阅读说明：本技术 一种新型酯型柴油抗磨剂的制备工艺方法 (A kind of process of preparing of novel ester type diesel antiwear additive ) 是由 赵迎秋 黄占凯 赵洪 魏清 张晓行 董广前 王会 于 2019-08-31 设计创作，主要内容包括：本发明提供了一种新型酯型柴油抗磨剂的制备工艺方法,其包括以下步骤：在氮气保护氛围下,以物质的量比为0.9～1.1的多元醇与直链脂肪酸在带水剂和分子筛负载型催化剂存在下、在125℃～140℃下进行酯化反应8～10h；酯化反应完成后进行自然降温,当温度降低至58-62℃时,减压条件下抽提除去带水剂然后再将产物过滤以滤除分子筛负载型固体催化剂；待产物体系降至室温,在除去反应产物中残余的微量水分及无机物杂质后加入支链聚醚型抗乳化剂,再经过充分搅拌混合后即得到酯型柴油抗磨剂产品。本发明方法所制备的酯型柴油抗磨剂具有极低的酸值,其抗磨性能好,凝点极低,还具有极好的抗乳化性。(The present invention provides a kind of process of preparing of novel ester type diesel antiwear additive; itself the following steps are included: under nitrogen protection atmosphere, the polyalcohol and straight chain fatty acid that are 0.9~1.1 with the mass ratio of the material in the presence of water entrainer and molecular sieve carried type catalyst, 8~10h of esterification is carried out at 125 DEG C~140 DEG C；Temperature fall is carried out after the completion of esterification, when temperature is reduced to 58-62 DEG C, extracting removes water entrainer and then again filters product to filter out molecular sieve carried type solid catalyst under reduced pressure；It is down to room temperature to product system, branched polyether type anti emulsifier is added after remaining micro-moisture and inorganic contaminants in removing reaction product, using obtaining ester type diesel antiwear additive product after being thoroughly mixed.Ester type diesel antiwear additive prepared by the method for the present invention has extremely low acid value, and abrasion resistance is good, and condensation point is extremely low, also has fabulous resistance to emulsion.)

1. a kind of process of preparing of novel ester type diesel antiwear additive, which is characterized in that comprise the following steps that

1) under nitrogen protection atmosphere, the polyalcohol for being 0.9~1.1 with the mass ratio of the material and straight chain fatty acid in water entrainer and divide In the presence of son sieve loaded catalyst, 8~10h of esterification is carried out at 125 DEG C~140 DEG C；

2) Temperature fall is carried out after the completion of esterification, when temperature is reduced to 58-62 DEG C, extracting removes band water under reduced pressure Agent；Then product is filtered to filter out molecular sieve carried type solid catalyst again.

3) it is down to room temperature to product system, it is miscellaneous to remove micro-moisture and inorganic matter remaining in reaction product with molecular sieve method for refining Branched polyether type anti emulsifier is added in matter, and anti emulsifier dosage is the 2.0% of esterification products theoretical yield, by being sufficiently stirred Ester type antiwear additive product is obtained after mixing.

The molecular sieve carried type catalyst accounts for the 15%~50% of reactant gross mass, and water entrainer accounts for reactant gross mass 130%~180%.

2. process of preparing according to claim 1, which is characterized in that the water entrainer is dimethylbenzene.

3. process of preparing according to claim 1, which is characterized in that the object of the polyalcohol and straight chain fatty acid The amount ratio of matter is 1.0~1.05, and molecular sieve carried type catalyst accounts for the 28%~34% of reactant gross mass, and dimethylbenzene accounts for reaction The 150%~160% of object gross mass, esterification reaction temperature are 128 DEG C~136 DEG C, and the reaction time is 9~9.5h.

4. process of preparing according to claim 1, which is characterized in that the polyalcohol is selected from ethylene glycol, 1,3- One of propylene glycol, glycerine, 1,3-BDO.

5. process of preparing according to claim 1, which is characterized in that the straight chain fatty acid be selected from linoleic acid, One of oleic acid.

Technical field

The present invention relates to the process of preparing of the diesel antiwear additive of product oil additive agent field and applications.

Background technique

As countries in the world are to the pay attention to day by day of environmental issue, environmental protection and automobile industry propose more diesel quality index Carry out higher requirement, nitrogen, sulphur, arene content in diesel product index is required accordingly also more stringent.Meanwhile China in Automobile-used VI standard of petrol and diesel oil state for starting to carry out comprehensively from January 1st, 2019 has also carried out more diesel oil polycyclic aromatic hydrocarbon content Stringent limitation drops to 7% by 11%, and fall is strict in the standard of European Union 8% up to 36%.

The reduction of sulphur and arene content will directly or indirectly cause the anti-wear lubricity of hydrofining diesel oil to be deteriorated, to make up The wear resistence deficiency of diesel oil just needs to increase wear-resistant agent dose or uses the better antiwear additive of wear-resistant efficiency.It can be improved at present The additive of diesel oil abrasion resistance mainly has the classes compound such as carboxylic acid, ester, amide, ether, alcohols of long-chain.But due to amide, ether And the anti-wear effect of alcohol compound can not show a candle to carboxylic acids and ester type compound is obvious, so current antiwear additive is mainly fatty acid Type and ester type antiwear additive.Currently, China acid type antiwear additive to add dosage be 200mg/kg, 300mg/kg when, will be so that bavin Oleic acid degree increases separately 3-4mgKOH/100mL, 4-6mgKOH/100mL, exists when acid type antiwear additive dosage is larger and adds The risk of agent diesel oil acidity exceeded (standard is no more than 7mgKOH/100mL).Additionally, due to the diesel oil acid that acid type antiwear additive is added Value is still larger, when with carbon steel material Long Term Contact, diesel engine service performance can be influenced because of etching problem.

Ester type antiwear additive can form fine and close absorption due to containing the highly polar group of ester oxygroup in its molecule in metal surface Film, it may have friction and wear can be effectively reduced in very excellent abrasion resistance, and abrasion resistance is even better than used Acid type antiwear additive.Meanwhile ester type diesel antiwear additive adds agent diesel oil acidity index due to can be effectively controlled with extremely low acid value, And advantageously reduce the corrosion of engine associated components.With the implementation of automobile-used VI standard of petrol and diesel oil state in January, 2019 China, ester Type antiwear additive will have the tendency that gradually substituting acid type antiwear additive.

Summary of the invention

The purpose of the present invention is to overcome the deficiency in the prior art, provides a kind of novel, capable of being industrialized, simple and efficient Ester type antiwear additive process of preparing.

The present invention provides a kind of process of preparing of novel ester type diesel antiwear additive comprising following steps:

1) under nitrogen protection atmosphere, the polyalcohol and straight chain fatty acid that are 0.9~1.1 with the mass ratio of the material are in water entrainer With in the presence of molecular sieve carried type catalyst, at 125 DEG C~140 DEG C carry out 8~10h of esterification；

2) Temperature fall is carried out after the completion of esterification, when temperature is reduced to 58-62 DEG C, extracts and remove under reduced pressure Water entrainer；Then product is filtered to filter out molecular sieve carried type solid catalyst again；

3) it is down to room temperature to product system, removes in reaction product remaining micro-moisture and inorganic with molecular sieve method for refining Object impurity；

4) branched polyether type anti emulsifier is added, anti emulsifier dosage is the 2.0% of esterification products theoretical yield, through overcharging Divide after being stirred and obtains ester type diesel antiwear additive product；

The molecular sieve carried type catalyst accounts for the 15%~50% of reactant gross mass, and water entrainer accounts for the total matter of reactant The 130%~180% of amount.

In above-mentioned process of preparing, the water entrainer is preferably dimethylbenzene.

The mass ratio of the material of the polyalcohol and straight chain fatty acid is 1.0~1.05, and molecular sieve carried type catalyst accounts for The 28%~34% of reactant gross mass, dimethylbenzene account for the 150%~160% of reactant gross mass, esterification reaction temperature 128 DEG C~136 DEG C, the reaction time is 9~9.5h.

The polyalcohol is selected from one of ethylene glycol, 1,3-PD, glycerine, 1,3-BDO.

The straight chain fatty acid is selected from one of linoleic acid, oleic acid.

The abrasion resistance for the ester type diesel antiwear additive product that process of preparing of the present invention obtains can use state The generally acknowledged high-frequency reciprocating tester standard method (HFRR) in border is measured, standard No. be ISO 12156-1:1997 and ASTMD6079, China standard SH/T 0765-2005 are equal to international standard.Its working principle is that a metal ball is pressed in test Then on piece is immersed in test fuel, drive metal ball to make high frequency short stroke under certain load by electromagnetic oscillation device reciprocal Movement.The polishing scratch of metal ball is measured after the test, and wear scar diameter is smaller, it was demonstrated that the lubricity of fuel is better.The automobile-used bavin in China Oil requires the correction grinding defect diameter WSD of oil product no more than 420 μm, uses products obtained therefrom of the present invention plus agent diesel oil correction polishing scratch Diameter can be effectively controlled within 400 μm.

The process of preparing of ester type antiwear additive of the present invention compared with the prior art, it has the advantage that:

1) preparation method of the present invention uses molecular sieve carried type catalyst, and this catalyst is gathered around compared with ordinary solid acid catalyst There are more bigger serface and robust construction, there is more efficient catalysis efficiency, reaction efficiency can be greatly improved, and urge after reacting The separating and recovering of agent is simple, does not need specially to set up the processing step for removing acidand basecatalysts as traditional handicraft again；Together Remaining inorganic contaminants, further simplify production technology in the water removal of Shi Caiyong molecular sieve method for refining and esterification products.

2) it is had the advantage that using the obtained ester type antiwear additive product of process of preparing of the present invention

A has extremely low acid value (being no more than 1mgKOH/kg), can comply fully with " the Q/SHCG57- of middle petrochemical industry latest edition 2017 diesel antiwear additive technical requirements " acid value standard, needing large dosage to make applied to the worse Base Diesel of self-lubricity Used time hardly increases diesel oil acidity itself, to avoid the problem that existing antiwear additive is also easy to produce plus agent diesel oil acidity is exceeded；

B. the abrasion resistance of product is good, and adding dosage is usually 100~250mg/kg, has on an equal basis plus under dosage better than acid The abrasion resistance of type antiwear additive can more efficiently reduce diesel oil grinding defect diameter；

C. product condensation point is extremely low, is not in muddy condensation phenomenon when using in winter and under psychro-environment, and existing Commercially available ester type antiwear additive product causes it muddiness easily occur when using in winter or under psychro-environment since condensation point is not inconsistent standardization Condensation phenomenon is to influence the normal use of antiwear additive；

D. it joined branched polyether type anti emulsifier, product has fabulous resistance to emulsion, can be to avoid adding agent diesel oil newborn Change, is not in emulsification haze problem.

Specific embodiment