CN110144246A - A kind of gasoline of motor fuel tank deicer and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of gasoline of motor fuel tank deicers and preparation method thereof, it is characterized in that the method described in the present invention is that the mutual solvent for being 1.5~3.5% by solubilizer, antirust agent, high-octane rating additive and weight percent is successively added in solvent step by step in the way of negative-pressure ward, each step is completed in closed kettle, to form the gasoline deicer.The method have the characteristics that not using surfactant; and it uses the mutual solvent tert-butyl alcohol and is added with weight percent for 1.5~3.5% ratio; and this product need to be only added in automotive oil tank with 0.3% ratio; it can achieve the effect that the moisture preferably removed in automotive oil tank and in transfer pipeline and improve octane number, while automotive oil tank and transfer pipeline metal can be protected not to generate corrosion.

Description

A kind of gasoline of motor fuel tank deicer and preparation method thereof

Technical field

The present invention relates to fuel system of automobile field more particularly to a kind of gasoline of motor fuel tank deicer and its preparation sides Method.

Background technique

Along with the fast development of auto industry, China has become main Automobile Market and automobile system in the world Make base.The power resources of automobile generally have fuel engines, gas engine according to the difference of power is provided in engine And the electronic energy.The fuel oil that fuel engines uses production, transport, storage process in, due to extraneous factor, no It is evitable to be mixed into micro moisture.First is that since fuel oil can dissolve micro moisture at a normal temperature, but dropped in temperature When low, the dissolubility of water accordingly becomes smaller, and the moisture of extra meltage will be assembled, since the specific gravity of water is greater than the specific gravity of oil, water Divide slowly to separate and be deposited in the knee or filter of oil circuit, causes fuel feeding discontinuous, and with the consumption of fuel oil It is cumulative；Second is that fuel tank will suck air to plug the gap, due to producing when fuel burning due to the consumption with fuel oil Biggish internal-external temperature difference is given birth to, the vapor in air can condense into liquid water in fuel tank and deposit, and air humidity is bigger Ponding is more.At this moment, when tank bottoms ponding is more and more, oil level is very low and refuels not in time, and oil pump can be by tank bottoms Water is directly pumped into engine, not only will affect fuel system normal fuel injection in this way, but also causes that gasoline combustion is insufficient, is difficult to Starting, unstable idle speed, asthma tremble, bad Acceleration and the failures such as flame-out, even results in the damage of fuel-system components.Automotive oil tank In these moisture two states are presented, one kind is dissolution water, and one kind is free water, and the two can be with temperature, humidity Variation mutually converts, and when ambient temperature is reduced to the freezing point of water, dissolution elutriation goes out, and is converted into free water；When ambient temperature and When humidity increases, free water will not be completely converted into dissolution water due to the relationship of solubility, these free waters can be in fuel tank Condense upon bottom.When fuel consumption it is more without being replenished in time when, free moisture will be pumped into engine and worked as by oil pump In, so that engine Idling wobble is occurred, is accelerated inability, or even can not start；It is aqueous in fuel tank when summer to also result in metal oil Chamber interior wall gets rusty, and on the strainer that scale crust is adsorbed on oil pump, the resistance of oil pump suction is made to become larger, causes engine oil suction not Foot, power dropping,；Temperature is too low when winter causes free water to condense the blocking that may cause oil circuit in oil circuit, causes to send out Motivation can not normally work.

Therefore addition deicer is usually required in vehicle fuel, using the hydrophilic interaction of deicer by the water in fuel oil Divide and dissolve each other, be evenly distributed on water in vehicle fuel, eliminates ponding and adversely affected caused by engine.

Various types of vehicle fuels on sale are with removing water emulsifier or fuel oil additive on the market.However for removing water and milk For agent, traditional emulsifier is larger, is added to fuel tank, can change the combustibility of fuel oil；And traditional fuel oil The emulsifier generally only effect of water removal cannot improve the comprehensive performance of gasoline without others additional technical effect.

Chinese patent (CN201210007792) discloses a kind of automotive oil tank water removal protective agent, it is characterized in that containing following The each component of mass percent: emulsifier 0.1-0.4%, metal corrosion inhibitor 0.01-0.5%, solvent 80-98%, solubilising Agent 1-15%.Its advantage is that: automotive oil tank water removal protective agent is added in automotive oil tank in 0.5% (V/V) ratio, not only The moisture in oil removal box and oil feed line can be quickly removed, winter combustion water content in oil ice blockage oil circuit and filter is prevented, disappears Except the engine shake that causes due to combustion water content in oil or the failures such as flame-out, it is ensured that engine work；It can also prevent The components such as fuel tank, oil pipe, oil pump corrode in fuel system, increasing service life of engine.Although above-mentioned patent is by using cream Agent solves the problems, such as moisture in automotive oil tank, still, except water emulsifier in immiscible each phase, often only one Single interaction point, emulsion stability is bad, can not reach preferable technical effect；In addition, the effect list of emulsifier One, it is not able to satisfy the multi-functional requirement of gasoline actual use.

Summary of the invention

For the deficiencies of the prior art, the present invention provides a kind of gasoline of motor fuel tank deicers and preparation method thereof, originally After mutual solvent is added in gasoline by invention, mutual solvent can increase the solubility of minor amount of water in the oil, when the temperature decreases Moisture not reason supersaturation and is precipitated, when humidity reduction, the moisture in fuel will not be to air evaporation.This is because mutually The hydroxyl of solvent has good hydrophily, it can form hydrogen bond association, and the hydrocarbon of mutual solvent with the minor amount of water molecule in fuel Base then has lipophilicity, can be dispersed in gasoline.Due to generating the reason of hydrogen bond between hydrone and mutual solvent, mutually Each molecule of solvent can at least will be kept in the solution, making water in fuel by the molecular associated matter of four moisture Solubility rises.While combining the solubility of increase water in the oil with dissolution water, mutual solvent shape in conjunction with free water At new drop, the drop freezing point of formation is significantly reduced, and a part is mutual with gasoline under the concussion of motor racing It is molten；Even if another part drop enters in fuel system, it will not be condensed in fuel system and block oil circuit, cause to send out Motivation can not work normally.

The present invention provides a kind of methods of mutual solvent miscible with water using addition gasoline, inhibit minor amount of water in gasoline Heavy poly- and removal the product and preparation method divided.Due to mutual solvent hydroxyl have good hydrophily, it can in fuel Minor amount of water molecule form hydrogen bond association, and the alkyl of mutual solvent then has lipophilicity, can be dispersed in gasoline.

A kind of preparation method of gasoline of motor fuel tank deicer of the invention, described method includes following steps: will be solubilized Agent, antirust agent, mutual solvent that high-octane rating additive and weight percent are 1.5~3.5% in the way of negative-pressure ward according to Secondary to be added in solvent step by step, each step is completed in closed kettle, to form the gasoline deicer.

According to a kind of preferred embodiment, the method includes at least step: by the solvent of total amount 1/2 and solubilizer according to It is secondary to be added in the way of negative-pressure ward in closed kettle, it is persistently stirred under closed environment and leads to nitrogen.

According to a kind of preferred embodiment, the method also includes steps: by the antirust agent of accurate measurement and remaining molten Agent is successively added in closed kettle in the way of negative-pressure ward, is persistently stirred under closed environment and is led to nitrogen.

According to a kind of preferred embodiment, the method also includes steps: by high-octane rating additive and weight percent It is successively added in the way of negative-pressure ward in closed kettle for 1.5~3.5% mutual solvent, is persistently stirred under closed environment It mixes and leads to nitrogen.

According to a kind of preferred embodiment, the method also includes steps: after each material all dissolution, stopping stirring And stand, container bottle is discarded in the way of being filtered under diminished pressure from the outlet of the lower end of closed kettle and obtains filtrate, i.e., the described gasoline removes Aqua.

According to a kind of preferred embodiment, the mutual solvent is the tert-butyl alcohol, and the high-octane rating additive is methyl- tert fourth Base ether.

According to a kind of preferred embodiment, the gasoline deicer is added by solubilizer, antirust agent, high-octane rating The mutual solvent that agent and weight percent are 1.5~3.5% is successively added in solvent step by step in the way of negative-pressure ward, Wherein, each step is completed in closed kettle,

Weight percentages of components in the gasoline of motor fuel tank deicer are as follows: solvent: 93.7~96.5%, solubilizer: 0.65~0.95%, mutual solvent: 1.5~3.5%, high-octane rating additive: 0.35~0.45%, antirust agent: 1~1.4%, Wherein, the weight percent of the solvent, the solubilizer, the mutual solvent, the high-octane rating additive and the antirust agent Than the sum of be 100%.

According to a kind of preferred embodiment, the solvent is one of methanol, ethyl alcohol, butanone and isopropanol or a variety of, Include in described 93.7~96.5% solvent weight percent be 53~58% methanol and 36.5~42.7% ethyl alcohol, Butanone or isopropanol.

According to a kind of preferred embodiment, the antirust agent includes at least benzotriazole and high base number calcium mahogany sulfonate, In described 1~1.4% antirust agent include weight percent be 0.5~0.7% benzotriazole and 0.5~0.7% height Base number calcium mahogany sulfonate.

According to a kind of preferred embodiment, the solubilizer includes at least dimethylformamide and triethylene glycol methyl ether, institute State 0.65~0.95% solubilizer include weight percent be 0.5~0.7% dimethylformamide and 0.15~0.25% Triethylene glycol methyl ether.

Advantageous effects of the invention are primarily present in the following aspects:

1, the method that the mutual solvent tert-butyl alcohol is added in the ratio that it is 1.5~3.5% with weight percent that the present invention, which is used, can The solubility of minor amount of water in the oil is dramatically increased, achievees the effect that preferably to remove minor amount of water in gasoline；When temperature reduces When, by the effect with mutual solvent, micro-moisture not reason supersaturation and is precipitated, when humidity reduction, the micro-moisture in fuel Will not solve the problems, such as that minor amount of water is heavy poly- to air evaporation；For having sunk poly- moisture, by with mutual solvent Effect, can significantly reduce freezing point, can also dissolve each other under earthquake with gasoline, reached water removal and protected engine Purpose.

2, the tert-butyl alcohol in deicer of the present invention serves not only as the effect that mutual solvent plays water removal, simultaneously because the tert-butyl alcohol The activation energy of hydro carbons, or a kind of apparent alcohols high-octane rating additive of cheap and effect can be greatly reduced, it can have Effect improves octane number, achievees the purpose that clean engine；Have simultaneously as high-octane rating additive with methyl tertiary butyl ether(MTBE) Similar function carries out technique preparation for the substitution of methyl tertiary butyl ether(MTBE).

3, the present invention is in such a way that methyl tertiary butyl ether(MTBE) and the tert-butyl alcohol are mixed in a certain ratio and deicer are added, methyl The synergistic effect generated between tertbutyl ether and the tert-butyl alcohol is significant, and the activation energy of hydro carbons can not only be greatly reduced, and enhances gasoline The capability of antidetonance, simultaneously because the molecular polarity of methyl tertiary butyl ether(MTBE) is smaller than alcohols, the presence of tert-butyl again to oxygen atom with Water, methanol forms hydrogen bond certain inhibition, and the hydrophilic group-OH in the tert-butyl alcohol can with-the OH in water and methanol with Hydrogen bond effectively connects, therefore the synergistic effect generated between methyl tertiary butyl ether(MTBE) and the tert-butyl alcohol also helps to obtain homogeneous stability Fuel oil system.

4, the antirust agent that the present invention selects, can either form firm protective film in metal surface, and can play with glue Micro water dispersion can be protected automotive oil tank and transfer pipeline metal not to generate corrosion by the form of beam.

5, the present invention is mixed in closed process units, and mixing uses the closed agitation of inert gas, is able to carry out In batches, it operates continuously, production safety is reliable.

6, product of the invention this product need to be only added in automotive oil tank with 0.3% ratio, so that it may be dramatically increased The solubility of minor amount of water in the oil.

Specific embodiment

Embodiment of the present invention is described in detail below with reference to embodiment.

A kind of gasoline of motor fuel tank deicer provided by the invention, the gasoline deicer, which includes at least, to be had by solvent, increases The deicer of one of solvent, mutual solvent, high-octane rating additive and antirust agent or various ingredients composition.The automobile By mass percentage, mass ratio includes at least one of the following or multiple combinations: solvent to fuel tank gasoline deicer: 93.7~96.5%, solubilizer: 0.65~0.95%, mutual solvent: 1.5~3.5%, high-octane rating additive: 0.35~ 0.45%, antirust agent: 1~1.4%.The solvent, the solubilizer, the mutual solvent, the high-octane rating additive and institute Stating the sum of weight percent of antirust agent is 100%.

According to a kind of preferred embodiment, the solvent is one of methanol, ethyl alcohol, butanone and isopropanol or a variety of. Wherein, the methanol for being 53~58% including weight percent in described 93.7~96.5% solvent.Described 93.7~96.5% Solvent in include 36.5~42.7% ethyl alcohol, butanone or isopropanol.

Methanol serves not only as a kind of excellent organic solvent, and due to the combustion characteristics of its own, can effectively disappear Except the carbon distribution at position each in combustion system, reduction causes power dropping because of the formation of carbon distribution, burns phenomena such as insufficient. But its corrosivity to fuel engines and the swelling ratio to rubber material are all larger, and are easy to and fuel layering.When methanol plus Enter the amount into fuel oil when less than 10%, methanol and fuel oil are in the equal phase region at phasor both ends, polar methanol phase and non-pole Property fuel oil when mixing, two-phase is not easy to dissolve each other as microemulsion system, and needing will complete nonpolar fuel oil by addition auxiliary agent Molecule is pulled together securely with highly polar methanol molecules, forms nearly homogeneous stable clear microemulsion liquid system.And make Methyl tertiary butyl ether(MTBE) for high-octane rating additive and the tert-butyl alcohol as mutual solvent can both improve the solubization of methanol, The stability of the clear microemulsion liquid system of fuel oil can be increased.Since the molecular polarity of methyl tertiary butyl ether(MTBE) is smaller than alcohols, uncle The presence of butyl, which forms hydrogen bond to oxygen atom and water, methanol again, certain inhibition, and the hydrophilic group-OH in the tert-butyl alcohol The methyl tertiary butyl ether(MTBE) that can be effectively connect with-the OH in water and methanol with hydrogen bond, therefore be added after mixing according to a certain percentage Synergistic effect between the tert-butyl alcohol can be conducive to the fuel oil system for obtaining stable and uniform.

According to a kind of preferred embodiment, the solubilizer includes triethylene glycol methyl ether and dimethylformamide.

Wherein, solubilising indicates that the substance for making not dissolving in or be slightly soluble in specific solvent is (i.e. solubilized in interfacial activity compound Agent) under the action of become soluble, thus solubilizer poorly water-soluble or substance not soluble in water can be converted to it is transparent, Most milky aqueous solutions, and the chemical structure of these poorly water-solubles or substance not soluble in water is not sent out in the process Changing.Mixture obtained is characterized in that poorly water-soluble or substance not soluble in water exist in the form that colloidal state dissolves In the surface active cpd molecular association complex for forming aqueous solution, i.e., so-called micella.Resulting solution is stable single-phase System, shows as visually being transparent to milky, and can prepare in the case where not needing input energy.In addition, The homogeneity of gasoline and the using effect of gasoline can also be improved by using solubilizer.

In general, the Free water being suspended in fuel oil condenses into when the temperature of ambient enviroment is lower than 0 DEG C of crystallization temperature of water Ice, or be present in fuel oil with the subcooled water of half stable state, such as cannot timely and effectively be removed will will lead to blocking engine The hidden danger such as pipeline.In order to reduce the generation of above-mentioned clogging, more widespread practice is at present: diethylene glycol dimethyl ether is made It is added in fuel oil for additive, reduces fuel oil and the paracrystalline temperature of solid hydrocarbons occur.However, diethylene glycol dimethyl ether have compared with Big corrosivity be easy to cause tank internal surface material coating to expand and paints for a long time with tank internal surface material Film hardness reduces, and there are security risks, and fuel tank is frequently overhauled or replaced, and will also result in the substantially increasing of expense Add, economy is poor.

The alcohol ethers compound triethylene glycol methyl ether itself that the present invention uses has hydrophilic and oleophilic double properties, can not only Free water in enough and fuel oil forms hydrogen bond, effectively increases solubility of the water in fuel oil, avoids Free water under low temperature Precipitation, and it and fuel system material compatible will not cause to corrode, can effectively extend fuel tank to tank surface material Service life.In addition, triethylene glycol methyl ether can also play the effect of anti-freezing agent, with water to form low crystal point by hydrogen bond molten Liquid reduces crystallization temperature of the Free water in fuel oil, a certain amount of ice crystal can be also dissolved, so as to effectively prevent fuel oil System freeze the problem of and efficiently solve the problems, such as cold-starting automobile hardly possible.

Wherein, dimethylformamide is non-protonic polar solvent.Dimethylformamide is to a variety of organic compounds and nothing Machine compound has good solvability, has good chemical stability.Dimethylformamide is as excellent organic molten Agent and important industrial chemicals, can be widely used as solvent.Dimethylformamide category polar aprotic solvent, except halogenation is with external enwergy It is arbitrarily mixed with water and most organic solvents, as solubilizer of the invention, helps to improve solution rate.

According to a kind of preferred embodiment, the mutual solvent is the tert-butyl alcohol.The tert-butyl alcohol is added in gasoline by the present invention can To increase the solubility of minor amount of water in the oil, when the temperature decreases moisture not reason supersaturation and is precipitated, humidity reduction when, Moisture in fuel will not be to air evaporation.This is because the hydroxyl of the tert-butyl alcohol has good hydrophily, it can be with combustion Minor amount of water molecule in material forms hydrogen bond association, and the alkyl of the tert-butyl alcohol then has lipophilicity, can be dispersed in gasoline In.Due to generating the reason of hydrogen bond between hydrone and the tert-butyl alcohol, each molecule of the tert-butyl alcohol can will be at least by four water The associated matter of molecular composition keeps in the solution, increase the solubility of water in fuel, and the saturation that can improve gasoline is steamed Vapour pressure prevents air-resistance phenomenon.With dissolve water combine increase water solubility in the oil while, the tert-butyl alcohol and free Water combines and forms new drop, and the drop freezing point of formation significantly reduces, a part of under the concussion of motor racing, with Gasoline dissolves each other；Even if another part drop enters in fuel system, it will not be condensed in fuel system and block oil circuit, Avoiding result in engine can not work normally.

According to a preferred embodiment, the high-octane rating additive is methyl tertiary butyl ether(MTBE).Octane number is automobile-used vapour The most important quality index of oil, determines the basic demand of burning, is the standard for measuring miscella pinking (knocking) degree size. Octane number is higher, and pinking degree is lower, that is, anti-knock properties are higher.The pungent of gasoline is improved in order to reduce the pinking degree of gasoline A small amount of raising octane number additive can be added in alkane value.The basic octane number RON of methyl tertiary butyl ether(MTBE) (MTBE) is 118, It is excellent ethers high-octane rating additive, chemical property is stablized, and oxygen content is relatively high, can significantly improve car tail Gas discharge reduces the content of carbon monoxide in tail gas, and high combustion efficiency, can inhibit the generation of ozone.Methyl- tert fourth Base ether is as high-octane rating additive, in addition to it can increase gasoline oxygen content, may additionally facilitate cleaning burning, it is harmful to reduce automobile Object exhaust emission.In the molecular structure of methyl tertiary butyl ether(MTBE), oxygen atom is connected directly with carbon atom, and the bond energy of C-O key is greater than C- The bond energy of C key, while there is the three-dimensional effect of tertiary carbon atom again, so that its molecule is difficult to break to form free radical.It ensure that The good chemical stability of methyl tertiary butyl ether(MTBE) and explosion-proof performance.Methyl tertiary butyl ether(MTBE) not only has very high clear octane number, and And there is quite high reconciliation octane number.As long as a small amount of methyl tertiary butyl ether(MTBE) is added in the oil, its octane number can be made Obtain larger raising.Methyl tertiary butyl ether(MTBE) is for direct steaming gasoline, catalytic reforming gasoline, catalytically cracked gasoline, gasoline alkylate etc. Suffer from good reconciliation effect.

However, since methyl tertiary butyl ether(MTBE) has the physical property for being highly soluble in water, and be not easy to be inhaled by soil particle It is attached, it can quickly enter underground water than gasoline and other components and be spread around in a manner of radiation, even if in very low concentrations When also result in water quality stench, therefore methyl tertiary butyl ether(MTBE) is a kind of reagent that there is dispute at present.Since it is not easy from water Volatilization and extraction, contaminated underground water can permeate during the decade several hundred rice and substantially non-degradable, than the degradation time of benzene It is also long.The ad hoc working group that Environmental Protection in America portion is set up investigate the whether harmful human health of methyl tertiary butyl ether(MTBE), as a result It was found that it is to the irritating effect of human respiratory tract mucosa；And have harmful effect to kidney and liver, it may cause after being absorbed by the body Cancer is fixed tentatively by U.S.EPA as carcinogen.However, being thought according to the current result of study of international cancer research institution, first Base tertbutyl ether is not belonging to carcinogen, and the use of to human body is safe in clean gasoline.National conditions special for China need It wants, it is still the most effective means for improving gasoline standard that octane number is improved in existing China, which to addition methyl tertiary butyl ether(MTBE), however beautiful Some areas and country including state, West Europe also tend to reduce methyl tertiary butyl ether(MTBE) dosage in the oil or be forbidden to use.Although There is not unified understanding to the harmfulness of methyl tertiary butyl ether(MTBE), but in the long run, should put forth effort to develop methyl- tert in gasoline additive The research of the production technology and methyl tertiary butyl ether(MTBE) substitute of butyl ether carries out technology standard for the future of methyl tertiary butyl ether(MTBE) It is standby.

Wherein, the tert-butyl alcohol is up to the apparent alcohols Gaoxin of 108, cheap and effect as its a kind of octane number simultaneously Alkane value additive has similar function with methyl tertiary butyl ether(MTBE), simultaneously because the tert-butyl alcohol can increase minor amount of water in the oil Solubility and price it is cheaper than methyl tertiary butyl ether(MTBE), the present invention using the tert-butyl alcohol as methyl tertiary butyl ether(MTBE) part substitute Product, which are added in gasoline, plays a dual role of high-octane rating additive and mutual solvent, gasoline of the invention add deicer by using The methyl tertiary butyl ether(MTBE) and the tert-butyl alcohol of certain proportion mixing, the two synergy is significant, and the activation energy of hydro carbons can be greatly reduced, Enhance the capability of antidetonance.

According to a preferred embodiment, methyl tertiary butyl ether(MTBE) of the invention and the tert-butyl alcohol use co-production preparation method, connection The preparation method of production methyl tertiary butyl ether(MTBE) and the tert-butyl alcohol includes at least the combination of one or more of following steps:

A, after the C-4-fraction containing isobutene is preheated with the containing a small amount of methanol that is generated from extraction tower bottom One aqueous solution counter current contacting in the first reactor.Under the effect of the catalyst, the isobutene and first in C-4-fraction is mixed A small amount of methanol reaction generates methyl tertiary butyl ether(MTBE) in aqueous solution.It is reacted simultaneously with water a large amount of in the first aqueous solution and generates the tert-butyl alcohol. Wherein lighter oil is mutually overflowed from the top of first reactor, and the is entered after mixing with the methanol feedstock after preheating through mixer Two reactors.Wherein heavier liquid phase flows out from the bottom of first reactor and inputs the middle part of first rectifying column.In the first essence Evaporate obtained at the top of tower 85% or so tertiary butanol and water azeotropic mixture.Purer water is obtained in the bottom of first rectifying column, as Extractant returns to the middle part of the first extraction tower.The operating pressure of first reactor be 0.67 ± 0.2MPa, operation temperature be 60 ± 20℃；The operating pressure of first rectifying column maintains 0.12~0.25MPa, and operation temperature is 110.9 ± 10 DEG C.

B, under the action of second reactor catalyst, the oil at the top of first reactor is mutually and from the first rectifying The tertiary butanol and water azeotropic mixture of top of tower.The reaction was continued generates with a small amount of water and excessive methanol respectively for isobutene in C-4-fraction The tert-butyl alcohol and methyl tertiary butyl ether(MTBE).So that isobutene reaches the conversion ratio of requirement.Reaction product (the first that second reactor obtains Base tertbutyl ether, the tert-butyl alcohol, C-4-fraction and a small amount of methanol) from the middle part of its first catalytic rectifying tower of bottom input.Second is anti- The operating pressure for answering device is 0.7 ± 0.1MPa, and operation temperature is 75 ± 5 DEG C.

C, remaining a small amount of isobutene and methanol in C-4-fraction under the action of the first catalytic rectifying tower catalyst, First catalytic rectifying tower the reaction was continued generate methyl tertiary butyl ether(MTBE).Contain less first what the first catalytic distillation top of tower distillated The first extraction of C-4-fraction input tower bottom, obtains methyl tertiary butyl ether(MTBE) and uncle in the first catalytic distillation tower bottom after the ether of alcohol The mixture of butanol, mixture input knockout tower isolate the methyl tertiary butyl ether(MTBE) of one-component and the tert-butyl alcohol of one-component.The One catalytic rectifying tower operating pressure is 0.7 ± 0.2MPa, and operation temperature is 130 ± 10 DEG C.It is evaporated from the first catalytic distillation top of tower The first extraction of C-4-fraction input tower bottom after the ether containing less methanol out, respectively and from first rectifying column bottom Desalted water counter current contacting is supplemented outside water and device, goes out device to C-4-fraction after purification ether at the top of the first extraction tower, at it The first aqueous solution containing a small amount of methanol that bottom obtains then returns to reuse at the top of first reactor.First knockout tower T03 operation Pressure is 0.15 ± 0.05MPa, and operation temperature is 95 ± 5 DEG C.

According to a kind of preferred embodiment, the gasoline of motor fuel tank deicer also contains protection automotive oil tank and conveying Pipeline metal does not generate the antirust agent of corrosion.Antirust agent is the important component of gasoline additive, with organic corrosion inhibitor Development and application, inorganic salts antirust agent are gradually substituted, and the organic corrosion inhibitor used is mostly by easily providing containing N, O, S, P etc. The organic compound of the active group of the atom or unsaturated bond of lone pair electrons, carboxyl are natural organic ligands, are and metal knot The essential groups of conjunction, the size of corrosion inhibition, depend primarily on molecular structure, play pass in metal surface to Molecular Adsorption Key effect.

According to a kind of preferred embodiment, the antirust agent is high base number calcium mahogany sulfonate and benzotriazole.

Wherein, high base number calcium mahogany sulfonate is using heavy alkylbenzene sulfonic acid as primary raw material.High base number calcium mahogany sulfonate is logical It crosses neutralization and high quaternization is made.It has excellent high temperature detergency and acid neutralization capacity, and has good rust-preventing characteristic Can, the high temperature deposition object on engine components, permanently effective protection hair can be effectively reduced with its IC engine lubricating oil modulated Motivation avoids the sour corrosion of parts, and can extend the oil draining period.One side high base number calcium mahogany sulfonate can wrap up water Micella is formed, prevents metal erosion or corrosion by reducing the contact probability of water and metal；Another aspect high base number petroleum sulphur The polar end of sour calcium molecule also has stronger adsorption capacity to metal, and non-polar end has grease soap body system preferable affine Power is deposited on metal surface even if can effectively adsorb the occasion of more water or seawater, forms deposition film or reaction film plays profit Sliding effect, under duplicate protection, high rust resistance.

Wherein, benzotriazole is that a kind of nitrogen heterocycles corrosion inhibiter by functional group and reaction can synthesize benzene The derivative of parallel triazole makes to increase water solubility, benzotriazole nitrogen containing more than two eluting groups in its molecule The derivative of heterocyclic compound has compact molecular structure, and good thermal stability, atomic radius is small, and electronegativity is high, absorption Intermolecular hydrogen bonding is easily formed at metal surface, enhances lateral gravitation, protection film strength is improved, to more effectively subtract It mitigates and inhibits corrosion of metal.

According to a kind of preferred embodiment, a kind of gasoline of motor fuel tank deicer, the gasoline deicer is will be solubilized Agent, antirust agent, mutual solvent that high-octane rating additive and weight percent are 1.5~3.5% in the way of negative-pressure ward according to It is secondary to be added in solvent step by step, wherein each step is completed in closed kettle, wherein the gasoline of motor fuel tank Weight percentages of components in deicer are as follows: the additional amount of methanol is 53%, and the additional amount of butanone is 41.5%, triethylene glycol The additional amount of methyl ether is 0.15%, and the additional amount of dimethylformamide is 0.4%, and the additional amount of the tert-butyl alcohol is 2.5%, methyl The additional amount of tertbutyl ether is 1.35%, and the additional amount of high base number calcium mahogany sulfonate is 0.6%, the additional amount of benzotriazole It is 0.5%.

According to a kind of preferred embodiment, the additional amount of the high base number calcium mahogany sulfonate is 0.6%, described benzene a pair of horses going side by side three The additional amount of nitrogen azoles is 0.5%.

Table 1~10 gives the technical indicator of each component.

1 methanol technical indicator of table

Project	Quality index
		20 DEG C of kg/m of density3	791~793
Boiling range (0 DEG C of 101.3kPa)/DEG C≤	1.5
		Water w/%≤	0.2
Carbonyls (in terms of HCHO) w/%≤	0.010

2 isopropanol technical indicator of table

Project	Quality index
		Isopropanol content % (mass fraction) >=	99.7
The content % (mass fraction) of water≤	0.2
		The mass fraction % (in terms of acetone) of carbonyl≤	0.02

3 ethyl alcohol technical indicator of table

Project	Quality index
		Ethanol content % (V/V) >=	96
Methanol content % (V/V)≤	0.03
		Soluble test	Without lacteous

4 butanone technical indicator of table

Project	Quality index
		Appearance	Colourless liquid
Purity % (mass fraction) >=	99.7
		Moisture % (mass fraction)≤	0.05
20 DEG C of kg/m3 of density	804~807

5 dimethylformamide technical indicator of table

Project	Quality index
		Dimethylformamide w/% >=	99.5
Water w/%≤	0.05
		PH value (25 DEG C of 20% aqueous solution)	6.5~8.0
Methanol w/%≤	0.0050

6 methyl tertiary butyl ether(MTBE) technical requirements of table

Project	Quality index
		MTBE content wt% is not less than	98
Methanol content wt% is not more than	0.5
		T butanol content wt% is not more than	0.4
Moisture wt%	Actual measurement
		20 DEG C of kg/m3 of density	Actual measurement

7 benzotriazole technical requirements of table

Project	Quality index
		Benzotriazole content % >=	99.0
Moisture %≤	0.1
		Fusing point DEG C	96~99

8 tert-butyl alcohol technical requirements of table

Project	Quality index
		25 DEG C of kg/m3 of density	0.81
Boiling point DEG C	83
		Fusing point DEG C	23-26

9 high base number calcium mahogany sulfonate technical requirements of table

Project	Quality index
		Transparency	It is transparent
20 DEG C of kg/m3 of density	1100~1200
		Moisture % (m/m)	No more than 0.10
Oil-soluble spot test	It is peace and quiet

10 triethylene glycol methyl ether technical indicator of table

Project	Quality index
		25 DEG C of g/mL of density	1.026
Boiling point DEG C	122
		Fusing point DEG C	-45

According to a kind of preferred embodiment, the preparation method of the deicer includes the following steps:

First by the methanol of total amount 1/2 and the ethyl alcohol (or isopropanol or butanone) of total amount 1/2 successively according to negative-pressure ward Mode is added in closed kettle, the maintaining nitrogen purge under closed environment, stirs 0.5 hour, obtains mixed solution, for use；

The dimethylformamide of accurate measurement and triethylene glycol methyl ether are successively added in the way of negative-pressure ward closed In kettle, the maintaining nitrogen purge under closed environment is stirred 0.5 hour；

Remaining methanol and remaining ethyl alcohol (or isopropanol or butanone) are added in the way of negative-pressure ward closed In kettle, the maintaining nitrogen purge under closed environment is stirred 0.5 hour；

The benzotriazole of accurate measurement and high base number calcium mahogany sulfonate are successively added in the way of negative-pressure ward close It closes in kettle, the maintaining nitrogen purge under closed environment, stirs 0.5 hour；

The methyl tertiary butyl ether(MTBE) of accurate measurement and the tert-butyl alcohol are successively added in closed kettle in the way of negative-pressure ward, The maintaining nitrogen purge under closed environment stirs 0.5 hour；

After each material all dissolution, stops stirring and stand 0.5 hour, export from the lower end of closed kettle according to decompression The mode of filtering is discarded to container bottle to get the gasoline deicer.

Table 11 shows the raw material composition of Examples 1 to 3.

The raw material of 11 Examples 1 to 3 of table forms wt%

Raw material composition	Embodiment 1	Embodiment 2	Embodiment 3
				Methanol	53	53	53
Ethyl alcohol	41.5
				Butanone		41.5
Isopropanol			41.5
				The tert-butyl alcohol	3.5	2.5	1.5
Benzotriazole	0.5	0.5	0.5
				Dimethylformamide	0.4	0.4	0.4
Triethylene glycol methyl ether	0.15	0.15	0.15
				Methyl tertiary butyl ether(MTBE)	0.35	1.35	2.35
High base number calcium mahogany sulfonate	0.6	0.6	0.6

Embodiment 1

First 41.5% ethyl alcohol of 53% methanol of total amount 1/2 and total amount 1/2 is added in the way of negative-pressure ward closed In kettle, the maintaining nitrogen purge under closed environment stirs 0.5 hour, obtains mixed solution, for use；

By 0.4% dimethylformamide of accurate measurement and 0.15% triethylene glycol methyl ether successively according to negative-pressure ward Mode is added in closed kettle, the maintaining nitrogen purge under closed environment, stirs 0.5 hour；

Remaining methanol and remaining ethyl alcohol are added in closed kettle in the way of negative-pressure ward, in closed environment Lower maintaining nitrogen purge stirs 0.5 hour；

By 0.5% benzotriazole of accurate measurement and 0.6% high base number calcium mahogany sulfonate successively according to negative-pressure ward Mode is added in closed kettle, the maintaining nitrogen purge under closed environment, stirs 0.5 hour；

0.35% methyl tertiary butyl ether(MTBE) of accurate measurement and 3.5% tert-butyl alcohol are successively added in the way of negative-pressure ward Enter in closed kettle, the maintaining nitrogen purge under closed environment, stirs 0.5 hour；

After each material all dissolution, stops stirring and stand 0.5 hour, export from the lower end of closed kettle according to decompression The mode of filtering is discarded to container bottle to get the gasoline deicer.

Embodiment 2

First 41.5% butanone of 53% methanol of total amount 1/2 and total amount 1/2 is added in the way of negative-pressure ward closed In kettle, the maintaining nitrogen purge under closed environment stirs 0.5 hour, obtains mixed solution, for use；

By 0.4% dimethylformamide of accurate measurement and 0.15% triethylene glycol methyl ether successively according to negative-pressure ward Mode is added in closed kettle, the maintaining nitrogen purge under closed environment, stirs 0.5 hour；

Remaining methanol and remaining butanone are added in closed kettle in the way of negative-pressure ward, in closed environment Lower maintaining nitrogen purge stirs 0.5 hour；

By 0.5% benzotriazole of accurate measurement and 0.6% high base number calcium mahogany sulfonate successively according to negative-pressure ward Mode is added in closed kettle, the maintaining nitrogen purge under closed environment, stirs 0.5 hour；

1.35% methyl tertiary butyl ether(MTBE) of accurate measurement and 2.5% tert-butyl alcohol are successively added in the way of negative-pressure ward Enter in closed kettle, the maintaining nitrogen purge under closed environment, stirs 0.5 hour；

After each material all dissolution, stops stirring and stand 0.5 hour, export from the lower end of closed kettle according to decompression The mode of filtering is discarded to container bottle to get the gasoline deicer.

Embodiment 3

First 41.5% isopropanol of 53% methanol of total amount 1/2 and total amount 1/2 is added in the way of negative-pressure ward close It closes in kettle, the maintaining nitrogen purge under closed environment, stirs 0.5 hour, obtain mixed solution, for use；

By 0.4% dimethylformamide of accurate measurement and 0.15% triethylene glycol methyl ether successively according to negative-pressure ward Mode is added in closed kettle, the maintaining nitrogen purge under closed environment, stirs 0.5 hour；

Remaining methanol and remaining isopropanol are added in closed kettle in the way of negative-pressure ward, in closed ring Maintaining nitrogen purge under border stirs 0.5 hour；

By 0.5% benzotriazole of accurate measurement and 0.6% high base number calcium mahogany sulfonate successively according to negative-pressure ward Mode is added in closed kettle, the maintaining nitrogen purge under closed environment, stirs 0.5 hour；

2.35% methyl tertiary butyl ether(MTBE) of accurate measurement and 1.5% tert-butyl alcohol are successively added in the way of negative-pressure ward Enter in closed kettle, the maintaining nitrogen purge under closed environment, stirs 0.5 hour；

After each material all dissolution, stops stirring and stand 0.5 hour, export from the lower end of closed kettle according to decompression The mode of filtering is discarded to container bottle to get the gasoline deicer.

Table 12 is technical target of the product.

12 technical target of the product of table

Wherein,

(1) detection test method miscible with water:

Instrument used includes: glass cylinder (50ml), pipette (1ml), teat glass (100ml)

Reagent used includes: pure water, 92# gasoline, deicer

Testing procedure includes:

1,50ml motor petrol at room temperature, is taken to be placed in 100ml tool plug graduated cylinder, and pipetted respectively with pipette (according to Poidometer) 0.08% pure water and 0.3% deicer, it is successively added dropwise in 100ml tool plug graduated cylinder.

2, sealing 100ml tool plug graduated cylinder, vibrates 5min.

3, it after placing for 24 hours, visually inspects gained sample and is compared with blank test group, record variation (muddy degree).

4, respectively using embodiment 1, embodiment 2, embodiment 3 and commercially available comparative example as the deicer in step 1, weight Multiple experimental procedure 1~3.

5, test stone: setting blank control group compares；Test atmosphere: (25~30) DEG C, (50~70) % RH

(2) water resistant of dissolving each other ability test method:

Instrument used includes: tool plug graduated cylinder (100ml), pipette (1ml)

Reagent used includes: distilled water, commercially available 90# gasoline, deicer

Testing procedure includes:

1,50ml motor petrol at room temperature, is taken to be placed in 100ml tool plug graduated cylinder, and pipetted respectively with pipette (according to Poidometer) a certain proportion of distilled water and 0.3% deicer, be successively added dropwise in 100ml tool plug graduated cylinder.

2, sealing 100ml tool plug graduated cylinder, vibrates 5min, visually inspects gained sample and compares with blank test group, observation Whether gained sample occurs mutually separating (not muddy, not stratified).

3, it measures and the most greatly water of distilled water that record sample required when becoming phase-separated state from clear homogeneous state Ratio (distilled water ml/ motor petrol ml).

4, respectively using embodiment 1, embodiment 2, embodiment 3 and commercially available comparative example as the deicer in step 1, weight Multiple experimental procedure 1~3.

5, test stone: setting blank control group compares；Test atmosphere: (25~30) DEG C, (50~70) % RH

(3) copper strip test method:

Instrument used includes: test tube, test tube bath, copper sheet, antimagnetic type tweezer, copper corrosion Standard colour board

Testing procedure includes:

1, miscible with water using embodiment 1, embodiment 2, embodiment 3 and commercially available comparative example as experiment (1) is repeated respectively Detection test method deicer, repeat test (1) step 1~2, successively obtain 1~sample of sample 4.

2, with antimagnetic type tweezer by the submergence of one piece of copper sheet polished in the sample, at room temperature, when test Between 3h ± 5min, after, take out copper sheet with antimagnetic type tweezer, immerse detergent, wash away the sample of attachment, then with qualitative filter Paper blots, and is then compared it with copper corrosion Standard colour board, evaluates copper sheet discoloration, determines corrosion level.

3, test stone: test basis is referring to GB17930-2013 " motor petrol " GB/T 5096

Test atmosphere: (25~30) DEG C, (50~70) %RH

4, according to a preferred embodiment, step 2 can be with are as follows: the copper for having been polished one piece with antimagnetic type tweezer Piece submerges in the sample, and heating water bath simultaneously controls temperature in (50 ± 1) DEG C, and test period 3h ± 5min terminates heating cycle Afterwards, copper sheet is taken out with antimagnetic type tweezer, immerses detergent, the sample of attachment is washed away, then blotted with qualitative filter paper, then by it It is compared with copper corrosion Standard colour board, evaluates copper sheet discoloration, determine corrosion level.

The result shows that

(1) by embodiment 1, embodiment 2 and embodiment 3 it is miscible with water after for 24 hours appearance compared with commercial products, the present invention The degree of automotive oil tank deicer muddiness be respectively less than commercial products, show that automotive oil tank deicer holding of the invention is dissolved each other The ability of effect is bigger, can achieve the effect that preferably to remove water and protect engine；And the product for obtaining embodiment 2 It compared with Example 1, is for 24 hours still transparency liquid after miscible with water.

(2) by the phase of dissolve each other the water resistant ability test result and commercial products of embodiment 1, embodiment 2 and embodiment 3 Than automotive oil tank deicer maximum water addition ratio example of the invention is all larger than commercial products, and in the embodiment of the present invention most greatly Water ratio can achieve 1%-2%, substantially better than the requirement of domestic common counter 0.2% at present, can dramatically increase water in vapour Solubility in oil, water resistant of dissolving each other ability is significant, the fuel oil system more stable and uniform obtained from；And embodiment 2 is obtained To product respectively compared with embodiment 1 and embodiment 3, maximum water addition ratio example can achieve 1.95%, and water resistant of dissolving each other ability is more It is good.

(3) by the organon of research octane number (RON) (RON) and commercial products of embodiment 1, embodiment 2 and embodiment 3 Octane number (RON) is compared, and automotive oil tank deicer research octane number (RON) (RON) of the invention is all larger than commercial products；It will implement Example 1, embodiment 2 compared with Example 3, can reduce methyl tertiary butyl ether(MTBE) while increasing the dosage of the tert-butyl alcohol respectively Dosage simultaneously obtains higher octane number.Therefore, the present invention is added with the ratio that weight percent is 1.5~3.5% in the tert-butyl alcohol Automotive oil tank deicer, can obtain compared with the better water removal effect of commercial products and improve octane number effect.

To sum up illustrate that effect is the most significant in example 2 for automotive oil tank deicer of the invention, component in embodiment 2 And proportion are as follows: the additional amount of methanol is 53%, and the additional amount of butanone is 41.5%, and the additional amount of triethylene glycol methyl ether is 0.15%, the additional amount of dimethylformamide is 0.4%, and the additional amount of the tert-butyl alcohol is 2.5%, the addition of methyl tertiary butyl ether(MTBE) Amount is 1.35%, and the additional amount of high base number calcium mahogany sulfonate is 0.6%, and the additional amount of benzotriazole is 0.5%.

It should be noted that above-mentioned specific embodiment is exemplary, those skilled in the art can disclose in the present invention Various solutions are found out under the inspiration of content, and these solutions also belong to disclosure of the invention range and fall into this Within the protection scope of invention.It will be understood by those skilled in the art that description of the invention is not constituted to power to be illustrative The limitation that benefit requires.Protection scope of the present invention is defined by the claims and their equivalents.

Claims (10)

1. a kind of preparation method of gasoline of motor fuel tank deicer, which is characterized in that described method includes following steps:

The mutual solvent that solubilizer, antirust agent, high-octane rating additive are 1.5~3.5% with weight percent is taken out according to negative pressure The mode of suction is successively added in solvent step by step, and each step is completed in closed kettle, to form the gasoline Deicer.

2. the preparation method of gasoline of motor fuel tank deicer as described in claim 1, which is characterized in that the method is at least wrapped Include step:

The solvent of total amount 1/2 and solubilizer are successively added in closed kettle in the way of negative-pressure ward, under closed environment It is lasting to stir and lead to nitrogen.

3. the preparation method of the gasoline of motor fuel tank deicer as described in one of preceding claims, which is characterized in that the side Method further comprises the steps of:

The antirust agent of accurate measurement and remaining solvent are successively added in closed kettle in the way of negative-pressure ward, closed It is persistently stirred under environment and leads to nitrogen.

4. the preparation method of the gasoline of motor fuel tank deicer as described in one of preceding claims, which is characterized in that the side Method further comprises the steps of:

The mutual solvent that high-octane rating additive and weight percent are 1.5~3.5% is successively added in the way of negative-pressure ward Enter in closed kettle, persistently stirred under closed environment and leads to nitrogen.

5. the preparation method of the gasoline of motor fuel tank deicer as described in one of preceding claims, which is characterized in that the side Method further comprises the steps of:

After each material all dissolution, stop stirring and standing, from the lower end of closed kettle, outlet is put in the way of being filtered under diminished pressure Filtrate is obtained to container bottle out, i.e., the described gasoline deicer.

6. the preparation method of the gasoline of motor fuel tank deicer as described in one of preceding claims, which is characterized in that described mutual Solvent is the tert-butyl alcohol, and the high-octane rating additive is methyl tertiary butyl ether(MTBE).

7. a kind of gasoline of motor fuel tank deicer, which is characterized in that the gasoline deicer is by solubilizer, antirust agent, height The mutual solvent that octane number additive is 1.5~3.5% with weight percent is successively added step by step in the way of negative-pressure ward Into solvent, wherein each step is completed in closed kettle,

Weight percentages of components in the gasoline of motor fuel tank deicer are as follows:

Solvent: 93.7~96.5%, solubilizer: 0.65~0.95%, mutual solvent: 1.5~3.5%, high-octane rating additive: 0.35~0.45%, antirust agent: 1~1.4%, wherein the solvent, the solubilizer, the mutual solvent, the high-octane rating The sum of weight percent of additive and the antirust agent is 100%.

8. the gasoline of motor fuel tank deicer as described in one of preceding claims, which is characterized in that the solvent is methanol, second One of alcohol, butanone and isopropanol are a variety of, in described 93.7~96.5% solvent include weight percent be 53~ 58% methanol and 36.5~42.7% ethyl alcohol, butanone or isopropanol.

9. the gasoline of motor fuel tank deicer as described in one of preceding claims, which is characterized in that the antirust agent at least wraps Include benzotriazole and high base number calcium mahogany sulfonate, include in described 1~1.4% antirust agent weight percent be 0.5~ 0.7% benzotriazole and 0.5~0.7% high base number calcium mahogany sulfonate.

10. the gasoline of motor fuel tank deicer as described in one of preceding claims, which is characterized in that the solubilizer at least wraps Include dimethylformamide and triethylene glycol methyl ether, described 0.65~0.95% solubilizer include weight percent be 0.5~ 0.7% dimethylformamide and 0.15~0.25% triethylene glycol methyl ether.