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CN112745983A - 无磷型碱性水基喷淋清洗防锈剂及其制备方法 - Google Patents

无磷型碱性水基喷淋清洗防锈剂及其制备方法 Download PDF

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CN112745983A
CN112745983A CN202011621968.8A CN202011621968A CN112745983A CN 112745983 A CN112745983 A CN 112745983A CN 202011621968 A CN202011621968 A CN 202011621968A CN 112745983 A CN112745983 A CN 112745983A
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phosphorus
alkaline water
agent
free alkaline
sodium
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孟晓光
贾晓清
张雪峰
杜朝波
柴寿庆
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Talent Biological Engineering Co ltd
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Talent Biological Engineering Co ltd
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Priority to CN202011621968.8A priority Critical patent/CN112745983A/zh
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Abstract

本发明公开了一种无磷型碱性水基喷淋清洗防锈剂及其制备方法，采用碳6异构双酶烷基糖苷与牛脂基双羟乙基改性脂肪醇聚氧乙烯醚(R＝C14～16,n＝7)及其它试剂复配并形成稳定体系，在清洗方面具有很好的净洗力，可清洗不同工况下的多种油污，适用范围广泛，可以有效减少清洗剂的种类选择及储备量。依靠有机多元羧酸铵盐进行防锈，与其它产品相比，体系不含亚硝酸钠，从而避免了使用此类物质带来的法律和道德风险；对碱性要求不高、pH较低，所以对人体影响极小，在使用过程中不会有致敏现象，且对设备和人体更加安全，不易导致腐蚀。

Description

无磷型碱性水基喷淋清洗防锈剂及其制备方法
技术领域
本发明属于防锈剂技术领域，涉及碱性水基防锈剂的技术创新，尤其是一种无磷型碱性水基喷淋清洗防锈剂及其制备方法。
背景技术
自2013年以来，中央加大了环境保护与治理的力度，尤其是2015年五中全会后，绿色发展成为未来中国发展的五大理念之一，自此，全国各地的环保部门对大气环境的治理、水资源的保护均出台了相关规定及标准。在这个大的环境下，工业污水处理成为重中之重。工业污水主要指工业生产过程中产生的废水和废液，比如生产废水、生产污水及冷却水等，其中含有随水流失的工业生产用料、中间产物、副产品以及生产过程中产生的污染物。
根据2020年最新版的《污水综合排放标准》，主要对含油废水排放标准、污水COD排放标准、重金属废水排放标准、总氮总磷排放标准、色度浊度排放标准、污水处理厂氨氮排放标准等提出具体要求。以总磷排放标准的要求为例：工业废水三级排放标准为≤5mg/L。而污水处理厂在按此标准执行的同时，对上游产生废水的企业也加大了环保要求，上游废水进入污水处理厂需对各污染物进行24小时监测，一旦超标，上游企业将受到相应处罚。
在机械制造业中，工业清洗剂是常用的试剂，其目的是对机械加工的钢件、铸铁件等的表面进行清洗，去除各种残留的金属加工液、防锈油、冲压油、拉拔油、淬火油等杂质。目前，市场上常见的清洗剂含有“磷”，而这样的清洗剂同样存在环境污染、需要处理后才能排放的缺点，有些厂家开发出不含“磷”的清洗剂，但清洗效果仍可以进一步增强，而且功能比较单一。
发明内容
本发明克服了现有技术的不足，提供一种无磷型碱性水基喷淋清洗防锈剂。本发明在清洗功能的基础上添加了新型原料，将清洗功能和防锈功能结合在一起，具有低泡沫、抑制起泡、不含亚硝酸钠，对人体影响极小且清洗防锈效率高的优点。
本发明为了解决上述问题而采用了如下的技术方案：
一种无磷型碱性水基喷淋清洗防锈剂，其特征在于：包括按重量百分比混合的以下组分：
Figure BDA0002878527960000011
Figure BDA0002878527960000021
再有，所述清洗助剂包括五水偏硅酸钠、碳酸钠、硅酸钠、4A沸石、氯化钠、元明粉中的任意一种、任意两种或任意三种。
再有，所述分散剂包括十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪酸聚乙二醇酯、葡萄糖酸钠、牛脂基双羟乙基改性脂肪醇聚氧乙烯醚中的任意一种、任意两种或任意三种。
再有，所述螯合剂包括氨羧络合剂、双硫腙、8-羟基喹啉、邻菲咯啉、酒石酸钾钠、柠檬酸铵中的任意一种、任意两种或任意三种。
再有，所述水基防锈剂为十二烯基丁二酸、三元聚羧酸、十一碳二元酸、十二碳二元酸、硼酸、氢氧化钠、碳酸钠、氢氧化钾、单乙醇胺、三乙醇胺、单异丙醇胺中的任意一种、任意两种或任意三种。
再有，所述乳化剂为异构脂肪醇聚氧乙烯醚、异构山梨醇酐油酸酯、烷基葡萄糖苷、蓖麻油聚氧乙烯醚、反式嵌段聚醚、烷基糖苷中的任意一种、任意两种或任意三种。
再有，所述增溶剂为聚氧乙烯硬化蓖麻油、聚氧乙烯蓖麻油、脂肪醇聚氧乙烯醚、脂肪醇聚氧乙烯-聚氧丙烯醚、聚氧乙烯失水山梨醇脂肪酸酯、聚甘油脂肪酸酯、碳6异构双酶烷基糖苷中的任意一种、任意两种或任意三种。
再有，所述添加剂为消泡剂、抑菌剂中的任意一种或全部两种。
本发明的另一个目的是提供一种无磷型碱性水基喷淋清洗防锈剂的制备方法，包括以下步骤：
将反应釜中注入适量的水；
将清洗助剂、分散剂、螯合剂加入反应釜中，搅拌均匀；
将水基防锈剂、乳化剂、增溶剂加入反应釜中，搅拌均匀后静置；
将添加剂加入后搅拌均匀，得到成品。
本发明的另一个目的是提供一种无磷型碱性水基喷淋清洗防锈剂的应用方法，包括以下步骤：
当工件在工序之间进行传递时，使用浓度为3-8％的清洗防锈液对工件进行喷淋处理；
当工件进行中期防锈时，使用浓度10-20％的清洗防锈液对工件进行喷淋处理。
本发明取得的技术效果是：
1.本发明中，采用碳6异构双酶烷基糖苷与牛脂基双羟乙基改性脂肪醇聚氧乙烯醚 (R＝C14～16,n＝7)及其它试剂复配并形成稳定体系，在清洗方面具有很好的净洗力，可清洗不同工况下的多种油污，适用范围广泛，可以有效减少清洗剂的种类选择及储备量。
2.本发明中，依靠有机多元羧酸铵盐进行防锈，与其它产品相比，体系不含亚硝酸钠，从而避免了使用此类物质带来的法律和道德风险；对碱性要求不高、pH较低，所以对人体影响极小，在使用过程中不会有致敏现象，且对设备和人体更加安全，不易导致腐蚀。
3.本发明中，在喷淋清洗过程中，泡沫低，同时兼具抑泡性能，可以避免因泡沫高而造成的泡沫溢槽问题，减少使用现场的环境污染，极大程度的控制了清洗现场的安全隐患。
4.本发明中，在实现了清洗防锈一步完成的同时，清洗能力明显优于市场同类产品，同时适用范围广泛，可清洗多种油污，并且在使用过程中具有极低泡沫性能，并具有极佳的持续抑泡能力，可以有效地提升制造件的清洗效率，提高制造件表面的洁净度，延迟制造件的防锈时间。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施例，进一步阐述本发明，但下述实施例仅仅为本发明的优选实施例，并非全部。基于实施方式中的实施例，本领域技术人员在没有做出创造性劳动的前提下所获得其它实施例，都属于本发明的保护范围。
一种无磷型碱性水基喷淋清洗防锈剂，本发明的创新在于：包括按重量百分比混合的以下组分：
Figure BDA0002878527960000031
其中，清洗助剂包括五水偏硅酸钠、碳酸钠、硅酸钠、4A沸石、氯化钠、元明粉中的任意一种、任意两种或任意三种。
优选的组合方式及比例为：
A组：五水偏硅酸钠4-6％；碳酸钠3-5％；氯化钠1-3％(以总原料重量的百分比计，下文的优选的组合方式中均相同)
B组：碳酸钠3-5％；硅酸钠3-5％；氯化钠1-3％
C组：五水偏硅酸钠4-6％；硅酸钠3-5％；氯化钠1-3％
D组：五水偏硅酸钠4-6％；碳酸钠3-5％；硅酸钠3-5％
E组：五水偏硅酸钠4-6％；碳酸钠3-5％；4A沸石3-5％
F组：碳酸钠3-5％；氯化钠1-3％；4A沸石3-5％
G组：硅酸钠3-5％；氯化钠1-3％；4A沸石3-5％
H组：五水偏硅酸钠4-6％；氯化钠1-3％；4A沸石3-5％
分散剂包括十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪酸聚乙二醇酯、葡萄糖酸钠、牛脂基双羟乙基改性脂肪醇聚氧乙烯醚(R＝C14～16,n＝7)中的任意一种、任意两种或任意三种。
优选的组合方式及比例为：
A组：牛脂基羟乙基改性脂肪醇聚氧乙烯醚(R＝C14～16,n＝7)4-6％；十二烷基硫酸钠1-3％；甲基戊醇1-3％
B组：牛脂基双羟乙基改性脂肪醇聚氧乙烯醚(R＝C14～16,n＝7)4-6％；十二烷基硫酸钠 1-3％；葡萄糖酸钠1-3％
C组：牛脂基双羟乙基改性脂肪醇聚氧乙烯醚(R＝C14～16,n＝7)4-6％；甲基戊醇1-3％；聚丙烯酰胺1-3％
D组：牛脂基双羟乙基改性脂肪醇聚氧乙烯醚(R＝C14～16,n＝7)4-6％；葡萄糖酸钠1-3％；聚丙烯酰胺1-3％
E组：牛脂基双羟乙基改性脂肪醇聚氧乙烯醚(R＝C14～16,n＝7)4-6％；葡萄糖酸钠1-3％；纤维素衍生物1-3％
F组：牛脂基双羟乙基改性脂肪醇聚氧乙烯醚(R＝C14～16,n＝7)4-6％；甲基戊醇1-3％；纤维素衍生物1-3％
G组：牛脂基双羟乙基改性脂肪醇聚氧乙烯醚(R＝C14～16,n＝7)4-6％；十二烷基硫酸钠 1-3％；聚丙烯酰胺1-3％
H组：牛脂基双羟乙基改性脂肪醇聚氧乙烯醚(R＝C14～16,n＝7)4-6％；十二烷基硫酸钠 1-3％；纤维素衍生物1-3％
螯合剂包括氨羧络合剂、双硫腙、8-羟基喹啉、邻菲咯啉(C12H8N2)、酒石酸钾钠、柠檬酸铵中的任意一种、任意两种或任意三种。上述氨羧络合剂包括氨基三乙酸即NTA、乙二胺四乙酸即EDTA等。
优选组合方式及比例为：
A组：氨基三乙酸0.5-2％；酒石酸钾钠0.5-2％；柠檬酸铵3-5％
B组：氨基三乙酸0.5-2％；柠檬酸铵3-5％；乙二胺四乙酸0.5-2％
C组：氨基三乙酸0.5-2％；酒石酸钾钠0.5-2％；乙二胺四乙酸0.5-2％
D组：酒石酸钾钠0.5-2％；柠檬酸铵3-5％；乙二胺四乙酸0.5-2％
E组：氨基三乙酸0.5-2％；酒石酸钾钠0.5-2％；8-羟基喹啉1-3％
F组：氨基三乙酸0.5-2％；柠檬酸铵3-5％；8-羟基喹啉1-3％
G组：酒石酸钾钠0.5-2％；乙二胺四乙酸0.5-2％；8-羟基喹啉1-3％
H组：柠檬酸铵3-5％；乙二胺四乙酸0.5-2％；8-羟基喹啉1-3％
水基防锈剂为十二烯基丁二酸、三元聚羧酸、十一碳二元酸、十二碳二元酸、硼酸、氢氧化钠、碳酸钠、氢氧化钾、单乙醇胺、三乙醇胺、单异丙醇胺中的任意一种、任意两种或任意三种。
优选组合方式及比例为：
A组：十二烯基丁二酸3-5％；硼酸2-5％；三乙醇胺4-6％
B组：硼酸2-5％；三乙醇胺4-6％；三元聚羧酸4-6％
C组：三乙醇胺4-6％；三元聚羧酸4-6％；碳酸钠4-6％
D组：十一碳二元酸4-6％；碳酸钠4-6％；单异丙醇胺4-6％
E组：硼酸2-5％；三乙醇胺4-6％；十一碳二元酸4-6％
F组：十一碳二元酸4-6％；碳酸钠4-6％；三乙醇胺4-6％
G组：三元聚羧酸4-6％；碳酸钠4-6％；单异丙醇胺4-6％
H组：十二烯基丁二酸3-5％；三乙醇胺4-6％；碳酸钠4-6％
乳化剂为异构脂肪醇聚氧乙烯醚、异构山梨醇酐油酸酯、烷基葡萄糖苷、蓖麻油聚氧乙烯醚、反式嵌段聚醚、烷基糖苷中的任意一种、任意两种或任意三种。
优选组合方式及比例为：
A组：异构脂肪醇聚氧乙烯醚1-3％；异构山梨醇酐油酸酯1-3％；烷基葡萄糖苷1-3％
B组：异构脂肪醇聚氧乙烯醚1-3％；异构山梨醇酐油酸酯1-3％；反式嵌段聚醚1-3％
C组：异构山梨醇酐油酸酯1-3％；烷基葡萄糖苷1-3％；反式嵌段聚醚1-3％
D组：异构脂肪醇聚氧乙烯醚1-3％；反式嵌段聚醚1-3％；烷基糖苷1-3％
E组：异构脂肪醇聚氧乙烯醚1-3％；烷基葡萄糖苷1-3％；烷基糖苷1-3％
F组：异构脂肪醇聚氧乙烯醚1-3％；异构山梨醇酐油酸酯1-3％；烷基糖苷1-3％
G组：反式嵌段聚醚1-3％；烷基葡萄糖苷1-3％；烷基糖苷1-3％
H组：异构山梨醇酐油酸酯1-3％；反式嵌段聚醚1-3％；烷基糖苷1-3％
增溶剂为聚氧乙烯硬化蓖麻油、聚氧乙烯蓖麻油、脂肪醇聚氧乙烯醚、脂肪醇聚氧乙烯- 聚氧丙烯醚、聚氧乙烯失水山梨醇脂肪酸酯、聚甘油脂肪酸酯、碳6异构双酶烷基糖苷中的任意一种、任意两种或任意三种。
优选组合方式及比例为：
A组：碳6异构双酶烷基糖苷3-5％；聚氧乙烯硬化蓖麻油1-3％；聚氧乙烯蓖麻油1-3％
B组：碳6异构双酶烷基糖苷3-5％；脂肪醇聚氧乙烯醚1-3％；脂肪醇聚氧乙烯-聚氧丙烯醚1-3％
C组：碳6异构双酶烷基糖苷3-5％；聚甘油脂肪酸酯1-3％；聚氧乙烯失水山梨醇脂肪酸酯1-3％
D组：碳6异构双酶烷基糖苷3-5％；聚氧乙烯硬化蓖麻油1-3％；脂肪醇聚氧乙烯醚1-3％
E组：碳6异构双酶烷基糖苷3-5％；聚氧乙烯硬化蓖麻油1-3％；脂肪醇聚氧乙烯-聚氧丙烯醚1-3％
F组：碳6异构双酶烷基糖苷3-5％；脂肪醇聚氧乙烯醚1-3％；聚氧乙烯失水山梨醇脂肪酸酯1-3％
G组：碳6异构双酶烷基糖苷3-5％；脂肪醇聚氧乙烯醚1-3％；聚甘油脂肪酸酯1-3％
H组：碳6异构双酶烷基糖苷3-5％；脂肪醇聚氧乙烯醚1-3％；聚氧乙烯蓖麻油1-3％
添加剂为消泡剂、抑菌剂中的任意一种或全部两种。消泡剂包括ACP-1400、DB110、DH13、 575，抑菌剂包括IPBC、MBM、BK、BBIT。优选的消泡剂为：575,优选的抑菌剂为：MBM。
上述各种组分均为市售产品。
上述清洗防锈剂的制备方法包括以下步骤：将反应釜中注入足量的水；
将清洗助剂、分散剂、螯合剂依次加入反应釜中，搅拌均匀；
将水基防锈剂、乳化剂、增溶剂依次加入反应釜中，搅拌均匀后静置；
将添加剂加入后搅拌均匀，得到成品。
实施例1
Figure BDA0002878527960000061
Figure BDA0002878527960000071
制备过程是：
将反应釜中注入足量的水，启动搅拌；
将实施例1中的清洗助剂依次加入反应釜中与水完全溶解(加入顺序无要求)，然后依次加入实施例1中的分散剂至反应釜中完全溶解(加入顺序无要求)，再依次加入实施例1中的螯合剂至反应釜至完全溶解(加入顺序无要求)，液相呈均一稳定的透明状态；
将实施例1中的水基防锈剂依次加入反应釜中至完全溶解(加入顺序无要求)，然后依次加入实施例1中的乳化剂至反应釜中完全溶解(加入顺序无要求)，再依次加入实施例1中的增溶剂至反应釜至完全溶解(加入顺序无要求)，继续搅拌15分钟后关闭搅拌器，静置30分钟，让物料自行反应，然后再次开启搅拌，使液相呈均一稳定的透明状态；
将剩余的两种其他添加剂依次加入反应釜中(加入顺序无要求)，搅拌至均一透明后即得到成品。
实施例2
Figure BDA0002878527960000081
制备方法与实施例1相同。
实施例3
Figure BDA0002878527960000082
Figure BDA0002878527960000091
制备方法与实施例1相同。
实施例4
Figure BDA0002878527960000092
Figure BDA0002878527960000101
制备方法与实施例1相同。
实施例5
Figure BDA0002878527960000102
Figure BDA0002878527960000111
制备方法与实施例1相同。
实施例6
Figure BDA0002878527960000112
Figure BDA0002878527960000121
制备方法与实施例1相同。
实施例7
Figure BDA0002878527960000122
Figure BDA0002878527960000131
制备方法与实施例1相同。
实施例8
Figure BDA0002878527960000132
Figure BDA0002878527960000141
制备方法与实施例1相同。
无磷型碱性水基喷淋清洗防锈剂与传统清洗液的性能对比，如：表1
Figure BDA0002878527960000142
表1：无磷型碱性水基喷淋清洗防锈剂与传统清洗液性能对
本发明使用水稀释原液使用，广泛适用于钢、铸铁等制造件的喷淋清洗防锈，具体配液浓度需要根据客户要求验证确定。
本发明使用时：
在储液槽中注入适量的水，开启清洗设备的槽液循环系统，再逐步向储液槽中添加本发明，根据清洗设备的槽液循环能力，初步判断本发明是否稀释完全，再使用手持式折光仪检测稀释液浓度是否达标；
如果使用一定浓度(3-8％)的本发明对制造件进行喷淋清洗，则在工序间不需要进行额外清洗、防锈过程；
如果使用较高浓度(10-20％)的本发明对制造件进行喷淋清洗后进行烘干，则可以满足一般中期防锈要求；
如果使用本发明对制造件喷淋清洗后进行烘干过程，需要中长期防锈时，无需清洗，可以直接浸涂防锈油；
每天进行工作液的折光以及pH值检测，以保障工作液的使用性能。
在清洗设备设计达标的基础上，需定期将工作液表面漂浮的油污从体系中分离，可以提高工作液使用寿命，保障制造件清洗后的清洁度。
本发明相关性能指标见表2：
Figure BDA0002878527960000151
Figure BDA0002878527960000161
表2：无磷型碱性水基喷淋清洗防锈剂相关性能指标。

Claims (10)

1.一种无磷型碱性水基喷淋清洗防锈剂，其特征在于：包括按重量百分比混合的以下组分：
Figure FDA0002878527950000011
2.根据权利要求1所述的一种无磷型碱性水基喷淋清洗防锈剂，其特征在于：所述清洗助剂包括五水偏硅酸钠、碳酸钠、硅酸钠、4A沸石、氯化钠、元明粉中的任意一种、任意两种或任意三种。
3.根据权利要求1所述的一种无磷型碱性水基喷淋清洗防锈剂，其特征在于：所述分散剂包括十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪酸聚乙二醇酯、葡萄糖酸钠、牛脂基双羟乙基改性脂肪醇聚氧乙烯醚中的任意一种、任意两种或任意三种。
4.根据权利要求1所述的一种无磷型碱性水基喷淋清洗防锈剂，其特征在于：所述螯合剂包括氨羧络合剂、双硫腙、8-羟基喹啉、邻菲咯啉、酒石酸钾钠、柠檬酸铵中的任意一种、任意两种或任意三种。
5.根据权利要求1所述的一种无磷型碱性水基喷淋清洗防锈剂，其特征在于：所述水基防锈剂为十二烯基丁二酸、三元聚羧酸、十一碳二元酸、十二碳二元酸、硼酸、氢氧化钠、碳酸钠、氢氧化钾、单乙醇胺、三乙醇胺、单异丙醇胺中的任意一种、任意两种或任意三种。
6.根据权利要求1所述的一种无磷型碱性水基喷淋清洗防锈剂，其特征在于：所述乳化剂为异构脂肪醇聚氧乙烯醚、异构山梨醇酐油酸酯、烷基葡萄糖苷、蓖麻油聚氧乙烯醚、反式嵌段聚醚、烷基糖苷中的任意一种、任意两种或任意三种。
7.根据权利要求2所述的一种无磷型碱性水基喷淋清洗防锈剂，其特征在于：所述增溶剂为聚氧乙烯硬化蓖麻油、聚氧乙烯蓖麻油、脂肪醇聚氧乙烯醚、脂肪醇聚氧乙烯-聚氧丙烯醚、聚氧乙烯失水山梨醇脂肪酸酯、聚甘油脂肪酸酯、碳6异构双酶烷基糖苷中的任意一种、任意两种或任意三种。
8.根据权利要求1所述的一种无磷型碱性水基喷淋清洗防锈剂，其特征在于：所述添加剂为消泡剂、抑菌剂中的任意一种或全部两种。
9.根据权利要求1-8任意一项所述的一种无磷型碱性水基喷淋清洗防锈剂的制备方法，其特征在于：包括以下步骤：
将反应釜中注入适量的水；
将清洗助剂、分散剂、螯合剂加入反应釜中，搅拌均匀；
将水基防锈剂、乳化剂、增溶剂加入反应釜中，搅拌均匀后静置；
将添加剂加入后搅拌均匀，得到成品。
10.根据权利要求1-8任意一项所述的一种无磷型碱性水基喷淋清洗防锈剂的应用方法，其特征在于：
当工件在工序之间进行传递时，使用浓度为3-8％的清洗防锈液对工件进行喷淋处理；
当工件进行中期防锈时，使用浓度10-20％的清洗防锈液对工件进行喷淋处理。
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