CN105779085B - A kind of diesel oil detergent and preparation method thereof for saving fuel oil containing friction improver - Google Patents

A kind of diesel oil detergent and preparation method thereof for saving fuel oil containing friction improver Download PDF

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Publication number
CN105779085B
CN105779085B CN201610108746.3A CN201610108746A CN105779085B CN 105779085 B CN105779085 B CN 105779085B CN 201610108746 A CN201610108746 A CN 201610108746A CN 105779085 B CN105779085 B CN 105779085B
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friction improver
oil
detergent
diesel oil
diesel
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CN105779085A (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
    • 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
    • C10M2207/10—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
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    • 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 present invention provides a kind of diesel oil detergent and preparation method thereof for saving fuel oil containing friction improver, the diesel oil detergent that fuel oil is saved containing friction improver is made of the raw material of following mass percents：Detersive 20-65%, dispersant 1-10%, friction improver 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.The diesel oil detergent that the present invention saves fuel oil containing friction improver assembles reasonable, science, diesel quality can be effectively improved, improve diesel cetane-number, improve flammability, oil-saving effect is apparent, and motor vehicle exhaust emission pollution can be reduced, reduce automobilism cost, with good economic efficiency and social benefit.

Description

A kind of diesel oil detergent and preparation method thereof for saving fuel oil containing friction improver
Technical field
The present invention relates to a kind of fuel oil additive, a kind of particularly diesel oil detergent for saving fuel oil containing friction improver And preparation method thereof.
Background technology
The appearance of low-sulfur, ultra-low-sulphur diesel makes the self lubricity of diesel oil become pole although meeting the requirement of environmental protection Difference results in the oil transfer pump by diesel oil self-lubrication, jerk pump excessive wear, atomizer, piston gas ring and gas Similarly therefore there are different degrees of fretting wear phenomenons with upper bit for ring, and greatly reduce fuel injection system uses the longevity Life and fuel economy.Diesel fuel lubricity additive is at effective means to solve this problem.Therefore in the base of diesel oil detergent On plinth, it is added to diesel fuel lubricity agent, exactly in order to solve the problems, such as diesel oil in this respect.Diesel oil detergent is with detergent-dispersant additive For host agent, detergent-dispersant additive is efficient surfactant, and polar group has very strong suction to established carbon distribution, deposit Attached ability can make carbon distribution, deposit gradually loose, and be washed down as little particle, while detergent-dispersant additive can prevent Little particle forms bulky grain aggregation on the metal surface, plays the role of keeping a public place clean, protection is played to engine work Effect；Diesel fuel lubricity agent, by antifriction function, protects the normal of fuel injection system during using Environment-friendlyfuel fuel Operating.
The present invention meets the requirement of environmental protection for present derv fuel, is occurred using the diesel oil of low-sulfur, super-low sulfur Oil transfer pump, jerk pump excessive wear, atomizer, piston gas ring and compression ring similarly exist different degrees of with upper bit Fretting wear, not only cause the fuel injection system lost of life and make fuel-oil atmozation it is bad, burning it is insufficient, oil consumption increase The problems such as；It is found by the application to a variety of diesel fuel lubricity agent, by the compound diesel additive of appropriate compounded diesel oil lubricant, Not only there is excellent lubricant effect, while protecting engine fuel injection system, can play the role of saving fuel oil.
Invention content
For the deficiencies in the prior art, technical problem to be solved by the invention is to provide one kind to improve containing friction The diesel oil detergent of fuel oil is saved in agent.
In order to reach the above effect, the Mannich base of one of host agent detergent-dispersant additive is synthesized, and to host agent and Friction improver is screened.
(1) synthesis of Mannich base：
The toluene of the p-tert-butylphenol of 0.1mol and 120ml are added in kettle, the p-methyl benzenesulfonic acid of 0.4g is added, is stirred Uniformly, polyamines polyene is added in kettle by charge door, is passed through nitrogen, be warming up to 80 DEG C, paraformaldehyde is added, is continuously heating to 120-130 DEG C, 3h is reacted, this temperature is kept, after water knockout drum no longer divides water, after the completion of reaction, 1h is stood, with 50--60 DEG C of heat Water washs organic layer 5 times, and decompression separation impurity is carried out after filter filters and both obtains this product.
In order to keep additive of the present invention lubricity more preferable, synthesized Mannich Base Detergent and fat are further utilized Acid has synthesized the multipurpose additive that existing detergent-dispersant performance has both excellent lubricity again.
By synthesized Mannich Base Detergent 0.05mol, toluene 60ml, p-methyl benzenesulfonic acid 0.2mol is added in reaction kettle, It is passed through nitrogen, is heated with stirring to 60 DEG C, by charge door, stearic acid is added, is continuously heating to 80 DEG C, reacts 1.5h, is stopped anti- It answers.By resulting material decompression separation impurity to get 18 fatty acid amine diesel antiwear additive of Mannich alkaline.
(2) selection of host agent：High-activity polyisobutene amine, polyetheramine etc. are cleaning intake valve, inlet and exhaust valve, atomizer etc. The effective additive in position, combustion chamber are the position that diesel engine temperature is high, carbon distribution is more difficult to remove, especially general detersive Heat decomposition temperature is difficult to meet the requirement of diesel engine, bad to the combustion chamber cleaning performance of hot environment, therefore, peace and quiet In the selection of agent host agent, other than selecting polyetheramine, high activity polybutene amine, high-activity polyisobutene succimide, Mannich base to can effectively clean combustion chamber has carried out focal selection.The Manny that four kinds are synthesized with different amines Uncommon alkali is added to as a certain amount of in diesel oil, detergency experiment is carried out using crankcase coking plate, to obtain the Mannich of best results Alkali.The experimental condition that crankcase coking plate uses for：120 DEG C of oil temperature, 310 DEG C of cokings of plate temperature, time 4h.Test result is as follows Table：
Test data (coke weight/mg)：
Sample 1-4 is respectively ethylenediamine, diethylenetriamine, triethylene tetramine, N, made from -1,3 propane diamine of N- dimethyl Mannich base.
Data show more preferable as diesel oil detergent effect by the Mannich base of polar group of ethylenediamine.Determine selection pair Diesel oil detergent component one of of the tert-butyl phenol ethylenediamine as the present invention.
(3) selection of friction improver：The type of diesel oil friction improver has alcohol, ether, ester, carboxylic acid and amine, amide etc. Reactive compound, wherein being excellent with aliphatic acid, fatty acid ester wear resistence, aliphatic acid antiwear additive has certain acidity, can lead The raising of corrosivity of diesel oil is caused, while promoting the generation etc. of carbon deposit and greasy filth in diesel engine, low-sulfur bavin cannot be met comprehensively The requirement of oily wear resistence.And the abrasion resistance of long chain fatty acid mono ester compound is good, oil-soluble is good, stable system, to diesel oil It can not negatively affect significantly, the carbochain of the aliphatic acid and alcohol that constitute ester is longer, and overall abrasion resistance is better, therefore adopts It is selected by four ball frictional testing machines with the long chain alkane ester type compound of different molecular weight.
The wear resistence of diesel antiwear additive is different from lubricating oil, therefore must reduce experiment with four-ball tester evaluation diesel oil wear resistence Load, shorten the time, we use the operating condition of four-ball tester for：(1) load 15kg, (2) rotating speed 1500r/min, (3) time 30min, (4) temperature：Room temperature.
Experiment compares sample two kinds of wear resistences added under dose profile in diesel oil.Following table is test result data.
Test result：(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 is respectively tetradecanoic acid monooctyl ester, hexadecanoic acid propyl ester, hexadecanoic acid monooctyl ester, tetradecanoic acid monooctyl ester and ten Six alkanoic acid monooctyl esters 1:1 mixture, by test result as can be seen that with the sour increase with the alkyl chain length of alcohol for constituting ester, Antifriction quality improves, and the single ester wear resistence of two kinds of ester mixing ratios is more preferable, therefore selects sample 4 for anti-friction agent of the present invention.
Purpose of the present invention is to what is be achieved through the following technical solutions：
A kind of diesel oil detergent for saving fuel oil containing friction improver, is made of the raw material of following mass percents：It is peace and quiet Agent 20-65%, dispersant 1-10%, friction improver 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.
Preferably, the detersive is or mixtures thereof one kind in Mannich base, polyetheramine.The polyetheramine can With using the polyetheramine of the model OGA-480 of commercially available Ao Lunnai companies.
Preferably, the dispersant is polyisobutylene succinamide or boronation polyisobutene succinimide.
Preferably, the friction improver is tetradecanoic acid monooctyl ester, hexadecanoic acid propyl ester, hexadecanoic acid butyl ester, ten One or more mixtures in six alkanoic acid monooctyl esters, tetradecanoic acid butyl ester.
It is highly preferred that the friction improver is by 40-60wt% hexadecanoic acids butyl ester and 40-60wt% tetradecanoic acids Butyl ester forms.
Preferably, the antioxidant can be mixture one or more in amine antioxidants, phenolic antioxidant, institute It is 4,4&apos to state amine antioxidants;Dioctyl diphenylamine, the phenolic antioxidant are 2,5- di-tert-butyl hydroquinones, 2,6- bis- One or more mixture in tert-butyl hydroquinone；The antioxidant can also use commercially available BASF Irganox64。
Preferably, the antirust agent is dodecenylsuccinic acid half ester or dodecenylsuccinic acid.
Preferably, the demulsifier is dimethicone or polyethers demulsifier, and city may be used in polyethers demulsifier The Lu Borun LZ5172 sold.
Preferably, the diluent is dimethyl carbonate.
Preferably, commercially available Ya Fudun H4103 may be used in the cetane number improver, can also be by 20- 40wt% cyclohexylamine and 60-80wt% isooctyl ester nitrates mix.
Preferably, the carrier oil is that city may be used in polyalkylene ether or tri trimellitate nonyl ester, polyalkylene ether The DOW Chemical OSP32 sold.
Preferably, a kind of diesel oil detergent for saving fuel oil containing friction improver, by the raw material group of following mass percents At：Mannich base 35-45%, boronation polyisobutene succinimide 3-7%, friction improver 8-12%, 4,4'Dioctyl two Aniline 0.1-0.3%, 2,5 di tert butyl hydroquinone 0.2-0.4%, dodecenylsuccinic acid 0.4-0.6%, dimethyl-silicon Oily 0.05-0.2%, cyclohexylamine 2-4%, isooctyl ester nitrate 5-9%, dimethyl carbonate 15-25%, surplus are tri trimellitate nonyl Ester.
The friction improver is by 40-60wt% hexadecanoic acids butyl ester and 40-60wt% tetradecanoic acid butyl ester groups At.
The present invention also provides the preparation methods of the above-mentioned diesel oil detergent that fuel oil is saved containing friction improver, by carrier oil It is added and reconciles in kettle, detersive, dispersant, friction improver, antioxidant, antirust agent is added in carrier oil, stirring is warming up to 70-80 DEG C, time 1.5-2.5h, it is cooled to 25-35 DEG C, diluent, demulsifier, cetane number improver is added, stirs 0.5- 1.5h is released after 5 μm of filters filter.
The present invention compared with previous technology, be it is a kind of have have the compound of excellent self lubricity to fuel system Type diesel fuel additives can prevent oil transfer pump, jerk pump and atomizer abrasion, reduce piston crown friction, keep whole A fuel path and atomizer, combustion chamber cleaning, increase power, save fuel oil, exhaust emissions is greatly reduced.The present invention, which contains, to rub The diesel oil detergent for wiping modifier saving fuel oil assembles reasonable, science, can effectively improve diesel quality, improve diesel fuel cetane Value improves flammability, and oil-saving effect is apparent, and can reduce motor vehicle exhaust emission pollution, reduces automobilism cost, has good Economic benefit and social benefit.
Specific implementation mode
With reference to embodiment, the present invention is described further, as described below, is only the preferable implementation to the present invention Example, not limits the present invention, any person skilled in the art is possibly also with the disclosure above Technology contents be changed to the equivalent embodiment changed on an equal basis.Without departing from the concept of the present invention, according to the present invention Technical spirit any simple modification that following embodiment is made or equivalent variations, all fall in protection scope of the present invention.
Each raw material introduction in embodiment 4-6：
Mannich base, synthetic method are as follows：The toluene of the p-tert-butylphenol of 0.1mol and 120ml are added in kettle, added The p-methyl benzenesulfonic acid for entering 0.4g, stirs evenly, and polyamines polyene is added in kettle by charge door, is passed through nitrogen, is warming up to 80 DEG C, Paraformaldehyde is added, is continuously heating to 120-130 DEG C, reacts 3h, keeps this temperature, after water knockout drum no longer divides water, reacted Cheng Hou stands 1h, is washed organic layer 5 times with 50-60 DEG C of hot water, and decompression separation impurity is carried out after filter filters and both obtains Manny Uncommon alkali.
Boronation polyisobutene succinimide, synthetic method is with reference to ten thousand strong heros, Feng Jieyong, Luo Xinping《Boronation ashless disperses The development and application of agent》, lubricating oil, 2001, structural formula is as follows：
Wherein, R is the polyisobutene that molecular weight is 1000, R'=H.
Hexadecanoic acid butyl ester, No. CAS：111-06-8.
Tetradecanoic acid butyl ester, No. CAS：110-36-1.
4,4'Dioctyl diphenylamine, 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
Prepare by raw material proportioning in table 1 and as follows the gasoline cleaning agent of the saving fuel oil containing friction improver.
Carrier oil is added and is reconciled in kettle, detersive, dispersant, friction improver, antioxidant, antirust agent is added in carrier In oil, stirring is warming up to 75 DEG C, time 2h, is cooled to 30 DEG C, and diluent, demulsifier, cetane number improver, stirring is added 1h is released after 5 μm of filters filter.
Table 1：Embodiment 1-5 raw material proportioning lists position：kg
Embodiment 6
The diesel oil detergent raw material (mass percent) of fuel oil is saved containing friction improver：Mannich base 40%, boronation are poly- Isobutene succimide 5%, friction improver 10%, 4,4'Dioctyl diphenylamine 0.2%, 2,5- di-t-butyls are to benzene two Phenol 0.3%, dodecenylsuccinic acid 0.5%, dimethicone 0.1%, cyclohexylamine 3%, isooctyl ester nitrate 7%, carbonic acid diformazan Ester 20%, surplus are tri trimellitate nonyl ester.
The friction improver is stirred by 50wt% hexadecanoic acids butyl ester and 50wt% tetradecanoic acid butyl esters Uniformly obtain.
It is prepared by the diesel oil detergent that fuel oil is saved containing friction improver：Tri trimellitate nonyl ester is added and is reconciled in kettle, is added Enter Mannich base, boronation polyisobutene succinimide, friction improver, 4,4'Dioctyl diphenylamine, 2,5- di-t-butyls pair In benzenediol, dodecenylsuccinic acid to tri trimellitate nonyl ester, 75 DEG C are warming up to, 400 revs/min of mixing time 2h are cooled to 30 DEG C, dimethyl carbonate, dimethicone, cyclohexylamine, isooctyl ester nitrate, 400 revs/min of stirring 1h, by 5 μm of filters are added Filtering.Obtain the diesel oil detergent that fuel oil is saved containing friction improver of embodiment 6.
Embodiment 7
The diesel oil detergent for saving fuel oil containing friction improver is prepared as described in Example 6, is differed only in：It is described Friction improver be only hexadecanoic acid butyl ester.Obtain the diesel oil detergent that fuel oil is saved containing friction improver of embodiment 7.
Embodiment 8
The diesel oil detergent for saving fuel oil containing friction improver is prepared as described in Example 6, is differed only in：It is described Friction improver be only tetradecanoic acid butyl ester.Obtain the diesel oil detergent that fuel oil is saved containing friction improver of embodiment 8.
Test case 1
The diesel oil detergent that fuel oil is saved containing friction improver prepared by above example 1-8 is subjected to analog detection experiment With the practical driving test of road.
1, detergency simulation test
Simulation test is carried out using thermal oxidation process to the detergency of above 8 embodiments.Method is the steel disc that will be polished It is put into 300 grams of diesel oil added with additive, steel disc addition is 0.3g, and 150 are heated and kept in the case of condensing reflux Degree, and air is continuously passed through 10 hours with the flow of 10ml/min, the deposit generated on experiment steel disc is measured after the test Weight evaluates the performance of detersive, and deposit weightening is fewer, then illustrate the property that diesel oil detergent inhibits diesel oil deposit to generate It can be better.Steel disc weightening data such as the following table 2：
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
Test result shows that the present invention saves the diesel oil detergent inhibition diesel oil oxidation deposition of fuel oil containing friction improver Effect is very good, has good cleaning dispersibility.
2, road real steering vectors
Test information of vehicles：
Testing scheme：Round-trip Beijing-the Baiyang Lake of test vehicle, each vehicle load 9000kg, one round-trip for primary examination It tests, Fuel Remained in fuel tank is put into net metering before setting out every time, by 1:700 ratio is added saves fuel oil containing friction improver Fuel tank is filled it up with after diesel oil detergent.
The diesel oil detergent that fuel oil is saved containing friction improver prepared by 8 embodiments of the present invention, carries out one respectively The fuel oil of secondary experiment, comparative example does not add any diesel oil detergent.Test result is as follows table 3.
Table 3：Oil-saving effect test data table
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 experiment on above-mentioned vehicle.
Vehicle successively using the present invention 8 embodiments obtained by containing friction improver save fuel oil diesel oil detergent into Row experiment, comparative example are to be not added with any diesel oil detergent, and test every time discharges stable situation after vehicle travels 50 kilometers Under, tail gas is detected with tail-gas analyzer, Vehicular exhaust smoke intensity is measured with auto smokemeter.Test result is as follows table 4.
Table 4：Exhaust emission testing result table
The diesel oil detergent that the present invention saves fuel oil containing friction improver assembles reasonable, science, can effectively improve diesel oil Quality improves diesel cetane-number, improves flammability, and oil-saving effect is apparent, and can reduce motor vehicle exhaust emission pollution, reduces vapour Vehicle operating cost, with good economic efficiency and social benefit.
Comparing embodiment 6 and embodiment 7-8, embodiment 6 (hexadecanoic acid butyl ester and tetradecanoic acid butyl ester compounding) are clear Net performance is substantially better than embodiment 7-8 (single raw material in hexadecanoic acid butyl ester and tetradecanoic acid butyl ester).

Claims (8)

1. a kind of diesel oil detergent for saving fuel oil containing friction improver, which is characterized in that by the raw material of following mass percents Composition：Detersive 20-65%, dispersant 1-10%, friction improver 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；
The friction improver is made of 40-60wt% hexadecanoic acids butyl ester and 40-60wt% tetradecanoic acid butyl esters.
2. the diesel oil detergent of fuel oil is saved containing friction improver as described in claim 1, which is characterized in that described is peace and quiet Agent is or mixtures thereof one kind in Mannich base, polyetheramine.
3. the diesel oil detergent of fuel oil is saved containing friction improver as described in claim 1, which is characterized in that the dispersion Agent is polyisobutylene succinamide or boronation polyisobutene succinimide.
4. the diesel oil detergent of fuel oil is saved containing friction improver as described in claim 1, which is characterized in that the antioxygen Agent can be 4,4&apos for mixture one or more in amine antioxidants, phenolic antioxidant, the amine antioxidants;Dioctyl Diphenylamines, the phenolic antioxidant are a kind of or more in 2,5- di-tert-butyl hydroquinones, 2,6- di-tert-butyl hydroquinones The mixture of kind.
5. the diesel oil detergent of fuel oil is saved containing friction improver as described in claim 1, which is characterized in that the antirust Agent is dodecenylsuccinic acid half ester or dodecenylsuccinic acid.
6. the diesel oil detergent of fuel oil is saved containing friction improver as described in claim 1, which is characterized in that the demulsification Agent is dimethicone or polyethers demulsifier, and the diluent is dimethyl carbonate, and the carrier oil is polyalkylene Ether or tri trimellitate nonyl ester.
7. the diesel oil detergent of fuel oil is saved containing friction improver as described in claim 1, which is characterized in that by following quality The raw material of percentage forms：Mannich base 35-45%, boronation 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%, dimethyl carbonate 15-25%, Surplus is tri trimellitate nonyl ester；
The friction improver is made of 40-60wt% hexadecanoic acids butyl ester and 40-60wt% tetradecanoic acid butyl esters.
8. the preparation method of the diesel oil detergent that fuel oil is saved containing friction improver as described in any one of claim 1-7, Carrier oil is added and is reconciled in kettle, detersive, dispersant, friction improver, antioxidant, antirust agent is added in carrier oil, stirs It mixes and is warming up to 70-80 DEG C, time 1.5-2.5h, be cooled to 25-35 DEG C, diluent, demulsifier, cetane number improver is added, 0.5-1.5h is stirred, is released after 5 μm of filterings.
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