CN111100721A - Lubricating oil base oil and preparation method thereof - Google Patents

Lubricating oil base oil and preparation method thereof Download PDF

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Publication number
CN111100721A
CN111100721A CN201811255638.4A CN201811255638A CN111100721A CN 111100721 A CN111100721 A CN 111100721A CN 201811255638 A CN201811255638 A CN 201811255638A CN 111100721 A CN111100721 A CN 111100721A
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reaction
acid
base oil
eleostearic acid
lubricating oil
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CN111100721B (en
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曹长海
李澜鹏
王宜迪
程瑾
李秀峥
彭绍忠
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/36—Esters of polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • 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
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C10M2207/2825—Esters of (cyclo)aliphatic oolycarboxylic acids used as base material

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)

Abstract

The invention relates to a preparation method of lubricating oil base oil, which comprises the steps of firstly, taking eleostearic acid as a raw material, stirring and simultaneously purging nitrogen in the presence of a polymerization inhibitor, heating to 180-230 ℃ for reaction, and removing monoacid after the reaction is finished to obtain a product; then mixing with monohydric alcohol, and carrying out esterification reaction in the presence of a catalyst to obtain the lubricating oil base oil. The lubricating oil base oil is prepared by using eleostearic acid as a raw material to prepare dimer acid and then reacting the dimer acid with monohydric alcohol, and has the advantages of low pour point, high flash point, good lubricating property, good bearing capacity and the like.

Description

Lubricating oil base oil and preparation method thereof
Technical Field
The invention belongs to the field of preparation of lubricating oil base oil, and particularly relates to lubricating oil base oil and a preparation method thereof.
Background
In recent years, with the development of economy, the demand of society for lubricating oils for vehicles has rapidly increased, and in some special applications such as open systems or disposable circulation systems using metal working oils, chainsaw oils, outboard two-stroke engine oils, open gear oils, and the like, the lubricating oils are inevitably discharged directly into the environment due to use, leakage, and the like. Mineral-based lubricating oils have poor biodegradability in the natural environment, accumulate in the environment and cause pollution to the ecological environment. Various large petroleum companies around the world have developed environment-friendly green lubricating oils to replace traditional mineral-based lubricating oils. The base oil is a determining factor influencing the biodegradability of the lubricating oil, compared with common mineral oil, the ester lubricating oil has better viscosity-temperature property and low temperature property, low volatility, stable chemical property, degradability, reproducibility and good flame resistance, and is widely used in various high-end fields such as aircraft engine lubricating oil, high-temperature chain oil, compressor oil, high-grade automobile engine oil, precision instrument oil, metal cutting fluid and the like.
CN102787001A discloses a dibasic acid diester-structured lubricating oil base oil and a preparation method thereof, wherein the base oil is prepared by esterifying long carbon chain dibasic acid and aliphatic monohydric alcohol with a branched chain. The chemical formula is R2-H2COOC-R1-COOCH2-R2Wherein: r1Is C9-C12 straight chain alkylene. The invention adopts long carbon chain dibasic acid as raw material to obtain diester base oil R1Is a straight chain alkylene group, and the carbon number is less than or equal to 12, so that the flash point and the pour point of the catalyst are influenced, namely the flash point is lower and the pour point is higher.
Wang fir, etc. (Synthesis of biodegradable dimer acid esters and research on frictional wear properties thereof [ J ]. Megaku Proc., 2005,25 (5): 403-. A series of dimer acid series esters are prepared by using industrial-grade dimer acid, and the synthesized dimer acid series esters have good viscosity-temperature performance. However, the raw materials for preparing dimer acid have a part of linear chain connection mode in the carbon chain connection between the diester, so that the pour point of dimer acid is higher, and the use of dimer acid is limited.
Therefore, the research and development of the lubricant base oil with lower pour point and higher flash point are of great significance.
Disclosure of Invention
The invention aims to provide lubricating oil base oil and a preparation method thereof. The lubricating oil base oil is prepared by using eleostearic acid as a raw material to prepare dimer acid and then reacting the dimer acid with monohydric alcohol, and has the advantages of low pour point, high flash point, good lubricating property, good bearing capacity and the like.
The preparation method of the lubricating oil base oil provided by the invention comprises the following steps:
(1) taking eleostearic acid as a raw material, stirring and simultaneously blowing nitrogen in the presence of a polymerization inhibitor, heating to 180-230 ℃ for reaction, and removing monoacid after the reaction is finished to obtain a product;
(2) and (2) mixing the product obtained in the step (1) with monohydric alcohol, and carrying out esterification reaction in the presence of a catalyst to obtain the lubricating oil base oil.
In the invention, the eleostearic acid in the step (1) can be commercial eleostearic acid or self-made eleostearic acid, and preferably the eleostearic acid with the iodine value of 160g/100g and the acid value of 150 mg KOH/g.
In the invention, the polymerization inhibitor in the step (1) may be one or more selected from a phenol polymerization inhibitor, a quinone polymerization inhibitor, an aromatic nitro compound polymerization inhibitor and the like, preferably at least one selected from hydroquinone, p-benzoquinone, methyl hydroquinone, tert-butyl hydroquinone, phenothiazine and the like, more preferably tert-butyl hydroquinone or/and phenothiazine, and the amount of the polymerization inhibitor is 1 per thousand-2%, preferably 5 per thousand-1% of the eleostearic acid by mass.
In the present invention, the stirring speed in step (1) is 50-500rpm, preferably 200-400 rpm. The nitrogen purging time is 1-30min, preferably 20-30 min. Furthermore, trace nitrogen purging is kept during the whole reaction process, and the flow rate is 0.1-1.0mL/min, preferably 0.5-0.7mL/min, so that the reaction is facilitated.
In the invention, the reaction temperature in the step (1) is 180-230 ℃, preferably 200-220 ℃; the reaction time is 2-7h, preferably 3-5 h.
In the invention, the unreacted monoacid removed in the step (1) is removed by adopting a molecular distillation method, and the distillation pressure is less than or equal to 3Pa, preferably 1-2 Pa; the distillation temperature is 140 ℃ to 180 ℃, preferably 160 ℃ to 180 ℃. The process and conditions only remove monoacid efficiently, and the obtained product is mainly dimer acid.
In the present invention, the monohydric alcohol in step (2) may be at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-octanol, isooctanol, etc., preferably isooctanol. The molar ratio of alcoholic hydroxyl groups to carboxyl groups in the reaction is from 2:1 to 6:1, preferably from 3:1 to 4: 1.
In the invention, the catalyst in the step (2) adopts an acid catalyst, for example, the catalyst can be a liquid acid catalyst, such as one or more of sulfuric acid, p-toluenesulfonic acid, heteropoly acid and the like, and the addition amount is 0.1-10%, preferably 1-5% of the total mass of the reaction system. (ii) a Or solid acid catalyst, such as one or more of cationic resin, HZSM-5, amberlyst15 resin, etc., and when fixed bed reactor is adopted, the reaction space velocity is 1-10h-1Preferably 1-5h-1Space velocity, defined as the feedstock mass flow rate (kilograms per hour)-1) Catalyst mass (kg).
In the invention, the esterification reaction in the step (2) can adopt a kettle type stirring reactor or a fixed bed reactor, and the reaction temperature is 100-180 ℃, preferably 110-160 ℃; the reaction time is 2-6h, preferably 2-4 h.
In the invention (2), an auxiliary agent, such as at least one of n-heptane, toluene, cyclohexane, etc., is further added during the esterification reaction, and the addition amount is 5-20% of the total mass of the reaction system.
The lubricating oil base oil is prepared by the method, and mainly contains dimeric tung oil acid diester, a small amount of trimeric tung oil acid triester and a trace amount of polyest. The chemical general formula of the dimer eleostearic acid diester in the lubricating oil base oil prepared by the invention is R2-H2COOC-R1-COOCH2-R2Wherein: r1Is an alkyl chain containing 34 carbons and also contains a ring structure; r2Is a branched alkyl group of C3-C8. Compared with the prior lubricating oil base oil, the molecular weight of the product of the inventionHigh, the carbon chains between the diester are mainly connected through a ring structure, so that the flash point is high and the pour point is low.
The tung oil-based lubricating oil base oil prepared by the invention can be used as aviation engine lubricating oil, air compressor lubricating oil, automobile engine lubricating oil, heavy-load gear oil or ultralow-temperature engine oil.
Compared with the prior art, the invention has the following advantages:
(1) the lubricating oil base oil prepared by the invention mainly contains dimeric tung oil acid diester, and carbon chains between the diester are mainly connected through a ring structure, so that the pour point is lower, the flash point is higher, and the practicability is higher.
(2) The product of tung oil-based dimer acid prepared by the invention only removes monoacid and retains trimer acid and poly-polyacid, so that the product contains a small amount of triester tripulowneate and polyester polyecuronoleic acid, thereby increasing the branching degree of the product, being beneficial to improving the flash point and reducing the pour point.
(3) The invention adds the auxiliary agent in the esterification reaction, which is beneficial to improving the esterification rate, and the esterification rate is more than 95 percent.
Detailed Description
The preparation method and effect of the lubricant base oil according to the present invention will be further described by examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified. Commercial eleostearic acid was purchased from Anhui ruifeng oil deep processing Co.
Esterification rate = (reaction starting acid value-reaction end acid value)/reaction starting acid value × 100%.
In the present invention, the acid value was measured in accordance with GB 5009.229-2016, the flash point was measured in accordance with GB/T3536-2006, and the pour point was measured in accordance with GB/T3535-2006. Before the flash point and pour point tests, the lubricating base oil in the step (2) needs to be refined by the steps of reduced pressure distillation, alkali washing, water washing and reduced pressure distillation.
Example 1
(1) Commercial eleostearic acid (iodine value 150g/100g, acid value 180 mgKOH/g) was used. Placing 100g of commercial eleostearic acid into a 250mL four-neck flask, simultaneously adding 0.5g of tert-butyl hydroquinone, stirring at the speed of 300rpm, purging with nitrogen for 30min, heating to 220 ℃ for reaction for 4h, stopping heating, performing separation and purification by molecular distillation, wherein the distillation pressure of a molecular distillation apparatus is less than or equal to 2Pa, the distillation temperature is 170 ℃, and removing unreacted monoacid to obtain a product mainly containing dimer acid.
(2) 55.7g of the product mainly containing dimer acid and 39.1g of isooctanol are taken and placed in a 250mL four-neck flask, 0.668g of p-toluenesulfonic acid is added as a catalyst at the same time, and the reaction is carried out for 4 hours at 120 ℃ to obtain the lubricating oil base oil product.
Example 2
(1) Commercial eleostearic acid (iodine value 150g/100g, acid value 180 mgKOH/g) was used. Placing 100g of commercial eleostearic acid into a 250mL four-neck flask, simultaneously adding 0.5g of tert-butyl hydroquinone, stirring at the speed of 300rpm, purging with nitrogen for 30min, heating to 220 ℃ for reaction for 4h, stopping heating, performing separation and purification by molecular distillation, wherein the distillation pressure of a molecular distillation apparatus is less than or equal to 2Pa, the distillation temperature is 170 ℃, and removing unreacted monoacid to obtain a product mainly containing dimer acid.
(2) 55.7g of the product mainly containing dimer acid and 39.1g of ethanol are put into a 250mL four-neck flask, 0.668g of p-toluenesulfonic acid is added as a catalyst at the same time, and the reaction is carried out for 4 hours at 120 ℃ to obtain the lubricating oil base oil product.
Example 3
(1) Commercial eleostearic acid (iodine value 150g/100g, acid value 180 mgKOH/g) was used. Placing 100g of commercial eleostearic acid into a 250mL four-neck flask, simultaneously adding 0.5g of tert-butyl hydroquinone, stirring at the speed of 300rpm, purging with nitrogen for 30min, heating to 220 ℃ for reaction for 4h, stopping heating, performing separation and purification by molecular distillation, wherein the distillation pressure of a molecular distillation apparatus is less than or equal to 2Pa, the distillation temperature is 170 ℃, and removing unreacted monoacid to obtain a product mainly containing dimer acid.
(2) 55.7g of the product mainly containing dimer acid and 39.1g of n-butanol are put into a 250mL four-neck flask, 0.668g of p-toluenesulfonic acid is added as a catalyst at the same time, and the reaction is carried out for 4 hours at 120 ℃ to obtain the lubricating oil base oil product.
Example 4
(1) Commercial eleostearic acid (iodine value 150g/100g, acid value 180 mgKOH/g) was used. Placing 100g of commercial eleostearic acid into a 250mL four-neck flask, simultaneously adding 0.5g of tert-butyl hydroquinone, stirring at the speed of 300rpm, purging with nitrogen for 30min, heating to 220 ℃ for reaction for 4h, stopping heating, performing separation and purification by molecular distillation, wherein the distillation pressure of a molecular distillation apparatus is less than or equal to 2Pa, the distillation temperature is 170 ℃, and removing unreacted monoacid to obtain a product mainly containing dimer acid.
(2) 55.7g of the product mainly containing dimer acid and 39.1g of n-amyl alcohol are put into a 250mL four-neck flask, 0.668g of p-toluenesulfonic acid is added as a catalyst at the same time, and the reaction is carried out for 4 hours at 120 ℃ to obtain the lubricating oil base oil product.
Example 5
(1) Commercial eleostearic acid (iodine value 150g/100g, acid value 180 mgKOH/g) was used. Placing 100g of commercial eleostearic acid into a 250mL four-neck flask, simultaneously adding 0.5g of tert-butyl hydroquinone, stirring at the speed of 300rpm, purging with nitrogen for 30min, heating to 220 ℃ for reaction for 4h, stopping heating, performing separation and purification by molecular distillation, wherein the distillation pressure of a molecular distillation apparatus is less than or equal to 2Pa, the distillation temperature is 170 ℃, and removing unreacted monoacid to obtain a product mainly containing dimer acid.
(2) 55.7g of the product mainly containing dimer acid and 39.1g of n-octanol are taken and placed in a 250mL four-neck flask, 0.668g of p-toluenesulfonic acid is added as a catalyst at the same time, and the reaction lasts for 4 hours at 120 ℃, so that the lubricating oil base oil product is obtained.
Example 6
(1) Commercial eleostearic acid (iodine value 150g/100g, acid value 180 mgKOH/g) was used. Placing 100g of commercial eleostearic acid into a 250mL four-neck flask, simultaneously adding 0.5g of tert-butyl hydroquinone, stirring at the speed of 300rpm, purging with nitrogen for 30min, heating to 220 ℃ for reaction for 4h, stopping heating, performing separation and purification by molecular distillation, wherein the distillation pressure of a molecular distillation apparatus is less than or equal to 2Pa, the distillation temperature is 170 ℃, and removing unreacted monoacid to obtain a product mainly containing dimer acid.
(2) 55.7g of the product mainly containing dimer acid and 39.1g of n-octanol are taken and placed in a 250mL four-neck flask, 0.668g of sulfuric acid is added as a catalyst at the same time, and the reaction is carried out for 4 hours at 120 ℃ to obtain the lubricating oil base oil product.
Example 7
(1) Commercial eleostearic acid (iodine value 150g/100g, acid value 180 mgKOH/g) was used. Placing 100g of commercial eleostearic acid into a 250mL four-neck flask, simultaneously adding 0.5g of tert-butyl hydroquinone, stirring at the speed of 300rpm, purging with nitrogen for 30min, heating to 220 ℃ for reaction for 4h, stopping heating, performing separation and purification by molecular distillation, wherein the distillation pressure of a molecular distillation apparatus is less than or equal to 2Pa, the distillation temperature is 170 ℃, and removing unreacted monoacid to obtain a product mainly containing dimer acid.
(2) Taking 55.7g of the product mainly containing dimer acid and 39.1g of n-octanol, putting the product in a 250mL four-neck flask, adding 0.668g of DNW-II resin catalyst (produced by special resin Co., Ltd., Dongming pearl) at the same time, and adopting a fixed bed reactor with a reaction space velocity of 1h-1And reacting for 4 hours at 120 ℃ to obtain the lubricating oil base oil product.
Example 8
(1) Commercial eleostearic acid (iodine value 150g/100g, acid value 180 mgKOH/g) was used. Placing 100g of commercial eleostearic acid into a 250mL four-neck flask, simultaneously adding 0.5g of tert-butyl hydroquinone, stirring at the speed of 300rpm, purging with nitrogen for 30min, heating to 220 ℃ for reaction for 4h, stopping heating, performing separation and purification by molecular distillation, wherein the distillation pressure of a molecular distillation apparatus is less than or equal to 2Pa, the distillation temperature is 170 ℃, and removing unreacted monoacid to obtain a product mainly containing dimer acid.
(2) 55.7g of the product mainly containing the dimer acid and 39.1g of n-octanol are taken and placed in a 250mL four-neck flask, 0.668g of sulfuric acid catalyst and 5 percent of n-heptane are simultaneously added, and the reaction is carried out for 4 hours at 120 ℃ to obtain the lubricating oil base oil product.
Example 9
(1) Commercial eleostearic acid (iodine value 150g/100g, acid value 180 mgKOH/g) was used. Placing 100g of commercial eleostearic acid into a 250mL four-neck flask, simultaneously adding 0.5g of tert-butyl hydroquinone, stirring at the speed of 300rpm, purging with nitrogen for 30min, heating to 220 ℃ for reaction for 4h, stopping heating, performing separation and purification by molecular distillation, wherein the distillation pressure of a molecular distillation apparatus is less than or equal to 2Pa, the distillation temperature is 170 ℃, and removing unreacted monoacid to obtain a product mainly containing dimer acid.
(2) 55.7g of the product mainly containing dimer acid and 39.1g of n-octanol are taken and placed in a 250mL four-neck flask, 0.668g of sulfuric acid catalyst and 5 percent of toluene are added simultaneously, and the reaction is carried out for 4 hours at 120 ℃ to obtain the lubricating oil base oil product.
Example 10
(1) Commercial eleostearic acid (iodine value 150g/100g, acid value 180 mgKOH/g) was used. Placing 100g of commercial eleostearic acid into a 250mL four-neck flask, simultaneously adding 0.5g of tert-butyl hydroquinone, stirring at the speed of 300rpm, purging with nitrogen for 30min, heating to 220 ℃ for reaction for 4h, stopping heating, performing separation and purification by molecular distillation, wherein the distillation pressure of a molecular distillation apparatus is less than or equal to 2Pa, the distillation temperature is 170 ℃, and removing unreacted monoacid to obtain a product mainly containing dimer acid.
(2) 55.7g of the product mainly containing dimer acid and 39.1g of n-octanol are taken and placed in a 250mL four-neck flask, 0.668g of sulfuric acid catalyst and cyclohexane are added simultaneously, the addition amount is 5 percent, and the reaction is carried out for 4 hours at 120 ℃ to obtain the lubricating oil base oil product.
Example 11
(1) Commercial eleostearic acid (iodine value 150g/100g, acid value 180 mgKOH/g) was used. Placing 100g of commercial eleostearic acid into a 250mL four-neck flask, simultaneously adding 0.5g of tert-butyl hydroquinone, stirring at the speed of 300rpm, purging with nitrogen for 30min, heating to 220 ℃ for reaction for 4h, stopping heating, performing separation and purification by molecular distillation, wherein the distillation pressure of a molecular distillation apparatus is less than or equal to 2Pa, the distillation temperature is 170 ℃, and removing unreacted monoacid to obtain a product mainly containing dimer acid.
(2) 55.7g of the product mainly containing dimer acid and 39.1g of isooctanol are taken and placed in a 250mL four-neck flask, 0.668g of p-toluenesulfonic acid is added as a catalyst at the same time, and the reaction is carried out for 2 hours at 160 ℃ to obtain the lubricating oil base oil product.
Example 12
(1) Commercial eleostearic acid (iodine value 150g/100g, acid value 180 mgKOH/g) was used. Placing 100g of commercial eleostearic acid into a 250mL four-neck flask, simultaneously adding 0.5g of phenothiazine, stirring at the speed of 300rpm, purging with nitrogen for 30min, heating to 220 ℃ for reaction for 4h, stopping heating, performing separation and purification by molecular distillation, wherein the distillation pressure of a molecular distillation apparatus is less than or equal to 2Pa, the distillation temperature is 170 ℃, and removing unreacted monoacid to obtain a product mainly containing dimer acid.
(2) 55.7g of the product mainly containing dimer acid and 39.1g of isooctanol are taken and placed in a 250mL four-neck flask, 0.668g of p-toluenesulfonic acid is added as a catalyst at the same time, and the reaction is carried out for 4 hours at 120 ℃ to obtain the lubricating oil base oil product.
Example 13
(1) Commercial eleostearic acid (iodine value 150g/100g, acid value 180 mgKOH/g) was used. Placing 100g of commercial eleostearic acid into a 250mL four-neck flask, simultaneously adding 0.5g of hydroquinone, stirring at the speed of 300rpm, purging with nitrogen for 30min, heating to 220 ℃ for reaction for 4h, stopping heating, performing separation and purification by molecular distillation, wherein the distillation pressure of a molecular distillation apparatus is less than or equal to 2Pa, the distillation temperature is 170 ℃, and removing unreacted monoacid to obtain a product mainly containing dimer acid.
(2) 55.7g of the product mainly containing dimer acid and 39.1g of isooctanol are taken and placed in a 250mL four-neck flask, 0.668g of p-toluenesulfonic acid is added as a catalyst at the same time, and the reaction is carried out for 4 hours at 120 ℃ to obtain the lubricating oil base oil product.
Example 14
(1) Commercial eleostearic acid (iodine value 150g/100g, acid value 180 mgKOH/g) was used. Placing 100g of commercial eleostearic acid into a 250mL four-neck flask, simultaneously adding 0.5g of tert-butyl hydroquinone, stirring at the speed of 300rpm, purging with nitrogen for 30min, heating to 220 ℃ for reaction for 4h, and keeping trace nitrogen purging at the flow rate of 0.6mL/min in the whole reaction process. Stopping heating, separating and purifying by molecular distillation, wherein the distillation pressure of a molecular distillation instrument is less than or equal to 2Pa, the distillation temperature is 170 ℃, and removing unreacted monoacid to obtain a product mainly containing dimer acid.
(2) 55.7g of the product mainly containing dimer acid and 39.1g of isooctanol are taken and placed in a 250mL four-neck flask, 0.668g of p-toluenesulfonic acid is added as a catalyst at the same time, and the reaction is carried out for 4 hours at 120 ℃ to obtain the lubricating oil base oil product.
Comparative example 1
The difference from example 1 is that: the dimer acid prepared from oleic acid is used for preparing the lubricating oil base oil.
Comparative example 2
The difference from example 1 is that: the dimer acid prepared from linoleic acid is used for preparing the lubricating oil base oil.
Comparative example 3
The difference from example 1 is that: the monoacid is not removed in the step (1), and the monoacid is directly used for preparing the lubricating oil base oil.
Comparative example 4
The difference from example 1 is that: and (2) removing the mono-acid, the trimer acid and the polyacid in the step (1), and only reserving the dimer acid for preparing the lubricating oil base oil.
The lubricating oils prepared in examples and comparative examples were evaluated for their properties, and the results are shown in Table 1.
TABLE 1 Experimental Effect of different examples and comparative examples
Figure DEST_PATH_IMAGE001
As can be seen from Table 1, the lubricating oil base oil prepared by the method of the present invention has high molecular weight compared with the existing lubricating oil base oil, and carbon chains between the diester are mainly connected through a ring structure, so the flash point is high, the pour point is low, and the practical performance is better.

Claims (15)

1. A preparation method of lubricating oil base oil is characterized by comprising the following steps:
(1) taking eleostearic acid as a raw material, stirring and simultaneously blowing nitrogen in the presence of a polymerization inhibitor, heating to 180-230 ℃ for reaction, and removing monoacid after the reaction is finished to obtain a product;
(2) and (2) mixing the product obtained in the step (1) with monohydric alcohol, and carrying out esterification reaction in the presence of a catalyst to obtain the lubricating oil base oil.
2. The method of claim 1, wherein: the eleostearic acid in the step (1) is commercial eleostearic acid or self-made eleostearic acid.
3. The method of claim 1, wherein: the polymerization inhibitor in the step (1) is selected from one or more of a phenol polymerization inhibitor, a quinone polymerization inhibitor and an aromatic nitro compound polymerization inhibitor, and the dosage of the polymerization inhibitor is 1 per thousand-2% of the mass of the eleostearic acid.
4. A method according to claim 1 or 3, characterized in that: the polymerization inhibitor in the step (1) is at least one of hydroquinone, p-benzoquinone, methyl hydroquinone, tert-butyl hydroquinone and phenothiazine, preferably tert-butyl hydroquinone or/and phenothiazine, and the using amount of the polymerization inhibitor is 5 per thousand-1% of the eleostearic acid by mass.
5. The method of claim 1, wherein: the stirring speed in the step (1) is 50-500rpm, preferably 200-400 rpm; the nitrogen purging time is 1-30min, preferably 20-30 min.
6. The method according to claim 1 or 5, characterized in that: in the step (1), trace nitrogen purging is kept in the whole reaction process, and the flow rate is 0.1-1.0mL/min, preferably 0.5-0.7 mL/min.
7. The method of claim 1, wherein: the reaction temperature in the step (1) is 180-230 ℃, preferably 200-220 ℃; the reaction time is 2-7h, preferably 3-5 h.
8. The method of claim 1, wherein: removing unreacted monoacid in the step (1) by adopting a molecular distillation method, wherein the distillation pressure is less than or equal to 3Pa, and preferably 1-2 Pa; the distillation temperature is 140 ℃ to 180 ℃, preferably 160 ℃ to 180 ℃.
9. The method of claim 1, wherein: the monohydric alcohol in the step (2) is at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, n-octanol, isooctanol and the like, and preferably isooctanol; the molar ratio of alcoholic hydroxyl groups to carboxyl groups in the reaction is from 2:1 to 6:1, preferably from 3:1 to 4: 1.
10. The method of claim 1, wherein: the catalyst in the step (2) is an acid catalyst, and the addition amount of the acid catalyst is 0.1-10%, preferably 1-5% of the total mass of the reaction system; or solid acid catalyst, when a fixed bed reactor is adopted, the reaction space velocity is 1-10h-1Preferably 1-5h-1。
11. The method according to claim 1 or 10, characterized in that: the esterification reaction in the step (2) adopts a kettle type stirring reactor or a fixed bed reactor, the reaction temperature is 100-180 ℃, and preferably 110-160 ℃; the reaction time is 2-6h, preferably 2-4 h.
12. The method of claim 1, wherein: and (3) adding at least one of auxiliary agents of n-heptane, toluene and cyclohexane in the esterification reaction process in the step (2), wherein the addition amount is 5-20% of the total mass of the reaction system.
13. A lubricant base oil characterized by: is prepared by the process of any one of claims 1 to 12.
14. The lubricant base oil of claim 13, further comprising: mainly contains dimeric eleostearic acid diester, a small amount of trimeric eleostearic acid triester and a trace amount of polyest of polyenoic acid, wherein the chemical general formula of dimeric eleostearic acid diester in lubricating oil base oil is R2-H2COOC-R1-COOCH2-R2，R1Is an alkyl chain containing 34 carbons and also contains a ring structure; r2Is a branched alkyl group of C3-C8.
15. Use of the lubricant base oil according to any one of claims 13 to 14 as an aircraft engine lubricant, an air compressor lubricant, an automotive engine lubricant, a heavy duty gear oil or an ultra-low temperature engine oil.
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