CN111676074A - 一种含氮柴油降凝剂组合物及其制备和应用 - Google Patents

一种含氮柴油降凝剂组合物及其制备和应用 Download PDF

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CN111676074A
CN111676074A CN202010479884.9A CN202010479884A CN111676074A CN 111676074 A CN111676074 A CN 111676074A CN 202010479884 A CN202010479884 A CN 202010479884A CN 111676074 A CN111676074 A CN 111676074A
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pour point
point depressant
depressant composition
nitrogen
diesel
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蔺华林
殷素雅
李欣
袁铭霞
解麦莹
陈凤飞
杨太顺
韩生
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Shanghai Institute of Technology
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Priority to US17/927,696 priority patent/US11999919B2/en
Priority to PCT/CN2021/096307 priority patent/WO2021244385A1/zh
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Abstract

本发明涉及一种含氮柴油降凝剂组合物及其制备和应用,该含氮柴油降凝剂组合物由以下重量百分比的组分组成:单异丙醇胺10‑40%;环己烷10‑40%;聚乙二醇0‑20%;N‑十四烷基甲基丙烯酰胺‑甲基丙烯酸十四酯40‑60%。将所得的柴油降凝剂组合物添加到市售0#柴油中,其冷凝点和冷滤点分别降低21‑25℃和9‑13℃。

Description

一种含氮柴油降凝剂组合物及其制备和应用
技术领域
本发明属于柴油降凝剂技术领域,涉及一种含氮柴油降凝剂组合物及其制备和应用。
背景技术
柴油因其耐用、高效、清洁、存储安全等特点,而倍受人们的关注。但是柴油的低温流动性能却制约着其使用性能,因此人们对低凝柴油特别是低冷滤点的柴油的需求更是迫切。比起其它工艺,添加降凝剂生产低凝柴油,可拓宽柴油馏程,节约资源;同时具有操作灵活、费用低、见效快和保留高十六烷值蜡组分等特点,是一种增产高品质柴油的有效方法。柴油降凝剂又称低温流动性改进剂,是柴油生产中一种重要的燃料添加剂,它在加入量很少时即能显著改变柴油的低温流动性能,降低凝点和冷滤点。但是,目前市面上的柴油降凝剂都具有添加量大,分散性不足等问题。
发明内容
本发明的目的就是为了提供一种含氮柴油降凝剂组合物及其制备和应用,具有在柴油中溶解性好,用量小且降凝降滤效果明显等优点。
本发明的目的可以通过以下技术方案来实现:
本发明的技术方案之一提供了一种含氮柴油降凝剂组合物,由以下重量百分比的组分组成:
Figure BDA0002516946950000011
进一步的,所述的N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯由N-十四烷基甲基丙烯酰胺和甲基丙烯酸十四酯在甲苯做溶剂、过氧化苯甲酰为引发剂的条件下反应得到。更进一步的,N-十四烷基甲基丙烯酰胺和甲基丙烯酸十四酯的摩尔比为1:10。更进一步的,反应温度为120℃,时间为8h。此方法将含氮极性基团引入聚合物中,并通过加入一定比例的助溶剂,使聚合物降凝剂的降凝效果有所提升,且实验过程简单、操作方便。十四烷基甲基丙烯酰胺在提供烷基长链的同时,还带有酰胺基团,因此N-十六烷基甲基丙烯酰胺-甲基丙烯酸十四酯聚合物中具有丰富的长链和极性基团,提供了丰富结晶位点,极性基团可延迟蜡晶的析出并排斥蜡晶的堆积。选择了单异丙醇胺、环己烷、聚乙二醇作为助溶剂与降凝剂混合微量加入到柴油中,提高降凝剂与柴油的感受性。
进一步的,其由以下重量百分比的组分组成:
Figure BDA0002516946950000021
进一步的,聚乙二醇为聚乙二醇200。
本发明的技术方案之二提供了一种含氮柴油降凝剂组合物的制备方法,按计量比称取N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯、单异丙醇胺、环己烷和聚乙二醇搅拌均匀,超声分散,即得到目的产物。
更进一步的,搅拌的温度为25-30℃,超声分散的时间为10-20min。
本发明的技术方案之三提供了一种含氮柴油降凝剂组合物的应用,使用时,将含氮柴油降凝剂组合物加入到柴油中,混合均匀并超声分散。
进一步的,含氮柴油降凝剂组合物与柴油的质量比为1:100-1000。
进一步的,混合的温度为30-45℃,超声分散的时间为30min。
进一步的,柴油优选为市售0#柴油。
本发明对其他助剂与聚合物降凝剂的添加量做出了限定,其中一组分浓度降低,降凝剂的浓度受到影响,则降凝效果有所下降。N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯的添加量是十分重要的,当降凝剂的添加量较少时,体系内没有足够的非极性长链烷烃与柴油的正构烷烃发生共晶,也没有足够极性基团保持体系内蜡晶的稳定。当降凝剂的添加量过多时,聚合物会发生团聚,造成相反的效果。因此适量的聚合物才能发挥出降凝剂最佳的效果。
与现有技术相比,本发明具有以下优点:
(1)由于所含的N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯起到主要降凝作用,它所占比例较高,通过共晶、吸附等作用改变柴油的结晶方式,能够有效改善柴油的低温流动性,所含环己烷和聚乙二醇(200)组分是良好的降凝剂助剂,使降凝剂组合物均匀分散在柴油中,同时N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯和单异丙醇胺起协同作用,从而进一步增强降凝效果。
(2)只需在超声波处理器上进行超声分散即可,其制备工艺简单、操作方便、效果明显。
(3)可提高降凝剂在市售0#柴油中的分散性,可使其冷凝点降低21-25℃、冷滤点降低9-13℃。
具体实施方式
下面结合具体实施例对本发明进行详细说明。本实施例以本发明技术方案为前提进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
本发明中冷滤点的测量方法依据《SH/T0248-2006柴油和民用取暖油冷滤点测定法》进行,冷凝点的测量方法依据《GB510-83石油产品凝点测定》进行。
本发明所用原料:
Figure BDA0002516946950000031
N-十四烷基甲基丙烯酰是通过酰基化反应得到的,在N,N二甲基甲酰胺作为溶剂条件下,将缚酸剂和十四胺搅拌溶解,再加入甲基丙烯酰氯,反应2h,水洗干燥后得到N-十四烷基甲基丙烯酰胺。N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯由N-十四烷基甲基丙烯酰胺和甲基丙烯酸十四酯在单体摩尔比1:10,反应温度为120℃,甲苯做溶剂,过氧化苯甲酰为引发剂反应8小时得到。
其余如无特别说明的原料或处理技术,则表明均为本领域的常规市售原料或常规处理技术。
实施例1:
一种柴油的降凝剂组合物,由N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯、单异丙醇胺、环己烷和聚乙二醇(200)混合而成,按质量百分比计算,其原料组成及含量如下:
Figure BDA0002516946950000041
上述的柴油的降凝剂组合物在柴油降凝中的应用,柴油的降凝剂组合物:柴油的比例,按质量比计算,优选为1:200,将柴油的降凝剂组合物按0.1%的质量比加入到60g松江0#柴油中50℃的温度下混合搅拌均匀后,超声分散15min,即得含有该柴油降凝剂组合物的柴油。
经测试上述实施例1所得的含有上述柴油降凝剂组合物的市售0#柴油的冷凝点和冷滤点分别降低25℃和13℃。
实施例2
一种柴油的降凝剂组合物,由N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯、单异丙醇胺、环己烷和聚乙二醇(200)混合而成,按质量百分比计算,其原料组成及含量如下:
Figure BDA0002516946950000042
上述的柴油的降凝剂组合物在柴油降凝中的应用,柴油的降凝剂组合物:柴油的比例,按质量比计算,优选为1:200,将柴油的降凝剂组合物按0.1%的质量比加入到60g松江0#柴油中50℃的温度下混合搅拌均匀后,超声分散15min,即得含有该柴油降凝剂组合物的柴油。
经测试上述实施例2所得的含有上述柴油降凝剂组合物的市售0#柴油的冷凝点和冷滤点分别降低24℃和12℃。
实施例3
一种柴油的降凝剂组合物,由N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯、单异丙醇胺、环己烷和聚乙二醇(200)混合而成,按质量百分比计算,其原料组成及含量如下:
Figure BDA0002516946950000051
上述的柴油的降凝剂组合物在柴油降凝中的应用,柴油的降凝剂组合物:柴油的比例,按质量比计算,优选为1:200,将柴油的降凝剂组合物按0.1%的质量比加入到60g松江0#柴油中50℃的温度下混合搅拌均匀后,超声分散15min,即得含有该柴油降凝剂组合物的柴油。
经测试上述实施例3所得的含有上述柴油降凝剂组合物的市售0#柴油的冷凝点和冷滤点分别降低23℃和11℃。
实施例4
一种柴油的降凝剂组合物,由N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯、单异丙醇胺、环己烷和聚乙二醇(200)混合而成,按质量百分比计算,其原料组成及含量如下:
Figure BDA0002516946950000052
上述的柴油的降凝剂组合物在柴油降凝中的应用,柴油的降凝剂组合物:柴油的比例,按质量比计算,优选为1:200,将柴油的降凝剂组合物按0.1%的质量比加入到60g松江0#柴油中50℃的温度下混合搅拌均匀后,超声分散15min,即得含有该柴油降凝剂组合物的柴油。
经测试上述实施例4所得的含有上述柴油降凝剂组合物的市售0#柴油的冷凝点和冷滤点分别降低22℃和10℃。
实施例5
一种柴油的降凝剂组合物,由N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯、单异丙醇胺、环己烷和聚乙二醇(200)混合而成,按质量百分比计算,其原料组成及含量如下:
Figure BDA0002516946950000061
上述的柴油的降凝剂组合物在柴油降凝中的应用,柴油的降凝剂组合物:柴油的比例,按质量比计算,优选为1:200,将柴油的降凝剂组合物按0.1%的质量比加入到60g松江0#柴油中50℃的温度下混合搅拌均匀后,超声分散15min,即得含有该柴油降凝剂组合物的柴油。
经测试上述实施例5所得的含有上述柴油降凝剂组合物的市售0#柴油的冷凝点和冷滤点分别降低21℃和10℃。
实施例6
一种柴油的降凝剂组合物,由N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯、单异丙醇胺、环己烷和聚乙二醇(200)混合而成,按质量百分比计算,其原料组成及含量如下:
Figure BDA0002516946950000062
上述的柴油的降凝剂组合物在柴油降凝中的应用,柴油的降凝剂组合物:柴油的比例,按质量比计算,优选为1:200,将柴油的降凝剂组合物按0.1%的质量比加入到60g松江0#柴油中50℃的温度下混合搅拌均匀后,超声分散15min,即得含有该柴油降凝剂组合物的柴油。
经测试上述实施例5所得的含有上述柴油降凝剂组合物的市售0#柴油的冷凝点和冷滤点分别降低21℃和9℃。
对比例1
将实施例1中所使用的N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯降凝剂不与单异丙醇胺、环己烷和聚乙二醇(200)混合使用,直接按0.1%的质量比加入到60g松江0#柴油中50℃的温度下混合搅拌均匀后,超声分散15min,经测试,加剂后的松江0#柴油的冷凝点和冷滤点分别降低19℃和7℃。
通过上述实施例和对比例1进行对比,可以看出N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯、单异丙醇胺、环己烷和聚乙二醇(200)混合而组成的柴油降凝剂组合物,即通过溶剂提高了降凝剂在柴油中的溶解性和分散性并通过降凝剂之间的协同作用,提高了降凝剂的降凝效果,改善了柴油的低温流动性。
对比例2
优选市售的聚甲酯丙烯酸酯类降凝剂T1804在柴油降凝中的应用,降凝剂与柴油的比例,按质量比计算,优选为1:200,将柴油的降凝剂组合物按0.1%的质量比加入到60g松江0#柴油中50℃的温度下混合搅拌均匀后,超声分散15min,即得含有该柴油降凝剂组合物的柴油。
经测试上述对比例2所得的含有上述柴油降凝剂组合物的市售0#柴油的冷凝点和冷滤点分别降低19℃和6℃。
通过上述实施例和应用实施例2进行对比,可以看出N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯、单异丙醇胺、环己烷和聚乙二醇(200)混合而组成的柴油降凝剂组合物对柴油的感受性更强,降凝效果更佳。
对比例3:
与实施例1相比,绝大部分都相同,除了将单异丙醇胺改为等质量的N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯。
经测试上述对比例3所得的含有上述柴油降凝剂组合物的市售0#柴油的冷凝点和冷滤点分别降低20℃和9℃。
通过上述实施例和应用实施例1进行对比,可以看出N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯、单异丙醇胺、环己烷和聚乙二醇(200)混合而组成的柴油降凝剂组合物对柴油的感受性更强,降凝效果更佳。
对比例4:
与实施例1相比,绝大部分都相同,除了将聚乙二醇改为等质量的环己烷。
经测试上述对比例4所得的含有上述柴油降凝剂组合物的市售0#柴油的冷凝点和冷滤点分别降低19℃和8℃。
通过上述实施例和应用实施例1进行对比,可以看出N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯、单异丙醇胺、环己烷和聚乙二醇(200)混合而组成的柴油降凝剂组合物对柴油的感受性更强,降凝效果更佳。
对比例5:
与实施例1相比,绝大部分都相同,除了将环己烷改为等质量的聚乙二醇。
经测试上述对比例5所得的含有上述柴油降凝剂组合物的市售0#柴油的冷凝点和冷滤点分别降低20℃和7℃。
通过上述实施例和应用实施例1进行对比,可以看出N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯、单异丙醇胺、环己烷和聚乙二醇(200)混合而组成的柴油降凝剂组合物对柴油的感受性更强,降凝效果更佳。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (10)

1.一种含氮柴油降凝剂组合物,其特征在于,由以下重量百分比的组分组成:
Figure FDA0002516946940000011
2.根据权利要求1所述的一种含氮柴油降凝剂组合物,其特征在于,所述的N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯由N-十四烷基甲基丙烯酰胺和甲基丙烯酸十四酯在甲苯做溶剂、过氧化苯甲酰为引发剂的条件下反应得到。
3.根据权利要求2所述的一种含氮柴油降凝剂组合物,其特征在于,N-十四烷基甲基丙烯酰胺和甲基丙烯酸十四酯的摩尔比为1:10。
4.根据权利要求2所述的一种含氮柴油降凝剂组合物,其特征在于,反应温度为120℃,时间为8h。
5.根据权利要求1所述的一种含氮柴油降凝剂组合物,其特征在于,其由以下重量百分比的组分组成:
Figure FDA0002516946940000012
6.如权利要求1-5任一所述的一种含氮柴油降凝剂组合物的制备方法,其特征在于,按计量比称取N-十四烷基甲基丙烯酰胺-甲基丙烯酸十四酯、单异丙醇胺、环己烷和聚乙二醇搅拌均匀,超声分散,即得到目的产物。
7.根据权利要求6所述的一种含氮柴油降凝剂组合物的制备方法,其特征在于,搅拌的温度为25-30℃,超声分散的时间为10-20min。
8.如权利要求1-5任一所述的一种含氮柴油降凝剂组合物的应用,其特征在于,使用时,将含氮柴油降凝剂组合物加入到柴油中,混合均匀并超声分散。
9.根据权利要求8所述的一种含氮柴油降凝剂组合物的应用,其特征在于,含氮柴油降凝剂组合物与柴油的质量比为1:100-1000。
10.根据权利要求8所述的一种含氮柴油降凝剂组合物的应用,其特征在于,混合的温度为30-45℃,超声分散的时间为30min。
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