CN1306075A

CN1306075A - Lead-free gasoline additive

Info

Publication number: CN1306075A
Application number: CN 00113712
Authority: CN
Inventors: 王聪; 郭秋宝; 郑远洋; 郭文林
Original assignee: XIBEI HIGH-TECH INDUSTRY CO LTD SHAANXI PROV
Current assignee: XIBEI HIGH-TECH INDUSTRY CO LTD SHAANXI PROV
Priority date: 2000-01-19
Filing date: 2000-01-19
Publication date: 2001-08-01
Anticipated expiration: 2020-01-19
Also published as: CN1120221C

Abstract

An efficient lead-free gasoline additive is prepared from multi-branched-chain emtrol, oxygen-contained heterocyclic amine, anti-oxidizing agent and co-solvent through mixing. Its advantages are high octane number of gasoline, higher power of engine and less harmful components is tail gas.

Description

Addition for leadless gasoline

The invention belongs to oil engine gasoline fuel additive technical field, relate to a kind of addition for leadless gasoline that increases substantially gasoline octane rating.

Along with growing with each passing day of current all kinds of Motor vehicles recoverable amounts, emission of automobile wastes is also more and more serious to the pollution suction harm of physical environment and HUMAN HEALTH, becomes the first pollution source of urban air.Contain a large amount of deleterious hydrocarbon polymers, carbon monoxide, oxynitride and lead in the vehicle exhaust, wherein plumbous share rate to topsoil is 80～90%.For a long time, the oil refining enterprise of China in order to reach the requirement of motor spirit to indexs such as octane value and anti-knock indexs, adds a large amount of hypertoxic raw material---tetraethylleads always in gasoline in the gasoline production process.Be the purifying city air, the General Office of the State Council had issued " stopping to produce and sell the notice of automobile-used doped fuel about time limit " in 1998, the requirement various places stop to produce automobile-used doped fuel from January 1st, 2000, rose on July 1st, 2000 to stop to sell and using automobile-used doped fuel in China.This area realizes that unleaded gasoline mainly contains three kinds of approach at present, that is: 1, refining process improves, 2, fusion technical octane, methyl tertiary butyl ether (MTBE), Aalcohols fuel etc. in gasoline, 3, metal or the nonmetal octane promoter of interpolation except that tetraethyllead in gasoline, wherein economical and convenient and proven technique are added MTBE exactly the most.But find again that in recent years MTBE has potential threat to human health, California, USA government has expressly provided to reduce and has used, stopped using fully to 2002.Known all kinds of gasoline dopes also have many drawbacks at present in a word.

The objective of the invention is to overcome the existing drawback of known technology, a kind of high-quality addition for leadless gasoline efficiently that increases substantially gasoline octane rating and reduce topsoil is provided.

Addition for leadless gasoline of the present invention is that the applicant develops acquisition by the technology that adopts the compound interpolations of component such as oxygen-bearing organic matter and oxygen heterocyclic ring amine organism, it by higly branched chain Fatty Alcohol(C12-C14 and C12-C18), oxygen heterocyclic ring amine, oxidation inhibitor and solubility promoter totally four kinds of material compositions mix and form, wherein:

The chemical general formula of higly branched chain Fatty Alcohol(C12-C14 and C12-C18) is (R ₁R ₂R ₃) COH, R in the formula ₁Be H or C ₁～C ₃Alkyl, R ₂Be H or C ₁～C ₃Alkyl, R ₃Be H or C ₁～C ₃Alkyl, R in the goods ₁, R ₂, R ₃Can be identical or different; The chemical general formula of oxygen heterocyclic ring amine is Or

R in the formula ₁, R ₂, R ₃, R ₄Be H or C ₁～C ₃Alkyl, they can be different in the goods; N=1～3;

Oxidation inhibitor is di-t-butyl mixed phenol (C ₁₄H ₂₄O);

Solubility promoter is ether (C ₅H ₁₂O, C ₆H ₁₄O) or alkylbenzene (C ₇H ₈, C ₈H ₁₀, C ₉H ₁₀O).

In additive materials prescription of the present invention, these two kinds of organism of higly branched chain Fatty Alcohol(C12-C14 and C12-C18) and oxygen heterocyclic ring amine have common anti-detonation, can increase substantially octane value, and then obviously improve automobile engine power and reduce objectionable constituent in the vehicle exhaust; Oxidation inhibitor and solubility promoter belong to the gasoline blending compound, and they can make the performance that improves gasoline octane rating and antiknock better.

The content range that constitutes each material composition of this addition for leadless gasoline is:

Higly branched chain Fatty Alcohol(C12-C14 and C12-C18) 65～75%;

Oxygen heterocyclic ring amine 20～30%;

Oxidation inhibitor 0.5～1.5%;

Solubility promoter 3～5%.

The production technique that is used to prepare this additive comprises three part technology contents, i.e. the complex process of the synthesis technique of the synthesis technique of higly branched chain Fatty Alcohol(C12-C14 and C12-C18) component, oxygen heterocyclic ring amine component and higly branched chain Fatty Alcohol(C12-C14 and C12-C18), oxygen heterocyclic ring amine, oxidation inhibitor and four kinds of components of solubility promoter.

One, preparation technology's flow process of higly branched chain Fatty Alcohol(C12-C14 and C12-C18) is: the acetylene gas that the calcium carbide hydrolysis is produced is through freezing, purify, neutralization, dry back is introduced and is equipped with in the reactor of industrial anhydrous fat ketone or aldehyde, keep temperature in the kettle at 50～80 ℃, stirring tank internal reaction thing is to not absorbing till the acetylene gas, stop logical acetylene gas, the reaction solution of producing put into fill metal catalyst (as palladium, platinum, catalyzer such as nickelalloy) in the autoclave, feed hydrogen, keep temperature in the kettle and pressure and be respectively 50～150 ℃ and 4～8MPa, stirring tank internal reaction thing and continuous hydrogen make-up are till pressure stops to descend; After treating that still internal reaction thing is cooled to below 40 ℃, reactant is pressed in the still kettle, keeps the interior boiling temperature of still and control reflux ratio 1～3 with nitrogen: 1, after packing tower rectifying gets the finished product component.

Two, preparation technology's flow process of oxygen heterocyclic ring amine is: the adding after the elevated dosing vessel metering of oxygen heterocyclic ring aldehyde is filled alloy catalyst (as XCr ₂O ₃YCuO, Ni-Cu, Cr-Cu catalyzer) autoclave pressure in, feed hydrogen, keep temperature in the kettle and pressure and be respectively 80～200 ℃ and 5～10MPa, repeatedly hydrogen make-up is till pressure stops decline; Cooling elimination catalyzer, the major product of filtrate after fractionation changes in another reactor that fills copper alloy catalyzer (as catalyzer such as copper-zinc, copper-chromium, copper-zinc-chromium, skeleton nickel) and aliphatic primary amine, the control temperature in the kettle is at 80～200 ℃, question response termination postcooling elimination catalyzer, crude product is through distillation, vacuum distilling remove anhydrate and unreacted raw material and by product after the component that gets product;

Three, the complex process flow process of four kinds of components is: epoxy heterocyclic amine finished product component slowly is added in the higly branched chain Fatty Alcohol(C12-C14 and C12-C18) finished product component, after the stirring heating dissolving, add oxidation inhibitor and solubility promoter successively, continue to stir until being uniform solution, thing to be mixed is cooled to the material that gets product after the room temperature.

Embodiment

1, higly branched chain Fatty Alcohol(C12-C14 and C12-C18) component synthesis technique example:

Implementation method one:

With the hydrolysis of 330kg calcium carbide, the acetylene gas that produces is introduced after operations such as cooling, purification, neutralization, drying and is equipped with in the reactor of 221kg anhydrous fat ketone, keep temperature in the kettle at 50～80 ℃, stirring reaction stops logical acetylene gas till stop to absorb acetylene gas; The reaction solution of producing is squeezed in the autoclave that fills metal catalyst, fed hydrogen, keep temperature in the kettle and pressure and be respectively 90～110 ℃ and 5MPa, stirring tank internal reaction thing and continuous hydrogen make-up are till pressure stops to descend; After still internal reaction thing is cooled to room temperature, reactant is pressed in the still kettle, keeps in the still boiling temperature and control reflux ratio at 3: 1 with nitrogen, after packing tower rectifying gets higly branched chain Fatty Alcohol(C12-C14 and C12-C18) 48kg, yield 96%, b.p.101～102 ℃

Implementation method two:

With the hydrolysis of 100kg calcium carbide wet method, the acetylene gas that is produced is introduced after operations such as cooling, purification, neutralization, drying and is equipped with in the reactor of the anhydrous higher alcohols of 67kg, keeps 60 ℃ of temperature of reaction, and 60 rev/mins of mixing speed reacted 10 hours; This reaction solution is squeezed in the reactor that fills metal catalyst, fed hydrogen, keep certain temperature stirring in the still, till pressure no longer descends; After being cooled to room temperature, reactant is pressed in the still kettle, keeps boiling temperature in the still with nitrogen, after packing tower rectifying gets higly branched chain Fatty Alcohol(C12-C14 and C12-C18) 14.5～15.0kg, yield 95.7～99.0%, b.p.101～103 ℃

2, oxygen heterocyclic ring amine component synthesis technique example:

Implementation method one:

43kg oxygen heterocyclic ring aldehyde is sent into the XCr that adds 0.6kg in the autoclave ₂O ₃The YCuO catalyzer feeds hydrogen, keeps temperature in the kettle and is respectively 150～170 ℃, and reactant is reacted under 6MPa pressure, and repeatedly hydrogen make-up till pressure no longer descends; Cooling, the elimination catalyzer, the product of filtrate after fractionation sent in another reactor that fills 0.8kg copper alloy catalyzer and 28.70kg aliphatic primary amine, control temperature in the kettle at 140～160 ℃, question response termination postcooling, elimination catalyzer, crude product is through distillation, vacuum distilling removes and anhydrates and unreacted raw material and by product, gets finished product 69.1kg oxygen heterocyclic ring amine, yield 98.7%.

Implementation method two:

14.5kg oxygen heterocyclic ring aldehyde is sent in the autoclave, added the alloy catalyst of 0.2kg, under agitation feed hydrogen, the pressure that makes the interior thing of still maintain 160 ℃ of temperature and 6MPa reacts down, till pressure no longer descends; Cooling, the elimination catalyzer, the product of filtrate after fractionation sent in another reactor that fills 0.3kg copper alloy catalyzer and 9.6kg fat primary amine again, boiling in the control still, question response termination postcooling, the elimination catalyzer, crude product is through dephlegmate and unreacted raw material and by product, get finished product oxygen heterocyclic ring amine 22.3kg, yield 96.7%.

3, complex process example:

Implementation method one:

Oxygen heterocyclic ring amine 20kg is slowly added in the 75kg higly branched chain Fatty Alcohol(C12-C14 and C12-C18), add 1kg oxidation inhibitor and 4kg solubility promoter after mixing again successively, heated and stirred is final addition for leadless gasoline product when agent liquid is the shallow dark brown liquid of homogeneous.

Implementation method two:

Oxygen heterocyclic ring amine 6.7kg is slowly added in the 25kg higly branched chain Fatty Alcohol(C12-C14 and C12-C18), under 50 ℃ of temperature, mix, add 1.3kg solubility promoter and 0.4kg oxidation inhibitor more successively, stir and made the dark brown liquid of homogeneous in the agent liquid in 8 hours, liquid is crossed promptly got the finished product after 0.12mm copper sieves.

The invention effect:

The unleaded gas that uses unleaded gas additive of the present invention to produce, SH0041-91 presses in department through the You pass Standard test, indices is qualified. In addition through platform experiment to being added with 0.5～5 ‰ this unleaded gas additive The unleaded gas experimental results show that this additive has following characteristic:

● can be with 70^#Gasoline brings up to 90^#Gasoline;

● the scrubbing rate is 50%;

● use RON90 unleaded gas dynamic property and improve, external characteristics maximum work rate improves 0.8KW; 2200r The Zui high pulling torque Zeng of/min adds 3.7Nm;

● use RON90 unleaded gas economy and improve, external characteristics rate of economizing gasoline 2.1%, part throttle characteristics joint You leads 2.6～3.5%.

Claims

1, a kind of addition for leadless gasoline, it is characterized in that it by higly branched chain Fatty Alcohol(C12-C14 and C12-C18), oxygen heterocyclic ring amine, oxidation inhibitor and solubility promoter totally four kinds of material compositions mix and form.

2, additive as claimed in claim 1 is characterized in that said oxidation inhibitor is the di-t-butyl mixed phenol, and said solubility promoter is ether or alkylbenzene.

3, as claim 1,2 described additives, the content range that it is characterized in that constituting each material composition of this additive is:

Higly branched chain Fatty Alcohol(C12-C14 and C12-C18) 65～75%;

Oxygen heterocyclic ring amine 20～30%;

Oxidation inhibitor 0.5～1.5%;

Solubility promoter 3～5%.

4, be exclusively used in the technology of preparation claim 1,2,3 described additives, it is characterized in that comprising the synthesis technique of higly branched chain Fatty Alcohol(C12-C14 and C12-C18) component, the synthesis technique of oxygen heterocyclic ring amine component and the complex process of higly branched chain Fatty Alcohol(C12-C14 and C12-C18), oxygen heterocyclic ring amine, oxidation inhibitor and four kinds of components of solubility promoter, wherein

4.1, preparation technology's flow process of higly branched chain Fatty Alcohol(C12-C14 and C12-C18) is: the acetylene gas that the calcium carbide hydrolysis is produced is through freezing, purify, neutralization, dry back is introduced and is equipped with in the reactor of industrial anhydrous fat ketone or aldehyde, keep temperature in the kettle at 50～80 ℃, stirring tank internal reaction thing is to not drawing till the acetylene gas, stop logical acetylene gas, the reaction solution of producing is put into the autoclave that fills metal catalyst, feed hydrogen, keep temperature in the kettle and pressure and be respectively 50～150 ℃ and 4～8MPa, stirring tank internal reaction thing and continuous hydrogen make-up are till pressure stops to descend, after treating that still internal reaction thing is cooled to below 40 ℃, with nitrogen reactant is pressed in the still kettle, keep the interior boiling temperature of still and control reflux ratio 1～3: 1, after packing tower rectifying gets the finished product component;

4.2, preparation technology's flow process of oxygen heterocyclic ring amine is: oxygen heterocyclic ring aldehyde is added after elevated dosing vessel metering fill in the autoclave pressure of alloy catalyst, feed hydrogen, keep temperature in the kettle and pressure and be respectively 80～200 ℃ and 5～10MPa, repeatedly hydrogen make-up is till pressure stops to descend, cooling elimination catalyzer, the major product of filtrate after fractionation changes in another reactor that fills copper alloy catalyzer and aliphatic primary amine, the control temperature in the kettle is at 80～200 ℃, question response termination postcooling elimination catalyzer, crude product is through distillation, vacuum distilling remove anhydrate and unreacted raw material and by product after the component that gets product;

4.3, the complex process flow process of four kinds of components is: epoxy heterocyclic amine finished product component slowly is added in the higly branched chain Fatty Alcohol(C12-C14 and C12-C18) finished product component, after the stirring heating dissolving, add oxidation inhibitor and solubility promoter successively, continue to stir until being uniform solution, thing to be mixed is cooled to the material that gets product after the room temperature.