磷石膏加压碳酸化转化过程中平衡转化率分析

doi:10.11949/j.issn.0438-1157.20161290

化工学报 ›› 2017, Vol. 68 ›› Issue (3): 1155-1162.DOI: 10.11949/j.issn.0438-1157.20161290

磷石膏加压碳酸化转化过程中平衡转化率分析

包炜军^1,2, 赵红涛^1,3,4, 李会泉^1,2,4, 李松庚^3,4, 林伟刚^3,4

1 中国科学院过程工程研究所绿色过程与工程重点实验室, 北京 100190;
2 中国科学院过程工程研究所湿法冶金清洁生产技术国家工程实验室, 北京 100190;
3 中国科学院过程工程研究所多相复杂系统国家重点实验室, 北京 100190;
4 中国科学院大学, 北京 100049

收稿日期:2016-09-14 修回日期:2016-11-08 出版日期:2017-03-05 发布日期:2017-03-05
通讯作者: 李会泉,hqli@ipe.ac.cn;李松庚,sgli@ipe.ac.cn
基金资助:
国家自然科学基金项目（21300212）；国家“十二五”科技支撑计划项目（2013BAC12B02）。

Equilibrium conversion analysis of pressurized carbonation with phosphogypsum

BAO Weijun^1,2, ZHAO Hongtao^1,3,4, LI Huiquan^1,2,4, LI Songgeng^3,4, LIN Weigang^3,4

1 Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
2 National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
3 State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
4 University of Chinese Academy of Sciences, Beijing 100049, China

Received:2016-09-14 Revised:2016-11-08 Online:2017-03-05 Published:2017-03-05
Contact: 10.11949/j.issn.0438-1157.20161290
Supported by:
supported by the National Natural Science Foundation of China (21300212) and the 12th Five-Year Plan of National Science and Technology Support (2013BAC12B02).

摘要/Abstract

摘要：

围绕磷石膏加压碳酸化转化过程，首先通过实验研究了原料种类对加压碳酸化转化过程的影响，进一步采用Aspen plus 流程模拟软件深入分析了各工艺参数对磷石膏加压碳酸化过程平衡转化率的影响规律。结果表明，在加压条件下碳酸化反应均可在5 min时达到平衡，其中分析纯无水硫酸钙更容易完全转化，而二水硫酸钙及磷石膏因含有结晶水或其他杂质，使得其难以完全转化。增大初始氨水浓度、N/S（氨和原料中SO₃的摩尔比）以及适量提高反应温度与体系压力，均能有效提高磷石膏加压碳酸化反应平衡转化率。特别是在高温和加压条件下，氨与CO₂反应生成的碳酸铵盐可以通过降压闪蒸操作实现其自分解，经吸收返回用于加压碳酸化转化过程，可有效提高氨的利用率，降低硫酸铵生产成本。

关键词: 磷石膏, 二氧化碳, 加压碳酸化, 模拟, 平衡

Abstract:

Based on the process of pressurized carbonation with phosphogypsum, the effect of raw material types on carbonation conversion was experimentally studied. In addition, the influence of some operation parameters on the conversion had been analyzed by Aspen plus process simulation software. The results showed that the carbonation reaction can reach equilibrium within 5 minutes under pressured conditions, and it was much more easily for pure anhydrous calcium sulfate to convert completely. However, because of containing crystal water or other impurities, it was difficult for both pure dihydrate calcium sulfate and phosphogypsum to convert completely. Besides, it was found that increasing the initial ammonia concentration, the mole ratio of added ammonia to SO₃ in the raw materials, and properly increasing the reaction temperature and system pressure can effectively improve the equilibrium carbonation conversion. Most importantly, the formed ammonium carbonate from the reaction between ammonia and CO₂ under high temperature and pressure condition is unstable when pressure decreased. Thus combing the flash operation after pressured carbonation, the formed ammonium carbonate can decompose to release ammonia and CO₂, which can further be absorbed and returned to the pressurized carbonation process. This could effectively improve the ammonia utilization rate and reduce the production cost of ammonium sulfate as well.

Key words: phosphogypsum, carbon dioxide, pressurized carbonation, simulation, equilibrium

中图分类号:

TQ110.9

包炜军, 赵红涛, 李会泉, 李松庚, 林伟刚. 磷石膏加压碳酸化转化过程中平衡转化率分析[J]. 化工学报, 2017, 68(3): 1155-1162.

BAO Weijun, ZHAO Hongtao, LI Huiquan, LI Songgeng, LIN Weigang. Equilibrium conversion analysis of pressurized carbonation with phosphogypsum[J]. CIESC Journal, 2017, 68(3): 1155-1162.

参考文献 30

[1]	HANAN T, MOHAMED C, FELIX A L, et al. Environmental impact and management of phosphogypsum[J]. Journal of Environmental Management, 2009, 90:2377-2386.
[2]	薄瀛, 袁铭, 刘安强. 我国磷肥产业现状、问题及发展建议[J]. 磷肥与复肥, 2016, 31(4):16-19. BO Y, YUAN M, LIU A Q. Status, problems and development suggestion of phosphate fertilizer industry in China[J]. Phosphate & Compound Fertilizer, 2016, 31(4):16-19.
[3]	王怀利, 高璐阳, 陈宏坤, 等. 我国磷石膏综合利用现状分析与展望[J]. 磷肥与复肥, 2016, 31(4):32-34. WANG H L, GAO L Y, CHEN H K, et al. Analysis and prospect of phosphogypsum comprehensive utilization in China[J]. Phosphate & Compound Fertilizer, 2016, 31(4):32-34.
[4]	孙志立. 中国磷石膏资源化利用的展望与思考[J]. 硫酸工业, 2016, 1:55-58. SUN Z L. Outlook and thinking of phosphogypsum comprehensive utilization in China[J]. Sulphuric Acid Industry, 2016, 1:55-58.
[5]	SHEN W, GAN G, DONG R. Utilization of solidified phosphogypsum as portland cement retarder[J]. Journal of Material Cycles and Waste Management, 2012, 14(3):228-233.
[6]	赵建国, 张应虎, 张宗凡, 等. 磷石膏转化制硫酸铵的发展前景分析[J]. 无机盐工业, 2013, 45(7):1-4. ZHAO J G, ZHANG Y H, ZHANG Z F, et al. Development prospect of preparation of ammonium sulfate from phosphogypsum[J]. Inorganic Chemicals Industry, 2013, 45(7):1-4.
[7]	谢和平, 谢凌志, 王昱飞, 等. 全球二氧化碳减排不应是CCS,应是CCU[J]. 四川大学学报(工程科学版), 2012, 44(4):1-5. XIE H P, XIE L Z, WANG Y F, et al. CCU:a more feasible and economic strategy than CCS for reducing CO2 emissions[J]. Journal of Sichuan University (Engineering Science Edition), 2012, 44(4):1-5.
[8]	XIE H P, YUE H R, ZHU J H, et al. Scientific and engineering progress in CO2 mineralization using industrial waste and natural minerals[J]. Engineering, 2015, 1(1):150-157.
[9]	MATTILA H P, ZEVENHOVEN R. Mineral carbonation of phosphogypsum waste for production of useful carbonate and sulfate salts[J]. Frontiers in Energy Research, 2015, DOI:10.3389/fenrg. 2015.00048
[10]	朱家骅, 谢和平, 夏素兰, 等. 烟气二氧化碳与磷石膏转化一步法节能节水清洁工艺:CN 201210223218.4[P]. 2014-10-15. ZHU J H, XIE H P, XIA S L, et al. One step clean process to convert flue gas CO2 by phosphogypsum with low energy and water cost:CN 201210223218.4[P]. 2014-10-15.
[11]	李季, 周加贝, 朱家骅, 等. 磷石膏强化氨法CO2捕集机理与模型[J]. 化工学报, 2015, 66(8):3218-3224. LI J, ZHOU J B, ZHU J H, et al. Mechanism and model of ammonia-based carbon dioxide trapping enhanced by gypsum particles[J]. CIESC Journal, 2015, 66(8):3218-3224.
[12]	LEE M G, JANG Y N, RYU K W, et al. Mineral carbonation of flue gas desulfurization gypsum for CO2 sequestration[J]. Energy, 2012, 47(1):370-377.
[13]	SONG K S, JANG Y N, KIM W, et al. Precipitation of calcium carbonate during direct aqueous carbonation of flue gas desulfurization gypsum[J]. Chemical Engineering Journal, 2012, 213:251-258.
[14]	SONG K S, JANG Y N, KIM W, et al. Factors affecting the precipitation of pure calcium carbonate during the direct aqueous carbonation of flue gas desulfurization[J]. Energy, 2014, 65:527-532.
[15]	SONG K S, KIM W, BANG J H, et al. Polymorphs of pure calcium carbonate prepared by the mineral carbonation of flue gas desulfurization gypsum[J]. Materials & Design, 2015, 83:308-313.
[16]	DING W J, YANG H M, OUYANG J. Mineral carbonation of a desulfurization residue for CO2 sequestration[J]. RSC Advances, 2015, 5:67184-67194.
[17]	AZDARPOUR A, ASADULLAH M, JUNIN R, et al. Direct carbonation of red gypsum to produce solid carbonates[J]. Fuel Processing Technology, 2014, 126:429-434.
[18]	AZDARPOUR A, ASADULLAH M, MOHAMMADIAN E, et al. Mineral carbonation of red gypsum via pH-swing process:effect of CO2 pressure on the efficiency and products characteristics[J]. Chemical Engineering Journal, 2015, 264:425-436.
[19]	AZDARPOUR A, ASADULLAH M, JUNIN R, et al. Extraction of calcium from red gypsum for calcium carbonate production[J]. Fuel Processing Technology, 2015, 130:12-19.
[20]	RAHMANI O, TYRER M, JUNIN R. Calcite precipitation from by-product red gypsum in aqueous carbonation process[J]. RSC Advances, 2014, 4:45548-45557.
[21]	PÉREZ-MORENO S, GÁZQUEZ M J, BOLÍVAR J P. CO2 sequestration by indirect carbonation of artificial gypsum generated in the manufacture of titanium dioxide pigments[J]. Chemical Engineering Journal, 2015, 262:737-746.
[22]	CÁRDENAS-ESCUDERO C, MORALES-FLÓREZ V, PÉREZ-LÓPEZ R, et al. Procedure to use phosphogypsum industrial waste for mineral CO2 sequestration[J]. Journal of Hazardous Materials, 2011, 196:431-435.
[23]	CONTRERAS M, PÉREZ-LÓPEZ R, GÁZQUEZ M J, et al. Fractionation and fluxes of metals and radionuclides during the recycling process of phosphogypsum wastes applied to mineral CO2 sequestration[J]. Waste Management, 2015, 45:412-419.
[24]	ZHAO H T, LI H Q, BAO W J, et al. Experimental study of enhanced phosphogypsum carbonation with ammonia under increased CO2 pressure[J]. Journal of CO2 Utilization, 2015, 11:10-19.
[25]	何思祺, 孙红娟, 彭同江, 等. 磷石膏碳酸化固定二氧化碳的实验研究[J]. 岩石矿物学杂志, 2013, 32(6):899-904. HE S Q, SUN H J, PENG T J, et al. A study of carbon dioxide sequestration by phosphogypsum carbonation[J]. Acta Petrologica Et Mineralogica, 2013, 32(6):899-904.
[26]	包炜军, 李会泉, 李松庚, 等. 一种氨介质体系强化钙基固废矿化固定二氧化碳的方法:CN 201310057123.4[P]. 2015-11-18. BAO W J, LI H Q, LI S G, et al. A method for enhancing CO2 mineral sequestration with calcium-based solid waste:CN 201310057123.4[P]. 2015-11-18.
[27]	MINDRUP E M, SCHNEIDER W F. Computational comparison of the reactions of substituted amines with CO2[J]. ChemSusChem, 2010, 3:931-938.
[28]	SHAKERIAN F, KIM K H, SZULEJKO J E, et al. A comparative review between amines and ammonia as sorptive media for post-combustion CO2 capture[J]. Applied Energy, 2015, 148:10-22.
[29]	WANG W L, ZENG D W, CHEN Q Y, et al. Experimental determination and modeling of gypsum and insoluble anhydrite solubility in the system CaSO4-H2SO4-H2O[J]. Chemical Engineering Science, 2013, 101:120-129.
[30]	QI G J, WANG S J, LU W Y, et al. Vapor-liquid equilibrium of CO2 in NH3-CO2-SO2-H2O system[J]. Fluid Phase Equilibria, 2015, 386:47-55.

磷石膏加压碳酸化转化过程中平衡转化率分析

Equilibrium conversion analysis of pressurized carbonation with phosphogypsum

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