CN102443447A - Diesel composition and method for improving oxidation stability of biodiesel - Google Patents

Abstract

Translated fromChinese

本发明提供了一种柴油组合物和提高生物柴油氧化安定性的方法，该柴油组合物含有基础柴油和添加剂，其特征在于，所述基础柴油含生物柴油，所述添加剂含有脒型化合物，所述脒型化合物为下述结构式(1)所示的化合物和/或具有两个环状结构的脒型化合物，结构式(1)中，R₁、R₂、R₃和R₄各自为H或碳原子数为1-30的烃基，且R₁、R₂、R₃和R₄中至少一个为碳原子数为1-30的烃基。本发明提供的柴油组合物具有较好的氧化安定性。

The invention provides a diesel oil composition and a method for improving the oxidation stability of biodiesel. The diesel oil composition contains base diesel oil and additives. It is characterized in that the base diesel oil contains biodiesel, and the additives contain amidine compounds. The amidine-type compound is a compound shown in the following structural formula (1) and/or an amidine-type compound with two ring structures. In the structural formula (1), R₁ , R₂ , R₃ and R₄ are each H or A hydrocarbon group with 1-30 carbon atoms, and at least one of R₁ , R₂ , R₃ and R₄ is a hydrocarbon group with 1-30 carbon atoms. The diesel composition provided by the invention has better oxidation stability.

Description

Translated fromChinese

柴油组合物和提高生物柴油氧化安定性的方法Diesel Compositions and Methods of Improving Oxidation Stability of Biodiesel

技术领域technical field

本发明是关于一种柴油组合物和提高生物柴油氧化安定性的方法。The invention relates to a diesel composition and a method for improving the oxidation stability of biodiesel.

背景技术Background technique

随着世界范围内车辆柴油化趋势的加快，柴油的需求量会愈来愈大，而石油资源的日益枯竭和人们环保意识的提高，大大促进了世界各国加快柴油替代燃料的开发步伐，生物柴油以其优越的环保性能和可再生性受到了各国的重视。With the acceleration of dieselization of vehicles worldwide, the demand for diesel will increase. The depletion of petroleum resources and the improvement of people's awareness of environmental protection have greatly promoted the development of diesel alternative fuels in countries around the world. Biodiesel It has been valued by various countries for its superior environmental protection performance and renewability.

生物柴油(BD100)又称脂肪酸甲酯(Fatty Acid Methyl Ester)，是以大豆和油菜籽等油料作物、油棕和黄连木等油料林木果实、工程微藻等油料水生植物的油脂以及动物油脂、废餐饮油等作原料，与醇类(甲醇、乙醇)经酯交换反应获得，是一种洁净的生物燃料。生物柴油具有可再生、清洁和安全三大优势，对我国农业结构调整、能源安全和生态环境综合治理有十分重大的战略意义。而我国目前是一个石油净进口国，石油储量又很有限，大量进口石油对我国的能源安全造成威胁；因此，生物柴油的研究和生产对我国有着重要的现实意义。Biodiesel (BD100), also known as fatty acid methyl ester (Fatty Acid Methyl Ester), is derived from oil crops such as soybeans and rapeseeds, oil-bearing forest fruits such as oil palm and pistachio, engineering microalgae and other oil-bearing aquatic plants, and animal fats, Waste cooking oil and other raw materials are obtained through transesterification with alcohols (methanol, ethanol). It is a clean biofuel. Biodiesel has the three major advantages of being renewable, clean and safe, and is of great strategic significance to the adjustment of my country's agricultural structure, energy security and comprehensive management of the ecological environment. But our country is a net importer of oil at present, and the oil reserves are very limited. Importing a large amount of oil poses a threat to our energy security; therefore, the research and production of biodiesel has important practical significance to our country.

但是，由于原料和加工工艺的原因，有些生物柴油的氧化安定性很差，对生物柴油的使用和贮存都造成很大的困难。氧化安定性差的生物柴油易生成如下老化产物：1)不溶性聚合物(胶质和油泥)，这会造成发动机滤网堵塞和喷射泵结焦，并导致排烟增大、启动困难；2)可溶性聚合物，其可在发动机中形成树脂状物质，可能会导致熄火和启动困难；3)老化酸，这会造成发动机金属部件腐蚀；4)过氧化物，这会造成橡胶部件的老化变脆而导致燃料泄漏等。However, due to raw materials and processing techniques, some biodiesel has poor oxidation stability, which causes great difficulties in the use and storage of biodiesel. Biodiesel with poor oxidation stability is prone to produce the following aging products: 1) insoluble polymers (colloids and sludge), which will cause engine filter blockage and injection pump coking, and lead to increased smoke exhaust and difficulty in starting; 2) soluble polymers 3) aging acids, which can cause corrosion of metal parts in the engine; 4) peroxides, which can cause aging of rubber parts to become brittle and cause Fuel leaks, etc.

欧洲生物柴油标准EN 14214：2003、澳大利亚生物柴油标准(Draft2003)、新西兰生物柴油标准NZS 7500：2005、巴西生物柴油标准ANP255(2003)、印度生物柴油标准IS 15607：2005、南非生物柴油标准SANS1935：2004以及我国柴油机燃料调合用生物柴油(BD100)国家标准GB/T20828-2007都规定生物柴油的氧化安定性为110C下的诱导期不低于6小时，测定方法为EN 14112：2003。European biodiesel standard EN 14214: 2003, Australian biodiesel standard (Draft2003), New Zealand biodiesel standard NZS 7500: 2005, Brazilian biodiesel standard ANP255 (2003), Indian biodiesel standard IS 15607: 2005, South African biodiesel standard SANS1935: Both 2004 and my country’s national standard GB/T20828-2007 for biodiesel (BD100) for blending diesel engine fuels stipulate that the oxidation stability of biodiesel is not less than 6 hours at 110C, and the measurement method is EN 14112:2003.

众所周知，石油柴油(即通常意义的柴油，此处为了与生物柴油相区分，特引入石油柴油)中的烯烃、双烯烃以及硫化物、氮化物等非烃化合物在氧的作用下，生成一系列的氧化中间产物，并经缩合作用产生不溶性的沉淀。这些在石油柴油储存过程中生成的不溶性颗粒会影响到燃料的使用性能，造成过滤系统堵塞，引起燃油系统部件故障，影响喷油雾化，导致不完全燃烧，甚至在发动机中形成过多积炭，使喷嘴堵塞。而生物柴油由于氧化安定性比石油柴油差，与石油柴油调合后会加重上述问题。最为明显的表现是含生物柴油的调合燃料的稳定性和消净分散性比石油柴油要差。As we all know, non-hydrocarbon compounds such as olefins, diolefins, sulfides, and nitrogen compounds in petroleum diesel oil (that is, diesel oil in the usual sense, here in order to distinguish it from biodiesel), generate a series of Oxidation intermediates, and condensation produces insoluble precipitates. These insoluble particles generated during the storage of petroleum diesel will affect the performance of the fuel, cause blockage of the filter system, cause failure of fuel system components, affect fuel injection atomization, cause incomplete combustion, and even form excessive carbon deposits in the engine , causing the nozzle to clog. Since biodiesel has poorer oxidation stability than petroleum diesel, blending with petroleum diesel will aggravate the above problems. The most obvious performance is that the stability and dispersibility of blended fuel containing biodiesel are worse than that of petroleum diesel.

上述问题可通过加入添加剂解决或缓解。一种方式是向纯生物柴油中加入抗氧剂以减缓其氧化，从而缓解老化产物的危害；另一种方式是向石油柴油或含生物柴油的调合燃料中加入稳定剂和清净分散剂，以改善调合燃料的稳定性和清净分散性。稳定剂可终止、减弱、或干扰各种氧化反应，以抑制油品变质，改善其安定性；清净分散剂可把喷嘴上已形成的积炭清洗下来，并在喷嘴表面形成保护膜，防止新的积炭产生，同时还可分散油中已形成的沉渣，改善滤清器和喷嘴堵塞，并改善尾气排放。The above problems can be solved or alleviated by adding additives. One way is to add antioxidants to pure biodiesel to slow down its oxidation, thereby alleviating the harm of aging products; the other way is to add stabilizers and detergents and dispersants to petroleum diesel or blended fuels containing biodiesel, To improve the stability and clean dispersibility of blended fuels. Stabilizers can terminate, weaken, or interfere with various oxidation reactions to inhibit oil deterioration and improve its stability; detergents and dispersants can clean the carbon deposits formed on the nozzles and form a protective film on the surface of the nozzles to prevent new At the same time, it can also disperse the sediment formed in the oil, improve the clogging of filters and nozzles, and improve exhaust emissions.

CN 1742072A公开了一种提高生物柴油储存稳定性的方法，该方法包括将含有以原液计为15-60重量％的溶于生物柴油的2，4-二叔丁基羟甲苯(BHT)的液态原液加入到待稳定化的生物柴油中，直至以生物柴油的总溶液计，2，4-二叔丁基羟甲苯的浓度达到0.005-2重量％。CN 1742072A discloses a method for improving the storage stability of biodiesel, which method includes dissolving 2,4-di-tert-butylhydroxytoluene (BHT) containing 15-60% by weight in stock solution The stock solution is added into biodiesel to be stabilized until the concentration of 2,4-di-tert-butylhydroxytoluene reaches 0.005-2% by weight based on the total solution of biodiesel.

CN 1847368A公开了一种提高生物柴油的氧化稳定性的方法，该方法包括将双酚型抗氧剂如4，4`-亚甲基二[2，6-二叔丁基苯酚]、2，2`-亚甲基二[6-叔丁基-4-甲基苯酚]以10-20000ppm(w/w)的量加入到待稳定的生物柴油中。CN 1847368A discloses a method for improving the oxidation stability of biodiesel, which method comprises bisphenol type antioxidant such as 4,4'-methylene bis[2,6-di-tert-butylphenol], 2, 2'-methylenebis[6-tert-butyl-4-methylphenol] is added to the biodiesel to be stabilized in an amount of 10-20000ppm (w/w).

CN 1847369A公开了一种提高生物柴油的氧化稳定性的方法，该方法包括将熔点小于或等于40℃的主抗氧化剂以10-20000ppm(w/w)的量加入到待稳定的生物柴油中，其中所述主抗氧化剂含有烷基酚。CN 1847369A discloses a method for improving the oxidation stability of biodiesel, which method comprises adding the primary antioxidant with a melting point of less than or equal to 40°C to the biodiesel to be stabilized in an amount of 10-20000ppm (w/w), Wherein said main antioxidant contains alkylphenol.

US 2007/113467A1公开了一种具有改进的氧化稳定性的燃料组合物，该组合物含有生物柴油和至少一种抗氧剂，所述抗氧剂选自没食子酸丙酯、1，2，3-三羟基苯、2，6-二叔丁基对甲基苯酚、丁基化羟基茴香醚、硫代二丙酸月桂酯、生育酚、喹啉衍生物中的一种。US 2007/113467A1 discloses a fuel composition with improved oxidation stability comprising biodiesel and at least one antioxidant selected from the group consisting of propyl gallate, 1,2,3 - One of trihydroxybenzene, 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, lauryl thiodipropionate, tocopherol, and quinoline derivatives.

以上使用传统的抗氧剂来提高生物柴油氧化安定性的方法虽然有一定效果，但效果不太明显或者需要较大用量的抗氧剂才能获得明显的改善效果。Although the above method of using traditional antioxidants to improve the oxidation stability of biodiesel has certain effects, the effect is not obvious or requires a large amount of antioxidants to obtain obvious improvement effects.

发明内容Contents of the invention

本发明的目的是为了克服上述现有技术提高生物柴油氧化安定性的方法效果不太明显或者需要较大用量的抗氧剂才能获得明显的改善效果的缺点，提供一种在较少量的抗氧剂下即可获得优异改善效果的柴油组合物以及提供一种提高生物柴油氧化安定性的方法。The purpose of the present invention is to overcome the shortcomings of the method for improving the oxidation stability of biodiesel in the above-mentioned prior art that the effect is not obvious or that a large amount of antioxidant is required to obtain a significant improvement effect, and to provide a A diesel composition with excellent improvement effect can be obtained under oxygen agent and a method for improving the oxidation stability of biodiesel.

本发明提供了一种柴油组合物，该柴油组合物含有基础柴油和添加剂，其中，所述基础柴油含有生物柴油，所述添加剂含有脒型化合物，所述脒型化合物为下述结构式(1)所示的化合物和/或具有两个环状结构的脒型化合物：The present invention provides a kind of diesel oil composition, and this diesel oil composition contains base diesel oil and additive, wherein, described base diesel oil contains biodiesel, and described additive contains amidine type compound, and described amidine type compound is following structural formula (1) Compounds shown and/or amidine-type compounds with two ring structures:

结构式(1)中，R₁、R₂、R₃和R₄各自为H或碳原子数为1-30的烃基，且R₁、R₂、R₃和R₄中至少一个为碳原子数为1-30的烃基。In the structural formula (1), R₁ , R₂ , R₃ and R₄ are each H or a hydrocarbon group with 1-30 carbon atoms, and at least one of R₁ , R₂ , R₃ and R₄ is a carbon atom number is a hydrocarbon group of 1-30.

本发明还提供一种提高生物柴油氧化安定性的方法，该方法包括，在含有生物柴油的基础柴油中，加入添加剂，所述添加剂含有脒型化合物，所述脒型化合物为下述结构式(1)所示的化合物和/或具有两个环状结构的脒型化合物：The present invention also provides a method for improving the oxidation stability of biodiesel, the method comprising, in the base diesel containing biodiesel, adding additives, the additives contain amidine compounds, the amidine compounds are the following structural formula (1 ) and/or amidine-type compounds with two ring structures:

R₁、R₂、R₃和R₄各自为H或碳原子数为1-30的烃基，且R₁、R₂、R₃和R₄中至少一个为碳原子数为1-30的烃基。R₁ , R₂ , R₃ and R₄ are each H or a hydrocarbon group with 1-30 carbon atoms, and at least one of R₁ , R₂ , R₃ and R₄ is a hydrocarbon group with 1-30 carbon atoms .

本发明提供的柴油组合物，无论是以纯生物柴油作为基础柴油还是以含有生物柴油的调合燃料作为基础柴油，在较小量的抗氧剂存在下即可获得优异的氧化安定性，因此，在达到相同的氧化安定性要求时，抗氧剂在生物柴油组合物中的量可以大大减少。而且，该抗氧剂毒性小，原料易得。The diesel composition provided by the present invention, no matter pure biodiesel is used as the base diesel or a blended fuel containing biodiesel is used as the base diesel, excellent oxidation stability can be obtained in the presence of a relatively small amount of antioxidant, therefore, When achieving the same oxidation stability requirements, the amount of antioxidants in the biodiesel composition can be greatly reduced. Moreover, the antioxidant has low toxicity and the raw materials are easy to obtain.

具体实施方式Detailed ways

根据本发明提供的柴油组合物中，所述添加剂的含量可以在较大范围内选择，例如相对于基础柴油的含量可以为10-10000ppm，优选为50-8000ppm，进一步优选为50-5000ppm，更进一步优选为100-3000ppm，更优选为500-3000ppm。According to the diesel oil composition provided by the present invention, the content of the additive can be selected in a wide range, for example, the content of the base diesel can be 10-10000ppm, preferably 50-8000ppm, more preferably 50-5000ppm, more preferably More preferably, it is 100-3000 ppm, and more preferably, it is 500-3000 ppm.

通常情况下，脒型化合物作为制备聚氨酯时的催化剂使用。生物柴油的抗氧剂一般为酚型抗氧剂如BHT或2，6-二叔丁基苯酚等以及芳胺型抗氧剂如4，4’-二辛基二苯胺(抗氧剂V81)。一方面，如上所述，BHT的抗氧效果非常有限。另一方面，4，4’-二辛基二苯胺具有一定毒性，因此，本领域迫切需要开发一种毒性小、价格低廉且抗氧效果优异的抗氧剂。Usually, amidine-type compounds are used as catalysts in the preparation of polyurethanes. Antioxidants for biodiesel are generally phenolic antioxidants such as BHT or 2,6-di-tert-butylphenol and aromatic amine antioxidants such as 4,4'-dioctyldiphenylamine (antioxidant V81) . On the one hand, as mentioned above, the antioxidant effect of BHT is very limited. On the other hand, 4,4'-dioctyldiphenylamine has certain toxicity, therefore, there is an urgent need in this area to develop an antioxidant with low toxicity, low price and excellent antioxidant effect.

本发明的发明人意外地发现，如下结构式(1)所示的脒型化合物以及具有两个环状结构的脒型化合物，一方面，与BHT、V81相比具有更加优异的抗氧效果，另一方面，与芳胺抗氧剂相比，毒性明显降低，原料也易得。The inventors of the present invention unexpectedly found that the amidine compound shown in the following structural formula (1) and the amidine compound with two ring structures, on the one hand, have a more excellent antioxidant effect compared with BHT and V81, and on the other hand On the one hand, compared with aromatic amine antioxidants, the toxicity is significantly lower, and the raw materials are also easy to obtain.

结构式(1)中，R₁、R₂、R₃和R₄各自为H或碳原子数为1-30的烃基，且R₁、R₂、R₃和R₄中至少一个为碳原子数为1-30的烃基。In the structural formula (1), R₁ , R₂ , R₃ and R₄ are each H or a hydrocarbon group with 1-30 carbon atoms, and at least one of R₁ , R₂ , R₃ and R₄ is a carbon atom number is a hydrocarbon group of 1-30.

本发明中，所述烃基是指由碳和氢组成的饱和或不饱和、坏状或非环状基团，可以是烷基、芳基、烷基芳基或芳基烷基。In the present invention, the hydrocarbon group refers to a saturated or unsaturated, halo-shaped or acyclic group composed of carbon and hydrogen, which may be an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group.

根据本发明，所述烷基可以是直链正构烷基，也可以是带有侧链的异构烷基，该烷基可以是甲基、乙基、丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十四烷基、正十六烷基、正十八烷基、正二十烷基、正二十二烷基；异丙基、异丁基、叔丁基、异戊基、新戊基，异己基、异庚基、异辛基(2-乙基己基)、异壬基、异癸基、异十二烷基、异十四烷基、异十六烷基、异十八烷基和异二十烷基中的一种或几种。烯基的例子包括9-十八烯基。According to the present invention, the alkyl group can be a straight chain normal alkyl group or an isomeric alkyl group with a side chain, and the alkyl group can be methyl, ethyl, propyl, n-butyl, n-pentyl Base, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl , n-eicosyl, n-docosyl; isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, isohexyl, isoheptyl, isooctyl (2-ethylhexyl ), isononyl, isodecyl, isododecyl, isotetradecyl, isohexadecyl, isoctadecyl and isoeicosyl in one or more. Examples of alkenyl groups include 9-octadecenyl.

芳基可以是苯基、苯甲基(苄基)、苯乙基和苯丙基中的一种或几种。The aryl group can be one or more of phenyl, benzyl (benzyl), phenethyl and phenylpropyl.

R₁、R₂、R₃、R₄为烷基的典型的例子如：Typical examples where R₁ , R₂ , R₃ , and R₄ are alkyl groups are:

N-十二烷基-N’，N’-二甲基乙基脒：N-dodecyl-N', N'-dimethylethylamidine:

其它的同类化合物例如但不限于如下：Other similar compounds are for example but not limited to the following:

N-己基-N’，N’-二甲基乙基脒；N-辛基-N’，N’-二甲基乙基脒；N-壬基-N’，N’-二甲基乙基脒：N-癸基-N’，N’-二甲基乙基脒；N-十四烷基-N’，N’-二甲基乙基脒；N-十六烷基-N’，N’-二甲基乙基脒；N-十八烷基-N’，N’-二甲基乙基脒；N-己基-N’，N’-二乙基乙基脒；N-辛基-N’，N’-二乙基乙基脒；N-癸基-N’，N’-二乙基乙基脒；N-十二烷基-N’，N’-二乙基乙基脒；N-十四烷基-N’，N’-二乙基乙基脒；N-十六烷基-N’，N’-二乙基乙基脒；N-十八烷基-N’，N’-二乙基乙基脒；N-己基-N’，N’-二甲基丙基脒；N-辛基-N’，N’-二甲基丙基脒；N-癸基-N’，N’-二甲基丙基脒；N-十二烷基-N’，N’-二甲基丙基脒；N-十四烷基-N’，N’-二甲基丙基脒；N-十六烷基-N’，N’-二甲基丙基脒；N-十八烷基-N’，N’-二甲基丙基脒等中的一种或多种。N-hexyl-N', N'-dimethylethylamidine; N-octyl-N', N'-dimethylethylamidine; N-nonyl-N', N'-dimethylethylamidine Amidines: N-decyl-N', N'-dimethylethylamidine; N-tetradecyl-N', N'-dimethylethylamidine; N-hexadecyl-N' , N'-dimethylethylamidine; N-octadecyl-N', N'-dimethylethylamidine; N-hexyl-N', N'-diethylethylamidine; N- Octyl-N', N'-diethylethylamidine; N-decyl-N', N'-diethylethylamidine; N-dodecyl-N', N'-diethyl Ethylamidine; N-tetradecyl-N', N'-diethylethylamidine; N-hexadecyl-N', N'-diethylethylamidine; N-octadecyl -N', N'-diethylethylamidine; N-hexyl-N', N'-dimethylpropylamidine; N-octyl-N', N'-dimethylpropylamidine; N -Decyl-N', N'-dimethylpropylamidine; N-dodecyl-N', N'-dimethylpropylamidine; N-tetradecyl-N', N'- One of N-hexadecyl-N', N'-dimethylpropylamidine; N-octadecyl-N', N'-dimethylpropylamidine, etc. one or more species.

所述具有两个环状结构的脒型有机胺优选脒型结构参与成环，这种脒型有机胺的具体例子有：The amidine-type organic amine having two cyclic structures preferably has an amidine-type structure participating in ring formation. Specific examples of this amidine-type organic amine include:

1，8-二氮杂双环[5，4，0]十一碳-7-烯(DBU)：1,8-diazabicyclo[5,4,0]undec-7-ene (DBU):

1，5-二氮杂双环1,5-diazabicyclo

1，5，7-三叠氮双环(4.4.0)癸-5-烯(TBD)：1,5,7-Triazidebicyclo(4.4.0)dec-5-ene (TBD):

7-甲基-1，5，7-三氮杂二环[4.4.0]癸-5-烯(MTBD)等。7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) and the like.

上述各种脒型化合物可以单独使用也可以两种或更多种配合使用。The various amidine compounds mentioned above may be used alone or in combination of two or more.

上述各种脒型化合物优选具有两个环状结构的脒型有机胺，尤其优选具有两个环状结构且脒型结构参与成环的有机胺。The amidine-type compounds mentioned above are preferably amidine-type organic amines having two cyclic structures, and particularly preferably organic amines having two cyclic structures in which the amidine-type structures participate in ring formation.

优选情况下，本发明提供的柴油组合物还含有结构式(2)所示的胍型化合物：Preferably, the diesel composition provided by the invention also contains a guanidine compound represented by structural formula (2):

结构式(2)中，R₈、R₉、R₁₀、R₁₁和R₁₂各自为H或者取代或未取代的碳原子数为1-30的烃基。所述烃基的定义与上述结构式(1)中烃基的定义相同，优选为烷基或芳基，进一步优选为甲基、丁基或苯基。结构式(2)所示胍型化合物的加入能够进一步明显提高含有结构式(1)所示添加剂的柴油组合物的氧化安定性。In the structural formula (2), each of R₈ , R₉ , R₁₀ , R₁₁ and R₁₂ is H or a substituted or unsubstituted hydrocarbon group with 1-30 carbon atoms. The definition of the hydrocarbon group is the same as the definition of the hydrocarbon group in the above structural formula (1), preferably an alkyl group or an aryl group, more preferably a methyl group, a butyl group or a phenyl group. The addition of the guanidine compound represented by the structural formula (2) can further significantly improve the oxidation stability of the diesel composition containing the additive represented by the structural formula (1).

进一步优选情况下，所述结构式(2)所示的胍型化合物与结构式(1)所示的脒型化合物的重量比为1∶0.01-1。Further preferably, the weight ratio of the guanidine-type compound represented by the structural formula (2) to the amidine-type compound represented by the structural formula (1) is 1:0.01-1.

根据原料的易得性，所述胍型化合物优选为1，1，3，3，-四甲基胍、1，2，3-三苯基胍、1，3-二苯基胍、1，1，2，3，3-五丁基胍中的一种或多种。According to the availability of raw materials, the guanidine type compound is preferably 1,1,3,3,-tetramethylguanidine, 1,2,3-triphenylguanidine, 1,3-diphenylguanidine, 1, One or more of 1,2,3,3-pentabutylguanidine.

本发明提供的柴油组合物还任选含有金属钝化剂。且所述组分脒型化合物与金属钝化剂的重量比可以为1∶0-1，优选所述脒型化合物与所述金属钝化剂的重量比为1∶0.01-1，进一步优选为1∶0.01-0.5，更进一步优选为1∶0.02-0.2。The diesel composition provided by the invention may also optionally contain a metal deactivator. And the weight ratio of the component amidine compound to the metal passivator may be 1:0-1, preferably the weight ratio of the amidine compound to the metal passivator is 1:0.01-1, more preferably 1:0.01-0.5, more preferably 1:0.02-0.2.

所述金属钝化剂可以为各种能与金属表面反应的金属减活剂和/或与金属或金属离子反应或者结合的金属蝥合剂。The metal deactivator can be various metal deactivators that can react with metal surfaces and/or metal complexes that can react or combine with metals or metal ions.

具体的，所述金属钝化剂可以为苯三唑及其衍生物、噻二唑及其衍生物、8-羟基喹啉、乙二胺四羧酸、酰肼、β-三酮、β-酮酯、席夫碱(Schiff bases)、有机多元羧酸及其衍生物中的一种或几种。由于苯三唑本身在生物柴油中的溶解性并不非常优异，因此，为了增加其在生物柴油中的溶解性，通常对苯三唑进行改性，改性的方法主要通过在苯三唑中引入油溶性基团如长链烃基。因此，所述苯三唑衍生物可以是各种在生物柴油中的溶解性较苯三唑本身好的各种衍生物。具体的，所述苯三唑衍生物可以是苯三唑与脂肪胺形成的铵盐以及苯三唑、甲醛与脂肪胺通过曼尼西反应得到的产物中的一种或几种。所述乙二胺四羧酸可以是乙二胺四乙酸(EDTA)，所述酰肼可以是N-水杨叉-N’-水杨酰肼和/或N，N’-二乙酰基己二酰基二酰肼。所述β-二酮如乙酰丙酮，所述β-酮酯如乙酰乙酸辛酯。所述席夫碱可以是N，N’-二水杨叉-1，2-乙二胺、N，N’-二水杨叉-1，2-丙二胺、N，N’-二水杨叉-1，2-环己二胺、N，N’-二水杨叉-N’-甲基二丙烯三胺中的一种或几种。所述有机多元羧酸及其衍生物例如可以是柠檬酸、酒石酸、苹果酸、琥珀酸(丁二酸)、马来酸、植酸等及其衍生物中的一种或几种。Specifically, the metal deactivator can be benzotriazole and its derivatives, thiadiazole and its derivatives, 8-hydroxyquinoline, ethylenediaminetetracarboxylic acid, hydrazide, β-triketone, β- One or more of ketone esters, Schiff bases, organic polycarboxylic acids and their derivatives. Since the solubility of benzotriazole itself in biodiesel is not very excellent, in order to increase its solubility in biodiesel, benzotriazole is usually modified, and the method of modification is mainly through Introduce oil-soluble groups such as long-chain hydrocarbon groups. Therefore, the benzotriazole derivatives may be various derivatives with better solubility in biodiesel than benzotriazole itself. Specifically, the benzotriazole derivatives may be one or more of the ammonium salts of benzotriazole and fatty amines and the products of benzotriazole, formaldehyde and fatty amines through Mannich reaction. The ethylenediaminetetracarboxylic acid can be ethylenediaminetetraacetic acid (EDTA), and the hydrazide can be N-salicylidene-N'-salicylhydrazide and/or N, N'-diacetyladipyl Dihydrazide. The β-diketone is such as acetylacetone, and the β-ketoester is such as octyl acetoacetate. The Schiff base can be N, N'-disalicylidene-1,2-ethylenediamine, N,N'-disalicylidene-1,2-propylenediamine, N,N'-dihydrate One or more of salicylidene-1,2-cyclohexanediamine and N,N'-disalicylidene-N'-methyldipropylenetriamine. The organic polycarboxylic acid and its derivatives can be, for example, one or more of citric acid, tartaric acid, malic acid, succinic acid (succinic acid), maleic acid, phytic acid, etc. and their derivatives.

本发明中，优选所述金属钝化剂为苯三唑与脂肪胺形成的铵盐，苯三唑、甲醛与脂肪胺通过曼尼西反应得到的产物(例如商品名为T551的商品添加剂)，席夫碱和有机多元羧酸及其与脂肪胺、或脂肪醇的缩合反应产物(即有机多元羧酸的酰胺类、酯类衍生物)中的一种或几种。In the present invention, it is preferred that the metal deactivator is an ammonium salt formed by benzotriazole and fatty amine, a product obtained by Mannich reaction of benzotriazole, formaldehyde and fatty amine (such as a commercial additive with a trade name of T551), One or more of Schiff bases, organic polycarboxylic acids and their condensation reaction products with fatty amines or fatty alcohols (ie amides and ester derivatives of organic polycarboxylic acids).

根据使用需要，本发明提供的柴油组合物还可以含有其它添加剂，如高分子胺型无灰分散剂、流动改进剂、十六烷值改进剂、抗静电剂、防腐剂、防锈剂、破乳剂等中的一种或几种。According to the needs of use, the diesel oil composition provided by the present invention can also contain other additives, such as polymer amine type ashless dispersant, flow improver, cetane number improver, antistatic agent, preservative, rust inhibitor, demulsifier One or more of these.

优选情况下，本发明提供的柴油组合物还含有高分子胺型无灰分散剂。所述脒型化合物与所述高分子胺型无灰分散剂的重量比优选为1∶0.1-10。所述高分子胺型无灰分散剂包括烯基丁二酰业胺和/或烯基丁二酸酰胺、曼尼西碱型无灰分散剂、聚醚胺型无灰分散剂和聚烯烃胺型无灰分散剂中的一种或多种。所述烯基丁二酰亚胺和/或基丁二酸酰胺无灰分散剂例如数均分于量在500-3000的聚烯烃基丁二酸酐和/或丁二酸与胺的反应产物，如国产商品牌号为T151A(单丁二酰业胺)、T151B(单丁二酰亚胺)、T152(双丁二酰亚胺)、T154(双丁二酰亚胺)、T155(多聚丁二酰亚胺)和/或T161(多聚丁二酰亚胺)等。进口添加剂如OLOA-1200、LZ894、Infineum C9238、9237、Hitec 644等。曼尼西碱型无灰分散剂例如数均分子量在500-3000的聚烯烃基苯酚与甲醛和胺的缩合产物；所述聚醚胺型无灰分散剂例如C8-C30烷基酚与环氧乙烷或环氧丙烷加合后再与胺缩合的产物或者是C8-C30醇与环氧乙烷或环氧丙烷加合后再与胺缩合的产物；所述聚烯烃胺型无灰分散剂例如氯化聚烯烃与胺反应生成的聚烯烃基胺。这里所说的胺都优选多胺，尤其是多烯多胺。所述烯基丁二酰亚胺和/或烯基丁二酸酰胺的制备方法可以为由聚烯烃基丁二酸和/或聚烯烃基丁二酸酐与胺进行脱水反应得到，所述脱水反应的条件包括胺与聚烯烃基丁二酸和/或聚烯烃基丁二酸酐总量的摩尔比为1∶0.1-2.5，反应温度可以为40-250℃，反应时间可以为1-10小时，反应的介质为苯、甲苯、二甲苯、C₉重芳烃、溶剂汽油和矿物油中的一种或几种，所述C₉重芳烃的馏程为159-185℃，所述矿物油的沸点为120℃以上。溶剂用量一般是单体物料总重量的30-150重量％。为了便于后序操作和储存，最后的产物可用芳烃稀释油配成约50重量％的稀释液。Preferably, the diesel composition provided by the invention also contains a high molecular weight amine type ashless dispersant. The weight ratio of the amidine compound to the polymer amine ashless dispersant is preferably 1:0.1-10. The polymer amine type ashless dispersant includes alkenyl succinamide and/or alkenyl succinamide, Mannich base type ashless dispersant, polyetheramine type ashless dispersant and polyolefin amine type ashless One or more of powders. The alkenyl succinimide and/or succinic acid amide ashless dispersant, for example, the reaction product of polyalkenyl succinic anhydride and/or succinic acid and amine in an amount of 500-3000, such as Domestic brands are T151A (monosuccinamide), T151B (monosuccinimide), T152 (bisuccinimide), T154 (bisuccinimide), T155 (polybutylene imide) and/or T161 (polysuccinimide), etc. Imported additives such as OLOA-1200, LZ894, Infineum C9238, 9237, Hitec 644, etc. Mannich base type ashless dispersants such as condensation products of polyolefin-based phenols with formaldehyde and amines with a number average molecular weight of 500-3000; said polyetheramine type ashless dispersants such as C8-C30 alkylphenols and ethylene oxide Or the product of condensation with amine after addition of propylene oxide or the product of condensation with amine after addition of C8-C30 alcohol with ethylene oxide or propylene oxide; the polyolefin amine type ashless dispersant such as chlorinated Polyolefin-based amines formed by reacting polyolefins with amines. The amines mentioned here are all preferably polyamines, especially polyene polyamines. The preparation method of the alkenyl succinimide and/or alkenyl succinic acid amide can be obtained by dehydration reaction of polyalkenyl succinic acid and/or polyalkenyl succinic anhydride and amine, and the dehydration reaction The conditions include that the molar ratio of amine to the total amount of polyalkenyl succinic acid and/or polyalkenyl succinic anhydride is 1:0.1-2.5, the reaction temperature can be 40-250°C, and the reaction time can be 1-10 hours, The medium of the reaction is one or more of benzene, toluene, xylene,_C9 heavy aromatics, solvent gasoline and mineral oil, the distillation range of the_C9 heavy aromatics is 159-185 ° C, the boiling point of the mineral oil It is above 120°C. The amount of solvent used is generally 30-150% by weight of the total weight of the monomer material. In order to facilitate subsequent operation and storage, the final product can be made into a dilution of about 50% by weight with aromatic diluent oil.

所述浓度根据浓度(重量％)＝(聚烯烃基丁二酸和/或聚烯烃基丁二酸酐的加入量+胺的加入量-反应中分出的水和溶剂量)/稀释液的总重量×100％计算得到。本发明中，除非特别说明，所述烯基丁二酰业胺和/或烯基丁二酸酰胺的含量以上述稀释液的量为基准，也即上述溶剂的量也作为组分a的一部分。Said concentration is based on the total amount of concentration (% by weight)=(the addition of polyalkenyl succinic acid and/or polyalkenyl succinic anhydride+the addition of amine-the water and the solvent amount separated in the reaction)/diluent Calculated by weight × 100%. In the present invention, unless otherwise specified, the content of the alkenyl succinamide and/or alkenyl succinamide is based on the amount of the above-mentioned diluent, that is, the amount of the above-mentioned solvent is also a part of component a .

优选胺与聚烯烃基丁二酸和/或聚烯烃基丁二酸酐摩尔比为1∶0.2-1.5、反应温度为50-200℃、反应时间为2-8小时。所述胺优选为多胺，尤其优选多烯多胺和含有多烯多胺的胺。Preferably, the molar ratio of amine to polyalkenyl succinic acid and/or polyalkenyl succinic anhydride is 1:0.2-1.5, the reaction temperature is 50-200°C, and the reaction time is 2-8 hours. The amines are preferably polyamines, particularly preferably polyene polyamines and polyene polyamine-containing amines.

聚烯烃基丁二酸和聚烯烃基丁二酸酐在本领域被称为“酰化剂”，该酰化剂与胺可进行酰化反应。根据反应条件不同，生成的产物也不同，即生成分别以烯基丁二酰亚胺或烯基丁二酸酰胺为主的产物。例如，反应温度低、胺过量时生成以烯基丁二酸酰胺为主的产物；反应温度高时生成以烯基丁二酰亚胺为主的产物；聚烯烃基丁二酸或聚烯烃基丁二酸酐与胺反应摩尔比不同可分别生成单丁二酸酰胺或单丁二酰亚胺、双丁二酸酰胺或双丁二酰亚胺以及多丁二酸酰胺或多丁二酰亚胺为主的产物。Polyalkenyl succinic acid and polyalkenyl succinic anhydride are known in the art as "acylating agents" which are capable of acylation reactions with amines. According to different reaction conditions, the products generated are also different, that is, the products mainly composed of alkenyl succinimide or alkenyl succinic acid amide are generated. For example, when the reaction temperature is low and the amine is excessive, the product mainly composed of alkenyl succinic acid amide is generated; when the reaction temperature is high, the product mainly composed of alkenyl succinimide is generated; polyolefin-based succinic acid or polyolefin-based Succinic anhydride and amine react with different molar ratios to generate monosuccinic acid amide or monosuccinimide, bisuccinic acid amide or bisuccinimide and polysuccinic acid amide or polysuccinimide respectively main product.

所述聚烯烃基可以是各种C₃-C₄单烯烃的共聚物或均聚物的取代基，例如可以是聚异丁烯基、聚丙烯基、无规或嵌段聚乙烯-丙烯基、聚异戊二烯基中的一种。优选聚异丁烯基。其中聚烯烃基的数均分子量优选为300-5000，优选为500-2500，更优选为800-2000；每个聚烯烃基上丁二酰基的取代度优选为0.5-1.0。所述聚烯烃基优选为数均分子量为500-2500的聚异丁烯基。The polyolefin group can be a substituent of various C₃ -C₄ monoolefin copolymers or homopolymers, such as polyisobutenyl, polypropylene, random or block polyethylene-propylene, poly One of the isoprenyl groups. Polyisobutenyl is preferred. The number average molecular weight of the polyolefin group is preferably 300-5000, preferably 500-2500, more preferably 800-2000; the degree of substitution of succinyl groups on each polyolefin group is preferably 0.5-1.0. The polyolefin group is preferably a polyisobutene group with a number average molecular weight of 500-2500.

多烯多胺的结构式为H₂N[(CH₂)_x2NH]_y1R₆，其中，x2可以为2-4的整数，优选为2或3，y1可以为1-8的整数，R₆可以是氢、碳数为1-30的烃基。例如，当R₆为H时，所述多烯多胺可以为乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺、六乙烯七胺、七乙烯八胺、丙二胺、二丙烯三胺、三丙烯四胺、四丙烯五胺和五丙烯六胺、六丙烯七胺、七丙烯八胺中的一种或几种。当R₆为碳数为1-30的烃基时，优选为C4-C22的烃基。该烃基可以是饱和的烷基，也可以是带有双键的烯基或带有苯环的芳基。烷基可以是直链正构烷基，也可以是带有侧链的异构烷基，该烷基的例子包括正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十四烷基、正十六烷基、正十八烷基、正二十烷基、正二十二烷基；异丁基、叔丁基、异戊基、新戊基、异己基、异庚基、异辛基(2-乙基己基)、异壬基、异癸基、异十二烷基、异十四烷基、异十六烷基、异十八烷基和异二十烷基中的一种或几种。烯基的例子包括9-十八烯基。带有苯环的芳基的例子包括苯甲基(苄基)、苯乙基和苯丙基中的一种或几种。其中，更优选C6-C20的烷基中的一种或几种。The structural formula of polyene polyamine is H₂ N[(CH₂ )_x2 NH]_y1 R₆ , wherein, x2 can be an integer of 2-4, preferably 2 or 3, y1 can be an integer of 1-8, R₆ It can be hydrogen or a hydrocarbon group with 1-30 carbons. For example, when R_is H, the polyene polyamine can be ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine , propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, hexapropyleneheptamine, heptapropyleneoctamine, or one or more of them. When R₆ is a hydrocarbon group with a carbon number of 1-30, it is preferably a C4-C22 hydrocarbon group. The hydrocarbon group may be a saturated alkyl group, an alkenyl group with a double bond or an aryl group with a benzene ring. The alkyl group can be a straight chain normal alkyl group or an isomeric alkyl group with a side chain. Examples of the alkyl group include n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-octyl, n- Nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, n-behenyl; Isobutyl, tert-butyl, isopentyl, neopentyl, isohexyl, isoheptyl, isooctyl (2-ethylhexyl), isononyl, isodecyl, isododecyl, isodeca One or more of tetraalkyl, isohexadecyl, isoctadecyl and isoeicosyl. Examples of alkenyl include 9-octadecenyl. Examples of the aryl group having a benzene ring include one or more of benzyl (benzyl), phenethyl and phenylpropyl. Among them, one or more of C6-C20 alkyl groups are more preferred.

制备所述烯基丁二酰亚胺和/或烯基丁二酸酰胺的具体操作方法已为本领域技术人员所公知，例如可以参见US 2,992,708、US3,172,892、US3,272,746、US 5,286,823等文献，在此不赘述。The specific operation method for preparing said alkenyl succinimide and/or alkenyl succinic acid amide is known to those skilled in the art, for example, refer to documents such as US 2,992,708, US 3,172,892, US 3,272,746, US 5,286,823 , which will not be described here.

用于本发明的烯基丁二酰亚胺进一步优选为单丁二酰亚胺；烯基丁二酸酰胺进一步优选为单丁二酸酰胺。The alkenyl succinimide used in the present invention is more preferably monosuccinimide; the alkenyl succinamide is further preferably monosuccinamide.

本发明提供的柴油组合物的制备简单，只需将组成柴油组合物的各组分混合均匀即可。可以直接将各添加剂成分与基础柴油混合，也可以先将各种添加剂成分混合均匀，得到添加剂后，再将所得添加剂与基础柴油混合。为了操作方便，在将各种添加剂成分混合均匀时，可以在溶剂存在下进行，这里的溶剂可以是极性溶剂如N，N-二甲基甲酰胺(DMF)、1，4-二氧六环、四氢呋喃(THF)、二甲基业砜(DMSO)、吡咯烷酮和甲基吡咯烷酮中的一种或几种。也可以是烃类尤其是芳烃如苯、甲苯、二甲苯、芳烃稀释油及其混合物，还可以是生物柴油。The preparation of the diesel composition provided by the invention is simple, and only needs to mix the components of the diesel composition uniformly. The various additive components can be directly mixed with the base diesel oil, or the various additive components can be mixed evenly first to obtain the additives, and then the obtained additives can be mixed with the base diesel oil. For the convenience of operation, when the various additive components are mixed uniformly, it can be carried out in the presence of a solvent, and the solvent here can be a polar solvent such as N, N-dimethylformamide (DMF), 1,4-dioxane One or more of ring, tetrahydrofuran (THF), dimethyl sulfone (DMSO), pyrrolidone and methylpyrrolidone. It can also be hydrocarbons, especially aromatics such as benzene, toluene, xylene, aromatics diluent oil and their mixtures, and biodiesel.

在本发明中，所述基础柴油可以为纯生物柴油，所述生物柴油是指油脂与低碳醇(如C₁-C₅脂肪醇)经酯交换(醇解)反应而生成的脂肪酸低碳醇酯，一般为脂肪酸甲酯，即油脂与甲醇的酯交换产物。In the present invention, the base diesel oil can be pure biodiesel, and the biodiesel refers to the low-carbon fatty acid produced by transesterification (alcoholysis) reaction of oil and low-carbon alcohol (such as C₁ -C₅ fatty alcohol). Alcohol esters are generally fatty acid methyl esters, which are transesterification products of oil and methanol.

所述的酯交换反应工艺可以是任何已知或未知的通过油指与低碳醇的酯交换反应得到生物柴油的工艺方法，例如酸催化法、碱催化法、酶催化法、超临界法，等等。具体可参考CN1473907A、DE3444893、CN1472280A、CN1142993C、CN1111591C、CN1594504A等文献。The transesterification process can be any known or unknown process for obtaining biodiesel through the transesterification of oil fingers and low-carbon alcohols, such as acid catalysis, alkali catalysis, enzyme catalysis, supercritical method, etc. For details, reference can be made to documents such as CN1473907A, DE3444893, CN1472280A, CN1142993C, CN1111591C, and CN1594504A.

所述的油脂具有本领域公知的一般含义，是油和脂的总称，主要成分是脂肪酸甘油三酯。一般常温为液体的称为油，常温为固体或半固体的称为脂肪(简称脂)。所述油脂包括植物油以及动物油，另外，还包括来自微生物、藻类等物质中的油料，甚至还可以是废油脂，例如餐饮废油、地沟油、泔水油、油脂厂的酸化油等使用过的油脂或变质的油脂。所述植物油可以是草本植物油也可以是木本植物油，如花生油、玉米油、棉籽油、菜子油、大豆油、棕榈油、红花油、业麻籽油、椰子油、橡树油、杏仁油、核桃油、蓖麻油、芝麻油、橄榄油、妥尔油(Tall Oil)、向日葵油、麻风树油、桐油、文冠果油、黄连木油、盐土植物如海滨锦葵、油莎豆等植物的油。所述动物油可以是猪油、鸡油、鸭油、鹅油、羊油、马油、牛油、鲸鱼油、鲨鱼油等。The fat has a general meaning known in the art, which is a general term for oil and fat, and its main component is fatty acid triglyceride. Generally, what is liquid at room temperature is called oil, and what is solid or semi-solid at room temperature is called fat (referred to as fat). The oils include vegetable oils and animal oils. In addition, oils from microorganisms, algae, etc. can even be waste oils, such as used oils such as waste catering oil, waste oil, swill oil, acidified oil from oil factories, etc. or spoiled grease. Described vegetable oil can be herbaceous vegetable oil also can be woody vegetable oil, as peanut oil, corn oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, safflower oil, linseed oil, coconut oil, oak oil, almond oil, Walnut oil, castor oil, sesame oil, olive oil, tall oil (Tall Oil), sunflower oil, jatropha oil, tung oil, sorbetia oil, pistachio oil, halo plants such as seaside mallow, oil sand bean and other plants Oil. The animal oil may be lard, chicken oil, duck oil, goose oil, suet oil, horse oil, tallow, whale oil, shark oil, etc.

在本发明的生物柴油组合物中，所述基础柴油也可以含有其它柴油，所述其它柴油为石油柴油、费-托合成柴油、加氢裂化生物柴油、含氧柴油调合物中的一种或几种，所述生物柴油与其它柴油的体积比优选为1∶2-99。In the biodiesel composition of the present invention, the base diesel oil may also contain other diesel oils, and the other diesel oils are one of petroleum diesel, Fischer-Tropsch synthetic diesel oil, hydrocracking biodiesel, and oxygenated diesel blends or several, the volume ratio of the biodiesel to other diesel is preferably 1:2-99.

其中石油柴油是指原油(石油)经炼油厂的各种炼制工艺如常减压、催化裂化、催化重整、焦化、加氢精制、加氢裂化等装置处理后的馏程在160-380℃之间的馏分，并经过调配而成的满足轻柴油国家标准GB 252-2000或车用柴油国家标准GB/T 19147-2003的压燃式内燃机用燃料。Among them, petroleum diesel refers to crude oil (petroleum) with a distillation range of 160-380°C after being treated by various refining processes in refineries, such as atmospheric and vacuum, catalytic cracking, catalytic reforming, coking, hydrofining, and hydrocracking. The fractions between them are blended to meet the national standard for light diesel oil GB 252-2000 or the national standard for vehicle diesel oil GB/T 19147-2003 as fuel for compression ignition internal combustion engines.

费-托合成柴油主要指以天然气或煤为原料经费-托(F-T)合成方法而生产的GTL柴油(Gas To Liquid)或CTL柴油(Coal To Liquid)，还可以是植物纤维经费-托合成方法而生产的BTL柴油(Biomass To Liquid)。费-托合成柴油基本上不含硫和芳烃，是非常洁净的燃料，但其润滑性却极差，与生物柴油调合后润滑性大大改善，但调合油的氧化安定性有可能变差，因此含生物柴油的调合燃料也需要加入抗氧剂。Fischer-Tropsch synthetic diesel mainly refers to GTL diesel (Gas To Liquid) or CTL diesel (Coal To Liquid) produced by the Fischer-Tropsch (F-T) synthesis method using natural gas or coal as raw material, and it can also be plant fiber by the Fischer-Tropsch synthesis method And the production of BTL diesel (Biomass To Liquid). Fischer-Tropsch synthetic diesel basically does not contain sulfur and aromatics, and is a very clean fuel, but its lubricity is extremely poor. After blending with biodiesel, the lubricity is greatly improved, but the oxidation stability of the blended oil may deteriorate , so blended fuels containing biodiesel also need to add antioxidants.

加氢裂化生物柴油也称为第二代生物柴油，是指由动植物油脂经过加氢和裂化反应后生成的以C₈-C₂₄烷烃为主，尤其是以C₁₂-C₂₀正构烷烃为主要成分的反应产物，这种加氢裂化生物柴油十六烷值高，疏和芳烃含量极低，作为柴油发动机燃料或调合组分可大大降低柴油机污染物的排放。Hydrocracking biodiesel, also known as second-generation biodiesel, refers to C₈ -C₂₄ alkanes, especially C₁₂ -C₂₀ normal alkanes, produced by hydrogenation and cracking reactions of animal and vegetable oils As the reaction product of the main component, this hydrocracking biodiesel has a high cetane number and extremely low content of hydrophobic and aromatic hydrocarbons. It can be used as a diesel engine fuel or a blending component to greatly reduce the emission of diesel engine pollutants.

含氧柴油调合组分是指可与各种柴油机燃料调配成符合一定规范要求的含氧化合物或含氧化合物的混合物，通常是醇类和醚类或其混合物，醇类例如C₁-C₁₈脂肪醇、优选C₁-C₁₂一元脂肪醇，如甲醇、乙醇、丙醇、丁醇、戊醇、己醇、庚醇、辛醇、壬醇、癸醇、十一碳醇、月桂醇及其各种异构体。醚类可以是二甲醚、甲基叔丁基醚、乙基叔丁基醚、C₆-C₁₄脂肪醇聚氧乙烯醚、C₆-C₁₄脂肪醇聚氧丙烯醚、C₆-C₁₄烷基酚聚氧乙烯醚、C₆-C₁₄烷基酚聚氧丙烯醚、聚氧化亚甲基二甲醚(Polyoxymethylene Dimethyl Ethers，CH₃O(CH₂O)_xCH₃，x＝1-8)等及其混合物。Oxygenated diesel blending components refer to oxygenated compounds or mixtures of oxygenated compounds that can be blended with various diesel fuels to meet certain specification requirements, usually alcohols and ethers or their mixtures, alcohols such as C₁ -C₁₈ Fatty alcohols, preferably C₁ -C₁₂ monohydric fatty alcohols, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecyl alcohol, lauryl alcohol and its various isomers. Ethers can be dimethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, C₆ -C₁₄ fatty alcohol polyoxyethylene ether, C₆ -C₁₄ fatty alcohol polyoxypropylene ether, C₆ -C₁₄ Alkylphenol polyoxyethylene ethers, C₆ -C₁₄ alkylphenol polyoxypropylene ethers, polyoxymethylene dimethyl ethers (Polyoxymethylene Dimethyl Ethers, CH₃ O(CH₂ O)_x CH₃ , x=1 -8) etc. and mixtures thereof.

本发明中，所述基础柴油为含生物柴油的调合燃料时，所述柴油组合物可以通过将所述添加剂、生物柴油和其它柴油直接混合而得到，也可以先将所述添加剂与生物柴油混合，然后再与其它柴油调合而得到。可以将添加剂的各种组分直接与基础柴油混合，也可以先将添加剂的各种组分预先混合，得到添加剂混合物后再与基础柴油。对添加剂的各种组分以及生物柴油和其它柴油的混合顺序没有特别限定，可以以各种顺序混合。混合的条件可以在各种不对柴油组合物造成不利影响的条件下进行，例如，可以在环境温度下混合。In the present invention, when the base diesel oil is a blended fuel containing biodiesel, the diesel oil composition can be obtained by directly mixing the additive, biodiesel and other diesel oils, or can first mix the additive with biodiesel Mixed, and then blended with other diesel obtained. The various components of the additive can be directly mixed with the base diesel, or the various components of the additive can be pre-mixed to obtain the additive mixture and then mixed with the base diesel. The mixing order of the various components of the additive and biodiesel and other diesel is not particularly limited, and may be mixed in various orders. The mixing conditions can be carried out under various conditions that do not adversely affect the diesel composition, for example, mixing can be at ambient temperature.

本发明提供的提高生物柴油氧化安定性的方法包括，在含有生物柴油的柴油组分中，加入添加剂，所述添加剂含有上述脒型化合物。The method for improving the oxidation stability of biodiesel provided by the invention includes adding an additive to the diesel component containing biodiesel, and the additive contains the above-mentioned amidine compound.

优选情况下，本发明提供的提高生物柴油氧化安定性的方法，所述添加剂还含有结构式(2)所示的胍型化合物和/或金属钝化剂，所述脒型化合物与结构式(2)所示的胍型化合物和所述金属钝化剂的重量比各自优选为1∶0.01-1。Preferably, in the method for improving the oxidation stability of biodiesel provided by the invention, the additive also contains a guanidine compound and/or a metal passivator shown in structural formula (2), and the amidine compound and structural formula (2) The weight ratio of the indicated guanidine-type compound and the metal deactivator is preferably 1:0.01-1 each.

优选情况下，本发明提供的提高生物柴油氧化安定性的方法还包括在含有生物柴油的基础柴油中，加入其它添加剂，如流动改进剂、十六烷值改进剂、抗静电剂、防腐剂、防锈剂、破乳剂等中的一种或几种。Preferably, the method for improving the oxidation stability of biodiesel provided by the present invention also includes adding other additives, such as flow improvers, cetane number improvers, antistatic agents, preservatives, One or more of rust inhibitors, demulsifiers, etc.

各种成分均已在上文中描述，在此不再重复描述。上述各种成分均可商购得到。Various components have been described above and will not be repeated here. Each of the ingredients described above is commercially available.

对添加剂的各种组分以及生物柴油和其它柴油的混合顺序没有特别限定，可以以各种顺序混合。混合的条件可以在各种不对柴油组合物造成不利影响的条件下进行，例如，可以在环境温度下混合。The mixing order of the various components of the additive and biodiesel and other diesel is not particularly limited, and may be mixed in various orders. The mixing conditions can be carried out under various conditions that do not adversely affect the diesel composition, for example, mixing can be at ambient temperature.

所述生物柴油既可以是前述纯的生物柴油，也可以是前述含生物柴油的调合燃料。The biodiesel can be the aforementioned pure biodiesel, or the aforementioned blended fuel containing biodiesel.

下面的实施例将对本发明做进一步的说明。以下参考例、实施例和对比例中，所用酸化油生物柴油是中海油海南生物能源公司提供的生物柴油产品，所用地沟油生物柴油均由福建龙岩卓越新能源有限公司提供，石油柴油均为中石化燕山分公司生产的京标B柴油。The following examples will further illustrate the present invention. In the following reference examples, examples and comparative examples, the acidified oil biodiesel used is the biodiesel product provided by CNOOC Hainan Bioenergy Company, the waste oil biodiesel used is provided by Fujian Longyan Excellence New Energy Co., Ltd., and the petroleum diesel is Sinopec Yanshan Jingbiao B diesel produced by the branch.

实施例1-18Examples 1-18

实施例1-18用于说明本发明提供的柴油组合物及其制备方法。Examples 1-18 are used to illustrate the diesel composition provided by the present invention and its preparation method.

按照下表1和2的组成制备柴油组合物。Diesel compositions were prepared according to the compositions in Tables 1 and 2 below.

对比例1-11Comparative example 1-11

对比例1-11用于说明现有技术的柴油组合物及其制备方法。Comparative Examples 1-11 are used to illustrate prior art diesel oil compositions and methods for their preparation.

按照下表1和2的组成制备柴油组合物。Diesel compositions were prepared according to the compositions in Tables 1 and 2 below.

性能测试Performance Testing

(1)纯生物柴油作为基础柴油的生物柴油组合物(1) Pure biodiesel is used as the biodiesel composition of base diesel oil

用EN14112：2003方法(Rancimat法)测定110℃下的诱导期来评定生物柴油氧化安定性，使用仪器为瑞士万通公司的743型油脂氧化稳定性测定仪，其中，诱导期越长则说明柴油组合物的抗氧化性越好，反之诱导期越短则说明柴油组合物的抗氧化性越差。其测试结果示于表1中。Use the EN14112:2003 method (Rancimat method) to measure the induction period at 110°C to evaluate the oxidation stability of biodiesel. The instrument used is Metrohm's 743 oil oxidation stability tester. The longer the induction period, the higher the oxidation stability of diesel oil. The better the oxidation resistance of the composition, on the contrary the shorter the induction period, the worse the oxidation resistance of the diesel oil composition. The test results are shown in Table 1.

表1Table 1

从表1中的数据可以看出，加入脒型化合物后，生物柴油的氧化安定性得到改善，效果比同等剂量的抗氧剂BHT或者4，4’-二辛基二苯胺要好。任选本发明所述的脒型化合物与无灰分散剂复合后，效果比单独加入这两者要好。It can be seen from the data in Table 1 that after adding amidine compounds, the oxidation stability of biodiesel is improved, and the effect is better than the same dose of antioxidant BHT or 4,4'-dioctyl diphenylamine. Optionally, after compounding the amidine compound described in the present invention with the ashless dispersant, the effect is better than adding the two alone.

(2)以生物柴油和石油柴油的混合物作为基础柴油的调合柴油组合物的抗氧化性的测试，所用生物柴油为地沟油生物柴油，测试燃料为B20(生物柴油的体积分数为20％)。(2) Taking the mixture of biodiesel and petroleum diesel as the test of the oxidation resistance of the blended diesel composition of base diesel oil, the biodiesel used is waste oil biodiesel, and the test fuel is B20 (the volume fraction of biodiesel is 20%) .

采用EN15751方法分别测定上述B20与不同的添加剂混合后得到的柴油组合物在110℃下的诱导期，使用仪器为瑞士万通公司的743型油脂氧化稳定性测定仪。其测试结果示于表2中。诱导期越长则说明生物柴油组合物的抗氧化性越好，反之诱导期越短则说明生物柴油组合物的抗氧化性越差，其测试结果示于表2中。The induction period at 110° C. of the diesel oil composition obtained by mixing the above-mentioned B20 with different additives was measured by using the EN15751 method, and the instrument used was a type 743 grease oxidation stability tester of Metrohm Company of Switzerland. The test results are shown in Table 2. The longer the induction period, the better the oxidation resistance of the biodiesel composition, and the shorter the induction period, the worse the oxidation resistance of the biodiesel composition. The test results are shown in Table 2.

表2Table 2

由表2的结果可以看出，本发明的脒型化合物可以明显改善生物柴油调合燃料的氧化安定性，效果好于同等剂量的抗氧剂BHT、4，4’-二辛基二苯胺或者1，3-二苯基胍。As can be seen from the results in Table 2, the amidine compound of the present invention can significantly improve the oxidation stability of biodiesel blended fuel, and the effect is better than that of the same dose of antioxidant BHT, 4,4'-dioctyldiphenylamine or 1,3-Diphenylguanidine.

Claims (18)

Translated fromChinese

1.一种柴油组合物，该柴油组合物含有基础柴油和添加剂，其特征在于，所述基础柴油含生物柴油，所述添加剂含有脒型化合物，所述脒型化合物为下述结构式(1)所示的化合物和/或具有两个环状结构的脒型化合物：1. a diesel oil composition, this diesel oil composition contains base diesel oil and additive, it is characterized in that, described base diesel oil contains biodiesel, and described additive contains amidine type compound, and described amidine type compound is following structural formula (1) Compounds shown and/or amidine-type compounds with two ring structures:

结构式(1)中，R₁、R₂、R₃和R₄各自为H或碳原子数为1-30的烃基，且R₁、R₂、R₃和R₄中至少一个为碳原子数为1-30的烃基。In the structural formula (1), R₁ , R₂ , R₃ and R₄ are each H or a hydrocarbon group with 1-30 carbon atoms, and at least one of R₁ , R₂ , R₃ and R₄ is a carbon atom number is a hydrocarbon group of 1-30.2.根据权利要求1所述的柴油组合物，其中，所述添加剂的含量为50-10000ppm。2. The diesel composition according to claim 1, wherein the content of the additive is 50-10000 ppm.3.根据权利要求1所述的柴油组合物，其中，所述脒型化合物为N-十二烷基-N’，N’-二甲基乙基脒、N-己基-N’，N’-二甲基乙基脒；N-辛基-N’，N’-二甲基乙基脒；N-壬基-N’，N’-二甲基乙基脒；N-癸基-N’，N’-二甲基乙基脒；N-十四烷基-N’，N’-二甲基乙基脒；N-十六烷基-N’，N’-二甲基乙基脒；N-十八烷基-N’，N’-二甲基乙基脒；N-己基-N’，N’-二乙基乙基脒；N-辛基-N’，N’-二乙基乙基脒；N-癸基-N’，N’-二乙基乙基脒；N-十二烷基-N’，N’-二乙基乙基脒；N-十四烷基-N’，N’-二乙基乙基脒；N-十六烷基-N’，N’-二乙基乙基脒；N-十八烷基-N’，N’-二乙基乙基脒；N-己基-N’，N’-二甲基丙基脒；N-辛基-N’，N’-二甲基丙基脒；N-癸基-N’，N’-二甲基丙基脒；N-十二烷基-N’，N’-二甲基丙基脒；N-十四烷基-N’，N’-二甲基丙基脒；N-十六烷基-N’，N’-二甲基丙基脒；N-十八烷基-N’，N’-二甲基丙基脒、1，8-二氮杂双环[5，4，0]十一碳-7-烯、1，5-二氮杂双环[4，3，0]壬烯-5、1，5，7-三叠氮双环(4.4.0)癸-5-烯、7-甲基-1，5，7-三氮杂二环[4.4.0]癸-5-烯中的一种或多种。3. The diesel composition according to claim 1, wherein the amidine compound is N-dodecyl-N', N'-dimethylethylamidine, N-hexyl-N', N' -Dimethylethylamidine; N-octyl-N', N'-dimethylethylamidine; N-nonyl-N', N'-dimethylethylamidine; N-decyl-N ', N'-dimethylethylamidine; N-tetradecyl-N', N'-dimethylethylamidine; N-hexadecyl-N', N'-dimethylethyl N-octadecyl-N', N'-dimethylethylamidine; N-hexyl-N', N'-diethylethylamidine; N-octyl-N', N'- Diethylethylamidine; N-decyl-N', N'-diethylethylamidine; N-dodecyl-N', N'-diethylethylamidine; N-tetradecane Base-N', N'-diethylethylamidine; N-hexadecyl-N', N'-diethylethylamidine; N-octadecyl-N', N'-diethyl N-hexyl-N', N'-dimethylpropylamidine; N-octyl-N', N'-dimethylpropylamidine; N-decyl-N', N' -Dimethylpropylamidine; N-dodecyl-N', N'-dimethylpropylamidine; N-tetradecyl-N', N'-dimethylpropylamidine; N- Hexadecyl-N', N'-dimethylpropylamidine; N-octadecyl-N', N'-dimethylpropylamidine, 1,8-diazabicyclo[5,4 ,0] Undec-7-ene, 1,5-diazabicyclo[4,3,0]nonene-5, 1,5,7-triazidebicyclo(4.4.0)decane-5- One or more of ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.4.根据权利要求1所述的柴油组合物，其中，所述添加剂还含有结构式(2)所示的胍型化合物：4. diesel oil composition according to claim 1, wherein, described additive also contains the guanidine type compound shown in structural formula (2):

结构式(2)中，R₈、R₉、R₁₀、R₁₁和R₁₂各自为H或者取代或未取代的碳原子数为1-30的烃基。In the structural formula (2), each of R₈ , R₉ , R₁₀ , R₁₁ and R₁₂ is H or a substituted or unsubstituted hydrocarbon group with 1-30 carbon atoms.5.根据权利要求4所述的柴油组合物，其中，所述结构式(2)所示的胍型化合物与结构式(1)所示的脒型化合物的重量比为1∶0.01-1。5. The diesel composition according to claim 4, wherein the weight ratio of the guanidine compound represented by the structural formula (2) to the amidine compound represented by the structural formula (1) is 1:0.01-1.6.根据权利要求4或5所述的柴油组合物，其中，所述胍型化合物为1，1，3，3，-四甲基胍、1，2，3-三苯基胍、1，3-二苯基胍、1，1，2，3，3-五丁基胍中的一种或多种。6. The diesel composition according to claim 4 or 5, wherein the guanidine compound is 1,1,3,3-tetramethylguanidine, 1,2,3-triphenylguanidine, 1, One or more of 3-diphenylguanidine and 1,1,2,3,3-pentabutylguanidine.7.根据权利要求1或4所述的柴油组合物，其中，所述添加剂还含有金属钝化剂，所述脒型化合物与所述金属钝化剂的重量比为1∶0.01-1。7. The diesel composition according to claim 1 or 4, wherein the additive further contains a metal deactivator, and the weight ratio of the amidine compound to the metal deactivator is 1:0.01-1.8.根据权利要求7所述的柴油组合物，其中，所述金属钝化剂为苯三唑及其衍生物、席夫碱和有机多元羧酸中的一种或几种。8. The diesel oil composition according to claim 7, wherein the metal deactivator is one or more of benzotriazole and its derivatives, Schiff bases and organic polycarboxylic acids.9.根据权利要求1所述的柴油组合物，其中，所述基础柴油还含有其它柴油，所述其它柴油为石油柴油、费-托合成柴油、加氢裂化生物柴油、含氧柴油调合物中的一种或几种，所述生物柴油与其它柴油的体积比为1∶2-99。9. diesel oil composition according to claim 1, wherein, described base diesel oil also contains other diesel oil, and described other diesel oil is petroleum diesel oil, Fischer-Tropsch synthetic diesel oil, hydrocracking biodiesel, oxygenated diesel blend One or more of them, the volume ratio of biodiesel to other diesel is 1:2-99.10.一种提高生物柴油氧化安定性的方法，该方法包括，在含有生物柴油的基础柴油中加入添加剂，所述添加剂含有脒型化合物，所述脒型化合物为下述结构式(1)所示的化合物和/或具有两个环状结构的脒型化合物：10. A method for improving the oxidation stability of biodiesel, the method comprises, in the base diesel oil containing biodiesel, add additive, described additive contains amidine type compound, and described amidine type compound is shown in following structural formula (1) and/or amidine-type compounds with two ring structures:

R₁、R₂、R₃和R₄各自为H或碳原子数为1-30的烃基，且R₁、R₂、R₃和R₄中至少一个为碳原子数为1-30的烃基。R₁ , R₂ , R₃ and R₄ are each H or a hydrocarbon group with 1-30 carbon atoms, and at least one of R₁ , R₂ , R₃ and R₄ is a hydrocarbon group with 1-30 carbon atoms .11.根据权利要求10所述的方法，其中，所述添加剂相对于基础柴油的加入量为50-10000ppm。11. The method according to claim 10, wherein the additive is added in an amount of 50-10000 ppm relative to the base diesel oil.12.根据权利要求10所述的方法，其中，所述脒型化合物为N-十二烷基-N’，N’-二甲基乙基脒、N-己基-N’，N’-二甲基乙基脒；N-辛基-N’，N’-二甲基乙基脒；N-壬基-N’，N’-二甲基乙基脒；N-癸基-N’，N’-二甲基乙基脒；N-十四烷基-N’，N’-二甲基乙基脒；N-十六烷基-N’，N’-二甲基乙基脒；N-十八烷基-N’，N’-二甲基乙基脒；N-己基-N’，N’-二乙基乙基脒；N-辛基-N’，N’-二乙基乙基脒；N-癸基-N’，N’-二乙基乙基脒；N-十二烷基-N’，N’-二乙基乙基脒；N-十四烷基-N’，N’-二乙基乙基脒；N-十六烷基-N’，N’-二乙基乙基脒；N-十八烷基-N’，N’-二乙基乙基脒；N-己基-N’，N’-二甲基丙基脒；N-辛基-N’，N’-二甲基丙基脒；N-癸基-N’，N’-二甲基丙基脒；N-十二烷基-N’，N’-二甲基丙基脒；N-十四烷基-N’，N’-二甲基丙基脒；N-十六烷基-N’，N’-二甲基丙基脒；N-十八烷基-N’，N’-二甲基丙基脒、1，8-二氮杂双环[5，4，0]十一碳-7-烯、1，5-二氮杂双环[4，3，0]壬烯-5、1，5，7-三叠氮双环(4.4.0)癸-5-烯、7-甲基-1，5，7-三氮杂二环[4.4.0]癸-5-烯中的一种或多种。12. The method according to claim 10, wherein the amidine compound is N-dodecyl-N', N'-dimethylethylamidine, N-hexyl-N', N'-di Methylethylamidine; N-octyl-N', N'-dimethylethylamidine; N-nonyl-N', N'-dimethylethylamidine; N-decyl-N', N'-dimethylethylamidine; N-tetradecyl-N', N'-dimethylethylamidine; N-hexadecyl-N', N'-dimethylethylamidine; N-octadecyl-N', N'-dimethylethylamidine; N-hexyl-N', N'-diethylethylamidine; N-octyl-N', N'-diethyl N-decyl-N', N'-diethylethylamidine; N-dodecyl-N', N'-diethylethylamidine; N-tetradecyl- N', N'-diethylethylamidine; N-hexadecyl-N', N'-diethylethylamidine; N-octadecyl-N', N'-diethylethylamidine N-hexyl-N', N'-dimethylpropylamidine; N-octyl-N', N'-dimethylpropylamidine; N-decyl-N', N'-di Methylpropylamidine; N-dodecyl-N', N'-dimethylpropylamidine; N-tetradecyl-N', N'-dimethylpropylamidine; N-hexadecyl Alkyl-N', N'-dimethylpropylamidine; N-octadecyl-N', N'-dimethylpropylamidine, 1,8-diazabicyclo[5,4,0 ] Undec-7-ene, 1,5-diazabicyclo[4,3,0]nonene-5, 1,5,7-triazidebicyclo(4.4.0)dec-5-ene, One or more of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.13.根据权利要求10所述的方法，其中，所述添加剂还含有结构式(2)所示的胍型化合物：13. method according to claim 10, wherein, described additive also contains the guanidine type compound shown in structural formula (2):

结构式(2)中，R₈、R₉、R₁₀、R₁₁和R₁₂各自为H或者取代或未取代的碳原子数为1-30的烃基。In the structural formula (2), each of R₈ , R₉ , R₁₀ , R₁₁ and R₁₂ is H or a substituted or unsubstituted hydrocarbon group with 1-30 carbon atoms.14.根据权利要求13所述的方法，其中，所述结构式(2)所示的胍型化合物与结构式(1)所示的脒型化合物的重量比为1∶0.01-1。14. The method according to claim 13, wherein the weight ratio of the guanidine-type compound represented by the structural formula (2) to the amidine-type compound represented by the structural formula (1) is 1:0.01-1.15.根据权利要求13或14所述的方法，其中，所述胍型化合物为1，1，3，3，-四甲基胍、1，2，3-三苯基胍、1，3-二苯基胍、1，1，2，3，3-五丁基胍中的一种或多种。15. The method according to claim 13 or 14, wherein the guanidine type compound is 1,1,3,3,-tetramethylguanidine, 1,2,3-triphenylguanidine, 1,3- One or more of diphenylguanidine and 1,1,2,3,3-pentabutylguanidine.16.根据权利要求10或13所述的方法，其中，所述添加剂还含有金属钝化剂，所述脒型化合物与所述金属钝化剂的重量比为1∶0.01-1。16. The method according to claim 10 or 13, wherein the additive further contains a metal deactivator, and the weight ratio of the amidine compound to the metal deactivator is 1:0.01-1.17.根据权利要求16所述的方法，其中，所述金属钝化剂为苯三唑及其衍生物、席夫碱和有机多元羧酸中的一种或几种。17. The method according to claim 16, wherein the metal deactivator is one or more of benzotriazole and its derivatives, Schiff bases and organic polycarboxylic acids.18.根据权利要求10所述的方法，其中，所述基础柴油还含有其它柴油，所述其它柴油为石油柴油、费-托合成柴油、加氢裂化生物柴油、含氧柴油调合物中的一种或几种，所述生物柴油与其它柴油的体积比为1∶2-99。18. The method according to claim 10, wherein the base diesel oil also contains other diesel oils, and the other diesel oils are petroleum diesel oil, Fischer-Tropsch synthetic diesel oil, hydrocracking biodiesel, and oxygenated diesel blends. One or more, the volume ratio of the biodiesel to other diesel is 1:2-99.