高盐脱硫废水水泥化固定技术的研究现状与发展

doi:10.16085/j.issn.1000-6613.2018-2422

摘要/Abstract

摘要：

脱硫废水作为电厂的末端废水，产生背景复杂，水质水量特征受燃煤、石灰石以及脱硫系统运行等多因素影响，处理难度大。本文从脱硫废水污染物成分示踪角度介绍了脱硫废水的性质和产生背景，归纳了当前主流的脱硫废水零排放处理技术，将其分解为预处理、浓缩减量以及转移与固化3个单元：预处理主要是双碱法，浓缩减量分为膜浓缩和蒸发浓缩两大类，转移与固化主要包括蒸发结晶、旁路蒸发和固定/稳定化等技术。结合目前脱硫废水零排放进展，提出了一种水泥固定/稳定化脱硫废水工艺，综述了水泥固化脱硫废水的研究进展，同时对水泥行业中影响氯离子固定的各项因素进行了总结，水泥固定/稳定化脱硫废水技术发展前景广阔，但需要从提升固化体性能角度开展更多研究。

关键词: 脱硫废水, 零排放, 浓缩减量, 旁路蒸发, 水泥固定化, 氯离子

Abstract:

As the terminal wastewater of power plant, desulfurization wastewater has complex background. The water quality and quantity characteristics are affected by coal, limestone and the operation of desulfurization system, etc. The characteristics of desulfurization wastewater are introduced from the aspects of the tracer of pollutant composition. At present, the common zero liquid discharge treatment technologies of desulfurization wastewater can be divided into three units: pretreatment, concentration and reduction, transfer and solidification. Pretreatment mainly refers to double alkali method. Concentration reduction can be divided into two categories: membrane concentration and evaporation concentration. Transfer and solidification mainly include evaporation crystallization, bypass evaporation and fixation/stabilization. In consideration of the progress of zero liquid discharge treatment technologies of desulfurization wastewater at present, the paper proposed a solidification/stabilization of desulfurization wastewater with cement, and summarized the factors affecting solidification of chloride ion in cement industry. The solidification/stabilization of desulfurization wastewater with cement has broad development prospects, but more research is needed to improve the performance of solidified blocks.

Key words: desulfurization wastewater, zero liquid discharge, concentration reduction, bypass evaporation, solidification with cement, chloride ion

中图分类号:

X701.3

马双忱,陈嘉宁,万忠诚,向亚军,张净瑞,曲保忠. 高盐脱硫废水水泥化固定技术的研究现状与发展[J]. 化工进展, 2019, 38(9): 4275-4283.

Shuangchen MA,Jianing CHEN,Zhongcheng WAN,Yajun XIANG,Jingrui ZHANG,Baozhong QU. Research status and development on solidification for high-salt desulfurization wastewater with cement[J]. Chemical Industry and Engineering Progress, 2019, 38(9): 4275-4283.

图/表 5

参考文献 46

10	Shuangchen MA , ZHU Sijie , ZHAO Xinghui , et al . Experimental study on the influences of recycled high salt water on desulfurization efficiency[J]. Chemical Industry and Engineering Progress, 2016, 35(s1): 304-310.
11	CORDOBA P . Status of flue gas desulfurization (FGD) systems from coal-fired power plants: overview of the physic-chemical control processes of wet limestone FGDs[J]. Fuel, 2015, 144: 274-286.
12	刘召平 . 某电厂脱硫废水处理系统的设计与运行[J]. 中国给水排水, 2011, 27(2): 65-67.
	LIU Zhaoping . Design and operation of FGD wastewater treatment system in a power plant[J]. China Water & Wastewater, 2011, 27(2): 65-67.
13	陈泽峰, 冯铁玲 . 电厂脱硫废水处理[J]. 工业水处理, 2006, 26(3): 91-93.
	CHEN Zefeng , FENG Tieling . Treatment of wastewater from FGD in power plants[J]. Industrial Water Treatment, 2006, 26(3): 91-93.
14	JIA Fei , WANG Jianlong . Treatment of flue gas desulfurization wastewater with near-zero liquid discharge by nanofiltration-membrane distillation process[J]. Separation Science & Technology, 2018, 53(1): 146-153.
15	刘亚鹏, 王金磊, 陈景硕, 等 . 火电厂脱硫废水预处理工艺优化及管式微滤膜实验研究[J]. 中国电力, 2016, 49(2): 153-158.
	LIU Yapeng , WANG Jinlei , CHEN Jingshuo , et al . Optimization of FGD wastewater pretreatment technique for thermal power plant and test studies on tubular crossflow microfiltration process[J]. Electric Power, 2016, 49(2): 153-158.
16	袁国全, 张江涛, 潘振波, 等 . 脱硫废水预处理系统软化设备的调试和分析[J]. 热力发电, 2011, 40(2): 76-78.
	YUAN Guoquan , ZHANG Jiangtao , PAN Zhenbo , et al . Commission debugging and analysis of the softening equipment in wastewater pretreatment system of FGD[J]. Thermal Power Generation, 2011, 40(2): 76-78.
17	连坤宙, 胡特立, 王永前, 等 . 燃煤电厂脱硫废水预处理装置设计与中试研究[J]. 中国电力, 2018, 51(6): 166-171.
1	马双忱, 于伟静, 贾绍广, 等 . 燃煤电厂脱硫废水处理技术研究与应用进展[J]. 化工进展, 2016, 35(1): 255-262.
	Shuangchen MA , YU Weijing , JIA Shaoguang , et al . Research and application progresses of flue gas desulfurization(FGD) wastewater treatment technologies in coal-fired plants[J]. Chemical Industry and Engineering Progress, 2016, 35(1): 255-262.
17	LIAN Kunzhou , HU Teli , WANG Yongqian , et al . Pretreatment device design and pilot application of desulfurization wastewater in coal-fired power plants[J]. Electric Power, 2018, 51(6): 166-171.
18	常亮, 欧阳白薇, 冯延林, 等 . 一种石灰石-石膏湿法烟气脱硫废水的软化处理方法: CN201710041317.3[P]. 2018-03-13.
	CHANG Liang , OUYANG Baiwei , FENG Yanlin , et al . A softening method for flue gas desulfurization wastewater from limestone gypsum wet process: CN201710041317.3[P]. 2018-03-13.
19	徐小生 . 基于纳滤技术深度处理燃煤电厂脱硫废水试验研究[D]. 邯郸: 河北工程大学, 2017.
	XU Xiaosheng . Experimental study on degradation of desulphurization wastewater from coal-fired power plant based on nanofiltration technology[D]. Handan: Hebei University of Engineering, 2017.
20	朱小强 . 膜分离技术在水处理中应用研究进展[J]. 污染防治技术, 2014(5): 42-44.
	ZHU Xiaoqiang . Progress of the application of membrane separation technology in wastewater treatment[J]. Pollution Control Technology, 2014(5): 42-44.
21	COB S S . Towards zero liquid discharge in the presence of silica: stable 98% recovery in nanofiltration and reverse osmosis[J]. Separation & Purification Technology, 2015, 140: 23-31.
22	徐光平, 李竹梅, 王建强, 等 . 膜蒸馏技术在电厂脱硫废水处理领域的中试应用[J]. 广东化工, 2018(5): 184-186.
	XU Guangping , LI Zhumei , WANG Jianqiang , et al . Pilot application of membrane distillation technology on FGD wastewater treatment in power plant[J]. Guangdong Chemical, 2008(5):184-186.
23	LI Xinyang , ZHANG Liwei , WANG Chengwen . Review of disposal of concentrate streams from nanofiltration (NF) or reverse osmosis (RO) membrane process[J]. Advanced Materials Research, 2012, 518-523: 3470-3475.
24	ALI A A M, ALI A K E . Robust model-based control of a tubular reverse-osmosis desalination unit[J]. Desalination, 2010, 255(1): 129-136.
25	万忠诚, 乔永成, 张鹏远, 等 . 燃煤电厂低成本脱硫废水零排放工艺研究[C]// 2017中国环境科学学会科学与技术年会论文集(第二卷). 2017.
	WAN Zhongcheng , QIAO Yongcheng , ZHANG Pengyuan , et al . Study on zero emission process of low-cost desulfurization wastewater in coal-fired power plants[C]// Proceedings of the 2017 Annual Meeting of the Chinese Society of Environmental Sciences Science and Technology (Volume Ⅱ), 2017.
26	甄胜利, 黄志亮, 罗彬, 等 . 机械雾化蒸发塘处理煤化工浓盐水技术分析[J]. 工业用水与废水, 2017, 48(3): 32-35.
	ZHEN Shengli , Zhiliang HAUNG , LUO Bin , et al . Technical analysis of mechanical atomization evaporation pond treating high salinity wastewater of coal chemical industry[J]. Industrial Water & Wastewater, 2017, 48(3): 32-35.
27	张琳, 高丽丽, 崔磊, 等 . MVR蒸发器管内沸腾传热传质数值模拟[J]. 化工进展, 2013, 32(3): 543-548.
	ZHANG Lin , GAO Lili , CUI Lei , et al . Numerical simulation of boiling heat and mass transfer in the tube for MVR evaporator[J]. Chemical Industry and Engineering Progress, 2013, 32(3): 543-548.
28	米云龙, 蒋道利 . 制盐蒸发结晶技术简述[J]. 中国井矿盐, 2013(4): 4-7.
	MI Yunlong , JIANG Daoli . Brief introduction of the evaporation crystallization technology of salt making[J]. China Well & Rock Salt, 2013(4): 4-7.
29	任丹丹, 冯罗澍, 陈颖 . 大型燃煤电厂脱硫废水烟气利用技术研究[J]. 浙江电力, 2018, 37(3): 82-85.
	REN Dandan , FENG Luoshu , CHEN Ying . Large coal-fired power plant flue gas desulfurization wastewater utilization technology research[J]. Zhejiang Electirc Power, 2018, 37(3): 82-85.
30	刘欣颖 . 燃煤电厂脱硫废水浓缩蒸干零排放技术路线分析[J]. 内蒙古电力技术, 2016(3): 11-15.
	LIU Xinying . Routine analysis of zero emissions desulfurization wastewater concentration and evaporation technology in coal-fired plant[J]. Inner Mongolia Electric Power, 2016(3): 11-15.
2	靳晓洁 . 石灰石-石膏湿法脱硫吸收塔中氯离子问题的探讨[J]. 电力科技与环保, 2012, 29(1): 46-47.
	JIN Xiaojie . Research on excessive Cl^- of absorption tower on limestone-gypsum desulfurization[J]. Electric Power Technology & Environmental Protection, 2012, 29(1): 46-47.
3	尹连庆, 徐铮 . 氯离子对脱硫石膏脱水影响研究及机理探讨[J]. 粉煤灰, 2008, 20(3): 12-13.
	YIN Lianqing , XU Zheng . Study of effect of chlorion on dewater of desulfurized gypsum and probe into its mechanism[J]. Coal Ash China, 2008, 20(3): 12-13.
4	康梅强 . 脱硫废水烟道蒸发处理工艺系统设计与试验研究[D]. 重庆: 重庆大学, 2013.
	KANG Meiqiang . Study on flue gas desulfurization wastewater duct evaporation treatment system design and experiment[D]. Chongqing: Chongqing University, 2013.
5	马双忱, 温佳琪, 万忠诚, 等中国燃煤电厂脱硫废水处理技术研究进展及标准修订建议 [J]. 洁净煤技术, 2017, 23(4): 18-28.
	Shuangchen MA , WEN Jiaqi , WAN Zhongcheng , et al . Treatment progress and standard modification suggestion for FGD wastewater from coal-fire power plants in China[J]. Clean Coal Technology, 2017, 23(4): 18-28.
6	周臣, 谭文轶 . 脱硫废水水量计算及烟道处理技术[J]. 热力发电, 2009, 38(3): 85-87.
	ZHOU Chen , TAN Wenyi . Calculation of wastewater amount for FGD system and its zero discharge technology[J]. Thermal Power Generation, 2009, 38(3): 85-87.
31	李玉, 张乔, 王群 . 蒸发结晶工艺在火电厂脱硫废水零排放中的应用[J]. 水处理技术, 2016(11): 121-122.
	LI Yu , ZHANG Qiao , WANG Qun . Application of evaporative crystallization process in the zero discharge of desulfurization waste water in thermal power plant[J]. Technology of water treatment, 2016(11): 121-122.
32	康梅强, 邓佳佳, 陈德奇, 等 . 脱硫废水烟道蒸发零排放处理的可行性分析[J]. 土木建筑与环境工程, 2013(s1): 238-240.
	KANG Meiqiang , DENG Jiajia , CHEN Deqi , et al . Analysis on feasibility of desulfurization wastewater evaporation treatment in flu gas duct without pollution discharge[J]. Journal of Civil Architectural & Environmental Engineering, 2013(s1): 238-240.
33	崔琳, 沈鲁光, 杨敦峰, 等 . 中温烟气蒸发脱硫废水干燥过程及产物特性分析[J]. 煤炭学报, 2017, 42(7): 1877-1883.
	CUI Lin , SHEN Luguang , YANG Dunfeng , et al . Drying properties and product characteristics of desulfurization wastewater evaporation by medium-temperature flue gas[J]. Journal of China Coal Society, 2017, 42(7): 1877-1883.
34	张净瑞, 梁海山, 郑煜铭, 等 . 基于旁路烟道蒸发的脱硫废水零排放技术在火电厂的应用[J]. 环境工程, 2017, 35(10): 5-9.
	ZHANG Jingrui , LIANG Haishan , ZHENG Yuming , et al . Application of zero liquid discharge system of the desulfurization wastewater based on bypass flue evaporation system in thermal power plants[J]. Environmental Engineering, 2017, 35(10): 5-9.
35	Shuangchen MA , CHAI Jin , CHEN Gongda , et al . Research on desulfurization wastewater evaporation: present and future perspectives [J]. Renewable & Sustainable Energy Reviews, 2016, 58: 1143-1151.
36	NORTEY Y N N , ELLISON K M , MINKARA R , et al . Treatment and disposal alternative for flue gas desulfurization wastewater[C] //2015 World of Coal Ash Conference, Nashville, America, 2015. .
37	RENEW J E , HUANG C H , BURNS S E , et al . Immobilization of heavy metals by solidification/stabilization of co-disposed flue gas desulfurization brine and coal fly ash[J]. Energy & Fuels, 2016, 30(6): 5042-5051.
38	WEE T H, WONG S F , SWADDIWUDHIPONG S , et al . A prediction method for long-term chloride concentration profiles in hardened cement matrix materials[J]. ACI Materials Journal, 1997, 94(6): 565-576.
39	王绍东, 黄煜镔, 王智 . 水泥组分对混凝土固化氯离子能力的影响[J]. 硅酸盐学报, 2000, 28(6): 570-574.
	WANG Shaodong , HUANG Yubin , WANG Zhi . Concrete resistance to chloride ingress effect of cement composition[J]. Journal of the Chinese Ceramic Society, 2000, 28(6): 570-574.
40	罗睿 . 磨细矿渣混凝土抗氯离子扩散的机理研究[D]. 南京: 河海大学, 2000.
	LUO Rui . Study on mechanism of chloride diffusion resistance of ground slag concrete[D]. Nanjing: Hohai University, 2000.
41	MEHTA P K . Effect of cement composition on corrosion of reinforcing steel in concrete[J]. Chloride Corrosion of Steel in Concrete, ASTM STP, 1977, 629: 12-19.
42	DIAMOND S . Chloride concentrations in concrete pore solutions resulting from calcium and sodium chloride admixtures[J]. Cement, Concrete and Aggregates, 1986, 8(2): 97-102.
7	中华人民共和国国务院 . 国务院关于印发水污染防治行动计划的通知[EB/OL]. [2018-11-10]. http: // .
	State Council of the People’s Republic of China . Notice of the state council on the issuance of action plans for the prevention and control of water pollution[EB/OL].[2018-11-10]. http: // .
8	中华人民共和国环境保护部 . 火电厂污染防治可行技术指南: HJ 2301—2017[S]. 北京: 中国环境科学出版社, 2017.
	Ministry of Environmental Protection of the People’s Republic of China . Guideline on available technologies of pollution prevention and control for thermal power plant: HJ 2301—2017[S]. Beijing: China Environmental Science Press, 2017.
9	叶春松, 罗珊, 张弦, 等 . 燃煤电厂脱硫废水零排放处理工艺[J]. 热力发电, 2016, 45(9): 105-108.
	YE Chunsong , LUO Shan , ZHANG Xian , et al . Key problems and developing trend of zero discharge technology of desulfurization waste water[J]. Thermal Power Generation, 2016, 45(9): 105-108.
10	马双忱, 朱思洁, 赵兴辉, 等 . 回用高浓度盐水对脱硫效率的影响[J]. 化工进展, 2016, 35(s1): 304-310.
43	TRITTHART J . Chloride binding in cement Ⅱ. The influence of the hydroxide concentration in the pore solution of hardened cement paste on chloride binding[J]. Cement and Concrete Research, 1989, 19(5): 683-691.
44	谢友均, 马昆林, 龙广成, 等 . 矿物掺合料对混凝土中氯离子渗透性的影响[J]. 硅酸盐学报, 2006, 34(11): 1345-1350.
	XIE Youjun , Kunlin MA , LONG Guangcheng , et al . Influence of mineral admixture on chloride ion permeability of concrete[J]. Journal of the Chinese Ceramic Society, 2006, 34(11): 1345-1350.
45	杨长辉, 晏宇, 欧忠文 . 偏高岭土水泥净浆结合氯离子性能的研究[J]. 混凝土, 2010(10): 1-3.
	YANG Changhui , YAN Yu , Zhongwen OU . Capability of cement paste binding chloride ions with metakaolin as admixture[J]. Concrete, 2010(10): 1-3.
46	CHEEWAKET T , JATURAPITAKKUL C , CHALEE W . Long term performance of chloride binding capacity in fly ash concrete in a marine environment[J]. Construction and Building Materials, 2010, 24(8): 1352-1357.

项目	RO	FO	NF	UF	ED	MD
操作压力/MPa	1.5～11.0	≤0.2	0.5～1.5	0.1～0.5	≤0.2	常压
能耗/kW·h·m^-3	2～12.7	21	≤10	20	7～15	40～45
盐去除率/%	95～97	98	90	90	90	近100
工艺路线	简单	复杂	简单	简单	复杂	较简单
成熟度	成熟	较成熟	较成熟	较成熟	较成熟	不成熟
优点	稳定，适应性强	清洗周期长	稳定，占地小	占地小，成本低	药剂耗量小	不易堵，操作温度低
缺点	易污染，易结垢	系统复杂，投资高	水回收率低	通量低，易污染	易结垢，耗水量大	通量低，技术不成熟

项目	RO	FO	NF	UF	ED	MD
操作压力/MPa	1.5～11.0	≤0.2	0.5～1.5	0.1～0.5	≤0.2	常压
能耗/kW·h·m^-3	2～12.7	21	≤10	20	7～15	40～45
盐去除率/%	95～97	98	90	90	90	近100
工艺路线	简单	复杂	简单	简单	复杂	较简单
成熟度	成熟	较成熟	较成熟	较成熟	较成熟	不成熟
优点	稳定，适应性强	清洗周期长	稳定，占地小	占地小，成本低	药剂耗量小	不易堵，操作温度低
缺点	易污染，易结垢	系统复杂，投资高	水回收率低	通量低，易污染	易结垢，耗水量大	通量低，技术不成熟

项目	旁路蒸发塔技术	旁路烟道蒸发技术
雾化器选型	旋流雾化器	双流体雾化器
蒸发器外型	直径较大，占地面积大	直径小，占地面积小
进水要求	不严格	含固量低
腐蚀结垢特性	不易堵塞和粘壁，有腐蚀风险	有粘壁风险，选用复合板，可减少腐蚀风险

项目	旁路蒸发塔技术	旁路烟道蒸发技术
雾化器选型	旋流雾化器	双流体雾化器
蒸发器外型	直径较大，占地面积大	直径小，占地面积小
进水要求	不严格	含固量低
腐蚀结垢特性	不易堵塞和粘壁，有腐蚀风险	有粘壁风险，选用复合板，可减少腐蚀风险

[1]	郑梦启, 王成业, 汪炎, 王伟, 袁守军, 胡真虎, 何春华, 王杰, 梅红. 菌藻共生技术在工业废水零排放中的应用与展望[J]. 化工进展, 2023, 42(8): 4424-4431.
[2]	顾丽燕, 董伟钢, 刘峰均, 蔡晨健, 陈恒, 杨林军. 脱硫废水热烟气蒸发过程中挥发性组分迁移转化特性研究进展[J]. 化工进展, 2021, 40(S1): 434-438.
[3]	赵宁, 冯永新, 林廷坤, 谢志文. 热烟气环境下脱硫废水液滴蒸发特性研究进展[J]. 化工进展, 2021, 40(8): 4508-4514.
[4]	肖国振, 仲兆平, 姜超, 韩磊, 马天霆, 张杉, 金保昇. 氯添加对燃煤过程中汞析出规律的影响[J]. 化工进展, 2021, 40(12): 6557-6563.
[5]	李飞, 陈海杰, 孙宗康, 谷小兵, 白玉勇, 高飞, 杨林军. 热风分布器结构对脱硫废水旋转喷雾蒸发特性影响的数值模拟[J]. 化工进展, 2020, 39(S2): 385-392.
[6]	刘威. 煤制烯烃含盐废水近零排放技术的应用[J]. 化工进展, 2020, 39(11): 4643-4650.
[7]	王兴俊, 周永春, 安德欣, 吴伟, 刘亚争, 林宸雨, 马双忱. 高镁脱硫废水软化和镁回收实验与机理分析[J]. 化工进展, 2019, 38(s1): 252-258.
[8]	颜海洋, 汪耀明, 蒋晨啸, 王晓林, 李传润, 吴亮, 徐铜文. 离子膜电渗析在高盐废水“零排放”中的应用、机遇与挑战[J]. 化工进展, 2019, 38(01): 672-681.
[9]	赵保华, 范紫瑄, 温佳琪, 张金柱, 马双忱. 燃煤电厂脱硫废水排放指标限值的计算方法研究[J]. 化工进展, 2018, 37(S1): 213-218.
[10]	马双忱, 范紫瑄, 温佳琪, 马岚, 赵保华, 张金柱, 孙尧. 基于模糊层次分析的燃煤电厂脱硫废水处理可利用技术评价[J]. 化工进展, 2018, 37(11): 4451-4459.
[11]	马双忱, 徐昉, 徐东升, 李德峰, 范紫瑄, 樊帅军, 庞蔚莹. 燃煤电厂脱硫废水氯离子检测现状与应用进展[J]. 化工进展, 2018, 37(10): 4044-4052.
[12]	张玉玲, 李旭东, 张利平, 王倩, 康少鑫. 磁性离子交换树脂的制备及其对Cl^–吸附性能[J]. 化工进展, 2018, 37(08): 3051-3055.
[13]	杨博, 李玉忠, 崔琳, 李广培, 董勇. Mg²⁺对脱硫废水电解-电渗析过程的影响[J]. 化工进展, 2017, 36(S1): 482-488.
[14]	张胜寒, 孙晨皓, 陈玉强. 燃煤电厂脱硫废水中硒元素脱除技术研究进展[J]. 化工进展, 2017, 36(04): 1460-1469.
[15]	马双忱, 朱思洁, 赵兴辉, 周朝阳, 吴伟, 翁小玉, 陈儒佳. 回用高浓度盐水对脱硫效率的影响[J]. 化工进展, 2016, 35(S1): 304-310.