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The sterilization effect of chlorine-containing disinfectants does not hinge on the total available chlorine concentration, but rather on the concentration of hypochlorous acid (HClO) molecules. To reduce the cost of circulating water sterilization in thermal power plants, HClO solution was used to sterilize circulating water. The HClO solution was prepared from sodium hypochlorite (NaClO) solution, CO2 and pure water by non-electrolytic method, and experimental study on application performance (including stability and sterilization effect) of the HClO solution was conducted. The results showed that, the mass concentration of HClO in NaClO solution was extremely low, the mass fraction of HClO to available chlorine was only 0.690%~0.012% in NaClO solution with mass concentration of available chlorine in the range of 100~2 000 mg/L, which could be increased to 94.91% by reacting with CO2, thereby improving the sterilization efficiency. When 30, 60, 80, and 90 mg/L stabilizer were added, the decomposition rate of HClO solution with mass concentrations of 500, 1 000, 1 500 and 2 000 mg/L could meet the requirements for a shelf life of one year of the Disinfection Technical Specification. When the dosage of NaClO and HClO (calculated by available chlorine) was 5 mg/L and 0.06 mg/L,the sterilizing time was 120 min and 15 min, the sterilizing rate could reach 90%, and it can be seen that HClO was more economical and efficient for sterilization. HClO solution can reduce the cost of circulating water bactericides in thermal power plants by more than 55% compared with that of conventional NaClO.

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含氯杀菌剂的杀菌效果不取决于总有效氯质量浓度,而取决于次氯酸(HClO)分子的质量浓度。为降低火电厂循环水杀菌成本,采用HClO溶液对循环水进行杀菌。以次氯酸钠(NaClO)溶液、CO2和纯水为原料,采用非电解法制备次氯酸溶液,并对其稳定性和杀菌效果2种应用性能进行实验研究。结果表明:NaClO溶液中的HClO质量浓度非常低,有效氯质量浓度在100~2 000 mg/L的NaClO溶液中,HClO占有效氯的质量分数仅为0.690%~0.012%,通入CO2后可提高至94.91%,从而提高杀菌效率;对于HCIO质量浓度为500、1 000、1 500、2 000 mg/L的溶液,当稳定剂投加量分别为30、60、80、90 mg/L时,HClO质量浓度下降率可满足《消毒技术规范》保质期1年的要求;NaClO和HClO的投加量(以有效氯计)分别为5 mg/L和0.06 mg/L,作用时间分别为120、15 min时,杀菌率均可达90%,HClO杀菌更为经济、高效,作为火电厂循环水杀菌剂,其成本较传统杀菌剂NaClO降低了55%以上。

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黄琼(1990),女,硕士,高级工程师,主要研究方向为火电厂水处理技术,

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黄琼(1990),女,硕士,高级工程师,主要研究方向为火电厂水处理技术,

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黄琼(1990),女,硕士,高级工程师,主要研究方向为火电厂水处理技术,

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Chinese Journal of Veterinary Drug, 2020, 54(9): 61-71., articleTitle=Applications and prospects of non-electrolytic micro-acidic hypochlorite water disinfectant in animal husbandry, refAbstract=null)], funds=null, companyList=[AuthorCompany(id=1236321547124798055, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, xref=1., ext=[AuthorCompanyExt(id=1236321547154158185, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, companyId=1236321547124798055, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.Xi’an Yitong Thermal Technology Service Co., Ltd., Xi’an 710032, China), AuthorCompanyExt(id=1236321547162546794, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, companyId=1236321547124798055, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, 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articleId=1236321542360068501, language=CN, label=图1, caption=HClO制备装置示意, figureFileSmall=IiLEQdcYKs1dLJiObvl1Qw==, figureFileBig=ONycH+ZXXUWstbVXPLA8hw==, tableContent=null), ArticleFig(id=1236321555190445030, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=EN, label=Fig.2, caption=The pH value and mass fraction of HClO to available chlorine in NaClO solution with the mass concentration of available chlorine, figureFileSmall=ePj8RUfZ13WXS2EVZTEpRw==, figureFileBig=puHOTBZe5Ypvj93TS5sDqw==, tableContent=null), ArticleFig(id=1236321555291108331, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=CN, label=图2, caption=NaClO溶液pH值和HClO占有效氯的质量分数随有效氯质量浓度的变化, figureFileSmall=ePj8RUfZ13WXS2EVZTEpRw==, figureFileBig=puHOTBZe5Ypvj93TS5sDqw==, tableContent=null), ArticleFig(id=1236321555463074803, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=EN, label=Fig.3, caption=Influence of the dosage of CO2 on mass concentration of available chlorine in generated solution, figureFileSmall=DRu6JRoKXLv8HC33hmx3hg==, figureFileBig=eYpH402fiB5zMoVEYtPzxA==, tableContent=null), ArticleFig(id=1236321555567932410, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=CN, label=图3, caption=CO2投加量对生成液有效氯质量浓度的影响, figureFileSmall=DRu6JRoKXLv8HC33hmx3hg==, figureFileBig=eYpH402fiB5zMoVEYtPzxA==, tableContent=null), ArticleFig(id=1236321555685372927, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=EN, label=Fig.4, caption=Effects of the dosage of CO2 on the pH value of generated solution, figureFileSmall=6OT40MRgrKO3ykKipjCYUA==, figureFileBig=ml8N79yl9qi3gwV1WE3OIA==, tableContent=null), ArticleFig(id=1236321555798618115, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=CN, label=图4, caption=CO2投加量对生成液pH值的影响, figureFileSmall=6OT40MRgrKO3ykKipjCYUA==, figureFileBig=ml8N79yl9qi3gwV1WE3OIA==, tableContent=null), ArticleFig(id=1236321555899281415, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=EN, label=Fig.5, caption=Influence of the dosage of CO2 on the mass fraction of HClO to available chlorine in generated solution, figureFileSmall=Q/rlxOGeUZa8qhdaUM5CmQ==, figureFileBig=nPozCfHybKeO09SW49qlcg==, tableContent=null), ArticleFig(id=1236321556029304843, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=CN, label=图5, caption=CO2投加量对生成液中HClO占有效氯质量分数的影响, figureFileSmall=Q/rlxOGeUZa8qhdaUM5CmQ==, figureFileBig=nPozCfHybKeO09SW49qlcg==, tableContent=null), ArticleFig(id=1236321556138356751, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=EN, label=Fig.6, caption=Variation of the mass concentration of HClO in generated solution with the mass concentration of available chlorine in NaClO solution, figureFileSmall=VouUP1xWwb/Z6m+MHuxXSw==, figureFileBig=zR7iMVWZuqMEo5rTrw/kog==, tableContent=null), ArticleFig(id=1236321556259991571, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=CN, label=图6, caption=生成液中HClO质量浓度随NaClO溶液有效氯质量浓度的变化, figureFileSmall=VouUP1xWwb/Z6m+MHuxXSw==, figureFileBig=zR7iMVWZuqMEo5rTrw/kog==, tableContent=null), ArticleFig(id=1236321556402597915, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=EN, label=Fig.7, caption=Experimental results of the stability of HClO, figureFileSmall=9WYT1sBg/OJ30eJANJWU0w==, figureFileBig=ssRffim4XdoxNTfPDuid0A==, tableContent=null), ArticleFig(id=1236321556486483998, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=CN, label=图7, caption=HClO稳定性实验结果, figureFileSmall=9WYT1sBg/OJ30eJANJWU0w==, figureFileBig=ssRffim4XdoxNTfPDuid0A==, tableContent=null), ArticleFig(id=1236321556616507430, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=EN, label=Fig.8, caption=Experimental results of sterilization effect of NaClO, figureFileSmall=60sPYu52iJtyrNWTV7rfNw==, figureFileBig=vYWvBN3fIpygWUatAEWgwQ==, tableContent=null), ArticleFig(id=1236321556708782124, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=CN, label=图8, caption=NaClO杀菌效果实验结果, figureFileSmall=60sPYu52iJtyrNWTV7rfNw==, figureFileBig=vYWvBN3fIpygWUatAEWgwQ==, tableContent=null), ArticleFig(id=1236321556822028333, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=EN, label=Fig.9, caption=Experimental results of sterilization effect of HClO, figureFileSmall=wTDgCXgxlNVegyaIaP9JUw==, figureFileBig=3xHbZcyZ7fwZ1h3NWyaLow==, tableContent=null), ArticleFig(id=1236321556931080240, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=CN, label=图9, caption=HClO杀菌效果实验结果, figureFileSmall=wTDgCXgxlNVegyaIaP9JUw==, figureFileBig=3xHbZcyZ7fwZ1h3NWyaLow==, tableContent=null), ArticleFig(id=1236321557061103668, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=EN, label=Tab.1, caption=

The testing standards

, figureFileSmall=null, figureFileBig=null, tableContent=
序号检测项目检测依据
1pH值《水质pH值的测定电极法》(HJ 1147—2020)
2有效氯质量浓度《含氯消毒剂卫生要求》(GB/T 36758—2018)
3次氯酸质量浓度
4细菌总数《水质 细菌总数的测定 平皿计数法》(HJ 1000—2018)
), ArticleFig(id=1236321557153378363, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=CN, label=表1, caption=

检测标准

, figureFileSmall=null, figureFileBig=null, tableContent=
序号检测项目检测依据
1pH值《水质pH值的测定电极法》(HJ 1147—2020)
2有效氯质量浓度《含氯消毒剂卫生要求》(GB/T 36758—2018)
3次氯酸质量浓度
4细菌总数《水质 细菌总数的测定 平皿计数法》(HJ 1000—2018)
), ArticleFig(id=1236321557291790397, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321542360068501, language=EN, label=Tab.2, caption=

Cost comparison of fungicides prepared from two kinds of raw materials

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10% NaClO来源材料成本电耗及设备维护折旧费合计
采购291~77368
电解法制备285~77362
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2种来源原料制备杀菌剂成本比较

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10% NaClO来源材料成本电耗及设备维护折旧费合计
采购291~77368
电解法制备285~77362
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非电解法制备次氯酸及其应用性能实验
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黄琼 1 , 刘树昌 2 , 苏艳 3, 4 , 杨阳 3, 4 , 黄倩 1 , 王正江 3, 4 , 姜琪 3, 4 , 王璟 3, 4 , 张益峰 3, 4
热力发电 | 发电技术论坛 2025,54(10): 143-148
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热力发电 | 发电技术论坛 2025, 54(10): 143-148
非电解法制备次氯酸及其应用性能实验
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黄琼1 , 刘树昌2, 苏艳3, 4, 杨阳3, 4, 黄倩1, 王正江3, 4, 姜琪3, 4, 王璟3, 4, 张益峰3, 4
作者信息
  • 1.西安益通热工技术服务有限责任公司,陕西 西安 710032
  • 2.华能甘肃能源开发有限公司,甘肃 兰州 730070
  • 3.西安西热水务环保有限公司,陕西 西安 710054
  • 4.高效灵活煤电及碳捕集利用封存全国重点实验室,北京 102200
  • 黄琼(1990),女,硕士,高级工程师,主要研究方向为火电厂水处理技术,

Experimental study on preparation of hypochlorous acid by non-electrolytic method and its application performance
Qiong HUANG1 , Shuchang LIU2, Yan SU3, 4, Yang YANG3, 4, Qian HUANG1, Zhengjiang WANG3, 4, Qi JIANG3, 4, Jing WANG3, 4, Yifeng ZHANG3, 4
Affiliations
  • 1.Xi’an Yitong Thermal Technology Service Co., Ltd., Xi’an 710032, China
  • 2.Huaneng Gansu Energy Development Co., Ltd., Lanzhou 730070, China
  • 3.Xi’an TPRI Water-Management & Environmental Protection Co., Ltd., Xi’an 710054, China
  • 4.State Key Laboratory of High-Efficiency Flexible Coal Power Generation and Carbon Capture Utilization and Storage, Beijing 102200, China
出版时间: 2025-10-25 doi: 10.19666/j.rlfd.202501002
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含氯杀菌剂的杀菌效果不取决于总有效氯质量浓度,而取决于次氯酸(HClO)分子的质量浓度。为降低火电厂循环水杀菌成本,采用HClO溶液对循环水进行杀菌。以次氯酸钠(NaClO)溶液、CO2和纯水为原料,采用非电解法制备次氯酸溶液,并对其稳定性和杀菌效果2种应用性能进行实验研究。结果表明:NaClO溶液中的HClO质量浓度非常低,有效氯质量浓度在100~2 000 mg/L的NaClO溶液中,HClO占有效氯的质量分数仅为0.690%~0.012%,通入CO2后可提高至94.91%,从而提高杀菌效率;对于HCIO质量浓度为500、1 000、1 500、2 000 mg/L的溶液,当稳定剂投加量分别为30、60、80、90 mg/L时,HClO质量浓度下降率可满足《消毒技术规范》保质期1年的要求;NaClO和HClO的投加量(以有效氯计)分别为5 mg/L和0.06 mg/L,作用时间分别为120、15 min时,杀菌率均可达90%,HClO杀菌更为经济、高效,作为火电厂循环水杀菌剂,其成本较传统杀菌剂NaClO降低了55%以上。

循环水  /  次氯酸  /  次氯酸钠  /  稳定性  /  杀菌效果

The sterilization effect of chlorine-containing disinfectants does not hinge on the total available chlorine concentration, but rather on the concentration of hypochlorous acid (HClO) molecules. To reduce the cost of circulating water sterilization in thermal power plants, HClO solution was used to sterilize circulating water. The HClO solution was prepared from sodium hypochlorite (NaClO) solution, CO2 and pure water by non-electrolytic method, and experimental study on application performance (including stability and sterilization effect) of the HClO solution was conducted. The results showed that, the mass concentration of HClO in NaClO solution was extremely low, the mass fraction of HClO to available chlorine was only 0.690%~0.012% in NaClO solution with mass concentration of available chlorine in the range of 100~2 000 mg/L, which could be increased to 94.91% by reacting with CO2, thereby improving the sterilization efficiency. When 30, 60, 80, and 90 mg/L stabilizer were added, the decomposition rate of HClO solution with mass concentrations of 500, 1 000, 1 500 and 2 000 mg/L could meet the requirements for a shelf life of one year of the Disinfection Technical Specification. When the dosage of NaClO and HClO (calculated by available chlorine) was 5 mg/L and 0.06 mg/L,the sterilizing time was 120 min and 15 min, the sterilizing rate could reach 90%, and it can be seen that HClO was more economical and efficient for sterilization. HClO solution can reduce the cost of circulating water bactericides in thermal power plants by more than 55% compared with that of conventional NaClO.

circulating water  /  hypochlorous acid  /  sodium hypochlorite  /  stability  /  sterilization effect
黄琼, 刘树昌, 苏艳, 杨阳, 黄倩, 王正江, 姜琪, 王璟, 张益峰. 非电解法制备次氯酸及其应用性能实验. 热力发电, 2025 , 54 (10) : 143 -148 . DOI: 10.19666/j.rlfd.202501002
Qiong HUANG, Shuchang LIU, Yan SU, Yang YANG, Qian HUANG, Zhengjiang WANG, Qi JIANG, Jing WANG, Yifeng ZHANG. Experimental study on preparation of hypochlorous acid by non-electrolytic method and its application performance[J]. Thermal Power Generation, 2025 , 54 (10) : 143 -148 . DOI: 10.19666/j.rlfd.202501002
火电厂的循环冷却水系统多为敞开式,循环水中的微生物繁殖会产生生物粘膜、黏泥以及藻类等[1-3],是影响提高浓缩倍率的一个重要因素。微生物在滋生和繁殖过程中产生的腐蚀性离子会加速凝汽器腐蚀,同时会在系统中形成大量的黏泥,使冷却塔的效率降低[4]。如果不进行杀菌处理,微生物的数量会成倍增加,直接影响火电机组的安全、经济和稳定运行。
为了控制微生物对循环冷却水系统运行的影响,常采用含氯杀菌剂对微生物进行处理,通过杀灭或抑制细菌活性来控制微生物的增殖。目前,国内外最常用的杀菌剂是次氯酸钠,次氯酸钠碱性强、易挥发、刺激性气味大、性质不稳定,储存时易衰减[5],投加量控制难度大,运输费用高,火电厂循环水水量较大,投加次氯酸钠的成本非常昂贵。也有部分电厂使用电解二氧化氯或氯气杀菌,该技术设备本体极易腐蚀,运行维护成本昂贵,实际使用价值低。
次氯酸(HClO)的杀菌效果远高于次氯酸钠、二氧化氯、氯气等杀菌剂,是一种广谱、高效的新型含氯杀菌剂,具有腐蚀性小、安全性高、不污染环境等优点[6-8]。HClO分子是对多种微生物具有最高杀菌活性的游离氯,杀菌效果远高于NaClO,且HClO杀菌反应完全后成为水溶液,不会产生任何有毒的灭菌副产物和残留杂质,有利于在消毒灭菌过程中保证循环冷却水系统安全性[9-10]。次氯酸最显著的化学性质是氧化性和不稳定性,因为在常温下很容易分解,需要现制现用[11-12]。次氯酸的常规制备方法为电解法,但因制备设备本体易腐蚀而无法长期使用,且运行维护费用高。非电解技术设备腐蚀性低,所需原料价格低廉,运行维护成本低,因此,从安全环保属性、杀菌效果及经济考虑,非电解法制备HClO溶液具有重要的现实意义[13-15]
基于此,本文通过非电解法制备HClO溶液的实验,分析不同原料配比对生成HClO溶液的pH值和浓度的影响,对HClO溶液的稳定性和杀菌效果2种应用性能进行实验研究,分析HClO对火电厂循环水杀菌的经济性,为HClO杀菌剂生产和杀菌的推广应用提供基础。
本研究包括HClO的制备实验、稳定性实验和杀菌效果实验3部分。HClO制备方法为非电解法,原理见反应方程式(1),制备过程即为次氯酸钠(NaClO)溶液酸化过程。采用原料为10%(有效氯质量浓度为100 000 mg/L)NaClO溶液、CO2和纯水,生成液为HClO溶液,制备装置示意见图1。文献[16]研究显示,HClO分子的杀菌效果是ClO离子的80~150倍。因此,本实验用纯水将NaClO质量分数10%的溶液中有效氯质量浓度稀释至100~2 000 mg/L,通过通入不同量的CO2反应生成不同质量浓度的HClO溶液。
NaClO+CO2+H2O=NaHCO3+HClO
稳定性实验采用纳米级氮化硼作为稳定剂,向不同质量浓度的HClO溶液加入不同量稳定剂,在设定条件下检测HClO质量浓度的下降率,并根据《消毒技术规范》[17]判定有效期。
杀菌效果实验是对HClO与NaClO的杀菌效果做对比实验,杀菌对象为火电厂循环冷却排污水。
本研究采用的检测标准见表1。《含氯消毒剂卫生要求》[18](GB/T 36758—2018)规定,溶液pH值大于5时,HClO测定方法是通过式(2)计算HClO占有效氯的质量分数,再结合测定的有效氯质量浓度计算出溶液中HClO的质量浓度。可见,溶液中的HClO质量浓度与有效氯质量浓度和pH值相关。
Y=11+ka×10pH×100
式中:Y为HClO占有效氯的质量分数,%;ka为次氯酸的电离平衡常数,常温下值为3.8×10–8
检测有效氯质量浓度为100~2 000 mg/L的NaClO稀释液pH值,并根据式(2)计算出HClO占有效氯的质量分数,结果见图2。实验结果表明,有效氯质量浓度为100~2 000 mg/L的NaClO溶液,其pH值在9.58~11.35,HClO占有效氯的质量分数在0.690%~0.012%间,HClO质量浓度均在1 mg/L以下。可见,NaClO溶液中的HClO含量非常低。
本实验按照不同CO2与ClO的摩尔比n,向上述不同有效氯质量浓度的NaClO稀释液中通入CO2气体,检测生成液的有效氯质量浓度和pH值,实验结果见图3图4,并根据pH值计算得到生成液中HClO占有效氯质量分数,结果见图5。由图4图5可见:在n相同的情况下,生成液的pH值不随NaClO溶液中有效氯质量浓度的变化而变化,pH值随n的增大而降低;且n=12:1时,pH值趋于稳定,稳定值为6.15,此时NaClO的酸化过程达到极限,HClO占有效氯质量分数为94.91%,达到NaClO溶液中HClO占比的几百甚至几千倍。这是由于CO2遇水产生的H2CO3溶液为弱酸,与强碱弱酸盐NaClO反应仅能到达弱酸阶段,因此pH=6.15时反应达到稳定。由图3可见,生成液与NaClO溶液中的有效氯质量浓度相同,且有效氯质量浓度不随CO2通入量的变化而变化,即不随pH值的变化而变化。这是由于NaClO酸化过程是将原液中的ClO-转化成HClO,ClO和HClO均为有效氯成分,因此反应前后溶液中的有效氯质量浓度不变。
在NaClO酸化过程达到极限,即n=12:1的情况下,根据3.1.2节得出的生成液中有效氯质量浓度和HClO占有效氯质量分数,计算出不同有效氯质量浓度下生成液中HClO的质量浓度,实验结果见图6。结果表明,n=12:1的情况下,生成液中HClO质量分数与NaClO溶液有效氯质量浓度成线性关系(式(3),R2=0.999 9),相关性好。
y=0.954 7x+2.470 3
《消毒技术规范》[17]中规定,消毒剂在54 ℃恒温箱内放置14天,有效成分下降率不大于10%,可将贮存有效期定为1年。本实验向自制的质量浓度为500、1 000、1 500、2 000 mg/L的HClO溶液中加入不同量的稳定剂,在恒温54 ℃、避光、密闭的恒温箱内放置14天,分别测定放置前、后HClO质量浓度并计算下降率,结果见图7。本实验采用的稳定剂为纳米级氮化硼(200 nm)。
实验结果表明:未投加稳定剂的质量浓度为500、1 000、1 500、2 000 mg/L的HClO溶液,在恒温54 ℃、避光、密闭的条件下放置14天后,有效成分的下降率分别为29.00%、32.70%、36.47%、41.50%,下降率均远超过10%,且HClO溶液质量浓度越高,下降率相对越高;稳定剂投加量分别为30、60、80、90 mg/L时,有效成分下降率分别为9.60%、9.75%、9.67%、9.40%,均低于10%,有效期可定为1年。产生上述现象的原因是HClO质量浓度越高,其本身电荷密度越高,越不稳定,越容易分解产生HCl和O2,而稳定剂中的硼原子具有较强的缺电性,与HClO中氧原子可紧密络合,降低HClO中氧原子的电荷密度,从而提高HClO的稳定性[19]
将自制的质量分数为0.1%的HClO溶液(HClO占有效氯质量分数为94.91%)与质量分数10%的NaClO溶液的杀菌效果进行对比,对比指标为杀菌效率和杀菌速率。向杀菌对象中加入不同量(以有效氯质量分数计)的0.1% HClO和10% NaClO,在不同作用时间下检测杀菌对象中的细菌总数,记录杀菌作用时间并计算出杀菌率,杀菌效果实验结果见图8图9。通常认为杀菌率高于90%的杀菌剂为合格[20-24]。实验用杀菌对象为某火电厂浓缩倍率为5倍(以氯离子计)的循环冷却排污水,细菌总数为45 000个/L。
实验结果表明,当NaClO的投加量和作用时间为5 mg/L(以有效氯计)、120 min,HClO的投加量和作用时间为0.06 mg/L(以有效氯计)、15 min时,杀菌率均可达90%,可见HClO的杀菌效率和杀菌速率均远高于NaClO。产生此现象的原因是: HClO的主要成分为HClO分子,而含氯杀菌剂起主要杀菌作用的是HClO分子,由于HClO分子不带电荷,可以穿透细胞膜与DNA和线粒体发生氧化反应,从而破坏细胞膜或细胞壁直接产生杀菌作用,利用较低浓度的HClO溶液作用较短的时间,即可达到很好的杀菌效果[22-25];NaClO的主要成分为ClO,ClO带负电荷,与细胞膜表面的负电荷排斥,不易浸入细胞壁,导致杀菌效率远低于HClO,并且ClO是通过水解作用形成HClO间接产生杀菌作用。
以循环冷却塔塔池保有水量V=20 000 m3为例,对质量分数为0.1%HClO和10%NaClO 2种杀菌剂进行经济性分析。
1)杀菌剂成本
制备1 m3质量分数0.1%的HClO需要质量分数10%的NaClO 14 L,水986 L,液体CO2 11.25 L。其中,10%的NaClO来源有直接采购和电解法制备2种方式,采购单价按1.4元/L计,电解法制备的运行成本(包含材料、电耗及设备维护折旧费)按0.98元/L计,水单价按0.001元/L计,液态CO2单价按24元/L计。则2种来源原料杀菌剂制备成本比较见表2
可见2种来源原料杀菌剂制备成本基本相同,且“电解法制备”还需考虑人工成本,因此下列经济分析以“采购10% NaClO”作为原料制备HClO为基础。
2)经济性分析
根据3.3小节杀菌实验结果,HClO投加质量浓度按0.06 mg/L(以有效氯计)计,NaClO投加质量浓度按5 mg/L(以有效氯计)计。杀菌持久性按1天考虑,保有水量20 000 m3的水池0.1% HClO的投加量为1.2 m3/天,成本价为442元/天;10%NaClO投加量为1 m3/天,若直接采购,成本价为1 400元/天,若采用电解法制备,成本价为980元/天。综上所述,采用非电解法制备HClO作为循环水杀菌较采购NaClO和电解法制备NaClO成本可分别降低68%和55%。
1)NaClO溶液中的HClO含量非常低。有效氯质量浓度在100~2 000 mg/L NaClO溶液中,HClO占有效氯的质量分数仅为0.690%~0.012%,通入CO2后可提高至94.91%,从而提高杀菌效率。
2)质量浓度为500、1 000、1 500、2 000 mg/L的HClO溶液,稳定剂投加量分别为30、60、80、90 mg/L时,HClO含量的下降率可满足《消毒技术规范》保质期1年的要求。
3)HClO溶液的杀菌效率和杀菌速率均远高于NaClO溶液。当杀菌率同时达到90%时,NaClO和HClO的投加量分别为5、0.06 mg/L(以有效氯计),作用时间分别为120、15 min。可见,HClO作为杀菌剂更经济、高效,用于火电厂循环水杀菌较传统NaClO材料费成本可降低55%以上。
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2025年第54卷第10期
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doi: 10.19666/j.rlfd.202501002
  • 接收时间:2025-01-03
  • 首发时间:2026-03-05
  • 出版时间:2025-10-25
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    1.西安益通热工技术服务有限责任公司,陕西 西安 710032
    2.华能甘肃能源开发有限公司,甘肃 兰州 730070
    3.西安西热水务环保有限公司,陕西 西安 710054
    4.高效灵活煤电及碳捕集利用封存全国重点实验室,北京 102200
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2种不同金属材料的力学参数

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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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