氟化氢铵气相法合成工艺开发
摘要
氟化氢铵是一种产量和用量都较大的无机氟盐，国内年产量在数万吨以上。氟化氢铵主要用于玻璃蚀刻剂、化学试剂、锅炉清洗剂、发酵工业消毒剂和钢板表面处理剂等。近年随着铝表面装饰工艺开始使用氟化氢铵作腐蚀剂，它的市场需求持续增加。目前国内生产厂家都采用液相法生产氟化氢铵，这种方法投资少，工艺简单，但液相法生产的氟化氢铵含水量高，纯度低，产品溶解速度慢，使用不方便，易结块，不能长期储存。而气相法生产的氟化氢铵含水量低，纯度高，可以长期储存，能适应医药工业、电子工业等行业的特殊要求。本文首先对氟化氢铵合成的反应机理进行了理论上的研究，同时，对气梧法合成中涉及到的粉末颗粒制备进行了详细的阐述，为气相法工艺开发奠定了理论基础。氟化氢铵合成存在几个相关的可逆反应，其平衡常数随着反应介质，温度条件的改变而改变。通过深入的研究，从理论上分析得出氟化氢铵产品所含水分难以通过一般的干燥方法除去，而且初步确定了气相法合成的几个关键工艺条件。其次，设计了几套不同的气相法合成工艺方案，根据实验过程中出现的问题不断改进，开发出了一条行之有效的合成路线。最后，在实验基础上进行了年产500吨的中试设计，为最终工业化打下基础。本文开发出的气相法合成工艺为国内氟化氢铵生产企业改进工艺水平，提高产品质量提供了可靠的依据。
Ammonium bifluoride is an inorganic fluoride salt, whose consumption and output exceed tmi thousand of tons in China. It is mainly used as glass etchent, chemical reagent, boiler purgemt, disinfector for ferment industry and used for surface treatment. The market need of ammonium bifluoride has been ever-increasing since it was used as corrosive in decoration technique of aluminum surface. Ammonium bifluonde is mainly produced with the method of liquid phase in our countly now, with low investment and simple technique. However, the method results in a little high content of water in aminonium bifluoride and low purity, slow dissolution speed of product and short storage period. Comparatively, some special requirements from pharmaceutical and electric industries can be met through gas phase meth4to produce ammonium biiluoride with low content of water, high purity and long storage period. In this paper, the reactive mechanism is theoretically researched, and the preparation method of powder granule used in gas phase method is expounded, which provides a theory for the technique of gas phase method. There are several reversible reactions in this synthetic reaction, and its equilibrium constant is subject to reactive medium and temperature. An in-depth theoretical research proves that the water in ammonium biiluoride is difficult to be removed through common drying method, then several key process parameters are got for gas phase method. By virtue of these parameters, several different processed are designed and the optimal one is elected after experiments. In this paper. a piloted experiment with yield of 500 tons per year is provided, which paves the way for the industrialization of this process. The synthetic process of ammonium bifluoride with phase method developed in this paper will provide well-founded basis for the improvement of product quality and the modification of productive technique.
Ammonium bifluoride is an inorganic fluoride salt, whose consumption and output exceed tmi thousand of tons in China. It is mainly used as glass etchent, chemical reagent, boiler purgemt, disinfector for ferment industry and used for surface treatment. The market need of ammonium bifluoride has been ever-increasing since it was used as corrosive in decoration technique of aluminum surface. Ammonium bifluonde is mainly produced with the method of liquid phase in our countly now, with low investment and simple technique. However, the method results in a little high content of water in aminonium bifluoride and low purity, slow dissolution speed of product and short storage period. Comparatively, some special requirements from pharmaceutical and electric industries can be met through gas phase meth4to produce ammonium biiluoride with low content of water, high purity and long storage period. In this paper, the reactive mechanism is theoretically researched, and the preparation method of powder granule used in gas phase method is expounded, which provides a theory for the technique of gas phase method. There are several reversible reactions in this synthetic reaction, and its equilibrium constant is subject to reactive medium and temperature. An in-depth theoretical research proves that the water in ammonium biiluoride is difficult to be removed through common drying method, then several key process parameters are got for gas phase method. By virtue of these parameters, several different processed are designed and the optimal one is elected after experiments. In this paper. a piloted experiment with yield of 500 tons per year is provided, which paves the way for the industrialization of this process. The synthetic process of ammonium bifluoride with phase method developed in this paper will provide well-founded basis for the improvement of product quality and the modification of productive technique.
引文
1. US2270498, Manufacture of Ammonium Bifluoride
2. US 2156273, Manufacture of Ammonium Hydrogen Fluoride
3．《化工工艺设计手册》(上、下册)，化学工业出版社，1998
4．《质量流量计》，中国石化出版社，1999
5．《化工过程的物料恒算和能量恒算》，高等教育出版社，1989
6．《换热器原理及计算》，清华大学出版社，1993
7．《换热器及其计算基础知识》，化学工业出版社，1995
8．《气固分离理论及技术》，浙江大学出版社，2001
9．《氯碱化工理化常数手册》，化学工业出版社，1969
10．胡黎明、沈卫．超细粉末制备技术进展，化工生产与技术1996年第4期
11．US,2156273
12．US,3310369
13．US,3767582
14．余尧楚、胡和方、刘创新等．某些氟化物的升华提纯，无机材料学报，Vol．9：No．3
15．张文昭、于广时等．NS型防结块氟化氢铵的制备，无机盐工业，1997年第1期
16 勾厚政．量热式质量流量计及其在氟化氢流量测量中的应用，仪表技术与传感器，1996年第12期
17. Higgins,W.F.,Light Met. Age, 17(12),8(1959)
18. Chem. Infor. Note, 16(34),34581k(1987)
19. Linke, W.F.,Solubilities of Inorganic and Metalorganic Compounds, 4th ed.,Vol. 2,1958
20．陈丽涛、陈光巨等．氨及其氟取代物与氟化氢形成氢键络合物的系列理论研究，高等学校学学报，Vol．20，No．1
21. S. Iwama, K.Hayakawa, et. al.,J. Crystal.Growth 1982,51(2)
22. F. Curcio et. al.,Applied Surface Science 1989(36)
23. R.F. Strickland. kinetics Mechanism of Crystallization, New York:Academic Press, 19
24．王敬义、王宇等．气相生长统一模型，华中理工大学学报，Vol.21,No.5
25．许宇庆、王幼文等．碳化硅超细粉末形核生长过程的研究，硅酸盐学报，Vol．20，No．1
26．曹茂盛．超微颗粒制备科学与技术，哈尔滨工业大学出版社，1995
27. C.E. Capes, R.D. Coleman and W.L. Thayer, The production of uniformith sized Spherical agglomerates in balling drums and discs, Int. Conf. Compact. and Consolid. Part. Matter, Proc.,1st ,London, 1972
2. US 2156273, Manufacture of Ammonium Hydrogen Fluoride
3．《化工工艺设计手册》(上、下册)，化学工业出版社，1998
4．《质量流量计》，中国石化出版社，1999
5．《化工过程的物料恒算和能量恒算》，高等教育出版社，1989
6．《换热器原理及计算》，清华大学出版社，1993
7．《换热器及其计算基础知识》，化学工业出版社，1995
8．《气固分离理论及技术》，浙江大学出版社，2001
9．《氯碱化工理化常数手册》，化学工业出版社，1969
10．胡黎明、沈卫．超细粉末制备技术进展，化工生产与技术1996年第4期
11．US,2156273
12．US,3310369
13．US,3767582
14．余尧楚、胡和方、刘创新等．某些氟化物的升华提纯，无机材料学报，Vol．9：No．3
15．张文昭、于广时等．NS型防结块氟化氢铵的制备，无机盐工业，1997年第1期
16 勾厚政．量热式质量流量计及其在氟化氢流量测量中的应用，仪表技术与传感器，1996年第12期
17. Higgins,W.F.,Light Met. Age, 17(12),8(1959)
18. Chem. Infor. Note, 16(34),34581k(1987)
19. Linke, W.F.,Solubilities of Inorganic and Metalorganic Compounds, 4th ed.,Vol. 2,1958
20．陈丽涛、陈光巨等．氨及其氟取代物与氟化氢形成氢键络合物的系列理论研究，高等学校学学报，Vol．20，No．1
21. S. Iwama, K.Hayakawa, et. al.,J. Crystal.Growth 1982,51(2)
22. F. Curcio et. al.,Applied Surface Science 1989(36)
23. R.F. Strickland. kinetics Mechanism of Crystallization, New York:Academic Press, 19
24．王敬义、王宇等．气相生长统一模型，华中理工大学学报，Vol.21,No.5
25．许宇庆、王幼文等．碳化硅超细粉末形核生长过程的研究，硅酸盐学报，Vol．20，No．1
26．曹茂盛．超微颗粒制备科学与技术，哈尔滨工业大学出版社，1995
27. C.E. Capes, R.D. Coleman and W.L. Thayer, The production of uniformith sized Spherical agglomerates in balling drums and discs, Int. Conf. Compact. and Consolid. Part. Matter, Proc.,1st ,London, 1972