.
[7] Richard C S, Lu J, Beranger G et al. Study of Cr2O3 Coating [J]. Journal of Thermal Spray Technology, 1995,4(4):342～352
[8] Leivo E M,Vippla M S, Soraa, P P et al. Wear and corrosion properties of plasma sprayed Al2O3 and Cr2O3 coatings sealed by aluminum hosphates [J]. Journal of Thermal Spray Technology, 1997,6(2):205～210
[9] 唐小真,杨宏秀,丁马太等.材料化学导论. 北京:高等教育出版社. 1997第1版.
[10] 陈肇友. Cr2O3在耐火材料中的行为. 耐火材料. 1990:第二期.37～43
[11] 张登高. 玻璃和陶瓷用无机颜料的现状与发展. 硅酸盐通报,1989,8(1), 30—33
[12] 罗谷风.《结晶学导论》.第一版.北京:地质出版社,1984.195～201
[13] 张红鸣, 徐捷. 工业产品着色与配色技术. 北京:中国轻工业出版社 2001.2.15
[14] 方容川. 固体光谱学.合肥:中国科技大学出版社.2001.5.71～82
[15] 方容川. 固体光谱学.合肥:中国科技大学出版社.2001.5. 68～70
[16] 周公度. 结构和物性化学原理的应用( 第二版）.北京:高等教育出版社. 2000.291～299
[17] 方容川. 固体光谱学.合肥:中国科技大学出版社. 2001.5. 139～142
[18] Mznsmann等.由红矾钠同铵盐制氧化铬绿.US 4040860(1977)
[19] William A.F.铬酐热分解制氧化铬绿.US 5380554 (1995)
[20] Chromium Sesquioxide. TakaTawa, Seiji; Yoshida, Masahiro; Arai satoshi(Nippon Chmical, Industrial CO.,Itd.). Japan,Kokai 7714,597c cl, COLG37/02),03 Feb 1997,Appl.75/90,214,25 Jul 1975.（CA 87:25442e）
[21] Chromium Sesquioxide. TakaTawa, Seiji; Yoshida, Masahiro; Arai satoshi(Nippon Chmical, Industrial CO.,Itd.). Japan,Kokai 7704,998c cl. COLG37/02),13 Jan 1997,Appl.75/80,078,30 Jun1975.（CA 86:157733q）
[22] Manufacture of Chromium Oxide. Imamura, Masao; Yoshida, Yasunodu; Kaneko,Tetsuo;
Mutsumoh, Yoshiharu (toyo Soda Mfg. CO., ltd). Jpn kokai Tokkyo kokho Jp 62, 153,174[81.153.124]cl.col G37/02, 08 Jul1987. Appl,85/192,235,2. Dec,1985.（CA 107:136950v）
[23] Labanowski J K. Andzelm J W. Density Function Methods in Chemistry. New York:Springer-Verlag,1991
[24] Hehre W J, Ditchfield R. pople J A. Self-consistent molecular orbital method. XII. Further extension of Gaussian-type basis sets for use in molecular orbital studies of organic moleculars. J Chem Phys,1972,56:2 257
[25] 工业三氧化二铬. 中华人民共和国化工行业标准 HG/T 2775—1996
[26] 傅献彩,沈文霞等. 物理化学. 北京:高等教育出版社1990.10（1999重印）
[27] R.W.卡恩, P.哈森. E.J.克雷默编. 材料科学与技术丛书第一卷—固体结构：David G.Pettifor.2晶体结构的电子理论. 科学出版社
[28] 温树林. 材料结构科学. 北京:科学出版社,1986:189～250.
[29] 徐光宪,黎乐民,王德民. 量子化学—基本原理和从头计算法. 科学出版社,1999,818
[30] Singh J P Diercks D R, Poeppel R B. Am Ceram Soc Bull, 1985;64(10):1373
[31] 方容川.固体光谱学. 中国科技大学出版社 2001.5 合肥,165～176
[32] K.拿骚著. 李士杰, 张志三译. 颜色的物理与化学. 北京:科学出版社. 1991.4,第一版
[33] 张海东.TiO2簇模型的 从头计算及DFT的研究.重庆大学硕士学位论文.2001.10—15
[34] Duke A JA Hartree-Fock study of the methyl anion and its inversion potential surface :Use of an augmented basis set for this species. Chem Phys Lett. 1993.21:275
[35] 张瑞勤,步宇翔,李述汤等. 一种选择从头算基函数的有效方法.中国科学（B辑）,30（5）,2000,10:419～427
[36] 方容川. 固体光谱学.合肥:中国科学技术大学出版社,2001:57～97
[37] 谢希德, 陆栋. 固体能带理论. 上海: 复旦大学出版社,1998:75～83
[38] F.A.Cotton,Chemical Application of Group Theory, 3rd edn. Wiley, Chichesterler, 1990
[39] Y.Tanable, S.Sugano,J.Phys.Soc.Jpn.9(1954)766
[40] S.Sugano,Y.Tanabe,J.Phys.Soc.Jpn.13(1958)880
[41] 颜料颜色的比较.中华人民共和国国家标准 GB 1864—89
[42]唐敖庆，杨忠志，李前树.量子化学. 北京：科学出版社，1982
[43] 廖沐真，吴国是，刘洪霖.量子化学从头计算方法，北京：清华大学出版社。1984
[44] Labanowski J K. Andzelm J W. Density Function Methods in Chemistry. New York:Springer-Verlag,1991
[2] Mznsmann等.由红矾钠同铵盐制氧化铬绿.US 4040860(1977)
[3] 李托文,韩绍娟,张立健等. 电熔淬冷制备工艺对氧化铬粉末和涂层性能的影响. 硅酸盐通报.1996. 第1期.27～30
[4] 麻鋶璜. 贾永昌. 刘维祥译. 热喷涂原理与应用技术. 美国焊接协会编.成都:四川科学技术出版社. 1987.3
[5] 李玉衡,朱冗民,梁绵长等. 中国热喷涂技术经验交流会论文集. 桂林:1988. 164—166，138.
[6] Ding C X,et al Thin solid Films,1984,118:485—493.
[7] Richard C S, Lu J, Beranger G et al. Study of Cr2O3 Coating [J]. Journal of Thermal Spray Technology, 1995,4(4):342～352
[8] Leivo E M,Vippla M S, Soraa, P P et al. Wear and corrosion properties of plasma sprayed Al2O3 and Cr2O3 coatings sealed by aluminum hosphates [J]. Journal of Thermal Spray Technology, 1997,6(2):205～210
[9] 唐小真,杨宏秀,丁马太等.材料化学导论. 北京:高等教育出版社. 1997第1版.
[10] 陈肇友. Cr2O3在耐火材料中的行为. 耐火材料. 1990:第二期.37～43
[11] 张登高. 玻璃和陶瓷用无机颜料的现状与发展. 硅酸盐通报,1989,8(1), 30—33
[12] 罗谷风.《结晶学导论》.第一版.北京:地质出版社,1984.195～201
[13] 张红鸣, 徐捷. 工业产品着色与配色技术. 北京:中国轻工业出版社 2001.2.15
[14] 方容川. 固体光谱学.合肥:中国科技大学出版社.2001.5.71～82
[15] 方容川. 固体光谱学.合肥:中国科技大学出版社.2001.5. 68～70
[16] 周公度. 结构和物性化学原理的应用( 第二版）.北京:高等教育出版社. 2000.291～299
[17] 方容川. 固体光谱学.合肥:中国科技大学出版社. 2001.5. 139～142
[18] Mznsmann等.由红矾钠同铵盐制氧化铬绿.US 4040860(1977)
[19] William A.F.铬酐热分解制氧化铬绿.US 5380554 (1995)
[20] Chromium Sesquioxide. TakaTawa, Seiji; Yoshida, Masahiro; Arai satoshi(Nippon Chmical, Industrial CO.,Itd.). Japan,Kokai 7714,597c cl, COLG37/02),03 Feb 1997,Appl.75/90,214,25 Jul 1975.（CA 87:25442e）
[21] Chromium Sesquioxide. TakaTawa, Seiji; Yoshida, Masahiro; Arai satoshi(Nippon Chmical, Industrial CO.,Itd.). Japan,Kokai 7704,998c cl. COLG37/02),13 Jan 1997,Appl.75/80,078,30 Jun1975.（CA 86:157733q）
[22] Manufacture of Chromium Oxide. Imamura, Masao; Yoshida, Yasunodu; Kaneko,Tetsuo;
Mutsumoh, Yoshiharu (toyo Soda Mfg. CO., ltd). Jpn kokai Tokkyo kokho Jp 62, 153,174[81.153.124]cl.col G37/02, 08 Jul1987. Appl,85/192,235,2. Dec,1985.（CA 107:136950v）
[23] Labanowski J K. Andzelm J W. Density Function Methods in Chemistry. New York:Springer-Verlag,1991
[24] Hehre W J, Ditchfield R. pople J A. Self-consistent molecular orbital method. XII. Further extension of Gaussian-type basis sets for use in molecular orbital studies of organic moleculars. J Chem Phys,1972,56:2 257
[25] 工业三氧化二铬. 中华人民共和国化工行业标准 HG/T 2775—1996
[26] 傅献彩,沈文霞等. 物理化学. 北京:高等教育出版社1990.10（1999重印）
[27] R.W.卡恩, P.哈森. E.J.克雷默编. 材料科学与技术丛书第一卷—固体结构：David G.Pettifor.2晶体结构的电子理论. 科学出版社
[28] 温树林. 材料结构科学. 北京:科学出版社,1986:189～250.
[29] 徐光宪,黎乐民,王德民. 量子化学—基本原理和从头计算法. 科学出版社,1999,818
[30] Singh J P Diercks D R, Poeppel R B. Am Ceram Soc Bull, 1985;64(10):1373
[31] 方容川.固体光谱学. 中国科技大学出版社 2001.5 合肥,165～176
[32] K.拿骚著. 李士杰, 张志三译. 颜色的物理与化学. 北京:科学出版社. 1991.4,第一版
[33] 张海东.TiO2簇模型的 从头计算及DFT的研究.重庆大学硕士学位论文.2001.10—15
[34] Duke A JA Hartree-Fock study of the methyl anion and its inversion potential surface :Use of an augmented basis set for this species. Chem Phys Lett. 1993.21:275
[35] 张瑞勤,步宇翔,李述汤等. 一种选择从头算基函数的有效方法.中国科学（B辑）,30（5）,2000,10:419～427
[36] 方容川. 固体光谱学.合肥:中国科学技术大学出版社,2001:57～97
[37] 谢希德, 陆栋. 固体能带理论. 上海: 复旦大学出版社,1998:75～83
[38] F.A.Cotton,Chemical Application of Group Theory, 3rd edn. Wiley, Chichesterler, 1990
[39] Y.Tanable, S.Sugano,J.Phys.Soc.Jpn.9(1954)766
[40] S.Sugano,Y.Tanabe,J.Phys.Soc.Jpn.13(1958)880
[41] 颜料颜色的比较.中华人民共和国国家标准 GB 1864—89
[42]唐敖庆，杨忠志，李前树.量子化学. 北京：科学出版社，1982
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