CN116286152A - 一种用于铝及铝合金的环保型热轧乳化油及其制备方法和应用 - Google Patents
一种用于铝及铝合金的环保型热轧乳化油及其制备方法和应用 Download PDFInfo
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- CN116286152A CN116286152A CN202310096798.3A CN202310096798A CN116286152A CN 116286152 A CN116286152 A CN 116286152A CN 202310096798 A CN202310096798 A CN 202310096798A CN 116286152 A CN116286152 A CN 116286152A
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- aluminum
- oil
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- emulsified oil
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 67
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- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 8
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 6
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- OSPSWZSRKYCQPF-UHFFFAOYSA-N dibutoxy(oxo)phosphanium Chemical compound CCCCO[P+](=O)OCCCC OSPSWZSRKYCQPF-UHFFFAOYSA-N 0.000 claims description 6
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- IVTHSFJXIARUFL-UHFFFAOYSA-N triazanium;thiophosphate Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=S IVTHSFJXIARUFL-UHFFFAOYSA-N 0.000 claims description 4
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明涉及金属加工润滑技术领域，具体涉及一种用于铝及铝合金的环保型热轧乳化油及其制备方法和应用。本发明以含适量芳烃加氢环烷基油作为基础油，其高蒸发损失特性使乳化液具备良好的清净性能够减少轧后铝板表面的残留，提高铝板表面质量和清净性。本发明还使用了复合乳化剂，除了起到乳化作用，其分子结构上的多功能基团能够实现提高防锈润滑等作用，同时乳化剂复合过程能够促进乳化剂在基础油中的溶解能力。除此之外，本发明还根据应用场景和环境，对其他的添加剂进行了合适的配伍，具有分散稳定性好、添加剂配伍性好、残炭少、无毒无害、无明显气味、油泥少，易维护等特点。
Description
技术领域
本发明涉及金属加工润滑技术领域，具体涉及一种用于铝及铝合金的环保型热轧乳化油及其制备方法和应用。
背景技术
铝热轧过程中轧件处于高温、高压以及高摩擦环境，极易产生粘辊等轧板表面缺陷，因此必须使用乳化液进行润滑和冷却。乳化液是控制铝及铝合金板形、色差等表面质量的重要因素。
目前市场上的铝热轧乳化液大多采用石蜡基油作为基础油，并使用大量毒性添加剂，以保证乳化液具备良好的润滑冷却性，并且存在清净性差、毒性强、有刺激性气味、易产生油泥等缺点，会造成严重的环境污染且给生产带来不便。
铝热轧过程不同于冷加工如冷轧、切削等工况，铝热轧一般处于400℃以上的高温环境，铝热轧乳化液起到润滑冷却作用后在铝板表面急剧蒸发，因此相较于冷加工工况，更注重乳化液的高温蒸发残留情况。传统铝热轧乳化液大部分使用石蜡基油作为基础油，由于蒸发损失小，会有部分油液蒸发不完全，在铝板表面形成残碳，影响铝板表面清净性，恶化表面质量。
发明内容
针对现有技术问题，本发明提供了一种用于铝及铝合金的环保型热轧乳化油及其制备方法和应用。本发明以含适量芳烃加氢环烷基油作为基础油，其高蒸发损失特性使乳化液具备良好的清净性，能够减少轧后铝板表面的残留，提高铝板表面质量和清净性。同时基础油中的单环芳烃能够改善基础油性能，增加其乳化液的抗杂油能力，避免热轧过程中产生的油泥和铝粉破坏乳化液的润滑性，并且提高其乳化液的抗磨减摩性能；另外含适量芳烃加氢环烷基油凭借其对添加剂良好的配伍性，可以有效减少添加剂的用量，同时保证其乳化液具备足够的润滑冷却性能。本发明还使用了复合乳化剂，除了起到乳化作用，其分子结构上的多功能基团能够实现提高防锈润滑等作用，同时乳化剂复合过程能够促进乳化剂在基础油中的溶解能力。本发明脂肪酸含量低，不易与金属离子产生金属皂，从而能够减少油泥等固体废物的产生，使用过后易于清洗，降低后续处理难度。除此之外，本发明还根据应用场景和环境，对其他的添加剂进行了合适的配伍，具有分散稳定性好、添加剂配伍性好、残炭少、无毒无害、无明显气味、油泥少，易维护等特点，解决了传统铝热轧乳化液添加剂含量高，毒性强，有刺激性气味，易产生油泥，对环境危害大的缺点，同时本发明还具备优异的润滑性和冷却性。
具体地，本发明技术方案包括：
第一方面，一种用于铝及铝合金的环保型热轧乳化油，按质量百分比计，其组成包括：植物油5.00％～10.00％，复合乳化剂5.00％～10.00％，极压剂1.00％～2.00％，防锈剂1.00％～5.00％，油性剂4.00％～5.00％，抗氧剂1％～1.5％，消泡剂0.02％～0.10％，余量为基础油；所述基础油为含芳烃加氢环烷基油。
优选的，所述含芳烃加氢环烷基油，其40℃运动黏度应控制在40～70mm2/s，芳烃含量在5％-9％，PCA＜3％。
所述的复合乳化剂为失水山梨醇油酸酯和聚氧乙烯失水山梨醇油酸酯复配，质量比为1:1.5-4。
所述极压剂为亚磷酸二正丁酯或硫代磷酸铵盐。
所述防锈剂为石油磺酸钠或烷基苯磺酸钠。
所述的油性剂为季戊四醇油酸酯和硬脂酸丁酯复配，质量比为1:3。
所述植物油选择现有常规技术即可；优选的，所述植物油为棕榈油和菜籽油中的一种或两种混合。
所述抗氧剂选择现有常规技术即可；优选的，所述抗氧剂为2,6-二叔丁基对甲酚和二烷基二硫代氨基甲酸盐中的一种或两种混合。
所述消泡剂为乙二胺PO-EO嵌段共聚物。
本发明的第二方面，提供了上述用于铝及铝合金的环保型热轧乳化油的制备方法，其具体步骤包括：
步骤一、制备复合乳化剂：将失水山梨醇油酸酯和聚氧乙烯失水山梨醇油酸酯进行混合，加热至40～50℃，并使用磁力搅拌器以300～400r/min的速度搅拌5～10min，得到复合乳化剂。
优选的，将失水山梨醇油酸酯和聚氧乙烯失水山梨醇油酸酯以质量比1:1.5-4混合。
步骤二、制备铝热轧乳化油：在基础油中依次加入植物油、复合乳化剂和防锈剂，在70～80℃的加热条件下，以300～400r/min的速度搅拌至均匀透明，然后依次加入极压剂、油性剂、抗氧剂和消泡剂，在40～50℃的加热条件下，以400～600r/min的速度搅拌15～20min，得到用于铝及铝合金的环保型热轧乳化油。步骤二以保证复合乳化剂与其它添加剂达到良好的协同效果，且油品外观透明。
本发明第三方面，提供上述用于铝及铝合金的环保型热轧乳化油的应用方法，使用去离子水将乳化油乳化为乳化液应用。
更优选的，乳化油乳化过程具体为：使用去离子将乳化油稀释至浓度为3％～5％，并且以600～800r/min的速度搅拌15～20min，得到用于铝及铝合金的环保型热轧乳化液。
本发明的有益效果在于：
本发明使用的复合乳化剂主要成分为非离子型乳化剂，分子结构中含有具有防锈功能的羟基、酯基等多功能基团。一方面具备良好的乳化能力，能使乳化液的粒径分布均匀，分散稳定性好，在常温状态下能够存放较长时间。另一方面，复合乳化剂分子结构中的基团能够使乳化剂具备多功能特性，从而减少添加剂的使用，防止与其余有效成分的拮抗作用。另外，失水山梨醇油酸酯的分子极性端吸附于金属表面形成一层吸附膜，阻止水、氧气、腐蚀性物质到达金属表面，能够提升轧后表面质量。复合乳化剂其它添加剂能够达到良好的协同效果，提升轧后板面光洁度，降低轧板的厚度。
本发明使用的含适量芳烃的加氢环烷基油中所含芳烃为单环芳烃，相较于稠环芳烃无致癌作用；抗氧化性强，能够抑制油品氧化；并且能够使油滴易于吸附在铝板表面形成薄吸附膜提高抗磨减摩性能；还能够提高基础油的溶解性，能够降低热轧过程中产生的铝粉和油泥带来的影响，提高乳化液抗杂油能力。同时芳烃能够降低基础油的粘度指数，防止低温和高温环境下油品的流动性产生较大变化。
铝热轧过程一般处于400℃以上的高温环境，铝热轧乳化液起到润滑冷却作用后在铝板表面急剧蒸发。传统铝热轧乳化液基础油大部分为石蜡基油，在热轧过程中不易挥发，在铝板表面形成残炭，从而影响表面质量和表面清净性。而含适量芳烃的加氢环烷基油的高蒸发损失特性使乳化液具备良好的清净性，能够减少轧后铝板表面的残留，残炭含量降低，提高表面清洁性。同时本发明使用的含适量芳烃的加氢环烷基油具有良好的配伍性，相较于传统石蜡基铝热轧乳化液，环烷基油能够充分发挥极压剂和油性剂的抗磨减摩作用，并且易于乳化，节省乳化剂用量，从而降低成本。
本发明所使用的添加剂绿色环保，无毒害物质，无明显气味，是一种环境友好型的乳化液。本发明脂肪酸含量低，不易与金属离子反应形成金属皂，进而避免乳化液循环系统中杂油等物质与金属皂形成油泥等固体杂质，方便乳化液系统的维护，对保护生态环境促进可持续发展也起到积极作用。
本发明具备优秀的抗磨性和润滑性，优于目前市场上国内外部分品牌的铝热轧乳化液。在铝材热轧过程中能起到良好的润滑、冷却的作用，能够广泛应用于铝板带的热轧轧制。
附图说明
图1为实施例2和对比例3乳化液析油析皂情况对比图。
图2为实施例2和对比例3乳化液采用EXXON退火盒法实验在高温铝板表面的残留情况。
图3为实施例1-3乳化油及乳化液外观。
图4为实施例1-3及对比例1-3四球长磨实验后的磨斑形貌。
具体实施方式
以下通过实施例形式的具体实施方式，对本发明的上述内容做进一步的详细说明，但不应将此理解为本发明上述主题的范围仅限于以下的实例。凡基于本发明上述内容所实现的技术均属于本发明的范围。除特殊说明外，以下实施例中均采用常规技术操作完成。
实施例1
实施例1乳化油的重量百分比为：菜籽油5％，复合乳化剂5％，亚磷酸二正丁酯1％，季戊四醇油酸酯1％，硬脂酸丁酯3％，石油磺酸钠3％，二烷基二硫代氨基甲酸钼1％，乙二胺PO-EO嵌段共聚物0.1％，余量为含适量芳烃46#号加氢环烷基油，CA值为8，PCA为1.8％。
1)制备复合乳化剂：将非离子表面活性剂失水山梨醇油酸酯和聚氧乙烯失水山梨醇油酸酯以质量比为1:4的形式混合，使用磁力搅拌器以300r/min的速度搅拌5min，得到具有防锈和乳化性能的复合乳化剂。
2)制备铝热轧乳化油：在基础油中依次加入菜籽油、复合乳化剂和石油磺酸钠，在70℃的加热条件下，以300r/min的速度搅拌至均匀透明，然后依次加入亚磷酸二正丁酯、季戊四醇油酸酯、硬脂酸丁酯、二烷基二硫代氨基甲酸钼、乙二胺PO-EO嵌段共聚物，在40℃的加热条件下，以500r/min的速度搅拌15min，得到用于铝及铝合金的环保型热轧乳化油。
根据需求可制备热轧乳化液：使用去离子水将乳化油稀释至浓度为5％，并且以600r/min的速度搅拌15min，得到一种用于铝及铝合金的环保型热轧乳化液。
实施例2
实施例2乳化油的重量百分比为：棕榈油10％，复合乳化剂10％，亚磷酸二正丁酯2％，石油磺酸钠5％，季戊四醇油酸酯1.5％，硬脂酸丁酯4.5％，2,6-二叔丁基对甲酚1.5％，乙二胺PO-EO嵌段共聚物0.05％，余量为含适量芳烃56#加氢环烷基油，CA值为5，PCA为2.1％。
1)制备复合乳化剂：将非离子表面活性剂失水山梨醇油酸酯和聚氧乙烯失水山梨醇油酸酯以质量比为1:1.5的形式混合，使用磁力搅拌器以300r/min的速度搅拌5min，得到具有防锈和乳化性能的复合乳化剂。
2)制备铝热轧乳化油：在基础油中依次加入棕榈油、复合乳化剂和石油磺酸钠，在70℃的加热条件下，以300r/min的速度搅拌至均匀透明，然后依次加入亚磷酸二正丁酯、季戊四醇油酸酯、硬脂酸丁酯、2,6-二叔丁基对甲酚、乙二胺PO-EO嵌段共聚物，在50℃的加热条件下，以600r/min的速度搅拌15min，得到用于铝及铝合金的环保型热轧乳化油。
根据需求可制备热轧乳化液：使用去离子将乳化油稀释至浓度为5％，并且以600r/min的速度搅拌15min，得到一种用于铝及铝合金的环保型热轧乳化液。
实施例3
实施例3乳化油的重量百分比为：棕榈油8％，复合乳化剂8％，硫代磷酸铵盐1.5％，烷基苯磺酸钠4％，季戊四醇油酸酯1.2％，硬脂酸丁酯3.6％，2,6-二叔丁基对甲酚1.2％，乙二胺PO-EO嵌段共聚物0.05％，余量为含适量芳烃56#号加氢环烷基油，CA值为5，PCA为2.1％。
1)制备复合乳化剂：将非离子表面活性剂失水山梨醇油酸酯和聚氧乙烯失水山梨醇油酸酯以质量比为1:2的形式混合，使用磁力搅拌器以300r/min的速度搅拌5min，得到具有防锈和乳化性能的复合乳化剂。
2)制备铝热轧乳化油：在基础油中依次加入棕榈油、复合乳化剂和烷基苯磺酸钠，在80℃的加热条件下，以300r/min的速度搅拌至均匀透明，然后依次加入硫代磷酸铵盐、季戊四醇油酸酯、硬脂酸丁酯、2,6-二叔丁基对甲酚、乙二胺PO-EO嵌段共聚物，在50℃的加热条件下，以600r/min的速度搅拌15min，得到用于铝及铝合金的环保型热轧乳化油。
根据需求可制备热轧乳化液：使用去离子水将乳化油稀释至浓度为5％，并且以600r/min的速度搅拌15min，得到一种用于铝及铝合金的环保型热轧乳化液。
对比例1
为国内某品牌铝热轧乳化油，使用去离子水将乳化油稀释至浓度为5％，并且以600r/min的速度搅拌15min，得到铝热轧乳化液。
对比例2
为国外某品牌铝热轧乳化油，使用去离子水将乳化油稀释至浓度为5％，并且以600r/min的速度搅拌15min，得到铝热轧乳化液。
对比例3
将实施例2中56#加氢环烷基油替换为粘度相近的350N石蜡基油，其他技术方案与实施例2相同。
(1)将实施例2所得乳化液与本对比例乳化液在相同室温条件下静置20min，观察其析油析皂情况如图1所示，本对比例3所采用的的石蜡基油乳化液析油析皂情况比较严重，本申请技术方案的实施例2所制备的乳化液稳定性更优。
(2)采用EXXON退火盒法实验即：使用一个Ф70mm×2mm铝盒，盒盖表面距边缘2mm处呈等边三角形顶点有三个Ф2mm的通孔，滴入盒中0.125ml乳化液，在350℃保温1h后，观察铝盒底面颜色的变化，判断退火后表面残留情况如图2所示，实施例2的乳化液比对比例3乳化液表现出显著的清净性。
使用四球摩擦磨损试验机，对各实施例及对比例的性能进行测定，参考GB/T3142－2019《润滑剂承载能力的测定(四球法)》，采用最大无卡咬负荷来反映油膜强度，在载荷392N、转速1200rpm温度25℃条件下，进行60min长磨实验，得到乳化液的平均摩擦系数，并测量磨斑直径，观察磨斑形貌，测得产品性能指标如下：
上表为本发明实施案例产品与普通乳化油质量检测数据对比。
由以上数据可以看出：1)本发明实施例摩擦系数低于对比例1和2，具有优秀的减摩能力，在轧制过程中能够减小轧制力，增加轧制变形效率；2)本发明实施例磨斑直径小于对比例，能够起到优秀的抗磨作用，提高轧后表面质量。3)本发明实施例乳化液的清净性和稳定性明显优于对比例3。综上所述本申请技术方案综合效果最佳，即能保证摩擦系数和磨斑直径的相关优异性能外，还能达到更好的稳定性和清净性。
上述实施例均为本发明效果较佳实施例，仅用来说明本发明的实际效果，并非本发明的限定，其它的任何未背离本发明的精神实质与原理下所作的改变、替代、简化，均应包含在本发明所提交的权利要求书确定的专利保护范围之内。
Claims (10)
1.一种用于铝及铝合金的环保型热轧乳化油，其特征在于，按质量百分比计，其组成包括：植物油5.00％～10.00％，复合乳化剂5.00％～10.00％，极压剂1.00％～2.00％，防锈剂1.00％～5.00％，油性剂4.00％～5.00％，抗氧剂1％～1.5％，消泡剂0.05％～0.10％，余量为基础油；所述基础油为含芳烃加氢环烷基油。
2.根据权利要求1所述的用于铝及铝合金的环保型热轧乳化油，其特征在于，所述含芳烃加氢环烷基油，其40℃运动黏度应控制在40～70mm2/s，芳烃含量在5％-9％，PCA＜3％。
3.根据权利要求1所述的用于铝及铝合金的环保型热轧乳化油，其特征在于，所述的复合乳化剂为失水山梨醇油酸酯和聚氧乙烯失水山梨醇油酸酯复配。
4.根据权利要求所述的用于铝及铝合金的环保型热轧乳化油，其特征在于，所述的失水山梨醇油酸酯和聚氧乙烯失水山梨醇油酸酯复配质量比为1:1.5-4。
5.根据权利要求1所述的用于铝及铝合金的环保型热轧乳化油，其特征在于，所述极压剂包括亚磷酸二正丁酯或硫代磷酸铵盐；所述防锈剂为石油磺酸钠或烷基苯磺酸钠；所述的油性剂为季戊四醇油酸酯和硬脂酸丁酯复配，质量比为1:3。
6.根据权利要求1所述的用于铝及铝合金的环保型热轧乳化油，其特征在于，所述植物油为棕榈油和菜籽油中的一种或两种混合；所述抗氧剂为2,6-二叔丁基对甲酚和二烷基二硫代氨基甲酸盐中的一种或两种混合；所述消泡剂为乙二胺PO-EO嵌段共聚物。
7.权利要求1所述的用于铝及铝合金的环保型热轧乳化油的制备方法，其特征在于，其具体步骤包括：
步骤一、制备复合乳化剂：将失水山梨醇油酸酯和聚氧乙烯失水山梨醇油酸酯进行混合，加热至40～50℃，并使用磁力搅拌器以300～400r/min的速度搅拌5～10min，得到复合乳化剂；
步骤二、制备铝热轧乳化油：在基础油中依次加入植物油、复合乳化剂和防锈剂，在70～80℃的加热条件下，以300～400r/min的速度搅拌至均匀透明，然后依次加入极压剂、油性剂、抗氧剂和消泡剂，在40～50℃的加热条件下以400～600r/min的速度搅拌15～20min，得到用于铝及铝合金的环保型热轧乳化油。
8.权利要求7所述的用于铝及铝合金的环保型热轧乳化油的制备方法，其特征在于，步骤一中将失水山梨醇油酸酯和聚氧乙烯失水山梨醇油酸酯以质量比1:1.5-4混合。
9.权利要求1所述的用于铝及铝合金的环保型热轧乳化油的应用方法，其特征在于，使用去离子水将乳化油乳化为乳化液应用。
10.根据权利要求9所述的用于铝及铝合金的环保型热轧乳化油的应用方法，其特征在于，乳化油乳化过程具体为：使用去离子将乳化油稀释至浓度为3％～5％，并且以600～800r/min的速度搅拌15～20min，得到用于铝及铝合金的环保型热轧乳化液。
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