CN105779085A - Diesel oil clearing agent containing friction modifier and saving fuel oil and preparing method thereof - Google Patents

Diesel oil clearing agent containing friction modifier and saving fuel oil and preparing method thereof Download PDF

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Publication number
CN105779085A
CN105779085A CN201610108746.3A CN201610108746A CN105779085A CN 105779085 A CN105779085 A CN 105779085A CN 201610108746 A CN201610108746 A CN 201610108746A CN 105779085 A CN105779085 A CN 105779085A
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friction improver
oil
diesel oil
ester
fuel oil
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CN105779085B (en
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赫常山
王宜献
蔡德华
肖颖
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Beijing Refined Scholar's Clariant Petrochemical Complex Co Ltd
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Beijing Refined Scholar's Clariant Petrochemical Complex Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/09—Diamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C233/05—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/70—Esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C10M157/10—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a compound containing atoms of elements not provided for in groups C10M157/02 - C10M157/08
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/285—Esters of aromatic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/32—Esters of carbonic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/20—Containing nitrogen-to-oxygen bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26—Amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/04—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having a silicon-to-carbon bond, e.g. organo-silanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubricants (AREA)

Abstract

The invention provides a diesel oil clearing agent containing friction modifier and saving fuel oil and a preparing method thereof.The diesel oil clearing agent containing friction modifier and saving fuel oil is prepared from, by mass, 20-65% of clearing agent, 1-10% of dispersing agent, 5-20% of the friction modifier, 0.1-0.8% of antioxidant, 0.1-1% of antirusting agent,0.01-0.5% of demulsifier, 5-30% of cetane number improver, 5-35% of diluent and the balance carrier oil.The diesel oil clearing agent containing friction modifier and saving fuel oil is reasonable and scientific in composition, capable of effectively improving quality of diesel oil, increasing diesel oil cetane number and improving combustibility, obvious in oil saving effect, and capable of reducing pollution caused by automobile exhaust emission and reducing automobile operation cost and has good economic benefits and social benefits.

Description

A kind of diesel oil detergent saving fuel oil containing friction improver and preparation method thereof
Technical field
The present invention relates to a kind of fuel oil additive, particularly a kind of saving containing friction improver is fired Diesel oil detergent of oil and preparation method thereof.
Background technology
Low-sulfur, the appearance of ultra-low-sulphur diesel, although meet the requirement of environmental protection, but make diesel oil Self lubricity become extreme difference, result in dependence the oil transfer pump of diesel oil self-lubrication, high pressure fuel Jet pump excessive wear, the most therefore atomizer, piston gas ring and compression ring exist with upper bit Fretting wear phenomenon in various degree, greatly reduces service life and the combustion of fuel injection system Oil economy.Diesel fuel lubricity additive becomes the effective means solving this problem.Therefore at bavin On the basis of oil detersive, with the addition of diesel fuel lubricity agent, it is simply that in order to solve diesel oil in this respect Problem.Diesel oil detergent is with detergent-dispersant additive as host, and detergent-dispersant additive is efficient table Face activating agent, its polar group has the strongest adsorption capacity to established carbon distribution, deposit, Carbon distribution, deposit can be made gradually to loosen, and become little particle and be washed down, the most peace and quiet point Powder can stop little particle to form bulky grain and assemble on the metal surface, serves the work kept a public place clean With, engine work is served protective effect；Diesel fuel lubricity agent is using environment-friendly type combustion During material, by antifriction function, protect the normal operation of fuel injection system.
The present invention is directed to present derv fuel to meet the requirement of environmental protection, use low-sulfur, ultralow The oil transfer pump of diesel oil appearance of sulphur, jerk pump excessive wear, atomizer, piston gas There is fretting wear in various degree too in ring and compression ring, not only cause fuel oil to spray with upper bit Penetrate lifetime of system to shorten and make that fuel-oil atmozation is bad, the problems such as insufficient, oil consumption increasing of burning； By the application of multiple diesel fuel lubricity agent is found, being combined by suitable compounded diesel oil lubricant Diesel fuel additives, not only has the lubricant effect of excellence, at protection engine fuel injection system While, it is possible to play the effect saving fuel oil.
Summary of the invention
For the deficiencies in the prior art, the technical problem to be solved is to provide A kind of diesel oil detergent saving fuel oil containing friction improver.
In order to reach above effect, the Mannich base of one of host detergent-dispersant additive is closed Become, and host and friction improver are screened.
(1) synthesis of Mannich base:
The toluene of the p-t-butyl phenol of 0.1mol with 120ml is added in still, adds 0.4g P-methyl benzenesulfonic acid, stir, by charge door add polyamines polyene in still, be passed through nitrogen Gas, is warming up to 80 DEG C, adds paraformaldehyde, is continuously heating to 120-130 DEG C, reacts 3h, Keep this temperature, after water knockout drum no longer divides water, after having reacted, stand 1h, with 50--60 DEG C Organic layer is washed 5 times by hot water, carries out decompression separation impurity and both obtained this product after filter filters.
In order to make additive lubricity of the present invention more preferable, the further Mannich synthesized by utilization Alkali detersive and aliphatic acid have synthesized existing detergent-dispersant performance and have had again the multiple-effect of excellent lubricity concurrently Additive.
By synthesized Mannich Base Detergent 0.05mol, toluene 60ml, p-methyl benzenesulfonic acid 0.2mol Add in reactor, be passed through nitrogen, be heated with stirring to 60 DEG C, by charge door, add ten Eight acid, are continuously heating to 80 DEG C, react 1.5h, stop reaction.By the decompression point of gained material From impurity, obtain Mannich alkaline 18 fatty acid amine diesel antiwear additive.
(2) selection of host: high-activity polyisobutene amine, polyetheramine etc. be clean intake valve, The effective additive in the position such as inlet and exhaust valve, atomizer, combustion chamber be Diesel engine temperature high, The position that carbon distribution is more difficult to remove, particularly general detersive heat decomposition temperature is difficult to meet diesel oil and sends out The requirement of motivation, the best to the combustion chamber cleaning performance of hot environment, therefore, detersive master In the selection of agent, except selecting polyetheramine, high activity polybutene amine, high-activity polyisobutene Beyond succimide, the Mannich base that can effectively clean combustion chamber is carried out emphasis choosing Select.The Mannich base that four kinds obtain with different amine synthesis is added in diesel oil as a certain amount of, profit Detergency test is carried out, to obtain the Mannich base of best results with crankcase coking plate.Bent axle The experimental condition that case coking plate uses is: oil temperature 120 DEG C, 310 DEG C of cokings of plate temperature, time 4h. Result of the test such as following table:
Test data (burnt weight/mg):
Sample 1-4 is respectively ethylenediamine, diethylenetriamine, triethylene tetramine, N, N-dimethyl The Mannich base that-1,3 propane diamine prepare.
Data show that the Mannich base using ethylenediamine as polar group is as diesel oil detergent effect More preferably.Determine select p-t-butyl phenol ethylenediamine as the present invention diesel oil detergent component it One.
(3) selection of friction improver: the kind of diesel oil friction improver have alcohol, ether, ester, Carboxylic acid and amine, acid amides isoreactivity compound, wherein with aliphatic acid, fatty acid ester wear resistence For excellent, aliphatic acid antiwear additive has certain acidity, and the corrosivity of diesel oil can be caused to improve, with Time promote carbon deposit and the generation etc. of greasy filth in Diesel engine, it is impossible to meet low-sulfur diesel-oil comprehensively and resist The requirement of mill property.And the abrasion resistance of long chain fatty acid mono ester compound is good, oil-soluble is good, body System is stable, the most significantly negatively affects diesel fuel characteristics, constitutes aliphatic acid and the carbon of alcohol of ester Chain is the longest, and its overall abrasion resistance is more excellent, therefore uses the long chain alkane ester of different molecular weight Compounds is selected by four ball frictional testing machines.
The wear resistence of diesel antiwear additive is different from lubricating oil, therefore evaluates diesel oil with four-ball tester wear-resistant Property must reduce test load, shorten the time, we use the operating condition of four-ball tester to be: (1) Load 15kg, (2) rotating speed 1500r/min, (3) time 30min, (4) temperature: normal temperature.
Test compares sample two kinds of wear resistences added under dose profile in diesel oil.Following table is examination Test result data.
Result of the test: (wear scar diameter/mm)
Addition μ g/g Sample 1 Sample 2 Sample 3 Sample 4
200 0.400 0.420 0.376 0.362
400 0.335 0.360 0.314 0.306
Sample 1-4 be respectively tetradecanoic acid monooctyl ester, hexadecanoic acid propyl ester, hexadecanoic acid monooctyl ester, Tetradecanoic acid monooctyl ester and hexadecanoic acid monooctyl ester 1:1 mixture, by result of the test it can be seen that Along with the increase of the alkyl chain length of the acid and alcohol constituting ester, antifriction quality improves, two kinds of ester mixing ratios Single ester wear resistence is more preferable, and therefore selecting sample 4 is anti-friction agent of the present invention.
The present invention seeks to be achieved through the following technical solutions:
A kind of diesel oil detergent saving fuel oil containing friction improver, by following mass percent Raw material forms: detersive 20-65%, dispersant 1-10%, friction improver 5-20%, anti- Oxygen agent 0.1-0.8%, antirust agent 0.1-1%, demulsifier 0.01-0.5%, cetane number improver 5-30%, diluent 5-35%, surplus are carrier oil.
Preferably, described detersive is the one in Mannich base, polyetheramine or its mixture. Described polyetheramine can use the polyethers of model OGA-480 of commercially available Ao Lunnai company Amine.
Preferably, described dispersant is polyisobutylene succinamide or boronation polyisobutene Succimide.
Preferably, described friction improver be tetradecanoic acid monooctyl ester, hexadecanoic acid propyl ester, ten Mixing of one or more in six alkanoic acid butyl esters, hexadecanoic acid monooctyl ester, tetradecanoic acid butyl ester Compound.
It is highly preferred that described friction improver by 40-60wt% hexadecanoic acid butyl ester and 40-60wt% tetradecanoic acid butyl ester forms.
Preferably, described antioxidant can be a kind of in amine antioxidants, phenolic antioxidant or Multiple mixture, described amine antioxidants is 4,4'-dioctyl diphenylamine, and described phenols resists Oxygen agent is one or more in 2,5 di tert butyl hydroquinone, 2,6-di-tert-butyl hydroquinone Mixture；Described antioxidant can also use commercially available BASF Irganox64.
Preferably, described antirust agent is dodecenylsuccinic acid half ester or laurylene base fourth two Acid.
Preferably, described demulsifier is dimethicone or polyethers demulsifier, and polyethers is broken Emulsion can use commercially available Lu Borun LZ5172.
Preferably, described diluent is dimethyl carbonate.
Preferably, described cetane number improver can use commercially available Ya Fudun H4103, Can also be mixed by 20-40wt% cyclohexylamine and 60-80wt% isooctyl ester nitrate.
Preferably, described carrier oil is polyalkylene ether or tri trimellitate nonyl ester, poly-alkylene Base ether can use commercially available DOW Chemical OSP32.
Preferably, a kind of diesel oil detergent saving fuel oil containing friction improver, by following quality The raw material composition of percentage: Mannich base 35-45%, boronation polyisobutene succinimide 3-7%, friction improver 8-12%, 4,4'-dioctyl diphenylamine 0.1-0.3%, 2,5-bis-tertiary fourth Base hydroquinones 0.2-0.4%, dodecenylsuccinic acid 0.4-0.6%, dimethicone 0.05-0.2%, cyclohexylamine 2-4%, isooctyl ester nitrate 5-9%, dimethyl carbonate 15-25%, Surplus is tri trimellitate nonyl ester.
Described friction improver is by 40-60wt% hexadecanoic acid butyl ester and 40-60wt% 14 Alkanoic acid butyl ester forms.
Present invention also offers the system of the above-mentioned diesel oil detergent saving fuel oil containing friction improver Preparation Method, adds carrier oil and is in harmonious proportion in still, add detersive, dispersant, friction improver, Antioxidant, antirust agent are in carrier oil, and stirring is warming up to 70-80 DEG C, time 1.5-2.5h, It is cooled to 25-35 DEG C, adds diluent, demulsifier, cetane number improver, stir 0.5-1.5h, Release after 5 μm filters filter.
The present invention compared with conventional technology, be a kind of have fuel system is had excellence The composite diesel additive of self lubricity, can prevent oil transfer pump, jerk pump and spray Oil nozzle weares and teares, and reduces piston crown friction, keeps whole fuel path and atomizer, combustion chamber Cleaning, increases power, saves fuel oil, exhaust emissions is greatly reduced.The present invention changes containing friction Enter agent save fuel oil diesel oil detergent assemble rationally, science, can effectively improve diesel quality, Improving diesel cetane-number, improve flammability, oil-saving effect is obvious, and can reduce vehicle exhaust Exhaust emission, reduces automobilism cost, has good economic benefit and social benefit.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, the following stated, is only to this The preferred embodiment of invention, not does the restriction of other forms to the present invention, any familiar Professional and technical personnel is changed to become on an equal basis possibly also with the technology contents of the disclosure above The Equivalent embodiments changed.Every without departing from the present invention program content, the technology according to the present invention is real Any simple modification that confrontation following example are done or equivalent variations, all fall within the guarantor of the present invention In the range of protecting.
Each raw material introduction in embodiment 4-6:
Mannich base, synthetic method is as follows: by p-t-butyl phenol and the 120ml of 0.1mol Toluene add in still, add the p-methyl benzenesulfonic acid of 0.4g, stir, pass through charge door Addition polyamines polyene, in still, is passed through nitrogen, is warming up to 80 DEG C, adds paraformaldehyde, continues Continue and be warming up to 120-130 DEG C, react 3h, keep this temperature, after water knockout drum no longer divides water, After having reacted, stand 1h, with 50-60 DEG C of hot water, organic layer is washed 5 times, through filter mistake Carry out decompression separation impurity after filter and both obtain Mannich base.
Boronation polyisobutene succinimide, synthetic method is with reference to ten thousand strong heros, Feng Jieyong, Luo Xin Flat " development of boronation ashless dispersant and application ", lubricating oil, 2001, its structural formula is as follows:
Wherein, R be molecular weight be the polyisobutene of 1000, R'=H.
Hexadecanoic acid butyl ester, No. CAS: 111-06-8.
Tetradecanoic acid butyl ester, No. CAS: 110-36-1.
4,4'-dioctyl diphenylamines, No. CAS: 101-67-7.
2,5-di-tert-butyl hydroquinones, No. CAS: 88-58-4.
Dodecenylsuccinic acid, No. CAS: 29658-97-7.
Dimethicone, No. CAS: 63148-62-9.
Dimethyl carbonate, No. CAS: 108481-44-3.
Cyclohexylamine, No. CAS: 108-91-8.
Isooctyl ester nitrate, No. CAS: 73513-43-6.
Tri trimellitate nonyl ester, No. CAS: 35415-27-1.
Embodiment 1-5
By raw material proportioning in table 1 and prepare as follows and save fuel oil containing friction improver Gasoline cleaning agent.
Carrier oil is added and is in harmonious proportion in still, add detersive, dispersant, friction improver, resist Oxygen agent, antirust agent are in carrier oil, and stirring is warming up to 75 DEG C, and time 2h is cooled to 30 DEG C, Add diluent, demulsifier, cetane number improver, stir 1h, through 5 μm filters Release after filtration.
Table 1: embodiment 1-5 raw material proportioning list position: kg
Embodiment 6
Diesel oil detergent raw material (mass percent) containing friction improver saving fuel oil: Manny Uncommon alkali 40%, boronation polyisobutene succinimide 5%, friction improver 10%, 4,4'-bis- Octyl diphenylamine 0.2%, 2,5 di tert butyl hydroquinone 0.3%, dodecenylsuccinic acid 0.5%, dimethicone 0.1%, cyclohexylamine 3%, isooctyl ester nitrate 7%, dimethyl carbonate 20%, surplus is tri trimellitate nonyl ester.
Described friction improver is by 50wt% hexadecanoic acid butyl ester and 50wt% tetradecanoic acid Butyl ester is uniformly mixed and obtains.
Prepared by the diesel oil detergent saving fuel oil containing friction improver: added by tri trimellitate nonyl ester Enter and be in harmonious proportion in still, add Mannich base, boronation polyisobutene succinimide, friction improver, 4,4'-dioctyl diphenylamine, 2,5 di tert butyl hydroquinone, dodecenylsuccinic acid are to inclined benzene In three sour three nonyl esters, it is warming up to 75 DEG C, 400 revs/min of mixings time 2h, it is cooled to 30 DEG C, Add dimethyl carbonate, dimethicone, cyclohexylamine, isooctyl ester nitrate, 400 revs/min of stirrings 1h, filters through 5 μm filters.Obtain embodiment 6 saves fuel oil containing friction improver Diesel oil detergent.
Embodiment 7
Prepare the diesel oil detergent saving fuel oil containing friction improver, district as described in Example 6 It is not only in that: described friction improver is only hexadecanoic acid butyl ester.Obtain embodiment 7 Containing friction improver save fuel oil diesel oil detergent.
Embodiment 8
Prepare the diesel oil detergent saving fuel oil containing friction improver, district as described in Example 6 It is not only in that: described friction improver is only tetradecanoic acid butyl ester.Obtain embodiment 8 Containing friction improver save fuel oil diesel oil detergent.
Test case 1
The diesel oil detergent containing friction improver saving fuel oil above example 1-8 prepared enters The test of row analog detection and road actual driving test.
1, detergency simulation test
Thermal oxidation process is used to be simulated test the detergency of above 8 embodiments.Method Being to be put into by the steel disc of polishing in 300 grams of diesel oil added with additive, steel disc addition is 0.3g, Heat in the case of condensing reflux and keep 150 degree, and leading to continuously with the flow of 10ml/min Enter air 10 hours, measure the deposit weight generated on test steel disc after off-test and evaluate The performance of detersive, deposit weightening finish is the fewest, then explanation diesel oil detergent suppression diesel oil deposit The performance generated is the best.Steel disc weightening finish data such as table 2 below:
Table 2: detergency simulation test experiment tables of data unit: mg
Steel disc increases weight
Embodiment 1 6.5
Embodiment 2 7.6
Embodiment 3 5.3
Embodiment 4 6.8
Embodiment 5 6.2
Embodiment 6 4.8
Embodiment 7 5.6
Embodiment 8 6.1
Result of the test shows that the present invention contains friction improver and saves the diesel oil detergent suppression of fuel oil The effect of diesel oil oxidation deposition is the best, has good cleaning dispersibility.
2, road real steering vectors
Test information of vehicles:
Testing scheme: test vehicle comes and goes Baiyang Lake, Beijing, each vehicle load 9000kg, One comes and goes as single test, Fuel Remained in fuel tank is put before setting out clean metering every time, presses Fuel tank is added after adding the diesel oil detergent saving fuel oil containing friction improver by the ratio of 1:700 Full.
The diesel cleaning saving fuel oil containing friction improver prepared by 8 embodiments of the present invention Agent, carries out a test respectively, and the fuel oil of comparative example is without any diesel oil detergent.Test Result such as table 3 below.
Table 3: oil-saving effect test tables of data
Project Oil consumption/L Rate of economizing gasoline/%
Embodiment 1 88.2 13.95
Embodiment 2 87.6 14.53
Embodiment 3 86.5 15.61
Embodiment 4 86.8 15.32
Embodiment 5 87.1 15.02
Embodiment 6 81.3 16.10
Embodiment 7 85.1 15.64
Embodiment 8 83.9 15.56
Diesel oil detergent of the present invention has also carried out emission detections test on above-mentioned vehicle.
Vehicle uses saving containing friction improver of 8 embodiment gained of the present invention to fire successively The diesel oil detergent of oil is tested, and comparative example, for being not added with any diesel oil detergent, is surveyed every time Examination is discharged in the case of stablizing after vehicle travels 50 kilometers, enters tail gas with tail-gas analyzer Row detection, measures Vehicular exhaust smoke intensity with auto smokemeter.Test result such as table 4 below.
Table 4: exhaust emission testing result table
The diesel oil detergent that the present invention saves fuel oil containing friction improver assembles rationally, science, energy Effectively improving diesel quality, improve diesel cetane-number, improve flammability, oil-saving effect is bright Aobvious, and motor vehicle exhaust emission pollution can be reduced, reduce automobilism cost, there is good warp Ji benefit and social benefit.
Comparing embodiment 6 and embodiment 7-8, embodiment 6 (hexadecanoic acid butyl ester and the tetradecane Acid butyl ester compounds) cleansing performance is substantially better than embodiment 7-8 (hexadecanoic acid butyl ester and ten Single raw material in four alkanoic acid butyl esters).

Claims (10)

1. the diesel oil detergent saving fuel oil containing friction improver, it is characterised in that by The raw material composition of following mass percent: detersive 20-65%, dispersant 1-10%, friction Modifier 5-20%, antioxidant 0.1-0.8%, antirust agent 0.1-1%, demulsifier 0.01-0.5%, Cetane number improver 5-30%, diluent 5-35%, surplus are carrier oil.
2. the diesel oil detergent saving fuel oil containing friction improver as claimed in claim 1, It is characterized in that, described detersive is the one in Mannich base, polyetheramine or its mixture.
3. the diesel oil detergent saving fuel oil containing friction improver as claimed in claim 1, It is characterized in that, described dispersant is polyisobutylene succinamide or boronation polyisobutene Succimide.
4. the diesel oil detergent saving fuel oil containing friction improver as claimed in claim 1, It is characterized in that, described friction improver be tetradecanoic acid monooctyl ester, hexadecanoic acid propyl ester, ten Mixing of one or more in six alkanoic acid butyl esters, hexadecanoic acid monooctyl ester, tetradecanoic acid butyl ester Compound.
5. the diesel oil detergent saving fuel oil containing friction improver as claimed in claim 4, It is characterized in that, described friction improver by 40-60wt% hexadecanoic acid butyl ester and 40-60wt% tetradecanoic acid butyl ester forms.
6. the diesel oil detergent saving fuel oil containing friction improver as claimed in claim 1, It is characterized in that, described antioxidant can be a kind of in amine antioxidants, phenolic antioxidant or Multiple mixture, described amine antioxidants is 4,4'-dioctyl diphenylamine, and described phenols resists Oxygen agent is one or more in 2,5 di tert butyl hydroquinone, 2,6-di-tert-butyl hydroquinone Mixture.
7. the diesel oil detergent saving fuel oil containing friction improver as claimed in claim 1, It is characterized in that, described antirust agent is dodecenylsuccinic acid half ester or laurylene base fourth two Acid.
8. the diesel oil detergent saving fuel oil containing friction improver as claimed in claim 1, It is characterized in that, described demulsifier is dimethicone or polyethers demulsifier, and described is dilute Releasing agent is dimethyl carbonate, and described carrier oil is polyalkylene ether or tri trimellitate nonyl ester.
9. the diesel oil detergent saving fuel oil containing friction improver as claimed in claim 1, It is characterized in that, be made up of the raw material of following mass percent: Mannich base 35-45%, boron Change polyisobutene succinimide 3-7%, friction improver 8-12%, 4,4'-dioctyl diphenylamine 0.1-0.3%, 2,5 di tert butyl hydroquinone 0.2-0.4%, dodecenylsuccinic acid 0.4-0.6%, Dimethicone 0.05-0.2%, cyclohexylamine 2-4%, isooctyl ester nitrate 5-9%, carbonic acid diformazan Ester 15-25%, surplus are tri trimellitate nonyl ester；
Described friction improver is by 40-60wt% hexadecanoic acid butyl ester and 40-60wt% 14 Alkanoic acid butyl ester forms.
10. the bavin of fuel oil is saved as claimed in any one of claims 1-9 wherein containing friction improver The preparation method of oil detersive, adds carrier oil and is in harmonious proportion in still, add detersive, dispersant, Friction improver, antioxidant, antirust agent are in carrier oil, and stirring is warming up to 70-80 DEG C, time Between 1.5-2.5h, be cooled to 25-35 DEG C, add diluent, demulsifier, Cetane number improve Agent, stirs 0.5-1.5h, releases after 5 μm filter.
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CN107488526A (en) * 2017-07-25 2017-12-19 中山市非特永旺汽车用品有限公司 A kind of anti-rust cleaning agent of turbocharger of motor and preparation method thereof
CN108728184A (en) * 2018-05-30 2018-11-02 青岛涌泉华能源科技有限公司 A kind of environmental protection and energy saving rose diesel exhaust detersive and preparation method thereof
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CN110157505A (en) * 2019-05-31 2019-08-23 钟幸华 High cleaning fuel oil carbon distribution detersive and preparation method thereof
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CN111019736A (en) * 2019-11-15 2020-04-17 山西潞安矿业(集团)有限责任公司 Sulfur-phosphorus-free organic friction modifier and preparation method thereof
CN111378516A (en) * 2020-04-23 2020-07-07 中国科学院上海高等研究院 Organic friction modifier with different isomeric alkyl end chains and preparation method thereof
CN116622423A (en) * 2023-04-20 2023-08-22 青岛威仕普环保节能科技有限公司 Multi-effect fuel oil detergent capable of reducing oil consumption and emission and preparation method thereof

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CN111378516B (en) * 2020-04-23 2022-04-12 中国科学院上海高等研究院 Organic friction modifier with different isomeric alkyl end chains and preparation method thereof
CN116622423A (en) * 2023-04-20 2023-08-22 青岛威仕普环保节能科技有限公司 Multi-effect fuel oil detergent capable of reducing oil consumption and emission and preparation method thereof
CN116622423B (en) * 2023-04-20 2024-03-15 青岛威仕普环保节能科技有限公司 Multi-effect fuel oil detergent capable of reducing oil consumption and emission and preparation method thereof

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