阅读说明：本技术 一种合成多环环醚生物质基润滑油的方法 (Method for synthesizing polycyclic cyclic ether biomass-based lubricating oil ) 是由 赵晨 陈爽 于 2021-08-06 设计创作，主要内容包括：本申请公开了一种高支链化多环环氧醚生物质基润滑油基础油的合成方法,所述合成方法包括以下步骤：步骤1,糠醛和呋喃制备三呋喃甲烷,然后加入脂肪醛经羟基烷基化反应制备润滑油中间体；步骤2,润滑油中间体环加氢为多环环醚生物质基润滑油。其优点表现在：采用绿色可再生的生物质糠醛、呋喃和脂肪醛为原料,通过巧妙地设计反应步骤和调控润滑油的结构,以制备高品质的支链化多环环醚生物质基润滑油基础油,避免了化石能源的使用,符合绿色可持续发展的理念。同时,选用廉价易得的糠醛、呋喃和脂肪醛化合物,极大地降低生物基全合成润滑油的成本,且本申请的生物质基全合成润滑油基础油的结构可调,使产品更具有市场竞争力。(The application discloses a synthetic method of highly branched polycyclic epoxy ether biomass-based lubricating oil base oil, which comprises the following steps: step 1, preparing trifuranomethane from furfural and furan, and then adding fatty aldehyde to prepare a lubricating oil intermediate through a hydroxyl alkylation reaction; and 2, circularly hydrogenating the lubricating oil intermediate to obtain the polycyclic cyclic ether biomass-based lubricating oil. Its advantages are: the green and renewable biomass furfural, furan and aliphatic aldehyde are used as raw materials, the reaction steps are skillfully designed, and the structure of the lubricating oil is regulated and controlled, so that the high-quality branched polycyclic cyclic ether biomass-based lubricating oil base oil is prepared, the use of fossil energy is avoided, and the concept of green sustainable development is met. Simultaneously, select low-priced easily available furfural, furan and fatty aldehyde compound, greatly reduce the cost of biobased total synthesis lubricating oil, and the structure of the biomass based total synthesis lubricating oil base oil of this application is adjustable, makes the product more have market competition.)

1. A synthesis method of polycyclic epoxy ether biomass-based lubricating oil base oil is characterized by comprising the following steps:

step 1, generating a lubricating oil precursor by performing a hydroxyl alkylation reaction on furfural, furan and fatty aldehyde

Adding furfural, furan and a catalyst into a round-bottom flask, adding a proper amount of catalyst, reacting at room temperature for 1-12h, adding a proper amount of fatty aldehyde, and transferring the round-bottom flask into an oil bath kettle at 100 ℃ for reacting for 1-12 h.

Step 2, hydrogenating the lubricating oil intermediate into highly branched polycyclic cyclic ether biomass-based lubricating oil base oil

Adding the lubricating oil intermediate, a solvent and a hydrogenation catalyst into a high-pressure reaction kettle, wherein the volume ratio of the lubricating oil intermediate to the solvent is 1:1-5, sealing the reaction kettle, and introducing H₂Replacing air in the reaction kettle, and introducing 1.0-6.0MPa H into the reaction kettle₂Heating the temperature of the reaction kettle to 100-350 ℃, reacting for 2.0-6.0H, and releasing H after the reaction kettle is cooled after the reaction is finished₂And separating out the solvent by distillation to obtain the polycyclic ether fully-synthetic lubricating oil.

2. The catalyst in step 1 is: P/SiO₂H-ZSM5, phosphoric acid, sulfuric acid, H-MOR, ZrOSO₄And Amberlyst.

3. The active center of the hydrogenation catalyst in the step 2 is Pd, Pt or Ni.

4. The loading of active centers in the hydrogenation catalyst in step 2 is 0.1-10 wt.%.

5. The cocatalyst of the hydrogenation catalyst in the step 2 is a simple substance or an oxide of Re, Sn or Ir.

6. The loading of active centers in the hydrogenation catalyst in step 2 is 0.1-5 wt.%.

7. The solvent in the step 2 is water, methanol and C₆-C₁₆Or a combination of one or more of linear alkanes or cyclic alkanes.

Technical Field

The application relates to the technical field of biomass-based fully-synthetic lubricating oil base oil, in particular to a preparation method of polycyclic epoxy ether biomass-based lubricating oil base oil.

Background

The development of global industrialization process can not be separated from the continuous improvement of the quality of lubricating oilAt present, the total synthetic lubricating oil mainly adopts petroleum-based or coal-based C oligomerized by ethylene₁₀Selective polymerization-hydrogenation of decene as raw material to C₃₀Comb-shaped hydrocarbon lubricating oil base oil. Chinese patent (CN 108559012A) reports that metallocene catalyzed polymerization C is adopted₈-C₁₂Preparing fully synthetic lubricating oil base oil by using alpha-olefin. Oligomerization of petroleum derived ethylene to C₁₀The selectivity of decene is poor, and the boiling points of long-chain olefin and alkane in the synthesis of F-T derived from coal chemical industry are very close and difficult to separate. And the consumption of non-renewable energy resources causes serious obstruction to the recycling of carbon resources. The adoption of renewable biomass raw materials to replace traditional petroleum-based or coal-based downstream chemicals is an effective way to solve the problem of carbon resource recycling performance, thereby being beneficial to realizing 'carbon peak reaching' and 'carbon neutralization'.

In order to reduce carbon emission pressure, development of renewable biomass-based lubricant base oil is continuously promoted, and at present, ester lubricant base oil and ether lubricant base oil are mainly used. Chinese patent (CN 107987938A) reports a method for preparing lubricating oil from mixed oils (soybean oil, castor oil, rapeseed oil, dodecenylsuccinic acid, eleostearic acid, tall oil acid, etc.) as raw materials. The method is only formed by heating and mixing a plurality of grease, and the components are complex, so that the performance of the method is far inferior to that of the fully synthetic lubricating oil. Raghunan et al (RAGHHANAN L C, NARINE S. engineering green phosphors I: Optimizing thermal and flow properties of linear descriptors from a cellular environment oils [ J].ACS Sustainable Chemistry&Engineering,2016,4(3):686-692.) use of long chain carboxylic acids (C)₁₇H₃₃COO)₂[CH₂]_nAnd C₂～C₁₀The long-chain diol is esterified under the action of sulfuric acid, the diester biomass-based lubricating oil base oil is successfully prepared, the influence of the carbon chain length of the fatty diol on the properties of the lubricating oil base oil is researched, and the lubricating oil is found to have good low-temperature viscosity but viscosity index less than 100. The ester lubricating base oil can be prepared by conventional esterification method, ring-opening esterification method, Sharma et al (SHARAMA R V, DALAI A K. Synthesis of bio-lubricating from epoxy oil using sulfated Ti-SBA-1)5catalyst[J]Applied Catalysis B, Environmental protection, 2013,142/143, 604-614.) rapeseed oil is firstly epoxidized under the condition of acetic acid and hydrogen peroxide, and then acetic anhydride is used for ring-opening esterification under the action of Ti-SBA-15 sulfide, and finally ester lubricating oil base oil is obtained. Tests show that the obtained lubricating oil base oil has the oxidation induction time of 56.1h, the condensation point of-3 ℃, the pour point of-9 ℃ and the kinematic viscosity of 670mm at 100 DEG C²And s. Because the grease contains double bonds, the oxidation stability and the acid value of the prepared lubricating oil base oil are seriously influenced, so that the application range of the lubricating oil base oil is limited. Wu et al (WU X, ZHANG X, YANG S, et al. the study of oxygenated rapeseed oil used as a potential bipolar lumen [ J]Journal of the American Oil Chemists Society, 2000,77(5): 561-. Researches show that the epoxidized rapeseed oil has better extreme pressure property and friction reduction property compared with rapeseed oil. The conventional epoxidation reaction is generally divided into two steps: (1) formation of peroxy acids; (2) formation of peroxy acids with unsaturated double bonds. The addition of hydrogen peroxide is effective in promoting the conversion of vinyl to epoxy compounds, but too high a concentration of hydrogen peroxide can cause it to form explosive mixtures, potentially dangerous. Although the cyclic ether lubricating oil has many advantages, the oxygen content of the base oil of the cyclic ether lubricating oil is larger than that of the base oil of the ester lubricating oil, and the problem of high oxygen content is not fundamentally solved, so that the low-temperature fluidity and the oxidation stability of the cyclic ether lubricating oil are poor. In addition, carbon chain structures in the grease are irregular, so that the structure of the base oil of the lubricating oil is not uniform, and the properties are unstable.

Disclosure of Invention

The application provides a method for preparing high-valued polycyclic epoxy ether fully-synthetic lubricating oil base oil by utilizing renewable biomass furan, furfural and fatty aldehyde, which has the advantages of green, environment-friendly, cheap and easily-obtained raw materials, simple and flexible process, high yield of lubricating oil and capability of realizing efficient conversion of furan, furfural and fatty aldehyde into fully-synthetic lubricating oil base oil. The synthetic route is shown in figure 1.

And (2) carrying out hydroxyl alkylation on furfural and furan to generate trifuranmethane, carrying out hydroxyl alkylation on the trifuranmethane and long-chain aldehyde again to generate a lubricating oil base oil precursor (step 1), and carrying out hydrogenation saturation on the prepared precursor (step 2).

The following technical scheme is adopted in the application:

a synthetic method of biomass-based polycyclic epoxy ether lubricating oil base oil is characterized by comprising the following steps:

step 1, generating a lubricating oil precursor by performing a hydroxyl alkylation reaction on furfural, furan and fatty aldehyde

Adding furfural, furan and a catalyst into a round-bottom flask, adding a proper amount of catalyst, reacting at room temperature for 1-12h, adding a proper amount of fatty aldehyde, and transferring the round-bottom flask into an oil bath kettle at 100 ℃ for reacting for 1-12 h. After the reaction is finished, a lubricating oil intermediate is separated by adopting a chromatographic column.

Step 2, hydrogenating the lubricating oil intermediate into highly branched polycyclic epoxy ether biomass-based lubricating oil base oil

Adding the lubricating oil intermediate, a solvent and a hydrogenation catalyst into a high-pressure reaction kettle, wherein the volume ratio of the lubricating oil intermediate to the solvent is 1:1-5, sealing the reaction kettle, and introducing H₂Replacing air in the reaction kettle, and introducing 1.0-6.0MPa H into the reaction kettle₂Heating the temperature of the reaction kettle to 100-350 ℃, reacting for 2.0-6.0H, and releasing H after the reaction kettle is cooled after the reaction is finished₂And separating out the solvent by distillation to obtain the polycyclic ether fully-synthetic lubricating oil.

Further, the catalyst in step 1 is: P/SiO₂H-ZSM5, phosphoric acid, sulfuric acid, H-MOR, ZrOSO₄And Amberlyst.

Furthermore, the active center of the hydrogenation catalyst is Pd, Pt or Ni.

Furthermore, the loading of the active center in the hydrogenation catalyst is 0.1-10 wt.%.

Furthermore, the cocatalyst of the hydrogenation catalyst is a simple substance or an oxide of Re, Sn or Ir.

Furthermore, the addition amount of the cocatalyst in the hydrogenation catalyst is 0.1-5.0 wt.%.

Further, the solvent is water, methanol and C₆-C₁₆Or a combination of one or more of linear alkanes or cyclic alkanes.

The above-mentioned at least one technical scheme that this application adopted can reach following beneficial effect:

the method adopts green renewable biomass-based aliphatic aldehyde, furfural and furan as raw materials, and prepares high-quality high-branched polycyclic epoxy ether fully-synthesized biomass-based lubricating oil base oil by skillfully designing reaction steps and regulating and controlling the structure of lubricating oil. According to the method, the carbon chain is increased through the hydroxyl alkylation reaction to obtain a long carbon chain branched structure precursor, and the precursor is further hydrogenated to be the high-quality fully-synthesized biomass-based lubricating oil.

The application avoids the use of fossil energy and accords with the concept of green sustainable development. Simultaneously, select for use the cheap biomass-based fatty aldehyde of easily getting, furfural and furan compound, greatly reduce raw materials cost and high-end total synthesis lubricating oil cost, and the structure of the biomass-based total synthesis lubricating oil of this application can be regulated and control, makes the product more have market competition.

Drawings

The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:

FIG. 1 is a synthetic route for highly branched polycyclic epoxy ether biomass based lube base oils.

FIG. 2 is C₃₀H₂₆O₆Structural characterization of Lubricant intermediates (a)¹H-NMR，(b)¹³C-NMR, (C) IR and (d) HR-MS.

FIG. 3 is C₃₀H₅₀O₆Structural characterization of Lubricant base oils (a)¹H-NMR, (b) IR and (d) HR-MS.

Detailed Description

In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail and completely with reference to the specific embodiments of the present application. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

Example 1

(1) Adding 20g of furan and 8g of furfural into a round-bottom flask, adding 1g of Amberlyst catalyst, reacting at room temperature for 12 hours, adding 2.88g of butyraldehyde into the reaction liquid, moving the round-bottom flask into an oil bath kettle at 100 ℃ for reaction for 12 hours, and separating a lubricating oil intermediate by using a chromatographic column, wherein the yield of the intermediate is 75C%. The intermediate structure is shown in figure 2.

(2) 0.05g of PdCl are weighed out₂Adding into 40mL of aqueous solution, stirring at 25 deg.C for 3.0h, adding 1.0g SiO₂Stirring for 3.0 h. Heating to 60 deg.C, stirring until water is completely evaporated, drying in 100 deg.C oven overnight, calcining in air at 450 deg.C for 4.0H, and adding high-purity H₂Reducing at 450 deg.C for 4.0h, cooling completely, and adding N at ratio of 5:1₂And air aged for future use.

0.5g of hydrogenation catalyst was added to the reaction vessel, and the prepared lubricant precursor and 80mL of n-hexane were added. Sealing the reaction kettle, and introducing H₂Replacing air in the reaction kettle, and introducing 4.0 MPa H into the reaction kettle₂And raising the temperature of the reaction kettle to 200 ℃ for reaction for 3.0 h. After the reaction is finished, cooling is carried out to release H₂And distilling to obtain the total synthetic lubricating oil base oil with the yield of 95C percent. The lubricant base oil structure is shown in fig. 3.

(3) The properties of the lubricating oil prepared were determined using the national standard method, as follows:

example 2

(1) Adding 20g of furan and 8g of furfural into a round-bottom flask, adding 0.5g of phosphoric acid catalyst, reacting at room temperature for 12 hours, adding 2.93g of hexanal into the reaction liquid, moving the round-bottom flask into a 100 ℃ oil bath pot for reaction for 12 hours, and separating a lubricating oil intermediate by using a chromatographic column, wherein the yield is 71C%.

(2) 0.12g of Ni (NO) was weighed₃)₂Adding into 40mL of aqueous solution, stirring at 25 deg.C for 3.0h, adding 1g of SiO₂Stirring for 3.0 h. Heating to 60 deg.C, stirring until water is completely evaporated, drying in 100 deg.C oven overnight, calcining in air at 450 deg.C for 4.0H, and adding high-purity H₂Reducing at 450 deg.C for 4.0h, cooling completely, and adding N at ratio of 5:1₂And air aged for future use.

0.1g of hydrogenation catalyst was added to the reaction vessel, and the prepared lubricant precursor and 80mL of n-hexane were added. Sealing the reaction kettle, and introducing H₂Replacing air in the reaction kettle, and introducing 4.0 MPa H into the reaction kettle₂And raising the temperature of the reaction kettle to 200 ℃ for reaction for 3.0 h. After the reaction is finished, cooling is carried out to release H₂And distilling to obtain the total synthetic lubricating oil base oil with the yield of 96C percent.

(3) The properties of the lubricating oil prepared were determined using the national standard method, as follows:

example 3

(1) Adding 20g of furan and 8g of furfural into a round-bottom flask, adding 0.5g of phosphoric acid catalyst, reacting at room temperature for 12 hours, adding 3.02g of octanal into the reaction solution, moving the round-bottom flask into a 100 ℃ oil bath pot for reaction for 12 hours, and separating a lubricating oil intermediate by using a chromatographic column, wherein the yield is 68C%.

(2) 0.05g of PtCl was weighed₄And 0.013g NH₄ReO₄Adding into 40mL of aqueous solution, stirring at 25 deg.C for 3.0h, adding 1g of SiO₂Stirring for 3.0 h. Heating to 60 deg.C, stirring until water is completely evaporated, drying in 100 deg.C oven overnight, calcining in air at 450 deg.C for 4.0H, and adding high-purity H₂Reducing at 450 deg.C for 4.0h, cooling completely, and adding N at ratio of 5:1₂And air aged for future use.

Adding 0.1g of hydrogenation catalyst into a reaction kettleThe prepared lubricant precursor and 80mL of n-hexane were added. Sealing the reaction kettle, and introducing H₂Replacing air in the reaction kettle, and introducing 4.0 MPa H into the reaction kettle₂And raising the temperature of the reaction kettle to 200 ℃ for reaction for 3.0 h. After the reaction is finished, cooling is carried out to release H₂And distilling to obtain the total synthetic lubricating oil base oil with the yield of 93C%.

(3) The properties of the lubricating oil prepared were determined using the national standard method, as follows:

example 4

(1) 20g of furan and 8g of furfural were charged into a round-bottomed flask, and 0.5g P/SiO was added₂After the catalyst is reacted for 12 hours at room temperature, 3.13g of decanal is added into the reaction solution, the round-bottom flask is moved into an oil bath kettle at 100 ℃ for reaction for 12 hours, and then a lubricating oil intermediate is separated by adopting a chromatographic column, wherein the yield is 68C%.

(2) 0.05g of PdCl are weighed out₂And 0.02g IrCl₃Adding into 40mL of aqueous solution, stirring at 25 deg.C for 3.0h, adding 1g of SiO₂Stirring for 3.0 h. Heating to 60 deg.C, stirring until water is completely evaporated, drying in 100 deg.C oven overnight, calcining in air at 450 deg.C for 4.0H, and adding high-purity H₂Reducing at 450 deg.C for 4.0h, cooling completely, and adding N at ratio of 5:1₂And air aged for future use.

0.1g of hydrogenation catalyst was added to the reaction vessel, and the prepared lubricant precursor and 80mL of n-hexane were added. Sealing the reaction kettle, and introducing H₂Replacing air in the reaction kettle, and introducing 4.0 MPa H into the reaction kettle₂And raising the temperature of the reaction kettle to 200 ℃ for reaction for 3.0 h. After the reaction is finished, cooling is carried out to release H₂And distilling to obtain the total synthetic lubricating oil base oil with the yield of 91C%.

(3) The properties of the lubricating oil prepared were determined using the national standard method, as follows:

the above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.