电解锰压滤渣高温脱硫研究

摘要/Abstract

摘要： 采用直接煅烧法、还原法及添加脱硫剂煅烧法对电解锰压滤渣进行了高温脱硫,研究了不同方法得到的脱硫产物的物相、残硫量和活性,并比较了几种方法的工业适用性。结果表明:直接煅烧法的脱硫渣和坩埚粘连严重,实际操作困难;加入煤粉并没有改善脱硫渣和坩埚的粘连问题,且脱硫渣中残硫量高;石灰石虽能减弱脱硫渣和坩埚的粘连,但由于生成惰性物质石英,降低了脱硫渣的活性;采用铝矾土作为脱硫剂进行脱硫,脱硫渣的残硫量低,脱硫渣和坩埚不粘连,脱硫渣活性高。铝矾土添加量为42%(质量分数),脱硫温度为1 250 ℃,脱硫保温时间为5 min时,脱硫渣中硫含量为0.089 4%(质量分数),达到脱硫要求。

关键词: 电解锰压滤渣, 高温脱硫, 脱硫剂, 残硫量, 铝矾土, 脱硫渣, 固废物

Abstract: The high temperature desulfurization of electrolytic manganese filter press residue was studied by direct calcination method, reduction method and calcination method with adding desulfurizer. The phase, residual sulfur content and activity of desulfurization products by different methods were studied, and the industrial applicability of several methods was compared. The results show that desulfurization slag by direct calcination method sticks seriously with crucible and it is difficult to operate in practice. The desulfurization slag by calcinations with adding coal still sticks with crucible, and contains high amount of residual sulfur. Although limestone weakens the adhesion between desulfurization slag and crucible, the activity of desulfurization slag reduces due to the formation of inert material quartz. Desulfurization slag from manganese residue with bauxite has low residual sulfur, high activity, and no adhesion to crucible. So, bauxite is a good desulfurizer for manganese residue. When the addition amount of bauxite is 42% (mass fraction), the desulfurization temperature is 1 250 ℃, and the desulfurization holding time is 5 min, the sulfur content in the desulfurization slag is 0.089 4% (mass fraction), which meets the desulfurization requirements.

Key words: electrolytic manganese filter press residue, high temperature desulfurization, desulfurizer, residual sulfur content, bauxite, desulfurization slag, solid waste

中图分类号:

TU525

卢清华, 林明跃, 金胜明. 电解锰压滤渣高温脱硫研究[J]. 硅酸盐通报, 2022, 41(2): 589-596.

LU Qinghua, LIN Mingyue, JIN Shengming. High Temperature Desulfurization of Electrolytic Manganese Filter Press Residue[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2022, 41(2): 589-596.

参考文献

[1] 何德军,舒建成,陈梦君,等.电解锰渣建材资源化研究现状与展望[J].化工进展,2020,39(10):4227-4237.
HE D J, SHU J C, CHEN M J, et al. Current status and future prospects of electrolytic manganese residue reused as building materials[J]. Chemical Industryand Engineering Progress, 2020, 39(10): 4227-4237 (in Chinese).
[2] 吴建锋,宋谋胜,徐晓虹,等.电解锰渣的综合利用进展与研究展望[J].环境工程学报,2014,8(7):2645-2652.
WU J F, SONG M S, XU X H, et al. Prospects and advances of comprehensive utilization of electrolytic manganese residue[J]. Chinese Journal of Environmental Engineering, 2014, 8(7): 2645-2652 (in Chinese).
[3] 张歆,刘方,朱健,等.基于电解锰渣-磷石膏复合胶凝材料的制备与表征[J].硅酸盐通报,2021,40(5):1610-1619.
ZHANG X, LIU F, ZHU J, et al. Preparation and characterization of composite cementitious material based on electrolytic manganese residue-phosphogypsum[J]. Bulletinofthe ChineseCeramic Society, 2021, 40(5): 1610-1619 (in Chinese).
[4] 季军荣,武双磊,陈宇,等.利用电解锰渣制备活性粉末混凝土的研究[J].混凝土与水泥制品,2021(5):91-94+99.
JI J R, WU S L, CHEN Y, et al. Study on the preparation of reactive powder concrete with electrolytic manganese residue[J]. China Concreteand Cement Products, 2021(5): 91-94+99 (in Chinese).
[5] 卢梦,秦松岩.铁矿石脱硫技术研究现状[J].天津理工大学学报,2021,37(4):54-57.
LU M, QIN S Y. Research status of iron ore desulfurization technology[J]. Journalof Tianjin Universityof Technology, 2021, 37(4): 54-57 (in Chinese).
[6] 王志超,曾鸣,张辰,等.煤矸石砖烧结固硫的实验研究[J].环境科学与技术,2021,44(8):24-29.
WANG Z C, ZENG M, ZHANG C, et al. Experimental study of sulfur-fixation in coal cangue brick sintering[J]. Environmental Science & Technology, 2021, 44(8): 24-29 (in Chinese).
[7] 章佳豪.白云石铝热原位脱硫的理论及实验研究[D].昆明:昆明理工大学,2021:8.
ZHANG J H. Theoretical and experimental study on dolomite aluminothermic in-situ desulfurization[D]. Kunming: Kunming University of Science and Technology, 2021: 8 (in Chinese).
[8] 白明,陈畅,王宇斌.煅烧化工废石膏对复合脱硫建筑石膏物理力学性能的影响[J].化工矿物与加工,2020,49(3):45-47.
BAI M, CHEN C, WANG Y B. Effect of calcined chemical waste gypsum on physical and mechanical properties of desulphurized building gypsum composites[J]. Industrial Minerals& Processing, 2020, 49(3): 45-47 (in Chinese).
[9] 闫友静,张贺,于世峰.脱硫石膏煅烧工艺及煅烧设备浅析[J].新型建筑材料,2018,45(2):100-102.
YAN Y J, ZHANG H, YU S F. Discussion on FGD gypsum calcination process and calcinationequipment[J]. New Building Materials, 2018, 45(2): 100-102 (in Chinese).
[10] 李扬涛,李刚,汤骅,等.基于正交试验分析的脱硫石膏煅烧工艺优化[J].非金属矿,2017,40(4):36-39.
LI Y T, LI G, TANG H, et al. Calcination process optimization of gypsum based on orthogonal experimental analysis[J]. Non-Metallic Mines, 2017, 40(4): 36-39 (in Chinese).
[11] 赵占冲,史谊峰,祝星,等.含砷石膏渣还原分解行为及砷迁移规律[J].中国有色金属学报,2017,27(1):187-197.
ZHAO Z C, SHI Y F, ZHU X, et al. Reductive decomposition behavior of arsenic bearing gypsum sludge with coal and arsenic migration rule[J]. The Chinese Journal of Nonferrous Metals, 2017, 27(1): 187-197 (in Chinese).
[12] 苏航,左海滨,赵骏.石膏在高温下的分解脱硫研究[J].无机盐工业,2019,51(7):68-73.
SU H, ZUO H B, ZHAO J. Desulphurization of gypsum at high temperature[J]. Inorganic Chemicals Industry, 2019, 51(7): 68-73 (in Chinese).
[13] 徐悦,林强,李建锡,等.磷石膏炭热分解的热动力学研究[J].硅酸盐通报,2017,36(3):839-845.
XU Y, LIN Q, LI J X, et al. Thermal and kinetic study on decomposition of phosphogypsum by carbon[J]. Bulletinofthe Chinese Ceramic Society, 2017, 36(3): 839-845 (in Chinese).
[14] 林明跃,崔葵馨,肖飞,等.电解锰压滤渣高温脱硫活化制备水泥混合材的研究[J].硅酸盐通报,2015,34(3):688-693.
LIN M Y, CUI K X, XIAO F, et al. Research on preparation of cement additivesfromelectrolytic manganese slag through high-temperature desulfurization and activation[J]. Bulletin of the Chinese Ceramic Society, 2015, 34(3): 688-693 (in Chinese).
[15] 熊玉路,徐子豪,李英杰,等.惰性气氛下电解锰渣高温还原焙烧脱硫[J].化工进展,2021,40(s1):319-325.
XIONG Y L, XU Z H, LI Y J, et al. Removal of sulfur from electrolytic manganese slag by high-temperature reduction roasting in an inert atmosphere[J]. Chemical Industry and Engineering Progress, 2021, 40(s1): 319-325 (in Chinese).
[16] 张海燕,杨飞豹.高温煅烧电解锰渣资源化利用途径探究[J].节能与环保,2021(9):77-78.
ZHANG H Y, YANG F B. The resource utilization of high temperature calcined electrolytic manganese slag[J]. Energy Conservation and Environmental Protection, 2021(9): 77-78 (in Chinese).
[17] 黄文凤,杨红梅,章慧.电解锰渣煅烧脱硫制硫酸锰资源化技术分析[J].中国锰业,2021,39(4):34-37.
HUANG W F, YANG H M, ZHANG H. An analysis on the resource utilization technology of producing manganese sulfate by calcination and desulfurization of electrolytic manganese slag[J]. China Manganese Industry, 2021, 39(4): 34-37 (in Chinese).
[18] 天津水泥工业设计研究院有限公司.水泥原料易磨性试验方法:GB/T 26567—2011[S].北京:中国建筑工业出版社,2011.
Tianjin Cement Industry Design and Research Institute Co., Ltd. Test method for grindability of cement raw materials: GB/T 26567—2011[S]. Beijing: China Construction Industry Press, 2011 (in Chinese).[19] 周丽娜,周亮亮.CaSO₄热分解反应机理的研究进展[J].化工中间体,2013,10(5):29-32.
ZHOU L N, ZHOU L L. Study process of calcium sulfate thermal decomposition reactionmechanism[J]. Chemical Intermediates, 2013, 10(5): 29-32 (in Chinese).
[20] 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,2004,24(6):889-892.
XIAO H P, ZHOU J H, CAO X Y, et al. Experimental study of decomosition behavior of CaSO₄ in different atmospheres[J]. Power Engineering, 2004,24(6): 889-892 (in Chinese).
[21] LIU H, KATAGIRI S, OKAZAKI K. Decomposition behavior and mechanism of calcium sulfate under the condition of O₂/CO₂ pulverized coal combustion[J]. Chemical Engineering Communications, 2001, 187(1): 199-214.