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(FattyAcidMethylEster)，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 (FattyAcidMethylEster), is based on 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, animal fats, and waste cooking oil. etc. as raw materials, obtained through transesterification with alcohols (methanol, ethanol), and 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EN14214：2003、澳大利亚生物柴油标准(Draft2003)、新西兰生物柴油标准NZS7500：2005、巴西生物柴油标准ANP255(2003)、印度生物柴油标准IS15607：2005、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110℃下的诱导期不低于6小时，测定方法为EN14112：2003。European biodiesel standard EN14214: 2003, Australian biodiesel standard (Draft2003), New Zealand biodiesel standard NZS7500: 2005, Brazilian biodiesel standard ANP255 (2003), Indian biodiesel standard IS15607: 2005, South African biodiesel standard SANS1935: 2004 and my country The national standard GB/T20828-2007 of biodiesel (BD100) for diesel fuel blending stipulates that the oxidation stability of biodiesel is not less than 6 hours at 110°C, and the measurement method is EN14112:2003.
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清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 cleanness and dispersibility of the 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.
CN1742072A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％。CN1742072A discloses a method for improving the storage stability of biodiesel, which method comprises adding a liquid stock solution containing 15-60% by weight of 2,4-di-tert-butylhydroxytoluene dissolved in biodiesel to the In the stabilized biodiesel, the concentration of 2,4-di-tert-butylhydroxytoluene reaches 0.005-2% by weight based on the total solution of biodiesel.
CN1847368A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。CN1847368A discloses a method for improving the oxidation stability of biodiesel, which method comprises bisphenol type antioxidants 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).
CN1847369A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。CN1847369A discloses a method for improving the oxidation stability of biodiesel, which method includes adding a 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 The primary antioxidant contains alkylphenols.
US2007/113467A1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。US2007/113467A1 discloses a fuel composition having improved oxidation stability, the composition 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，但对于生物柴油没有清净分散效果，对于使用纯生物柴油的柴油机来说不能改善其清净性。同时对含生物柴油的调合燃料的稳定性和清净分散性的改善效果也不太好。Although the above method of using traditional antioxidants to improve the oxidation stability of biodiesel has certain effects, it has no cleaning and dispersing effect on biodiesel, and cannot improve the detergency of diesel engines using pure biodiesel. At the same time, the effect of improving the stability and clean dispersibility of the blended fuel containing biodiesel is not very good.
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的以纯生物柴油为基础柴油的柴油组合物的氧化安定性较差以及以生物柴油与其它柴油的调合燃料为基础柴油的柴油组合物的稳定性和清净分散性较差的缺点，提供一种氧化安定性和清净性均较好或者稳定性和清净分散性均较好的柴油组合物。The purpose of the present invention is to overcome the poor oxidation stability of the diesel oil composition based on pure biodiesel and the stability and stability of the diesel composition based on the blended fuel of biodiesel and other diesel oil in order to overcome the above-mentioned prior art. The disadvantage of poor detergency and dispersibility is to provide a diesel composition with good oxidation stability and detergency or good stability and detergency and dispersibility.
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，所述添加剂含有组分a和组分b，所述组分a含有曼尼西碱无灰分散剂；所述组分b为芳胺型抗氧剂和/或受阻酚型抗氧剂。The invention provides a diesel oil composition, the diesel oil composition contains base diesel oil and additives, wherein, the base diesel oil contains biodiesel, the additive contains component a and component b, and the component a contains Manny West alkali ashless dispersant; the component b is aromatic amine antioxidant and/or hindered phenol antioxidant.
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油中，加入添加剂，所述添加剂含有组分a和组分b，所述添加剂的组分a含有曼尼西碱无灰分散剂；所述组分b为芳胺型抗氧剂和/或受阻酚型抗氧剂。The present invention also provides a method for improving the oxidation stability of biodiesel, which method includes adding an additive to the base oil containing biodiesel, the additive contains component a and component b, and component a of the additive contains Mannich base ashless dispersant; the component b is aromatic amine antioxidant and/or hindered phenol antioxidant.
本发明提供的柴油组合物，当以纯生物柴油作为基础柴油时，该柴油组合物具有较好的氧化安定性，组分a与组分b之间令人惊异的出现协同效应，抗氧化效果比单独使用抗氧剂要好很多。组分a可以看作是辅助抗氧剂，其可以使抗氧剂的效果出人意料地大大增强。因此，在达到相同的氧化安定性要求时，组分b在生物柴油组合物中的量可以大大减少，尤其使组分b特别昂贵或组分b有一定毒性或腐蚀性的情况下，减少了其用量具有很大意义。当以含有生物柴油的调合燃料作为基础柴油时，该柴油组合物的稳定性和清净分散性均较好。特别是根据本发明提供的优选实施方式，当所述添加剂同时含有组分a、组分b，或者还同时含有任选的组分c时，由于各添加剂之间明显的协同效应，本发明提供的柴油组合物的抗氧性和清净分散性明显提高。The diesel oil composition provided by the present invention, when pure biodiesel is used as the base diesel oil, the diesel oil composition has better oxidation stability, surprisingly there is a synergistic effect between component a and component b, and the antioxidant effect is higher than Antioxidants alone are much better. Component a can be regarded as an auxiliary antioxidant, which can unexpectedly greatly enhance the effect of the antioxidant. Therefore, when achieving the same oxidation stability requirements, the amount of component b in the biodiesel composition can be greatly reduced, especially when component b is particularly expensive or component b has certain toxicity or corrosiveness. Its dosage is of great significance. When the blended fuel containing biodiesel is used as the base diesel oil, the diesel oil composition has good stability and clean dispersibility. Especially according to the preferred embodiment provided by the present invention, when the additive contains component a, component b, or also contains optional component c at the same time, due to the obvious synergistic effect between the additives, the present invention provides The oxidation resistance and detergency and dispersibility of the diesel oil composition are obviously improved.
具体实施方式detailed description
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。In the diesel composition provided by the present invention, the content of the additive can be selected within a wide range, for example, the content relative to the base diesel can be 10-10000ppm, preferably 50-8000ppm.
所述组分b与组分a的重量比可以为0.01-100∶1，优选为0.1-10∶1，进一步优选为0.2-5∶1。The weight ratio of component b to component a may be 0.01-100:1, preferably 0.1-10:1, more preferably 0.2-5:1.
组分aComponent a
所述组分a是曼尼西碱无灰分散剂。The component a is a Mannich base ashless dispersant.
所述曼尼西碱由聚烯烃基酚、醛与胺通过曼尼西反应制得，三者摩尔比一般为1∶0.1-10∶0.1-10，优选为1∶1-4∶0.5-2。曼尼西反应温度一般为50-200℃，最好在70-150℃范围之内。反应介质可以是碳氢化合物如苯、甲苯、二甲苯、芳烃稀释油(馏程为159-185℃)、溶剂汽油或矿物油(沸点在120℃以上)，或者是它们的混合物。溶剂用量一般是单体物料总重量的30-150重量％。反应体系内可用氮气保护，或者让体系在溶剂回流的条件下进行。制备方法在US3,413,347、US3,649,229、US3,798,165、US4,116,644、US4,553,979等专利文献中皆有描述。也可以直接选用商品剂如AMOCO公司生产的牌号为AMOCO9250的曼尼西碱无灰分散剂。The Mannich base is prepared by Mannich reaction of polyalkenyl phenol, aldehyde and amine, and the molar ratio of the three is generally 1:0.1-10:0.1-10, preferably 1:1-4:0.5-2 . The Mannich reaction temperature is generally 50-200°C, preferably within the range of 70-150°C. The reaction medium can be hydrocarbons such as benzene, toluene, xylene, aromatic diluent oil (distillation range 159-185°C), solvent gasoline or mineral oil (boiling point above 120°C), or their mixtures. The amount of solvent used is generally 30-150% by weight of the total weight of the monomer material. The reaction system can be protected with nitrogen, or the system can be carried out under the condition of solvent reflux. The preparation methods are described in US3,413,347, US3,649,229, US3,798,165, US4,116,644, US4,553,979 and other patent documents. It is also possible to directly select a commercial agent such as Mannich base ashless dispersant produced by AMOCO Company with the brand name AMOCO9250.
其中的聚烯烃基酚可以是具有如下结构式A所示的高分子化合物，Wherein the polyalkenyl phenol can be a macromolecular compound shown in the following structural formula A,
其中R可以为各种聚烯烃基，如聚丙烯、聚丁烯、聚异丁烯或乙丙共聚物，R的数均分子量可以为300-3000，优选为500-2000。聚烯烃基酚的制备可采用现有的苯酚烷基化技术。例如，在少量酸性催化剂作用下，将0.1-10摩尔酚(优选为1-2.5摩尔)和1摩尔聚烯烃在50-150℃下进行烷基化反应。酸性催化剂可以是硫酸、磷酸或Lewis酸，如BF3-乙醚溶液、BF3-乙醇溶液、BF3-酚溶液等，优选Lewis酸。反应结束后用蒸馏水洗去催化剂，再减压蒸馏或水蒸气蒸馏除去未反应的苯酚。Wherein R can be various polyolefin groups, such as polypropylene, polybutene, polyisobutylene or ethylene-propylene copolymer, and the number average molecular weight of R can be 300-3000, preferably 500-2000. The preparation of polyolefin-based phenol can adopt the existing phenol alkylation technology. For example, under the action of a small amount of acidic catalyst, 0.1-10 moles of phenol (preferably 1-2.5 moles) and 1 mole of polyolefin are subjected to alkylation reaction at 50-150°C. The acidic catalyst can be sulfuric acid, phosphoric acid or Lewis acid, such as BF3 -ether solution, BF3 -ethanol solution, BF3 -phenol solution, etc., preferably Lewis acid. After the reaction is finished, the catalyst is washed away with distilled water, and unreacted phenol is removed by distillation under reduced pressure or steam distillation.
其中所述醛可以为C1-C6的醛，所述C1-C6的醛可以是甲醛、乙醛、丙醛、丁醛、戊醛、己醛中的一种或几种。还可以是其它醛如苯甲醛、水杨醛中的一种或几种，优选甲醛、36重量％的甲醛溶液、福尔马林和多聚甲醛中的一种或几种。Wherein the aldehyde may be a C1 -C6 aldehyde, and the C1 -C6 aldehyde may be one or more of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, and hexanal. It can also be one or more of other aldehydes such as benzaldehyde and salicylaldehyde, preferably one or more of formaldehyde, 36% by weight formaldehyde solution, formalin and paraformaldehyde.
所述胺可以是具有结构式(B)所示结构的有机胺：The amine can be an organic amine having a structure shown in structural formula (B):
(1)R1、R2可以各自为H或碳原子数为1-30的烃基。(1) R1 and R2 may each be H or a hydrocarbon group having 1-30 carbon atoms.
R1、R2其中之一可以为H，另外一个可以为碳原子数为1-30的烃基，或者都可以为碳原子数为1-30的烃基，即有机胺可以是伯胺，也可以是仲胺。“烃基”指烃取代基，即脂肪族、脂环族、芳族以及环式取代基中的一种或几种。脂肪族烃基可以是饱和的也可以是不饱和的带双键或三键的烃基。其中伯胺可以是碳原子数为1-30的脂肪胺，也可以是碳原子数为1-30的芳胺，优选脂肪胺，脂肪伯胺中可以是直链的脂肪胺，如甲胺、乙胺、正丙胺、正丁胺、正戊胺、正己胺、正庚胺、正辛胺、正壬胺、正癸胺、正十一胺、正十二胺(月桂胺)、正十四胺、正十六胺、正十八胺、正二十胺、正二十二胺中的一种或几种，也可以是带有支链的脂肪伯胺，这些带有支链的脂肪伯胺是上述直链脂肪伯胺的各种异构体，例如异丙胺，异丁胺、叔丁胺、异戊胺、新戊胺，异己胺、异庚胺、异辛胺(2-乙基己胺)、异壬胺、异癸胺、异十二胺、异十四胺、异十六胺、异十八胺、异二十胺中的一种或几种。脂肪伯胺还可以是带有脂肪环的胺如环戊胺、环己胺。也可以是碳链中含有不饱和双键或三键的脂肪伯胺如油胺(十八烯胺)、棕榈油胺(十六烯胺)，还可以是叔碳伯胺，例如Rohm&Haas公司生产的商品牌号为Primere81R的叔碳伯胺。One of R1 and R2 can be H, and the other can be a hydrocarbon group with 1-30 carbon atoms, or both can be hydrocarbon groups with 1-30 carbon atoms, that is, the organic amine can be a primary amine, or is a secondary amine. "Hydrocarbyl" refers to a hydrocarbon substituent, that is, one or more of aliphatic, alicyclic, aromatic and cyclic substituents. Aliphatic hydrocarbon groups can be saturated or unsaturated hydrocarbon groups with double or triple bonds. Wherein the primary amine can be a fatty amine with a carbon number of 1-30, or an aromatic amine with a carbon number of 1-30, preferably a fatty amine, and the fatty primary amine can be a straight-chain fatty amine, such as methylamine, Ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine (laurylamine), n-tetradecylamine One or more of amine, n-hexadecylamine, n-octadecylamine, n-eicosylamine, n-docosylamine, or aliphatic primary amines with branched chains, these fatty primary amines with branched chains Amines are various isomers of the above-mentioned straight-chain fatty primary amines, such as isopropylamine, isobutylamine, tert-butylamine, isopentylamine, neopentylamine, isohexylamine, isoheptylamine, isooctylamine (2-ethylhexylamine ), isononylamine, isodecylamine, isododecylamine, isotetradecylamine, isohexadecylamine, isostearylamine, and isoeicosylamine. Primary aliphatic amines can also be amines with aliphatic rings such as cyclopentylamine and cyclohexylamine. It can also be aliphatic primary amines containing unsaturated double bonds or triple bonds in the carbon chain, such as oleylamine (octadecenylamine), palm oilamine (hexadecenylamine), or tertiary carbon primary amines, such as those produced by Rohm&Haas The trade name of the tertiary carbon primary amine of Primere81R.
如果是仲胺，其中R1、R2可以相同，也可以不同，各自可以是正构烷基如甲基、乙基、正丙基、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(月桂基)、正十四烷基、正十六烷基、正十八烷基、正二十烷基或正二十二烷基，也可以是带有支链的异构烷基如异丙基、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、异十八烷基或异二十烷基。优选伯胺，即优选R9、R10其中一个为H。If it is a secondary amine, wherein R1 and R2 can be the same or different, each can be a normal alkyl such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl (lauryl), n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosane base or n-docosyl, also can be branched isomeric alkyl such as isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, isohexyl, isoheptyl, iso Octyl (2-ethylhexyl), isononyl, isodecyl, isododecyl, isotetradecyl, isohexadecyl, isostearyl or isoeicosyl. Primary amines are preferred, that is, preferably one of R9 and R10 is H.
(2)R1、R2可以各自为H或碳原子数为1-30的带杂原子的基团。(2) R1 and R2 may each be H or a heteroatom-bearing group with 1-30 carbon atoms.
这里带杂原子的基团可以是羰基、羟基、羧基、酯基、酰基、烷氧基、硝基、氰基、卤基、胺基、氨基中的一种或几种。The group with heteroatoms here can be one or more of carbonyl, hydroxyl, carboxyl, ester, acyl, alkoxy, nitro, cyano, halo, amino, amino.
含有羟基的胺例如乙醇胺、二乙醇胺、N-烷基乙醇胺、N-烯基乙醇胺、N-烷基异丙醇胺、N-烯基异丙醇胺、异丙醇胺、二异丙醇胺、三羟甲基氨基甲烷、3-氨基-1，2-丙二醇、2-氨基-1，3-丙二醇、3-氨基丙醇、4-氨基-1-丁醇、5-氨基-1-戊醇、6-氨基-1-己醇、4-氨基苯酚中的一种或几种。Amines containing hydroxyl groups such as ethanolamine, diethanolamine, N-alkylethanolamine, N-alkenylethanolamine, N-alkylisopropanolamine, N-alkenylisopropanolamine, isopropanolamine, diisopropanolamine , trishydroxymethylaminomethane, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 3-aminopropanol, 4-amino-1-butanol, 5-amino-1-pentane One or more of alcohol, 6-amino-1-hexanol, and 4-aminophenol.
含有胺基或氨基的胺为多胺化合物，这里的多胺指分子中含有两个或两个以上氮原子的胺，如结构式为H2N-R3-NHR4的胺，这里的R3可以是碳数为1-30的亚烷基，烯基、环烷基、芳基等；R4可以是氢、碳数为1-30的烃基。例如乙二胺、丙二胺、丁二胺、戊二胺、己二胺、庚二胺、辛二胺、癸二胺、椰子油基1，3-丙二胺、油基1，3-丙二胺、牛脂基1，3-丙二胺中的一种或几种。Amines containing amine groups or amino groups are polyamine compounds, where polyamines refer to amines containing two or more nitrogen atoms in the molecule, such as amines with a structural formula of H2 NR3 -NHR4 , where R3 can be An alkylene group with a carbon number of 1-30, alkenyl group, cycloalkyl group, aryl group, etc.;R4 can be hydrogen or a hydrocarbon group with a carbon number of 1-30. For example, ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octyldiamine, decanediamine, coconut oil-based 1,3-propylenediamine, oleyl-1,3- One or more of propylenediamine and tallow 1,3-propylenediamine.
多胺还可以是多烯多胺，多烯多胺的结构式为H2N[(CH2)nNH]mH，其中，n可以为2-4的整数，优选为2或3，m可以为1-8的整数，例如，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。还可以是结构式为H2N[(CH2)nNH]mH的多烯多胺与环氧乙烷、环氧丙烷的缩合物。前者是优选的。The polyene polyamine can also be polyene polyamine, the structural formula of polyene polyamine is H2 N[(CH2 )n NH]m H, wherein, n can be an integer of 2-4, preferably 2 or 3, and m can be is an integer of 1-8, for example, 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. It can also be a condensation product of polyene polyamine with structural formula H2 N[(CH2 )n NH]m H, ethylene oxide and propylene oxide. The former is preferred.
本发明优选胺为多胺，进一步优选多烯多胺如二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺、六乙烯七胺中的一种或几种。In the present invention, the preferred amines are polyamines, more preferably polyene polyamines such as one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine.
作为本发明组分a的所述曼尼西碱进一步优选为聚烯烃基酚、甲醛与多烯多胺按照三者摩尔比为1∶1-2∶1-2反应所得的产物。The Mannich base as component a of the present invention is further preferably a product obtained by reacting polyalkenylphenol, formaldehyde and polyene polyamine according to the molar ratio of the three being 1:1-2:1-2.
本发明组分a除含有曼尼西碱无灰分散剂外进一步还可含有本领域所公知的其它类型无灰分散剂的一种或多种，这些无灰分散剂包括烯基丁二酰亚胺、烯基丁二酸酰胺、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几种。所述烯基丁二酰亚胺和/或基丁二酸酰胺无灰分散剂例如平均分子量在500-3000的聚烯烃基丁二酸酐和/或丁二酸与胺的反应产物；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，尤其是如上文所说的多烯多胺。Component a of the present invention can further contain one or more of other types of ashless dispersants known in the art in addition to the Mannich base ashless dispersant, and these ashless dispersants include alkenyl succinimide, alkenyl One or more of succinic acid amide, polyetheramine type ashless dispersant and polyolefin amine type ashless dispersant. The alkenyl succinimide and/or succinic acid amide ashless dispersant such as the reaction product of polyalkenyl succinic anhydride and/or succinic acid and amine with an average molecular weight of 500-3000; the polyether Amine-type ashless dispersants such as C8-C30 alkylphenols are adducted with ethylene oxide or propylene oxide and then condensed with amines, or C8-C30 alcohols are adducted with ethylene oxide or propylene oxide and then combined with Amine condensation products; said polyolefin amine ashless dispersants such as polyolefin-based amines formed by the reaction of chlorinated polyolefins and amines. The amines mentioned here are all preferably polyamines, especially polyene polyamines as mentioned above.
组分bComponent b
组分b为芳胺型抗氧剂和/或受阻酚型抗氧剂。Component b is an aromatic amine antioxidant and/or a hindered phenol antioxidant.
作为组分b的所述芳胺型抗氧剂可以选自萘胺衍生物、二苯胺衍生物、对苯二胺衍生物、喹啉衍生物中的至少一种。The aromatic amine antioxidant as component b may be selected from at least one of naphthylamine derivatives, diphenylamine derivatives, p-phenylenediamine derivatives, and quinoline derivatives.
其中萘胺衍生物包括但不限于下列物质中的一种或多种：Wherein the naphthylamine derivatives include but not limited to one or more of the following substances:
苯基-α-萘胺(抗氧剂T531，防老剂甲)；Phenyl-α-naphthylamine (antioxidant T531, antioxidant A);
苯基-β-萘胺(防老剂丁)；Phenyl-β-naphthylamine (antiaging agent D);
N-对甲氧基苯基α-萘胺(防老剂102)；N-p-methoxyphenyl α-naphthylamine (antiaging agent 102);
对羟苯基-β-萘胺(防老剂D-OH)；p-Hydroxyphenyl-β-naphthylamine (antiaging agent D-OH);
丁间醇醛-α-萘胺(防老剂AP)Aldol-α-Naphthylamine (Antioxidant AP)
2-羟基-1，3-双[对(β-萘胺)苯氧基]丙烷(防老剂C-49)；2-Hydroxy-1,3-bis[p-(β-naphthylamine)phenoxy]propane (antiaging agent C-49);
二甲基双[对(β-萘胺)苯氧基]硅烷(防老剂C-41)；Dimethylbis[p-(β-naphthylamine)phenoxy]silane (antiaging agent C-41);
二乙基双[对(β-萘胺)苯氧基]硅烷(防老剂C-41-乙基)；Diethylbis[p-(β-naphthylamine)phenoxy]silane (antiaging agent C-41-ethyl);
2，2’-双[对(β-萘胺)苯氧基]二乙醚(防老剂C-41-乙醚)。2,2'-bis[p-(β-naphthylamine)phenoxy]diethyl ether (antiaging agent C-41-ethyl ether).
其中，萘胺衍生物优选苯基萘胺，例如苯基-α-萘胺、苯基-β-萘胺、N-对甲氧基苯基α-萘胺中的一种或多种。尤其优选苯基-α-萘胺。Among them, the naphthylamine derivative is preferably phenylnaphthylamine, such as one or more of phenyl-α-naphthylamine, phenyl-β-naphthylamine, and N-p-methoxyphenyl α-naphthylamine. Phenyl-α-naphthylamine is especially preferred.
其中二苯胺衍生物包括但不限于下列物质中的一种或多种：Wherein diphenylamine derivatives include but not limited to one or more of the following substances:
4，4’-二氨基二苯胺(防老剂APA)；4,4'-diaminodiphenylamine (antiaging agent APA);
对，对’-二甲氧基二苯胺；p, p'-dimethoxydiphenylamine;
N，N，N’，N’-四苯基二胺甲烷(防老剂350)；N, N, N', N'-tetraphenyldiaminemethane (antiaging agent 350);
N，N’-二苯基乙二胺；N,N'-diphenylethylenediamine;
N，N’-二苯基丙二胺；N,N'-diphenylpropylenediamine;
N，N’-二邻甲苯基乙二胺；N,N'-di-o-tolylethylenediamine;
2-羟基-1，3-双-(对苯胺苯氧基)丙烷(防老剂C-47)；2-Hydroxy-1,3-bis-(p-anilinephenoxy)propane (antiaging agent C-47);
2，2’-双(对苯胺苯氧基)-二乙醚(防老剂H-1)；2,2'-bis(p-anilinephenoxy)-diethyl ether (antiaging agent H-1);
二甲基双(对苯胺-苯氧基)-硅烷(防老剂C-1)；Dimethylbis(p-aniline-phenoxy)-silane (antiaging agent C-1);
对异丙氧基二苯胺(防老剂ISO)；p-isopropoxy diphenylamine (antiaging agent ISO);
对，对’-二异丙氧基二苯胺(防老剂DISO)；Right, right'-diisopropoxy diphenylamine (antiaging agent DISO);
4，4’-双(α，α′-二甲基苄基)二苯胺(防老剂KY-405)；4,4'-bis(α,α'-dimethylbenzyl)diphenylamine (antiaging agent KY-405);
对羟基二苯胺(防老剂AO3920)；p-Hydroxydiphenylamine (antiaging agent AO3920);
二-(1，1，3，3-四甲基乙基)二苯胺(防老剂ODA)；Di-(1,1,3,3-tetramethylethyl)diphenylamine (antiaging agent ODA);
4，4’-二辛基二苯胺；4,4'-Dioctyldiphenylamine;
4，4’-二异辛基二苯胺；4,4'-Diisooctyldiphenylamine;
4，4’-二庚基二苯胺；4,4'-Diheptyldiphenylamine;
4，4’-二壬基二苯胺；4,4'-Dinonyldiphenylamine;
辛基化二苯胺(一辛基化二苯胺和二辛基化二苯胺的混合物，防老剂OD)；Octylated diphenylamine (a mixture of monooctylated diphenylamine and dioctylated diphenylamine, antioxidant OD);
辛基/丁基二苯胺(抗氧剂L-57)；Octyl/butyl diphenylamine (antioxidant L-57);
苯乙烯化二苯胺(防老剂DFL，DFC-34)；Styrenated diphenylamine (antiaging agent DFL, DFC-34);
以及烷基化二苯胺的混合物，其中烷基可以为庚基、辛基、壬基中的一种或几种，其工业产品的例子有美国Pennwalt公司商品名为PennoxA、PennoxA-“S”，美国Nationalpolychem公司商品名为WytoxADP、ADP-X，美国Vanderbilt公司商品名为AgeriteStalite、AgeriteStaliteS、AgeriteNepa、AgeriteGel，美国Uniroyal公司商品名为Polylite、Antioxidant445、以及国内代号为T534的抗氧剂产品。And the mixture of alkylated diphenylamine, wherein alkyl can be one or more in heptyl, octyl, nonyl, the example of its industrial product has U.S. Pennwalt company trade name to be PennoxA, PennoxA-"S", U.S. Nationalpolychem company trade name is WytoxADP, ADP-X, U.S. Vanderbilt company trade name is AgeriteStalite, AgeriteStaliteS, AgeriteNepa, AgeriteGel, U.S. Uniroyal company trade name is Polylite, Antioxidant445, and domestic code name is the antioxidant product of T534.
二苯胺衍生物型抗氧剂优选烷基化二苯胺及其混合物，尤其优选烷基碳原子数在4-10之间的烷基化二苯胺及其混合物，如：4，4’-二辛基二苯胺、4，4’-二异辛基二苯胺、4，4’-二庚基二苯胺、4，4’-二壬基二苯胺、辛基化二苯胺(一辛基化二苯胺和二辛基化二苯胺的混合物)、辛基/丁基二苯胺、商品抗氧剂T534中的一种或多种。Diphenylamine derivative antioxidants are preferably alkylated diphenylamines and mixtures thereof, especially alkylated diphenylamines with alkyl carbon atoms between 4-10 and mixtures thereof, such as: 4,4'-dioctyl Diphenylamine, 4,4'-diisooctyldiphenylamine, 4,4'-diheptyldiphenylamine, 4,4'-dinonyldiphenylamine, octylated diphenylamine (one-octylated diphenylamine One or more of the mixture of dioctylated diphenylamine), octyl/butyl diphenylamine, commercial antioxidant T534.
其中对苯二胺衍生物型抗氧剂包括但不限于下列物质中的一种或多种：Wherein p-phenylenediamine derivative antioxidants include but not limited to one or more of the following substances:
N-苯基-N’-环己基对苯二胺(防老剂4010)；N-phenyl-N'-cyclohexyl-p-phenylenediamine (antiaging agent 4010);
N，N-(1，3-二甲基丁基)-N’-苯基对苯二胺(防老剂4020)；N, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (antiaging agent 4020);
N，N’-双-(1，4-二甲基戊基)对苯二胺(防老剂4030)；N, N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine (antiaging agent 4030);
N-对甲苯基-N’-(1，3-二甲基丁基)对苯二胺(防老剂4040)；N-p-tolyl-N'-(1,3-dimethylbutyl) p-phenylenediamine (antiaging agent 4040);
N，N’-二庚基对苯二胺(防老剂788)；N, N'-diheptyl-p-phenylenediamine (antiaging agent 788);
N-异丙基-N’-苯基对苯二胺(防老剂4010NA)；N-isopropyl-N'-phenyl-p-phenylenediamine (antiaging agent 4010NA);
N-异丙基-N’-对甲基苯基对苯二胺(防老剂甲基4010NA)；N-isopropyl-N'-p-methylphenyl-p-phenylenediamine (antiaging agent methyl 4010NA);
N，N’-二甲苯基对苯二胺(防老剂PPD-A)；N, N'-xylyl-p-phenylenediamine (antiaging agent PPD-A);
N，N’-二苯基对苯二胺(防老剂H)；N, N'-diphenyl-p-phenylenediamine (antiaging agent H);
N，N’-二-(β-萘基)对苯二胺(防老剂DNP)；N, N'-di-(β-naphthyl)-p-phenylenediamine (antiaging agent DNP);
N，N’-二仲丁基对苯二胺(防老剂U-5)；N, N'-di-sec-butyl-p-phenylenediamine (antiaging agent U-5);
N，N’-二辛基对苯二胺(防老剂88)；N, N'-dioctyl-p-phenylenediamine (antiaging agent 88);
N，N’-双-(1-甲基庚基)对苯二胺(防老剂288)；N, N'-bis-(1-methylheptyl)-p-phenylenediamine (antiaging agent 288);
N，N’-双-(1-乙基-3-甲基戊基)对苯二胺(防老剂8L)；N, N'-bis-(1-ethyl-3-methylpentyl) p-phenylenediamine (antiaging agent 8L);
N，N’-双-(1，4-二甲基丁基)对苯二胺(防老剂66)；N, N'-bis-(1,4-dimethylbutyl)-p-phenylenediamine (antioxidant 66);
N-辛基-N’-苯基对苯二胺(防老剂688)；N-octyl-N'-phenyl-p-phenylenediamine (antiaging agent 688);
N-异丁基-N’-苯基对苯二胺(防老剂5L)；N-isobutyl-N'-phenyl-p-phenylenediamine (anti-aging agent 5L);
N，N’-二甲基-N，N’-双-(1-甲丙基)对苯二胺(防老剂32)；N, N'-dimethyl-N, N'-bis-(1-methylpropyl)-p-phenylenediamine (antiaging agent 32);
N-(对甲苯基磺酰基)-N’-苯基对苯二胺(防老剂TPPD)；N-(p-tolylsulfonyl)-N'-phenyl-p-phenylenediamine (anti-aging agent TPPD);
N-(3-甲基丙烯基酰氧代-2-羟基丙基)-N’-苯基对苯二胺(防老剂G-1)；N-(3-methacryloyloxy-2-hydroxypropyl)-N'-phenyl-p-phenylenediamine (antiaging agent G-1);
N-(3-苯胺基苯基)甲基丙烯酰胺；N-(3-anilinophenyl)methacrylamide;
N-己基-N’-苯基对苯二胺；N-hexyl-N'-phenyl-p-phenylenediamine;
对苯二胺衍生物型抗氧剂优选二烷基对苯二胺，尤其优选烷基碳原子数在4-10之间的二烷基对苯二胺，如：N，N’-二庚基对苯二胺；N，N’-二仲丁基对苯二胺；N，N’-二辛基对苯二胺；N，N’-双-(1-甲基庚基)对苯二胺中的一种或多种。The p-phenylenediamine derivative antioxidant is preferably dialkyl-p-phenylenediamine, especially dialkyl-p-phenylenediamine with an alkyl carbon number between 4-10, such as: N, N'-diheptyl N,N'-di-sec-butyl-p-phenylenediamine; N,N'-dioctyl-p-phenylenediamine; N,N'-bis-(1-methylheptyl)-p-phenylenediamine One or more of diamines.
其中的喹啉衍生物包括但不限于：Among them, quinoline derivatives include but are not limited to:
6-乙氧基-2，2，4-三甲基-1，2-二氢化喹啉(防老剂AW)；6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (antiaging agent AW);
6-苯基-2，2，4-三甲基-1，2-二氢化喹啉(防老剂PMQ)；6-phenyl-2,2,4-trimethyl-1,2-dihydroquinoline (antiaging agent PMQ);
6-十二烷基-2，2，4-三甲基-1，2-二氢化喹啉(防老剂DD)；6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline (antiaging agent DD);
2，2，4-三甲基-1，2-二氢化喹啉聚合体(防老剂RD、防老剂124)；2,2,4-trimethyl-1,2-dihydroquinoline polymer (antiaging agent RD, antiaging agent 124);
二苯胺与丙酮低温反应产物(防老剂BAS)；Low temperature reaction product of diphenylamine and acetone (antiaging agent BAS);
二苯胺与丙酮高温反应产物(防老剂BLE)；High temperature reaction product of diphenylamine and acetone (antiaging agent BLE);
二苯胺与丙酮和醛的反应产物(防老剂BXA)；The reaction product of diphenylamine with acetone and aldehyde (antiaging agent BXA);
苯基-β-萘胺与丙酮的反应产物(防老剂APN、防老剂AM)。The reaction product of phenyl-β-naphthylamine and acetone (antiaging agent APN, antiaging agent AM).
芳胺抗氧剂优选对苯二胺类芳胺抗氧剂。The aromatic amine antioxidant is preferably p-phenylenediamine aromatic amine antioxidant.
组分b中所述酚型抗氧剂可以是单酚、双酚、二酚和多酚，也可以是它们任意比例的混合物。The phenolic antioxidant in component b can be monophenol, bisphenol, diphenol and polyphenol, or a mixture of them in any proportion.
其中单酚是有一个苯环/并且苯环上有一个羟基的取代的苯酚，而且取代基中至少有一个是叔丁基，其它取代基可以是烃基或含有杂原子的取代基，其中的烃基选自C1-C10烷基，例如甲基、乙基、烯丙基、正丁基、仲丁基、壬基等，含有杂原子的取代基选自含氧的取代基如甲氧基、甲氧基取代的甲基、羟甲基，含氮的取代基如α-二甲胺基甲基。例如可以是下面结构的单酚：邻叔丁基苯酚、对叔丁基苯酚、2-叔丁基-4-甲基苯酚、6-叔丁基-2-甲基苯酚、6-叔丁基-3-甲基苯酚；4-叔丁基-2，6-二甲基苯酚、6-叔丁基-2，4-二甲基苯酚；2，4-二叔丁基苯酚、2，5-二叔丁基苯酚、2，6-二叔丁基苯酚；2，5-二叔丁基-4-甲基苯酚、2，6-二叔丁基-4-甲基苯酚(BHT，抗氧剂T501)、4，6-二叔丁基-2-甲基苯酚；2，4，6-三叔丁基苯酚、2-烯丙基-4-甲基-6-叔丁基苯酚、2-仲丁基-4-叔丁基苯酚、4-仲丁基-2，6-二叔丁基苯酚、4-壬基-2，6-二叔丁基苯酚、2，6-二叔丁基-4-乙基苯酚(抗氧剂DBEP)、2，6-二叔丁基-4-正丁基苯酚(抗氧剂678)；叔丁基羟基茴香醚(BHA)、2，6-二叔丁基-α-甲氧基-对甲酚(BHT-MO)、4-羟甲基-2，6-二叔丁基苯酚(抗氧剂754)、2，6-二叔丁基-α-二甲氨基-对甲酚(抗氧剂703)、各种3，5-二叔丁基-4-羟基苯基丙酸酯和3，5-二叔丁基-4-羟基苯基丙酸酰胺等。Among them, the monophenol is a substituted phenol with a benzene ring/and a hydroxyl group on the benzene ring, and at least one of the substituents is a tert-butyl group, and other substituents can be hydrocarbon groups or substituents containing heteroatoms, wherein the hydrocarbon group Selected from C1 -C10 alkyl groups, such as methyl, ethyl, allyl, n-butyl, sec-butyl, nonyl, etc., and the substituents containing heteroatoms are selected from oxygen-containing substituents such as methoxy , methoxy-substituted methyl, hydroxymethyl, nitrogen-containing substituents such as α-dimethylaminomethyl. For example, it can be a monophenol of the following structure: o-tert-butylphenol, p-tert-butylphenol, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2-methylphenol, 6-tert-butyl -3-methylphenol; 4-tert-butyl-2,6-dimethylphenol, 6-tert-butyl-2,4-dimethylphenol; 2,4-di-tert-butylphenol, 2,5 -Di-tert-butylphenol, 2,6-di-tert-butylphenol; 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol (BHT, anti Oxygen T501), 4,6-di-tert-butyl-2-methylphenol; 2,4,6-tri-tert-butylphenol, 2-allyl-4-methyl-6-tert-butylphenol, 2-sec-butyl-4-tert-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol, 4-nonyl-2,6-di-tert-butylphenol, 2,6-di-tert-butylphenol Butyl-4-ethylphenol (antioxidant DBEP), 2,6-di-tert-butyl-4-n-butylphenol (antioxidant 678); tert-butylhydroxyanisole (BHA), 2,6 -Di-tert-butyl-α-methoxy-p-cresol (BHT-MO), 4-hydroxymethyl-2,6-di-tert-butylphenol (antioxidant 754), 2,6-di-tert-butyl Base-α-dimethylamino-p-cresol (antioxidant 703), various 3,5-di-tert-butyl-4-hydroxyphenylpropionates and 3,5-di-tert-butyl-4-hydroxy Phenylpropionamide, etc.
其中单酚抗氧剂优选至少有一个叔丁基在酚羟基邻位的受阻单酚，如：Wherein the monophenol antioxidant preferably has at least one tert-butyl hindered monophenol at the ortho position of the phenolic hydroxyl group, such as:
2-叔丁基-4-甲基苯酚、6-叔丁基-2，4-二甲基苯酚、2，6-二叔丁基苯酚、2，6-二叔丁基-4-甲基苯酚(BHT，抗氧剂T501)、2，4，6-三叔丁基苯酚、4-仲丁基-2，6-二叔丁基苯酚、4-壬基-2，6-二叔丁基苯酚、2，6-二叔丁基-4-乙基苯酚(抗氧剂DBEP)、叔丁基羟基茴香醚(BHA)、2，6-二叔丁基-α-甲氧基-对甲酚(BHT-MO)、4-羟甲基-2，6-二叔丁基苯酚(抗氧剂754)、2，6-二叔丁基-α-二甲氨基-对甲酚(抗氧剂703)中的一种或几种。2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol Phenol (BHT, antioxidant T501), 2,4,6-tri-tert-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol, 4-nonyl-2,6-di-tert-butyl 2,6-di-tert-butyl-4-ethylphenol (antioxidant DBEP), tert-butylhydroxyanisole (BHA), 2,6-di-tert-butyl-α-methoxy-p Cresol (BHT-MO), 4-hydroxymethyl-2,6-di-tert-butylphenol (antioxidant 754), 2,6-di-tert-butyl-α-dimethylamino-p-cresol (antioxidant Oxygen agent 703) in one or more.
双酚是指由两个单酚通过硫或碳原子相连的酚型抗氧剂，例如：Bisphenols refer to phenolic antioxidants that are connected by two monophenols through sulfur or carbon atoms, such as:
(1)由碳原子相连的双酚(1) Bisphenol linked by carbon atoms
4，4’-异丙叉双酚(双酚A)；4,4'-isopropylidene bisphenol (bisphenol A);
2，2’-双-(3-甲基-4羟基苯基)丙烷(双酚C)；2,2'-bis-(3-methyl-4-hydroxyphenyl)propane (bisphenol C);
4，4’-二羟基联苯(抗氧剂DOD)；4,4'-dihydroxybiphenyl (antioxidant DOD);
4，4’-二羟基-3，3’，5，5’-四-叔丁基联苯(抗氧剂712)；4,4'-dihydroxy-3,3',5,5'-tetra-tert-butylbiphenyl (antioxidant 712);
2，2’-亚甲基-双-(4-甲基-6-叔丁基苯酚)(抗氧剂双酚2246)；2,2'-methylene-bis-(4-methyl-6-tert-butylphenol) (antioxidant bisphenol 2246);
4，4’-亚甲基-双-(2-甲基-6-叔丁基苯酚)(抗氧剂甲叉736)；4,4'-methylene-bis-(2-methyl-6-tert-butylphenol) (antioxidant methylene 736);
2，2’-亚甲基-双-(4-乙基-6-叔丁基苯酚)(抗氧剂425)；2,2'-methylene-bis-(4-ethyl-6-tert-butylphenol) (antioxidant 425);
2，2’-亚甲基-双-(4-甲基-6-环己基苯酚)(抗氧剂ZKF)；2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol) (antioxidant ZKF);
2，2’-亚甲基-双[4-甲基-6-(α-甲基环己基)苯酚](抗氧剂WSP)；2,2'-methylene-bis[4-methyl-6-(α-methylcyclohexyl)phenol] (antioxidant WSP);
2，2’-亚甲基-双-(6-α-甲基苄基对甲酚)；2,2'-methylene-bis-(6-α-methylbenzyl-p-cresol);
4，4’-亚甲基-双-(2，6-二叔丁基苯酚)(抗氧剂T511)；4,4'-methylene-bis-(2,6-di-tert-butylphenol) (antioxidant T511);
4，4’-亚甲基-双-(2-叔丁基苯酚)(抗氧剂702)；4,4'-methylene-bis-(2-tert-butylphenol) (antioxidant 702);
2，2’-亚乙基-双-(4-甲基-6-叔丁基苯酚)；2,2'-Ethylene-bis-(4-methyl-6-tert-butylphenol);
4，4’-亚乙基-双-(2-甲基-6-叔丁基苯酚)；4,4'-Ethylene-bis-(2-methyl-6-tert-butylphenol);
4，4’-亚乙基-双-(2，6-二叔丁基苯酚)；4,4'-Ethylene-bis-(2,6-di-tert-butylphenol);
4，4’-亚丁基-双-(6-叔丁基-间甲酚)(抗氧剂BBM、抗氧剂TCA)；4,4'-butylene-bis-(6-tert-butyl-m-cresol) (antioxidant BBM, antioxidant TCA);
4，4’-亚异丁基-双-(2，6-二叔丁基苯酚)等。4,4'-isobutylene-bis-(2,6-di-tert-butylphenol), etc.
(2)由硫原子相连的双酚(2) bisphenols connected by sulfur atoms
4，4’-硫代双-(3-甲基-6-叔丁基苯酚)(抗氧剂300或AO-1)；4,4'-thiobis-(3-methyl-6-tert-butylphenol) (antioxidant 300 or AO-1);
2，2’-硫代双-(4-甲基-6-叔丁基苯酚)(抗氧剂2246-S)；2,2'-thiobis-(4-methyl-6-tert-butylphenol) (antioxidant 2246-S);
4，4’-硫代双-(2-甲基-6-叔丁基苯酚)(抗氧剂736)；4,4'-thiobis-(2-methyl-6-tert-butylphenol) (antioxidant 736);
4，4’-硫代双-(5-甲基-2-叔丁基苯酚)；4,4'-thiobis-(5-methyl-2-tert-butylphenol);
4，4’-硫代双-(2，6-二叔丁基苯酚)(Nocrac300)；4,4'-thiobis-(2,6-di-tert-butylphenol) (Nocrac300);
2，2’-硫代双-(4-辛基苯酚)等。2,2'-thiobis-(4-octylphenol), etc.
(3)由碳原子相连但含有杂原子的双酚(3) Bisphenols connected by carbon atoms but containing heteroatoms
N，N’-六甲撑双-(3，5-二叔丁基-4-羟基苯丙酰胺)(抗氧剂1098)；N, N'-hexamethylene bis-(3,5-di-tert-butyl-4-hydroxyphenylpropanamide) (antioxidant 1098);
己二醇双[β-(3，5-二叔丁基-4-羟基苯基)丙酸酯](抗氧剂259)；Hexylene glycol bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 259);
双-(3，5-二叔丁基-4-羟基苯基丙酸丙酰)联氨(抗氧剂BPP)；Bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl propionyl) hydrazine (antioxidant BPP);
双-(3，5-二叔丁基-4-羟基苄基)硫醚(抗氧剂甲叉4426-S)；Bis-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide (antioxidant methylene 4426-S);
2，2’-亚硫基乙二醇双[β-(3，5-二叔丁基-4-羟基苯基)丙酸酯](抗氧剂1035)；2,2'-thioethylene glycol bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1035);
三甘醇双-3-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯(抗氧剂245)等。Triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate (antioxidant 245), etc.
双酚型抗氧剂优选由至少有一个叔丁基在酚羟基邻位的单酚通过亚甲基或硫相连的双酚，例如：Bisphenol antioxidants are preferably bisphenols that have at least one tert-butyl group in the ortho-position of the phenolic hydroxyl group through methylene or sulfur-linked bisphenols, such as:
2，2’-亚甲基-双-(4-甲基-6-叔丁基苯酚)(抗氧剂2246)；2,2'-methylene-bis-(4-methyl-6-tert-butylphenol) (antioxidant 2246);
4，4’-亚甲基-双-(2-甲基-6-叔丁基苯酚)(抗氧剂甲叉736)；4,4'-methylene-bis-(2-methyl-6-tert-butylphenol) (antioxidant methylene 736);
4，4’-亚甲基-双-(2，6-二叔丁基苯酚)(抗氧剂T511)；4,4'-methylene-bis-(2,6-di-tert-butylphenol) (antioxidant T511);
4，4’-亚甲基-双-(2-叔丁基苯酚)(抗氧剂702)；4,4'-methylene-bis-(2-tert-butylphenol) (antioxidant 702);
4，4’-硫代双-(3-甲基-6-叔丁基苯酚)(抗氧剂300或AO-1)；4,4'-thiobis-(3-methyl-6-tert-butylphenol) (antioxidant 300 or AO-1);
2，2’-硫代双-(4-甲基-6-叔丁基苯酚)(抗氧剂2246-S)；2,2'-thiobis-(4-methyl-6-tert-butylphenol) (antioxidant 2246-S);
4，4’-硫代双-(2-甲基-6-叔丁基苯酚)(抗氧剂736)；4,4'-thiobis-(2-methyl-6-tert-butylphenol) (antioxidant 736);
4，4’-硫代双-(2，6-二叔丁基苯酚)(Nocrac300)；4,4'-thiobis-(2,6-di-tert-butylphenol) (Nocrac300);
双-(3，5-二叔丁基-4-羟基苄基)硫醚(抗氧剂甲叉4426-S)等。Bis-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide (antioxidant methylene 4426-S), etc.
这里的二酚是指一个苯环上有两个羟基的酚型抗氧剂，可以是下面结构的二酚：对苯二酚、叔丁基对苯二酚(TBHQ)、2，5-二叔丁基对苯二酚、2，5-二叔戊基对苯二酚中的一种或几种。The diphenol here refers to a phenolic antioxidant with two hydroxyl groups on a benzene ring, which can be a diphenol with the following structure: hydroquinone, tert-butylhydroquinone (TBHQ), 2,5-diphenol One or more of tert-butylhydroquinone and 2,5-di-tert-amylhydroquinone.
所述多酚抗氧剂指分子中由至少三个单酚基团的大分子抗氧剂优选由至少有一个叔丁基在酚羟基邻位的单酚基团组成的多酚，尤其优选有两个叔丁基在酚羟基邻位的受阻多酚，例如：The polyphenol antioxidant refers to a macromolecular antioxidant consisting of at least three monophenolic groups in the molecule, preferably a polyphenol consisting of a monophenolic group with at least one tert-butyl group in the ortho position of the phenolic hydroxyl group, especially preferably having Hindered polyphenols with two tert-butyl groups ortho to the phenolic hydroxyl group, for example:
1，3，5-三甲基-2，4，6-三-(4’-羟基-3’，5’-二叔丁基)苯(抗氧剂330)；1,3,5-Trimethyl-2,4,6-tri-(4'-hydroxy-3',5'-di-tert-butyl)benzene (antioxidant 330);
三[2-(3，5-二叔丁基-4-羟基苯基)丙酰基氧乙基]异氰酸酯(抗氧剂3125)；Tris[2-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanate (antioxidant 3125);
四(3，5-二叔丁基-4-羟基苯基丙酸)季戊四醇酯(抗氧剂1010)；Tetrakis(3,5-di-tert-butyl-4-hydroxyphenylpropionic acid) pentaerythritol ester (antioxidant 1010);
1，3，5-三(3，5-二叔丁基-4-羟基苄基)均三嗪-2，4，6-(1H，3H，5H)(抗氧剂3114)；1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H) (antioxidant 3114);
1，1，3-三-(2-甲基-4-羟基-5-叔丁基苯基)丁烷(抗氧剂CA)；1,1,3-tri-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (antioxidant CA);
1，3，5-三(2，6-二甲基-4-叔丁基-3-羟基苄基)均三嗪-2，4，6-(1H，3H，5H)(抗氧剂1790)；1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H) (antioxidant 1790 );
双[3，3-双-(3’-叔丁基-4’-羟基苄基)丁酸]乙二醇酯等。Bis[3,3-bis-(3'-tert-butyl-4'-hydroxybenzyl)butanoic acid]ethylene glycol ester, etc.
这里的多酚还可以是苯环中带有三个羟基的酚，例如焦性没食子酸、没食子酸酯如没食子酸甲酯、没食子酸乙酯、没食子酸丙酯、没食子酸丁酯、没食子酸戊酯、没食子酸己酯、没食子酸庚酯、没食子酸辛酯、没食子酸壬酯、没食子酸癸酯、没食子酸十二酯、没食子酸十四酯、没食子酸十六酯、没食子酸十八酯、没食子酸十八烯酯等；以及中国专利申请号200810115581.8所公开的没食子酸酰胺或氨盐。多酚型抗氧剂优选没食子酸衍生物尤其是没食子酸丙酯。The polyphenols here can also be phenols with three hydroxyl groups in the benzene ring, such as pyrogallic acid, gallic acid esters such as methyl gallate, ethyl gallate, propyl gallate, butyl gallate, pentyl gallate ester, hexyl gallate, heptyl gallate, octyl gallate, nonyl gallate, decyl gallate, lauryl gallate, tetradecyl gallate, cetyl gallate, octadecyl gallate, Octadecenyl gallate, etc.; and gallic acid amide or ammonia salt disclosed in Chinese Patent Application No. 200810115581.8. The polyphenolic antioxidant is preferably a gallic acid derivative, especially propyl gallate.
上述酚型抗氧剂优选至少有一个叔丁基在酚羟基邻位的双酚型抗氧剂，特别是通过亚甲基或硫相连的双酚型抗氧剂，二酚型抗氧剂中的叔丁基对苯二酚、2，5-二叔丁基对苯二酚，以及多酚抗氧剂中没食子酸酯、没食子酸酰胺或氨盐。The above-mentioned phenolic antioxidant preferably has at least one tert-butyl group in the bisphenolic antioxidant at the ortho position of the phenolic hydroxyl group, especially the bisphenolic antioxidant linked by methylene or sulfur, among the diphenolic antioxidants tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, and gallate, gallic acid amide or ammonium salt in polyphenol antioxidants.
组分b还可以是上述芳胺型抗氧剂与与上述酚型抗氧剂的复合抗氧剂。Component b can also be a composite antioxidant of the above-mentioned aromatic amine antioxidant and the above-mentioned phenolic antioxidant.
本发明提供的柴油组合物还任选含有组分c。且所述组分a与组分c的重量比可以为1∶0-1，优选所述组分a与所述组分c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 present invention also optionally contains component c. And the weight ratio of the component a to the component c can be 1:0-1, preferably the weight ratio of the component a to the component c is 1:0.01-1, more preferably 1:0.01-1 0.5, more preferably 1:0.02-0.2.
所述组分c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螯合剂。The component c can be various metal deactivators that can react with metal surfaces and/or metal chelating agents that can react or combine with metals or metal ions.
具体的，所述组分c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-二酮、β-酮酯、席夫碱(Schiffbases)、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 component c can be benzotriazole and its derivatives, thiadiazole and its derivatives, 8-hydroxyquinoline, ethylenediaminetetracarboxylic acid, hydrazide, β-diketone, β-ketone One or more of 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，优选所述组分c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、酯类衍生物)中的一种或几种。In the present invention, it is preferred that the component c 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 the alkali and organic polycarboxylic acids and their condensation reaction products with fatty amines or fatty alcohols (i.e. 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 one or more of flow improvers, cetane number improvers, antistatic agents, preservatives, rust inhibitors, demulsifiers, etc. .
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)、二甲基亚砜(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 sulfoxide (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脂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 transesterification of oils and low-carbon alcohols, such as acid catalysis, alkali catalysis, enzyme catalysis, supercritical method, etc. Wait. 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、亚麻籽油、椰子油、橡树油、杏仁油、核桃油、蓖麻油、芝麻油、橄榄油、妥尔油(TallOil)、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 tree 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, saline plants such as sea mallow, oil sand beans and other plant oils. 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GB252或车用柴油国家标准GB19147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 GB252 for light diesel oil or the national standard GB19147 for automotive diesel 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(GasToLiquid)或CTL柴油(CoalToLiquid)，还可以是植物纤维经费-托合成方法而生产的BTL柴油(BiomassToLiquid)。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 (GasToLiquid) or CTL diesel (CoalToLiquid) produced by using natural gas or coal as a raw material through the Fischer-Tropsch (F-T) synthesis method, and it can also be BTL produced by plant fiber through the Fischer-Tropsch synthesis method Diesel (BiomassToLiquid). 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，硫和芳烃含量极低，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 sulfur and aromatic content. As a diesel engine fuel or a blending component, it can 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(PolyoxymethyleneDimethylEthers，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 (PolyoxymethyleneDimethylEthers, 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 It can be obtained by mixing with other diesel oils. Various components of the additives can be directly mixed with the base diesel oil, or the various components of the additives can be pre-mixed to obtain the additive mixture and then mixed with the base diesel oil. 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，在含有生物柴油的基础柴油中，加入添加剂，所述添加剂含有组分a和组分b，所述添加剂的组分a含有曼尼西碱无灰分散剂；所述组分b为芳胺型抗氧剂和/或受阻酚型抗氧剂。The method for improving the oxidation stability of biodiesel provided by the present invention comprises adding an additive to base diesel oil containing biodiesel, the additive contains component a and component b, and component a of the additive contains Mannich base Ashless dispersant; the component b is aromatic amine antioxidant and/or hindered phenol antioxidant.
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，所述添加剂还包括组分c，所述组分c为金属钝化剂。Preferably, in the method for improving the oxidation stability of biodiesel provided by the present invention, the additive further includes component c, and the component c is a metal deactivator.
所述添加剂的组分a、添加剂的组分b和组分c各自与上述柴油组合物中的组分a、组分b和组分c相同，其种类和用量己在前文描述，在此不再赘述。Component a of the additive, component b and component c of the additive are respectively the same as component a, component b and component c in the above-mentioned diesel oil composition, and their types and amounts have been described above, and are not described herein. Let me repeat.
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.
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。The following examples will further illustrate the present invention.
实施例1-2用于说明聚烯烃基酚的制备。Examples 1-2 illustrate the preparation of polyalkenylphenols.
实施例1Example 1
在1000ml三颈瓶中，加入363.3克聚异丁烯(聚异丁烯数均相对分子质量Mn＝1100、来源为锦州石化公司)和62.1克苯酚，搅拌加热至50℃，将14.1克BF3-乙醚溶液分三次在两小时内滴加到反应体系中。升温至60℃，计时反应4.5小时。停止反应，用40℃的蒸馏水洗三次，再减压蒸馏除去未反应的苯酚。采用柱色谱分析方法分析出未反应的聚异丁烯为32％，由此计算出聚异丁烯的烷基化转化率为68％。In a 1000ml three-necked bottle, add 363.3 grams of polyisobutene (the number-average molecular weight of polyisobutene Mn=1100, the source is Jinzhou Petrochemical Company) and 62.1 grams of phenol, stir and heat to 50 ° C, and divide 14.1 grams of BF3 -ether solution Add dropwise to the reaction system three times within two hours. The temperature was raised to 60°C, and the reaction was timed for 4.5 hours. Stop the reaction, wash with 40°C distilled water three times, and then distill under reduced pressure to remove unreacted phenol. The unreacted polyisobutene was analyzed by column chromatography to be 32%, and the alkylation conversion rate of polyisobutene was calculated to be 68%.
实施例2Example 2
在500ml三颈瓶中，加入100克聚异丁烯(聚异丁烯数均相对分子质量Mn＝1000、来源为德国BASF公司)和18.8克苯酚，搅拌加热至60℃，将4.3克BF3-乙醚溶液分三次在两小时左右滴加到反应体系中。升温至70℃，计时反应4小时。停止反应，用50℃的蒸馏水洗三次，再减压蒸馏除去未反应的苯酚。采用柱色谱分析方法分析出未反应的聚异丁烯为30％，由此计算出聚异丁烯的烷基化转化率为70％。In a 500ml three-necked bottle, add 100 grams of polyisobutene (polyisobutene number-average molecular weight Mn=1000, the source is BASF, Germany) and 18.8 grams of phenol, stir and heat to 60 ° C, and divide 4.3 grams of BF3 -ether solution Add it dropwise to the reaction system three times in about two hours. The temperature was raised to 70°C, and the reaction was timed for 4 hours. Stop the reaction, wash with 50°C distilled water three times, and then distill off unreacted phenol under reduced pressure. The unreacted polyisobutene was analyzed by column chromatography to be 30%, and the alkylation conversion rate of polyisobutene was calculated to be 70%.
实施例3-4用于说明曼尼西碱无灰分散剂的合成。Examples 3-4 illustrate the synthesis of Mannich base ashless dispersants.
实施例3Example 3
在三颈瓶中，加入100克由实施例1制备的聚烯烃基酚、9.4克三乙烯四胺和120克甲苯，加热搅拌至70℃，将13.4克36重量％的甲醛溶液在2小时内滴加到反应体系中(聚烯烃基酚、甲醛、三乙烯四胺的摩尔比为1∶3∶1.2)。滴完后升温到100℃，并在100℃计时反应2小时。然后用减压蒸馏除去甲苯溶剂和水，再补加50克芳烃稀释油，配成50重量％的稀释液。In the three-necked flask, add 100 grams of polyalkenyl phenol prepared by Example 1, 9.4 grams of triethylenetetramine and 120 grams of toluene, heat and stir to 70 ° C, and dissolve 13.4 grams of 36% by weight formaldehyde solution within 2 hours Add it dropwise into the reaction system (the molar ratio of polyalkenylphenol, formaldehyde and triethylenetetramine is 1:3:1.2). After dropping, the temperature was raised to 100°C, and the reaction was timed at 100°C for 2 hours. Then, the toluene solvent and water were removed by distillation under reduced pressure, and 50 grams of aromatic hydrocarbon diluent oil was added to form a 50% by weight dilution.
实施例4Example 4
在三颈瓶中，加入100克由实施例2制备的聚烯烃基酚、1.9克多聚甲醛、11.8克四乙烯五胺和50克芳烃稀释油(聚烯烃基酚、甲醛、四乙烯五胺的摩尔比约为1∶1∶1)，加热搅拌至95℃，在氮气吹扫下反应6小时，分出水，再补加5克芳烃稀释油，配成50重量％的稀释液。In the three-necked flask, add 100 gram of polyalkenyl phenols, 1.9 gram of paraformaldehyde, 11.8 gram of tetraethylenepentamine and 50 gram of aromatics diluent oils (polyalkenyl phenol, formaldehyde, tetraethylenepentamine) prepared by embodiment 2 The molar ratio is about 1:1:1), heated and stirred to 95° C., reacted under nitrogen purging for 6 hours, separated water, and added 5 grams of aromatic hydrocarbon diluent oil to form a 50% by weight dilution.
实施例5-9Example 5-9
实施例5-9用于说明添加剂的组成。Examples 5-9 serve to illustrate the composition of the additives.
将选自实施例3、4的组分a以及组分b和c按照表1所示的重量比混合。Component a selected from Examples 3 and 4 and components b and c were mixed according to the weight ratio shown in Table 1.
表1Table 1
性能测试Performance Testing
以下测试中，所用棉籽油生物柴油是中石化石家庄炼化分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。In the following tests, the cottonseed oil biodiesel used is the biodiesel product provided by Sinopec Shijiazhuang Refining and Chemical Branch, the gutter oil biodiesel used is provided by Fujian Longyan Excellence New Energy Co., Ltd., and the petroleum diesel is Beijing standard produced by Sinopec Yanshan Branch B diesel.
(1)纯生物柴油作为基础柴油的生物柴油组合物的氧化安定性测试(1) Oxidation stability test of biodiesel composition with pure biodiesel as base diesel
用EN14112：2003方法(Racimat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2中。Use the EN14112:2003 method (Racimat 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 2.
表2Table 2
从表2中的数据可以看出，与对比例相比，本发明提供的生物柴油组合物具有明显更好的氧化安定性。曼尼西碱无灰分散剂(组分a)与组分b配合作用后，生物柴油组合物的氧化安定性比单独使用组分a、组分b的效果之和要好很多，由此可见组分a、b之间令人惊奇地出现了很明显的协同作用。任选的组分c加入后，效果进一步增强。It can be seen from the data in Table 2 that, compared with the comparative example, the biodiesel composition provided by the present invention has significantly better oxidation stability. After the Mannich base ashless dispersant (component a) is combined with component b, the oxidation stability of the biodiesel composition is much better than the sum of the effects of component a and component b alone, so it can be seen that the components Surprisingly, there is an obvious synergistic effect between a and b. After the optional component c is added, the effect is further enhanced.
由对比例1、3、6结果可以看出，单独加入组分a，生物柴油的氧化安定性几乎没有提高，但组分a与组分b的抗氧剂复合使用后，效果却出人意料的增强，如实施例5、6、7、8、9所示，即组分a能使抗氧剂的性能大大增强。From the results of comparative examples 1, 3, and 6, it can be seen that the oxidation stability of biodiesel is hardly improved by adding component a alone, but the effect is unexpectedly enhanced after component a is used in combination with the antioxidant of component b , as shown in Examples 5, 6, 7, 8, and 9, that is, component a can greatly enhance the performance of the antioxidant.
通过实施例5与实施例6相比可以看出，选用任选的组分c后，所得生物柴油组合物的氧化安定性进一步增强。It can be seen from the comparison between Example 5 and Example 6 that after the optional component c is selected, the oxidation stability of the obtained biodiesel composition is further enhanced.
(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、稳定性和清净分散性的测试，所用生物柴油为地沟油生物柴油。(2) The oxidation resistance, stability and clean dispersibility of the blended diesel oil composition using the mixture of biodiesel and petroleum diesel as the base diesel oil. The biodiesel used is waste oil biodiesel.
采用PrEN15751：2008的方法分别测定各柴油组合物、石油柴油和调合柴油在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，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3中。The method of PrEN15751:2008 was used to measure the induction period of each diesel composition, petroleum diesel and blended diesel oil at 110°C. The instrument used was Metrohm’s 743 oil oxidation stability tester. The longer the induction period, the more The better the oxidation resistance of the biodiesel composition, on the contrary the shorter the induction period, the worse the oxidation resistance of the biodiesel composition. The test results are shown in Table 3.
根据CN1940524A所公开的方法采用车用柴油清净性测定仪(由兰州维科石化仪器公司生产、L-3型)分别测定各调合柴油组合物的清净分散性。其具体操作包括：称量一洁净的沉积物收集器的重量，然后将该沉积物收集器加热至250℃，之后以2毫升/分钟的速度将调合柴油组合物流到沉积物收集器的工作面上，形成一层均匀流动的油膜，经过50分钟后将沉积物收集器工作面上的油膜在180℃的高温下烘烤，氧化生成一层漆膜，然后将该沉积物收集器浸渍于正庚烷中2分钟，然后称量附着有沉积物的沉积物收集器的重量，并记录沉积物收集器的增重，即为沉积物收集器的沉积量A(单位：mg)。可以根据沉积量的大小评定调合柴油组合物的清净分散性，若沉积量越大则清净分散性越差，反之若沉积量越小则清净分散性越好。其测试结果示于表3中。According to the method disclosed in CN1940524A, the detergency and dispersibility of each blended diesel oil composition was measured with a vehicle diesel detergency tester (manufactured by Lanzhou Veken Petrochemical Instrument Co., Ltd., L-3 type). Its specific operations include: weighing a clean sediment collector, then heating the sediment collector to 250°C, and then flowing the blended diesel composition to the sediment collector at a speed of 2 ml/min After 50 minutes, bake the oil film on the working surface of the sediment collector at a high temperature of 180°C to oxidize to form a layer of paint film, and then immerse the sediment collector in In n-heptane for 2 minutes, then weigh the weight of the sediment collector attached to the sediment, and record the weight gain of the sediment collector, which is the deposition amount A (unit: mg) of the sediment collector. The detergency and dispersibility of the blended diesel oil composition can be evaluated according to the amount of deposition. The larger the deposition amount, the worse the detergency and dispersibility. On the contrary, the smaller the deposition amount, the better the detergency and dispersibility. The test results are shown in Table 3.
另外，采用CN1351132A公开的金属片沉积法根据上述生物柴油清净分散性的评价方法评定调合柴油组合物的清净分散性，得到钢片的增重即为沉积物收集器的沉积量B(mg)。根据沉积量的大小评定柴油组合物的清净分散性，若沉积量越大则清净分散性越差，反之若沉积量越小则清净分散性越好。其测试结果示于表3中。In addition, the metal sheet deposition method disclosed in CN1351132A is used to evaluate the clean dispersibility of the blended diesel oil composition according to the above-mentioned evaluation method of biodiesel clean dispersibility, and the weight gain of the steel sheet is the deposition amount B (mg) of the sediment collector . The detergency and dispersibility of the diesel composition is evaluated according to the amount of deposition. The greater the deposition amount, the worse the detergency and dispersibility. On the contrary, the smaller the deposition amount, the better the detergency and dispersibility. The test results are shown in Table 3.
采用SH/T0175的方法测定各种调合柴油组合物总不溶物的量(单位：mg/100mL)，从而评定它们的稳定性。总不溶物的量越大则稳定性越差，反之若总不溶物的量越小则稳定性越好，其测试结果示于表3中。The method of SH/T0175 was used to measure the amount of total insoluble matter (unit: mg/100mL) of various blended diesel oil compositions, so as to evaluate their stability. The greater the amount of total insolubles, the poorer the stability; on the contrary, the smaller the amount of total insolubles, the better the stability. The test results are shown in Table 3.
表3table 3
由表3的结果可以看出，加入生物柴油后，含生物柴油的调合燃料的氧化安定性、稳定性以及清净分散性与石油柴油相比都变差。含有组分a和组分b或者组分a与组分b和组分c的混合物作为添加剂而得到的本发明的生物柴油组合物的氧化安定性、稳定性和分散性都有很大程度的改善，组分a和组分b效果出现协同效应，其效果比对比例效果明显增强。而仅含有传统酚型或胺型抗氧剂作为抗氧剂时，所得生物柴油调合燃料的稳定性和清净分散性的改善效果不明显。From the results in Table 3, it can be seen that after adding biodiesel, the oxidation stability, stability and detergency of the blended fuel containing biodiesel are all worse than those of petroleum diesel. The oxidation stability, stability and dispersibility of the biodiesel composition of the present invention obtained by containing component a and component b or a mixture of component a and component b and component c as additives are all greatly improved Improvement, a synergistic effect appears in the effect of component a and component b, and its effect is obviously stronger than that of the comparative example. However, when only traditional phenolic or amine antioxidants were used as antioxidants, the stability and detergency and dispersibility of biodiesel blended fuels were not significantly improved.
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| CN103254945B (en)* | 2012-02-17 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of method of Dresel fuel compositions and raising oxidation stability of biodiesel |
| CN103254944B (en)* | 2012-02-17 | 2015-10-28 | 中国石油化工股份有限公司 | A kind of method of Dresel fuel compositions and raising oxidation stability of biodiesel |
| CN104946352B (en)* | 2014-03-25 | 2017-11-03 | 中国石油化工股份有限公司 | Lubricant oil composite |
| CN105779085B (en)* | 2016-02-26 | 2018-10-23 | 北京雅士科莱恩石油化工有限公司 | A kind of diesel oil detergent and preparation method thereof for saving fuel oil containing friction improver |
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