CN110747037A - 一种小桐子绝缘油及其制备方法 - Google Patents

一种小桐子绝缘油及其制备方法 Download PDF

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CN110747037A
CN110747037A CN201911046727.2A CN201911046727A CN110747037A CN 110747037 A CN110747037 A CN 110747037A CN 201911046727 A CN201911046727 A CN 201911046727A CN 110747037 A CN110747037 A CN 110747037A
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oil
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曾伟
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Liangshan Denong Bioenergy Co Ltd
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Abstract

本发明提出一种小桐子绝缘油,属于植物绝缘油的制备技术领域。包括以下重量份的原料:100份小桐子精炼油、0.1‑0.2份油溶性抗氧剂、0.01‑0.1份钝化剂、0.001‑0.02份降凝剂;小桐子精炼油中单不饱和脂肪酸含量大于50%。其制备方法为:将100份小桐子精炼油、0.1‑0.2份油溶性抗氧剂、0.01‑0.1份钝化剂、0.001‑0.02份降凝剂装入25℃的混合釜中,在氮气保护下,采用160‑200转/分的转速均匀混合30‑40分钟,真空脱泡得小桐子绝缘油。由本发明制备的小桐子绝缘油成本低、耐高温、易降解、稳定性好、低温冷凝性好的绝缘油,使其满足变压器、断路器、电流和电压互感器、套管等油浸绝缘高电压设备的应用需求。

Description

一种小桐子绝缘油及其制备方法
技术领域
本发明属于植物绝缘油的制备技术领域,具体涉及一种小桐子绝缘油及其制备方法。
背景技术
绝缘油是一种重要的绝缘介质,通过将其以浸渍和填充的方式应用于变压器、断路器、电流和电压互感器、套管等油浸绝缘高电压设备中,达到消除设备内绝缘中的气隙、提高绝缘的电气强度、改善设备的散热性能的效果。传统的矿物绝缘油存在燃点低、生物降解性能差的缺点,不能满足高防火性能的环保型高电压设备的设计和制造要求,而植物绝缘油的开发正是顺应这一要求,植物绝缘油来自天然植物,随着杂交和转基因技术的发展,植物油料单产不断提高,成本相对较低,同时植物绝缘油的主要成分是酯类物质,酯基链中的不饱和双键易受微生物攻击发生β氧化,使得植物油具有良好的生物降解性,同时植物油脂中的天然脂肪酸可在生物降解过程中起促进作用。因此,植物油类液体绝缘介质受到越来越多科学工作者的重视。
CN202042320U就公开了一种山茶籽绝缘油配电变压器,其特征在于变压器中装入的植物绝缘油不含毒物,不会对人体造成伤害,可以快速而彻底的生物降解,是一种环保型绝缘液体。但山茶籽油含有大量不饱和脂肪酸,该专利未对绝缘油的抗氧化性和稳定性进行调控,继而造成实际使用的不安全性和不稳定性。CN102222537A公开了一种用于变压器的植物绝缘油及其制备方法,通过制备工艺的调整和抗氧剂、增效剂等辅料的添加达到提高变压器绝缘油的稳定性和介电性能和简化变压器绝缘油的制备工艺的目的,该专利在绝缘油的制备过程中,对植物油的提炼过程未见报道,而是直接选用现有的植物油进行后处理、共混得到绝缘油,无法控制植物油源的酸值。
在植物绝缘油的使用过程中,为了兼具油品的抗氧化性和低温流动性,具有高单不饱和脂肪酸含量的油料种子是制备植物绝缘油的最佳选择。在常见的玉米油(单不饱和脂肪酸含量:24.2%)、棉籽油(单不饱和脂肪酸含量:17.8%)、葵花籽油((单不饱和脂肪酸含量:19.6%))、菜籽油(单不饱和脂肪酸含量:55.9%)、橄榄油(73.3%)[李剑,姚舒瀚,杜斌,等.植物绝缘油及其应用研究关键问题分析与展望[J].高电压技术,2015(2):353-363.]等植物油料中小桐子油具有较高的单不饱和脂肪酸含量(油酸:56.63%),而成本又比橄榄油低。此外,依托凉山德农生物能源有限公司年产量为300公斤/亩的200万亩小桐子基地,可以保证植物绝缘油的原料丰富,成本低。以上优势使小桐子油基植物绝缘油在液体绝缘介质领域具有大的应用前景。而目前利用小桐子制备绝缘油的技术正式本领域技术人员研究的方向。
发明内容
本发明的目的是针对现有技术存在的不足,提供一种小桐子绝缘油及其制备方法,利用小桐子油来源丰富、成本低、富含单不饱和脂肪酸等特点,同时添加抗氧剂、钝化剂、降凝剂得到一种成本低、耐高温、易降解、稳定性好、低温冷凝性好的绝缘油,使其满足变压器、断路器、电流和电压互感器、套管等油浸绝缘高电压设备的应用需求。
为了实现上述目的,本发明采用以下技术方案:
一种小桐子绝缘油,包括以下重量份的原料:100份小桐子精炼油、0.1-0.2份油溶性抗氧剂、0.01-0.1份钝化剂、0.001-0.02份降凝剂;小桐子精炼油中单不饱和脂肪酸含量大于50%。
作为优选,所述抗氧化剂为维生素E、虾青素、β胡萝卜素、SOD、迷迭香类物质、茶多酚等的一种或几种。
作为优选,所述钝化剂为金属离子螯合剂,用于消除植物中微量金属元素以及制备、运输过程中与容器接触产生的金属元素,结构式为X[(CR2)nY]m,其中X为P,S,N等含有孤对电子、易于金属离子络合的元素,Y为强酸性基团,R为氢元素、烷基、芳基中的一种或几种。
作为优选,所述钝化剂为乙二胺四乙酸、苯并三氮唑、Irgamet39、T501、EVA、WHP中的一种或几种。
本发明还提供了上述小桐子精炼油的制备方法为:将小桐子种子在75℃-92℃下进行20-30分钟的蒸炒,蒸炒后进行压榨得压榨饼,随后将压榨饼放到60℃-75℃下继续二次压榨,得到小桐子毛油;向100份小桐子毛油中加入m份质量分数为w%的NaOH溶液,在75℃下加热30分钟进行碱炼脱酸,再快速升温到90℃,加速皂粒生长、分离,之后进行水洗、干燥得到脱酸小桐子油,再向其中加入活性炭,在70℃下加热40分钟进行脱色,经过过滤得到脱酸-脱色的小桐子油,在真空180℃下,通入水蒸气,蒸馏30分钟进行脱臭,冷却后即可得到小桐子精炼油。
上述小桐子精炼油的制备方法中,所用NaOH溶液的用量如下:其中m为理论质量分数为w%氢氧化钠溶液的质量,M0是NaOH溶液中和前小桐子毛油的质量;AV是NaOH溶液中和前小桐子毛油的酸值。实际用碱量略大于m。
优选的,所述NaOH溶液的质量分数w%为4%-7%。
本发明还提供了一种小桐子绝缘油的制备方法,包括以下步骤,
(1)将100份小桐子精炼油、0.1-0.2份油溶性抗氧剂、0.01-0.1份钝化剂、0.001-0.02份降凝剂装入25℃的混合釜中,在氮气保护下,采用160-200转/分的转速均匀混合30-40分钟,真空脱泡得小桐子绝缘油。
本发明与现有技术相比具有的有益效果是:
(1)本发明的小桐子绝缘油以天然植物小桐子作为原料进行提纯,成分天然,来源广泛,成本低。
(2)本发明的小桐子提纯油中含有大量单不饱和脂肪酸,具有良好的抗氧化性和低温流动性。
(3)本发明的小桐子提纯油能实现现取现用,保证了产品的稳定性。
(4)本发明的小桐子绝缘油在制备过程中,采用边搅拌边通氮气的方式,既可以去除混合液中的空气,也可以提高氮气的溶解量,使制得的绝缘油具有稳定性好、品质均匀的特点。
(5)本发明的小桐子绝缘油通过加入抗氧剂、钝化剂和降凝剂等辅料,协同作用,提高植物绝缘油的稳定性和低温性能。
具体实施方式
下面结合实施例对本发明作进一步的描述,所描述的实施例仅仅是本发明一部分实施例,并不是全部的实施例。基于本发明中的实施例,本领域的普通技术人员在没有做出创造性劳动前提下所获得的其他所用实施例,都属于本发明的保护范围。值得说明的是,以下实施例中所用物料份数均为重量份。
值得说明的是,以下实施例中所用物料份数均为重量份。绝缘油凝固点测定方法参照GB/T510-83《石油产品凝点测定法》;绝缘油闪点的测试参考GB/T261—83《石油产品闪点测定法(闭口杯法)》;绝缘油的介电性能主要根据GB/T507-86《绝缘油介电强度测定法》进行试验。酸值的测定参考GB/T5530-《动植物油脂酸值和酸度测定》。
实施例1
材料:小桐子种子,氢氧化钠溶液,活性炭,维生素E、乙二酸四乙胺,T501。
制备方法:
将100份小桐子种子进行在75℃进行30分钟的蒸炒,接着将油籽进行初榨,随后将压榨饼放到60℃下继续二次压榨,得到小桐子毛油,得到的小桐子毛油酸值为3.37mgKOH/g,向100份小桐子毛油中加入4份质量分数为7%的NaOH溶液,在75℃加热30分钟进行碱炼脱酸,再快速升温到90℃,静置分离,进行水洗、干燥得到脱酸小桐子油,再向其中加入活性炭,在70℃加热40分钟进行脱色,经过过滤得到脱酸-脱色的小桐子油,在真空180℃,通入水蒸气,蒸馏30分钟进行脱臭,冷却后即可得到小桐子精炼油。取100分小桐子精炼油,加入0.2%份维生素E、0.01%份乙二酸四乙胺、0.001%份T501在25℃的混合釜中,在氮气保护下,采用160转/分的转速均匀混合30分钟,真空脱泡、得到小桐子精炼油,再进行灌装。
本实施例制备的得到小桐子精炼油的性能参数如下:
参数 小桐子油基绝缘油 测试标准
工频击穿电压/kV 82 GB/T507-86
酸值/mgKOH g<sup>-1</sup> 0.007 GB/T5530
凝点 -24 GB/T510-83
实施例2
材料:小桐子种子,氢氧化钠溶液,活性炭,SOD、苯丙三氮唑,EVA。
制备方法:
将100份小桐子种子进行在80℃进行25分钟的蒸炒,接着将油籽进行初榨,随后将压榨饼放到65℃下继续二次压榨,得到小桐子毛油,得到的小桐子毛油酸值为3.59mgKOH/g,向100份小桐子毛油中加入5份质量分数为6%的NaOH溶液,在75℃加热30分钟进行碱炼脱酸,再快速升温到90℃,静置分离,进行水洗、干燥得到脱酸小桐子油,再向其中加入活性炭,在70℃加热40分钟进行脱色,经过过滤得到脱酸-脱色的小桐子油,在真空180℃,通入水蒸气,蒸馏30分钟进行脱臭,冷却后即可得到小桐子精炼油。取100分小桐子精炼油,加入0.15%份SOD、0.05%份苯丙三氮唑、0.002%份EVA在25℃的混合釜中,在氮气保护下,采用170转/分的转速均匀混合25分钟,真空脱泡、得到小桐子精炼油,再进行灌装。
本实施例制备的得到小桐子精炼油的性能参数如下:
参数 小桐子油基绝缘油 测试标准
工频击穿电压/kV 86 GB/T507-86
酸值/mgKOH g<sup>-1</sup> 0.006 GB/T5530
凝点 -26 GB/T510-83
实施例3
材料:小桐子种子,氢氧化钠溶液,活性炭,虾青素、Irgamet39,WHP。
制备方法:
将100份小桐子种子进行在85℃进行20分钟的蒸炒,接着将油籽进行初榨,随后将压榨饼放到70℃下继续二次压榨,得到小桐子毛油,得到的小桐子毛油酸值为3.65mgKOH/g,向100份小桐子毛油中加入8份质量分数为4%的NaOH溶液,在75℃加热30分钟进行碱炼脱酸,再快速升温到90℃,静置分离,进行水洗、干燥得到脱酸小桐子油,再向其中加入活性炭,在70℃加热40分钟进行脱色,经过过滤得到脱酸-脱色的小桐子油,在真空180℃,通入水蒸气,蒸馏30分钟进行脱臭,冷却后即可得到小桐子精炼油。取100分小桐子精炼油,加入0.1%份虾青素、0.03%份Irgamet39、0.003%份WHP在25℃的混合釜中,在氮气保护下,采用200转/分的转速均匀混合20分钟,真空脱泡、得到小桐子精炼油,再进行灌装。
本实施例制备的得到小桐子精炼油的性能参数如下:
参数 小桐子油基绝缘油 测试标准
工频击穿电压/kV 89 GB/T507-86
酸值/mgKOH g<sup>-1</sup> 0.004 GB/T5530
凝点 -28 GB/T510-83
实施例4
材料:小桐子种子,氢氧化钠溶液,活性炭,虾青素、Irgamet39,EVA。
制备方法:
将100份小桐子种子进行在92℃进行20分钟的蒸炒,接着将油籽进行初榨,随后将压榨饼放到75℃下继续二次压榨,得到小桐子毛油,得到的小桐子毛油酸值为3.89mgKOH/g,向100份小桐子毛油中加入5份质量分数为7%的NaOH溶液,在75℃加热30分钟进行碱炼脱酸,再快速升温到90℃,静置分离,进行水洗、干燥得到脱酸小桐子油,再向其中加入活性炭,在70℃加热40分钟进行脱色,经过过滤得到脱酸-脱色的小桐子油,在真空180℃,通入水蒸气,蒸馏30分钟进行脱臭,冷却后即可得到小桐子精炼油。取100分小桐子精炼油,加入0.1%份虾青素、0.01%份Irgamet39、0.001%份EVA在25℃的混合釜中,在氮气保护下,采用200转/分的转速均匀混合20分钟,真空脱泡、得到小桐子精炼油,再进行灌装。
本实施例制备的得到小桐子精炼油的性能参数如下:
参数 小桐子油基绝缘油 测试标准
工频击穿电压/kV 92 GB/T507-86
酸值/mgKOH g<sup>-1</sup> 0.002 GB/T5530
凝点 -25 GB/T510-83
实施例5
材料:小桐子种子,氢氧化钠溶液,活性炭,茶多酚、乙二胺四乙酸,T501。
制备方法:
将100份小桐子种子进行在92℃进行20分钟的蒸炒,接着将油籽进行初榨,随后将压榨饼放到75℃下继续二次压榨,得到小桐子毛油,得到的小桐子毛油酸值为3.89mgKOH/g,向100份小桐子毛油中加入5份质量分数为7%的NaOH溶液,在75℃加热30分钟进行碱炼脱酸,再快速升温到90℃,静置分离,进行水洗、干燥得到脱酸小桐子油,再向其中加入活性炭,在70℃加热40分钟进行脱色,经过过滤得到脱酸-脱色的小桐子油,在真空180℃,通入水蒸气,蒸馏30分钟进行脱臭,冷却后即可得到小桐子精炼油。取100分小桐子精炼油,加入0.2%份虾青素、0.1%份茶多酚、0.01%份T501在25℃的混合釜中,在氮气保护下,采用200转/分的转速均匀混合20分钟,真空脱泡、得到小桐子精炼油,再进行灌装。
本实施例制备的得到小桐子精炼油的性能参数如下:
参数 小桐子油基绝缘油 测试标准
工频击穿电压/kV 84 GB/T507-86
酸值/mgKOH g<sup>-1</sup> 0.01 GB/T5530
凝点 -33 GB/T510-83
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。

Claims (8)

1.一种小桐子绝缘油,其特征在于,包括以下重量份的原料:100份小桐子精炼油、0.1-0.2份油溶性抗氧剂、0.01-0.1份钝化剂、0.001-0.02份降凝剂;小桐子精炼油中单不饱和脂肪酸含量大于50%。
2.根据权利要求1所述的一种小桐子绝缘油,其特征在于,所述抗氧化剂为维生素E、虾青素、β胡萝卜素、SOD、迷迭香类物质、茶多酚等的一种或几种。
3.根据权利要求1所述的一种小桐子绝缘油,其特征在于,所述钝化剂为金属离子螯合剂,用于消除植物中微量金属元素以及制备、运输过程中与容器接触产生的金属元素,结构式为X[(CR2)nY]m,其中X为P,S,N等含有孤对电子、易于金属离子络合的元素,Y为强酸性基团,R为氢元素、烷基、芳基中的一种或几种。
4.根据权利要求1所述的一种小桐子绝缘油,其特征在于,所述钝化剂为乙二胺四乙酸、苯并三氮唑、Irgamet39、T501、EVA、WHP中的一种或几种。
5.根据权利要求1所述的一种小桐子绝缘油,其特征在于,所述小桐子精炼油的制备方法为:将小桐子种子在75℃-92℃下进行20-30分钟的蒸炒,蒸炒后进行压榨得压榨饼,随后将压榨饼放到60℃-75℃下继续二次压榨,得到小桐子毛油;向100份小桐子毛油中加入m份质量分数为w%的NaOH溶液,在75℃下加热30分钟进行碱炼脱酸,再快速升温到90℃,加速皂粒生长、分离,之后进行水洗、干燥得到脱酸小桐子油,再向其中加入活性炭,在70℃下加热40分钟进行脱色,经过过滤得到脱酸-脱色的小桐子油,在真空180℃下,通入水蒸气,蒸馏30分钟进行脱臭,冷却后即可得到小桐子精炼油。
6.根据权利要求5所述的一种小桐子绝缘油,其特征在于,所用NaOH溶液的用量如下:
Figure FDA0002254321740000011
其中m为理论质量分数为w%氢氧化钠溶液的质量,M0是NaOH溶液中和前小桐子毛油的质量;AV是NaOH溶液中和前小桐子毛油的酸值。
7.根据权利要求5所述的一种小桐子绝缘油,其特征在于,所述NaOH溶液的质量分数w%为4%-7%。
8.一种小桐子绝缘油的制备方法,包括权利要求1-7任一所述的一种小桐子绝缘油,其特征在于,包括以下步骤,
(1)将100份小桐子精炼油、0.1-0.2份油溶性抗氧剂、0.01-0.1份钝化剂、0.001-0.02份降凝剂装入25℃的混合釜中,在氮气保护下,采用160-200转/分的转速均匀混合30-40分钟,真空脱泡得小桐子绝缘油。
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