A biomass-based ester base oil, a method for preparing the same, and use thereof in the preparation of hydrocarbon lubricating oil base oils

Abstract

The application belongs to the technical field of biomass-based lubricating oil base oil, and more particularly relates to a biomass-based ester base oil, a preparation method thereof and application of the biomass-based ester base oil in preparation of a hydrocarbon lubricating oil base oil. After oil and fat compounds, aromatic hydrocarbons and a Lewis acid catalyst are reacted at a certain temperature for a period of time, the reaction is quenched by dilute hydrochloric acid, and then the biomass-based ester base oil is separated by rotary evaporation. The preparation method avoids the use of fossil energy, solves the problem of complex synthesis steps of bio-based lubricating oil, and has important significance for high-value utilization of biomass resources.

Description

Technical Field

[0001] This invention belongs to the field of biomass-based lubricating oil base oil technology, and more specifically, relates to a biomass-based ester base oil, its preparation method and its application in the preparation of hydrocarbon lubricating oil base oil. Background Technology

[0002] Lubricating oils are widely used in many fields such as automobiles, ships, aviation, and agricultural machinery, and are an important means of improving friction and wear. By replacing dry friction with intermolecular friction on the friction contact surfaces of equipment, they achieve the goals of reducing friction, decreasing wear, and improving efficiency, thus greatly extending the service life of equipment. Synthetic lubricating oils, in particular, possess superior oxidation stability, thermal stability, viscosity-temperature characteristics, and corrosion resistance, making them suitable for harsher working environments and significantly reducing equipment maintenance cycles and costs. With the rapid development of China's economy, the demand for high-quality lubricating oils is constantly increasing.

[0003] Currently, synthetic lubricating oils are mainly prepared by α-olefin polymerization followed by hydrogenation. Chinese patent (CN108559012A) reports the preparation of polyalphaolefin (PAO) synthetic oil using a metallocene α-olefin catalyst; Chinese patent (CN106281434A) reports the preparation of PAO using aluminum trichloride and co-catalysts (water, methanol, ethanol, isopropanol, n-butanol, n-octanol, etc.). However, the resulting hydrocarbon base oils have a wide carbon number distribution, uncontrollable structure, and high separation costs, which undoubtedly increases production costs. Furthermore, α-olefins are mainly derived from petroleum resources, which are non-renewable, have low biodegradability, and are harmful to the environment.

[0004] To reduce dependence on petroleum resources, Chinese patent (CN110804476A) reports a method for preparing lubricating oil base oils using oleic acid or methyl oleate, widely available and inexpensive natural oil compounds, as substitutes for petroleum-based feedstocks. The reaction pathway includes the oxidative cleavage of oleic acid or methyl oleate, selective hydrogenation of nonanoic acid to nonanol, bromination of nonanol to prepare bromoalkanes, preparation of dimethyl azelaic acid from azelaic acid or monomethyl azelaic acid, reaction of a brominated Grignard reagent with dimethyl azelaic acid to synthesize a dendritic tertiary alcohol precursor, and further hydrogenation to obtain a low-viscosity lubricating oil with a dendritic structure. The selective hydrogenation of nonanoic acid to nonanol uses a RuSn / SiO2 catalyst, and the hydrogenation of the dendritic tertiary alcohol precursor uses a Pd / C catalyst, achieving a yield of up to 100%.

[0005] Compared to petroleum-based lubricants, biomass-based lubricants offer superior biodegradability. However, their synthesis process involves more steps, increasing costs and hindering large-scale production. Summary of the Invention

[0006] The purpose of this application is to prepare two types of biomass-based lubricating oil base oils—ester-based and alkane-based—using renewable oleoyl compounds and aromatics, thus avoiding the use of fossil fuels. The raw materials are inexpensive and readily available, green and renewable, the process is simple, the base oil product yield is high, and the structure is controllable, enabling the efficient conversion of oleoyl compounds into ester-based and alkane-based lubricating oil base oils.

[0007] A method for preparing a biomass-based ester base oil includes the following steps:

[0008] After reacting oily compounds, aromatics, and Lewis acid catalysts at a certain temperature for a period of time, the reaction is quenched by dilute hydrochloric acid, and then separated by rotary evaporation to obtain biomass-based ester base oil.

[0009] Furthermore, in terms of molar ratio, the ratio of oily compounds to aromatics is 30:1 to 1:1, and the ratio of oily compounds to Lewis acid catalysts is 0.5:1 to 5:1.

[0010] Furthermore, the oily compound is methyl oleate or methyl linoleate, the aromatic hydrocarbon is one of benzene, toluene, ethylbenzene, propylbenzene, cumene, o-xylene, m-xylene, p-xylene, 4-isopropyltoluene, and 1,4-diisopropylbenzene, and the Lewis acid catalyst is one of anhydrous aluminum chloride, anhydrous gallium chloride, anhydrous tungsten chloride, anhydrous ferric chloride, and anhydrous molybdenum chloride.

[0011] Furthermore, the reaction temperature conditions are 20–100°C, and the time conditions are 1 min–4 h.

[0012] The biomass-based ester base oil obtained by the above preparation method.

[0013] The above-mentioned biomass-based ester base oils are used in the preparation of hydrocarbon lubricating oil base oils.

[0014] A method for preparing a hydrocarbon-based lubricating oil base oil includes the following steps:

[0015] The biomass-based ester base oil, hydrodeoxygenation catalyst, and cyclohexane solvent prepared above are mixed in proportion and reacted under a hydrogen atmosphere and at a certain temperature and pressure. After the reaction is completed, the mixture is cooled to release H2, and the alkane lubricating oil base oil is obtained by rotary evaporation.

[0016] Furthermore, the hydrodeoxygenation catalyst is a supported metal-metal oxide catalyst, wherein the metal component is one or more of Pt, Pd, Rh, Ir, and Ru, and the metal oxide component is MoO. x ReO x NbO x VO x WO x One or more of them.

[0017] Furthermore, in terms of molar ratio, the ratio of biomass-based ester base oil to hydrodeoxygenation catalyst is 30:1 to 1:1, and in terms of mass ratio, the ratio of biomass-based ester base oil to cyclohexane is 1:1 to 40.

[0018] Furthermore, the hydrogen pressure is 0.1–10 MPa, the reaction temperature is 140–280 °C, and the reaction time is 1–24 h.

[0019] Compared with the prior art, this application has the following technical effects:

[0020] (1) This invention uses biomass-based oil compounds and aromatics as raw materials to prepare aryl ester lubricating oils in one step and alkane lubricating oil base oils in two steps. The reaction steps are simple, the product yield is high, the performance is excellent, and it has extremely broad commercial application prospects.

[0021] (2) In this invention, the raw materials are renewable biomass oil compounds and aromatics. Alkylation reaction and hydrodeoxygenation reaction are constructed. By regulating the structure of aromatics, the carbon chain and structure of aryl ester base oil and alkane base oil can be regulated, thereby regulating the properties of lubricating oil base oil.

[0022] (3) The preparation method described in this invention avoids the use of fossil energy and solves the problem of complex synthesis steps of bio-based lubricating oil, which is of great significance for the high-value utilization of biomass resources. Attached Figure Description

[0023] Figure 1 This invention provides a synthetic route for preparing alkane-based lubricating oil base oils. Detailed Implementation

[0024] To make the technical problems, technical solutions, and beneficial effects of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0025] It should be understood that in the various embodiments of this application, the order of the above processes does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0026] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms “a,” “the,” and “the” used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0027] The weights of the relevant components mentioned in the embodiments of this application can refer not only to the specific content of each component, but also to the proportional relationship between the weights of the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this application is within the scope disclosed in the embodiments of this application. Specifically, the mass described in the embodiments of this application can be a mass unit known in the chemical industry, such as μg, mg, g, or kg.

[0028] In one aspect of the present invention, a method for preparing biomass-based ester base oil is provided, comprising the following steps:

[0029] After reacting oleic acid compounds, aromatic hydrocarbons, and Lewis acid catalysts at a certain temperature for a period of time, the reaction is quenched with dilute hydrochloric acid, and then separated by rotary evaporation to obtain biomass-based ester base oil. Specifically, the molar ratio of oleic acid compounds to aromatic hydrocarbons is 30:1 to 1:1, with specific ratios of 1:1, 5:1, 10:1, 15:1, 20:1, 25:1, and 30:1. The molar ratio of oleic acid compounds to Lewis acid catalysts is 0.5:1 to 5:1, with specific ratios of 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, and 5:1. The oleic compounds are methyl oleate or methyl linoleate; the aromatic hydrocarbons are one of benzene, toluene, ethylbenzene, propylbenzene, cumene, o-xylene, m-xylene, p-xylene, 4-isopropyltoluene, and 1,4-diisopropylbenzene; and the Lewis acid catalyst is one of anhydrous aluminum chloride, anhydrous gallium chloride, anhydrous tungsten chloride, anhydrous ferric chloride, and anhydrous molybdenum chloride. The concentration of the dilute hydrochloric acid is 0.1 mol / L.

[0030] Specifically, the temperature conditions for the reaction of oily compounds, aromatics, and Lewis acid catalysts are 20 to 100°C, specifically 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, and 100°C, and the time conditions are 1 min to 4 h, specifically 1 min, 30 min, 1 h, 2 h, 3 h, and 4 h.

[0031] In another aspect of the invention, a biomass-based ester base oil is provided, which is prepared by the above-described preparation method.

[0032] In another aspect, the present invention also provides a method for preparing an alkane-based lubricating oil base oil, comprising the following steps:

[0033] The biomass-based ester base oil, hydrodeoxygenation catalyst, and cyclohexane solvent prepared above are mixed in proportion and reacted under a hydrogen atmosphere and at a certain temperature and pressure. After the reaction is completed, the mixture is cooled to release H2, and the alkane lubricating oil base oil is obtained by rotary evaporation. Specifically, the molar ratio of biomass-based ester base oil to hydrodeoxygenation catalyst is 30:1-1:1, and the mass ratio of biomass-based ester base oil to cyclohexane solvent is 1:1-40. Specifically, the molar ratio of biomass-based ester base oil to hydrodeoxygenation catalyst can be 1:1, 5:1, 10:1, 15:1, 20:1, 25:1, and 30:1, and the mass ratio of biomass-based ester base oil to cyclohexane solvent can be 1:1, 1:10, 1:20, 1:30, and 1:40. The hydrodeoxygenation catalyst is a supported metal-metal oxide catalyst, wherein the metal component is one or more of Pt, Pd, Rh, Ir, and Ru, and the metal oxide component is MoO. x ReO x NbO x VO x WO x One or more of them.

[0034] Specifically, the hydrogen pressure is 0.1–10 MPa, specifically 0.1 MPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, and 10 MPa; the reaction temperature is 140–280℃, specifically 140℃, 160℃, 180℃, 200℃, 220℃, 240℃, 260℃, and 280℃; and the reaction time is 1–24 h, specifically 1 h, 2 h, 4 h, 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h, and 24 h.

[0035] This invention uses biomass-based oil compounds and aromatics as raw materials to prepare aryl ester lubricating oils in a one-step process and alkane lubricating oil base oils in a two-step process. The reaction steps are simple, the product yield is high, the performance is excellent, and it has extremely broad commercial application prospects.

[0036] Example 1

[0037] (1) The alkylation reaction of methyl oleate with benzene to prepare C 25 Phenyl ester base oils

[0038] 0.90 g of methyl oleate, 3.77 g of benzene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 10 min. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of phenyl ester base oil was 98.6%.

[0039] (2) Preparation of C by hydrodeoxygenation reaction of ester base oils 24 Alkane-based lubricating oil base oil

[0040] Take 0.5g of phenyl ester base oil and 0.1g of Ir-ReO. x SiO2 catalyst and 10g cyclohexane solvent were added to a reactor, which was then sealed. H2 was introduced into the reactor at 4.0MPa. The reactor was heated to 180℃, stirred at 500rpm, and reacted for 12h. After the reaction was completed, the reactor was cooled, H2 was released, and C was obtained by rotary evaporation. 24 Alkane-based lubricating oil base oil, with a product yield of 88%.

[0041] Example 2

[0042] (1) The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0043] 0.90 g of methyl oleate, 4.47 g of toluene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of toluene-based ester base oil was 99%.

[0044] (2) Preparation of C by hydrodeoxygenation reaction of ester base oils 25 Alkane-based lubricating oil base oil

[0045] Take 0.5g of toluene ester base oil and 0.1g of Ir-ReO. x SiO2 catalyst and 10g cyclohexane solvent were added to a reactor. The reactor was sealed, and H2 was introduced to replace the air in the reactor. H2 at 4.0MPa was introduced into the reactor, the temperature was raised to 180℃, the stirring rate was 500rpm, and the reaction was carried out for 6 hours. After the reaction was completed, the reactor was cooled, H2 was released, and the alkane-based lubricating oil base oil C was obtained by rotary evaporation. 25 Alkane-based lubricating oil base oil, with a product yield of 93.4%.

[0046] Example 3

[0047] (1) The alkylation reaction of methyl oleate with ethylbenzene to prepare C 27 Ethylphenyl ester base oils

[0048] 0.90 g of methyl oleate, 5.12 g of ethylbenzene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of ethylbenzene ester base oil was 96.7%.

[0049] (2) Preparation of C by hydrodeoxygenation reaction of ester base oils 26 Alkane-based lubricating oil base oil

[0050] Take 0.5g of ethyl phenyl ester base oil and 0.1g of Ir-ReO. x SiO2 catalyst and 10g cyclohexane solvent were added to a reactor. The reactor was sealed, and H2 was introduced to displace the air in the reactor. H2 at 4.0MPa was introduced into the reactor. The reactor was heated to 180℃, stirred at 500rpm, and reacted for 6 hours. After the reaction was completed, the reactor was cooled, H2 was released, and C was obtained by rotary evaporation. 26 Alkane-based lubricating oil base oil, with a product yield of 92.9%.

[0051] Example 4

[0052] (1) The alkylation reaction of methyl oleate with propylbenzene prepares C 28 propyl phenyl ester base oils

[0053] 0.90 g of methyl oleate, 5.83 g of propylbenzene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 2 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of propylbenzene ester base oil was 98.3%.

[0054] (2) Preparation of C by hydrodeoxygenation reaction of ester base oils 27 Alkane-based lubricating oil base oil

[0055] Take 0.5g of propylphenyl ester base oil and 0.1g of Ir-ReO. x SiO2 catalyst and 10g cyclohexane solvent were added to a reactor. The reactor was sealed, and H2 was introduced to displace the air in the reactor. H2 at 4.0MPa was introduced into the reactor. The reactor was heated to 180℃, stirred at 500rpm, and reacted for 6 hours. After the reaction was completed, the reactor was cooled, H2 was released, and C was obtained by rotary evaporation. 27 Alkane-based lubricating oil base oil, with a product yield of 92.7%.

[0056] Example 5

[0057] (1) The alkylation reaction of methyl oleate with o-xylene to prepare C 27 o-xylyl ester base oils

[0058] 0.90 g of methyl oleate, 5.20 g of o-xylene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of o-xylene ester base oil was 99.9%.

[0059] (2) Preparation of C by hydrodeoxygenation reaction of ester base oils 26 Alkane-based lubricating oil base oil

[0060] Take 0.5g of o-xylyl ester base oil and 0.1g of Ir-ReO. x SiO2 catalyst and 10g cyclohexane solvent were added to a reactor. The reactor was sealed, and H2 was introduced to displace the air in the reactor. H2 at 4.0MPa was introduced into the reactor. The reactor was heated to 180℃, stirred at 500rpm, and reacted for 6 hours. After the reaction was completed, the reactor was cooled, H2 was released, and C was obtained by rotary evaporation. 26 Alkane-based lubricating oil base oil, with a product yield of 93.5%.

[0061] Example 6

[0062] (1) The alkylation reaction of methyl oleate with m-xylene to prepare C 27 m-Xylyl ester base oil

[0063] 0.90 g of methyl oleate, 5.15 g of m-xylene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of m-xylene ester base oil was 99.9%.

[0064] (2) Preparation of C by hydrodeoxygenation reaction of ester base oils 26 Alkane-based lubricating oil base oil

[0065] Take 0.5g of m-xylyl ester base oil and 0.1g of Ir-ReO. x SiO2 catalyst and 10g cyclohexane solvent were added to a reactor. The reactor was sealed, and H2 was introduced to displace the air in the reactor. H2 at 4.0MPa was introduced into the reactor. The reactor was heated to 180℃, stirred at 500rpm, and reacted for 6 hours. After the reaction was completed, the reactor was cooled, H2 was released, and C was obtained by rotary evaporation. 26 Alkane-based lubricating oil base oil, with a product yield of 92.4%.

[0066] Example 7

[0067] (1) The alkylation reaction of methyl oleate with p-xylene prepares C 27 p-Xylyl ester base oils

[0068] 0.90 g of methyl oleate, 5.15 g of p-xylene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of p-xylene ester base oil was 99.9%.

[0069] (2) Preparation of C by hydrodeoxygenation reaction of ester base oils 26 Alkane-based lubricating oil base oil

[0070] Take 0.5g of p-xylyl ester base oil and 0.1g of Ir-ReO. x SiO2 catalyst and 10g cyclohexane solvent were added to a reactor. The reactor was sealed, and H2 was introduced to displace the air in the reactor. H2 at 4.0MPa was introduced into the reactor. The reactor was heated to 180℃, stirred at 500rpm, and reacted for 6 hours. After the reaction was completed, the reactor was cooled, H2 was released, and C was obtained by rotary evaporation. 26 Alkane-based lubricating oil base oil, with a product yield of 96.3%.

[0071] Example 8

[0072] The alkylation reaction of methyl oleate with 4-isopropyltoluene prepares C 27 4-Isopropyltolyl ester base oil

[0073] 0.90 g of methyl oleate, 6.57 g of 4-isopropyltoluene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of 4-isopropyltoluene ester base oil was 96.5%.

[0074] Example 9

[0075] The alkylation reaction of methyl oleate with 1,4-diisopropylbenzene prepares C 27 1,4-Diisopropylphenyl ester base oils

[0076] 0.90 g of methyl oleate, 7.95 g of 1,4-diisopropylbenzene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of 1,4-diisopropylbenzene ester base oil was 96.5%.

[0077] Example 10

[0078] The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0079] 0.90 g of methyl oleate, 4.47 g of toluene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 40 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of toluene-based ester base oil was 83.9%.

[0080] Example 11

[0081] The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0082] 0.90 g of methyl oleate, 4.47 g of toluene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 80 °C for 1 h. After the reaction was complete, the mixture was quenched with dilute hydrochloric acid and separated by rotary evaporation to obtain the ester base oil. Methyl oleate was completely converted, and the yield of toluene-based ester base oil was 91.9%.

[0083] Example 12

[0084] The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0085] 0.90 g of methyl oleate, 4.47 g of toluene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 min. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of toluene-based ester base oil was 81.6%.

[0086] Example 13

[0087] The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0088] 0.90 g of methyl oleate, 4.47 g of toluene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 6 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of toluene-based ester base oil was 99.9%.

[0089] Example 14

[0090] The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0091] 0.90 g of methyl oleate, 1.12 g of toluene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of toluene-based ester base oil was 62.1%.

[0092] Example 15

[0093] The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0094] 0.90 g of methyl oleate, 5.58 g of toluene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of toluene-based ester base oil was 97.5%.

[0095] Example 16

[0096] The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0097] 0.90 g of methyl oleate, 4.47 g of toluene, and 0.2 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. All methyl oleate was converted, and the yield of toluene-based ester base oil was 28.2%.

[0098] Example 17

[0099] The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0100] 0.90 g of methyl oleate, 4.47 g of toluene, and 0.6 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of toluene-based ester base oil was 68.6%.

[0101] Example 18

[0102] The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0103] 0.90 g of methyl oleate, 4.47 g of toluene, and 0.5 g of anhydrous gallium chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of toluene-based ester base oil was 91.3%.

[0104] Example 19

[0105] The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0106] 0.90 g of methyl oleate, 4.47 g of toluene, and 0.5 g of anhydrous tungsten chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of toluene-based ester base oil was 47.0%.

[0107] Example 20

[0108] The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0109] 0.90 g of methyl oleate, 4.47 g of toluene, and 0.5 g of anhydrous ferric chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. All methyl oleate was converted, and the yield of toluene-based ester base oil was 17.1%.

[0110] Example 21

[0111] The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0112] 0.90 g of methyl oleate, 4.47 g of toluene, and 0.5 g of anhydrous molybdenum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of toluene-based ester base oil was 23.7%.

[0113] Example 22

[0114] The alkylation reaction of methyl linoleate with toluene to prepare C 26 Toluene ester base oils

[0115] 0.89 g of methyl linoleate, 2.23 g of toluene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. All methyl oleate was converted, and the yield of toluene-based ester base oil was 16.5%.

[0116] Example 23

[0117] The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0118] 0.89 g of methyl linoleate, 4.47 g of toluene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. Methyl oleate was completely converted, and the yield of toluene-based ester base oil was 28.8%.

[0119] Example 24

[0120] The alkylation reaction of methyl linoleate with toluene to prepare C 26 Toluene ester base oils

[0121] 0.89 g of methyl linoleate, 4.47 g of toluene, and 0.2 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. All methyl oleate was converted, and the yield of toluene-based ester base oil was 3.9%.

[0122] Example 25

[0123] The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0124] 0.89 g of methyl linoleate, 4.47 g of toluene, and 0.6 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. All methyl oleate was converted, and the yield of toluene-based ester base oil was 26.1%.

[0125] Example 26

[0126] The alkylation reaction of methyl linoleate with toluene to prepare C 26 Toluene ester base oils

[0127] 0.89 g of methyl linoleate, 4.47 g of toluene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 25 °C for 5 min. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. All methyl oleate was converted, and the yield of toluene-based ester base oil was 20.3%.

[0128] Example 27

[0129] The alkylation reaction of methyl linoleate with toluene to prepare C 26 Toluene ester base oils

[0130] 0.89 g of methyl linoleate, 4.47 g of toluene, and 0.5 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 80 °C for 2.5 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. All methyl oleate was converted, and the yield of toluene-based ester base oil was 28.8%.

[0131] Example 28

[0132] Preparation of C by hydrodeoxygenation of ester base oils 25 Alkane-based lubricating oil base oil

[0133] Take 0.5g of toluene ester base oil and 0.1g of Ir-MoO. x SiO2 catalyst and 10g cyclohexane solvent were added to a reactor, which was then sealed. H2 was introduced into the reactor at 4.0MPa. The reactor was heated to 180℃, stirred at 500rpm, and reacted for 12h. After the reaction was completed, the reactor was cooled, H2 was released, and C was obtained by rotary evaporation. 24 Alkane-based lubricating oil base oil, with a product yield of 92%.

[0134] Among them, the toluene ester base oil is C obtained in Example 2. 26 Toluene ester base oils.

[0135] Example 29

[0136] Preparation of C by hydrodeoxygenation of ester base oils 25 Alkane-based lubricating oil base oil

[0137] Take 0.5g of toluene ester base oil and 0.1g of Ru-ReO. x SiO2 catalyst and 10g cyclohexane solvent were added to a reactor, which was then sealed. H2 was introduced into the reactor at 4.0MPa. The reactor was heated to 180℃, stirred at 500rpm, and reacted for 12h. After the reaction was completed, the reactor was cooled, H2 was released, and C was obtained by rotary evaporation. 24 Alkane-based lubricating oil base oil, with a product yield of 82%.

[0138] Among them, the toluene ester base oil is C obtained in Example 2. 26 Toluene ester base oils.

[0139] Example 30

[0140] Preparation of C by hydrodeoxygenation of ester base oils 25 Alkane-based lubricating oil base oil

[0141] Take 0.5g of toluene ester base oil and 0.1g of Pt-WO3. x SiO2 catalyst and 10g cyclohexane solvent were added to a reactor, which was then sealed. H2 was introduced into the reactor at 4.0MPa. The reactor was heated to 200℃, stirred at 500rpm, and reacted for 12h. After the reaction was completed, the reactor was cooled, H2 was released, and C was obtained by rotary evaporation. 24 Alkane-based lubricating oil base oil, with a product yield of 86%.

[0142] Among them, the toluene ester base oil is C obtained in Example 2. 26 Toluene ester base oils.

[0143] Comparative Example 1

[0144] The alkylation reaction of methyl oleate with toluene to prepare C 26 Toluene ester base oils

[0145] 0.90 g of methyl oleate, 4.47 g of toluene, and 0 g of anhydrous aluminum chloride were added to a 25 ml flask and stirred at 60 °C for 1 h. After the reaction was complete, the mixture was quenched with 0.1 mol / L dilute hydrochloric acid, and the ester base oil was obtained by rotary evaporation. All methyl oleate was converted, and the yield of toluene-based ester base oil was 0%.

[0146] The basic properties of the prepared biomass-based aryl ester and alkane lubricating oil base oils, including viscosity, viscosity coefficient, and pour point, were tested using standard methods. The viscosity of the biomass-based aryl ester base oil was slightly higher than that of the alkane lubricating oil base oil. The pour point of the biomass-based alkane lubricating oil base oil was lower than that of the ester lubricating oil base oil. Compared with the naphthenic lubricating oil KN4006 produced by PetroChina Kunlun Lubricating Oil Company, the prepared alkane lubricating oil base oil showed significantly better viscosity index and pour point.

[0147] Properties of the prepared lubricating oils (Table 1)

[0148]

[0149]

[0150] It should be noted that C in the table above 26Toluene ester base oils correspond to the product obtained in Example 2, C 27 p-Xylyl ester base oils correspond to the product obtained in Example 4, C 28 The propylphenyl ester base oil corresponds to the product obtained in Example 7, C 25 The alkane-based lubricating oil base oil corresponds to the product obtained in Example 2, C 26 The alkane-based lubricating oil base oil corresponds to the product obtained in Example 4, C 27 The alkane-based lubricating oil base oil corresponds to the product obtained in Example 7.

[0151] The above embodiments merely illustrate several implementation methods of this application, and their descriptions are relatively specific and detailed. However, they should not be construed as limiting the scope of this patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A method for preparing a biomass-based ester base oil, characterized in that, Includes the following steps: After reacting oleic compounds, aromatics, and Lewis acid catalysts at a certain temperature for a period of time, the reaction is quenched with dilute hydrochloric acid, and then separated by rotary evaporation to obtain biomass-based ester base oil. The Lewis acid catalyst is one of anhydrous aluminum chloride, anhydrous gallium chloride, anhydrous tungsten chloride, anhydrous ferric chloride, and anhydrous molybdenum chloride. The reaction temperature conditions for oleic compounds, aromatics, and Lewis acid catalysts are 20–100°C, and the time conditions are 10 min–4 h. The oily compound is methyl oleate or methyl linoleate, and the aromatic hydrocarbon is one of benzene, toluene, ethylbenzene, propylbenzene, isopropylbenzene, o-xylene, m-xylene, p-xylene, 4-isopropyltoluene, and 1,4-diisopropylbenzene.

2. The method for preparing a biomass-based ester base oil according to claim 1, characterized in that, In terms of molar ratio, the ratio of oily compounds to aromatics is 30:1 to 1:1, and the ratio of oily compounds to Lewis acid catalysts is 0.5:1 to 5:

1.

3. A method for preparing a hydrocarbon-based lubricating oil base oil, characterized in that, Includes the following steps: The biomass-based ester base oil prepared by the method described in claim 1 or 2, the hydrodeoxygenation catalyst, and the cyclohexane solvent are mixed in proportion, reacted under a hydrogen atmosphere and at a certain temperature and pressure, cooled, and H2 is released. The mixture is then separated by rotary evaporation to obtain the alkane lubricating oil base oil.

4. The method for preparing a hydrocarbon lubricating oil base oil according to claim 3, characterized in that, The hydrodeoxygenation catalyst is a supported metal-metal oxide catalyst, wherein the metal component is one or more of Pt, Pd, Rh, Ir, and Ru, and the metal oxide component is MoO. x ReO x NbO x VO x WO x One or more of them.

5. The method for preparing a hydrocarbon lubricating oil base oil according to claim 3, characterized in that, In terms of molar ratio, the ratio of biomass-based ester base oil to hydrodeoxygenation catalyst is 30:1 to 1:1; in terms of mass ratio, the ratio of biomass-based ester base oil to cyclohexane is 1:1 to 40.

6. The method for preparing a hydrocarbon lubricating oil base oil according to claim 5, characterized in that, The hydrogen pressure conditions are 0.1–10 MPa, the reaction temperature conditions are 140–280 °C, and the reaction time conditions are 1–24 h.

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