工业副产石膏热分解脱硫的研究进展

doi:10.16085/j.issn.1000-6613.2017.02.031

摘要/Abstract

摘要： 热分解工业副产石膏回收利用SO₂和固体剩余物是一种有效资源化利用工业副产石膏的方式，但普遍存在利用成本高、能耗高、效率低等缺点，严重限制其循环利用的发展。本文介绍了近年来热分解工业副产石膏的研究进展。从气氛条件、还原剂与CaSO₄的配比、添加剂或杂质的促进作用，加热温度等方面回顾了不同条件对工业副产石膏分解率和脱硫率的影响，对比研究了微波加热相对于常规加热还原分解工业副产石膏的优势，分析了不同反应条件下CaSO₄与C/CO的反应机理模型。同时对工业副产石膏热分解的发展方向和趋势进行了展望。通过优化反应条件能够有效提高工业副产石膏的热分解效率和脱硫率，但成本依旧较高。指出微波加热分解工业副产石膏可能成为未来工业化的一个重要方向。

关键词: 工业副产石膏, 脱硫, 微波加热

Abstract: Thermal decomposition of industrial by-product gypsum is one of the most effective ways to recycle SO₂ and the corresponding solid residues. The high cost,high energy-consuming,and low efficiency,seriously limit the reutilization of industrial by-product gypsum. This paper reviewed the recent advances on the research of thermal decomposition of industrial by-product gypsum. Based on the influence of atmospheric conditions,the ratio of reductant to CaSO₄,the facilitation of addictive or impurity,and heating temperatures,the decomposition and desulfurization degree were analyzed. The advantages of microwave heating method were highlighted compared to conventional heating,and the decomposition mechanisms of CaSO₄ with C/CO were also summarized under different conditions. The research trend for thermal decomposition of industrial by-product gypsum in the future was discussed as well. The decomposition and desulfurization degree of industrial by-product gypsum can be effectively improved by optimizing reaction condition to reduce the high cost. The results showed that microwave assisted heating desulphurization of industrial by-product gypsum will be a promising direction for industry in the future.

Key words: industrial by-product gypsum, desulphurization, microwave heating

中图分类号:

TF044

孟令佳, 吉忠海, 陈津. 工业副产石膏热分解脱硫的研究进展[J]. 化工进展, 2017, 36(02): 626-633.

MENG Lingjia, JI Zhonghai, CHEN Jin. Advance of the thermal decomposition of industrial by-product gypsum[J]. Chemical Industry and Engineering Progree, 2017, 36(02): 626-633.

参考文献

[1] 张娟,艾华. 我国火电厂烟气脱硫工艺现状及发展综述[J]. 环境节约与环保,2016(4):22-27. ZHANG J,AI H. Discussion on heat recovery and utilization in sulfuric acid engineering[J]. Resources Economization & Environmental Protection,2016(4):22-27.
[2] JIANG G M,WANG H,CHEN Q S,et al. Preparation of alpha-calcium sulfate hemihydrate from FGD gypsum in chloride-free Ca(NO₃)₂ solution under mild conditions[J]. Fuel,2016,174:235-241.
[3] 韩灵翠,王永昌. 节能减排与综合利用并重是化学产业发展方向[J]. 磷肥与复肥,2010,25(6):11-13. HAN L C,WANG Y C. Development of chemical gypsum industry depends on the integration of energy saving and emission reduction with comprehensive utilization[J]. Phosphate & Compound Fertilizer,2010,25(6):11-13.
[4] LEIVA C,ARENAS C G,VILCHES L F,et al. Use of FGD gypsum in fire resistant panels[J]. Waste Management,2010,30(6):1123-9.
[5] TZOUVALAS G,RANTIS G,TSIMAS S. Alternative calcium-sulfate-bearing materials as cement retarders:Part Ⅱ. FGD gypsum[J]. Cement & Concrete Research,2004,34(11):2119-2125.
[6] TELESCA A,MARROCCOLI M,CALABRESE D,et al. Flue gas desulfurization gypsum and coal fly ash as basic components of prefabricated building materials[J]. Waste Management,2013,33(3):628-633.
[7] LI X P,MAO Y M,LIU X C. Flue gas desulfurization gypsum application for enhancing the desalination of reclaimed tidal lands[J]. Ecological Engineering,2015,82:566-570.
[8] LI J,ZHUANG X G,LEIVA C,et al. Potential utilization of FGD gypsum and fly ash from a Chinese power plant for manufacturing fire-resistant panels[J]. Construction & Building Materials,2015,95:910-921.
[9] 郝继斌,庞仁杰. 磷石膏制酸联产水泥的生产与操作[J]. 磷肥与复肥,1998(6):57-63. HAO J B,PANG R J. Operation and production of cement and acid from phosphogypsum[J]. Phosphate & Compound Fertilizer,1998(6):57-63.
[10] 吕鹏飞,费德君,党亚固. Fe³⁺对水热合成硫酸钙晶须性能的影响[J]. 化工进展,2014,33(1):165-168. LÜ P F,FEI D J,DANG Y G. Influence of Fe³⁺ on calcium sulfate whisker by hydrothermal synthesis[J]. Chemical Industry and Engineering Progress,2014,33(1):165-168.
[11] 吕鹏飞,费德君,党亚固. 磷石膏制备硫酸钙晶须及晶须造纸应用的研究进展[J]. 化工进展,2013,32(4):842-847. LÜ P F,FEI D J,DANG Y G. Preparation of calcium sulfate whisker from phosphogypsum and its application[J]. Chemical Industry and Engineering Progress,2013,32(4):842-847.
[12] 钟世云,陈维灯,贺鸿珠. 脱硫石膏应用技术现状及其发展趋势[J]. 粉煤灰,2009,21(6):35-37. ZHONG S Y,CHEN W D,HE H Z. The state-of-the-art of applied technology for FGD gypsum and its developing tedency[J]. Coal Ash,2009,21(6):35-37.
[13] 郑达. 脱硫石膏还原分解特性及反应机理研究[D]. 南京:南京理工大学,2013. ZHENG D. Reductive decomposition and reaction mechanism of FGD gypsum[D]. Nanjing:Nanjing University of Science & Technology,2013.
[14] 曾亚平,党亚固,费德君. 制备高品质磷石膏的湿法磷酸新工艺的开发[J]. 化工进展,2015,34(s1):167-172. ZENG Y P,DANG Y G,FEI D J. Development of the new wet phosphoric process of preparing high-quality phosphogypsum[J]. Chemical Industry and Engineering Progress,2015,34(s1):167-172.
[15] 赵建国,李晓强,杨妍慧. 磷石膏制硫酸联产水泥(或熟料)技术进展评述[J]. 云南化工,2007,34(s2):6-12. ZHAO J G,LI X Q,YANG Y H. Discussion on technology advance for the combined production of cement and sulfuric acid from phosphogypsum[J]. Yunnan Chemical Technology,2007,34(s2):6-12.
[16] 刘少文,张茜,吴元欣,等. 热分析在磷石膏制酸反应研究中的应用[J]. 化工进展,2008,27(5):761-764. LIU S W,ZHANG Q,WU Y X,et al. Thermal analysis and its application in the investigation of reaction process for sulfuric acid production from phosphogypsum[J]. Chemical Industry and Engineering Progress,2008,27(5):761-764.
[17] 王艳梅,刘梅堂,孙华,等. 磷石膏转氨法制硫酸技术原理与过程评价[J]. 化工进展,2015,34(s1):196-201. WANG Y M,LIU M T,SUN H,et al. Preparation of sulfuric acid from phosphogypsum by ammonium-transferred method:technical principle and process evalution[J]. Chemical Industry and Engineering Progress,2015,34(s1):196-201.
[18] 鲍树涛. 鲁北大型磷石膏制硫酸联产水泥装置运行及其技术、经济综述[C]//全国磷肥、硫酸行业年会,2008. BAO S T. Discussion on technology advance for the combined production of cement and sulfuric acid from phosphogypsum in Lubei[C]//The Sulfuric Acid Phosphate Fertilizer Industry Convention,2008.
[19] YAN B,MA L P,MA J,et al. Mechanism analysis of Ca,S transformation in phosphogypsum decomposition with Fe catalyst[J]. Industrial & Engineering Chemistry Research,2014,53(18):7648-7654.
[20] SONG T,ZHENG M,SHEN L H,et al. Mechanism investigation of enhancing reaction performance with CaSO₄/Fe₂O₃ oxygen carrier in chemical-looping combustion of coal[J]. Industrial & Engineering Chemistry Research,2013,52(11):4059-4071.
[21] MIAO Z,YANG H R,WU Y X,et al. Experimental studies on decomposing properties of desulfurization gypsum in a thermogravimetric analyzer and multiatmosphere fluidized beds[J]. Industrial & Engineering Chemistry Research,2012,51:5419-5423.
[22] MA L,DU Y L,NIU X K,et al. Thermal and kinetic analysis of the process of thermochemical decomposition of phosphogypsum with CO and additives[J]. Industrial & Engineering Chemistry Research,2012,51(19):6680-6685.
[23] ZHANG X M,SONG X F,SUN Z,et al. Density functional theory study on the mechanism of calcium sulfate reductive decomposition by carbon monoxide[J]. Industrial & Engineering Chemistry Research,2012,110(18):204-211.
[24] ZHENG S C,NING P,MA L P,et al. Reductive decomposition of phosphogypsum with high-sulfur-concentration coal to SO₂,in an inert atmosphere[J]. Chemical Engineering Research & Design,2011,89(12A):2736-2741.
[25] 方祖国,宁平,杨月红,等. 复合还原剂还原分解磷石膏的影响因素[J]. 化工进展,2009,28(3):522-527. FANG Z G,NING P,YANG Y H,et al. Influence factors of deoxidizing phosphogypsum by compound reducing agent[J]. Chemical Industry and Engineering Progress,2009,28(3):522-527.
[26] 肖海平,周俊虎,曹欣玉,等. CaSO₄在不同气氛下分解特性的实验研究[J]. 动力工程学报,2004,24(6):889-892. XIAO H P,ZHOU J H,CAO X Y,et al. Experimental study of decomposition behavior of CaSO₄ in different atmospheres[J]. Power Engineering,2004,24(6):889-892.
[27] 陈升,刘少文. 氢气还原分解硫酸钙的热力学研究[J]. 化学工业与工程技术,2012,33(5):7-11. CHEN S,LIU S W. Thermodynamic study on reductive decomposition of calcium sulfate with hydrogen[J]. Journal of Chemical Industry & Engineering,2012,33(5):7-11.
[28] 张雪梅,徐仁伟,孙淑英,等. 硫酸钙的还原热分解特性研究[J]. 环境科学与技术,2010(s2):144-148. ZHANG X M,XU R W,SUN S Y,et al. Study on the character of calcium sulfate reducing decomposition[J]. Environmental Science & Technology,2010(s2):144-148.
[29] 刘家祥,吴华夏. 氟石膏分解特性的实验研究[J]. 北京化工大学学报(自然科学版),2003,30(6):36-40. LIU J X,WU H X. Experimental research on fluorgypsum decomposition characters[J]. Journal of Beijing University of Chemical Technology,(Natural Science Edition)2003,30(6):36-40.
[30] ZHENG D,LU H L,SUN X Y,et al. Reaction mechanism of reductive decomposition of FGD gypsum with anthracite[J]. Thermochimica Acta,2013,559(2):23-31.
[31] MA L Z,NING P,QING S. Study on influence factors between high sulfur coal and phosphogypsum[J]. Acta Scientiarum Naturalium Universitatis Sunyatseni,2009,48(2):85-89.
[32] 方祖国,宁平,杨月红,等. 复合还原剂还原分解磷石膏制取高浓度二氧化硫[J]. 无机盐工业,2009,41(1):48-50. FANG Z G,NING P,YANG Y H,et al. Preparation of high-concentration sulfur dioxide from deoxidizing phosphogypsum with compound reducing agent[J]. Inorganic Chemicals Industry,2009,41(1):48-50.
[33] 郑绍聪,宁平,马丽萍,等. 高硫煤还原磷石膏制SO₂[J]. 化学工程,2010,38(8):35-38. ZHENG S C,NING P,MA L P,et al. Reduction of phosphogypsm to sulfur dioxide with high sulfur coal[J]. Chemical Engineering(China),2010,38(8):35-38.
[34] JI Z H,CHEN J,GUO Y,et al. Magnetite and anthracite assisted microwave heating flue gas desulfurization gypsum[J]. Chemical Engineering & Processing Process Intensification,2016,105:73-78.
[35] 郑绍聪,宁平,马丽萍,等. 不同气氛下磷石膏热分解的反应特性[J]. 武汉理工大学学报(交通科学与工程版),2010,34(3):580-583. ZHENG S C,NING P,MA L P,et al. Reaction properties of thermal decomposition of phosphogypsum in different atmospheres[J]. Journal of Wuhan University of Technology(Transportation Science & Engineering),2010,34(3):580-583.
[36] 徐仁伟. 焦炭及其杂质对硫酸钙热解过程影响的研究[D]. 上海:华东理工大学,2011. XU R W. Study on the influence of cake and its impurities on pyrolysis process of calcium sulfate[D]. Shanghai:East China University of Science and Technology,2011.
[37] VAN DER MERWE E M,STYDOM C A,POTGIETER J H. Thermogravimetric analysis of the reaction between carbon and CaSO₄·2H₂O,gypsum and phosphogypsum in an inert atmosphere[J]. Thermochimica Acta,1999,S340/341(7):431-437.
[38] MIHARA N,KUCHAR D,KOJIMA Y,et al. Reductive decomposition of waste gypsum with SiO₂,Al₂O₃,and Fe₂O₃ additives[J]. Journal of Material Cycles & Waste Management,2007,9(1):21-26.
[39] 邓少刚,王俊哲,黄鹏辉,等. FeS还原CaSO₄的热分解动力学研究[J]. 磷肥与复肥,2015,30(3):5-10. DENG S G,WANG J Z,HUANG P H,et al. Study on thermal decomposition kinetics of CaSO₄ reduced with FeS[J]. Phosphate & Compound Fertilizer,2015,30(3):5-10.
[40] 吉忠海,陈津,郭宇,等. 微波加热分解脱硫石膏生产烧结矿研究[J]. 化工进展,2016,35(7):2251-2258. JI Z H,CHEN J,GUO Y,et al. Decomposition of flue gas desulfurization(FGD) gypsum under microwave heating to produce sinter ore[J]. Chemical Industry and Engineering Progress,2016,35(7):2251-2258.
[41] YAN B,MA L P,XIE L G,et al. Reaction mechanism for iron catalyst in the process of phosphogypsum decomposition[J]. Industrial & Engineering Chemistry Research,2013,52(49):17383-17389.
[42] KATO T,MURAKAMI K,SUGAWARA K. Carbon reduction of gypsum produced from flue gas desulfurization[J]. Archiv Für Klinische Und Experimentelle Dermatologie,2012,29(1):805-810.
[43] MONTAGNA J C,LENC J F,VOGEL G J,et al. Regeneration of sulfated dolomite from a coal-fired FBC process by reductive decomposition of calcium sulfate in a fluidized bed[J]. Industrial & Engineering Chemistry Process Design & Development,1977,16(2):230-236.
[44] 孙宏飞,陈津,张猛,等. 微波场中高碳锰铁粉及固相脱碳物料的电磁性能[J]. 钢铁研究学报,2012,24(8):12-15. SUN H F,CHEN J,ZHANG M,et al. Electromagnetic properties of solid phase decarburization of high carbon ferromanganese powders[J]. Journal of Iron and Steel Research,2012,24(8):12-15.
[45] 邝焯荣,吴笑梅,樊粤明,等. 预分解窑结皮与窑皮的X射线衍射分析[J]. 水泥,2011(6):26-28. KUANG Z R,WU X M,FAN Y M,et al. The XRD analysis of curst and coating in PC kiln[J]. Cement,2011(6):26-28.
[46] 张杭,马丽萍,胡建红,等. 不同分解工艺下磷石膏分解制水泥熟料的LCA研究[J]. 材料导报:2013,27(1):302-305. ZHANG H,MA L P,HU J H,et al. LCA study on the preparation of cement clinker by the phosphogypsum decomposition under different decomposition process[J]. Materials Review,2013,27(1):302-305.
[47] THOSTENSON E T,CHOU T W. Microwave processing:fundamentals and applications[J]. Composites Part A Applied Science & Manufacturing,1999,30(9):1055-1071.
[48] ZHAO X Q,WANG W L,LIU H Z,et al. Temperature rise and weight loss characteristics of wheat straw under microwave heating[J]. Journal of Analytical & Applied Pyrolysis,2014,107(9):59-66.
[49] JI Z H,GUO Y,CHEN J,et al. Microwave-assisted decomposition of FGD gypsum in the presence of magnetite and anthracite[J]. Chemical Papers,2016,70:1-9.
[50] TURKDOGAN E T,VINTERS J V. Reduction of calcium sulphate by carbon[J]. Trans. Inst. Mining Metall,1976,85:C117-Cl23.
[51] 肖海平,周俊虎,曹欣玉,等. CaSO₄在CO气氛下的平行竞争反应实验与模型研究[J]. 燃料化学学报,2005,33(2):150-154. XIAO H P,ZHOU J H,CAO X Y,et al. Experiments and model of the decomposition of CaSO₄ under CO atmosphere[J]. Journal of Fuel Chemistry and Technology,2005,33(2):150-154.
[52] SUYADAL Y,ÖZTURK A,OGUZ H,et al. Thermochemical decomposition of phosphogypsum with oil shale in a fluidized-bed reactor:a kinetic study[J]. Industrial & Engineering Chemistry Research,1997,36(7):2849-2854.
[53] ZHENG M,SHEN L,FENG X Q,et al. Kinetic model for parallel reactions of CaSO₄ with CO in chemical-looping combustion[J]. Ind. Eng. Chem. Res.,2011,50(9):5414-5427.
[54] JAE O S,WHEELOCK T D. Reductive decomposition of calcium sulfate with carbon monoxide:reaction mechanism[J]. Industrial & Engineering Chemistry Research,2002,29(4):544-550.
[55] KAMPHUIS B,POTMA A W,PRINS W,et al. The reductive decomposition of calcium sulphate-Ⅰ. Kinetics of the apparent solid-solid reaction[J]. Chemical Engineering Science,1992,48(1):105-116.
[56] DAVIES N H,HAYHURST A N. On the formation of liquid melts of CaSO₄ and CaSO₄ and their importance in the absorption of SO₂ by CaO[J]. Combustion & Flame,1996,106(3):359-362..
[57] 肖海平,周俊虎,刘建忠,等. CaSO₄与CaS在N₂气氛下反应动力学[J]. 化工学报,2005,56(7):1322-1326. XIAO H P,ZHOU J H,LIU J Z,et al. Kinetics of reaction between CaS and CaSO₄ under N₂ atmosphere[J]. Journa of Chemical Industry and Engineering(China),2005,56(7):1322-1326.
[58] KOSTYLKOV I G,NOSOV V N. Mechanism of the reduction of calcium sulfate[J]. Zh. Prik. Khim,1982,55:1925-1930.