CN108048194A - 一种水溶液硬度大于200ppm的钢制工件精细加工用乳化液及其制备方法和后处理工艺 - Google Patents
一种水溶液硬度大于200ppm的钢制工件精细加工用乳化液及其制备方法和后处理工艺 Download PDFInfo
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- CN108048194A CN108048194A CN201810005707.XA CN201810005707A CN108048194A CN 108048194 A CN108048194 A CN 108048194A CN 201810005707 A CN201810005707 A CN 201810005707A CN 108048194 A CN108048194 A CN 108048194A
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- emulsion
- oil
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- 200ppm
- hardness
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Classifications
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/0016—Working-up used lubricants to recover useful products ; Cleaning with the use of chemical agents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/0058—Working-up used lubricants to recover useful products ; Cleaning by filtration and centrifugation processes; apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2207/283—Esters of polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
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Abstract
本发明提供一种水溶液硬度大于200ppm的钢制工件精细加工用乳化液及其制备方法和后处理方法，所述乳化液包括精制机械复合基础油、复合酯、阴离子表面活性剂、有机硅非离子表面活性剂、极压剂、杀菌剂、pH值调整剂、硬度大于200ppm的非自来水和抗硬水剂。该乳化液润滑性能优越、抗腐蚀性能好，稳定性强，使用寿命长，制备方法简单，成分少，处理后的废弃乳化液对环境无污染，且分离的油相可以循环利用。
Description
技术领域
本发明涉及金属制品加工领域，具体涉及一种钢制工件精细加工用乳化液及其制备方法和处理工艺。
背景技术
乳化液，是指用于金属及其合金切削、冲压、轧制和拉拔等各种加工过程中所使用的润滑剂，乳化液应当具有防止金属零件锈蚀、带走加工过程中产生的热量、有效清除零件和刀具表面上的切屑和其它粉粒等作用。最早触及的乳化液是纯水，然后慢慢发展出水或者油为基础的乳化液。
根据乳化液的组成和介质的不同，可将乳化液分为油基和水基两类：（1）油基乳化液是使用油脂类化合物（矿物油、植物油），添加油性防锈剂以及其他油性添加剂包括含氯、磷、硫的极压剂配制而成。其优点为润滑性和防锈性优秀，但是冷却作用极差，容易产生油雾、油烟，甚至引发火灾。（2）水基乳化液：水基乳化液中的水的比热较大，热导率高，汽化热大，具备优秀的冷却性能，而且成本很低，加工后清洗也比较便捷，水基乳化液主要有乳化液、半合成液和合成液三种。乳化液含油量较高，由不溶于水的矿物油、脂肪油与表面活性剂组成，润滑性和切削性很好；半合成液由少量矿物油、适量的水和适当的添加剂组成，可应用性很广，它的寿命、防腐性、极压性能均超过乳化液；合成液含大量水和多种水溶性功能添加剂，但不含油，加水稀释后呈透明状态，冷却性很好，润滑性较差，容易造成工件的腐蚀。目前主流的乳化液为半合成液，具有乳化液和合成液的优良特性，但依旧存在乳化液和合成液的缺点，如半合成水基乳化液由于含有矿物油、脂肪酸皂、胺、磺酸盐和水等成分，因此易遭受微生物的侵袭，导致腐败变质，使用寿命缩短。特别是在南方炎热的夏天使用周期只有一个星期，甚至只有两三天就发臭，给操作工人带来了很多麻烦。这既增加了更换加工液的工时及生产成本，又污染了工作环境，再如半合成水基乳化液中含有大量的水，导致乳化液的润滑性、切削性、耐腐蚀性均有待提高。
此外，对于精细切削钢制基材而言，合成液和半合成液的润滑性和切削性远远不能达到制造标准，此时，乳化液的优良润滑性和切削性就显得尤为重要，但其使用寿命太短，且润滑性和切削性依旧有待提高，使用后乳化液废弃液也亟需处理。
发明内容
为了解决背景技术提到的当前乳化液存在的问题，本发明提供了一种水溶液硬度大于200ppm的钢制工件精细加工用乳化液、乳化液的制备及废液处理工艺，该乳化液具有润滑性能优越、抗腐蚀性能好，稳定性强及使用寿命长等优点，制备乳化液的方法简单，成分少，处理后的废弃乳化液对环境无污染，且分离的油相可以循环利用。
为达到上述目的，本发明所采取的技术方案为：
一种水溶液硬度大于200ppm的钢制工件精细加工用乳化液，包括如下成分：
精制机械复合基础油：选自L-AN10、L-AN15 或L-AN32中的一种与磺化蓖麻油的混合物，质量比为1：（0.2~0.4），20~65wt.%；
复合酯：油酸异丙醇胺硼酸复合酯，3~15wt.%；
阴离子表面活性剂：石油磺酸钠，0.5~1wt.%；
有机硅非离子表面活性剂：聚醚改性硅油，0.05~0.2%；
极压剂：二烷基二硫代磷酸锌或环己烷二醇的链烷酸酯，1~5wt.%；
杀菌剂：甲基异噻唑酮、亚甲二氯化酚或亚甲基双吗啉中的一种或几种，1~2wt.%；
pH值调整剂：NaOH或Na2CO3，调整pH至8~10；
剩余为非自来水，当非自来水的硬度大于200ppm时，加入0.1~1wt.%的抗硬水剂，抗硬水剂选自EDTA或EDTA-Na中的一种。
乳化液的制备方法如下：首先，将油酸、硼酸和异丙醇胺按摩尔比为1：（1~2）：（4~6）在140~155oC下酯化反应2~3h，冷却，静置获得复合酯A溶液；然后称取一定比例的精制机械油和磺化蓖麻油放入反应釜中，再加入适量复合酯A溶液，于60-80oC下缓慢搅拌1~2h获得混合均匀的油相B液；然后称取硬度>200ppm的非自来水放入搅拌反应釜中，加入抗硬水剂，搅拌，之后向其中加入石油磺酸钠和聚醚改性硅油，加热至60-80oC，搅拌1~2h，获得均匀的溶液C，然后将C液倒入B液混合，60-80oC保温搅拌0.5h获得均匀O/W乳化液，然后降温至40oC加入极压剂和杀菌剂，继续搅拌1~1.5h，冷却至室温，然后使用NaOH或Na2CO3调节乳化液的pH值至8~10，最终获得钢制工件加工用乳化液。
本发明还提供一种水溶液硬度大于200ppm的钢制工件精细加工用乳化液的后处理方法，其特征在于所述乳化液为使用后的废弃乳化液，首先收集使用后的废弃乳化液于收集箱中，通过离心机和过滤器分离固体钢屑杂质和液体，然后向液体中加入5wt.%的硫酸、盐酸和氯化钙的混合液，其中硫酸、盐酸和氯化钙的质量比为1：0.5：（0.1~0.3），使液体的pH值位于6~7，以实现油和废水的分离，获得的废水经过活性煤吸附和电凝器处理，除去多余的有机物质，净化废水，最终排放的废水含油量低于5mg/L，悬浮物低于300mg/L，化学耗氧量（COD）低于80mg/L，而获得的油相通过高温杀菌、除杂，可再生循环用于钢制工件精细加工用的乳化液基础油。
有益效果
本发明能达到以下有益的技术效果：
（1）该乳化液的制备工艺简单，使用方便，尤其适用于钢制件精细切削制造；
（2）该乳化液安全、环保，成本较低，且乳化液的油相可循环利用；
（3）该乳化液的润滑性能优越、抗腐蚀性能好，且稳定性强，使用寿命长，在清洗性、防锈性、冷却性、加工可视性等方面均为优良；
（4）该乳化液可降低对溶剂水的要求，可实现水硬度>200ppm的要求。
具体实施方式
对比例1
一种钢制工件乳化液，该乳化液包括：
基础油：L-AN15，40 wt.%；
复合酯：油酸异丙醇胺硼酸复合酯，10wt.%；
阴离子表面活性剂：石油磺酸钠，0.75wt.%；
有机硅非离子表面活性剂：聚醚改性硅油，0.1 wt.%；
极压剂：二烷基二硫代磷酸锌；3wt.%；
杀菌剂：甲基异噻唑酮，1wt.%；
pH值调整剂： Na2CO3，调整pH至8~10；
抗硬水剂：EDTA-Na，0.5wt.%；
剩余为非自来水，水的硬度>200ppm；标记为D-1。
对比例2
一种钢制工件乳化液，该乳化液包括：
精制机械复合基础油：L-AN15与磺化蓖麻油的混合物，质量比为1：0.3，总量40wt.%；
阴离子表面活性剂：石油磺酸钠，0.75wt.%；
有机硅非离子表面活性剂：聚醚改性硅油，0.1 wt.%；
极压剂：二烷基二硫代磷酸锌，3wt.%；
杀菌剂：甲基异噻唑酮，1wt.%；
抗硬水剂：EDTA-Na， 0.5wt.%；
pH值调整剂： Na2CO3，调整pH至8~10；
剩余为非自来水，水的硬度>200ppm；标记为D-2。
对比例3
一种钢制工件乳化液，该乳化液包括：
精制机械复合基础油：L-AN15与磺化蓖麻油的混合物，质量比为1：0.3，总量40wt.%；
油酸，1.25wt.%
硼酸，2.5wt.%
异丙醇胺，6.25wt.%；
阴离子表面活性剂：石油磺酸钠，0.75wt.%；
有机硅非离子表面活性剂：聚醚改性硅油，0.1 wt.%；
极压剂：二烷基二硫代磷酸锌，3wt.%；
杀菌剂：甲基异噻唑酮，1wt.%；
抗硬水剂：EDTA-Na， 0.5wt.%；
pH值调整剂： Na2CO3，调整pH至8~10；
剩余为非自来水，水的硬度>200ppm，且油酸、硼酸和异丙醇胺为单独加入乳化液，不制备复合酯A溶液，标记为D-3。
对比例4
一种钢制工件乳化液，该乳化液包括：
精制机械复合基础油：L-AN15与磺化蓖麻油的混合物，质量比为1：0.3，总量40wt.%；
复合酯：油酸异丙醇胺硼酸复合酯，10wt.%；
阴离子表面活性剂：石油磺酸钠，0.75wt.%；
有机硅非离子表面活性剂：聚醚改性硅油，0.1 wt.%；
极压剂：二烷基二硫代磷酸锌，3wt.%；
抗硬水剂：EDTA-Na，0.5wt.%；
pH值调整剂：Na2CO3，调整pH至8~10；
剩余为非自来水，水的硬度>200ppm，标记为D-4。
实施例1
一种水溶液硬度大于200ppm的钢制工件精细加工用乳化液，该乳化液包括：
精制机械复合基础油：选自L-AN10与磺化蓖麻油的混合物，质量比为1：0.2，总量20wt.%；
复合酯：油酸异丙醇胺硼酸复合酯，3wt.%；
阴离子表面活性剂：石油磺酸钠，0.5wt.%；
有机硅非离子表面活性剂：聚醚改性硅油，0.05wt.%；
极压剂：二烷基二硫代磷酸锌或环己烷二醇的链烷酸酯，1wt.%；
杀菌剂：甲基异噻唑酮、亚甲二氯化酚或亚甲基双吗啉中的一种或几种，1wt.%；
pH值调整剂：NaOH或Na2CO3，调整pH至8~10；
抗硬水剂：EDTA-Na，0.1wt.%；
剩余为非自来水，水的硬度>200ppm。
乳化液的制备方法如下：首先，将油酸、硼酸和异丙醇胺按摩尔比为1：（1~2）：（4~6）在140~155oC下酯化反应2~3h，冷却，静置获得复合酯A溶液；然后称取一定比例的精制机械油和磺化蓖麻油放入反应釜中，再加入适量复合酯A溶液，于60-80oC下缓慢搅拌1~2h获得混合均匀的油相B液；然后称取硬度>200ppm的非自来水放入搅拌反应釜中，加入抗硬水剂，搅拌，之后向其中加入石油磺酸钠和聚醚改性硅油，加热至60-80oC，搅拌1~2h，获得均匀的溶液C，然后将C液倒入B液混合，60-80oC保温搅拌0.5h获得均匀O/W乳化液，然后降温至40oC加入极压剂和杀菌剂，继续搅拌1~1.5h，冷却至室温，然后使用NaOH或Na2CO3调节乳化液的pH值至8~10，最终获得钢制工件加工用乳化液。
对于使用后的废弃乳化液的处理工艺，首先收集使用后的废弃乳化液于收集箱中，通过离心机和过滤器分离固体钢屑杂质和液体，然后向液体中加入5wt.%的硫酸、盐酸和氯化钙的混合液，其中硫酸、盐酸和氯化钙的质量比为1：0.5：（0.1~0.3），使液体的pH值位于6~7，以实现油和废水的分离，获得的废水经过活性煤吸附和电凝器处理，除去多余的有机物质，净化废水，最终排放的废水含油量低于5mg/L，悬浮物低于300mg/L，化学耗氧量（COD）低于80mg/L，而获得的油相可再生，循环用于钢制工件精细加工用的乳化液基础油。
实施例2
一种水溶液硬度大于200ppm的钢制工件精细加工用乳化液，该乳化液包括：
精制机械复合基础油：选自L-AN15与磺化蓖麻油的混合物，质量比为1：0.3，总量40wt.%；
复合酯：油酸异丙醇胺硼酸复合酯，10wt.%；
阴离子表面活性剂：石油磺酸钠，0.75wt.%；
有机硅非离子表面活性剂：聚醚改性硅油，0. 1wt.%；
极压剂：二烷基二硫代磷酸锌，3wt.%；
杀菌剂：甲基异噻唑酮，1wt.%；
抗硬水剂：EDTA-Na，0.5wt.%；
pH值调整剂：Na2CO3，调整pH至8~10；
剩余为非自来水，水的硬度>200ppm，标记为S-1。
实施例3
一种水溶液硬度大于200ppm的钢制工件精细加工用乳化液，该乳化液包括：
精制机械复合基础油：L-AN32与磺化蓖麻油的混合物，质量比为1：0.4，总量65wt.%；
复合酯：油酸异丙醇胺硼酸复合酯，15wt.%；
阴离子表面活性剂：石油磺酸钠，1wt.%；
有机硅非离子表面活性剂：聚醚改性硅油，0.2 wt %；
极压剂：环己烷二醇的链烷酸酯，5wt.%；
杀菌剂：亚甲基双吗啉中的一种或几种，2wt.%；
抗硬水剂：EDTA，1wt.%；
pH值调整剂：NaOH或Na2CO3，调整pH至8~10；
剩余为非自来水，水的硬度>200ppm。
表1为乳化液性能测试结果。
表1
首先，对于乳化液而言，基础油是其主要成分，与润滑性密切相关，L-AN机械油，由精制矿物油制得，通常负荷轻、转速快的机械设备可选用低粘度机械油，负荷重，转速快的设备选用高粘度的机械油，但是其粘附性、极压性和抗腐蚀性均有待提高，如D-1中，当基础油仅仅为机械油L-AN时，其摩擦系数远远高于D-3，D-4，S-1，因此，本发明先从基础油着手，加入改性蓖麻油，改性蓖麻油是蓖麻油经硫酸磺化生成的磺化油，能显著改善基础油的润滑性，即降低其摩擦系数，如在同参数的情况下，D-1的摩擦系数为0.069，而S-1的摩擦系数为0.037，此外，改性蓖麻油除了有提高基础油的润滑性，降低基础油的用量的优点外，还是一种优良的乳化剂，如近来出现的蓖麻油酸烷醇酰胺、十一烯酸烷醇酰胺等均能提高乳化液的油水稳定性。
其次，通常乳化液中会添加多元醇与脂肪酸，其中多元醇一般作为防锈剂或者稳定剂或缓蚀剂，而脂肪酸作为极压剂，均是与金属表面发生吸附，形成保护膜，但是若单独加入，其极压效果和稳定效果并没有相互辅助加成，反而相互影响，降低乳化O/W体系的稳定性和金属表面吸附膜的稳定性，如D-3和S-1对比，但是若不添加防锈剂和极压剂，其切削效果又极差，因此本发明通过脂肪酸油酸、无机酸硼酸和多元醇胺预先酯化反应，生成油酸异丙醇胺硼酸复合酯，该复合酯对于乳化液稳定性和防锈性具有显著作用，对于一个成熟的乳化液体系而言，对于精细加工钢制件而言，单纯依靠油酸异丙醇胺硼酸复合酯并不能有效的在基材表面生成适宜润滑膜。通常极压剂的作用原理是在摩擦与高温下极压抗磨剂发生分解并与金属反应生成剪切应力和熔点都比纯金属低的化合物，从而防止接触表面咬合和焊接使金属表面得到有效保护。目前主流的极压剂有以下几种：(1)硫系添加剂：含硫添加剂是目前金属加工液行业中普遍应用的最有效的极压抗磨剂，硫或氯添加剂主要通过热分解起作用；(2)磷系添加剂，含磷添加剂是应用较早的一种抗磨剂。它的作用机理是：先在金属表面吸附，经过水解生成酸性磷酸酯，在金属表面上形成有机金属磷酸盐，最后，在极压条件下进一步水解，生成无机亚硫酸铁膜，起到极压抗磨作用；(3)氯系添加剂，氯系极压剂中用的最多的是氯化石蜡、氯化油脂等脂肪族氯化物。含氯极压抗磨剂的作用机理是：受热分解，生成FeCl2、FeCl3、FeOCl等氯化铁膜，起到抗磨损、防烧结作用；(4)硼系添加剂，硼是一种相对较新型的抗磨元素。硼的抗磨作用机理是通过在金属表面上形成硼酸而体现，硼通过沉积起作用。但目前倡导“环境友好型”产品，要求(1)不含氯和氮；(2)不含重金属；(3)低毒；(4)可生物降解。因此本发明使用环己烷二醇的链烷酸酯作为极压剂，当然也提出了并列技术方案，使用二烷基二硫代磷酸锌作为极压剂，通过吸附和热分解来起作用。
接着，阴离子表面活性剂石油磺酸钠和有机硅非离子表面活性剂聚醚改性硅油，是乳化剂中必不可少的成分，如果没有表面活性剂，就无法生成有效的乳化液体系。
杀菌剂，对于乳化液的使用寿命至关重要，由于乳化液中含有大量的矿物油、脂肪酸皂、胺、磺酸盐和水等成分，易受到微生物的侵袭，而且细菌、真菌等微生物在水中大量繁殖会导致乳化液腐败变质。其中厌氧菌能还原硫酸盐，放出硫化氢气体，产生恶臭；好氧菌能产生有机酸等腐蚀金属，而真菌的大量繁殖将导致块状物产生，易堵塞机床的冷却液循环管线和滤网，并且，D-4和S-1数据显示杀菌剂的存在不会对摩擦系数造成明显影响。
此外，乳化液的水质也对乳化液的乳化体系至关重要，水质太硬必须经过预处理，可在水中加入EDTA或EDTA-Na，便可起到降低水质硬度的作用；如上述表中显示水质不同对菌落数有明显影响，且用硬水配制的乳化液常会迅速分层，析出大量的油和不溶于水的皂，影响使用效果，而影响O/W体系的稳定，本发明的乳化液pH值应呈碱性，即pH值应为8-10，使用NaOH或Na2CO3作为调节剂。主要考虑杀菌性，以及避免由于菌落的出现导致pH低于6，进而造成破乳和油水分离的现象。最后，当水的硬度>200ppm时，可以通过加入适当的抗硬水剂调节。
以上对本发明的具体实施例进行了详细描述，但其只是作为范例，本发明并不限制于以上描述的具体实施例。对于本领域技术人员而言，任何对本发明进行的等同修改和替代也都在本发明的范畴之中。因此，在不脱离本发明的精神和范围下所作的均等变换和修改，都应涵盖在本发明的范围内。
Claims (3)
1.一种水溶液硬度大于200ppm的钢制工件精细加工用乳化液，其特征在于所述乳化液包括：
精制机械复合基础油：选自L-AN10、L-AN15 或L-AN32中的一种与磺化蓖麻油的混合物，质量比为1：（0.2~0.4），总量20~65wt.%；
复合酯：油酸异丙醇胺硼酸复合酯，3~15wt.%；
阴离子表面活性剂：石油磺酸钠，0.5~1wt.%；
有机硅非离子表面活性剂：聚醚改性硅油，0.05~0.2 wt.%；
极压剂：二烷基二硫代磷酸锌或环己烷二醇的链烷酸酯，1~5wt.%；
杀菌剂：甲基异噻唑酮、亚甲二氯化酚或亚甲基双吗啉中的一种或几种，1~2wt.%；
pH值调整剂：NaOH或Na2CO3，调整pH至8~10；
剩余为非自来水，非自来水的硬度大于200ppm，加入0.1~1wt.%的抗硬水剂，抗硬水剂选自EDTA或EDTA-Na中的一种。
2.如权利要求1所述的一种水溶液硬度大于200ppm的钢制工件精细加工用乳化液的制备方法，其特征在于：首先，将油酸、硼酸和异丙醇胺按摩尔比为1：（1~2）：（4~6）在140~155oC下酯化反应2~3h，冷却，静置获得复合酯A溶液；然后称取一定比例的精制机械油和磺化蓖麻油放入反应釜中，再加入适量复合酯A溶液，于60-80oC下缓慢搅拌1~2h获得混合均匀的油相B液；然后称取硬度>200ppm的非自来水放入搅拌反应釜中，加入抗硬水剂，搅拌，之后向其中加入石油磺酸钠和聚醚改性硅油，加热至60-80oC，搅拌1~2h，获得均匀的溶液C，然后将C液倒入B液混合，60-80oC保温搅拌0.5h获得均匀O/W乳化液，然后降温至40oC加入极压剂和杀菌剂，继续搅拌1~1.5h，冷却至室温，然后使用NaOH或Na2CO3调节乳化液的pH值至8~10，最终获得所述乳化液。
3.如权利要求1所述的一种水溶液硬度大于200ppm的钢制工件精细加工用乳化液的后处理方法，其特征在于所述乳化液为使用后的废弃乳化液，首先收集使用后的废弃乳化液于收集箱中，通过离心机和过滤器分离固体钢屑杂质和液体，然后向液体中加入5wt.%的硫酸、盐酸和氯化钙的混合液，其中硫酸、盐酸和氯化钙的质量比为1：0.5：（0.1~0.3），使液体的pH值位于6~7，以实现油和废水的分离，获得的废水经过活性煤吸附和电凝器处理，除去多余的有机物质，净化废水，最终排放的废水含油量低于5mg/L，悬浮物低于300mg/L，化学耗氧量（COD）低于80mg/L，而获得的油相可再生，循环用于钢制工件精细加工用的乳化液基础油。
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