WO2013078631A1

WO2013078631A1 - Anti-wear agent of hydrocarbon fuel and use method thereof

Info

Publication number: WO2013078631A1
Application number: PCT/CN2011/083194
Authority: WO
Inventors: 熊靓
Original assignee: Xiong Liang
Priority date: 2011-11-30
Filing date: 2011-11-30
Publication date: 2013-06-06
Also published as: CN104024387A

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 Ν, Ν'-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

Hydrocarbon fuel antiwear agent and using method thereof

Technical field

The present invention relates to an antiwear agent suitable for use in a hydrocarbon fuel and a method of using the same, which is particularly suitable for use in gasoline and diesel for internal combustion engines, and can effectively improve stability and low temperature during storage of an antiwear agent. The operability of the engine, oil pump and nozzle surface deposition and wear, improve the use of hydrocarbon fuels such as gasoline and diesel.

Background technique

Detergents have been widely used as additives in gasoline and diesel to prevent surface deposition of the oil system and improve the surface finish and service life of the engine, especially in low-sulfur fuels with poor lubricity, to improve the lubricity of the oil. Required, otherwise the service life of the grease pump will be greatly affected. In the preparation of low-sulfur fuels, the removal of sulfur does not affect the lubricating properties of the fuel itself. However, when the deep hydrodesulfurization process is adopted, the lubricants naturally carried in the fuels such as aromatic organic compounds, carboxylic acids and lipids are also different. Removal of the degree. Commercially available gasoline and diesel detergents or dispersants, unless they are added in large amounts, they have a very limited effect on improving the lubricity of the oil, and the addition of high concentrations of detergents and dispersants will inevitably lead to the combustion of gasoline. Combustion chamber deposits (CCD) become unacceptable.

US Pat. No. 4,729,769 describes a gasoline carburetor detergent used as a gasoline component, which is a fatty acid composed of 6-20 carbon atoms (such as coconut oil) and single or two. ^: a product obtained by reacting a mono-, di-hydroxy hydrocarbyl amine, or a diethnol amine, but the gasoline added with the detergent needs to be added with an anti-icing agent when used in winter. .

Can replace the detergent or the use of detergent to reduce the frictional resistance of hydrocarbon fuels or increase Additives that add lubricity (commonly known as antiwear agents or lubricant improvers) are various types of fatty acids, fatty esters, amine and amide organics, and mixtures thereof. As previously studied, it has been found that saturated, haplotype or diploid linear fatty acids containing from 12 to 54 carbon atoms can be used as additives to enhance the lubricating properties of hydrocarbon fuels.

The linear fatty acids used as anti-wear agents or lubricant improvers are mostly natural products extracted from animals or plants, such as oleic acid, linoleic acid, stearic acid, tall. Tail oil fatty acid, linolenic acid, palmitic acid, coco fatty acid, and ricinoleic acid, but a few are synthetic products. For example, an anti-wear agent extracted from a fuel is disclosed in the international patent WO 01/72930 A2, which may also be combined with some polyetheramines (polyisobutene amines, Mannich bases and succinimides, etc.). use. Fatty acid esters, unsaturated dimerization are mentioned in the references of the patents (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). Formed by unsaturated dimerized fatty acids, primary aliphatic amines, diethanolamine, and long-chain aliphatic monocarboxylic acids Fatty acid amides. U.S. Patent No. 4,427,562, the disclosure of which is incorporated herein by reference to the entire entire entire entire entire entire entire entire entire entire entire disclosure The resulting anti-wear agent.

U.S. Patent No. 5,858,029 discloses an antiwear agent for fuels and lubricating oils comprising hydroxyamides which are the reaction products of primary etheramine and hydrocarboxylic acid. The reported anti-wear agent active ingredients are fatty acid formamides (US Pat No 4,789,493, 4,808,196,4, 867,752), fatty acids. Fatty acid amides (US Pat No. 4280916), amides obtained from mono or polyhydroxy substituted alphatic monocarboxylic acids and amine reactions (US Pat No 4,512,903), some acid and heterocyclic aromatic amines ( heterocyclixaromatic amine ) (US Pat No 6,328,771), a salt formed by a carboxylic acid and an aliphatic amine or a product of dehydration condensation (EP 0 798364 ) between a carboxylic acid and a fatty amine. JHI 夕卜洲洲 EP EP EP EP EP EP EP EP EP EP EP EP EP EP EP EP EP EP EP pat pat pat pat pat pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe pe No 4, 409, 000 and US Pat No 4, 836, 829 propose various uses of hydroxylamines as antiwear agents in fuels and lubricating oils, and US Pat. No. 2004/0010967 A1 also proposes saturated fatty acids and Alkoxyamine or etheramine is mixed as a drag reducer.

Some lubricating additives currently used, such as fatty acids, fatty acid amines or fatty acid amides, generally have a relatively large molecular weight, which solidifies at low temperatures, and sometimes even at room temperature, solidification occurs during the placement, and the solidified crystals are precipitated from the solution, thereby Causes trouble in operation. Dilution with an organic solvent can increase the crystallization temperature, which is called a cloud point or a cloud point, but this can only partially solve the problem because some components are still crystallized after dilution, and the solvent is also possible. It is colloidized and cured. Thus, when a large molecular weight fatty acid, a fatty acid amine or a fatty acid amide is used as a lubricating additive, it must be diluted in a large amount or stored in a heated container or added through a heating tube.

US Pat. No. 7,867, 295 B2 discloses that a branched carboxylic acid having 6 to 14 carbons can be used as a lubricant improver for hydrocarbon fuels (diesel, kerosene, gasoline, etc.), typical banding The carboxylic acids of the chain are isostearic acid, neodecanoic acid, isophthalic acid, neodecanoic acid and isodecanoic acid, etc. They may be saturated or unsaturated, and they may be saturated with other linear chains. Saturated carboxylic acids, as well as mono-, di- and tricarboxylic acids, etc. Typical linear carboxylic acids are oleic acid, linoleic acid, stearic acid, tall oil Tall oil fatty acid, linolenic acid, palmitic acid, coco fatty acid, and ricinoleic Acid) and so on. When a linear proportion of the branched carboxylic acid is mixed into the linear carboxylic acid, the cloud point of the mixture can be lowered by 3-6. C, wear scar diameter can be reduced by 5-10%, however, these branched carboxylic acids are low in nature, complex in synthesis, and generally costly.

In summary, some of the lubricating additives currently used, such as fatty acids, fatty acid amines or fatty acid amides, generally have a relatively large molecular weight, solidify at low temperatures, and solidify even at room temperature, and the solidified crystals are precipitated from the solution. This causes trouble in operation. Dilution with an organic solvent can only partially solve the problem because some components are still crystallized after dilution, and the solvent may be colloidalized and cured. Moreover, most organic solvents are not effective in reducing linear carboxylic acid antiwear agents. Therefore, when fatty acids, fatty acid amines or fatty acid amides are used as antiwear additives, they must be diluted or stored in heated containers. Or added by a heating tube, all of which will undoubtedly reduce the use efficiency of the anti-wear agent, increase the cost of use and the trouble of operation. Further, the use of a branched carboxylic acid mixed with a linear carboxylic acid can lower the cloud point and improve the lubricating performance, but the addition amount is relatively high and the use cost is also large.

Summary of the invention

The application of the present invention is to solve the above problems of the anti-wear agent used in the current hydrocarbon fuel, and to provide an anti-wear agent which can improve the low-temperature stability and flowability of the existing anti-wear agent. New antiwear agents for performance and methods of use.

One of the objects of the present application is to provide an antiwear agent for a hydrocarbon fuel. Specifically, the antiwear agent comprises a short chain fatty acid amide and a linear fatty acid, wherein the short chain fatty acid amide has the following formula compound of: Wherein R1, R2, and R3 are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and the total number of carbon atoms contained in R1, R2, and R3 is ≤10.

Further, in the anti-wear agent, the mass ratio of the short-chain fatty acid amide to the linear fatty acid is 1:100-10:1, preferably 1:50-2:1, more preferably 1:20-1: 1 , the best is 1: 10~1: 4.

Further, in the anti-wear agent, the short-chain fatty acid amide comprises dimethylformamide (DMF) or N, N, N, N'-dimethylacetamide (DMAC).

Further, in the anti-wear agent, the linear fatty acid includes a natural or artificially synthesized fatty acid having 3 to 60 carbon atoms or a mixture of one or more thereof, preferably a long-chain fatty acid having 10 to 60 carbon atoms. Or a mixture of one or more thereof; including oleic acid, linoleic acid, stearic acid, tall oil fatty acid, linolenic acid, palm Oil (palitic acid), coco fatty acid, ricinoleic acid, coconut oil, etc., and various synthetic fatty acids or a mixture of one or more thereof.

In the anti-wear agent, the ratio of the mixture of the short-chain fatty acid amide and the linear fatty acid varies depending on the type of the short-chain fatty acid amide and the linear fatty acid selected, and generally the pour point and the cloud point decrease with the short chain. The proportion of the fatty acid amide increases and the specific addition amount can be determined by the test depending on the temperature of the use region. If the lowest temperature in the area is -5 °C, different amounts of short-chain fatty acid amide can be added to the linear fatty acid, and the cloud point and pour point are measured. The cloud point refers to the liquid sample such as oil and varnish under standard conditions. Cooling to the temperature at which turbidity begins to appear; Pour point is the lowest temperature at which the cooled sample can flow under the specified test conditions, and is one of the parameters reflecting the low temperature fluidity of the oil. The lower the pour point, the better the low temperature fluidity of the oil; until the cloud point and pour point are higher than -5 °C.

Another object of the present application is to provide an anti-wear agent for use in a hydrocarbon-based fuel. The application includes adding the anti-wear agent into a hydrocarbon fuel (including gasoline and diesel), effectively improving the stability during storage of the linear fatty acid anti-wear agent and the operability at low temperatures, reducing the engine The surface of the oil pump and the nozzle is deposited and worn to improve the use of hydrocarbon fuels such as gasoline and diesel.

The anti-wear agent described in the present application includes, in addition to short-chain fatty acid amides and linear fatty acids, other hydrocarbon fuel additives, including detergents, antiknock agents, combustion catalysts, and cetane number improvement. Agent, pour point depressant, low temperature fluidity improver, anti-clouding agent, corrosion inhibitor, fungicide, antioxidant, stabilizer, fixative, demulsifier, copper corrosion inhibitor, conductivity additive, dyeing Or tracer (dye / marker), etc.

The anti-wear agent described in the application of the invention can improve the stability and fluidity of the existing long-chain fatty acid anti-wear agent under low temperature conditions, further improve the lubrication or drag reduction performance, and increase the operation convenience of the anti-wear agent. Compared with other similar methods, the degree and efficiency of use are relatively low, and the effect is good. In cold regions, especially in remote areas, when the pipeline heating is difficult to achieve, the anti-wear agent has a practical value of 4 艮.

detailed description

The anti-wear agent described in the present application is described below in conjunction with specific embodiments for the purpose of better understanding the technical content of the public, rather than limiting the technical content, in fact, in the same Or the principle of approximation, the addition, subtraction or replacement of the main components in the anti-wear agent, and the improvement of the ratio between the components to achieve the same effect are all foreseen by those skilled in the art. All of the technical solutions claimed in the application of the present invention.

Example 1

As shown in Table 1, the cloud point and the pour point are greatly reduced after adding different proportions of dimercaptophthalamide (DMF) in tall oil. The magnitude of the decrease varies with the amount of DMF added. By As can be seen from Table-1, the cloud point and the pour point gradually decrease as the amount of DMF added increases. Add 10% DMF (ie DMF as a percentage of the mixture of short-chain fatty acid amide and linear fatty acid), cloud point and pour point of tall oil and DMF mixture (measurement of cloud point is ASTM D2500, pour point) The measurement method is ASTM D97, which is a common technical means in the field, and will not be described here. The Tall oil without DMF is reduced by 3 °C. If 20% DMF is added, the cloud point and pour point are lowered respectively. 8 ! And 9 °C. Changes in cloud point and pour point after adding DMF to tall oil fatty acid FA-2

Example 2 As shown in Table 2, the addition of DMF to another tall oil fatty acid having a different origin also significantly reduced the cloud point and pour point of tall oil. Adding 20% DMF to tall oil, the cloud point and pour point of the mixture were reduced by 9 °C compared to the absence of DMF. Table-2 Changes in cloud point and pour point after adding DMF to tall oil fatty acid FA-2. Tall oil fatty acid 2 - LT 100 85 80 75 ( % ) DMF 0 15 20 25 Cloud point ( °C ) - 12 - 19 -21 -28 Pour point ( °c ) -17 -23 -26 -36 Example 3 Different amounts of DMF were added to oleic acid, linoleic acid and ricinoleic acid, respectively, and the pour point was significantly reduced, see Table-3: Effects of different amounts of DMF on the pour point of oleic acid, linoleic acid and ricinoleic acid

Different amounts of DMF were added to oleic acid, linoleic acid and ricinoleic acid, respectively, and the pour point was significantly reduced. See Table-4: Table-4 in oleic acid, linoleic acid and ricinoleic acid respectively. The effect of different amounts of DMAC on its pour point

Example 5 After adding different amounts of DMF to palm oil, cocoa fatty acid and coconut oil, the pour point was significantly reduced. See Table-5: Table-5 Adding different amounts to palm oil, cocoa fatty acid and coconut oil respectively Effect of DMF on its pour point

Example 6 After adding different amounts of DMAC to palm oil, cocoa fatty acid and coconut oil, the pour point was significantly reduced, as shown in Table-6: Table-6. Different amounts were added to palm oil, cocoa fatty acid and coconut oil. Effect of DMAC on its pour point

DMAC and linear fat palm oil cocoa fatty acid coconut oil fatty acid mass ratio pure agent (no DMAC) 17 °C -5 °C _4 °C

1: 100 8°C -17°C -13°C 1: 50 2°C _25°C or less _25°C or less

1: 20 -8 ° C _25 ° C or less _25 ° C or less

1: 10 -10 °C _25 °C or less _25 °C or less

1: 4 -12 ° C _25 ° C or less _25 ° C or less

1: 1 -14°C _25°C or less _25°C or less

2: 1 -17°C _25°C or less _25°C or less

10: 1 -20 °C _25 °C or less _25 °C or less

Example 7 In the application of an antiwear agent, the method using a mixture of a short chain fatty acid amide and a linear fatty acid did not reduce the abrasion resistance of the method using a linear fatty acid alone. The measurement method of diesel abrasion resistance is ASTM D6079 (Standard Test Method for Evaluating Lubricity of Diesel Fuels by the High - Frequency Reciprocating Rig (HFRR)), and the anti-wear agent A of Table-7 is 100% octadecadiene. Acid, anti-wear agent B is 80% octadecadienoic acid + 20% DMAC.

Diesel lubricity (measuring method of wear scar diameter ASTM D6079, unit μηι) Daqing 0 # diesel Antiwear agent

Oppm lOOppm 15 Oppm 200ppm

Antiwear agent A 440 359 340 339

Antiwear agent B 452 350 335 316 Example 8

Antiwear agent C is 100% tall oil fatty acid, and antiwear agent D is 80% tall oil fatty acid + 20% DMF.

Diesel lubricity (measurement method for wear scar diameter ASTM D6Q79, unit μηι)

It can be seen that the product with the mixed formula has a lower pour point, but the anti-wear performance is not affected.

Claims

An anti-wear agent for a hydrocarbon fuel, characterized in that: the anti-wear agent comprises a short-chain fatty acid amide and a linear fatty acid, wherein the short-chain fatty acid amide is a compound having the following formula:

〇 RP

II! ^

R L "~~ Ν "~~ R丄 · wherein R1, R2, and R3 are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and the total number of carbon atoms contained in R1, R2, and R3 is ≤10.

The antiwear agent according to claim 1, wherein in the antiwear agent, the mass ratio of the short-chain fatty acid amide to the linear fatty acid is 1:100-10:1.

The antiwear agent according to claim 2, wherein in the antiwear agent, the mass ratio of the short-chain fatty acid amide to the linear fatty acid is 1:50-2:1.

The antiwear agent according to claim 3, wherein in the antiwear agent, the mass ratio of the short-chain fatty acid amide to the linear fatty acid is 1:20-1:1.

The antiwear agent according to claim 4, wherein in the antiwear agent, the mass ratio of the short-chain fatty acid amide to the linear fatty acid is 1:10-1:4.

The antiwear agent according to any one of claims 1 to 5, wherein, in the antiwear agent, the short chain fatty acid amide comprises dinonyl amide or N, N, dimercaptoacetamide.

The antiwear agent according to any one of claims 1 to 5, wherein: in the antiwear agent, the linear fatty acid comprises a natural or synthetic fatty acid having 3 to 60 carbon atoms or a More than one mixture.

The antiwear agent according to claim 7, wherein in the antiwear agent, the linear fatty acid comprises a long chain fatty acid having 10 to 60 carbon atoms or a mixture of one or more thereof.

The antiwear agent according to claim 7, wherein: the anti-wear agent, a linear fat The acid includes oleic acid, linolenic acid, stearic acid, tall oil fatty acid, linseed oil, palm oil, cocoa fatty acid, castor oil or coconut oil or a mixture of one or more thereof.

10. Use of an antiwear agent according to claims 1-9 in a hydrocarbon fuel, said use comprising the addition of said antiwear agent to a hydrocarbon fuel.

11. The use of an antiwear agent according to claim 10 in a hydrocarbon fuel, characterized in that: the antiwear agent can be combined with a detergent, an antiknock agent, a combustion catalyst, a cetane improver. , pour point depressants, low temperature fluidity improvers, anti-clouding agents, corrosion inhibitors, fungicides, antioxidants, stabilizers, demulsifiers, copper corrosion inhibitors, antistatic agents, dyes or tracers One or several additives are used together.