CN107746117B - 一种电化学水质稳定与净化方法及装置 - Google Patents
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Abstract
本发明公开了一种电化学水质稳定与净化方法及装置,属于水质净化与水化学稳定化处理技术领域。以PLC控制为基础自动控制结垢、腐蚀、杀菌、管路沉积物溶出等水质稳定相关指数计算、控制和并可自动报警,调节。该装置同时实现降低水硬度和杀菌除藻的效果,并使用除泥装置对水垢进行高效排除,该电解装置的电源可以使用太阳能,达到环保节能的目的,在工业上应用时,具有自动化程度高,能实时高效保障水质稳定,成本低廉,易于推广。
Description
技术领域
本发明属于水质净化和节水技术领域,涉及到一种电解处理管网水的方法。该方法可以采用控制***装置和除泥装置,以及带有溜槽和凸起的不对称电极,能够调节水质参数,如浊度、pH值、碱度、硬度以及电导率,具有除垢,杀藻以及防腐特性,在工业上具有应用前景的水质稳定化技术方法。
背景技术
随着世界经济的迅猛发展,全球性的水资源匮乏及水质污染问题已经越来越严峻地摆在人们面前。目前大部分水质输送过程和工业冷却水过程中,出现腐蚀、结垢和沉淀物溶解出来以及细菌、藻类等繁殖等问题。尤其是工业冷却水都采用循环***,一般工业用水占总用水量的80%,而其中的2/3为冷却用水。要节约水资源,应尽可能减少循环冷却水***的排污,提高冷却水的浓缩倍率。同时利用反渗透膜制备脱盐水产生大量的高盐度的浓水,也可以回收利用作为循环水。冷却水在使用时不断循环和浓缩,水中的矿物质含量也会不断增加,各种物质沉积在换热器表面,形成沉积物。结垢、腐蚀、微生物滋生是循环水***面临的三大问题。目前对于处理循环冷却水等高硬度水的常用方法就是使用阻垢缓蚀剂,但化学药剂的使用存在需反复投药、剂量与时间难以掌握、外排造成二次污染等缺点。
现有文献中,公开号CN201169550Y的专利“微电解阻垢、杀菌处理装置”,主要是设计了一种微电解装置进行循环水的杀菌、阻垢处理,该装置具有无需投加任何药剂、阻垢效果稳定、无污染等优点,但存在耗电量大,处理费用高的不足之处。公开号为CN101182056A的发明专利“一种利用电气石复合催化氧化去除水藻的方法”提及了一种用改性电气石为填料,协同微电解进行杀菌除藻的方法。此种方法仅针对海水、地表水等进行杀藻净化处理,没有涉及高硬度、高碱度、高微生物污染的循环冷却水的净化处理。
论文文献中也有电解法处理循环水的研究报道,如李敏哲,迟娟等在《工业水处理》(2006/02)发表的“微电解用于循环冷却水的实验研究”,***的探讨了微电解法的阻垢、缓蚀、杀菌效果;周群英等在《上海环境科学》(1998/01)发表的“微电解杀藻研究”;王雪峰等在《给水排水》(2001//11)发表的“微电解水处理器的杀菌作用研究”等一系列论文,主要是微电解法对水中污垢、藻类、细菌的去除技术和理论研究。上述文献提到的方法虽然对循环水的处理起到一定作用,但都没有考虑电极结构、水质调节以及水质稳定系数的评估控制问题,应用范围受到水质类型的限制等缺点。为此,需要从水质化学基本原理上,不仅考虑水质类型,通过不对称电极和引入不同电解质,对水中离子进行微调靠强化水质稳定的效果。
发明内容
本发明提供了一种电解处理高硬度循环冷却水和反渗透浓水的方法和设备,同时实现降低水硬度和杀菌除藻的效果,并使用除泥装置对水垢进行高效排除,该电解装置的电源可以使用太阳能,达到环保节能的目的,在工业上应用时,具有自动化程度高,能实时高效保障水质稳定,成本低廉,易于推广。
本发明针对管网循环水易于结垢腐蚀,造成经济损失的问题,本发明根据循环水化学性质,提供了一种控制***装置和除泥装置,以及带有溜槽和凸起的不对称异形电极,对循环水进行实时检测和处理。
本发明提供的水处理方法和装置不仅能够高效实时保证循环水水质稳定,防止管网结垢腐蚀,而且具有价格低廉,环保节能的应用价值。
本发明的技术方案:
一种电化学水质稳定与净化装置,包括循环水槽、电极、pH传感器、电导率传感器、碱度传感器、钙离子传感器、碳酸氢根传感器、浮位球、光电传感器、单色光源和微控制器;
所述的循环水槽为上端开口的反应槽,其上设有进水口,连接外部进水管路;循环水槽下部设有固体物出口和出水口,固体物出口用于定期排出反应生成的沉淀物,用出水口用于排出处理后的水;
所述的电极为阴极和阳极一体结构,可根据需求互换角色,为第一电极和第二电极;第一电极和第二电极外表面具有溜槽和凸起,溜槽上设有通孔,溜槽用于投放和定向输送药剂,凸起部位有利于放电电解;第一电极外依次包裹有离子交换膜和陶瓷膜,第二电极包围于第一电极外;根据电解需要,改变阴极和阳极的角色,保证阴极和阳极的面积比为10~5000:1,调节电源电压使电流密度为0.1-1000mA/cm2;
第一电极和第二电极的材质为复合导电碳基材料、导电塑料或导电合金,为圆柱或方形实体或空心结构。
所述的pH传感器、电导率传感器、碱度传感器、钙离子传感器和碳酸氢根传感器***至循环水槽的水体中,相互间不影响检测,实现pH、电导率、碱度、钙离子浓度和碳酸氢根浓度的实时监测;
所述的浮位球通过开关控制,固定于循环水槽的内壁,用于定位入水高度;
所述的光电传感器和单色光源对称布置于循环水槽的外侧,二者配合测量水体中水藻浓度;
所述的电极、pH传感器、电导率传感器、碱度传感器和光电传感器均连接至微控制器,微控制器实现各部分的实时监测和控制。
所述的微控制器为PLC,辅以触摸屏、继电器或光电耦合器、开关、AD转换器运作。
电化学水质稳定与净化装置中使用的电源可由太阳能转化为电能提供。
所述的单色光源的波长为300~1000nm。
一种电化学水质稳定与净化方法,步骤如下:
(1)藻类污染程度指数WZI与设定值进行对比:
确定设定值为1,当WZI值比设定值1大时,将大面积电极设置为阳极,电解电压设为0.1-60V,在阳极溜槽内通入0.01-2.5mol/L氯化钠或氯化钾,加快氧化物质析出进入溶液,对藻类进行有效去除;当WZI小于设定值1时,表示藻类去除完毕;
(2)通过微处理器判断WZI值小于设定值1后,等待1-20分钟;由pH传感器、电导率传感器、碱度传感器、钙离子传感器、碳酸氢根传感器检测水体的相关参数;根据公式(a)、(b)、(c)计算腐蚀指数WFI,判断水质腐蚀性;
pHj=lg(Alk)+5.14; (a)
pHs=pK2-pKs-lgc(Ca2+)-lg c(HCO3-); (b)
WFI=(2pHs-pHj)/6.6; (c)
式中:pHj表示溶解碱性物质达到饱和时的pH值,Alk表示碱度,pHs表示碳酸钙溶液达到饱和时的pH值;pK2是碳酸钙的第二级电离的平衡常数;pKs是碳酸钙的溶度积常数;
当WFI小于1时,阳极电极溜槽通入0.01-2.5mol/L硫酸盐、碳酸盐和磷酸盐溶液,根据水质情况调节硫酸盐与碳酸盐的质量比为0.1-100,碳酸盐与磷酸盐的质量比为0.1-100,阴极电极溜槽通入0.01-2.5mol/L硫酸钠溶液;调节pH值和离子含量,直到WFI值大于1,检测钙离子、硫酸根离子和碳酸根离子浓度;通过判断硫酸根离子浓度与碳酸根离子浓度的比值t与1000的关系,由***判断选择公式(d)、(e)计算结垢指数WGI;
当t>1000时:WGI=(k*Ksp/[Ca2+]m/[CO3 2-]m/8)-1 (d)
当t≤1000时:WGI=(k*Ksp/[Ca2+]m/[SO4 2-]m/8)-1 (e)
其中,Ksp表示碳酸钙的离子积常数;k值由水中溶解性固体总量TDS决定,或根据水质具体试验确定k值;
(1)当TDS≧5000,k=7.2;
(2)当3000≤TDS≤5000,k=6.8;
(3)当TDS<3000时,k=6.4;
若WGI≥1,易结垢,调整大面积为阴极,溜槽通入0.01-1mol/L的碳酸盐、碳酸氢盐或二氧化碳,去除钙、镁等离子,降低溶液中硬度;维持电压不变,为0.1-60V;调节硬度值,使WGI<1,待该结垢指数稳定后继续检测水中的绿藻含量、pH值。
本发明的有益效果:本发明的装置和方法能够对管网循环水的水质情况进行实时检测,同时能够根据水质情况精确投药,从而防止管网腐蚀结垢,具有高效智能,节能环保,价格低廉的应用价值。
附图说明
图1是除垢流程图。
图2是带有液体溜槽的圆形电极的结构图。
图3是带有液体溜槽的方形电极的结构图。
具体实施方式
以下结合附图和技术方案,进一步说明本发明的具体实施方式。
实施例1
取水样,测得其pH为8.15,硬度为600(mg/L CaCO3),电导率为1760μS/cm。在进行电解处理,处理后,测其pH、硬度、藻去除率和电导率。
实验条件:采用圆柱型溜槽电极和1厘米宽片状构成不对称电极,水样体积800mL,电流密度20mA/cm2,处理时间40min,60min实验结果如下表所示。
处理方法 | pH | 硬度(CaCO<sub>3</sub>mg/L) | 藻去除率(%) | 电导率(μS/cm) |
处理t1 | 6.89 | 420 | 98 | 1530 |
处理t2 | 7.12 | 400 | 100 | 1522 |
从上表可以看出,处理时间pH的升高,有利于防止腐蚀,对硬度和藻类的去除率都有一定的提高。
实施例2
取循环水水样,测得其pH为8.15,硬度为600(mg/L CaCO3),电导率为1760μS/cm。在不同电流密度条件下进行电解处理,处理后,测其pH、硬度、藻去除率和电导率。采用方型溜槽电极和1厘米宽片状构成不对称电极;溜槽加入硫酸钠溶液,加入0.5mol/l加入速度0.05ml/min.
实验条件:水样体积800mL,处理时间为60min,加入电气石为填料,处理效果如下:
由上面的结果可以看出,随着电流密度的增加,水样硬度和电导率都不断降低,同时除藻率不断增加。当电流密度达到10mA/cm2时,加入硫酸钠也有利于加快藻类去除效率,水样硬度和电导率也下降至适中水平。
实施例3
采用方型溜槽电极和1厘米宽片状构成不对称电极取高硬度循环水水样,分别以直流电源和太阳能电池为电源进行电解处理。循环水初始pH为8.56,硬度为1060(mg/LCaCO3),电导率为1721μS/cm。
实验条件:水样体积800mL,电流密度为15mA/cm2,加入0.5mol/l加入速度0.01ml/min,处理时间为60min,处理效果如下:采用圆柱型溜槽电极和1厘米宽片状构成不对称电极,加入0.5mol/l加入速度0.05ml/min.
通过对比发现,加入少量的碳酸钠促进了硬度的降低。对除藻和脱盐的影响不大。
实施例4
取反渗透膜制备脱盐水时产生的高盐度浓水作为水样,以进行处理。
实验条件:采用圆柱型溜槽电极和1厘米宽片状构成不对称电极,水样体积800mL,电流密度10mA/cm2,加入碳酸氢钠,加入量,0.5mol/l碳酸氢钠溶液,加入速度0.01ml/min,,处理时间为60min,处理效果如下:
此方法对于反渗透浓水也有较好的处理效果,经处理后的水可作为循环水回用,达到节约用水的目的。
实施例5
动态试验旁路水质稳定实验条件:阳极惰性电极宽2.5cm长75cm,阴极不锈钢电极直径65cm深80cm的带有液体溜槽圆柱型,溜槽中微量注入碳酸氢钠液体,控制加入速度0.1ml/min的0.1mol/L。开始工作电压6V,测的电流0.233A,100L模拟循环冷却水进行微电解,静态处理22小时后,实验数据见表下表。通过实验数据分析得到WSI:1.0-2.0之间,pH在6.8-7.5之间,不易结垢,不腐蚀,水质稳定;可以补充新水,暂定交换量为水量的16%,补水水质由检测仪表显示,硬度740mg/L碱度585.6mg/L,pH7.78,TDS 1240mg/L等参数,循环运行至30小时后,硬度、碱度和pH逐步增加,WSI指数显示具有结垢倾向,停加外部水,进行静态处理,稳定运行至44小时,根据自动检测的数据和计算的WSI指数可以作补水处理,引入***水硬度740mg/L碱度585.6mg/L,pH7.78,TDS 1240mg/L,并调节补水量,为旁路***的12%,逐步得到最佳动态进水量,出水水质相对稳定,保持稳定连续运行。
Claims (4)
1.一种电化学水质稳定与净化装置,其特征在于,所述的电化学水质稳定与净化装置包括循环水槽、电极、pH传感器、电导率传感器、碱度传感器、钙离子传感器、碳酸氢根传感器、浮位球、光电传感器、单色光源和微控制器;
所述的循环水槽为上端开口的反应槽,其上设有进水口,连接外部进水管路;循环水槽下部设有固体物出口和出水口,固体物出口用于定期排出反应生成的沉淀物,出水口用于排出处理后的水;
所述的电极为阴极和阳极一体结构,可根据需求互换角色,为第一电极和第二电极;第一电极和第二电极外表面具有溜槽和凸起,溜槽上设有通孔,溜槽用于投放和定向输送药剂,凸起部位有利于放电电解;第一电极外依次包裹有离子交换膜和陶瓷膜,第二电极包围于第一电极外;根据电解需要,改变阴极和阳极的角色,保证阴极和阳极的面积比为10~5000:1,调节电源电压使电流密度为0.1-1000mA/cm2;
所述的pH传感器、电导率传感器、碱度传感器、钙离子传感器和碳酸氢根传感器***至循环水槽的水体中,相互间不影响检测,实现pH、电导率、碱度、钙离子浓度和碳酸氢根浓度的实时监测;
所述的浮位球通过开关控制,固定于循环水槽的内壁,用于定位入水高度;
所述的光电传感器和单色光源对称布置于循环水槽的外侧,二者配合测量水体中水藻浓度,所述的单色光源的波长为300~1000nm;
所述的电极、pH传感器、电导率传感器、碱度传感器和光电传感器均连接至微控制器,微控制器实现各部分的实时监测和控制;
所述的第一电极和第二电极的材质为复合导电碳基材料、导电塑料或导电合金,为圆柱或方形实体或空心结构。
2.根据权利要求1所述的电化学水质稳定与净化装置,其特征在于,所述的微控制器为PLC,辅以触摸屏、继电器或光电耦合器、开关、AD转换器运作。
3.根据权利要求1或2所述的电化学水质稳定与净化装置,其特征在于,电化学水质稳定与净化装置中使用的电源可由太阳能转化为电能提供。
4.一种电化学水质稳定与净化方法,步骤如下:
(1)藻类污染程度指数WZI与设定值进行对比:
确定设定值为1,当WZI值比设定值1大时,将大面积电极设置为阳极,电解电压设为0.1-60V,在阳极溜槽内通入0.01-2.5mol/L氯化钠或氯化钾,加快氧化物质析出进入溶液,对藻类进行有效去除;当WZI小于设定值1时,表示藻类去除完毕;
(2)通过微处理器判断WZI值小于设定值1后,等待1-20分钟;由pH传感器、电导率传感器、碱度传感器、钙离子传感器、碳酸氢根传感器检测水体的相关参数;根据公式(a)、(b)、(c)计算腐蚀指数WFI,判断水质腐蚀性;
pHj=lg(Alk)+5.14; (a)
pHs=pK2-pKs-lgc(Ca2+)-lg c(HCO3 -); (b)
WFI=(2pHs-pHj)/6.6; (c)
式中:pHj表示溶解碱性物质达到饱和时的pH值,Alk表示碱度,pHs表示碳酸钙溶液达到饱和时的pH值;pK2是碳酸钙的第二级电离的平衡常数;pKs是碳酸钙的溶度积常数;
当WFI小于1时,阳极电极溜槽通入0.01-2.5mol/L硫酸盐、碳酸盐和磷酸盐溶液,根据水质情况调节硫酸盐与碳酸盐的质量比为0.1-100,碳酸盐与磷酸盐的质量比为0.1-100,阴极电极溜槽通入0.01-2.5mol/L硫酸钠溶液;调节pH值和离子含量,直到WFI值大于1,检测钙离子、硫酸根离子和碳酸根离子浓度;通过判断硫酸根离子浓度与碳酸根离子浓度的比值t与1000的关系,由***判断选择公式(d)、(e)计算结垢指数WGI;
当t>1000时:WGI=(k*Ksp/[Ca2+]m/[CO3 2-]m/8)-1 (d)
当t≤1000时:WGI=(k*Ksp/[Ca2+]m/[SO4 2-]m/8)-1 (e)
其中,Ksp表示碳酸钙的离子积常数;k值由水中溶解性固体总量TDS决定,或根据水质具体试验确定k值;
(1)当TDS≧5000,k=7.2;
(2)当3000≤TDS≤5000,k=6.8;
(3)当TDS<3000时,k=6.4;
若WGI≥1,易结垢,调整大面积为阴极,溜槽通入0.01-1mol/L的碳酸盐、碳酸氢盐或二氧化碳,去除钙、镁等离子,降低溶液中硬度;维持电压不变,为0.1-60V;调节硬度值,使WGI<1,待该结垢指数稳定后继续检测水中的绿藻含量、pH值。
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