CN116948733B - 烃制冷剂用冷冻机油组合物及其制备方法 - Google Patents

烃制冷剂用冷冻机油组合物及其制备方法 Download PDF

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CN116948733B
CN116948733B CN202310886898.6A CN202310886898A CN116948733B CN 116948733 B CN116948733 B CN 116948733B CN 202310886898 A CN202310886898 A CN 202310886898A CN 116948733 B CN116948733 B CN 116948733B
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refrigerating machine
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袁俊洲
窦剑武
宋来功
乔良
赵金伟
曹克强
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SHANDONG YUANGEN PETROLEUM CHEMICAL CO Ltd
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Abstract

本发明涉及一种烃制冷剂用冷冻机油组合物及其制备方法,属于润滑油技术领域,其特征在于,包括如下组分及其重量份数:基础油,所述基础油由直链烷基苯和聚碳酸酯组成,所述直链烷基苯与聚碳酸酯的质量比为5.5‑6:1;石墨烯,其相对基础油的添加量为0.02‑0.05wt%;添加剂,所述添加剂包括助分散剂,还包括抗磨剂、抗氧剂、抗泡剂、酸捕捉剂和金属减活剂中的至少一种;本发明通过设置的由直链烷基苯和聚碳酸酯组成的基础油,同时配以石墨烯、助分散剂及其他添加剂,能够获得40℃运动粘度范围宽广、低温性能优异的冷冻机油产品,且本发明的原料简单易得。

Description

烃制冷剂用冷冻机油组合物及其制备方法
技术领域
本发明涉及润滑油技术领域,具体涉及一种烃制冷剂用冷冻机油组合物及其制备方法。
背景技术
冷冻机系统,一般是用压缩机压缩制冷剂,用冷凝器使成为高压、高温的制冷剂散发热,此后,用膨胀机构(例如膨胀阀)形成低压,当制冷剂在蒸发器中蒸发时,由于从周围夺走蒸发热而成为低温,进行冷却。该冷冻机系统,可在冰箱、冷冻库、空调、陈列橱、清凉饮料或冰淇淋等自动售货机等中使用。
以往的制冷剂多采用三氯氟甲烷、二氯二氟甲烷、氯二氟甲烷等含氯的氟化烃,但是这些会引起破坏臭氧层的环境问题。现在正改换为不含氯的制冷剂如二氟甲烷、四氟甲烷以及低级烃制冷剂如丙烷、异丁烷等。
现有技术中,为适于低级烃制冷剂的使用,公布号为CN114381325A的中国发明专利公开了一种冷冻机油组合物,其基础油包括:C10-C13直链烷基苯合成润滑油基础油以及氢环烷基矿物润滑油窄馏程基础油,该冷冻机油能够适用于低分子烷烃制冷剂如异丁烷、丙烷。但是其所使用的氢环烷基矿物润滑油窄馏程基础油制备工艺较为复杂。
现有技术中,为提高冷冻机油的润滑性能,公布号为CN114517123A的中国发明专利申请公开了一种冷冻机油,其以金刚石颗粒和石墨烯同时作为润滑添加剂,通过控制所用添加剂原料为纳米级,实现添加剂在基础油中的良好分散,从而提升润滑油的润滑性能。但是,其对于原料尺寸要求较高,要求添加剂原料需为纳米级,而采用一般尺寸的添加剂则又存在易团聚的问题。
发明内容
本发明针对现有技术中所存在的上述问题提供了一种烃制冷剂用冷冻机油组合物及其制备方法,其原料简单易得,获得产品综合性能良好,而且本发明的制备方法简单,对于原料要求较低,无需限定原料尺寸在纳米级。
本发明解决上述技术问题的技术方案如下:
一方面,本发明提供一种烃制冷剂用冷冻机油组合物,适用于氢氟烃类及低级烃等制冷剂,其特征在于,包括如下组分及其重量份数:
基础油,所述基础油由直链烷基苯和聚碳酸酯组成,所述直链烷基苯与聚碳酸酯的质量比为5.5-6:1;
石墨烯,其相对基础油的添加量为0.02-0.05wt%;
添加剂,所述添加剂包括助分散剂,还包括抗磨剂、抗氧剂、抗泡剂、酸捕捉剂和金属减活剂中的至少一种。其中,相对于基础油而言,助分散剂的添加量优选2wt%,抗磨剂的添加量优选0.9-1.1wt%,抗氧剂的添加量优选0.4-0.6wt%,抗泡剂的添加量优选4.5-5.2mg/kg,酸捕捉剂的添加量优选0.07-0.1wt%,金属减活剂的添加量优选0.02wt%。
进一步的,所述直链烷基苯选自C10、C11、C12、C13的直链烷基苯中的至少一种,优选包括C10、C11、C12、C13的工业直链烷基苯。
进一步的,所述聚碳酸酯优选聚乙二醇碳酸酯、聚乙二醇二琥珀酰亚胺碳酸酯。
进一步的,所述助分散剂采用甘油单油酸酯和1,2-十二烷二醇。
进一步的,所述抗磨剂为二烷基二硫代磷酸锌。
进一步的,所述抗氧剂为烷基化二苯胺。
进一步的,所述抗泡剂为乳化硅油、聚氧乙烯聚氧丙烯季戊四醇醚或聚氧乙烯聚氧丙醇胺醚中的至少一种。
进一步的,所述酸捕捉剂为新戊二醇二缩水甘油醚、辛基缩水甘油醚或碳二亚胺中的至少一种。
进一步的,所述金属减活剂为烷基三唑或其衍生物。
另一方面,本发明提供一种所述的烃制冷剂用冷冻机油组合物的制备方法,其特征在于,包括如下步骤:
1)将石墨烯分散至水中制成石墨烯分散液;
2)将步骤1)所得石墨烯分散液加入至直链烷基苯中,搅拌,待体系分层后,取其油相清液;
3)在调配釜内,将步骤2)所得油相清液与配方量的聚碳酸酯及添加剂混合均匀,然后经釜底向釜内通入惰性气体,以排出物料中的水分,即得烃制冷剂用冷冻机油组合物。
本发明的有益效果是:
1.本发明通过设置的由直链烷基苯和聚碳酸酯组成的基础油,同时配以石墨烯、助分散剂及其他添加剂,能够获得40℃运动黏度范围宽广的冷冻机油产品,适用于氢氟烃类及低级烃等不同种类的制冷剂,且本发明的原料简单易得。
2.本发明进一步通过先将石墨烯制成是分散液形式,然后将分散液加入到基础油中的制备方法,辅以特定的助分散剂甘油单油酸酯和1,2-十二烷二醇的使用,能够实现石墨烯在所述基础油中的分散,而无需限定添加剂必须为纳米级,对原料尺寸要求较低,克服了石墨烯极易团聚、难分散的难题,使石墨烯应用于冷冻机油更加简单易行。
3.本发明的制备方法制得的冷冻机油,倾点可达-66℃,具有优异的低温性能,即通过简单易得的原料辅以较为简单的加工工艺即可获得倾点-66℃的低温性能。
具体实施方式
下面对本发明的原理和特征进行描述,所举实施例只用于解释本发明,并非用于限定本发明的范围。
实施例1
本实施例的烃制冷剂用冷冻机油组合物包括如下组分及其重量份数:
基础油,由工业直链烷基苯和聚碳酸酯(PC)组成;其中,工业直链烷基苯与聚碳酸酯的质量比为6:1,工业直链烷基苯为包括C10、C11、C12、C13的直链烷基苯,购自中国石化集团金陵石油化工有限责任公司烷基苯厂,产品批号WJB20220612-301-2-02;聚碳酸酯采用聚乙二醇碳酸酯;
石墨烯,石墨烯片径在1nm-10μm之间,其相对基础油的添加量为0.04wt%;
及添加剂,其包括甘油单油酸酯1wt%和1,2-十二烷二醇1wt%,二烷基二硫代磷酸锌1wt%,烷基化二苯胺0.5wt%,聚氧乙烯聚氧丙烯季戊四醇醚5mg/kg,新戊二醇二缩水甘油醚0.08wt%,十二烷基三唑0.02wt%;上述添加剂的添加量均为相对于基础油的添加量。
其制备方法包括如下步骤:
1)将配方量的石墨烯分散至水中制成1wt%的石墨烯分散液;
2)将步骤1)所得石墨烯分散液加入至直链烷基苯中,并适当搅拌,待体系分层,取其油相清液;
3)在调配釜内,将步骤2)所得油相清液与配方量的聚碳酸酯及添加剂混合均匀,然后经釜底向釜内通入惰性气体如氮气,以排出物料中的水分,即得烃制冷剂用冷冻机油组合物。
实施例2
本实施例的烃制冷剂用冷冻机油组合物包括如下组分及其重量份数:
基础油,由工业直链烷基苯和聚碳酸酯(PC)组成;其中,工业直链烷基苯与聚碳酸酯的质量比为5.5:1,工业直链烷基苯包括C10、C11、C12、C13的直链烷基苯,购自中国石化集团金陵石油化工有限责任公司烷基苯厂,产品批号WJB20220612-301-2-02;聚碳酸酯采用聚乙二醇碳酸酯;
石墨烯,石墨烯片径在1nm-10μm之间,其相对基础油的添加量为0.02wt%;
及添加剂,其包括甘油单油酸酯1.2wt%和1,2-十二烷二醇0.8wt%,二烷基二硫代磷酸锌0.9wt%,烷基化二苯胺0.4wt%,乳化硅油4.5mg/kg,辛基缩水甘油醚0.1wt%,癸基三唑0.02wt%;上述添加剂的添加量均为相对于基础油的添加量。
其制备方法包括如下步骤:
1)将配方量的石墨烯分散至水中制成2wt%的石墨烯分散液;
2)将步骤1)所得石墨烯分散液加入至直链烷基苯中,并适当搅拌,待体系分层,取其油相清液;
3)在调配釜内,将步骤2)所得油相清液与配方量的聚碳酸酯及添加剂混合均匀,然后经釜底向釜内通入惰性气体如氩气,以排出物料中的水分,即得烃制冷剂用冷冻机油组合物。
实施例3
本实施例的烃制冷剂用冷冻机油组合物包括如下组分及其重量份数:
基础油,由工业直链烷基苯和聚碳酸酯(PC)组成;其中,工业直链烷基苯与聚碳酸酯的质量比为5.8:1,工业直链烷基苯包括C10、C11、C12、C13的直链烷基苯,购自中国石化集团金陵石油化工有限责任公司烷基苯厂,产品批号WJB20220612-301-2-02;聚碳酸酯采用聚乙二醇二琥珀酰亚胺碳酸酯;
石墨烯,石墨烯片径在1nm-10μm之间,其相对基础油的添加量为0.05wt%;
及添加剂,其包括甘油单油酸酯0.5wt%和1,2-十二烷二醇1.5wt%,二烷基二硫代磷酸锌1.1wt%,烷基化二苯胺0.6wt%,乳聚氧乙烯聚氧丙醇胺醚5.2mg/kg,碳二亚胺0.07wt%,辛基三唑0.02wt%;上述添加剂的添加量均为相对于基础油的添加量。
其制备方法包括如下步骤:
1)将配方量的石墨烯分散至水中制成3%的石墨烯分散液;
2)将步骤1)所得石墨烯分散液加入至直链烷基苯中,并适当搅拌,待体系分层,取其油相清液;
3)在调配釜内,将步骤2)所得油相清液与配方量的聚碳酸酯及添加剂混合均匀,然后经釜底向釜内通入惰性气体如氩气,以排出物料中的水分,即得烃制冷剂用冷冻机油组合物。
对比例1
本对比例的冷冻机油的原料组分、用量及制备方法基本同实施例1,所不同是,其中未添加聚碳酸酯。
对比例2
本对比例的冷冻机油的原料组分、用量及制备方法基本同实施例1,所不同是,其中工业直链烷基苯与聚碳酸酯的质量比为7:1。
对比例3
本对比例的冷冻机油的原料组分、用量及制备方法基本同实施例1,所不同是,其中工业直链烷基苯与聚碳酸酯的质量比为4:1。
对比例4
本对比例的冷冻机油的原料组分、用量及制备方法基本同实施例1,所不同是,其中未添加助分散剂甘油单油酸酯。
对比例5
本对比例的冷冻机油的原料组分、用量及制备方法基本同实施例1,所不同是,其中未添加助分散剂1,2-十二烷二醇。
对比例6
本对比例的冷冻机油的原料组分、用量及制备方法基本同实施例1,所不同是,其中的助分散剂替换为等质量的十二烷基苯磺酸钠。
对比例7
本对比例的冷冻机油的原料组分、用量基本同实施例1,所不同是,其制备方法为:将工业直链烷基苯、聚碳酸酯及石墨烯及各种添加剂直接共混,搅拌后即得冷冻机油。
以异丁烷R600A为制冷剂,分别对上述实施例及对比例进行应用性能测试,结果见表1。
表1冷冻机油性能测试结果
表2冷冻机油性能测试结果
由表1和表2可以看出,实施例1-3与对比例1-3相比,本发明以直链烷基苯和聚碳酸酯为基础油原料,制得的冷冻机油产品的40℃运动黏度范围宽广,适用于氢氟烃类及低级烃等不同种类的制冷剂,且本发明的原料简单易得。实施例1与对比例4-6相比,甘油单油酸酯、1,2-十二烷二醇二者缺少其中任一种均无法使片径在1nm-10μm的石墨烯在本发明的基础油中得到良好分散,尤其是1,2-十二烷二醇的使用,其常规作为医药中间体,应用于本发明的配方体系中,与甘油单油酸酯协同配合,大大提升了石墨烯在直链烷基苯和聚碳酸酯基础油中的分散性,取得了预料不到的技术效果。实施例1与对比例7相比,改变了制备方法,所得冷冻机油混合均匀性差,这可能是由于石墨烯自身极易团聚,其与基础油的相容性较差,采用常规的简单混合方式无法实现石墨烯在其中的分散。

Claims (8)

1.烃制冷剂用冷冻机油组合物,其特征在于,包括如下组分:
基础油,所述基础油由直链烷基苯和聚碳酸酯组成,所述直链烷基苯与聚碳酸酯的质量比为5.5-6:1;
石墨烯,其相对基础油的添加量为0.02-0.05wt%;
添加剂,所述添加剂包括助分散剂,还包括抗磨剂、抗氧剂、抗泡剂、酸捕捉剂和金属减活剂中的至少一种;所述助分散剂采用甘油单油酸酯和1,2-十二烷二醇;
所述烃制冷剂用冷冻机油组合物的制备方法包括如下步骤:
1)将石墨烯分散至水中制成石墨烯分散液;
2)将步骤1)所得石墨烯分散液加入至直链烷基苯中,搅拌,待体系分层后,取其油相清液;
3)在调配釜内,将步骤2)所得油相清液与配方量的聚碳酸酯及添加剂混合均匀,然后经釜底向釜内通入惰性气体,以排出物料中的水分,即得烃制冷剂用冷冻机油组合物。
2.根据权利要求1所述的烃制冷剂用冷冻机油组合物,其特征在于,相对于基础油而言,助分散剂的添加量为2wt%,抗磨剂的添加量为0.9-1.1wt%,抗氧剂的添加量为0.4-0.6wt%,抗泡剂的添加量为4.5-5.2mg/kg,酸捕捉剂的添加量为0.07-0.1wt%,金属减活剂的添加量为0.02wt%。
3.根据权利要求1所述的烃制冷剂用冷冻机油组合物,其特征在于,所述直链烷基苯选自C10、C11、C12、C13的直链烷基苯中的至少一种。
4.根据权利要求1所述的烃制冷剂用冷冻机油组合物,其特征在于,所述抗磨剂为二烷基二硫代磷酸锌。
5.根据权利要求1所述的烃制冷剂用冷冻机油组合物,其特征在于,所述抗氧剂为烷基化二苯胺。
6.根据权利要求1所述的烃制冷剂用冷冻机油组合物,其特征在于,所述抗泡剂为乳化硅油、聚氧乙烯聚氧丙烯季戊四醇醚或聚氧乙烯聚氧丙醇胺醚中的至少一种。
7.根据权利要求1所述的烃制冷剂用冷冻机油组合物,其特征在于,所述酸捕捉剂为新戊二醇二缩水甘油醚、辛基缩水甘油醚或碳二亚胺中的至少一种。
8.根据权利要求1所述的烃制冷剂用冷冻机油组合物,其特征在于,所述金属减活剂为烷基三唑或其衍生物。
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