CN113105933A - Biological lubricating oil based on waste cooking oil and preparation method thereof - Google Patents
Biological lubricating oil based on waste cooking oil and preparation method thereof Download PDFInfo
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- 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
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
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Abstract
The invention relates to a preparation method of biological lubricating oil based on waste cooking oil. On one hand, the method utilizes cheap waste cooking waste oil to synthesize high-performance biological lubricating oil through the reconstruction of a molecular structure; on the other hand, the high-efficiency green catalyst (lipase and functional ionic liquid) with high reaction selectivity is used for replacing the traditional catalyst (such as H) with poor reaction selectivity and strong corrosivity2SO4Amberlite120, etc.) for biological and chemical treatment of unsaturated fats and oilsThe modified high-performance biological lubricating oil is prepared by modifying and synthesizing, so that the use of solvents (such as boron trifluoride diethyl etherate, dichloromethane, toluene, benzene and the like) is avoided, the generation of byproducts is reduced, and the steps and the cost of separation and purification of products are reduced. In addition, the reusability of the catalyst is increased. The performance of the biological lubricating oil prepared by the invention is obviously superior to that of mineral-based lubricating oil with the same viscosity. The method for preparing the high-performance biological lubricating oil by using the waste cooking oil has potential industrial value.
Description
Technical Field
The invention belongs to the technical field of new energy, and relates to biological lubricating oil based on waste cooking oil and a preparation method thereof.
Background
In 2017, the global automobile oil demand is about 3900 ten thousand tons, wherein the automobile oil consumption exceeds 60%. With the increasing number of automobiles and the increasing degree of machine industrialization, the consumption of lubricating oil will continue to increase at a rate of 2% per year. In addition, the non-renewable petroleum-based lubricating oil with poor environmental compatibility accounts for 85% -90% of the total consumption, and is extremely dangerous to the environment, so that the greenhouse gas emission and the water pollution are aggravated. Accordingly, biological lubricants that replace petroleum-based lubricants are receiving increased attention.
The biological lubricating oil is a raw material derived from animal and vegetable oils and has lubricating properties incomparable with petroleum-based lubricants. Such as low volatility, wide viscosity range and high temperature resistance, excellent viscosity temperature performance, sustainability and environmental friendliness. However, the production of biological lubricating oil from edible vegetable oils such as soybean oil and rapeseed oil causes a contradiction between energy sustainability and food, resulting in an increase in food prices and a crisis of hunger. Meanwhile, inedible oil such as jatropha curcas oil and castor oil is usually perennial plant, the planting area is limited by regions or climate, and the requirement of future biofuel is difficult to meet. On the other hand, approximately 1500 million tons of waste cooking oil are discharged into water or soil at will every year. About 500 million tons of waste cooking oil are generated in China every year, and 200-. Most importantly, the biggest obstacle to the development of biological lubricating oil is its high cost, 70-80% of which is concentrated on raw materials, and the cost of animal and vegetable oil is 2-3 times that of waste cooking oil. Therefore, the waste cooking oil is converted into the biological lubricating oil, which plays an important role in the future energy field, so as to relieve the dispute of energy and grains and realize reasonable cyclic utilization. However, the fatty acid composition of the waste cooking oil mainly comprises 60-80% of oleic acid and polyunsaturated fatty acid, and the balance is high-melting-point substrates of saturated fatty acid such as palmitic acid, stearic acid and the like. Further chemical modifications are therefore required to obtain a biolubricant with better low temperature performance and thermo-oxidative stability. The method of epoxidizing, ring-opening branching and further acylating the unsaturated fatty acid and the derivative thereof by the method described in patents CN104449945A and CN107338082A to synthesize the branched biological lubricating oil is an important method for improving the low-temperature performance and the thermal oxidation stability of the branched biological lubricating oil. However, as the catalysts for preparing biological lubricating oil by epoxy and ring-opening branching are used in patents CN109055019A, CN110272447A and CN103805308A, the catalysts are mostly acidic inorganic acids and resins with poor reaction selectivity, or solid acids and rare metal supported catalysts with high preparation cost, etc.; the reaction process does not need to be carried out in a solvent (such as boron trifluoride diethyl etherate, dichloromethane, toluene, benzene and the like), and a large amount of side reactions are generated, so that the cost of separation and purification of a final product is increased; in addition, reuse of the catalyst is difficult to achieve.
Therefore, in order to solve the problems of illegal utilization of waste cooking oil, environmental pollution and resource exhaustion of mineral-based lubricating oil, large amount of solvents used in the production process of biological lubricating oil, poor selectivity of the catalyst, difficulty in repeated use and the like, the development of a green and efficient catalyst for modifying the waste cooking oil to synthesize the cheap biological lubricating oil with excellent low-temperature performance and lubricating performance and high thermal oxidation stability is imperative.
Disclosure of Invention
One of the objectives of the present invention is to solve the above technical problems and to provide a biological lubricating oil based on waste cooking oil, which is prepared from waste cooking oil as a raw material, has an extremely low pour point and a high thermal stability, and belongs to a high-performance biological lubricating oil.
The invention also aims to provide a preparation method of the biological lubricating oil, which takes lipase and ionic liquid with mild reaction conditions and high catalytic efficiency as catalysts to carry out green chemical modification on waste cooking oil to obtain the biological lubricating oil with high performance. The reaction is completely carried out in a solvent-free system, the reaction selectivity is high, the side reaction is less, and the catalyst and the product are simple to separate and can be repeatedly used.
To this end, the invention provides a biological lubricating oil based on waste cooking oil, which is prepared by using waste cooking oil as a raw material, and has a kinematic viscosity of 2.83-10.74cSt at 100 ℃, a pour point of-61-41 ℃, a flash point of 213-303 ℃, an initial temperature of 326.35 ℃, an oxidation initial temperature of 312.06 ℃, a COF of 0.089 and a WSD of 203 μm.
The second aspect of the invention provides a preparation method of biological lubricating oil based on waste cooking oil, which comprises the following steps:
step A, mixing waste cooking oil, phosphate buffer solution and lipase I, stirring, carrying out hydrolysis reaction, carrying out centrifugal treatment on a hydrolysate, drying an upper oil phase, carrying out short-range molecular distillation under low vacuum, and collecting light phase components to obtain free fatty acid after molecular distillation;
step B, mixing free fatty acid after molecular distillation with urea and methanol, refluxing and stirring until the free fatty acid is completely dissolved, cooling and crystallizing, filtering and separating a solid-liquid mixture after crystallization, removing the methanol in the filtrate through rotary evaporation, removing the dissolved urea through water washing, and drying an upper oil phase to obtain unsaturated fatty acid;
step C, mixing unsaturated fatty acid and branched chain alcohol, reacting under the catalysis of lipase II and under vacuum conditions, after the reaction is finished, carrying out short-range molecular distillation on the oil phase from which the enzyme is removed by centrifugal separation under low vacuum, and removing redundant alcohol and unreacted acid to obtain unsaturated branched chain ester;
step D, mixing the unsaturated branched chain ester, the fatty acid and the lipase III, stirring for reaction, and simultaneously feeding H into the reaction system2O2Finally, centrifuging to remove the III lipase and water, and drying the upper oil phase to obtain branched chain epoxy ester;
and step E, mixing the branched chain epoxy ester and the fatty acid, then mixing the mixture with the ionic liquid, stirring the mixture for reaction, cooling the reaction mixture to room temperature for layering, carrying out short-range molecular distillation on the upper oil phase under low vacuum, and removing excessive acid and by-products with low molecular weight to obtain the biological lubricating oil.
According to the invention, in step A, the lipase I is Candida sp.99-125 lipase; preferably, the dosage of the I lipase is 600-1000U/g waste cooking oil.
In some embodiments of the invention, in step a, the pH of the phosphate buffer is 7-8; preferably, the mass ratio of the waste cooking oil to the phosphate buffer is 1 (1-2).
According to the invention, in the step A, the temperature of the hydrolysis reaction is 30-40 ℃, and the time of the hydrolysis reaction is 72-120 h.
In some embodiments of the invention, in step a, the upper oil phase is dried over anhydrous sodium sulfate.
In other embodiments of the present invention, in step A, the temperature of the short-range molecular distillation is 130-140 ℃.
According to the invention, in step B, the mass ratio of free fatty acid to urea and methanol after molecular distillation is 1:2: 5.
In some embodiments of the invention, in step B, the temperature of the dissolution is 50-80 ℃.
In some embodiments of the invention, in step B, the temperature of the cooling crystallization is-20-0 ℃, and the time of the cooling crystallization is 2-10 h.
According to the invention, in step C, the branched alcohol comprises one or more of isopropanol, isobutanol, isoamyl alcohol and isooctanol; preferably, the molar ratio of the unsaturated fatty acid to the branched alcohol is 1 (1-1.3).
In some embodiments of the invention, in step C, the second lipase is Novozym 435 lipase; preferably, the dosage of the II lipase is 1 wt% -5 wt% of the dosage of a reaction substrate, and the dosage of the reaction substrate is the total amount of unsaturated fatty acid and branched chain alcohol.
In other embodiments of the present invention, in step C, the temperature of the reaction is 40 to 60 ℃ and the time of the reaction is 6 to 12 hours.
In other embodiments of the present invention, in step C, the temperature of the short path molecular distillation is from 80 to 100 ℃.
According to the invention, in step D, the amount of free fatty acid is between 5% and 10% by weight of the amount of unsaturated branched ester.
In some embodiments of the invention, in step D, the iii lipase is Novozym 435 lipase; preferably, the amount of the third lipase is 3-5 wt% of the amount of the unsaturated branched chain ester.
In other embodiments of the present invention, in step D, the temperature of the reaction is 40 to 55 ℃ and the time of the reaction is 24 to 36 hours.
In still other embodiments of the present invention, in step D, H is2O2The concentration of (2) is 30%; preferably, the unsaturated branched ester is reacted with H2O2The molar ratio of (1) to (1.2-1.5).
According to the process of the present invention, in step D, H is continuously fed into the reaction system by means of a syringe pump2O2。
According to the invention, in step E, the molar ratio of the branched epoxy ester to the fatty acid is 1 (3-10).
In some embodiments of the invention, in step E, the ionic liquid is present in an amount of 5 wt% to 10 wt% of the amount of branched epoxy ester.
In other embodiments of the present invention, in step E, the temperature of the reaction is 130-160 ℃, and the time of the reaction is 18-32 h;
in still other embodiments of the present invention, in step E, the temperature of the short-path molecular distillation is 170-200 ℃.
In the present invention, the fatty acid in the step D, E is a saturated fatty acid with a chain length of C6-C12.
According to the invention, in step D, the ionic liquid is mainly a disubstituted functional imidazole ionic liquid comprising 1-hexyl-3 methylimidazole hexafluorophosphate: [ HMIm][PF6]1-hexyl-3 methylimidazolium tetrafluoroborate: [ HMIm][BF4]1-butyl-3-methylimidazole hydrogensulfate: [ BMIm][HSO4]One or more of them.
In some embodiments of the invention, in step E, the lower ionic liquid layer is washed with n-hexane for 2-3 times to remove acid and ester, and then dried in an oven at 80-100 ℃ for 12-24h and recycled.
The invention provides a preparation method of biological lubricating oil based on waste cooking oil. On one hand, the method utilizes cheap waste cooking waste oil to synthesize high-performance biological lubricating oil through the reconstruction of a molecular structure; on the other hand, the high-efficiency green catalyst (lipase and functional ionic liquid) with high reaction selectivity is used for replacing the traditional catalyst (such as H) with poor reaction selectivity and strong corrosivity2SO4Amberlite120, etc.) to carry out biological and chemical modification on unsaturated grease to synthesize high-performance biological lubricating oil, thereby avoiding the use of solvents (such as boron trifluoride diethyl etherate, dichloromethane, toluene, benzene, etc.), reducing the generation of byproducts, and reducing the separation and purification steps and cost of products. In addition, the reusability of the catalyst is increased. The performance of the biological lubricating oil prepared by the invention is obviously superior to that of mineral-based lubricating oil with the same viscosity. The method for preparing the high-performance biological lubricating oil by using the waste cooking oil has potential industrial value.
Drawings
In order that the invention may be readily understood, a more particular description thereof will be rendered by reference to the appended drawings.
FIG. 1 is a schematic diagram of a green synthetic biological lubricating oil route using waste cooking oil as a raw material in the present invention; wherein 1 and 2 represent unsaturated fatty acid; 3, 4 represents 2-ethylhexyl ester; 5, 6 represents an epoxy branched ester oxirane; 7, 8 represent octylated branched biolubricants.
FIG. 2 shows [ HMIm ] in example 5][PF6]The reusability of (2).
FIG. 3 is an infrared spectrum of the product of each step in examples 3-5.
FIG. 4 shows the thermogravimetric curves (with nitrogen) of the bio-lubricating oil synthesized in example 5 compared with the waste cooking oil before modification.
FIG. 5 shows the thermogravimetric curves (aeration) of the bio-lubricating oil synthesized in example 5 compared with the waste cooking oil before modification.
FIG. 6 shows the results of the change in the coefficient of friction of the bio-lubricating oil synthesized in example 5 with waste cooking oil and mineral oil before the modification.
FIG. 7 is an electron micrograph of the wear marks of the bio-lubricating oil, the used cooking oil and the mineral oil before the modification, synthesized in example 5.
Detailed Description
In order that the invention may be readily understood, a more particular description thereof will be rendered by reference to the appended drawings. However, before the invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Where a range of values is provided, it is understood that each intervening value, to the extent that there is no stated or intervening value in that stated range, to the extent that there is no such intervening value, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where a specified range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.
Term of
The term "biological lubricant" as used herein refers to a biomass lubricant which is a lubricant made from a vegetable oil or an animal oil as a base oil, and is different from a conventional lubricant made from a mineral oil, and the biomass lubricant is a biological oil as a base oil.
The term "branched chain biological lubricating oil" used in the present invention refers to biological lubricating oil containing a branched chain generated by ring opening of an epoxy branched chain ester, and particularly to C6-C12 branched chain ester biological lubricating oil generated by attacking an epoxy group with a saturated fatty acid of C6-C12.
The term "high performance biological lubricant" as used herein refers primarily to biological lubricants having better low temperature performance and thermal oxidation stability relative to mineral-based lubricants.
II, embodiments
As mentioned above, in order to solve the problems of illegal utilization of waste cooking oil, environmental pollution and resource exhaustion of mineral-based lubricating oil, large amount of solvents used in the production process of biological lubricating oil, poor selectivity of the catalyst, difficulty in repeated use and the like, it is imperative to develop a green and efficient catalyst for modifying waste cooking oil to synthesize cheap biological lubricating oil with excellent low-temperature performance and lubricating performance and high thermal oxidation stability.
In order to solve the technical problems, one strategy of the invention is to synthesize high-performance biological lubricating oil by reconstructing a molecular structure by using cheap waste cooking waste oil. The specific reconstruction measures are: removing high-melting-point saturated fatty acid by urea complexation, esterifying high-content unsaturated fatty acid with branched-chain alcohol, eliminating C-C double bond at active site by epoxidation, and attacking epoxy group with saturated fatty acid with chain length of C6-C12 to generate branched-chain ester. The biological lubricating oil with low pour point, high thermal oxidation stability and excellent lubricating performance is synthesized by eliminating unsaturated sites and introducing branched chains.
The second strategy of the invention is to replace the traditional catalyst (such as H) with poor reaction selectivity and strong corrosivity by using the high-efficiency green catalyst (lipase and functional ionic liquid) with high reaction selectivity2SO4Amberlite120, etc.) to chemically modify unsaturated oil and fat to synthesize high-performance biological lubricating oil, thereby avoiding the use of solvents (such as boron trifluoride diethyl etherate, dichloromethane, toluene, benzene, etc.), reducing the generation of byproducts, and reducing the separation and purification steps and cost of products. In addition, the reusability of the catalyst is increased.
The scheme of the green synthetic biological lubricating oil with waste cooking oil as the raw material is shown in figure 1, and as can be seen from figure 1, the green synthetic biological lubricating oil with waste cooking oil as the raw material comprises the following specific steps:
(1) the lipase hydrolyzes the waste cooking oil.
Adding waste cooking oil, a phosphate buffer solution with the pH value of 7-8 and lipase I into a three-neck flask, then placing the three-neck flask in an oil bath, stirring at the temperature of 30-40 ℃, preferably 35-40 ℃, more preferably 35 ℃ at 800rpm, preferably 350rpm, and carrying out hydrolysis reaction for 72-120h, preferably 72 h; centrifuging at 10000rpm of 5000-.
In the step, the mass ratio of the waste cooking oil to the phosphate buffer solution is 1 (1-2), preferably 1 (1.2-2), and more preferably 1: 1.2; the first lipase is Candida sp.99-125, and the dosage of the first lipase is 600 and 1000U/g waste cooking oil, and the first lipase is preferably 600U/g waste cooking oil.
(2) The catering waste oil fatty acid subjected to urea complexing hydrolysis is used for obtaining high-content unsaturated free fatty acid.
Mixing the free fatty acid obtained in the step (1) after molecular distillation with urea and methanol, adding the mixture into a three-neck flask provided with a reflux and mechanical stirring device, stirring the mixture at 50-80 ℃, preferably 50 ℃ and 500rpm and 1000rpm, preferably 500rpm for 0.5-1h, preferably 1h till complete dissolution, and then putting the mixture into an environment with-20-0 ℃, preferably 0 ℃ for cooling crystallization for 2-10h, preferably 2 h; separating the crystallized solid-liquid mixture by a Buchner funnel, separating out a complex formed by saturated fatty acid and urea and filtering, removing methanol from the filtrate by a rotary evaporator, adding hot water for 2-3 times to wash the dissolved urea sufficiently, and drying the upper oil phase to obtain unsaturated fatty acid.
In the step, the mass ratio of the free fatty acid after molecular distillation to urea and methanol is 1:2: 5.
(3) Esterification of unsaturated fatty acids with branched alcohols.
Mixing the unsaturated fatty acid obtained in the step (2) with branched alcohol, and reacting the mixture at the temperature of 350-500rpm, preferably 350rpm, 40-60 ℃, preferably 50-60 ℃, more preferably 50 ℃ for 6-12h, preferably 12h under the catalysis of the II lipase; the water generated in the reaction process is removed in time under low vacuum in the reaction process, so that the accumulation of ester is promoted; after completion of the reaction, the oil phase after the enzyme separation by centrifugation is subjected to short-path molecular distillation at 80 to 100 ℃ and preferably at 80 ℃ under a low vacuum to remove excess alcohol and unreacted acid, thereby obtaining an unsaturated branched ester.
In this step, the molar ratio of the unsaturated fatty acid to the branched alcohol is 1 (1 to 1.3), preferably 1 (1.1 to 1.3), and more preferably 1: 1.1.
The second lipase is Novozym 435, and the dosage of the second lipase is 1 wt% -5 wt%, preferably 5 wt% of the dosage of reaction substrates, and the dosage of the reaction substrates is the total amount of unsaturated fatty acid and branched chain alcohol.
(4) Enzymatic epoxidation of unsaturated branched esters.
Mixing the unsaturated branched ester obtained in the step (3), the saturated fatty acid of C6-C12 and Novozym 435 at 350-500rpm, preferably 350rpm, reacting at 40-55 ℃, preferably 40-50 ℃, more preferably 50 ℃ for 24-36H, preferably 24H, while feeding 30% H to the reaction system by a syringe pump2O2(ii) a Finally, the lipase and water are removed by centrifugation, and the upper oil phase is dried with anhydrous sodium sulfate to obtain the branched epoxy ester.
In this step, saturated fatty acids with a chain length of C6-C12 are added to form peroxy acids, which transfer oxygen to enhance epoxidation of the ester, in an amount of 5% to 10% by weight, preferably 5% by weight, of the amount of unsaturated branched ester.
The lipase III is Novozym 435, and the dosage of the lipase III is 3-5 wt% of the dosage of the unsaturated branched chain ester, and the preferred dosage is 5 wt%.
In the invention, 30% H is fed into a reaction system by a syringe pump2O2In order to prevent H in the epoxidation of 2-ethylhexyl ester2O2Too high a level causes inactivation of lipase H2O2The molar ratio to the unsaturated branched ester is (1.2-1.5):1, preferably 1.2:1, abbreviated to [ N ] in the present inventionH2O2:NC＝C＝(1.2-1.5):1]。
The branched alcohol comprises one or more of isopropanol, isobutanol, isoamyl alcohol and isooctanol.
(5) The ionic liquid catalyzes the ring opening of the epoxy branched chain ester to prepare the biological lubricating oil.
After mixing the branched epoxy ester obtained in the step (4), the saturated fatty acid with the chain length of C6-C12 and the ionic liquid, reacting at 350-500rpm, preferably 500rpm, 130-160 ℃, preferably 130-150 ℃, more preferably 150 ℃ for 18-32h, preferably 24-32h, more preferably 24 h; after the reaction is finished, cooling the reaction mixture to room temperature and layering; removing excessive acid and low molecular weight by-products from the upper oil phase by short-path molecular distillation at 175 ℃ under low vacuum to obtain biological lubricating oil; washing the lower layer ionic liquid with n-hexane for 2-3 times to remove acid and ester. Drying in an oven at 80-100 deg.C, preferably 100 deg.C for 12-24h, preferably 12h, recovering for reuse, and observing the service life of the catalyst.
In the step, saturated fatty acid with the chain length of C6-C12 is added as a nucleophilic reagent for cracking epoxy groups, and the molar ratio of the branched epoxy ester to the saturated fatty acid with the chain length of C6-C12 is 1 (3-10), preferably 1 (5-10), and more preferably 1: 5.
The ionic liquid is mainly disubstituted functional imidazole ionic liquid which comprises 1-hexyl-3 methylimidazole hexafluorophosphate: [ HMIm][PF6]1-hexyl-3 methylimidazolium tetrafluoroborate: [ HMIm][BF4]1-butyl-3-methylimidazole hydrogensulfate: [ BMIm][HSO4]The dosage of the ionic liquid is 5 wt% -10 wt% of the dosage of the branched epoxy ester, and 5 wt% is preferable.
The main components of the waste cooking oil are hydrolyzed fatty acid and glyceride (monoglyceride, diglyceride and triglyceride), the waste cooking oil in the step (1) still has the glyceride which is not hydrolyzed after being hydrolyzed by enzyme, the purpose of molecular distillation is to obtain free fatty acid which is used as light phase distillate, and the heavy phase is the unnecessary glyceride with larger molecular weight; thus the free fatty acids obtained in step (1) above after molecular distillation are light molecular weight fatty acids relative to the non-hydrolyzed and fully hydrolyzed glycerides.
The saturated fatty acid with the chain length of C6-C12 in the steps (4) and (5) comprises one or more of linear or branched chain saturated fatty acids of C6, C7, C8, C9, C10, C11 and C12, and preferably caprylic acid.
The pressure of the low vacuum in each step is 0.001-0.005 mbar.
It will be appreciated by those skilled in the art that in step (3) above, the molar equivalent of carboxyl groups (COOH) can be calculated by titration of the acid ester of the fatty acid during esterification of the unsaturated fatty acid with the branched alcohol, and the molar ratio of unsaturated fatty acid to branched alcohol is obtained by the COOH: OH molar ratio.
The biological lubricating oil prepared by the method is characterized in that: the kinematic viscosity at 100 ℃ is 2.83-10.74cSt, the pour point is-61 ℃ to-41 ℃, the flash point is 213-303 ℃, the initiation temperature is 326.35 ℃, the oxidation initiation temperature is 312.06 ℃, the COF is 0.089, and the WSD is 203 μm.
The molecular of the biological lubricating oil provided by the invention contains a large number of branched chains, is branched biological lubricating oil, has obvious advantages as a substitute lubricating oil for industrial and agricultural application due to the excellent quality of the biological lubricating oil, and the main applications of the biological lubricating oil comprise: agricultural and industrial oils such as engine oils, compressor oils, metal working fluids and hydraulic, stamping oils, and the like; locomotive oils, such as engine oils, (high-speed rail) transmission oils, gearbox oils, aerospace oils, and brake and hydraulic oils; and special environmental oils such as process oils, sealing greases, tool oils, military machine oils, etc.
From the above, the invention provides a synthesis strategy for green synthesis of high-performance biological lubricating oil by using waste cooking oil as a raw material, which comprises the following steps: hydrolyzing waste edible oil with Candida sp.99-125 lipase, and complexing with urea to obtain high-content Unsaturated Fatty Acids (UFAs); UFAs and branched chain alcohol are used as substrates, Novozym 435 catalyzes to generate new ester, and enzymatic epoxidation is further carried out; disubstituted imidazole functional ionic liquids ([ HMIm)][PF6]、[HMIm][BF4]、[BMIm][HSO4]Etc.) as a catalyst, opening ethylene oxide with a saturated fatty acid having a carbon chain length of C6-C12 to prepare a branched bio-lubricant. The ionic liquid can still maintain the reaction conversion rate and selectivity of more than 80 percent after being repeatedly used for 3-5 times. Taking the product obtained in the specific example as an example, the modified biological lubricating oil has a wider viscosity range, a viscosity index of 149, a pour point of-61 ℃, a flash point of 303 ℃, remarkably improved thermal oxidation stability (an initial temperature of 326.35 ℃ and an oxidation initial temperature of 312.06 ℃), and obviously better lubricating performance (a COF of 0.089 and a WSD of 203 mu m) than a mineral-based lubricating oil with the same viscosity. The method for preparing the high-performance biological lubricating oil by using the waste cooking oil has potential industrial value.
III example
In order that the present invention may be more readily understood, the following detailed description will proceed with reference being made to examples, which are intended to be illustrative only and are not intended to limit the scope of the invention. The starting materials or components used in the present invention may be commercially or conventionally prepared unless otherwise specified.
In the following examples:
the low vacuum has a pressure of 0.001-0.005 mbar.
In the esterification of unsaturated fatty acids with branched alcohols, the molar equivalents of carboxyl groups (COOH) can be calculated by titration of the acid esters of the fatty acids, the molar ratio of unsaturated fatty acids to branched alcohols being obtained from the COOH: OH molar ratio.
Example 1: the lipase hydrolyzes the waste cooking oil.
A2L three-necked flask hydrolysis system contained 400g waste cooking oil, 480g phosphate buffer pH7.5 and 600U/g oil of Candida sp.99-125 lipase. The flask was placed in an oil bath and stirred at 350rpm for 72h at 35 ℃ and then centrifuged at 8000rpm for 5min and dried with anhydrous sodium sulfate to give an oil phase acid value of 184.92mgNaOH/g, a theoretical acid value of 204.13mgNaOH/g for complete hydrolysis, and a hydrolysis rate of 90.57%. After the reaction is finished, centrifuging the dried oil phase, performing short-range molecular distillation at 140 ℃ under low vacuum, and collecting light phase components to obtain free fatty acid after molecular distillation.
Example 2: the catering waste oil fatty acid subjected to urea complexing hydrolysis is used for obtaining high-content unsaturated free fatty acid.
The distilled free fatty acid of example 1, urea and methanol (1:2:5, w/w) were mixed and charged into a three-necked flask equipped with reflux and mechanical stirring means, stirred at 500rpm for 1 hour at 50 ℃ and then put into an environment of 0 ℃ to be cooled and crystallized for 2 hours. The solid-liquid mixture was separated by buchner funnel and the filtered liquid was passed through a rotary evaporator to remove methanol. Washing with hot water for 2-3 times, and drying the oil phase to obtain unsaturated fatty acid. The fatty acid composition before and after urea complexation is shown in table 1. The saturated fatty acid and urea form composite crystal, and the composite crystal is removed by filtration. The content of unsaturated fatty acid in the filtrate was 98.04%, and the yield of non-urea complex (unsaturated fatty acid yield) was 61.28%.
TABLE 1 comparison of the composition of the catering waste oil fatty acids before and after Urea complexation
Example 3: esterification of unsaturated fatty acids with branched alcohols.
The esterification reaction of unsaturated fatty acid and isooctanol in example 2 was carried out in a 250mL three-necked flask. Fatty acid, isooctanol (molar ratio 1:1.1), 5 wt% (based on substrate) Novozym 435 were mixed at 350rpm for 12h at 50 ℃ and water generated during the reaction was removed in time by a vacuum pump at low pressure to promote the accumulation of ester. 1.0mL of the sample was centrifuged every 1h and the acid value was titrated. The final esterification rate calculated by acid value titration was 98.78%. Finally, removing redundant isooctanol and unreacted acid by short-path molecular distillation under the low vacuum condition of 80 ℃ through the oil phase dried by centrifugation to obtain the unsaturated branched-chain ester. The acid value of 2-ethylhexyl ester was 0.49 mgNaOH/g.
Example 4: enzymatic epoxidation of unsaturated branched esters.
The branched ester from example 3, 5 wt% (based on the ester) octanoic acid (forming peroxyacid to enhance epoxidation of the ester) and 5 wt% (based on the substrate) Novozym 435 were mixed in a 250mL three-necked flask at 350rpm at 50 ℃ for 24H while uniformly adding 30% H by means of a syringe pump to the reaction system over 24H2O2(NH2O2:NC＝C1.2:1), 3.0mL of the sample was taken out every 3 hours, centrifuged, and the upper oil phase was dried over anhydrous sodium sulfate to measure the iodine value and epoxy value. And finally, centrifuging to remove lipase and water, and drying the upper oil phase to obtain the unsaturated branched ester. The content of ethylene oxide in the epoxy branched ester was 5.37% (theoretical ethylene oxide content: 6.03%) and the conversion of epoxy was 89.05%.
Example 5: the ionic liquid catalyzes the ring opening of the epoxy branched chain ester to prepare the biological lubricating oil.
To further improve the low temperature properties of epoxy compounds, [ HMIm ]][PF6]With the catalysis of (2), cracking the epoxy group with a nucleophile (octanoic acid) to form a dioctylated biolubricant: the branched epoxy ester from example 4 was mixed with octanoic acid (molar ratio 1:5) and 5 wt.% [ HMIm%][PF6](based on ester) was stirred at 500rpm and 150 ℃ for 24h in a 250mL three-necked flask. Samples were taken at 2h intervals during the reaction, and all samples were centrifuged and dissolved in n-hexane for gas phase analysis. Conversion and selectivity were calculated by area normalization. The reaction mixture was cooled to room temperature and further centrifuged. And obtaining the octylated biological lubricating oil by short-path molecular distillation of the upper oil phase under the condition of low vacuum at 175 ℃. Washing the lower layer ionic liquid with n-hexane for 2-3 times to remove acid and ester. The service life of the catalyst is inspected after the catalyst is dried in a 100 ℃ oven for 12h and recycled.
Example 6: examination [ HMIm][PF6]The reusability of (2).
The [ HMIm recovered in example 5][PF6]Test wipe [ HMIm ] was performed under the conditions of example 5][PF6]Reusability of (c): epoxy branched ester of example 4 with octanoic acid (molar ratio 1:5) and 5 wt% recovered [ HMIm][PF6](based on ester) was stirred at 500rpm and 150 ℃ for 24h in a 250mL three-necked flask. All samples were centrifuged and dissolved in n-hexane for gas phase analysis. Conversion and selectivity were calculated by area normalization. The results are shown in FIG. 2, for an ionic liquid [ HMIm][PF6]Reacting for 24h, wherein the conversion rate is 85.14%, the selectivity is 86.15%, and the ionic liquid [ HMIm ] is obtained after 3 times of circulation][PF6]The stability is kept high (the conversion rate is 81.22%, and the selectivity is 82.10%).
Infrared spectroscopic analysis of the products of examples 3-5 [ Nicolet 8 Fourier Infrared Spectroscopy, Saimer Feishale science, USA (original thermoelectric Co., Ltd.)]The infrared spectrum is shown in FIG. 3. As can be seen from FIG. 3, 3006cm when 2-ethylhexyl ester is converted to 2-ethylhexyl epoxy ester-1(stretching of C-H in the vicinity of double bond) and 1654cm-1The characteristic peak at (stretching of double bond) clearly disappeared. At 826 and 842cm-1An absorption peak (stretching of the epoxy ring C-O-C bond) appears, confirming that the C ═ C double bond is converted into an epoxy group by epoxidation.
826-842cm when the oxirane ring is attacked by the nucleophile (octanoic acid) and cleaved to form a branched biolubricant-1The characteristic peak (stretching of the C-O-C bond of the oxirane ring) at (A) disappears completely. This indicates that the ethylene oxide is opened to form the octylated branched biolube. It should be noted that in FIG. 3, 2-ethylhexyl epoxy is at 3500cm-1A characteristic peak (stretching of the OH groups) occurs, mainly due to hydroxyl by-products produced by auto-cleavage of the oxirane ring.
The results of the measurements of the physical and chemical properties of the products obtained in examples 3, 4 and 5 and of the used cooking oil before modification are shown in Table 2. The final bio-lubricant obtained according to the specific examples has good lubricating properties such as low pour point-61 deg.C, high viscosity index 149 and high flash point 303 deg.C, high thermal oxidation stability (onset temperature 326.35 deg.C, oxidation onset temperature 312.06 deg.C, RPVOT oxidation induction time 21min) (RP-0193-1 automatic tester of oxidation stability of lubricant, Repu instruments, Inc., Hello, N.K.). The HRFF results show that the lubricating performance (COF of 0.089 and WSD of 203 μm) is obviously better than that of mineral-based lubricating oil with the same viscosity.
The thermogravimetric curve comparison result (nitrogen gas introduction) of the bio-lubricating oil synthesized in example 5 with that of the waste cooking oil before the modification is shown in FIG. 5, and it can be seen from FIG. 5 that the initial temperatures of the waste edible oil and the octyl branched bio-lubricating oil are 221.67 ℃ and 326.35 ℃ respectively. The results show that the thermal stability of the octylated branched biolubricant is greatly improved due to the disappearance of unsaturated sites and the increase of branching degree. According to the DTG curve, the weight loss of the octylated branched chain biological lubricating oil is mainly the evaporation and decomposition of hydrocarbons at the temperature of 250-450 ℃, and the first weight loss of the waste edible oil is mainly the evaporation of free fatty acid at the temperature of 180-320 ℃. The second weight loss (320-.
The oxidation stability of the waste edible oil and the octylated branched biolubricant were compared in air (see figure 6). The oxidation initiation temperatures of the used cooking oil and the octyl branched chain bio-lubricating oil were 213.45 ℃ and 312.06 ℃, respectively, indicating that the oxidation stability of the octyl branched chain bio-lubricating oil was improved. Because the easily oxidizable site C ═ C double bond is substituted by the acylated branch, the formation of oxidative radicals is avoided. Interestingly, the weight loss process of waste edible oils in air is three stages. The first weight loss (150 ℃ C. -. The resulting weight loss is due to further combustion and volatilization of low molecular hydrocarbons, carbon dioxide and carbon monoxide.
The biological lubricating oil synthesized in example 5, the used cooking oil and the mineral oil before the modification were subjected to a friction test (K9345 high frequency reciprocating friction tester, Koehler, USA), the results of the change in the coefficient of friction between the biological lubricating oil synthesized in example 5 and the used cooking oil and the mineral oil before the modification are shown in FIG. 6, and the electron microscope images of the wear scar diameters of the biological lubricating oil synthesized in example 5, the used cooking oil and the mineral oil before the modification are shown in FIG. 7. As can be seen from fig. 6, the friction coefficient of the octyl branched biolube oil was stable at 0.089, while the friction coefficient of the waste edible oil fluctuated between 0.06 and 0.09. As can be seen from FIG. 7, the worn-out edible oil having an octyl branched biolubricant oil wear scar diameter of 203 μm during the rubbing test had a wear scar diameter of 345 μm. In general, the wear of metal parts by used cooking oils and octyl branched biolubricants is much lower than that of mineral-based lubricants of the same viscosity grade (WSD 343 μm, COF 0.154). Because polar functional groups (carboxyl, ester group and hydroxyl) exist in the waste edible oil and the octylated branched chain biological lubricating oil, molecules between metal parts can be better adhered to the metal surface to form a stable lubricating film, and the direct friction and movement between the metal parts are reduced. In addition, the friction coefficient of the waste edible oil is smaller than that of the branched chain biological lubricating oil (0.073 is larger than 0.089), but the diameter of the abrasion mark is larger (345 mu m is larger than 203 mu m), the main reason is that the waste edible oil contains free fatty acid, carboxyl has corrosion effect on the metal surface, and the thicker octylated branched chain biological lubricating oil (the viscosity is 67.51cSt at 40 ℃) can provide a thicker oil film so as to ensure that the friction part is covered as much as possible (the oil film coverage rate is 90%).
In general, the biological lubricating oil obtained by removing saturated fatty acid through enzymatic hydrolysis and urea complexation, modifying the waste cooking oil through enzymatic esterification and epoxy, and ring-opening branching modification has wider viscosity range, lower low-temperature performance, high flash point and obvious improvement on lubricating performance and thermal oxidation stability due to elimination of double bond sites and introduction of branch branches, and provides a basis for developing high-performance biological lubricating oil for replacing petroleum-based lubricating oil.
TABLE 2 physicochemical Properties of the purified product of examples 3-5
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. The biological lubricating oil based on waste cooking oil is prepared by using waste cooking oil as a raw material, and has the kinematic viscosity of 2.83-10.74cSt at 100 ℃, the pour point of-61-41 ℃, the flash point of 213-303 ℃, the starting temperature of 326.35 ℃, the oxidation starting temperature of 312.06 ℃, the COF of 0.089 and the WSD of 203 mu m.
2. A preparation method of biological lubricating oil based on waste cooking oil comprises the following steps:
step A, mixing waste cooking oil, phosphate buffer solution and lipase I, stirring, carrying out hydrolysis reaction, carrying out centrifugal treatment on a hydrolysate, drying an upper oil phase, carrying out short-range molecular distillation under low vacuum, and collecting light phase components to obtain free fatty acid after molecular distillation;
step B, mixing free fatty acid after molecular distillation with urea and methanol, refluxing and stirring until the free fatty acid is completely dissolved, cooling and crystallizing, filtering and separating a solid-liquid mixture after crystallization, removing the methanol in the filtrate through rotary evaporation, removing the dissolved urea through water washing, and drying an upper oil phase to obtain unsaturated fatty acid;
step C, mixing unsaturated fatty acid and branched chain alcohol, reacting under the catalysis of lipase II and under vacuum conditions, after the reaction is finished, carrying out short-range molecular distillation on the oil phase from which the enzyme is removed by centrifugal separation under low vacuum, and removing redundant alcohol and unreacted acid to obtain unsaturated branched chain ester;
step D, mixing the unsaturated branched chain ester, the fatty acid and the lipase III, stirring for reaction, and simultaneously feeding H into the reaction system2O2Finally, centrifuging to remove the III lipase and water, and drying the upper oil phase to obtain branched chain epoxy ester;
and step E, mixing the branched chain epoxy ester and the fatty acid, then mixing the mixture with the ionic liquid, stirring the mixture for reaction, cooling the reaction mixture to room temperature for layering, carrying out short-range molecular distillation on the upper oil phase under low vacuum, and removing excessive acid and by-products with low molecular weight to obtain the biological lubricating oil.
3. The production method according to claim 2, wherein, in the step A,
the first lipase is Candida sp.99-125 lipase; preferably, the dosage of the I lipase is 600-1000U/g waste cooking oil;
and/or the pH value of the phosphate buffer solution is 7-8; preferably, the mass ratio of the waste cooking oil to the phosphate buffer solution is 1 (1-2);
and/or the temperature of the hydrolysis reaction is 30-40 ℃, and the time of the hydrolysis reaction is 72-120 h;
and/or, the upper oil phase is dried by anhydrous sodium sulfate;
and/or the temperature of the short-path molecular distillation is 130-140 ℃.
4. The production method according to claim 2, wherein, in step B,
the mass ratio of free fatty acid to urea to methanol after molecular distillation is 1:2: 5;
and/or the dissolving temperature is 50-80 ℃;
and/or the temperature of the cooling crystallization is-20-0 ℃, and the time of the cooling crystallization is 2-10 h.
5. The production method according to claim 2, wherein, in step C,
the branched alcohol comprises one or more of isopropanol, isobutanol, isoamyl alcohol and isooctanol; preferably, the molar ratio of the unsaturated fatty acid to the branched alcohol is 1 (1-1.3);
and/or, the II lipase is Novozym 435 lipase; preferably, the dosage of the II lipase is 1 wt% -5 wt% of the dosage of a reaction substrate, and the dosage of the reaction substrate is the total amount of unsaturated fatty acid and branched chain alcohol;
and/or the reaction temperature is 40-60 ℃, and the reaction time is 6-12 h;
and/or the temperature of the short-path molecular distillation is 80-100 ℃.
6. The production method according to claim 2, wherein, in step D,
the dosage of the free fatty acid is 5-10 wt% of that of the unsaturated branched chain ester;
and/or, the III lipase is Novozym 435 lipase; preferably, the amount of the third lipase is 3-5 wt% of the amount of the unsaturated branched chain ester;
and/or the reaction temperature is 40-55 ℃, and the reaction time is 24-36 h;
and/or, the H2O2The concentration of (2) is 30%; preferably, H2O2The molar ratio of the unsaturated branched ester to the unsaturated branched ester is (1.2-1.5) 1.
7. The production process according to claim 6, wherein in the step D, H is continuously fed into the reaction system by means of a syringe pump2O2。
8. The production method according to claim 2, wherein, in step E,
the molar ratio of the branched chain epoxy ester to the fatty acid is 1 (3-10);
and/or the dosage of the ionic liquid is 5 wt% -10 wt% of that of the branched chain epoxy ester;
and/or the reaction temperature is 130-160 ℃, and the reaction time is 18-32 h;
and/or the temperature of the short-path molecular distillation is 170-200 ℃.
9. The method according to claim 8,
the fatty acid in step D, E is a saturated fatty acid with a chain length of C6-C12;
and/or in the step D, the ionic liquid is mainly disubstituted functional imidazole ionic liquid which comprises 1-hexyl-3 methylimidazole hexafluorophosphate: [ HMIm][PF6]1-hexyl-3 methylimidazolium tetrafluoroborate: [ HMIm][BF4]1-butyl-3-methylimidazole hydrogensulfate: [ BMIm][HSO4]One or more of them.
10. The preparation method according to claim 8 or 9, wherein in the step E, the ionic liquid at the lower layer is washed with n-hexane for 2-3 times, acid and ester are removed, and the ionic liquid is dried in an oven at 80-100 ℃ for 12-24h and then recycled.
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