CN102977949B - Low-proportion methanol gasoline compound additive - Google Patents
Low-proportion methanol gasoline compound additive Download PDFInfo
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- CN102977949B CN102977949B CN201210547871.6A CN201210547871A CN102977949B CN 102977949 B CN102977949 B CN 102977949B CN 201210547871 A CN201210547871 A CN 201210547871A CN 102977949 B CN102977949 B CN 102977949B
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Abstract
The invention discloses a low-proportion methanol gasoline compound additive. The low-proportion methanol gasoline compound additive is formed by mixing 40-60% by weight of power promoting agent with 40-60% by weight of anti-phase separation agent, wherein the power promoting agent is obtained by taking aviation kerosene and unsymmetrical dimethylhydrazine as raw materials, performing reflux reaction under the action of cerium nitrate and further performing decompression separation; and the anti-phase separation agent is obtained by mixing 15-25% by weight of methoxyethoxy methane mixture, 30-40% by weight of methylal, 20-30% by weight of isooctanol, 15-25% by weight of xylene and 0.1-0.5% by weight of polyethenoxy ether type surface active agent, and performing heating reflux for 4-5 hours. The additive disclosed by the invention can significantly improve the power performance of methanol gasoline and enhances the stability of the methanol gasoline, and the adding quantity is small.
Description
Technical field
The invention belongs to methanol fuel for vehicles technical field, relate to a kind of Vehicular methanol petrol additive.
Background technology
China is the few oily country of a rich coal, and rationally utilizing coal resource, Development of Coal chemical industry is the necessary means that solves energy problem in China's Economic development.Methyl alcohol aboundresources, can regenerate, and belongs to biomass energy.Methanol fuel is uniquely now can with coal and Sweet natural gas etc., make the economical liquid fuel of raw material scale operation, and mature production technology, stores easy to use.
Methyl alcohol is added on and in gasoline, is prepared into methanol gasoline and mixes burning in the mode of blending, is the simplest methanol fuel using method, and countries in the world all conduct extensive research this.With methanol fuel and the composite M of solubility promoter series clean methanol gasoline, especially the low ratio methanol gasoline of M5～M30, if M15 (adding 15% methyl alcohol in gasoline) methanol gasoline is as automobile-used propellant combination, be applied to respectively various petrol engines, can under the condition that does not change existing engine structure, substitute gasoline product and use (substituting than 1:1.05), and can be mixed with processed oil.
Yet, in the production and use of methanol gasoline, find that it exists following problem.
1. poor water resistance
The water tolerance problem of low ratio methanol gasoline is a problem of puzzlement methanol gasoline research always, in transportation, storage process, in low ratio methanol gasoline, sneak into micro-water, for example in M15, surpass 1 ‰, can destroy system balance, make methanol gasoline occur the phenomenons such as muddiness, layering, have a strong impact on use.
2. calorific value reduces
The calorific value of methyl alcohol is 1916MJ/kg, is only 45% of gasoline heat value (43150MJ/kg).Therefore, use after methanol gasoline, the oil consumption of engine increases with the increase of methyl alcohol incorporation.Bibliographical information, while using M10 methanol gasoline, oil consumption increases approximately 5%.
Research through many decades, the technical problem that low ratio methanol gasoline runs in using is resolved substantially, as 200510012700.3 employing Methylal(dimethoxymethane) and the butanols composition of proportions mutual soluble additive with 4:6, add-on approximately 3% can solve the lamination problem of methanol gasoline substantially.Yet its add-on is large, and higher according to account cost.
People have carried out large quantity research for the dynamic property of low ratio methanol gasoline, find that the high benzene class organic compound, nitro-compound etc. of some high ratio of carbon-hydrogen have promoter action to burning.As 200510012700.3 disclosed power promotors make as follows: aviation kerosene and anhydrous diamine (H
2nNH
2) with the weight proportion of 8:2, mix, under 80 ℃ of steam heating, isothermal reaction is 4 hours, then rectifying under 120～140 ℃, 0.09MPa vacuum tightness, and overhead product regulates pH value to 8.5, obtains power promotor; The aromatic hydrocarbons of 200810233186.X, 200810000485.9,200610056902.2,200610018445.8,200610008261.3, the employing ferrocene such as 01104115.3 and high ratio of carbon-hydrogen, isomeric alkane ether etc. improve the combustion heat value of methanol gasoline.Superoxide is made to mixture with 7～25% ratio and methanol mixed as special dibutyl superoxide, again this mixture is mixed and makes methanol gasoline with the ratio of 1:1 with gasoline, have good dynamic property, stability, cold start-up power is not less than single gasoline.Add a certain proportion of ether compound and the methanol gasoline that a small amount of anticorrosive agent, sanitising agent mediation form, during use, do not need to transform engine parts, also there is good dynamic property, intermiscibility and cold starting property.Other additive can improve the package stability (content of methyl alcohol in gasoline) of methanol gasoline as Methylal(dimethoxymethane).
Summary of the invention
The object of this invention is to provide a kind of low ratio methanol gasoline composite additive, the object that can significantly improve methanol gasoline dynamic property and strengthen methanol gasoline stability to reach a small amount of addition.
Low ratio methanol gasoline composite additive of the present invention is comprised of the power promotor of 40～60wt% and the resisting phase separation agent of 40～60wt% mixing.
Wherein, described power promotor is that to take aviation kerosene and unsymmetrical dimethyl hydrazine be raw material, and under cerous nitrate effect, back flow reaction obtains, and engine pedestal test result shows, its dynamic property increases by 35%.
The concrete preparation method of described power promotor is: 80～90wt% aviation kerosene is mixed with 5～8wt% unsymmetrical dimethyl hydrazine, add 0.5～2wt% cerous nitrate, under reflux temperature, isothermal reaction is 4～6 hours, cut before distilling out 190 ℃ under normal pressure, pH value to 6.5～8.5 that regulate overhead product, obtain power promotor.
Described resisting phase separation agent is that the polyethenoxy ether class tensio-active agent by 15～25wt% methoxy ethoxy methane mixture, 30～40wt% methylal, 20～30wt% isooctyl alcohol, 15～25wt% dimethylbenzene and 0.1～0.5wt% is used after reflux 4～5h.
The methyl alcohol of polarity and nonpolar gasoline system are the partial miscibility Two Liquid Phases systems with upper critical temperature.When methanol content is less than 5% and while being greater than 70%, the intermiscibility of methyl alcohol and gasoline is fine, and methanol content is between 5～70% time, and demixing phenomenon can occur for the two.Methanol gasoline as automobile fuel must evenly be stablized, and prevent layering, makes uniform and stable methanol gasoline, generally need to take to add the way of solubility promoter.Aromatic hydrocarbons has significant polarity and hydrogen bond avidity, and the polarity that the existence of Aromatic Hydrocarbon in Gasoline can reduce between methyl alcohol-gasoline is poor, and its stability is strengthened.The oil product phase separation temperature that aromaticity content is high is lower.Isomerization of paraffins degree is higher, and phase separation temperature is lower, and stability is also better.Therefore, the present invention adopts the mixture of methoxy ethoxy methane, methylal, isooctyl alcohol, dimethylbenzene as resisting phase separation agent.
Low-proportion methanol gasoline additive provided by the invention can significantly improve the dynamic property of methanol gasoline and can strengthen the stability of methanol gasoline, and it uses addition is only 0.5～5%, and addition is few.Low-proportion methanol gasoline additive preparation method of the present invention is simple, and cost is low, efficiently solves dynamic property and the resisting phase separation performance of low ratio methanol gasoline.
Embodiment
Embodiment 1
In the four-hole bottle with stirring, thermometer, feed hopper and prolong, add 90g aviation kerosene, the anhydrous unsymmetrical dimethyl hydrazine of 8g, under stirring, be warming up to 25 ℃, add 2g cerous nitrate, be warming up to reflux temperature, isothermal reaction 2h.Filter out after completion of the reaction the solid particulate in reaction solution, air distillation goes out the cuts before 190 ℃, and the pH value of Glacial acetic acid regulator solution of take is 8.5, obtains power promotor 95g.
In the four-hole bottle with stirring, thermometer, prolong, add 15mL methyl alcohol (0.375mol), 19mL formalin (containing formaldehyde 0.25mol), 21.5mL ethanol (0.375mol), 10g molecular sieve, mix and be warming up to 80 ℃, the disposable 2g cation exchange resin catalyst that adds, after reaction 2h, distillation obtains the clarified liq 40.5g of methoxy ethoxy methane blended liquid.GC analyzes formaldehyde residue 10%, oxyethyl group methoxy methylmethane productive rate 45%.
In the four-hole bottle with stirring, thermometer, prolong, add the above-mentioned methoxy ethoxy methane blended of 20g liquid, 35g methylal, 25g isooctyl alcohol, 20g dimethylbenzene and 0.2g tween-80, reflux 4h at 40 ℃, reaction finishes rear cooling and obtains light yellow clarifying liquid body and be resisting phase separation agent.
300g power promotor is mixed with the agent of 200g resisting phase separation, and allotment obtains low ratio methanol gasoline composite additive.
In the M15 of 100kg methanol gasoline, add 500g composite additive, evidence, solubization is increased to 0.55% from original 0.25% at 25 ℃.Bench testing shows, in M15 methanol gasoline, adds after composite additive, and during full load different tests rotating speed, the maximum amplification of torque is 5.39%, minimum amplification 0.61%.
Embodiment 2
The additive 700g of embodiment 1 preparation is added in 100kgM30 methanol gasoline, evidence, solubization is increased to 0.65% from original 0.50% at 25 ℃.Bench testing shows, in M15 methanol gasoline, adds after composite additive, and during full load different tests rotating speed, the maximum amplification of torque is 8.25%, and minimum amplification is 1.30%.
Embodiment 3
The additive 100g of embodiment 1 preparation is added in 100kgM5 methanol gasoline, evidence, solubization is increased to 0.15% from original 0.10% at 25 ℃.Bench testing shows, in M15 methanol gasoline, adds after composite additive, and during full load different tests rotating speed, the maximum amplification of torque is 6.30%, and minimum amplification is 4.25%.
Embodiment 4
Resisting phase separation agent raw material replaces isooctyl alcohol with n-Octanol, and consumption is still 25g, and other are with embodiment 1.At 25 ℃ of the composite additives that prepare, solubization is 0.58%.
Embodiment 5
Resisting phase separation agent stock chart surface-active agent replaces tween-80 with sorbester p17, and consumption is constant, and other conditions are 0.50% with solubization at 1,25 ℃ of embodiment.
Embodiment 6
The composite additive that adds 1kg embodiment 5 in the M15 of 100kg methanol gasoline, evidence, solubization is 0.75% at 25 ℃.Bench testing shows, in M15 methanol gasoline, adds after composite additive, and during full load different tests rotating speed, the maximum amplification of torque is 6.39%, minimum amplification 1.10%.
Claims (1)
1. a low ratio methanol gasoline composite additive, is mixed and is formed by the power promotor of 40～60wt% and the resisting phase separation agent of 40～60wt%;
Wherein, described power promotor is that to take 90wt% aviation kerosene and 8wt% unsymmetrical dimethyl hydrazine be raw material, and under the effect of 2wt% cerous nitrate, under reflux temperature, isothermal reaction is 4～6 hours, cut before distilling out 190 ℃ under normal pressure, regulates pH value to 6.5～8.5 of overhead product to obtain;
Described resisting phase separation agent is by 15～25wt% methoxy ethoxy methane mixture, 30～40wt% methylal, 20～30wt% isooctyl alcohol, after polyethenoxy ether class tensio-active agent Hybrid Heating backflow 4～5h of 15～25wt% dimethylbenzene and 0.1～0.5wt%, obtain, wherein, described methoxy ethoxy methane mixture is prepared by the following method: by 0.375mol methyl alcohol, formalin containing 0.25mol formaldehyde, 0.375mol ethanol, the mixing of 10g molecular sieve is warming up to 80 ℃, the disposable 2g cation exchange resin catalyst that adds, reaction 2h, distillation obtains methoxy ethoxy methane blended liquid clarified liq.
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| CN201210547871.6A CN102977949B (en) | 2012-12-18 | 2012-12-18 | Low-proportion methanol gasoline compound additive |
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| CN102977949B true CN102977949B (en) | 2014-08-13 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR3041360B1 (en) * | 2015-09-22 | 2019-07-12 | IFP Energies Nouvelles | OPTIMAL COMPOSITION OF CARBUREACTOR WITH THERMAL STABILITY AND IMPROVED OXIDATION |
| CN108300526A (en) * | 2018-03-12 | 2018-07-20 | 安徽淼淼新能源有限公司 | A kind of fuel oil additive formula and preparation method thereof |
| CN108384590A (en) * | 2018-03-20 | 2018-08-10 | 孙高杰 | A kind of gasoline additive and preparation method thereof |
| CN113088347B (en) * | 2021-04-09 | 2023-02-07 | 重庆邑丰新能源有限公司 | Modified methanol fuel for ignition type vehicle and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1727452A (en) * | 2005-07-29 | 2006-02-01 | 阳红纲 | High-powered methanol gasoline in high assay |
| CN101508919A (en) * | 2009-03-06 | 2009-08-19 | 张犀诚 | Methanol gasoline mixed fuel and method of preparing the same |
| CN101724474A (en) * | 2008-10-14 | 2010-06-09 | 陈若歆 | Mode for preparing M15-M100 complexing methanol petrol and gas normal-temperature liquefaction mixed combustion technology |
| CN102071075A (en) * | 2009-11-20 | 2011-05-25 | 济南开发区星火科学技术研究院 | Methanol gasoline solubilizer |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1727452A (en) * | 2005-07-29 | 2006-02-01 | 阳红纲 | High-powered methanol gasoline in high assay |
| CN101724474A (en) * | 2008-10-14 | 2010-06-09 | 陈若歆 | Mode for preparing M15-M100 complexing methanol petrol and gas normal-temperature liquefaction mixed combustion technology |
| CN101508919A (en) * | 2009-03-06 | 2009-08-19 | 张犀诚 | Methanol gasoline mixed fuel and method of preparing the same |
| CN102071075A (en) * | 2009-11-20 | 2011-05-25 | 济南开发区星火科学技术研究院 | Methanol gasoline solubilizer |
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Effective date of registration: 20160705 Address after: 030006, Wharton building, 88 development road, 12 hi tech Development Zone, Shanxi, Taiyuan Patentee after: Shanxi alcohol ether cleaning fuel industry technology center (Co., Ltd.) Address before: 030006 No. 266, Changzhi Road, hi tech Zone, Shanxi, Taiyuan Patentee before: Shanxi Huadun Industry Co., Ltd. |
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Effective date of registration: 20190716 Address after: Room 410, Office Building, Venous Industry Park, Zhenjiang New District, Jiangsu Province Patentee after: CRPC Innovation Energy Co., Ltd. Address before: 030006, Wharton building, 88 development road, 12 hi tech Development Zone, Shanxi, Taiyuan Patentee before: Shanxi alcohol ether cleaning fuel industry technology center (Co., Ltd.) |