CN104024387A

CN104024387A - Anti-wear agent of hydrocarbon fuel and use method thereof

Info

Publication number: CN104024387A
Application number: CN201180075206.5A
Authority: CN
Inventors: 熊靓
Original assignee: Individual
Current assignee: Individual
Priority date: 2011-11-30
Filing date: 2011-11-30
Publication date: 2014-09-03
Also published as: WO2013078631A1

Abstract

This application provides an anti-wear agent of hydrocarbon fuel. Main constituents of the anti-wear agent comprise short chain fatty acid amide and straight chain fatty acid. The short chain fatty acid amide is a compound with a general formula (I), R1, R2, and R3 being hydrogen atoms or alkyls each comprising 1 to 10 carbon atoms, and the total number of carbon atoms comprised in R1, R2, and R3 being less than or equal to 10. The mass ratio of the short chain fatty acid amide to the straight chain fatty acid is 1:100 to 10:1. The short chain fatty acid amide comprises dimethyl formamide or Nu, Nu'-dimethyl acetamide. The straight chain fatty acid comprises natural or synthetic fatty acid comprising 3 to 60 carbon atoms or a mixture comprising more than one kind of the natural or synthetic fatty acid. Compared with the existing long chain fatty acid anti-wear agent, the anti-wear agent of the present invention can improve the stability and fluidity at a low temperature, further improve the lubrication or drag reduction performance, and increase the operation convenience degree and use performance, and has a low cost, good effect, and wide application prospect.

Description

ANTI-WEAR AGENT OF HYDROCARBON FUEL AND USE METHOD THEREOF

A kind of hydrocarbon fuel antiwear additive and its application method

Technical field

The present application relates to a kind of antiwear additive and its application method suitable for hydrocarbon fuel, the antiwear additive is particularly suitable for use in the gasoline and diesel oil of internal combustion engine, operability when stability and the low temperature during antiwear additive is stored can be effectively improved, reduce the surface deposition of engine, oil pump and oil nozzle and wear and tear, improve the use function of the hydrocarbon fuels such as gasoline, diesel.

Background technology

Detersive is widely used as gasoline and procetane to prevent the surface of oil piping system from depositing and improve the surface smoothness and service life of engine, especially in the poor low-sulphur fuel of greasy property, the lubricity for improving oil product is required, and otherwise the service life of oil nozzle oil pump will be a greater impact.In the preparation of low-sulphur fuel, the removal of sulphur has no effect on the greasy property of fuel in itself, but when taking deep hydrodesulfurizationof technique, the lubricant carried naturally in the fuel such as aromatic series organic matter, carboxylic acid and lipid is also by different degrees of removal.Commercialized gasoline and diesel oil detergent or dispersant, unless the dosage of addition is very big, they are very limited to the effect for improving the lubricity of oil product, and the detersive and dispersant of addition high concentration will necessarily cause the combustion chamber deposit of gasoline（Combustion chamber deposits, CCD) become unacceptable.

United States Patent (USP) US Pat No 4,729,769 describe a kind of Petrol carburetter detersive as gasolene ingredient, and it is from the aliphatic acid being made up of 6-20 carbon atom（Such as coconut oil coconut oil) and single or two ^：Base base amine (mono-, di-hydroxy hydrocarbyl amine) product of ^ mouthfuls of diethyl tenth of the twelve Earthly Branches an ancient wind instrument amine (diethnol amine) reaction derives from, but the gasoline for adding the detersive needs to add anti-icer when using in winter.

Detersive or the reduction hydrocarbon fuel frictional resistance performance being used together with detersive or increasing can be substituted Plus the additive of its greasy property（It is commonly called as antiwear additive or lubrication modifier）There are all kinds of aliphatic acid, fatty ester, amine and acid amides type organic and its their mixture.As previous studies have been found that the straight chain fatty acid of saturation, single times containing 12-54 carbon atom or diploid is used as to improve the additive of hydrocarbon fuel greasy property.

Straight chain fatty acid as antiwear additive or lubrication modifier is generally the natural goods being extract from animal or plant, such as oleic acid（Oleic acid), leukotrienes（Linoleic acid), stearic acid (stearic acid), ready denier oil acid (tall oil fatty acid), linseed oil（Linolenic acid), the ^^ gates of a village oil（Palmitic acid), coconut fatty acid（Coco fatty acid) and castor oil (ricinoleic acid) etc., but also there is minority to be synthetic product.As disclosed a kind of antiwear additive extracted from fuel in the A2 of international monopoly WO 01/72930, it 1] it can also so expect detergent-dispersant additive (^ mouthfuls of polyetheramines with some, polyisobutene amines, Mannich bases and succinimides etc.）It is used together.In the bibliography of the patent（US Pat No 2, 252, 889, US Pat No 4, 185, 594, US Pat No US Pat No 4, 208, 190, US Pat No 4, 204, 481 and US Pat No 4, 428, 182) it refer to fatty acid ester (fatty acid esters), unsaturated dimerization month purport fat is sour (unsaturated dimerized fatty acids), the white amine of Yue Zhi fat race (primary aliphatic amines), the moon purport Fang Suan Ugly amine (fatty acid amides) that diethyl tenth of the twelve Earthly Branches an ancient wind instrument amine (diethanolamine) and long-chain month purport fat list are formed as sour (long-chain aliphatic monocarboxylic acids).United States Patent (USP) US Pat No 4,427,562 refer to one kind by alkoxyalkyl primary amine（Primary alkoxyalkylamines) and antiwear additive as produced by the ammonolysis (aminolysis) of sour (carboxylic acids) reaction or some Yue acid cruel (formate ester).

United States Patent (USP) US Pat No 5,858,029 disclose a kind of antiwear additive for fuel and lubricating oil, they include by primary ether amine (primary etheramine) and;Base is as the reaction product hydroxy amide of sour (hydrocarboxylic acid)（ hydroxyamides ).The antiwear additive active ingredient being reported also has aliphatic acid Yue acid amides（Fatty acid formamides) (US Pat No 4,789,493,4,808,196,4,867,752), aliphatic acid Acid amides (fatty acid amides) (US Pat No 4280916), the aliphatic mono-carboxylic acids substituted from single or multiple hydroxyl（Alphatic monocarboxylic acids) and amine reaction obtain acid amides (US Pat No 4,512,903), some are as sour and different ring aromatic amine (heterocyclixaromatic amine) (US Pat No 6,328,771), carboxylic acid and fatty amine（Aliphatic amine) between the salt that is generated or carboxylic acid and fatty amine dehydrogenation condense (dehydration condensation) (EP 0 798364) product.Foretell the g deficient A1 of continent patent EP 0 869 163 JHI sunset and (be related to alcohol epoxide amine（Ethoxylated amine)), US Pat No 4,086,172, US Pat No 4,129,508th, US Pat No 4,231,883, US Pat No 4,409,000 and US Pat No 4,836,829 propose various usage of the hydroxylamine as antiwear additive in fuel and lubricating oil, and the A 1 of US Pat No 2004/0010967 it is also proposed saturated fatty acid and alkoxyamine or ether amines mixing as drag reducer.

Some lubricating additives used at present are as larger such as molecular weight aliphatic acid, fatty acid amine or fatty acid amide, it can be solidified in low temperature, solidification phenomenon also even occurs in placement process in room temperature sometimes, the crystal of solidification can be separated out from solution, so as to cause operational trouble.Crystallization can be improved and form temperature, referred to as cloud point or cloud point by being diluted with organic solvent（Cloud point), but this can only partly solve problem, and because some components still can be come out by partial crystallization after dilution, and solvent is also possible to by colloidization and solidification.Thus, when the aliphatic acid, fatty acid amine or fatty acid amide of macromolecule are when as lubricating additive, it is necessary to diluted in large quantities or be stored in the container of heating or added by heating tube.

The B2 of United States Patent (USP) US Pat No 7,867,295, which are disclosed, to be used as hydrocarbon fuel with the branched carboxylic acid with 6-14 carbon（Diesel oil, kerosene, gasoline etc.）Lubrication modifier, typical branched carboxylic acid has sour isostearic acid, neodecanoic acid, isodecyl, new n-nonanoic acid and different n-nonanoic acid etc., they can be that saturation can also be undersaturated, they can with the saturations of other straight chains in unsaturated carboxylic acid and it is single, double be used together with tricarboxylic acids etc., the carboxylic acid of typical straight chain has oleic acid（Oleic acid), leukotrienes（Linoleic acid), stearic acid (stearic acid), ready denier oil acid（Tall oil fatty acid), linseed oil（Linolenic acid), palm oil (palmitic acid), cocoa month purport fat sour (coco fatty acid) and sesame oil (ricinoleic Acid) etc..It is mixed into the carboxylic acid of straight chain after a certain proportion of branched carboxylic acids, the cloud point of mixture can reduce 3-6.C, grinding defect diameter（Wear scar diameter) 5-10 % can be reduced, but these branched carboxylic acid contents in nature are low, artificial synthesized more complicated, cost is typically higher.

In summary, some lubricating additives used at present are as larger such as molecular weight aliphatic acid, fatty acid amine or fatty acid amide, can be solidified in low temperature, or even can also solidify in room temperature placement process, the crystal of solidification can be separated out from solution, so as to cause operational trouble.Being diluted with organic solvent also can only partly solve problem, because some components still can be come out by partial crystallization after dilution, and solvent is also possible to by colloidization and solidification.And most of organic solvent is bad for the effect of the carboxylic acid antiwear additive of reduction straight chain, thus, when aliphatic acid, fatty acid amine or fatty acid amide are when as antiwear additive, it must in large quantities be diluted or be stored in the container of heating or added by heating tube, all these effective utilizations that can certainly reduce antiwear additive, increase use cost and operational trouble.In addition, although cloud point and raising greasy property can be reduced by being mixed into straight-chain carboxylic acid using branched carboxylic acid, addition is higher, and use cost is also larger.

The content of the invention

The present patent application is the above mentioned problem existed for antiwear additive used in current hydrocarbon fuel, offer is a kind of can to improve the low-temperature stability and mobile performance of existing antiwear additive, while can also improve New Kind of Anti-Abrasion agent and its application method of the abrasion resistance of antiwear additive.

The first purpose of the present patent application is to provide a kind of antiwear additive of hydrocarbon fuel, specifically, and described antiwear additive includes short chain fatty acids acid amides and straight chain fatty acid, wherein, short chain fatty acids acid amides is the compound with below formula： Wherein, Rl, R2, R3 are hydrogen atom or are the alkyl containing 1 ~ 10 carbon atom, and the total number of carbon atoms≤10 contained in Rl, R2, R3.

Further, in the antiwear additive, the mass ratio of short chain fatty acids acid amides and straight chain fatty acid is 1: 100-10:1, preferably 1: 50~2：1, more preferably 1: 20~1：1, most preferably 1: 10~1： 4.

Further, in the antiwear additive, short chain fatty acids acid amides includes two Yue base Yue acid amides (dimethylformamide, DMF) or N, N, two Yue Ji Yi Ugly amine (N, N'- dimethylacetamide, DMAC)

Further, in the antiwear additive, straight chain fatty acid includes natural or synthetic aliphatic acid or its more than one mixture containing 3 ~ 60 carbon atoms, long chain fatty acids or its more than one mixture preferably containing 10 ~ 60 carbon atoms；Including oleic acid（Oleic acid), leukotrienes（Linoleic acid), stearic acid (stearic acid), ready denier oil acid（Tall oil fatty acid), linseed oil（Linolenic acid), palm oil (palmitic acid), coconut fatty acid (coco fatty acid), sesame oil (ricinoleic acid) and coconut oil（Coconut oil) etc. and various artificial synthesized aliphatic acid or its more than one mixture.

In described antiwear additive, short chain fatty acids acid amides is different with the species of straight chain fatty acid and different with selected short chain fatty acids acid amides with the ratio of the mixing of straight chain fatty acid, the reduction of general pour point and cloud point is as the ratio of short chain fatty acids acid amides increases and increases, and specific addition can be determined according to the temperature conditions of territory of use by testing.It it is -5 °C such as using region minimum temperature, different amounts of short chain fatty acids acid amides can then be added into straight chain fatty acid, and cloud point and pour point are determined, cloud point refers to that the fluid samples such as oils, varnish are cooled to the temperature for starting to become turbid in normal conditions；Pour point (Pour point) refers to oil product under prescribed test conditions, the flowable minimum temperature of cooled sample, is to reflect one of fine or not parameter of oil low-temperature mobility, pour point is lower, and the low temperature flow of oil product is better；Until the cloud point and pour point that are obtained all are higher than -5 °C.

Another purpose of the present patent application is to provide the application in hydrocarbon class A fuel A of above-mentioned antiwear additive, institute The application stated includes described antiwear additive being added into hydrocarbon class A fuel A（Including gasoline and diesel oil）, operability when stability and the low temperature during straight chain fatty acid antiwear additive is stored is effectively improved, the surface deposition of engine, oil pump and oil nozzle is reduced and weares and teares, improve the use function of the hydrocarbon fuels such as gasoline, diesel oil.

Antiwear additive described in the present patent application, in addition to short chain fatty acids acid amides and straight chain fatty acid, also include other hydrocarbon fuel additives, described additive include detersive, anti-knock agent, combustion catalyst, cetane number improver, pour-point depressant, low temperature flow promoter, anti-turbid dose, Slow erosions agent, bactericide, antioxidant, it is steady, determine agent, demulsifier, copper corrosion inhibitor, antistatic additive（Conductivity additive), dyeing or tracer (dye/marker) etc..

Antiwear additive described in the present patent application, the stability and mobility of existing long-chain fat acids antiwear additive under cryogenic can be improved, further improve its lubrication or resistance reducing performance, increase the operation convenience degree and effective utilization of this kind of antiwear additive, compared with other similar methods, advantage of lower cost, effect is preferable, in cold district particularly isolated area, when pipeline heating is difficult to, this antiwear additive has 4 blunt high practical values.

Embodiment

Below in conjunction with specific embodiment; the antiwear additive described in the present patent application to be described; purpose is in order to which the public is better understood from described technology contents; rather than the limitation to the technology contents; in fact; with identical or approximate principle; the increase and decrease or replacement carried out to main component in the antiwear additive; and between each component its ratio improvement; for the purpose of realizing identical effect; all it is that those of ordinary skill in the art can appreciate that, all within the present patent application technical scheme claimed.

Embodiment 1

As shown in table 1, two Yue base Yue acid amides of different proportion are added in tall oil（DMF) cloud point and pour point are all reduced significantly afterwards, and the amplitude of reduction is different and different with DMF addition, by Table -1 understands that cloud point and pour point are gradually reduced with the increase of DMF additions.(i.e. DMF accounts for the percentage composition of the mixture of whole short chain fatty acids acid amides and straight chain fatty acid to the DMF of addition 10%）, the cloud point and pour point of tall oil and DMF mixtures（The measuring method of cloud point is ASTM D2500, and the measuring method of pour point is ASTM D97, is all common technical means in the art, repeats no more here）, control, which is not added with DMF tall oil, all reduces by 3 °C, such as the DMF of addition 20%, and cloud point and pour point reduce by 8 respectively！With 9 °C.Added in ready denier oil acid FA -2 after DMF, the change of cloud point and pour point

Embodiment 2 as shown in table 2, at source adds DMF in different another ready denier oil acids, equally there is the cloud point and pour point of obvious reduction tall oil.The DMF of addition 20% contrasts the situation without DMF, the cloud point and pour point of mixture all reduce 9 °C into tall oil.Table-2 is added after DMF in ready denier oil acid FA-2, the cloud points of change component ready denier oil acid 2-LT 100 85 80 75 (%) DMF 0 15 20 25 of cloud point and pour point（ °C ) - 12 - 19 -21 -28 Pour point（° c)-17-23-26-36 embodiments 3 are separately added into different amounts of DMF in oleic acid, linoleic acid, castor oil acid, and its pour point has obvious reduction, is shown in Table-3:Influences of the different amounts of DMF to its pour point is separately added into oleic acid, linoleic acid, castor oil acid

Different amounts of DMF is separately added into oleic acid, linoleic acid, castor oil acid, its pour point has obvious reduction, is shown in Table -4:Table -4 is separately added into influences of the different amounts of DMAC to its pour point in oleic acid, linoleic acid, castor oil acid

Added in the palm oil of embodiment 5, coconut fatty acid and coconut oil after different amounts of DMF, its pour point has obvious reduction, is shown in Table -5:Table -5 is separately added into influences of the different amounts of DMF to its pour point in palm oil, coconut fatty acid, coconut oil

Added in the palm oil of embodiment 6, coconut fatty acid and coconut oil after different amounts of DMAC, its pour point has obvious reduction, is shown in Table -6:Table -6 is separately added into influences of the different amounts of DMAC to its pour point in palm oil, coconut fatty acid, coconut oil

DMAC and straight chain fat palm oil coconut fatty acid coconut oil fat acid 17 °C -5 °C _ 4 °C of pure dose of mass ratio (no DMAC)

1: 100 8°C -17°C -13°C 1:50 2 °C _ less than 25 °C _ less than 25 °C

1:20-8 °C _ less than 25 °C _ less than 25 °C

1:10-10 °C _ less than 25 °C _ less than 25 °C

1:4-12 °C _ less than 25 °C _ less than 25 °C

1:1-14 °C _ less than 25 °C _ less than 25 °C

2:1-17 °C _ less than 25 °C _ less than 25 °C

10:1-20 °C _ less than 25 °C _ less than 25 °C

For embodiment 7 is with the application of antiwear additive, using the method for short chain fatty acids acid amides and straight chain fatty acid blend, relatively individually using the method for straight chain fatty acid, its abrasion resistance does not decline.The measuring method of diesel oil wear resistence uses ASTM D6079 (Standard Test Method for Evaluating Lubricity of Diesel Fuels by the High-Frequency Reciprocating Rig (HFRR)), antiwear additive A is 100% octadecadienoic acid in table -7, and antiwear additive B is the % DMAC of 80 % octadecadienoic acids+20.

Diesel fuel lubricity（Grinding defect diameter measuring method ASTM D6079, unit μ η ι) 0 # diesel antiwear additive dosages of grand celebration

Oppm lOOppm 15 Oppm 200ppm

Antiwear additive A 440 359 340 339

Antiwear additive B 452 350 335 316 Embodiment 8

Antiwear additive C is 100% ready denier oil acid, and antiwear additive D is the % of 80% ready denier oil acid+20 DMF.

Diesel fuel lubricity（Grinding defect diameter measuring method ASTM D6Q79, unit μ η ι)

It can be seen that, it is lower using the product pour point of mixing formula, but abrasion resistance is not affected.

Claims

1st, a kind of antiwear additive of hydrocarbon fuel, it is characterised in that：Described antiwear additive includes short chain fatty acids acid amides and straight chain fatty acid, wherein, short chain fatty acids acid amides is the compound with below formula：

〇 RP

II ！ ^

Wherein, Rl, R2, R3 are hydrogen atom or are the alkyl containing 1 ~ 10 carbon atom R L " ~ ~ Ν " ~ ~ R Shang, and the total number of carbon atoms≤10 contained in Rl, R2, R3.

2nd, antiwear additive according to claim 1, it is characterised in that：In the antiwear additive, the mass ratio of short chain fatty acids acid amides and straight chain fatty acid is 1: 100-10: 1 .

3rd, antiwear additive according to claim 2, it is characterised in that：In the antiwear additive, the mass ratio of short chain fatty acids acid amides and straight chain fatty acid is 1: 50-2: 1.

4th, antiwear additive according to claim 3, it is characterised in that：In the antiwear additive, the mass ratio of short chain fatty acids acid amides and straight chain fatty acid is 1: 20-1 : 1.

5th, antiwear additive according to claim 4, it is characterised in that：In the antiwear additive, the mass ratio of short chain fatty acids acid amides and straight chain fatty acid is 1: 10-1 : 4.

6th, according to any described antiwear additives of claim 1-5, it is characterised in that：In the antiwear additive, short chain fatty acids acid amides includes two Yue base Yue acid amides or N, N, two Yue yl acetamides.

7th, according to any described antiwear additives of claim 1-5, it is characterised in that：In the antiwear additive, straight chain fatty acid includes natural or synthetic aliphatic acid or its more than one mixture containing 3 ~ 60 carbon atoms.

8th, antiwear additive according to claim 7, it is characterised in that：In the antiwear additive, straight chain fatty acid includes being long chain fatty acids or its more than one mixture containing 10-60 carbon atom.

9th, antiwear additive according to claim 7, it is characterised in that：In the antiwear additive, straight chain fatty Acid includes oleic acid, leukotrienes, stearic acid, ready denier oil acid, linseed oil, palm oil, coconut fatty acid, castor oil or coconut oil or its more than one mixture.

10th, application of the antiwear additive described in claim 1-9 in hydrocarbon class A fuel A, described application includes described antiwear additive being added into hydrocarbon class A fuel A.

11st, application of the antiwear additive according to claim 10 in hydrocarbon class A fuel A, it is characterised in that：Described antiwear additive can be with being used in conjunction with including one or more of additives in detersive, anti-knock agent, combustion catalyst, cetane number improver, pour-point depressant, low temperature flow promoter, anti-turbid dose, Slow erosions agent, bactericide, antioxidant, stabilizer, demulsifier, copper corrosion inhibitor, antistatic additive, coloring agent or tracer.