循环冷却水软化微碱化协同防垢防腐防污研究
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摘要
工业上用水量最大的循环冷却水系统,最常见的问题是结垢、腐蚀、微生物污染、浓水排放与环境污染。针对这些问题,本文提出的循环冷却水软化微碱化处理方法,无需外加化学药剂,通过杂质减量和水质调节,协同防垢、防腐蚀、防微生物污染。取得“三防”功效,同时实现节水和污染物减排。
本文通过系列模型计算和试验研究,取得主要成果如下：
1、提出了离子交换软化微碱化方法及工艺
文中计算了铁、铜、锌—碳酸盐溶液三个体系中的热力学平衡,进行了碳钢和黄铜的腐蚀控制试验,结果显示：在全碱度为6-10mmol/L (pH为9.2-9.5)的钠型碳酸盐溶液中,碳钢和黄铜表面都形成稳定氧化膜,腐蚀速率低于循环冷却水系统腐蚀控制国家标准。同时进行了RHCO3型树脂特性试验,研究了RHCO3型树脂中HCO3-/CO32-反应机理和平衡常数,优化了其运行及再生工艺参数。
在此基础上,提出了适用于小型循环冷却水系统(如中央空调循环冷却系统)的离子交换软化微碱化方法,设计了针对两种循环冷却水系统的微碱化工艺：对无铜循环系统,补给水处理采用RNa型树脂和RHCO3型树脂串联工艺；对有铜循环系统,补给水处理采用2个串联流程进行并联的工艺,分配流量调节水质,一个是RNa型树脂和ROH型树脂串联,另一个是弱酸树脂、RH强酸树脂和弱碱树脂串联。同时研究了工艺的经济性,结果表明：与加药法相比,该工艺运行费用节省35%-44%。
2、提出了纳滤—阴离子交换软化微碱化方法及工艺
对于大型循环冷却水系统(如火力发电厂循环冷却系统),文中提出了利用纳滤去除水中全部硬度和部分一价离子,再利用RHCO3型树脂将产水中阴离子交换成碳酸氢根,实现软化微碱化。进行了NF90纳滤膜与RHCO3树脂串联工艺试验,结果表明：该工艺可同时实现部分脱盐(脱盐率约为80%)和软化微碱化,产水达到软化微碱化系统补水要求,预处理可采用超滤。
3、研究了微碱化系统稳定性及“三防”效果
本文进行了微碱化水中CO2传质模型计算和动态模拟试验,模拟计算了循环系统水质水量变化过程,结果表明：运行中的微碱化系统受到弱酸性补水冲击时,系统将在1-2h内与空气中CO2达成平衡而恢复。循环流量上升或系统碱度增大都有助于提高系统抗冲击性能,保持水质和水量稳定。
之后,研究了调质水的“三防”效果,黄铜试片表面成膜动力学研究表明：微碱化调质水中,黄铜表面氧化膜稳定化过程只需24h,膜层致密,对电子传递起阻隔作用,具有良好的防腐效果；微碱化循环系统防微生物污染效果试验表明：微碱化方法控制了循环冷却水中的氮磷元素含量,同比之下,微生物总量减少了68%；去除硬度在防止污垢生成同时,使好氧异养菌总量减少33%。
试验研究结果证实了循环冷却水软化微碱化方法的可行性,基于2个技术创新点,申请了2项发明专利,可望在此基础上开发出循环冷却水处理的实用性新技术。
The recirculating cooling water system is the biggest water consumer in industrial field, in which the normal problem is scaling, corrosion and microbial reproduction as well as drainage pollution and water resource waste. Accordingly, the paper proposes recirculating cooling water softening and micro-alkalizing through removing contamination and adjusting water quality, which can prevent scaling, corrosion and microorganism pollution without any chemicals coordinately. In the same time, it succeeds to save water resource and decrease drainage.
After a series of model calculation and experiment, the main achievements are listed:
1. A method and a process of ion-exchange softening and micro-alkalizing has been proposed
The thermodynamic balance of the three system-Fe, Cu and Zn in carbonate slution has been calculated, and the corrosion contraling experiment of carbon steel and brass has been carried out, the result tells that:when the total alkalinity of the sodium carbonate solution is adjusted to 6-10mmol/L(pH=9.2-9.5), the A3 carbon steel and the brass is coated well by oxide film, of which the corrosion speed is controlled under the Chinese national standard in anti-corrosion of the recirculating cooling system. In the same time, the property test of RHCO3 resin has been carried out. The change merchanism and the equilibrium constant between HCO3- and CO32- in the resin have been researched, and the operation and regeneration process parameters have been optimized.
Based on the test, a method of ion-exchange softening and micro-alkalizing, which was suitable to small-sized recirculating cooling water system (such as central air conditioning system), has been proposed, and the process for two different systems has been designed:for the recirculating cooling system without copper, the makeup water treating used the series connection process between RNa resin and RHCO3 resin. And for that containing copper is the parallel connection of between the two series connection, one conclude RNa resin and ROH resin, and the other conclude weak acidic resin, RH strong acerbic resin and weak anionic resin. In the same time, the economic characteric of the process has beed researched, the results tells that:it can save 35～44% operational fee than the process of adding chemicals.
2. A method and a process of nanofiltration combining with anion-exchange softening and micro-alkalizing has been proposed
For the large-scale recirculating cooling system (such as the cooling recirculating cooling system in thermal power plant), the paper propose that softening and micro-alkalizing by removing all the hardness and a part of monovolant ions in water with nanofiltration and then change the anion into HCO3 with RHCO3 resin. The process experiment of series connecting between NF90 membrane and RHCO3 resin has been carried out, the results tell that:when the nanofiltraion membrane-NF90 is series connected with RHCO3 anionic resin, the process can remove much monovalent ion (about 80%), and can soften as well as alkalize the water. The product water quality will fill the makeup water quality requirement of softening and micro-alkalizing system.
3. The stability of softening and micro-alkalizing system and the "three preventing effects" has been studied
The model calculation of the CO2 mass transfer from the adjusted water to the air and the simulating test has been carried out, the result tells that:when flushed by weak acidic makeup water in running, the micro-alkalized system will recover in 1-2 hours and kept balance with the CO2 in the air. The increasing of the flow rate and the system alkality will help increasing resistance capacity and keeping water quality and quantity stable.
Then, the "three preventing effects" of the adjusted water has been studied, the kinetic experiment results of coating on brass surface tell that:there will need 24 hours to create an integrated film on the brass surface. The oxide film is much dense and cover the surface to prevent the brass corrosion; the preventing microorganism effect tests results tell that:the population of the microorganism will decrease 68% after removing nitrogen and phosphorus by softening and micro-alkalizing process, and the population of aerobic heterotrophic bacteria will decrease 33% and there is no scaling after softening.
The fesxibility of the recirculating cooling water softening and micro-alkalizing method is confirmed by the experimental results. Based on the two innovative points, we have appled for two invention patents. We hope that a new pratical technique will be exploited to treat with the recirculating cooling water.
本文通过系列模型计算和试验研究,取得主要成果如下：
1、提出了离子交换软化微碱化方法及工艺
文中计算了铁、铜、锌—碳酸盐溶液三个体系中的热力学平衡,进行了碳钢和黄铜的腐蚀控制试验,结果显示：在全碱度为6-10mmol/L (pH为9.2-9.5)的钠型碳酸盐溶液中,碳钢和黄铜表面都形成稳定氧化膜,腐蚀速率低于循环冷却水系统腐蚀控制国家标准。同时进行了RHCO3型树脂特性试验,研究了RHCO3型树脂中HCO3-/CO32-反应机理和平衡常数,优化了其运行及再生工艺参数。
在此基础上,提出了适用于小型循环冷却水系统(如中央空调循环冷却系统)的离子交换软化微碱化方法,设计了针对两种循环冷却水系统的微碱化工艺：对无铜循环系统,补给水处理采用RNa型树脂和RHCO3型树脂串联工艺；对有铜循环系统,补给水处理采用2个串联流程进行并联的工艺,分配流量调节水质,一个是RNa型树脂和ROH型树脂串联,另一个是弱酸树脂、RH强酸树脂和弱碱树脂串联。同时研究了工艺的经济性,结果表明：与加药法相比,该工艺运行费用节省35%-44%。
2、提出了纳滤—阴离子交换软化微碱化方法及工艺
对于大型循环冷却水系统(如火力发电厂循环冷却系统),文中提出了利用纳滤去除水中全部硬度和部分一价离子,再利用RHCO3型树脂将产水中阴离子交换成碳酸氢根,实现软化微碱化。进行了NF90纳滤膜与RHCO3树脂串联工艺试验,结果表明：该工艺可同时实现部分脱盐(脱盐率约为80%)和软化微碱化,产水达到软化微碱化系统补水要求,预处理可采用超滤。
3、研究了微碱化系统稳定性及“三防”效果
本文进行了微碱化水中CO2传质模型计算和动态模拟试验,模拟计算了循环系统水质水量变化过程,结果表明：运行中的微碱化系统受到弱酸性补水冲击时,系统将在1-2h内与空气中CO2达成平衡而恢复。循环流量上升或系统碱度增大都有助于提高系统抗冲击性能,保持水质和水量稳定。
之后,研究了调质水的“三防”效果,黄铜试片表面成膜动力学研究表明：微碱化调质水中,黄铜表面氧化膜稳定化过程只需24h,膜层致密,对电子传递起阻隔作用,具有良好的防腐效果；微碱化循环系统防微生物污染效果试验表明：微碱化方法控制了循环冷却水中的氮磷元素含量,同比之下,微生物总量减少了68%；去除硬度在防止污垢生成同时,使好氧异养菌总量减少33%。
试验研究结果证实了循环冷却水软化微碱化方法的可行性,基于2个技术创新点,申请了2项发明专利,可望在此基础上开发出循环冷却水处理的实用性新技术。
The recirculating cooling water system is the biggest water consumer in industrial field, in which the normal problem is scaling, corrosion and microbial reproduction as well as drainage pollution and water resource waste. Accordingly, the paper proposes recirculating cooling water softening and micro-alkalizing through removing contamination and adjusting water quality, which can prevent scaling, corrosion and microorganism pollution without any chemicals coordinately. In the same time, it succeeds to save water resource and decrease drainage.
After a series of model calculation and experiment, the main achievements are listed:
1. A method and a process of ion-exchange softening and micro-alkalizing has been proposed
The thermodynamic balance of the three system-Fe, Cu and Zn in carbonate slution has been calculated, and the corrosion contraling experiment of carbon steel and brass has been carried out, the result tells that:when the total alkalinity of the sodium carbonate solution is adjusted to 6-10mmol/L(pH=9.2-9.5), the A3 carbon steel and the brass is coated well by oxide film, of which the corrosion speed is controlled under the Chinese national standard in anti-corrosion of the recirculating cooling system. In the same time, the property test of RHCO3 resin has been carried out. The change merchanism and the equilibrium constant between HCO3- and CO32- in the resin have been researched, and the operation and regeneration process parameters have been optimized.
Based on the test, a method of ion-exchange softening and micro-alkalizing, which was suitable to small-sized recirculating cooling water system (such as central air conditioning system), has been proposed, and the process for two different systems has been designed:for the recirculating cooling system without copper, the makeup water treating used the series connection process between RNa resin and RHCO3 resin. And for that containing copper is the parallel connection of between the two series connection, one conclude RNa resin and ROH resin, and the other conclude weak acidic resin, RH strong acerbic resin and weak anionic resin. In the same time, the economic characteric of the process has beed researched, the results tells that:it can save 35～44% operational fee than the process of adding chemicals.
2. A method and a process of nanofiltration combining with anion-exchange softening and micro-alkalizing has been proposed
For the large-scale recirculating cooling system (such as the cooling recirculating cooling system in thermal power plant), the paper propose that softening and micro-alkalizing by removing all the hardness and a part of monovolant ions in water with nanofiltration and then change the anion into HCO3 with RHCO3 resin. The process experiment of series connecting between NF90 membrane and RHCO3 resin has been carried out, the results tell that:when the nanofiltraion membrane-NF90 is series connected with RHCO3 anionic resin, the process can remove much monovalent ion (about 80%), and can soften as well as alkalize the water. The product water quality will fill the makeup water quality requirement of softening and micro-alkalizing system.
3. The stability of softening and micro-alkalizing system and the "three preventing effects" has been studied
The model calculation of the CO2 mass transfer from the adjusted water to the air and the simulating test has been carried out, the result tells that:when flushed by weak acidic makeup water in running, the micro-alkalized system will recover in 1-2 hours and kept balance with the CO2 in the air. The increasing of the flow rate and the system alkality will help increasing resistance capacity and keeping water quality and quantity stable.
Then, the "three preventing effects" of the adjusted water has been studied, the kinetic experiment results of coating on brass surface tell that:there will need 24 hours to create an integrated film on the brass surface. The oxide film is much dense and cover the surface to prevent the brass corrosion; the preventing microorganism effect tests results tell that:the population of the microorganism will decrease 68% after removing nitrogen and phosphorus by softening and micro-alkalizing process, and the population of aerobic heterotrophic bacteria will decrease 33% and there is no scaling after softening.
The fesxibility of the recirculating cooling water softening and micro-alkalizing method is confirmed by the experimental results. Based on the two innovative points, we have appled for two invention patents. We hope that a new pratical technique will be exploited to treat with the recirculating cooling water.
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