WO2018000181A1 - 醇基燃料及其应用 - Google Patents

醇基燃料及其应用 Download PDF

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Publication number
WO2018000181A1
WO2018000181A1 PCT/CN2016/087416 CN2016087416W WO2018000181A1 WO 2018000181 A1 WO2018000181 A1 WO 2018000181A1 CN 2016087416 W CN2016087416 W CN 2016087416W WO 2018000181 A1 WO2018000181 A1 WO 2018000181A1
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fuel
gasoline
alcohol
methanol
mixed
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PCT/CN2016/087416
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English (en)
French (fr)
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陈鸿林
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陈鸿林
陈淑敏
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Priority to PCT/CN2016/087416 priority Critical patent/WO2018000181A1/zh
Publication of WO2018000181A1 publication Critical patent/WO2018000181A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only

Definitions

  • the invention relates to the field of fuel, in particular to an alcohol-based fuel prepared by blending a lower aliphatic alcohol with an aromatic component, which can be used for a gasoline vehicle, and is more efficient and environmentally friendly.
  • the raw materials for the production of methanol are mainly coal, natural gas, coalbed methane, coke oven gas, etc., and even high-sulfur inferior coal and coke oven gas can be used to produce methanol.
  • methanol fuels namely methanol gasoline and ethanol gasoline.
  • Ethanol gasoline refers to motor gasoline containing 10% ethanol, and so-called methanol fuel is made by using methanol (usually industrial methanol or fuel methanol) through appropriate denatured alcohol additives and national standard gasoline (or component oil).
  • methanol fuel usually industrial methanol or fuel methanol
  • national standard gasoline or component oil
  • methanol fuel The characteristics and application research of methanol fuel have confirmed that the calorific value of methanol is low and the swelling property is not good. If it is directly used as a fuel for engines or combustion equipment, unless the injection mechanism is modified to increase the instantaneous discharge amount of methanol, Otherwise, it is difficult to meet the requirements of light-off and full combustion, especially when replacing gasoline for vehicles, increasing the amount of methanol injection.
  • the methanol that is not fully burned not only produces toxic emissions, but also has a cold start performance of the car.
  • the retention of methanol also causes some corrosion to the fuel tank and carburetor. Therefore, the use of methanol to mix gasoline to replace the use of fuel requires not only the modification of the equipment, but also the introduction of suitable additives in the fuel composition to make it a denatured alcohol to improve combustion performance.
  • patent application CN201510360721.8 discloses a highly efficient methanol gasoline additive which is prepared from the following parts by weight of raw materials: ethyl oleate 5 ⁇ 10 parts, 3 ⁇ 5 parts of xylene, 7 ⁇ 9 parts of octane, 0.5 ⁇ 2 parts of potassium chloride, 5 ⁇ 9 parts of di-tert-butyl-p-cresol and 11 ⁇ 14 parts of 2-methoxybenzothiazole.
  • Patent application CN201410552679.5 discloses a methanol gasoline for vehicles, which is prepared from the following raw materials by weight: 65-85 parts of methanol, 5-12 parts of gasoline, 0.8-1.5 parts of paraffin oil, and 2-6 parts of glycerin. 1 to 5 parts of acetone, 1 to 5 parts of amide, 0.8 to 3 parts of t-butyl acetate, 1 to 4 parts of dibutyl phthalate, 0.5 to 1.5 parts of glyceryl monostearate, 1 to 5 of ethylbenzene Parts, 1 to 4 parts of t-butanol, 0.2 to 0.5 parts of ferric chloride.
  • the methanol used in the methanol gasoline of the vehicle has high oxygen content, complete combustion, no black smoke, no carbon deposit, no black bottom, no residual liquid residue, low exhaust gas emission after combustion, clean and environmental protection, stable product performance, and calorific value. High, low cost, safe and reliable, no need to modify the engine, can directly replace gasoline, a wide range of applications.
  • Patent application CN201410574610 discloses a methanol gasoline gasoline compounding agent for vehicle and a preparation method thereof, and the methanol gasoline gasoline compounding agent for vehicle is prepared from the following mass percentage materials: triethanolamine: 4%-5%, liquid paraffin wax: 30%-35 %, Tween-80:3%-5%, oleic acid: 3.5%-6%, butanol: 25%-28%, isoprene Alcohol: 12% - 14%, acetone: 5% - 8%, ethylene glycol monobutyl ether: 1% - 5%, kerosene: 5% - 6%, benzene: 6% - 10%, the preparation method is as follows: In one step, the liquid paraffin is mixed with butanol, triethanolamine and isoamyl alcohol in a ratio of 6:5:1:2.4-8.75:7:1:3.5, and the second step is Tween-80 and oleic acid.
  • Acetone is mixed in a ratio of 1:0.7:1 ⁇ 1:2:2.67.
  • the third step is the ratio of ethylene glycol monobutyl ether to kerosene and benzene according to 1:1:1.2 ⁇ 1:6:10. Mix and reserve, and finally take the three kinds of blends to be the finished product.
  • the raw materials required for the methanol-gasoline compounding agent for the vehicle are abundant and easy to obtain, and there is no "three wastes", which is safe, environmentally friendly, and simple in process, and can effectively solve the series of technical problems existing in the high-low vehicle methanol gasoline finished products.
  • the invention provides an alcohol-based fuel, which has simple composition and convenient deployment, and can not only fully utilize the excess resources of the coal chemical industry, and the prepared fuel can be directly used by a gasoline engine without black smoke emission.
  • the alcohol-based fuel provided by the present invention comprises a lower aliphatic alcohol and a methyl aromatic hydrocarbon which are mixed in a mass ratio of 15-85%: 85-15%, and a gasoline fraction added in a mass ratio of 0-70%.
  • the present invention provides an alcohol-based fuel, wherein the lower aliphatic alcohol is usually methanol, ethanol or a mixture thereof.
  • the present invention provides an alcohol-based fuel, wherein the methyl aromatic hydrocarbon is preferably toluene, xylene or a mixture thereof.
  • the alcohol-based fuel of the present invention can be obtained by blending only a lower aliphatic alcohol with a methyl aromatic hydrocarbon, or an appropriate amount of a gasoline fraction can be blended by an external method to further improve the combustion performance of the fuel.
  • the invention also provides for the use of the alcohol based fuel as a fuel for a gasoline vehicle.
  • the alcohol-based fuel of the present invention solves the low calorific value of the lower aliphatic alcohol, the insufficient combustion, and thus the methanol fuel such as poor high-speed power performance, poor acceleration, and emission of black smoke by introducing appropriate methyl aromatic hydrocarbons into the lower aliphatic alcohol.
  • the common drawback is that the alcohol-based fuel can directly replace the motor gasoline without modifying the automobile engine, and is more convenient to be used as an alternative fuel for gasoline; the introduction of the alcohol-based fuel of the invention is beneficial to make full use of the surplus industry in the coal chemical product chain. Methanol and ethanol provide a better and cheaper alternative to the fuel market.
  • the alcohol-based fuel of the present invention may further comprise an added gasoline fraction, which not only helps to increase the octane number and flash point of the alcohol-based fuel, but also adds the alcohol-based fuel of the present invention to the gasoline as a large proportion of additives.
  • an added gasoline fraction which not only helps to increase the octane number and flash point of the alcohol-based fuel, but also adds the alcohol-based fuel of the present invention to the gasoline as a large proportion of additives.
  • As a mixed fuel while ensuring the combustibility of existing gasoline, it introduces green energy and reduces the cost and price of existing gasoline.
  • the inventors of the present invention have fully studied various alcohol-based fuels which have been reported and used, and determined that the octane numbers of pure methanol ethanol and toluene xylene are both more than 100, and it has been found that methyl aromatic hydrocarbons such as toluene and xylene are Low-grade fatty alcohols, such as methanol and ethanol, are appropriately formulated without the need for components such as various fatty acids (fats), organic acid salts, emulsifiers, etc., which are more convenient to prepare and use, and which are advantageous for fuel quality due to less added components. Stable.
  • the alcohol-based fuel provided by the present invention comprises a lower aliphatic alcohol and a methyl aromatic hydrocarbon which are mixed in a mass ratio of 15-85%: 85-15%, and a gasoline fraction added in a mass ratio of 0-70%.
  • the lower aliphatic alcohol of the alcohol-based fuel is usually industrial ethanol or industrial methanol, and the methyl aromatic hydrocarbon is generally selected from toluene and/or xylene, for example, an appropriate amount of toluene or xylene or a mixture thereof is introduced in industrial methanol, and the calorific value of the fuel Significantly improved, no need to modify the engine, the use of the existing gasoline engine can meet the needs of light-off and full combustion.
  • the lower aliphatic alcohol is The mass ratio of the methyl aromatic hydrocarbon may be 15-85%: 85-15%; more specifically, the mass ratio of the lower aliphatic alcohol to the methyl aromatic hydrocarbon may be 30-70%: 70-30%, or 40-60%: 60-40%, the lower aliphatic alcohol and methyl aromatic hydrocarbon can be controlled in the implementation process, which is more convenient for operation.
  • the alcohol-based fuel of the present invention may further comprise a certain amount of gasoline fraction in an externally added manner, and may be a commercial gasoline of various specifications (labels), or may be a corresponding gasoline segment distillate oil from the oil industry chain.
  • it may be straight-run gasoline, coker gasoline (thermal cracked gasoline), catalytic cracking gasoline, catalytic reforming gasoline, hydrocracked gasoline, alkylated gasoline, synthetic gasoline, etc., or the main component is C5-C12.
  • Distillates such as aliphatic hydrocarbons and naphthenes, the distillation range is generally 30 ° C - 220 ° C.
  • the addition of the gasoline fraction facilitates an increase in the octane number of the fuel while also increasing the flash point, and the added gasoline fraction may be added in an amount of 0-70%.
  • the addition of the gasoline fraction is not too high (except for the case where the alcohol-based fuel of the present invention is used as a gasoline additive), that is, the external ratio should not exceed 70% (in the case of lower aliphatic alcohols and The total mass of the aromatic hydrocarbons is based on the basis), especially not more than 40%, for example, the gasoline fraction is 10-40%.
  • the addition of the gasoline fraction is based on the total amount of the lower aliphatic alcohol and methyl aromatic hydrocarbon compound.
  • the alcohol-based fuel of the invention can be directly used as the fuel oil of the gasoline vehicle without adjusting or modifying the automobile engine.
  • the on-road test of the gasoline vehicle shows that the engine is started and driven by using the alcohol-based fuel. The situation is no different from ordinary gasoline vehicles, and it can achieve basically no black smoke emissions.
  • test methods for the obtained octane number and flash point (closed flash point) of the alcohol-based fuel in the examples are standard operations or conventional methods in the art, and will not be further described herein.
  • the "mixed industrial methanol ethanol” used means work unless otherwise specified.
  • the product of methanol and industrial ethanol mixed in any ratio, the ratio of the two alcohols is not limited, and has no effect on the detection of the properties of the final fuel oil; similarly, “mixed toluene xylene” also refers to a mixture of toluene and xylene.
  • mixing ratio of the two kinds of toluene there is no influence on the property detection of the final fuel oil.
  • the methanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the methanol fuel was tested to have an octane number of 98 and a flash point of 5 °C.
  • the methanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 98 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the mixed industrial methanol ethanol and the mixed toluene xylene were mixed at a mass ratio of 70%: 30%, and the mixed methyl ethoxide fuel of the present example was obtained after blending.
  • the methyl alcohol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the mixed industrial methanol ethanol and the mixed toluene xylene were mixed at a mass ratio of 80%: 20%, and the mixed methyl ethanol fuel of the present example was obtained after blending.
  • the methyl alcohol fuel was tested to have an octane number of 98 and a flash point of 5 °C.
  • the mixed industrial methanol ethanol and the mixed toluene xylene were mixed at a mass ratio of 60%:40%, and the mixed methyl ethoxide fuel of the present example was obtained after blending.
  • the methyl alcohol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the methanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the methanol fuel was tested to have an octane number of 98 and a flash point of 5 °C.
  • Industrial methanol and mixed toluene xylene are mixed according to a mass ratio of 60%:40%, and are obtained after blending.
  • the methanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 98 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the methanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the methanol fuel was tested to have an octane number of 98 and a flash point of 5 °C.
  • the methanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 98 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the mixed industrial methanol ethanol and the mixed toluene xylene were mixed at a mass ratio of 70%: 30%, and 10% of No. 90 gasoline was added, and the mixed methyl ethoxide fuel of the present example was obtained after blending.
  • the methyl alcohol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the methyl alcohol fuel was tested to have an octane number of 98 and a flash point of 5 °C.
  • the methyl alcohol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the methanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • Industrial methanol and mixed toluene xylene are mixed according to 80%: 20% by mass, adding 10% straight-run gasoline (or gasoline fraction, distillation range 30 °C -220 °C, the main component is C5-C12 aliphatic hydrocarbons and naphthenes) After the blending, the methanol fuel of the present example was obtained.
  • the methanol fuel was tested to have an octane number of 98 and a flash point of 5 °C.
  • the methanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 98 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the methanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the methanol fuel was tested to have an octane number of 98 and a flash point of 5 °C.
  • the methanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 98 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the mixed industrial methanol ethanol and mixed toluene xylene were mixed at a mass ratio of 70%: 30%, and 40% of No. 90 gasoline was added, and the mixed methyl ethoxide fuel of the present example was obtained after blending.
  • the mixed methyl ethanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the mixed methyl ethanol fuel was tested to have an octane number of 98 and a flash point of 5 °C.
  • the mixed industrial methanol ethanol and the mixed toluene xylene were mixed at a mass ratio of 60%:40%, and 40% of the No. 90 gasoline was added, and the mixed methyl ethanol fuel of the present example was obtained after blending.
  • the mixed methyl ethanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the methanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the methanol fuel was tested to have an octane number of 98 and a flash point of 5 °C.
  • the methanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 98 and a flash point of 5 °C.
  • the ethanol fuel was tested to have an octane number of 97 and a flash point of 5 °C.
  • Test 1 Gasoline engine test
  • the alcohol-based fuel of the above embodiment is used for a gasoline engine to test the power and emissions;
  • Test car BMW 530 sedan
  • test fuel oil was 70% industrial ethanol + 30% xylene (Example 4), 70% industrial ethanol + 30% toluene (fuel detection index is the same as in Example 4), and the comparative test used petrochemical gasoline No. 95, the same operation and test;
  • the driving distance is 10 kilometers.
  • the driving operation includes constant speed driving and instant acceleration after deceleration.
  • the test driver reviews the operation feeling and visually checks the black smoke emission.
  • the ignition engine can start the vehicle immediately within 0.5 seconds, the alcohol-based fuel of the invention has no significant difference with the No. 95 petrochemical gasoline; the idle vehicle accelerates 20 times, the comparison test vehicle (95 No. of petrochemical gasoline) can observe more obvious black smoke emissions; the test vehicle (ethanol fuel) has not observed black smoke emissions visually;
  • Test equipment KEMA Koma small gasoline generator, 3KW3 kW single phase 220V;
  • the equipment is started 20 times under idling; 2) The equipment has no load and no power generation; 3) The equipment is under heavy load power generation;
  • the fuel oil for the test equipment is 70% industrial ethanol + 30% xylene (Example 4), 70% industrial ethanol + 30% toluene (fuel detection index is the same as in Example 4). Comparative test equipment using petrochemical gasoline No. 95;
  • the ignition engine of the test machine using the fuel of the invention can be started immediately within 0.5 seconds, and there is no significant difference from the equipment of the petrochemical gasoline No. 95, that is, the testing machine and the use of the fuel of the invention.
  • the comparison test machines for petrochemical gasoline all showed good startability, and there was no significant difference; the visual discharge situation was considered as no obvious black smoke emission;
  • the equipment has no load and no power generation.
  • the visual discharge is regarded as no obvious black smoke emission.
  • the alcohol-based fuel of the present invention is used in a gasoline engine and a gasoline small generator engine, and the combustion efficiency is significantly improved compared to petrochemical gasoline.

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Abstract

一种醇基燃料，其组成包括按照15‐85％：85‐15％的质量比相混配的低级脂肪醇和甲基芳烃，还包括按照0‐70％质量比外加的汽油馏分。该醇基燃料作为汽油的替代燃料更便于选择使用，更加高效环保，更加优质廉价。

Description

醇基燃料及其应用 技术领域
本发明涉及燃料领域，具体是涉及一种利用低级脂肪醇与芳烃组分调配而成的醇基燃料，该醇基燃料可以用于汽油车，更加高效和环保。
背景技术
全球能源的紧缺和环境问题的日益严重，迫使人们必须提升对燃料资源开发以及控制燃料对环境影响的关注和投入，寻求新的清洁替代能源已经成为全球性的课题。石油资源和煤炭资源作为多年来赖以生存的二大资源，在全球的存有量极不均衡。例如在中国，煤炭资源非常丰富而石油资源则相对匮乏，也导致石油制品日趋供应紧张且价格不断上涨，而石油资源的匮乏也制约了世界多数国家和地区的能源使用。为缓解石油供应紧张和环境污染问题，关注以替代石油能源为目的的可再生能源开发以及波及世界各主要国家和地区。
生产甲醇的原料主要是煤、天然气、煤层气、焦炉气等，甚至可以利用高硫劣质煤和焦炉气生产甲醇，由于煤炭行业的产业链转换，工业甲醇原料已经成为煤化工行业中的严重过剩产物，本身有毒性，需要严格控制排放。扩大甲醇资源的应用途径，既可以提高资源综合利用又可减少环境污染，已经是业内共识。近年来对甲醇制油的研究也非常多，除了煤化工行业通过MTO、MTP工艺等技术进行甲醇烃化、叠合、芳构等反应过程最终制成高清洁汽油的化学过程，另一个被关注的产品就是甲醇燃料，即甲醇汽油和乙醇汽油。乙醇汽油是指含10％乙醇的车用汽油，而所谓甲醇燃料是利用甲醇(一般是工业甲醇或燃料甲醇)通过适当的变性醇添加剂与国标汽油(或组分油)，按一定比例经严格调配而得到的一种新型清洁燃料，可以替代汽油用于各种汽油燃烧装置和引擎。
对于甲醇燃料的特性及应用研究已经证实，甲醇的热值偏低，溶胀性不好，如果直接作为燃料用于引擎或燃烧设备，除非对喷射机构加以改造来加大甲醇的瞬间喷出量，否则难以满足起燃和充分燃烧的要求，尤其是替代车用汽油时，增加甲醇喷射量，未能充分燃烧的甲醇不仅产生有毒物排放，而且车的冷启动性能明显不好，另一方面，甲醇的存留也会对油箱、化油器产生一定的腐蚀。所以，利用甲醇调配汽油来替代燃料的使用，不仅需要对设备进行改造，还需要在燃料组成中引入合适的添加剂，使之成为变性醇，达到提高燃烧性能的目的。
已经有报道的各种变性醇添加剂一般是多种成分的组合物，例如，专利申请CN201510360721.8，公开了一种高效的甲醇汽油添加剂，由以下重量份数的原料制成：油酸乙酯5‐10份，二甲苯3‐5份，辛烷7‐9份，氯化钾0.5‐2份，二叔丁基对甲酚5‐9份，2‐巯基苯并噻唑11‐14份，石油醚1‐3份，酰胺4‐5份，二乙二醇脂肪酸酯10‐13份，叔丁醇7‐10份，甲基叔丁基醚4‐8份，异戊醇2‐6份，二氧化钛9‐12份，山梨醇酐单油酸酯7.2‐10份，丙烯醇1.2‐3份。有益效果是可减少尾气中有毒物质的排放，提高燃烧效率，同时用量少，成本低。专利申请CN201410552679.5，公开了一种车用甲醇汽油，由以下重量份的原料配制而成：甲醇65～85份，汽油5～12份，石蜡油0.8～1.5份，甘油2～6份，丙酮1～5份，酰胺1～5份，乙酸叔丁酯0.8～3份，邻苯二甲脂二丁酯1～4份，单硬脂酸甘油酯0.5～1.5份，乙苯1～5份，叔丁醇1～4份，氯化铁0.2～0.5份。该车用甲醇汽油中甲醇的含氧量高，燃烧充分，无黑烟、不积炭、不黑锅底，无残液残渣，燃烧后的废气排放量低，清洁环保，产品性能稳定，热值高，成本低，安全可靠，无需改装发动机，可直接替代汽油，适用范围广。专利申请CN201410574610，公开一种车用甲醇汽油复合剂及其制备方法，车用甲醇汽油复合剂由以下质量百分数的原料配制而成：三乙醇胺：4％‐5％，液体石蜡：30％‐35％，吐温‐80：3％‐5％，油酸：3.5％‐6％，丁醇：25％‐28％，异戊 醇：12％‐14％，丙酮：5％‐8％，乙二醇一丁醚：1％‐5％，煤油：5％‐6％，苯：6％‐10％，制备方法如下：第一步将液体石蜡与丁醇、三乙醇胺、异戊醇按照6:5:1:2.4‐8.75:7:1:3.5之间的比例混合备用，第二步为吐温‐80与油酸、丙酮按照1:0.7：1‐1:2:2.67之间的比例混合备用，第三步为乙二醇一丁醚与煤油、苯按照1:1:1.2‐1:6:10之间的比例混合备用，最后取三种混合后即为成品。该车用甲醇汽油复合剂所需的原料丰富易得，无“三废”产生，安全、环保、工艺简单，能有效的解决现在高低车用甲醇汽油成品存在的系列技术问题。
类似的醇基燃料添加剂还有更多公开，可以看到，目前已经有报道的添加剂都是多种成分调配而成，通常研究和使用者根据自己的需要选择，所以选择的原料之间差异很大，有些还需要对添加剂的制备过程、以及最终的醇基燃料制备过程有特殊要求，导致成本增加，燃料性能的稳定和一致性也难保证。
发明内容
本发明提供一种醇基燃料，其组成简单，调配方便，不仅能充分利用煤化工行业的过剩资源，所制成的燃料可直接供汽油引擎使用，且无黑烟排放。
本发明提供的醇基燃料，其组成包括按照15‐85％：85‐15％的质量比相混配的低级脂肪醇和甲基芳烃，还包括按照0‐70％质量比外加的汽油馏分。
本发明提供的醇基燃料，其中，所述低级脂肪醇通常为甲醇、乙醇或它们的混合物。
本发明提供的醇基燃料，其中，所述甲基芳烃最好为甲苯、二甲苯或它们的混合物。
本发明的醇基燃料，可以仅利用低级脂肪醇与甲基芳烃调配得到，也可以通过外加方式调配进适量的汽油馏分，更进一步提升燃料的燃烧性能。
本发明还提供了所述醇基燃料作为汽油车燃料的应用。
本发明的醇基燃料通过在低级脂肪醇中引入适当的甲基芳烃，解决了低级脂肪醇热值偏低，燃烧不充分，以及因此产生高速动力表现差、加速不良及排放黑烟等甲醇燃料常见弊端，该醇基燃料可以直接替代车用汽油而无需对汽车引擎进行改造，作为汽油的替代燃料更便于选择使用；本发明醇基燃料的推出，利于充分利用煤化工产品链上过剩的工业甲醇和乙醇，为燃油市场提供更加优质廉价的石油替代品。另一方面，本发明的醇基燃料还可包括外加的汽油馏分，不仅利于提升醇基燃料的辛烷值和闪点，亦可以将本发明的醇基燃料作为大比例的添加剂加入汽油中，成为混合燃油，在保证现有汽油的燃烧性同时，引入了绿色能源，降低了现有汽油的成本与价格。
具体实施方案
本案发明人充分研究了目前已有报道和使用的各种醇基燃料，以及确定纯甲醇乙醇及甲苯二甲苯的辛烷值都超过100以上，发现将甲基芳烃，例如甲苯、二甲苯，与低级脂肪醇，例如甲醇、乙醇，加以适当调配，而不再需要诸如各种脂肪酸(脂)、有机酸盐、乳化剂等组分，制备和使用更加方便，由于添加组分少，利于燃料品质的稳定。
本发明提供的醇基燃料，其组成包括按照15‐85％：85‐15％的质量比相混配的低级脂肪醇和甲基芳烃，还包括按照0‐70％质量比外加的汽油馏分。所述醇基燃料的低级脂肪醇常用工业乙醇或工业甲醇，甲基芳烃一般选择甲苯和/或二甲苯，例如在工业甲醇中引入适量的甲苯或二甲苯或者它们的混合物，燃料的热值能显著提高，不需改造引擎，使用现有的汽油车引擎即可满足起燃和充分燃烧的需要。发明人的测试发现，甲基芳烃的加入量不宜过高，在上述范围内可根据所使用的低级脂肪醇的性质加以调整确定，以燃烧效率提高且无明显黑烟排放为宜。具体实施方案中，低级脂肪醇与 甲基芳烃的质量比可以为15‐85％：85‐15％；更具体地，低级脂肪醇与甲基芳烃的质量比可以为30‐70％：70‐30％，或者40‐60％：60‐40％，实施过程中可以控制低级脂肪醇与甲基芳烃基本等量，更便于操作。
本发明的醇基燃料中，还可以外加的方式包含一定量的汽油馏分，可以是目前的各类规格(标号)的商品化汽油，也可以是来自油品产业链上的相应汽油段馏分油，例如，可以为直馏汽油、焦化汽油(热裂化汽油)、催化裂化汽油、催化重整汽油、加氢裂化汽油、烷基化汽油、合成汽油等，也可以是主要成分为C5‐C12的脂肪烃和环烷烃等馏分油，馏程一般为30℃‐220℃。
汽油馏分的加入利于提高燃料的辛烷值，同时还起到升高闪点的效果，所述外加的汽油馏分的加入量可以为0‐70％。作为本发明提出的醇基燃料，外加汽油馏分的加入量不易过高(仅将本发明的醇基燃料作为汽油添加剂使用的情况除外)，即外加比例不应超过70％(以低级脂肪醇和甲基芳烃的总质量为基准)，尤其是一般不超过40％，例如外加汽油馏分为10‐40％。作为公知的知识，所述外加汽油馏分的加入量是以低级脂肪醇和甲基芳烃混配的总量为基准。
本发明的醇基燃料，特别是甲醇燃料油及乙醇燃料油，可以直接作为汽油车的燃料油，无需调整或改造汽车引擎，汽油车的上路试验显示，使用该醇基燃料，引擎发动和行驶状况均与普通汽油车无差别，且可以做到基本无黑烟排放。
以下通过具体实施例方案详细说明本发明的醇基燃料以及该醇基燃料的性质和特点，但不能理解为对本发明请求保护范围的任何限定。
实施例中对所得到的醇基燃料辛烷值和闪点(闭口闪点)的测试方法均为本领域的标准操作或常规方法，文中不再赘述。
实施例中，除非特别说明外，所使用的“混合工业甲醇乙醇”是指工 业甲醇与工业乙醇以任何比例混合的产物，二种醇的比例不受限制，对于最终燃料油的性质检测也没有影响；同样的，“混合甲苯二甲苯”也是指甲苯与二甲苯的混合物，二种甲苯在其中的混合比例亦没有限制，对于最终燃料油的性质检测也没有影响。
实施例1
工业甲醇与甲苯按照70％:30％的质量比混合，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值97，闪点5℃。
实施例2
工业甲醇与甲苯按照80％:20％的质量比混合，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值98，闪点5℃。
实施例3
工业甲醇与甲苯按照60％:40％的质量比混合，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值97，闪点5℃。
实施例4
工业乙醇与二甲苯按照70％:30％的质量比混合，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值97，闪点5℃。
实施例5
工业乙醇与二甲苯按照80％:20％的质量比混合，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值98，闪点5℃。
实施例6
工业乙醇与二甲苯按照60％:40％的质量比混合，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值97，闪点5℃。
实施例7
混合工业甲醇乙醇与混合甲苯二甲苯按照70％:30％的质量比混合，调配后得到本实施例的混合甲乙醇燃料。
经检测，该甲乙醇燃料的辛烷值97，闪点5℃。
实施例8
混合工业甲醇乙醇与混合甲苯二甲苯按照80％:20％的质量比混合，调配后得到本实施例的混合甲乙醇燃料。
经检测，该甲乙醇燃料的辛烷值98，闪点5℃。
实施例9
混合工业甲醇乙醇与混合甲苯二甲苯按照60％:40％质量比混合，调配后得到本实施例的混合甲乙醇燃料。
经检测，该甲乙醇燃料的辛烷值97，闪点5℃。
实施例10
工业甲醇与混合甲苯二甲苯按照70％:30％的质量比混合，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值97，闪点5℃。
实施例11
工业甲醇与混合甲苯二甲苯按照80％:20％的质量比混合，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值98，闪点5℃。
实施例12
工业甲醇与混合甲苯二甲苯按照60％:40％的质量比混合，调配后得到 本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值97，闪点5℃。
实施例13
工业乙醇与混合甲苯二甲苯按照70％:30％的质量比混合，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值97，闪点5℃。
实施例14
工业乙醇与混合甲苯二甲苯按照80％:20％的质量比混合，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值98，闪点5℃。
实施例15
工业乙醇与混合甲苯二甲苯按照60％:40％的质量比混合，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值97，闪点5℃。
实施例16
工业甲醇与甲苯按照70％:30％的质量比混合，并加入10％(以工业甲醇与甲苯的总质量计，以下相同)的90号汽油，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值97，闪点5℃。
实施例17
工业甲醇与甲苯按照80％:20％的质量比混合，加入10％的直馏汽油(或汽油馏分，馏程30℃‐220℃，主要成分为C5‐C12的脂肪烃和环烷烃)，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值98，闪点5℃。
实施例18
工业甲醇与甲苯按照60％:40％的质量比混合，并加入10％的90号汽油， 调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值97，闪点5℃。
实施例19
工业乙醇与二甲苯按照70％:30％的质量比混合，并加入10％的90号汽油，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值97，闪点5℃。
实施例20
工业乙醇与二甲苯按照80％:20％的质量比混合，加入10％的直馏汽油(或汽油馏分，馏程30℃‐220℃，主要成分为C5‐C12的脂肪烃和环烷烃)，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值98，闪点5℃。
实施例21
工业乙醇与二甲苯按照60％:40％的质量比混合，并加入10％的90号汽油，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值97，闪点5℃。
实施例22
混合工业甲醇乙醇与混合甲苯二甲苯按照70％:30％的质量比混合，并加入10％的90号汽油，调配后得到本实施例的混合甲乙醇燃料。
经检测，该甲乙醇燃料的辛烷值97，闪点5℃。
实施例23
混合工业甲醇乙醇与混合甲苯二甲苯按照80％:20％的质量比混合，加入10％的直馏汽油(或汽油馏分，馏程30℃‐220℃，主要成分为C5‐C12的脂肪烃和环烷烃)，调配后得到本实施例的混合甲乙醇燃料。
经检测，该甲乙醇燃料的辛烷值98，闪点5℃。
实施例24
混合工业甲醇乙醇与混合甲苯二甲苯按照60％:40％的质量比混合，并 加入10％的90号汽油，调配后得到本实施例的混合甲乙醇燃料。
经检测，该甲乙醇燃料的辛烷值97，闪点5℃。
实施例25
工业甲醇与混合甲苯二甲苯按照70％:30％的质量比混合，并加入10％的90号汽油，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值97，闪点5℃。
实施例26
工业甲醇与混合甲苯二甲苯按照80％:20％质量比混合，加入10％的直馏汽油(或汽油馏分，馏程30℃‐220℃，主要成分为C5‐C12的脂肪烃和环烷烃)，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值98，闪点5℃。
实施例27
工业甲醇与混合甲苯二甲苯按照60％:40％质量比混合，并加入10％的90号汽油，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值97，闪点5℃。
实施例28
工业乙醇与混合甲苯二甲苯按照70％:30％质量比混合，并加入10％的90号汽油，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值97，闪点5℃。
实施例29
工业乙醇与混合甲苯二甲苯按照80％:20％质量比混合，加入10％的直馏汽油(或汽油馏分，馏程30℃‐220℃，主要成分为C5‐C12的脂肪烃和环烷烃)，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值98，闪点5℃。
实施例30
工业乙醇与混合甲苯二甲苯按照60％:40％质量比混合，并加入10％ 的90号汽油，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值97，闪点5℃。
实施例31
工业甲醇与甲苯按照70％:30％质量比混合，并加入40％的90号汽油，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值97，闪点5℃。
实施例32
工业甲醇与甲苯按照80％:20％质量比混合，加入40％的直馏汽油(或汽油馏分，馏程30℃‐220℃，主要成分为C5‐C12的脂肪烃和环烷烃)，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值98，闪点5℃。
实施例33
工业甲醇与甲苯按照60％:40％质量比混合，并加入40％的90号汽油，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值97，闪点5℃。
实施例34
工业乙醇与二甲苯按照70％:30％质量比混合，并加入40％的90号汽油，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值97，闪点5℃。
实施例35
工业乙醇与二甲苯按照80％:20％质量比混合，加入40％的直馏汽油(或汽油馏分，馏程30℃‐220℃，主要成分为C5‐C12的脂肪烃和环烷烃)，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值98，闪点5℃。
实施例36
工业乙醇与二甲苯按照60％:40％质量比混合，并加入40％的90号汽油， 调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值97，闪点5℃。
实施例37
混合工业甲醇乙醇与混合甲苯二甲苯按照70％:30％质量比混合，并加入40％的90号汽油，调配后得到本实施例的混合甲乙醇燃料。
经检测，该混合甲乙醇燃料的辛烷值97，闪点5℃。
实施例38
混合工业甲醇乙醇与混合甲苯二甲苯按照80％:20％质量比混合，加入40％的直馏汽油(或汽油馏分，馏程30℃‐220℃，主要成分为C5‐C12的脂肪烃和环烷烃)，调配后得到本实施例的混合甲乙醇燃料。
经检测，该混合甲乙醇燃料的辛烷值98，闪点5℃。
实施例39
混合工业甲醇乙醇与混合甲苯二甲苯按照60％:40％质量比混合，并加入40％的90号汽油，调配后得到本实施例的混合甲乙醇燃料。
经检测，该混合甲乙醇燃料的辛烷值97，闪点5℃。
实施例40
工业甲醇与混合甲苯二甲苯按照70％:30％质量比混合，并加入40％的90号汽油，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值97，闪点5℃。
实施例41
工业甲醇与混合甲苯二甲苯按照80％:20％质量比混合，加入40％的直馏汽油(或汽油馏分，馏程30℃‐220℃，主要成分为C5‐C12的脂肪烃和环烷烃)，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值98，闪点5℃。
实施例42
工业甲醇与混合甲苯二甲苯按照60％:40％质量比混合，并加入40％的 90号汽油，调配后得到本实施例的甲醇燃料。
经检测，该甲醇燃料的辛烷值97，闪点5℃。
实施例43
工业乙醇与混合甲苯二甲苯按照70％:30％质量比混合，并加入40％的90号汽油，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值97，闪点5℃。
实施例44
工业乙醇与混合甲苯二甲苯按照80％:20％质量比混合，加入40％的直馏汽油(或汽油馏分，馏程30℃‐220℃，主要成分为C5‐C12的脂肪烃和环烷烃)，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值98，闪点5℃。
实施例45
工业乙醇与混合甲苯二甲苯按照60％:40％质量比混合，并加入40％的90号汽油，调配后得到本实施例的乙醇燃料。
经检测，该乙醇燃料的辛烷值97，闪点5℃。
试验例
试验一：汽油车引擎试验
将上述实施例的醇基燃料用于汽油车引擎，测试动力性和排放情况；
试验用车：宝马530轿车；
试验用燃料油为70％工业乙醇+30％二甲苯(实施例4)、70％工业乙醇+30％甲苯(燃料检测指标同实施例4)，对比试验采用95号石化汽油，同样的操作和测试；
试验过程：
1)停车状态下，反复熄火和启动引擎20次，测试冷启动性能；
2)停车状态，空转急加速20次，目测黑烟排放情况；
3)行驶距离10公里，行驶操作包括匀速行驶和减速后瞬间加速，试车员评述操作感受，目测黑烟排放情况。
试验现象评述：
所有车辆空转冷启动20次启动表现情况良好，点火引擎在0.5秒内可立即启动车辆，本发明的醇基燃料与95号石化汽油无明显差异；空转车辆急加速20次，对比试验车(95号石化汽油)目测能观察到较明显黑烟排放；试验车(乙醇燃料)目测已未观察到黑烟排放；
重载加速性及高速行驶下的黑烟排放观测，所有试验车和对比试验车无明显差异，均能看到较明显排放，重载加速性及高速行驶的动力表现情况，试验车优于对比试验车；感觉加速性及高速性反应，试验车优于对比试验车。
更换以上实施例记载的其它醇基燃料油，试验结果基本相同。
试验二、汽油小型发动机试验
试验设备：KEMA科马小型汽油发电机，3KW3千瓦单相220V；
试验内容：
1)设备空转下启动20次；2)设备无载不发电工作状态；3)设备重载发电工作状态；
分别观察动力性表现，并目测排放情况；试验设备用燃料油为70％工业乙醇+30％二甲苯(实施例4)、70％工业乙醇+30％甲苯(燃料检测指标同实施例4)，对比试验设备用95号石化汽油；
试验现象评述：
1)设备空转下启动20次情况下，使用本发明燃料的试验机点火引擎在0.5秒内能立即启动，与95号石化汽油的设备无明显差异，即，使用本发明燃料的试验机和使用石化汽油的对比试验机均表现良好的启动性，无明显差异；目测排放情况视为二者均无明显黑烟排放；
2)设备无载不发电工作状态：目测排放情况视为二者均无明显黑烟排放
3)重载发电工作状态，二者均表现正常，但使用本发明醇基燃料油的试验机目测无明显黑烟，而使用石化汽油的对比试验机则目测到轻微黑烟。
另外，使用80％甲醇或乙醇加20％甲苯或二甲苯或混合甲苯二甲苯的醇基燃料、使用70％甲醇或乙醇加30％甲苯或二甲苯或混合甲苯二甲苯的醇基燃料重复上述试验，均得到相似的结果。
结论：本发明的醇基燃料用于汽油车引擎和汽油小型发电机引擎，相比于石化汽油，燃烧效率明显提高。

Claims (9)

  1. 一种醇基燃料，其组成包括按照15‐85％：85‐15％的质量比相混配的低级脂肪醇和甲基芳烃，还包括按照0‐70％质量比外加的汽油馏分。
  2. 根据权利要求1所述的醇基燃料，其中，所述低级脂肪醇为甲醇、乙醇或它们的混合物。
  3. 根据权利要求1或2所述的醇基燃料，其中，所述甲基芳烃为甲苯、二甲苯或它们的混合物。
  4. 根据权利要求1‐3任一项所述的醇基燃料，其中，低级脂肪醇与甲基芳烃的质量比为20‐80％：80‐20％。
  5. 根据权利要求4所述的醇基燃料，其中，低级脂肪醇与甲基芳烃的质量比为30‐70％：70‐30％。
  6. 根据权利要求4所述的醇基燃料，其中，低级脂肪醇与甲基芳烃的质量比为40‐60％：60‐40％。
  7. 根据权利要求1‐6任一项所述的醇基燃料，其中，所述外加的汽油馏分的加入量不超过40％。
  8. 根据权利要求1或7所述的醇基燃料，其中，所述汽油馏分为商品化汽油，或来自油品产业链汽油馏分油。
  9. 权利要求1‐8任一项所述的醇基燃料作为汽油车及汽油燃烧系统燃料的应用。
PCT/CN2016/087416 2016-06-28 2016-06-28 醇基燃料及其应用 WO2018000181A1 (zh)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4357146A (en) * 1980-03-12 1982-11-02 Heeren James K Synthetic fuel for internal combustion engine
KR20020009543A (ko) * 2001-12-12 2002-02-01 성정숙, 김일두 알코올 연료 조성물
WO2003064567A1 (fr) * 2002-01-31 2003-08-07 Qiang Zhu Carburant complexe contenant de l'alcool, pouvant s'allumer facilement a basse temperature et degageant autant d'energie que de l'essence
CN1824738A (zh) * 2006-04-05 2006-08-30 黑龙江建业燃料有限责任公司 一种高效醇基汽油燃料添加剂的制备方法
CN101168688A (zh) * 2006-10-24 2008-04-30 张劲松 高适应性车用环保甲醇汽油

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4357146A (en) * 1980-03-12 1982-11-02 Heeren James K Synthetic fuel for internal combustion engine
KR20020009543A (ko) * 2001-12-12 2002-02-01 성정숙, 김일두 알코올 연료 조성물
WO2003064567A1 (fr) * 2002-01-31 2003-08-07 Qiang Zhu Carburant complexe contenant de l'alcool, pouvant s'allumer facilement a basse temperature et degageant autant d'energie que de l'essence
CN1824738A (zh) * 2006-04-05 2006-08-30 黑龙江建业燃料有限责任公司 一种高效醇基汽油燃料添加剂的制备方法
CN101168688A (zh) * 2006-10-24 2008-04-30 张劲松 高适应性车用环保甲醇汽油

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