CN104386854A - 一种电炉炼钢纯水循环系统水处理工艺方法 - Google Patents

一种电炉炼钢纯水循环系统水处理工艺方法 Download PDF

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CN104386854A
CN104386854A CN201410613028.2A CN201410613028A CN104386854A CN 104386854 A CN104386854 A CN 104386854A CN 201410613028 A CN201410613028 A CN 201410613028A CN 104386854 A CN104386854 A CN 104386854A
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water
inhibiter
acid
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sterilant
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CN104386854B (zh
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马景辉
刘家节
顿士超
肖知
吴新国
姜宝安
王乃琳
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Tianjin Zhengda Science & Technology Co ltd
China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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TIANJIN ZHENGDA TECHNOLOGY Co Ltd
China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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Abstract

本发明为一种电炉炼钢纯水循环系统水处理工艺方法，其特征在于采用一种缓蚀剂和杀菌剂应用于电炉炼钢纯水循环冷却水系统，通过在水系统中投加缓蚀剂和杀菌剂，利用缓蚀剂各组分之间产生的协同效应，和其与杀菌剂之间产生的缓蚀增效作用，降低使用量，提高缓蚀效果。解决了原有的电炉炼钢纯水系统由于对循环水电导率有严格上限要求，而不得不降低缓蚀剂用量，牺牲缓蚀效果来控制水体电导率的难题。

Description

一种电炉炼钢纯水循环系统水处理工艺方法
技术领域
本发明属于循环冷却水处理技术领域，具体涉及一种电炉炼钢纯水循环系统水处理工艺方法。
背景技术
电炉连铸生产中需要大量的冷却水,一般可分为二部分:一是间接冷却水,主要用于设备冷却(包括电炉炉壳、炉盖、烟道、底电极、液压空调及辅助设备)和结晶器的初冷；二是直接冷却水,又称为二冷喷啉,用于经结晶器初冷的钢包水型钢坯的冷却。
在间接设备冷却中，由于水冷钢棒式底电极、短网铜管、水冷电缆、导电横臂及电极夹头等导电材料的特殊性，为防止设备击穿，对冷却水的电导率有较高的要求(<500μs/cm)。故该类循环冷却水系统，一方面，采用纯水(或除盐水)作为补水来直接冷却；另一方面，循环冷却水系统中使用的缓蚀剂，则要严格控制使用浓度，以确保水系统的电导率在规定范围内。
一般来说，纯水密闭循环水系统中的缓蚀剂采用氧化型缓蚀剂，主要有亚硝酸盐、钼酸盐、钨酸盐等。这类缓蚀剂随着使用浓度的增加，水处理效果更好。但由于这类缓蚀剂均属于离子型物质，它的使用也随之造成水系统电导的快速上升。
现阶段的处理方式，主要是降低缓蚀剂的使用量，以牺牲一定的水处理效果，来满足循环水系统的水质对电导率控制上限这一特殊要求。这样，既造成了水处理效果变差，也会因水系统电导贴近上限运行加大水系统的日常运行控制难度。
为此，开发一种适用于电炉炼钢纯水循环系统水处理工艺方法，具有重要的实际意义。
发明内容
本发明所要解决的技术问题是提供一种电炉炼钢纯水循环系统的水处理工艺方法，以克服现有技术存在的水处理效果差、水系统日常运行控制难度大的不足。
本发明的设计思路是将阴极与阳极缓蚀剂、吸附型与氧化型缓蚀剂进行组合，通过各组分之间产生的协同效应，降低各组分的用量，尤其是降低氧化型缓蚀剂组分的用量，并通过与杀菌剂之间产生的缓蚀增效作用，进一步降低使用量，提高缓蚀效果。这样，就解决了原有的电炉炼钢纯水系统由于对循环水电导率有严格上限要求，而不得不降低缓蚀剂用量，牺牲缓蚀效果来控制水体电导率的难题。具体是通过以下技术方案予以实现：
本发明为一种电炉炼钢纯水循环水系统水处理工艺方法，其特征在于：所述方法包括：
1)制备缓蚀剂：
所述的缓蚀剂按重量百分比由以下组分组成：水溶性钼酸盐10～15％、聚环氧琥珀酸4～10％、硼砂2～16％、丙烯酸/丙烯酸羟丙酯/顺丁烯二酸酐/2-丙烯酰胺-2-甲基丙磺酸四元共聚物2～5％、有机羧酸盐1～4％、唑类0.1～2％，余量为水；
将聚环氧琥珀酸、丙烯酸/丙烯酸羟丙酯/顺丁烯二酸酐/2-丙烯酰胺-2-甲基丙磺酸四元共聚物、有机羧酸盐、水溶性钼酸盐置于密闭或压力容器中，搅拌条件下，控制反应温度的条件范围为40～70℃，控制压力为0.1Mpa，加入硼砂、水，搅拌均匀，再加入唑类，保持40～70℃，搅拌均匀至完全溶解后制得；
2)制备杀菌剂：
所述的杀菌剂含有重量百分比的含有多个胍基的有机胍聚合化合物5～30％、异噻唑啉酮1～10％、戊二醛20～30％、余量为有机溶剂；
将有机胍聚合化合物置于密闭或压力容器中，搅拌条件下，控制反应温度的条件范围为40～50℃，控制压力为0.1Mpa，加入有机溶剂、异噻唑啉酮、戊二醛，搅拌均匀至完全溶解后制得；
3)通过在水系统中投加所述缓蚀剂，加药浓度为1000～1500mg/L；在循环水中定期投加所述杀菌剂，加药浓度为20～200mg/L；缓蚀剂投加浓度通过钼酸根或pH值控制；
所述的聚环氧琥珀酸的结构式为：
其中，M为Na+、H+或K+；；聚合度n为4～30的整数，较佳聚合度范围4～15；
所述的水溶性钼酸盐为钼酸钠和钼酸钾的一种或两种；
所述的有机羧酸盐为葡萄糖酸、酒石酸、柠檬酸、月桂酸和苯甲酸的钠盐或钾盐的一种或几种；
所述的唑类为苯并三氮唑和疏基苯并唑的一种或两种。
本发明方法的有益效果在于：钼酸盐以MoO4 2-计控制在50.0～100.0mg/L；或pH值控制在9.5～11.0；可使纯水循环水系统的电导可控制在500us/cm以下；循环水中碳钢挂片和试管的腐蚀率小于0.075mm/a、不锈钢的腐蚀率小于0.005mm/a、铜合金的腐蚀率小于0.005mm/a、粘附速率小于15mg/cm2·月、污垢热阻值小于3.44×10-4m2·K/W、异养菌数小于1×105个/mL、铁细菌数小于5×102个/mL、硝化菌数小于1×102个/mL。本发明可应用于绝大部分纯水(软水)密闭循环水系统中，尤其可应用于对水系统电导有严格上限要求的电炉炼钢纯水密闭循环水系统中。
具体实施方式
为了更好地理解本发明，下面结合实施方式进一步阐明本发明的内容，但本发明内容不仅仅局限于下面的实施方式。
实施例1
按以下重量百分比的物质制备缓蚀剂：
将聚环氧琥珀酸10％(市售的液体制剂，聚合度为4～10，固含量为40％)、丙烯酸/丙烯酸羟丙酯/顺丁烯二酸酐/2-丙烯酰胺-2-甲基丙磺酸四元共聚物2％、柠檬酸钠2％、钼酸钠10％置于密闭或压力容器中，搅拌条件下，控制反应温度的条件范围为60℃(控制反应温度为55℃)，控制压力为0.1Mpa，加入硼砂8％、水67.9％，搅拌均匀，再加入苯并三氮唑0.1％，保持60℃，搅拌均匀至完全溶解，得到淡黄色的适于电炉炼钢纯水循环水系统的缓蚀剂I。
实施例2
按以下重量百分比的物质制备缓蚀剂：
将聚环氧琥珀酸6％(市售的液体制剂，聚合度为4～10，固含量为40％)、丙烯酸/丙烯酸羟丙酯/顺丁烯二酸酐/2-丙烯酰胺-2-甲基丙磺酸四元共聚物2％、月桂酸钾3％、钼酸钾12％置于密闭或压力容器中，搅拌条件下，控制反应温度的条件范围为50℃，控制压力为0.1Mpa，加入硼砂10％、水66.8％，搅拌均匀，再加入疏基苯并唑0.2％，保持50℃，搅拌均匀至完全溶解，得到无色的适于电炉炼钢纯水循环水系统的缓蚀剂II。
实施例3
按以下重量百分比的物质制备杀菌剂：
将醋酸双氯苯双胍己烷(市售商品，醋酸洗必泰)20％置于密闭或压力容器中，搅拌条件下，控制反应温度的条件范围为40～50℃，控制压力为0.1Mpa，加入异丙醇55％、异噻唑啉酮5％、戊二醛20％，搅拌均匀至完全溶解，得到黄绿色的适于电炉炼钢纯水循环水系统的杀菌剂I。
实施例4
按以下重量百分比的物质制备杀菌剂：
将聚二亚己基三胺盐酸胍10％置于密闭或压力容器中，搅拌条件下，控制反应温度的条件范围为40～50℃，控制压力为0.1Mpa，加入乙二醇50％、异噻唑啉酮10％、戊二醛30％，搅拌均匀至完全溶解，得到黄绿色的适于电炉炼钢纯水循环水系统的杀菌剂II。
其中聚二亚己基三胺盐酸胍制备方法按照专利CN201310512932中所涉及的方法。即：向装有冷凝器和氨气回收装置的反应瓶中，加入二亚己基三胺215g、盐酸胍95.5g和乙二醇200g，升温到80℃反应4h，再升温到180℃反应2h后制得聚二亚己基三胺盐酸胍。
实施例5
按照本发明所述的电炉炼钢纯水循环水系统循环水处理工艺方法，在电炉炼钢纯水循环系统中确保缓蚀剂I含量1000mg/L左右,每周投加一次杀菌剂I，用量150mg/L，水系统的钼酸盐以MoO4 2-计控制在50.0～75.0mg/L；pH值控制在9.5～10.5；可使纯水循环水系统的电导可控制在400us/cm左右，实现循环冷却水的稳定运行。本发明所述的缓蚀剂和杀菌剂可应用于补水为纯水的密闭循环水系统，尤其可应用于对水系统电导有严格上限要求的电炉炼钢纯水密闭循环水系统中。循环水中碳钢挂片和试管的腐蚀率小于0.075mm/a、不锈钢的腐蚀率小于0.005mm/a、铜合金的腐蚀率小于0.005mm/a、粘附速率小于15mg/cm2·月、污垢热阻值小于3.44×10-4m2·K/W、异养菌数小于1×105个/mL。铁细菌数小于5×102个/mL、硝化菌数小于1×102个/mL。
实施例6
按照本发明所述的电炉炼钢纯水循环水系统循环水处理工艺方法，在电炉炼钢纯水循环系统中确保缓蚀剂II含量1500mg/L左右,每周投加一次杀菌剂II，用量100mg/L，水系统的钼酸盐以MoO4 2-计控制在70.0～100.0mg/L；pH值控制在10.0～11.0；可使纯水循环水系统的电导可控制在小于500us/cm，实现循环冷却水的稳定运行。本发明所述的缓蚀剂和杀菌剂可应用于补水为纯水的密闭循环水系统，尤其可应用于对水系统电导有严格上限要求的电炉炼钢纯水密闭循环水系统中。循环水中碳钢挂片和试管的腐蚀率小于0.075mm/a、不锈钢的腐蚀率小于0.005mm/a、铜合金的腐蚀率小于0.005mm/a、粘附速率小于15mg/cm2·月、污垢热阻值小于3.44×10-4m2·K/W、异养菌数小于1×105个/mL。铁细菌数小于5×102个/mL、硝化菌数小于1×102个/mL。

Claims (2)

1.一种电炉炼钢纯水循环水系统水处理工艺方法，其特征在于：所述方法包括： 
1)制备缓蚀剂: 
所述的缓蚀剂按重量百分比由以下组分组成：水溶性钼酸盐10～15％、聚环氧琥珀酸4～10％、硼砂2～16％、丙烯酸/丙烯酸羟丙酯/顺丁烯二酸酐/2-丙烯酰胺-2-甲基丙磺酸四元共聚物2～5％、有机羧酸盐1～4％、唑类0.1～2％，余量为水； 
将聚环氧琥珀酸、丙烯酸/丙烯酸羟丙酯/顺丁烯二酸酐/2-丙烯酰胺-2-甲基丙磺酸四元共聚物、有机羧酸盐、水溶性钼酸盐置于密闭或压力容器中，搅拌条件下，控制反应温度的条件范围为40～70℃，控制压力为0.1Mpa，加入硼砂、水，搅拌均匀，再加入唑类，保持40～70℃，搅拌均匀至完全溶解后制得； 
2)制备杀菌剂： 
所述的杀菌剂按重量百分比由以下组分组成：含有多个胍基的有机胍聚合化合物5～30％、异噻唑啉酮1～10％、戊二醛20～30％、余量为有机溶剂； 
将有机胍聚合化合物置于密闭或压力容器中，搅拌条件下，控制反应温度的条件范围为40～50℃，控制压力为0.1Mpa，加入有机溶剂、异噻唑啉酮、戊二醛，搅拌均匀至完全溶解后制得； 
3)通过在水系统中投加所述缓蚀剂，加药浓度为1000～1500mg/L；在循环水中定期投加所述杀菌剂，加药浓度为20～200mg/L； 
其中所述的聚环氧琥珀酸的结构式为： 
聚合度n为4～30的整数；M为Na+、H+或K+ 。
2.根据权利要求1所述的方法，其特征在于，所述的水溶性钼酸盐为钼酸钠和钼酸钾的一种或两种；所述的有机羧酸盐为葡萄糖酸、酒石酸、柠檬酸、月桂酸和苯甲酸的钠盐或钾盐的一种或几种；所述的唑类为苯并三氮唑和疏基苯并唑的一种或两种。 
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