电石渣制备高附加值碳酸钙的研究进展

doi:10.16085/j.issn.1000-6613.2017.01.047

摘要/Abstract

摘要： 电石渣制备碳酸钙可实现电石渣的高附加值利用，是实现电石行业可持续发展的有效途径。本文总结了电石渣制备碳酸钙的方法，着重介绍了电石渣中钙的提取和碳化两个主要工艺过程。综述了电石渣在制备轻质碳酸钙、纳米碳酸钙及其表面改性和晶型控制方面的研究进展。分析认为，氯化铵浸取CO₂碳化工艺易于实现浸取剂的循环利用，同时又能利用废气中的CO₂，具有较大的利用潜能和广阔前景。在电石渣制备碳酸钙的过程中，可以同时实现纳米碳酸钙的表面改性，并通过控制碳化温度、加入添加剂等实现晶型控制，制得不同晶型和形状的碳酸钙产品。电石渣资源化应用制备碳酸钙，呈现出从低附加值向高附加值发展的趋势。未来电石渣资源化利用制备碳酸钙应进一步完善循环工艺，并深入进行碳酸钙的超细化、表面改性化和晶型控制研究。

关键词: 电石渣, 资源化, 碳酸钙, 循环工艺, 晶型控制

Abstract: Preparation of calcium carbonate can achieve high value-added utilization of carbide slag,which is important to the sustainable development of chemical engineering of carbide. Preparation method,especially the process of leaching and carbonation were introduced. The progress in producing calcium carbonate with carbide slag as well as its surface modification and crystal controlling were reviewed. In leaching-carbonization method,ammonium chloride acting as leaching agent is recyclable,CO₂ from waste gas can be used as carbonation agent,which is considered to have great potential and prospects. In preparation of calcium carbonate,surface modification of nano-calcium carbonate can be made as well. Calcium carbonate with different crystals and amorphous can be achieved through crystal control. Utilization of carbide slag in preparation of calcium carbonate shows the trend of elevation of added value. Study in the future should focus on the improving of circulative technic and deepen the study on ultra-fining,surface modification and crystal controlling of calcium carbonate in the utilization of carbide slag.

Key words: carbide slag, resource utilization, calcium carbonate, circulative technic, crystal control

中图分类号:

TQ09

郭琳琳, 范小振, 张文育, 张翠华, 李煦. 电石渣制备高附加值碳酸钙的研究进展[J]. 化工进展, 2017, 36(01): 364-371.

GUO Linlin, FAN Xiaozhen, ZHANG Wenyu, ZHANG Cuihua, LI Xu. Research progress on preparation of calcium carbonate with carbide slag[J]. Chemical Industry and Engineering Progree, 2017, 36(01): 364-371.

参考文献

[1] 包先法. 浅析资源化利用电石渣的途径和发展趋势[J]. 中国资源综合利用,2008(4):33-36. BAO X F. Analysis on utilization of carbide slag and its development trend[J]. China Resources Comprehensive Utilization,2008(4):33-36.
[2] 曹建尉,王志,任丽会,等. 化工冶金固废资源化中的"减法型"与"加法型"工艺[J]. 工程研究:跨学科视野中的工程,2015,7(3):180-188. CAO J W,WANG Z,REN L H,et al. "Addition" and "Subtraction" processes in the chemical and metallurgical solid waste recycling[J]. Journal of Engineering Studies,2015,7(3):180-188.
[3] DAS B,PRAKASH S,REDDY P S R,et al. An overview of utilization of slag and sludge from steel industries[J]. Resources,Conservation and Recycling,2007,50(1):40-57.
[4] 时婷,王新刚,巫建锋,等. 磷石膏脱硫钙渣制备轻质碳酸钙[J]. 化工进展,2015,34(1):178-182. SHI T,WANG X G,WU J F,et al. Preparation of light calcium carbonate from phosphorus gypsum desulfurization slag[J]. Chemical Industry and Engineering Progress,2015,34(1):178-182.
[5] FAN J J,CAO D G,JING Z Z,et al. Synthesis and microstructure analysis of autoclaved aerated concrete with carbide slag addition[J]. Journal of Wuhan University of Technology(Materials Science Edition),2014,29(5):1005-1010.
[6] LI Y J,SU M Y,XIE X,et al. CO₂ capture performance of synthetic sorbent prepared from carbide slag and aluminum nitrate hydrate by combustion synthesis[J]. Applied Energy,2015,145:60-68.
[7] LI Y J,WANG W J,CHENG X X,et al. Simultaneous CO₂/HCl removal using carbide slag in repetitive adsorption/desorption cycles[J]. Fuel,2015,142:21-27.
[8] CAO J X,LIU F,LIN Q,et al. Hydrothermal synthesis of xonotlite from carbide slag[J]. Progress in Natural Science,2008,18(9):1147-1153.
[9] WANG Y Q,LI Y C,YUAN A,et al. Preparation of calcium sulfate whiskers by carbide slag through hydrothermal method[J]. Crystal Research and Technology,2014,49(10):800-807.
[10] 颜鑫. 电石渣生产纳米碳酸钙的工艺研究[J]. 化工科技,2007(5):70-72. YAN X. Study on the technology of producing nano-CaCO₃ from carbide mud residue[J]. Science and Technology in Chemical Industry,2007(5):70-72.
[11] 刘飞,祝博,李静,等. 改性工艺对电石渣乳液活性的影响[J]. 化工进展,2010,29(1):34-38. LIU F,ZHU B,LI J,et al. Effect of modification process on emulsion activity of carbide slag[J]. Chemical Industry and Engineering Progress,2010,29(1):34-38.
[12] 袁可,尹应武,谢增勇,等. 利用电石渣制备球形碳酸钙的新工艺[J]. 硅酸盐通报,2008,27(3):597-600. YUAN K,YIN Y W,XIE Z Y,et al. New technology for preparing of spherical calcium carbonate from calcium carbide residue[J]. Bulletin of the Chinese Ceramic Society,2008,27(3):597-600.
[13] 尹应武,袁可,冯天瀚,等. 微细碳酸钙制备工艺:101293663B[P]. 2011-05-25. YIN Y W,YUAN K,FENG T H,et al. Preparation technology of fine calcium carbonate:101293663B[P]. 2011-05-25.
[14] 周密,董卫龙,钱欣. 一种用电石渣制备轻质碳酸钙的方法:102992373 B[P]. 2015-01-28. ZHOU M,DONG W L,QIAN X. A method of preparation of light calcium carbonate with carbide slag:102992373 B[P]. 2015-01-28.
[15] 郭俊文,王俊中,孙炜岩. 利用电石渣和碳酸钠制备轻质碳酸钙的研究[J]. 合成材料老化与应用,2015,44(3):85-88. GUO J W,WANG J Z,SUN W Y. Research on preparation of light calcium carbonate from carbide slag and sodium carbonate[J]. Synthetic Materials Aging and Application,2015,44(3):85-88.
[16] HAN Y S,HADIKO G,FUJI M,et al. Effect of flow rate and CO₂ content on the phase and morphology of CaCO₃ prepared by bubbling method[J]. Journal of Crystal Growth,2005,276(3):541-548.
[17] 李东霞,王会昌,武建国. 利用电石渣和模拟烟道气生产纳米碳酸钙的实验室研究[J]. 中国氯碱,2011(7):44-45. LI D X,WANG H C,WU J G. Research of using calcium carbide slag and simulation flue gas to produce nano calcium carbonate[J]. China Chlor-Alkali,2011(7):44-45.
[18] 张宏,刘跃进. 电石渣制备纳米碳酸钙的研究[J]. 天津化工,2005,19(4):25-27. ZHANG H,LIU Y J. Preparation of nanometer calcium carbonate by calcium carbide residue[J]. Tianjin Chemical Industry,2005,19(4):25-27.
[19] 冯冬梅,刘渊,汤升亮,等. 电石渣制备轻质碳酸钙循环工艺条件的优化[J]. 现代化工,2014,34(5):117-121. FENG D M,LIU Y,TANG S L,et al. Optimization of recycling process for light calcium carbonate produced from calcium carbide residue[J]. Modern Chemical Industry,2014,34(5):117-121.
[20] 刘润静,李锐,胡永琪,等. 电石渣和烟道气为原料生产碳酸钙[J]. 无机盐工业,2013,45(2):50-52. LIU R J,LI R,HU Y Q,et al. Preparation of calcium carbonate from calcium carbide residue and flue gas[J]. Inorganic Chemicals Industry,2013,45(2):50-52.
[21] 韦筠寰. 电石渣在酸性废水治理中的应用[J]. 化工进展,2003,22(4):410-412. WEI J H. Application of calcium carbide sediment in the treatment of acidity waste water[J]. Chemical Industry and Engineering Progress,2003,22(4):410-412.
[22] 易争明,李群生. 烟道气脱硫新工艺[J]. 化工进展,2007,26(10):1505-1507. YI Z M,LI Q S. New process of flue gas desulfurization[J]. Chemical Industry and Engineering Progress,2007,26(10):1505-1507.
[23] LIU C T,LI Y J,SUN R Y,et al. Cyclic CO₂ capture of carbide slag modified by pyroligneous acid in calcium looping cycles[J]. Asia-Pacific Journal of Chemical Engineering,2014,9(5):678-685.
[24] SUN J,LIU W Q,HU Y C,et al. Enhanced performance of extruded-spheronized carbide slag pellets for high temperature CO₂ capture[J]. Chemical Engineering Journal,2016,285:293-303.
[25] SAID A,MATTILIA H P,JARVINEN M,et al. Production of precipitated calcium carbonate (PCC) from steelmaking slag for fixation of CO₂[J]. Applied Energy,2013,112:765-771.
[26] 潘丹萍,郭彦鹏,陈浩,等. 铵基循环碳酸化固定CO₂[J]. 化工学报,2013,64(6):2232-2239. PAN D P,GUO Y P,CHEN H,et al. CO₂ carbonation sequestration by cycling of ammonium[J]. CIESC Journal,2013,64(6):2232-2239.
[27] 舒均杰. 电石渣制备轻质碳酸钙的研究[J]. 广东化工,2012,39(14):60-62. SHU J J. Study on Preparation of light calcium carbonate with carbide slag[J]. Guangdong Chemical Industry,2012,39(14):60-62.
[28] 田飞宇,牟豪杰,顾卫荣. 电石渣两步法制备轻质碳酸钙的研究[J]. 现代化工,2013,33(4):95-99. TIAN F Y,MU H J,GU W R. Preparation of light calcium carbonate from carbide slag by two-step method[J]. Modern Chemical Industry,2013,33(4):95-99.
[29] 侯清麟,刘奇龙,段利艳. 株洲清水塘地区工业废弃物的循环利用技术[J]. 化工进展,2009,28(2):349-353. HOU Q L,LIU Q L,DUAN L Y. Recycling and disposal of industrial waste in Qingshui Tang area of Zhuzhou[J]. Chemical Industry and Engineering Progress,2009,28(2):349-353.
[30] SAHEBIAN S,ZEBARJAD S M,KHAKI J V,et al. The effect of nano-sized calcium carbonate on thermodynamic parameters of HDPE[J]. Journal of Materials Processing Technology,2009,209(3):1310-1317.
[31] 童忠良. 中国纳米碳酸钙工业生产现状及应用[J]. 化工进展,2003,22(4):372-375. TONG Z L. Production situation of nano-calcium carbonate and its application process in China[J]. Chemical Industry and Engineering Progress,2003,22(4):372-375.
[32] 马空军,包文忠,赵文新,等. 超声法以电石渣制备纳米碳酸钙的方法:102515237A[P]. 2012-06-27. MA K J,BAO W Z,ZHAO W X,et al. A method of preparation of nano-calcium carbonate with carbide slag by ultrasonic method:102515237A[P]. 2012-06-27.
[33] 吴琦文,施利毅,张仲燕. 利用电石渣制备纳米碳酸钙的研究[J]. 上海大学学报(自然科学版),2002,8(3):247-250. WU Q W,SHI L Y,ZHANG Z Y. Preparation of nanometer calcium carbonate particles by calcium carbide residue[J]. Journal of Shanghai University(Natural Science),2002,8(3):247-250.
[34] 范广能,陈红,胡坤宏,等. 电石渣制备超细碳酸钙的工艺研究[J]. 安徽化工,2005(6):8-10. FAN G N,CHEN H,HU K H,et al. Preparation of superfine calcium carbonate particles from calcium carbide residue[J]. Anhui Chemical Industry,2005(6):8-10.
[35] 林倩,王晓芳,曹建新,等. 电石渣制备纳米碳酸钙的初步研究[J]. 贵州化工,2006,31(3):5-7. LIN Q,WANG X F,CAO J X,et al. Preparation of nano-sized calcium carbonate from calcium carbide residue[J]. Guizhou Chemical Industry,2006,31(3):5-7.
[36] 范广能,陈红,胡坤宏,等. 电石渣制备纳米晶碳酸钙的液相法工艺研究[J]. 合肥工业大学学报(自然科学版),2006,29(3):264-266,271. FAN G N,CHEN H,HU K H,et al. Preparation of calcium carbonate nano-crystallites from the calcium carbide residue by the liquid-state method[J]. Journal of Hefei University of Technology (Natural Science),2006,29(3):264-266,271.
[37] 闫琨,周康根. 利用电石渣液相法制备纳米碳酸钙[J]. 化工环保,2008,28(6):535-537. YAN K,ZHOU K G. Preparation of nano calcium carbonate from calcium carbide residue by liquid phase process[J]. Environmental Protection of Chemical Industry,2008,28(6):535-537.
[38] 张果龙,刘跃进,罗云峰,等. 电石渣制备立方体晶型纳米碳酸钙研究[J]. 河北化工,2008,31(6):14-16. ZHANG G L,LIU Y J,LUO Y F,et al. Study on preparation cubical nanometer calcium carbonate by calcium carbide residue[J]. Hebei Chemical Industry,2008,31(6):14-16.
[39] 高传平,曹建新,杨林,等. 盐酸处理电石渣制备球形超细CaCO₃的研究[J]. 贵州大学学报(自然科学版),2009,26(3):90-94. GAO C P,CAO J X,YANG L,et al. A study on preparation of spherical and ultrafine calcium carbonate from carbide slag treated by HCl[J]. Journal of Guizhou University (Natural Sciences),2009,26(3):90-94.
[40] 刘飞,袁铭鸿,曹建新. 利用电石渣制备碳酸钙晶须的初步研究[J]. 贵州大学学报(自然科学版),2010,27(2):126-128. LIU F,YUAN M H,CAO J X. Primary research of calcium carbonate whisker prepared from carbide slag[J]. Journal of Guizhou University (Natural Sciences),2010,27(2):126-128.
[41] 曾蓉,乔秀文,齐誉,等. 针状纳米活性碳酸钙合成改性一体化的研究[J]. 石河子大学学报(自然科学版),2013,31(6):752-758. ZENG R,QIAO X W,QI Y,et al. Study on integration of preparation and modification of acicular nanometer active calcium carbonate[J]. Journal of Shihezi University (Natural Sciences),2013,31(6):752-758.
[42] 张爱华,朱敏,关云山,等. 氯化铵处理电石渣制备纳米碳酸钙的实验研究[J]. 科学技术与工程,2013,13(10):2880-2883. ZHANG A H,ZHU M,GUAN Y S,et al. Experimental study on preparation of nano-sized calcium carbonate from carbide slag treated by ammonium chloride[J]. Science Technology and Engineering,2013,13(10):2880-2883.
[43] 陈红,范广能,胡坤宏,等. 电石渣制备超细碳酸钙过程中的表面改性研究[J]. 安徽化工,2006(1):37-39. CHEN H,FAN G N,HU K H,et al. Surface modification of ultrafine calcium carbonate particles prepared from calcium carbide residue[J]. Anhui Chemical Industry,2006(1):37-39.
[44] 王志,曹建尉,任丽会,等. 一种电石渣制备微细碳酸钙的表面改性方法:201410466786.6[P]. 2014-12-24. WANG Z,CAO J W,REN L H,et al. A method of surface modification of ultrafine calcium carbonate prepared from calcium carbide residue:201410466786.6[P]. 2014-12-24.
[45] 王向科,尹荔松. 不同形态纳米碳酸钙制备及应用的研究进展[J]. 硅酸盐通报,2014,33(5):1103-1106. WANG X K,YIN L S. Research progress on the preparation and application of different morphology nano calcium carbonate[J]. Bulletin of the Chinese Ceramic Society,2014,33(5):1103-1106.
[46] YU J G,LEI M,CHENG B,et al. Effects of PAA additive and temperature on morphology of calcium carbonate particles[J]. Journal of Solid State Chemistry,2004,177(3):681-689.
[47] ALTAY E,SHAHWAN T,TANOGLU M. Morphosynthesis of CaCO₃ at different reaction temperatures and the effects of PDDA,CTAB,and EDTA on the particle morphology and polymorph stability[J]. Powder Technology,2007,178(3):194-202.
[48] CHEN J,XIANG L. Controllable synthesis of calcium carbonate polymorphs at different temperatures[J]. Powder Technology,2009,189(1):64-69.
[49] PRAH J,MACEK J,DRAZRC G. Precipitation of calcium carbonate from a calcium acetate and ammonium carbamate batch system[J]. Journal of Crystal Growth,2011,324(1):229-234.
[50] 卢忠远,姜彩荣,涂铭旌. 电石渣制备高白度板状碳酸钙的研究[J]. 西安交通大学学报,2004,38(9):989-990. LU Z Y,JIANG C R,TU M S. Spherical calcium carbonate prepared by calcium carbide residue[J]. Journal of Xian Jiaotong University,2004,38(9):989-990.
[51] 卢忠远,康明,姜彩荣,等. 利用电石渣制备针叶形碳酸钙的研究[J]. 功能材料,2005,36(8):1238-1241. LU Z Y,KANG M,JIANG C R,et al. Needle-like calcium carbonate synthesized by carbide residue[J]. Journal of Functional Materials,2005,36(8):1238-1241.
[52] 卢忠远,姜彩荣,王恩泽,等. 利用电石渣制备球形碳酸钙的研究[J]. 西安交通大学学报,2005,39(11):127-130. LU Z Y,JIANG C R,WANG E R,et al. Spherical calcium carbonate prepared by calcium carbide residue[J]. Journal of Xi'an Jiaotong University,2005,39(11):127-130.
[53] 曹建新,杨林,偰南杰,等. 一种电石渣制备不同晶形微细和超细碳酸钙的方法:101264920A[P]. 2008-09-17. CAO J X,YANG L,QI N J,et al. A method of preparation of fine and ultrafine calcium carbonate with different crystalline by calcium carbide residue:101264920A[P]. 2008-09-17.
[54] 偰南杰,曹建新,高传平,等. 反应温度对电石渣合成纳米碳酸钙形貌的影响[J]. 中国粉体技术,2015,21(1):22-26. QI N J,CAO J X,GAO C P,et al. Effect of reaction temperature on morphology of calcium carbonate nano-particles prepared from carbide slag[J]. China Powder Science and Technology,2015,21(1):22-26.
[55] 马俊,刘华彦,梁锦,等. 两种重要形貌的碳酸钙的可控合成及生长机理探讨[J]. 材料科学与工程学报,2011,29(2):227-232. MA J,LIU H Y,LIANG J,et al. Controllable synthesis of calcium carbonate with needle-like and cubic morphologies and the crystal growth mechanisms[J]. Journal of Materials Science & Engineering,2011,29(2):227-232.
[56] 乔叶刚. 用电石废渣制备纳米碳酸钙的研究[J]. 中国粉体技术,2005,11(1):39-41. QIAO Y G. Study on preparation of nano-sized calcium carbonate by calcium carbide waste residue[J]. China Powder Science and Technology,2005,11(1):39-41.
[57] 孙念超. 以电石渣为原料制取纳米碳酸钙的方法:201310691661.9[P]. 2014-04-23. SUN N C. A method of preparation of nano-meter calcium carbonate by carbide slag:201310691661.9[P]. 2014-04-23.
[58] HU Z S,SHAO M H,CAI Q,et al. Synthesis of needle-like aragonite from limestone in the presence of magnesium chloride[J]. Journal of Materials Processing Technology,2009,209(3):1607-1611.
[59] PARK W K,KO S J,LEE S W,et al. Effects of magnesium chloride and organic additives on the synthesis of aragonite precipitated calcium carbonate[J]. Journal of Crystal Growth,2008,310(10):2593-2601.
[60] VOGELS C,CAVALIER K,SY D,et al. Method for obtaining precipitated calcium carbonate particles of nanometric scale structure:US7708973B2[P]. 2010-05-04.