CN104245900A - 具有清净作用的添加剂用于进一步增加燃料油的十六烷值的用途 - Google Patents
具有清净作用的添加剂用于进一步增加燃料油的十六烷值的用途 Download PDFInfo
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- CN104245900A CN104245900A CN201380021556.2A CN201380021556A CN104245900A CN 104245900 A CN104245900 A CN 104245900A CN 201380021556 A CN201380021556 A CN 201380021556A CN 104245900 A CN104245900 A CN 104245900A
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- AGDYNDJUZRMYRG-UHFFFAOYSA-N hexyl nitrate Chemical class CCCCCCO[N+]([O-])=O AGDYNDJUZRMYRG-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- GAPFWGOSHOCNBM-UHFFFAOYSA-N isopropyl nitrate Chemical compound CC(C)O[N+]([O-])=O GAPFWGOSHOCNBM-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229960004232 linoleic acid Drugs 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LRMHVVPPGGOAJQ-UHFFFAOYSA-N methyl nitrate Chemical group CO[N+]([O-])=O LRMHVVPPGGOAJQ-UHFFFAOYSA-N 0.000 description 1
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- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DRWPPPBQWZDUQC-UHFFFAOYSA-N n',n'-bis(2-methylpropyl)butane-1,4-diamine Chemical compound CC(C)CN(CC(C)C)CCCCN DRWPPPBQWZDUQC-UHFFFAOYSA-N 0.000 description 1
- SYBRKHKSXSENCQ-UHFFFAOYSA-N n',n'-bis(2-methylpropyl)propane-1,3-diamine Chemical compound CC(C)CN(CC(C)C)CCCN SYBRKHKSXSENCQ-UHFFFAOYSA-N 0.000 description 1
- BZRGXOVBRVLLMG-UHFFFAOYSA-N n',n'-di(propan-2-yl)hexane-1,6-diamine Chemical compound CC(C)N(C(C)C)CCCCCCN BZRGXOVBRVLLMG-UHFFFAOYSA-N 0.000 description 1
- QPGRDTXELAFGRG-UHFFFAOYSA-N n',n'-di(propan-2-yl)propane-1,3-diamine Chemical compound CC(C)N(C(C)C)CCCN QPGRDTXELAFGRG-UHFFFAOYSA-N 0.000 description 1
- JILXUIANNUALRZ-UHFFFAOYSA-N n',n'-diethylbutane-1,4-diamine Chemical compound CCN(CC)CCCCN JILXUIANNUALRZ-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- GCOWZPRIMFGIDQ-UHFFFAOYSA-N n',n'-dimethylbutane-1,4-diamine Chemical compound CN(C)CCCCN GCOWZPRIMFGIDQ-UHFFFAOYSA-N 0.000 description 1
- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TXQBMQNFXYOIPT-UHFFFAOYSA-N octyl nitrate Chemical compound CCCCCCCCO[N+]([O-])=O TXQBMQNFXYOIPT-UHFFFAOYSA-N 0.000 description 1
- 229960002969 oleic acid Drugs 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- PCMORTLOPMLEFB-ONEGZZNKSA-N sinapic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-ONEGZZNKSA-N 0.000 description 1
- PCMORTLOPMLEFB-UHFFFAOYSA-N sinapinic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-UHFFFAOYSA-N 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229960005137 succinic acid Drugs 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- AZAKMLHUDVIDFN-UHFFFAOYSA-N tert-butyl nitrate Chemical compound CC(C)(C)O[N+]([O-])=O AZAKMLHUDVIDFN-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Abstract
本发明涉及具有清净作用的添加剂用于进一步增加含十六烷值改进剂的燃料油的十六烷值的用途,所述添加剂选自:(ⅰ)具有衍生自琥珀酸酐的部分且具有羟基和/或氨基和/或酰胺基和/或亚氨基的化合物;(ⅱ)以无酸的方式季铵化的氮化合物,其可通过含有能与酸酐反应的含氧或含氮的基团且另外含有可季铵化的氨基的化合物加成到多羧酸酐化合物上且随后季铵化而获得;(ⅲ)聚四氢苯并噁嗪和双四氢苯并噁嗪。此外,本发明涉及一种含添加剂(ⅰ)至(ⅲ)、十六烷值改进剂、有机稀释剂或溶剂、和可能的常规的共添加剂的燃料添加剂浓缩物。
Description
技术领域
本发明涉及至少一种具有清净作用的添加剂用于进一步增加含至少一种十六烷值改进剂的燃料油的十六烷值的用途,所述添加剂选自以下物质:
(ⅰ)具有衍生自琥珀酸酐的部分且具有羟基和/或氨基和/或酰胺基和/或亚氨基(imido)的化合物;
(ⅱ)以无酸的方式季铵化的氮化合物,其可通过含有至少一个能与酸酐反应的含氧或含氮的基团且另外含有至少一个可季铵化的氨基的化合物加成到多羧酸酐化合物上且随后季铵化而获得;
(ⅲ)聚四氢苯并噁嗪和双四氢苯并噁嗪。
此外,本发明涉及一种燃料添加剂浓缩物,其由一种或多种上述(ⅰ)至(ⅲ)类的具有清净作用的添加剂、一种或多种十六烷值改进剂、溶剂和常规的共添加剂组成。
燃料油通常含有十六烷值改进剂,其也称作着火加速剂或燃烧改进剂。为此,通常使用有机硝酸酯,其已经已知在燃料油或中间馏分如柴油中作为十六烷值改进剂一段时间了,且已用于其中。越高的十六烷值导致发动机起动越快,特别是在寒冷的天气中,且发动机噪音越小、燃烧越完全、释放烟雾越少且在某些情况下减少喷油器碳化。
在燃料油特别是在柴油中适合作为十六烷值改进剂的典型的有机硝酸酯为短链和中链、直链和支链烷醇的硝酸酯和环烷醇的硝酸酯,如硝酸正己酯、硝酸2-乙基己酯、硝酸正庚酯、硝酸正辛酯、硝酸异辛酯、硝酸仲辛酯、硝酸正壬酯、硝酸正癸酯、硝酸正十二烷基酯、硝酸环戊酯、硝酸环己酯、硝酸甲基环己酯和硝酸异丙基环己酯。在WO 2008/092809中还推荐特定支化的式R1R2CH-CH2-O-NO2的硝酸癸酯作为燃烧改进剂或十六烷值改进剂,其中R1表示正丙基或异丙基且R2表示具有5个碳原子的直链或支链烷基。然而,市售最重要的十六烷值改进剂是硝酸2-乙基己酯。
然而,用于进一步增加燃料油中的十六烷值的现有技术方法仍需要在作用方面进行改进。因此,本发明的目的是在没有增加已存在于燃料油中的十六烷值改进剂量的情况下通过合适的措施进一步增加燃料油特别是柴油和生物燃料油与化石来源、植物来源或动物来源的中间馏分的混合物的十六烷值。
因此发现了选自如上定义的(ⅰ)至(ⅲ)类的具有清净作用的添加剂的用途。
本发明的十六烷值的进一步增加可例如在下述燃料油中确定,所述燃料油已包含一种或多种在燃料油中规定的浓度的十六烷值改进剂。规定的浓度意指没有加入额外量的十六烷值改进剂以增加十六烷值,所述进一步增加是仅通过加入的一种或多种选自(ⅰ)至(ⅲ)类的具有清净作用的添加剂而实现。
本发明的进一步增加燃料油中的十六烷值的另一方面包括使燃料油中十六烷值改进剂的量从零或从给定的低含量增加且同时加入(ⅰ)至(ⅲ)类的具有清净作用的添加剂。然后,通过在不存在(ⅰ)至(ⅲ)类的具有清净作用的添加剂的情况下加入十六烷值改进剂引起的十六烷值的增加比通过在存在(ⅰ)至(ⅲ)类的具有清净作用的添加剂的情况下加入相同量的十六烷值改进剂引起的十六烷值的增加要小。
本发明的进一步使十六烷值增加可通过将额外的(ⅰ)至(ⅲ)类的具有清净作用的添加剂加入已含有十六烷值改进剂和任选不同于(ⅰ)至(ⅲ)类的那些具有清净作用的添加剂(例如其已经以柴油清净剂包的形式提供给燃料油中)的燃料油中而实现,或可通过向燃料油提供含(ⅰ)至(ⅲ)类的具有清净作用的添加剂和与之前使用或推荐的具有较低十六烷值改进剂量的相应的燃料油清净剂包特别是柴油清净剂包相比更高量的十六烷值改进剂的燃料油清净剂包特别是柴油清净剂包而实现。
国际专利申请文件号PCT/EP2011/072449公开了下述混合物用于增加含有至少一种具有清净作用的添加剂和至少一种十六烷值改进剂的燃料油的十六烷值的用途,所述混合物包含
(A)具有12至24个碳原子的脂族饱和或不饱和一元羧酸或其二聚或三聚产物,其可以游离羧酸和/或以铵盐、酰胺、酯和/或腈的形式存在,以及
(B)可从天然油的蒸馏残余物中获得的多环烃化合物,所述天然油从树生树脂(tree resin)中提取出来,
组分(A)和(B)的混合物的使用浓度为10至500重量ppm,基于燃料油的总量计。
所述一元羧酸或其二聚或三聚产物(A)和所述可从树生树脂中提取出来的天然油的蒸馏残余物中获得的多环碳化合物(B)的混合物记载于WO 2007/082825中,其用于改进含至少一种清净剂和至少一种十六烷值改进剂的燃料添加剂浓缩物的存储稳定性。所述组分(A)的一元羧酸或脂肪酸和其二聚或三聚产物可作为游离羧酸和/或作为铵盐存在。特别合适的组分(A)和(B)的混合物为妥尔油脂肪酸或二聚妥尔油脂肪酸的那些。
在一个优选的实施方案中,本发明的主题为上述定义的至少一种选自(ⅰ)至(ⅲ)类的具有清净作用的添加剂的用途,其中燃料油不含有以下物质的混合物:
(A)具有12至24个碳原子的脂族饱和或不饱和一元羧酸或其二聚或三聚产物,其可以游离羧酸和/或以铵盐、酰胺、酯和/或腈的形式存在,和
(B)可从天然油的蒸馏残余物中获得的多环烃化合物,所述天然油从树生树脂中提取出来。
当组分(A)和(B)的混合物使用浓度基于燃料油的总量计为10至500重量ppm时,优选采用上述实施方案。
为避免疑义,上述实施方案中组分(A)和(B)皆不存在,即组分(A)和(B)不允许同时存在于燃料油中。
在本发明上下文中,(ⅰ)至(ⅲ)类的具有清净作用的添加剂为这样的化合物,其在内燃机特别是柴油发动机的影响主要由或至少基本上由消除和/或避免沉积构成。清净剂通常为具有至少一个疏水性烃基和至少一个极性部分的两亲性物质,所述疏水性烃基的数均分子量(Mn)为85至20000,特别是300至5000,且特别是500至2500。
含衍生自琥珀酸酐的部分并具有羟基和/或氨基和/或酰胺基和/或亚氨基的(ⅰ)类的添加剂优选为相应的聚异丁烯琥珀酸酐的衍生物,其可通过使Mn=300至5000特别是Mn=500至2500的常规或高反应性的聚异丁烯与顺丁烯二酸酐通过热途径或经由氯化聚异丁烯的反应而获得。在本文中,特别关注具有脂族多胺(例如乙二胺、二乙三胺、三乙四胺或四乙五胺)的衍生物。具有羟基和/或氨基和/或酰胺基和/或亚氨基的部分例如为羧酸基、酸性酰胺、二胺或多胺的酸性酰胺(其除酰胺官能外还具有游离氨基)、具有酸官能和酰胺官能的丁二酸衍生物、具有一元胺的羧酰亚胺、具有二胺或多胺的羧酰亚胺(其除了酰亚胺官能外还具有游离氨基)、以及通过二胺或多胺与两种丁二酸衍生物的反应形成的二酰亚胺。所述燃料添加剂特别是记载于US-A 4849572中。
WO 2012/004300中记载了(ⅱ)类的以无酸的方式季铵化的氮化合物,所述化合物可通过含至少一个能与酸酐反应的含氧或含氮基和另外至少一个可季铵化的氨基的化合物加成到多羧酸酐化合物上且随后季铵化特别是在不存在游离酸的情况下用环氧化物季铵化而获得。合适的具有至少一个能与酸酐反应的含氧或含氮基团和另外至少一个可季铵化的氨基的化合物特别是具有至少一个伯氨基或仲氨基和至少一个叔氨基的多胺。有用的多羧酸酐特别是二羧酸如丁二酸,所述二羧酸具有相对长链的烃基取代基,且烃基取代基优选具有的数均分子量Mn为200至10000,特别是350至5000。典型的季铵化氮化合物为例如在40℃下获得的聚异丁烯琥珀酸酐与3-(二甲氨基)丙胺的反应产物,所述聚异丁烯基团通常具有的Mn为1000,所述反应产物构成聚异丁烯-琥珀单酰胺且随后在不存在游离酸的情况下于70℃下用氧化苯乙烯季铵化。
在一个优选的实施方案中,至少一种(ⅱ)类的具有清净作用的添加剂为在25至60℃、优选35至50℃的反应温度下获得的聚异丁烯琥珀酸酐与一种或多种N,N-二(C1-至C4-烷基)氨基-C2-至C4-亚烷基胺的反应产物,所述聚异丁烯琥珀酸酐中聚异丁烯基具有的Mn通常为500至2500、优选700至2300,所述反应产物构成聚异丁烯-琥珀单酰胺,且随后在不存在游离酸的情况下于50至100℃、优选60至80℃的温度下用选自环氧乙烷、环氧丙烷、1,2-环氧丁烷、2,3-环氧丁烷和氧化苯乙烯(最优选为环氧丙烷)的环氧化物季铵化。
合适的N,N’-二(C1-至C4-烷基)氨基-C2-至C4-亚烷基胺为例如2-(N,N-二甲基氨基)乙胺、2-(N,N-二乙基氨基)乙胺、2-(N,N-二正丙基-氨基)乙胺、2-(N,N-二异丙基氨基)乙胺、2-(N,N-二正丁基氨基)乙胺、2-(N,N-二异丁基氨基)乙胺、2-(N,N-二仲丁基氨基)乙胺、2-(N,N-二叔丁基氨基)乙胺、3-(N,N-二甲基氨基)丙胺、3-(N,N-二乙基氨基)丙胺、3-(N,N-二正丙基氨基)丙胺、3-(N,N-二异丙基-氨基)丙胺、3-(N,N-二正丁基氨基)丙胺、3-(N,N-二异丁基氨基)-丙胺、3-(N,N-二仲丁基氨基)丙胺、3-(N,N-二叔丁基氨基)丙胺、2-(N,N-二甲基氨基)丙胺、2-(N,N-二乙基氨基)丙胺、2-(N,N-二正丙基氨基)丙胺、2-(N,N-二异丙基氨基)丙胺、2-(N,N-二正丁基氨基)丙胺、2-(N,N-二异丁基氨基)丙胺、2-(N,N-二仲丁基-氨基)丙胺、2-(N,N-二叔丁基氨基)丙胺、4-(N,N-二甲基氨基)丁胺、4-(N,N-二乙基氨基)丁胺、4-(N,N-二正丙基氨基)丁胺、4-(N,N-二异丙基氨基)丁胺、4-(N,N-二正丁基氨基)丁胺、4-(N,N-二异丁基氨基)丁胺、4-(N,N-二仲丁基氨基)丁胺和4-(N,N-二叔丁基氨基)丁胺。
(ⅲ)类的聚四氢苯并噁嗪和双四氢苯并噁嗪记载于EP专利申请文件号10194307.4中。所述聚四氢苯并噁嗪和双四氢苯并噁嗪可通过以下连续反应而获得:在第一反应步骤中,在20至80℃的温度下,将具有两个伯氨基官能的C1-至C20-亚烷基二胺(例如1,2-乙二胺)与C1-至C12-醛(例如甲醛)和C1-至C8-烷醇进行反应并消除和除去水,其中醛和醇相对于二胺各自以两倍以上的摩尔量使用,特别是在每种情况下以4倍摩尔量使用;在第二反应步骤中,在30至120℃的温度下,将由此获得的缩合产物与具有至少一个具有6至3000个碳原子的长链取代基(例如叔辛基、正壬基、正十二烷基或Mn为1000的聚异丁基)的苯酚进行反应,相对于原来所用的亚烷基二胺,此化学计量比为1.2:1至3:1;以及任选地在第三反应步骤中,加热由此获得的双四氢苯并噁嗪至125至280℃的温度并保持至少10分钟。
至少一种用于本发明的具有清净作用的添加剂更优选为(ⅱ)类的化合物。
所用的十六烷值改进剂通常为有机硝酸酯。所述有机硝酸酯特别为未取代或取代的脂族或环脂族醇的硝酸酯,所述醇通常具有最高达约10、特别是具有2至10个碳原子。在这些硝酸酯中的烷基可为直链或支链,以及饱和或不饱和的。所述硝酸酯的典型实例为硝酸甲酯、硝酸乙酯、硝酸正丙酯、硝酸异丙酯、硝酸烯丙酯、硝酸正丁酯、硝酸异丁酯、硝酸仲丁酯、硝酸叔丁酯、硝酸正戊酯、硝酸异戊酯、硝酸2-戊基酯、硝酸3-戊基酯、硝酸叔戊酯、硝酸正己酯、硝酸正庚酯、硝酸仲庚酯、硝酸正辛酯、硝酸2-乙基己酯、硝酸仲辛酯、硝酸正壬酯、硝酸正癸酯、硝酸环戊酯、硝酸环己酯、硝酸甲基环己酯和硝酸异丙基环己酯以及式R1R2CH-CH2-O-NO2的支链硝酸癸酯,其中R1为正丙基或异丙基且R2为具有5个碳原子的直链或支链烷基,如WO 2008/092809中所记载。另外适合的为例如烷氧基取代的脂族醇的硝酸酯如硝酸2-乙氧基乙基酯、硝酸2-(2-乙氧基-乙氧基)乙基酯、硝酸1-甲氧基丙基酯或硝酸4-乙氧基丁基酯。另外适合的还为二醇硝酸酯如二硝酸1,6-六亚甲基酯。在所述的十六烷值改进剂类别中,优选为硝酸伯戊基酯、硝酸伯己基酯、硝酸辛酯及其混合物。
在一个优选的实施方案中,硝酸2-乙基己酯作为唯一的十六烷值改进剂或以与其他十六烷值改进剂的混合物存在于燃料油中。
(ⅰ)至(ⅲ)类的具有清净作用的添加剂原则上可用于增加任何含十六烷值改进剂的燃料油中的十六烷值。然而,它们特别适合用于中间馏分燃料中,特别是柴油燃料中。然而,也可用于加热油或煤油中。柴油燃料或中间馏分燃料通常为沸程为100至400℃的矿物油残油液。这些通常为具有95%点最高达360℃或更高的馏出物。然而,这些也可为所谓的“超低硫柴油”或“城市用柴油”,其特征在于95%点例如不超过345℃且硫含量不超过0.005重量%,或95%点例如为285℃且硫含量不超过0.001重量%。除了可通过精炼获得的主要成分为相对长链的链烷烃的柴油燃料之外,可通过煤的气化或气体液化[“气到液”(GTL)燃料]获得的那些燃料是合适的。上述柴油燃料与可再生燃料(生物燃料)如生物柴油或生物乙醇的混合物也是合适的。目前特别关注具有低硫含量的柴油燃料,即硫含量小于0.05重量%、优选小于0.02重量%、特别是小于0.005重量%且尤其是小于0.001重量%的硫。柴油燃料也可包含例如含量最高达20重量%的水,例如以柴油-水微乳液的形式或以所谓的“白色柴油”的形式包含水。
在一个优选的实施方案中,所述(ⅰ)至(ⅲ)类的具有清净作用的添加剂与本发明的十六烷值改进剂一起用于燃料油中,所述燃料油由以下组成:
(a)0.1至100重量%、优选0.1至小于100重量%、特别是10至95重量%且特别是30至90重量%的至少一种基于脂肪酸酯的生物燃料油,和
(b)0至99.9重量%、优选多于0至99.9重量%、特别是5至90重量%且特别是10至70重量%的化石来源和/或植物来源和/或动物来源的中间馏分,其主要为烃混合物且不含有脂肪酸酯。
因此,所述(ⅰ)至(ⅲ)类的具有清净作用的添加剂可与十六烷值改进剂一起用于燃料油中,所述燃料油由100重量%的至少一种基于脂肪酸酯的生物燃料油(a)组成。
当然,所述(ⅰ)至(ⅲ)类的具有清净作用的添加剂也可根据本发明与十六烷值改进剂一起用于组分(b)的燃料油中,所述燃料油由100重量%的化石来源和/或植物来源和/或动物来源的中间馏分组成,其主要为烃混合物且不含有脂肪酸酯。作为燃料组分(b),化石来源的燃料油是最重要的。
燃料油组分(a)通常还称为“生物柴油”。这种组分优选主要包含衍生自植物和/或动物油和/或脂肪的脂肪酸的烷基酯。烷基酯通常是指低级烷基酯,特别是C1-至C4-烷基酯,其可通过借助于低级醇,例如乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇或特别是甲醇,对在植物和/或动物油和/或脂肪中存在的甘油酯,特别是甘油三酯进行酯交换而得到(FAME)。
可以转化为相应的烷基酯并因此可作为生物柴油的基础的植物油的实例是蓖麻油、橄榄油、花生油、棕榈仁油、椰子油、芥子油、棉籽油,并且特别是葵花油、棕榈油、豆油和菜籽油。其他实例包括可从小麦、黄麻、芝麻和乳油木坚果中获得的油;另外还可以使用落花生油、麻风树油(Jatropha oil)和亚麻籽油。这些油的萃取及其转化为烷基酯可从现有技术中知晓或可由此推出。
也可以将已使用过的植物油,例如使用过的深色油炸用油,在任选地适当清洗后转化为烷基酯且因此它们可作为生物柴油的基础。
植物脂肪原则上同样可用作生物柴油的来源,但只占很小部分。
可以转化为相应的烷基酯并因此可作为生物柴油的基础的动物油和脂肪的实例是鱼油、牛油、猪油或在家畜或野生动物的屠宰或利用中作为废料获得的类似的脂肪和油。
所述的植物和/或动物油和/或脂肪的母体饱和或不饱和脂肪酸特别为月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、油酸、亚油酸、亚麻酸、反油酸、芥子酸和/或蓖麻油酸,所述饱和或不饱和脂肪酸通常具有12至22个碳原子且可带有额外的官能团如羟基,且存在烷基酯中。
用作生物柴油或生物柴油组分的基于植物和/或动物油和/或脂肪的典型低级烷基酯为,例如,葵花甲基酯、棕榈油甲基酯("PME")、豆油甲基酯("SME")以及特别是菜籽油甲基酯("RME")。
然而,也可使用甘油单酯、甘油二酯以及特别是甘油三酯本身例如蓖麻油,或者这些甘油酯的混合物,作为生物柴油或生物柴油组分。
在本发明的上下文中,燃料油组分(b)应理解为是指上述中间馏分燃料,特别是柴油燃料,特别是在120至450℃范围内沸腾的那些燃料。
在进一步优选的实施方案中,所述(ⅰ)至(ⅲ)类的具有清净作用的添加剂根据本发明与十六烷值改进剂一起用于燃料油中,所述燃料油具有以下特性中的至少一个:
(α)硫含量小于50mg/kg(相应于0.005重量%),特别是小于10mg/kg(相应于0.001重量%);
(β)多环芳烃的最大含量为8重量%;
(γ)不高于360℃的95%蒸馏点(vol/vol)。
在(β)中多环芳烃应理解为意指根据标准EN 12916的多环芳烃。它们根据这个标准进行测定。
在燃料油中十六烷值改进剂或多种十六烷值改进剂的混合物的存在量通常为10至10000重量ppm、特别是20至5000重量ppm、甚至更优选为50至2500重量ppm且特别是100至1000重量ppm,例如150至500重量ppm。
在燃料油中(ⅰ)至(ⅲ)类的具有清净作用的添加剂或多种所述的具有清净作用的添加剂的混合物的存在量通常为10至2000重量ppm、特别是20至1000重量ppm、甚至更优选为50至500重量ppm且特别是30至250重量ppm,例如50至150重量ppm。
所述燃料油如柴油燃料或中间馏分燃料,或如所述生物燃料油和化石、植物或动物来源的中间馏分的混合物除(ⅰ)至(ⅲ)类的具有清净作用的添加剂和十六烷值改进剂之外可包含稀释剂和溶剂和其他常规添加剂组分,作为共添加剂,特别是低温流动改进剂、腐蚀抑制剂、破乳剂、去雾剂、消泡剂、抗氧化剂和稳定剂、金属钝化剂、抗静电剂、润滑改进剂和染料和标记物。
适合作为其他共添加剂的低温流动改进剂为,例如,乙烯和至少一种其他的不饱和单体的共聚物,特别是乙烯-乙酸乙烯酯共聚物。
适合作为其他共添加剂的腐蚀抑制剂为,例如,琥珀酸酯,特别是与多元醇的琥珀酸酯、脂肪酸衍生物、例如油酸酯、低聚脂肪酸和取代的乙醇胺。
适合作为其他共添加剂的破乳剂为,例如,烷基取代的酚-和萘磺酸酯的碱金属盐和碱土金属盐和脂肪酸的碱金属盐和碱土金属盐、以及醇烷氧基化物,例如醇乙氧基化物、酚烷氧基化物,例如叔丁基酚乙氧基化物或叔戊基酚乙氧基化物、脂肪酸、烷基酚、环氧乙烷和环氧丙烷的缩合产物,例如环氧乙烷-环氧丙烷嵌段共聚物、聚乙烯亚胺和聚硅氧烷。
适合作为其他共添加剂的去雾剂为,例如,烷氧基化酚-甲醛缩合物。
适合作为其他共添加剂的消泡剂为,例如,聚醚改性的聚硅氧烷。
适合作为其他共添加剂的抗氧化剂为,例如,取代的酚,例如2,6-二叔丁基酚和2,6-二叔丁基-3-甲基酚,以及苯二胺,例如N,N’-二仲丁基-对-苯二胺。
适合作为其他共添加剂的金属钝化剂为,例如,水杨酸衍生物,例如N,N’-二亚水杨基-1,2-丙二胺。
适合作为其他共添加剂的润滑改进剂为,例如,单油酸甘油酯。
合适的溶剂,特别是用于柴油性能包的溶剂,为,例如非极性有机溶剂,特别是芳族和脂族烃,例如甲苯、二甲苯、白油(white spirit)和名称为(生产商:Royal Dutch/Shell Group)、(生产商:ExxonMobil)和溶剂石脑油的工业级溶剂混合物。在此,还可以使用的是极性有机溶剂,特别是与上述非极性有机溶剂的共混物中,特别是醇如2-乙基己醇、癸醇和异十三醇。
当另外使用上述共添加剂和/或溶剂时,它们以其常规用量使用。
本发明的主题也为适合用于燃料油中的燃料添加剂浓缩物-也称之为“燃料添加剂包”或特别为“柴油清净剂包”-其由以下组成:
(C1)5至45重量%、优选10至30重量%的至少一种具有清净作用的添加剂,其选自以下物质:
(ⅰ)具有衍生自琥珀酸酐的部分且具有羟基和/或氨基和或酰胺基和/或亚氨基的化合物;
(ⅱ)以无酸的方式季铵化的氮化合物,其可通过含有至少一个能与酸酐反应的含氧或含氮的基团且另外含有至少一个可季铵化的氨基的化合物加成到多羧酸酐化合物上且随后季铵化而获得;
(ⅲ)聚四氢苯并噁嗪和双四氢苯并噁嗪;
(C2)20至90重量%、优选50至80重量%的至少一种十六烷值改进剂;
(C3)5至35重量%、优选10至20重量%的至少一种选自芳族和脂族烃和醇的有机稀释剂或溶剂;
(C4)0至10重量%、优选0.1至5重量%的一种或多种常规共添加剂,其选自以下物质:
(ⅳ)除下述组分的混合物之外的腐蚀抑制剂,(A)具有12至24个碳原子的脂族饱和或不饱和一元羧酸或其二聚或三聚产物,其可以游离羧酸和/或以铵盐、酰胺、酯和/或腈的形式存在,和(B)可从树生树脂中提取出来的天然油的蒸馏残余物中获得的多环烃化合物;
(ⅴ)破乳剂;
(ⅵ)去雾剂;
(ⅶ)消泡剂;
(ⅷ)抗氧化剂和稳定剂;
(ⅸ)金属钝化剂;
(ⅹ)抗静电剂;
(xi)润滑改进剂;
(xii)染料和标记物;
所有组分(C1)至(C4)的总量为100重量%。
组分(C2)、(C3)和(C4)(ⅳ)至(xii)的实例如上所述。
以下实施例将阐明本发明而非对其进行限制。
实施例
在对于欧洲市场来说典型的、符合标准EN 590B7且包含比例为6.1重量%的生物柴油(FAME)的柴油燃料中,在具有以下添加物的情况下根据EN ISO 5165测定十六烷值:
*DCA=在40℃下获得的聚异丁烯琥珀酸酐与3-(N,N-二甲基-氨基)丙胺的反应产物,其中在聚异丁烯琥珀酸酐中聚异丁烯基的Mn通常为1000,所述反应产物构成聚异丁烯-琥珀单酰胺且其随后在不存在游离酸的情况下于70℃下用环氧丙烷季铵化(通过类似于WO 2012/004300的制备实施例1进行制备)。
Claims (8)
1.至少一种具有清净作用的添加剂用于进一步增加含至少一种十六烷值改进剂的燃料油的十六烷值的用途,所述添加剂选自以下物质:
(ⅰ)具有衍生自琥珀酸酐的部分且具有羟基和/或氨基和/或酰胺基和/或亚氨基的化合物;
(ⅱ)以无酸的方式季铵化的氮化合物,其可通过含有至少一个能与酸酐反应的含氧或含氮的基团且另外含有至少一个可季铵化的氨基的化合物加成到多羧酸酐化合物上且随后季铵化而获得;
(ⅲ)聚四氢苯并噁嗪和双四氢苯并噁嗪。
2.权利要求1的用途,其中燃料油不含有以下物质的混合物:
(A)具有12至24个碳原子的脂族饱和或不饱和一元羧酸或其二聚或三聚产物,其可以游离羧酸和/或以铵盐、酰胺、酯和/或腈的形式存在,和
(B)可从天然油的蒸馏残余物中获得的多环烃化合物,所述天然油从树生树脂中提取出来。
3.权利要求1或2的用途,至少一种具有清净作用的添加剂选自(ⅱ)类。
4.权利要求3的用途,其中至少一种(ⅱ)类的具有清净作用的添加剂为在25至60℃的反应温度下获得的聚异丁烯琥珀酸酐与一种或多种N,N-二(C1-至C4-烷基)氨基-C2-至C4-亚烷基胺的反应产物,其中所述聚异丁烯琥珀酸酐中聚异丁烯基具有的Mn为500至2500,所述反应产物构成聚异丁烯-琥珀单酰胺,且其随后在不存在游离酸的情况下于50至100℃的温度下用选自环氧乙烷、环氧丙烷、1,2-环氧丁烷、2,3-环氧丁烷和氧化苯乙烯的环氧化物季铵化。
5.权利要求1至4的用途,其中燃料油包含硝酸2-乙基己酯作为至少一种十六烷值改进剂。
6.权利要求1至5的用途,其中燃料油由以下组成:
(a)0.1至100重量%的至少一种基于脂肪酸酯的生物燃料油,和
(b)0至99.9重量%的化石来源和/或植物和/或动物来源的中间馏分,其主要为烃混合物且不含脂肪酸酯。
7.权利要求1至6的用途,其中燃料油具有以下特性中的至少一个:
(α)硫含量小于50mg/kg;
(β)多环芳烃的最大含量为8重量%;
(γ)不高于360℃的95%蒸馏点(vol/vol)。
8.一种燃料添加剂浓缩物,其由以下组成:
(C1)5至45重量%的至少一种具有清净作用的添加剂,其选自以下物质:
(ⅰ)具有衍生自琥珀酸酐的部分且具有羟基和/或氨基和/或酰胺基和/或亚氨基的化合物;
(ⅱ)以无酸的方式季铵化的氮化合物,其可通过含有至少一个能与酸酐反应的含氧或含氮的基团且另外含有至少一个可季铵化的氨基的化合物加成到多羧酸酐化合物上且随后季铵化而获得;
(ⅲ)聚四氢苯并噁嗪和双四氢苯并噁嗪;
(C2)20至90重量%的至少一种十六烷值改进剂;
(C3)5至35重量%的至少一种选自芳族和脂族烃和醇的有机稀释剂或溶剂;
(C4)0至10重量%的一种或多种常规共添加剂,其选自以下物质:
(ⅳ)除下述组分的混合物之外的腐蚀抑制剂,(A)具有12至24个碳原子的脂族饱和或不饱和一元羧酸或其二聚或三聚产物,其可以游离羧酸和/或以铵盐、酰胺、酯和/或腈的形式存在,和(B)可从树生树脂中提取出来的天然油的蒸馏残余物获得的多环烃化合物;
(ⅴ)破乳剂;
(ⅵ)去雾剂;
(ⅶ)消泡剂;
(ⅷ)抗氧化剂和稳定剂;
(ⅸ)金属钝化剂;
(ⅹ)抗静电剂;
(xi)润滑改进剂;
(xii)染料和标记物;
所有的组分(C1)至(C4)的总量为100重量%。
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GB9122158D0 (en) * | 1991-10-18 | 1991-11-27 | Exxon Chemical Patents Inc | Fuel oil compositions |
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US20050268536A1 (en) * | 2004-06-02 | 2005-12-08 | Polar Molecular Corporation | Diesel motor fuel additive composition |
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US7648539B2 (en) * | 2005-11-25 | 2010-01-19 | Tellus Renewables Llc | Diesel Fuel composition |
KR20080089450A (ko) | 2006-01-18 | 2008-10-06 | 바스프 에스이 | 연료 첨가제 농축액의 저장 안정성을 개선시키기 위한모노카르복실산과 다환식 탄화수소 화합물의 혼합물의 용도 |
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