CN1225667A - 添加剂组合物 - Google Patents

添加剂组合物 Download PDF

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Publication number
CN1225667A
CN1225667A CN97196519A CN97196519A CN1225667A CN 1225667 A CN1225667 A CN 1225667A CN 97196519 A CN97196519 A CN 97196519A CN 97196519 A CN97196519 A CN 97196519A CN 1225667 A CN1225667 A CN 1225667A
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composition
oil
fuel
silicone oil
lubricating oil
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M·S·宾格莱
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M T Selby
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M T Selby
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Abstract

一种用于内燃机并可以加到燃料或润滑油中的添加剂组合物,包括硅油和有机钛化合物,例如有机钛酸酯,任意的加有溶剂和润滑油,该添加剂组合物降低无铅燃料的阀和阀座磨损,改善废气排放物的质量和减少发动机磨损。

Description

添加剂组合物
本发明涉及用于烃燃料的燃料添加剂,该添加剂可以改善内燃机的操作和性能,本发明特别涉及用于机动车辆的燃料添加剂。
已经提出和使用各种类型的燃料添加剂,它们改善内燃机的性能,例如改善输出功率和输出转矩和改善燃料消耗。其它的燃料添加剂,例如清净剂和抗磨添加剂改善了发动机及其附件的清洁度和寿命。
在EP0006000中,公开了含有润滑油的组合物,其加入了硅氧烷液,该组合物可以加到汽油中。该组合物可以通过磁处理和热处理来稳定。
当该组合物用作汽油添加剂时,发现其改善了燃料消耗和提高了发动机的清洁度。
铅是最广泛用于汽油的添加剂,其改善抗爆性能,但是,铅危害健康,因此在汽油中遭到淘汰。与无铅汽油比较,含铅汽油除了它的抗爆性能外,发现含铅的汽油改善了阀和阀座磨损。在现代的发动机中已经使用硬化的阀和阀座等来降低阀和阀座磨损,但是,在很多的发动机中,特别是较老的发动机中,在汽油中除去铅,使得增加了阀和阀座磨损的严重问题。
已经提出了很多添加剂来代替汽油中的铅,并且已经提出在某些阶段用某形式的几乎每种金属或化合物来代替铅,虽然要求保护,但是还没有人发现是完全满意的。
我们已经发明了一种含有硅氧烷的改进的组合物,它可以用作燃料或油添加剂。
根据本发明,提供一种含有硅油和有机钛化合物的组合物。
本发明也提供一种含有矿物润滑油、硅油和有机钛化合物的润滑油。
本发明还提供一种含有烃燃料例如汽油、柴油、瓦斯油等和上述润滑组合物的燃料组合物。
当钛化合物加到硅油或含有浓缩的硅油的溶液中时,通常会发生化学反应,并且形成沉淀或其它化合物,使得该混合物不适合使用。
我们已经发现,如果硅油和钛化合物分别以要用的量加到汽油中,在混合时不发生该反应。但是,认为在火花塞处该钛化合物与硅油一起反应得到一种配合物,它作为一种催化剂,并且使燃烧性能得到改善。
令人惊奇的是已经发现,使用含有本发明的添加剂制剂的无铅燃料得到出人意料好的排放物水平。所达到的该水平可以达到使用催化转化器的汽车所要求的水平,并且可以使得另外的不能满足所要求的排放物水平的汽车能够使用。
该硅油可以是任何常规的硅油,优选在室温和操作温度范围内,该硅油的粘度与矿物润滑油的粘度一个等级。
可以使用的硅油的例子是苯基硅氧烷、同源的系列硅氧烷或卤化的硅氧烷,但是在本发明中所用的硅油优选的是二甲基硅氧烷。使用一半在25℃的通常粘度为300厘沲的二甲基硅氧烷液和一半在25℃的通常粘度为50厘沲的二甲基硅氧烷液的混合物已经得到特别好的结果。
当所提供的硅油组合物是加入到润滑油中时,用于形成硅油组合物的该润滑油可以是任何合适的矿物油、植物油或合成油,例如烷烃或环烷烃矿物润滑油、蓖麻油、聚异丙烯或聚异丁烯等。但是,优选的该油是烷烃矿物油,并且可以含有不同烷烃矿物油的混合物。为了得到最好的结果,在本发明的方法中所用的该油应该是基本上无水的(小于每百万份30份重),优选其硫含量要小于1%重,更优选小于0.3%重。从这一点考虑,特别是关于低水含量,所销售的最标准的SAE 30烷烃油会是满意的。
在本发明的方法中所用的该硅氧烷优选的分子链长基本上与该油匹配,换句话说,至少在室温和操作温度范围内,该硅氧烷的粘度与该油的粘度优选彼此在同一个等级。
在常温下硅氧烷和油不能很好的混合,虽然如果温度升到足够的高,硅氧烷会溶解在该油中,但是,通常是硅氧烷、该油和其中该硅氧烷至少部分溶解的溶剂混合在一起形成悬浮液。
当使用的时候,该溶剂优选是全氯乙烯,其可以是工业级或分析级,但是其它通常的脂族溶剂或芳族溶剂也可以使用,例如四氯化碳、氯仿、二氯乙烯、三氯乙烯、苯、甲苯、二甲苯、二乙醚、二异丙基醚或石油溶剂油。可以使用较少量的环己烷、石油醚、汽油、乙酸戊酯、石油溶剂油、2-乙基己醇、二噁烷或二乙基溶纤剂,并且可以使用某些醇,只要可以使得该硅氧烷至少部分成为溶液即可。
当打算把按照本发明制备的硅油用作二冲程油或用作四冲程汽油机和柴油机的上部汽缸润滑剂或实际上作为发动机污油时,所生产的该硅油优选地含有(按体积计)不大于1%的硅氧烷、不大于4%的溶剂和作为其余物质的油(包括可以认为是合乎要求的任何其它的添加剂)。人们认为,按照本发明的方法以少到0.001%的量把硅氧烷加到油中在改善油的润滑性能方面会有一定的效果,但是,一般的该硅油应该含有不少于0.02%的硅氧烷。优选的是该硅油应该含有约0.2%的硅氧烷和至少0.4%的溶剂。
该有机钛化合物优选的是能溶解在该油组合物中的化合物或可以在该油组合物中保持悬浮状态的化合物。合适的化合物包括有机钛酸酯,例如辛二醇钛酸酯、钛酸丁酯、聚钛酸丁酯、钛酸四壬基(monyl)酯和钛酸四异辛酯。该钛化合物可以分别以油溶液的形式或以汽油溶液的形式或以化合物本身加到汽油中。如上所提到的,重要的是该钛化合物和该硅油不混合,直到它们都在汽油中。
可能的话,按硅油或硅油加润滑油的体积计,在汽油中该钛酸酯的优选含量为50-150%(体积)。
使用EP 0006000中所公开的方法可以制备润滑油/硅油组合物,这些方法包括把该组合物进行磁处理或热处理,以改善该组合物的性能。
在本发明的组合物加到污油中的情况下,可以用作润滑油添加剂。当在燃料搀混的过程或在油罐中它们可以加到燃料中时,它们也可以用作二冲程润滑油或作为二冲程润滑油的添加剂和作为燃料添加剂,例如作为上部汽缸润滑剂。
但是,如果需要的话,前面所述的本发明的组合物它们本身可以用作机油添加剂,它是富硅氧烷的,可以按需要少量加到普通的污油中。在这种情况下,该添加剂可以包括(按体积)不大于20%的硅氧烷、不大于40%的油和作为其余物质的溶剂,其是本发明的要以污油体积的1-5%的量加到污油中的这样一种添加剂。该添加剂的制备与在早期的EP 0006000中所介绍的该油组合物的制备方法是极为相同的。在这种情况下,该油优选应该是烷烃工业白油和SAE 30烷烃矿物油,优选以4∶1的比例的混合物。一般的,柴油机污油添加剂与汽油机污油添加剂比较,硅氧烷和溶剂的含量要少。
本发明的组合物当用作润滑油添加剂或燃料添加剂时,其可以改善燃料消耗、降低操作温度、提高抗爆性能和改善发动机的清洁度。实施例1:制备硅油组合物
制备二甲基硅氧烷的混合物,它由50%的可由ICI作为F111/50(在25℃的正常粘度为50厘沲)得到的二甲基硅氧烷液和50%的可由ICI作为F111/300(在25℃的正常粘度为300厘沲)得到的二甲基硅氧烷液组成。另外,制备载油混合物,其由(按体积)80%烷烃工业白油和20%的标准SAE 30烷烃油组成。该油以SAE 30 Castrol110 A得到,其水含量少于30ppm重,硫含量少于0.3%重。
然后,用该二甲基硅氧烷混合物和该载油混合物与一定量的全氯乙烯一起制备富硅氧烷载体,该载体由(按体积)20%的二甲基硅氧烷、30%的载油和50%的全氯乙烯组成。在制备该富硅氧烷载体的过程中,把该载油和全氯乙烯混合在一起而没有硅氧烷混合物,在合适的容器中加热到127℃,该温度是全氯乙烯的沸点。把容器中的氧气驱除之后,通过注射把该二甲基硅氧烷混合物直接加到容器中的混合物中。短时间保持沸腾以保证该硅氧烷与油和溶剂完全混合,并防止空气再进入容器。然后密封该容器,在不存在氧气的情况下把该混合物慢慢冷却,得到的混合物是富硅氧烷载体。
然后,把标准SAE 30烷烃矿物油(以SAE 30 Castrol 110 A得到)用作基础润滑油,在该基础润滑油中加入富硅氧烷载体,形成硅油,如下。把基础油放在一个闭合的容器中,加热到60℃,同时搅拌该油,使空气从容器中排出,但是不进入。当达到60℃时,把少量的富硅氧烷载体加到容器中的基础油中,其量是总混合物的5%(体积),把剩余的空气排除后,密封该容器。在不存在氧气的情况下把该混合物慢慢冷却之前,在60℃连续搅拌容器中的基础油和富硅氧烷载体的混合物15分钟。所得到的混合物是高质量的硅油,其含有(体积)0.2%的硅氧烷、3.5%的全氯乙烯、1.04%的工业白油和作为其余量的SAE 30烷烃油。
本发明的一个特征是,与已经提出的重金属添加剂比较,该添加剂不合有毒或有害的组分。
参考下面的实施例介绍本发明。实施例2:制备本发明的组合物
把等量的实施例1制备的硅油组合物和钛酸辛二醇酯分开加到无铅汽油中,加入的比例为1加仑汽油4毫升混合的添加剂。在内燃机试验的的过程中,与同样的没有添加剂的燃料比较,该燃料组合物得到较低的运转温度、无爆运转、功率增加和在燃烧室中不存在含烃沉淀物。试验
用实施例2的燃料组合物运转1975 125bhp Triumph TR6。该TR6有一台发动机,该发动机用从市场上买到的无铅汽油是不能运转的,该汽车的行车试验用实施例2的不加本发明的添加剂的汽油,运转时有爆震,短距离行车之后检验发现严重的阀座磨损。目视检验发动机的排气,显示烟雾排气,表明有未燃烧的烃,该排气通过纤维过滤器显示分割脱色。用实施例2的汽油制剂开车,运转40000多英里没有爆震,基本上没有阀座磨损,并且没有问题;排气通过纤维过滤器显示非常小的脱色。也发现该发动机可以用比起始规定差的混合物开车而没有问题,也发现该发动机具有很好的排放特性,可能是由于可以使用该较差的混合物。
测定用加入添加剂的汽油运转的发动机的排放情况,结果下面列出。试验1 CO排放物
车辆是1972 TR6 Commission no.CP76096-0。所用的燃料是市场上买到的95辛烷值的汽油。在很好的天气条件下开车。使用移动的German Blue Point计进行该试验,该German Blue Point计是用该车的12伏动力电提供动力。收集废气进行测定。使该发动机升到车辆平稳操作的操作温度,以800rpm运转,测定CO排放物为0.1%。
该运转试验包括:
1.在30m.p.h.的基础下观察:排放物波动<0.1%
2.在55m.p.h.的基础下观察:排放物0.00%
3.在35m.p.h.爬坡,从3档变到2档,排放物从0.00%暂时变到1.4%,又降到0.1%,总的变化时间2秒。
在30分钟的运转中,排放物超过0.1%的时间仅在爬坡时。
下面是装有催化转化器的汽车的UK MOT试验的结果。试验2排气排放物
台架试验发动机的排放物流中的CO;CO2;O2和HC。试验开始前,把所有的仪器用N2吹扫,活化的N2作为示O气,而后用生成气标定和漂移校正。
N2中的HC己烷为1435vmp(每百万体积份)
N2中的CO为2.651%(26510vmp)
N2中的CO2为15.014%(15014vmp)
N2中的O2为4.967%(49670vmp)
方法:把1/4″口径的不锈钢管插入24″的两个尾喷管中的一个,该管通过快速配合的连接器直接加入到气体台架上,在其中样品被过滤,冷却等。
该车辆彻底点火并处于空转状态,在开始读数之前其运转5分钟。
结果时间     COvpm  CO2%   O2% HCvpm12.28    2951    15.08    5.7   206/20012.30    3190    15.80    5.75    15512.32    3022    15.90    5.74    16312.34    2892    16.01    5.86    16712.36    3092    16.61    5.82    185平均值
     2879.8  15.88    5.774   175.2
为了进行比较,取Ford Fiesta 1.1升作为参考,其有一个先进的发动机以减少排放物。
COvpm   CO2%  O2%  HCvpm
2450    16.8    3.45    305
由上可以看出,使用本发明的添加剂能够使1976发动机所具有的排放物特性达到现代发动机的水平。

Claims (22)

1.一种燃料组合物,其包括烃燃料、硅油和有机钛化合物。
2.根据权利要求1的燃料组合物,其加入一种润滑油。
3.根据权利要求1或2的燃料组合物,其中硅油是二甲基硅氧烷。
4.根据权利要求3的燃料组合物,其中硅油是一半在25℃的正常粘度为300厘沲的二甲基硅氧烷液和一半在25℃的正常粘度为50厘沲的二甲基硅氧烷液的混合物。
5.根据权利要求1-4之一的燃料组合物,其中有机钛化合物是能够溶解在该燃料组合物中或可以在该燃料组合物中保持悬浮状态的化合物。
6.根据权利要求5的燃料组合物,其中有机钛化合物是辛二醇钛酸酯、钛酸丁酯、聚钛酸丁酯、钛酸四壬酯和钛酸四异辛酯。
7.根据上述任一权利要求的组合物,其中硅油的存在量为燃料体积的0.01%-1.5%。
8.根据上述任一权利要求的组合物,根据它们可能的情况,其中钛酸酯的存在量为硅油的体积或硅油加润滑油体积的50%-150%。
9.一种润滑油添加剂组合物,其包括润滑油、硅油和有机钛化合物。
10.根据权利要求9的组合物,其中硅油是二甲基硅氧烷。
11.根据权利要求10的组合物,其中硅油是一半在25℃的正常粘度为300厘沲的二甲基硅氧烷液和一半在25℃的正常粘度为50厘沲的二甲基硅氧烷液的混合物。
12.根据权利要求11的组合物,其中硅油在室温和操作温度范围内的粘度与矿物润滑油的粘度在同一个等级。
13.根据权利要求9-12之一的组合物,其中该润滑油基本上是无水的,硫含量小于0.3%重。
14.根据权利要求9-13之一的组合物,其中加入溶剂。
15.根据权利要求14的组合物,其中溶剂是全氯乙烯。
16.根据权利要求9-16之一的润滑油添加剂组合物,其按体积计,包括小于20%的硅氧烷、小于40%的油和其余为溶剂。
17.根据权利要求9-16之一的润滑油添加剂组合物,其中有机钛化合物是能够溶解在该润滑油组合物中或可以在该润滑油组合物中保持悬浮状态的化合物。
18.根据权利要求17的组合物,其中有机钛化合物是辛二醇钛酸酯、钛酸丁酯、聚钛酸丁酯、钛酸四壬酯和钛酸四异辛酯。
19.一种润滑油组合物,其包括润滑油和上述权利要求9-18之一的润滑油添加剂,其中基于润滑油的体积,硅油的存在量为1-5%。
20.根据权利要求9-19之一的组合物,其中在该润滑油组合物中有机钛化合物的存在量为硅油体积的50-150%。
21.一种用于二冲程内燃机的燃料/油组合物,它包括汽油和权利要求9-18之一的组合物。
22.根据权利要求21的用于二冲程内燃机的燃料/油组合物,其中加入1-5%重的该油组合物。
CN97196519A 1996-07-01 1997-07-01 添加剂组合物 Pending CN1225667A (zh)

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CN112342065A (zh) * 2020-11-11 2021-02-09 信阳师范学院 有机钛酸酯或有机硅酸酯在提高碳氢燃料裂解性能方面的应用及方法
CN112342065B (zh) * 2020-11-11 2021-07-20 信阳师范学院 有机钛酸酯或有机硅酸酯在提高碳氢燃料裂解性能方面的应用及方法
CN113502175A (zh) * 2020-11-11 2021-10-15 信阳师范学院 有机钛酸酯在提高碳氢燃料裂解性能方面的应用及方法
CN113502175B (zh) * 2020-11-11 2023-01-10 信阳师范学院 有机钛酸酯在提高碳氢燃料裂解性能方面的应用及方法

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