JADHAV PRAVIN DIGAMBAR (IN)
PATWARDHAN ANAND VINAYAK (IN)
KULKARNI RAVINDRA DATTATRAY (IN)
| WO2021154925A1 | 2021-08-05 | |||
| WO2014149723A1 | 2014-09-25 |
| CN103709125A | 2014-04-09 |
KULKARNI, R. D. ET AL.: "Epoxidation of mustard oil and ring opening with 2-ethylhexanol for biolubricants with enhanced thermo-oxidative and cold flow characteristics", INDUSTRIAL CROPS AND PRODUCTS, vol. 49, 2013, pages 586 - 592, XP055889624, DOI: 10.1016/j.indcrop.2013.06.006
| CLAIMS 1 . A method of preparing the bio-plasticizer using fatty acid methyl ester comprises the steps of: i. mixing fatty acid methyl ester with hexane in a flask placed in oil bath to obtain a first mixture, wherein the fatty acid methyl ester and hexane are used in a ratio of 1 :1 by weight; ii. adding oxygen carrier and inorganic acid one after another into the mixture to obtain a second mixture, wherein the oxygen carrier is used in an amount ranging between 0.25 mole to 0.75 mole and wherein the inorganic acid is used in an amount ranging between 1% to 3% by weight of the first mixture; iii. adding hydrogen peroxide into the second mixture drop-wise at a constant rate of 2 ml/min under constant stirring in a temperature ranging between 40°C to 70°C for a time period ranging between 30 minutes to 40 minutes to produce a third mixture, wherein the hydrogen peroxide is used in an amount ranging between 1.0 mole to 2.5 mole; iv. continuing the reaction for a time period of 6 hours at a temperature ranging between 55°C to 70°C, wherein the third mixture is stirred vigorously throughout the duration at a speed ranging between 600 rpm to 800 rpm until a fine dispersion of oil was obtained; v. transferring the oil into a separating unit to obtain two layers, wherein the top layer is aqueous layer containing acetic acid, water and traces of sulphuric acid and wherein the bottom layer is organic layer containing epoxidized fatty acid methyl ester and acids; vi. isolating and treating the organic layer distilled water to obtain acid-free organic layer; and vii. passing the acid-free organic layer through a bed of anhydrous sodium sulphate to remove water and obtain moisture-free organic layer; and viii. removing the hexane from the moisture-free organic layer using evaporator unit to obtain solvent-free epoxidized fatty acid methyl ester, wherein the solvent-free epoxidized fatty acid methyl ester is the bio-plasticizer. 2. The method as claimed in claim 1 , wherein the oxygen carrier is selected from the group consisting of acetic acid, formic acid, glacial acetic acid and any combinations thereof. 3. The method as claimed in claim 1 , wherein the oxygen carrier is glacial acetic acid. 4. The method as claimed in claim 1 , wherein the inorganic acid is selected from the group consisting of phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid and any combinations thereof. 5. The method as claimed in claim 1 , wherein the inorganic acid is sulfuric acid. 6. A method of producing bio-lubricant using the fatty acid methyl ester comprises the steps of: i. mixing fatty acid methyl ester with hexane in a flask placed in oil bath to obtain a first mixture, wherein the fatty acid methyl ester and hexane are used in a ratio of 1 :1 by weight; ii. adding oxygen carrier and inorganic acid one after another into the mixture to obtain a second mixture, wherein the oxygen carrier is used in an amount ranging between 0.25 mole to 0.75 mole and wherein the inorganic acid is used in an amount ranging between 1% to 3% by weight of the first mixture; Hi. adding hydrogen peroxide into the second mixture drop-wise at a constant rate of 2 ml/min under constant stirring in a temperature ranging between 40°C to 70°C for a time period ranging between 30 minutes to 40 minutes to produce a third mixture, wherein the hydrogen peroxide is used in an amount ranging between 1 .0 mole to 2.5 mole; iv. continuing the reaction for a time period of 6 hours at a temperature ranging between 55°C to 70°C, wherein the third mixture is stirred vigorously throughout the duration at a speed ranging between 600 rpm to 800 rpm until a fine dispersion of oil was obtained; v. transferring the oil into a separating unit to obtain two layers, wherein the top layer is aqueous layer containing acetic acid, water and traces of sulphuric acid and wherein the bottom layer is organic layer containing epoxidized fatty acid methyl ester and acids; vi. isolating and treating the organic layer distilled water to obtain acid-free organic layer; and vii. passing the acid-free organic layer through a bed of anhydrous sodium sulphate to remove water and obtain moisture-free organic layer; viii. removing the hexane from the moisture-free organic layer using evaporator unit to obtain solvent-free epoxidized fatty acid methyl ester; ix. adding 2-ethyl hexanol and sulphamic acid one after another into the solvent-free epoxidized fatty acid methyl ester while heating at a temperature ranging between 100°C to 105°C to obtain a fourth mixture and the reaction is continued for a time period ranging between 3 hours to 6 hours while vigorously stirring throughout the duration at a speed ranging between 600 rpm to 800 rpm until reaction mixture was obtained; x. transferring the reaction mixture into a separating unit to obtain two layers, wherein the top layer is aqueous layer containing traces of sulphamic acid and wherein the bottom layer is organic layer containing solvent and ring-opened fatty acid methyl ester with acid traces; xi. isolating and treating the organic layer with distilled water to obtain acid-free organic layer; xii. passing the acid-free organic layer through a bed of anhydrous sodium sulphate to remove traces of water and obtain moisture-free organic layer; and xiii. removing the ethanol from the moisture-free organic layer using evaporator unit to obtain solvent-free bio-lubricant. 7. The method as claimed in claim 6, wherein the oxygen carrier is selected from the group consisting of acetic acid, formic acid, glacial acetic acid and any combinations thereof. 8. The method as claimed in claim 6, wherein the oxygen carrier is glacial acetic acid. 9. The method as claimed in claim 6, wherein the inorganic acid is selected from the group consisting of phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid and any combinations thereof. 10. The method as claimed in claim 6, wherein the inorganic acid is sulfuric acid. 11 . The method as claimed in claim 6, wherein the 2-ethyl hexanol is used in an amount of 2 to 4 moles of for every 100 grams of the solvent-free epoxidized fatty acid methyl ester. 12. The method as claimed in claim 6, wherein the sulphamic acid is used in an amount of 2% by weight of the solvent-free epoxidized fatty acid methyl ester. 13. A method of preparing the bio-lubricant using solvent-free epoxidized fatty acid methyl ester comprises the steps of: i. adding 2-ethyl hexanol and sulphamic acid one after another into the solvent-free epoxidized fatty acid methyl ester while heating at a temperature ranging between 100°C to 105°C to obtain a fourth mixture and the reaction is continued for a time period ranging between 3 hours to 6 hours while vigorously stirring throughout the duration at a speed ranging between 600 rpm to 800 rpm until reaction mixture was obtained; ii. transferring the reaction mixture into a separating unit to obtain two layers, wherein the top layer is aqueous layer containing traces of sulphamic acid and wherein the bottom layer is organic layer containing solvent and ring-opened fatty acid methyl ester with acid traces; iii. isolating and treating the organic layer with distilled water to obtain acid-free organic layer; iv. passing the acid-free organic layer through a bed of anhydrous sodium sulphate to remove traces of water and obtain moisture-free organic layer; and v. removing the ethanol from the moisture-free organic layer using evaporator unit to obtain solvent-free bio-lubricant. 14. The method as claimed in claim 13, wherein the 2-ethyl hexanol is used in an amount of 2 to 4 moles of for every 100 grams of the solvent-free epoxidized fatty acid methyl ester. 15. The method as claimed in claim 13, wherein the sulphamic acid is used in an amount of 2% by weight of the solvent-free epoxidized fatty acid methyl ester. |
FIELD OF THE INVENTION
The present invention relates to a method of producing plasticizer and lubricant from fatty acid methyl ester, particularly relates to a method of producing bio-plasticizer and biolubricant from fatty acid methyl ester derived from palm-based source.
BACKGROUND OF THE INVENTION
The uses of plant oil-based products as an alternative source of petroleum-based products are beneficial since the plant oil-based products are environment-friendly, bio-degradable, and low in cost. In addition, the cost of petroleum is rising and the public is more concerned about environmental sustainability.
Separately, plant oil has some drawback such as poor low-temperature properties which include cloudiness, precipitation, poor flowability and solidification at relatively high temperatures. The low-temperature properties can be improved by molecule structural redesign through the chemical modification process. In general, one of the important modifications in plant oils is epoxidation to produce plasticizer and lubricant.
Moreover, conventional plasticizer and lubricant require additives to exhibit lower pour point and higher flash point values, which would otherwise could not be able to exhibit desired pour point and flash point values. The latter is undesirable, particularly for transportation since the characteristics of the plasticizer and lubricant showing signs of easy combustion.
In view of the above, there is a need to develop a plasticizer and lubricant that is environmentally friendly using palm-based methyl ester, which has improved characteristics such as lower pour point and a higher flash point even without any additives in comparison with conventional plasticizer and lubricant. The latter is important, specifically for transportation to prevent easy combustion.
SUMMARY OF THE INVENTION
Present invention discloses a method of preparing the bio-plasticizer using fatty acid methyl ester. Present invention also discloses a method of preparing the bio-lubricant using fatty acid methyl ester and solvent-free epoxidized fatty acid methyl ester. DETAILED DESCRIPTION OF THE INVENTION
A detailed description of preferred embodiments of the present invention is disclosed herein. It should be understood, however, that the embodiments are merely exemplary of the present invention, which may be embodied in various forms. Therefore, the details disclosed herein are not to be interpreted as limiting, but merely as the basis for the claims and for teaching one skilled in the art of the invention. The numerical data or ranges used in the specification are not to be construed as limiting.
The present invention relates to a method of producing plasticizer and lubricant from fatty acid methyl ester, particularly relates to a method of producing bio-plasticizer and biolubricant from fatty acid methyl ester derived from palm-based source.
The fatty acid methyl ester is selected from the group consisting of (i) oleic methyl ester (C1898ME) which is suitable for all climate conditions, (ii) palm methyl ester (PME) which is suitable for only tropical climate condition and (iii) blend of oleic methyl ester and PME (C1875ME), which is made by blending 75.0% oleic methyl ester with 25.0% PME. The latter may also be obtained as a by-product of fractional distillation of palm kernel methyl ester but not limited thereto.
The first aspect of the present invention discusses the method of producing bio-plasticizer from fatty acid methyl ester. The bio-plasticizer is an epoxidized fatty acid methyl ester.
The method of preparing the bio-plasticizer comprises the steps of: i. mixing fatty acid methyl ester with hexane in a flask placed in oil bath to obtain a first mixture, wherein the fatty acid methyl ester and hexane are used in a ratio of 1 :1 by weight; ii. adding oxygen carrier and inorganic acid one after another into the mixture to obtain a second mixture, wherein the oxygen carrier is used in an amount ranging between 0.25 mole to 0.75 mole, preferably used in an amount of 0.5 moles and wherein the inorganic acid is used in an amount ranging between 1 % to 3% by weight of the first mixture, preferably used in an amount of 2% by weight of the first mixture. The oxygen carrier is selected from the group consisting of acetic acid, formic acid, glacial acetic acid and any combinations thereof, preferably glacial acetic acid. The inorganic acid is selected from the group consisting of phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid and any combinations thereof, preferably sulfuric acid; iii. adding hydrogen peroxide into the second mixture drop-wise at a constant rate of 2 ml/min under constant stirring in a temperature ranging between 40°C to 70°C for a time period ranging between 30 minutes to 40 minutes to produce a third mixture, wherein the hydrogen peroxide is used in an amount ranging between 1.0 mole to 2.5 mole, preferably used in amount of 2 moles; iv. continuing the reaction for a time period of 6 hours at a temperature ranging between 55°C to 70°C, wherein the third mixture is stirred vigorously throughout the duration at a speed ranging between 600 rpm to 800 rpm until a fine dispersion of oil was obtained; v. transferring the oil into a separating unit to obtain two layers, wherein the top layer is aqueous layer containing acetic acid, water and traces of sulphuric acid and wherein the bottom layer is organic layer containing epoxidized fatty acid methyl ester and acids; vi. isolating and treating the organic layer distilled water to obtain acid-free organic layer; and vii. passing the acid-free organic layer through a bed of anhydrous sodium sulphate, anhydrous calcium chloride preferably anhydrous sodium sulphate to remove water and obtain moisture-free organic layer; and viii. removing the hexane from the moisture-free organic layer using evaporator unit to obtain solvent-free epoxidized fatty acid methyl ester, wherein the solvent-free epoxidized fatty acid methyl ester is the bio-plasticizer of the present invention.
With reference to step (iv), the vigorous stirring is necessary to avoid formation of high peroxide concentration zones that could result in producing explosive mixtures. Meanwhile, 2 ml of samples were withdrawn at definite time intervals from the third mixture to determine the completion of reaction. It is important to recognize that the reactions from steps (i) to (vi) are carried out in-situ.
For the purpose of the present invention, the term “acid-free organic layer” may include insignificant and/or traces amount of the acid. For the purpose of the present invention, the term “moisture-free organic layer” may include insignificant and/or traces amount of moisture. For the purpose of the present invention, the term “solvent-free epoxidized fatty acid methyl ester” may include insignificant and/or traces amount of solvent.
The epoxidized fatty acid methyl ester is analysed for iodine value (IV), epoxy oxirane oxygen content (OOC), epoxy equivalent weight (EEW), and hydroxyl value (HV), outcome of which is observable from Table 1 . The second aspect of the present invention discusses the method of producing bio-lubricant using the fatty acid methyl ester. The method of producing bio-lubricant using fatty acid methyl ester comprises the following steps: i. mixing fatty acid methyl ester with hexane in a flask placed in oil bath to obtain a first mixture, wherein the fatty acid methyl ester and hexane are used in a ratio of 1 :1 by weight; ii. adding oxygen carrier and inorganic acid one after another into the mixture to obtain a second mixture, wherein the oxygen carrier is used in an amount ranging between 0.25 mole to 0.75 mole, preferably used in an amount of 0.5 moles and wherein the inorganic acid is used in an amount ranging between 1 % to 3% by weight of the first mixture, preferably used in an amount of 2% by weight of the first mixture. The oxygen carrier is selected from the group consisting of acetic acid, formic acid, glacial acetic acid and any combinations thereof, preferably glacial acetic acid. The inorganic acid is selected from the group consisting of phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid and any combinations thereof, preferably sulfuric acid; iii. adding hydrogen peroxide into the second mixture drop-wise at a constant rate of 2 ml/min under constant stirring in a temperature ranging between 40°C to 70°C for a time period ranging between 30 minutes to 40 minutes to produce a third mixture, wherein the hydrogen peroxide is used in an amount ranging between 1 .0 mole to 2.5 mole, preferably used in amount of 2 moles; iv. continuing the reaction for a time period of 6 hours at a temperature ranging between 55°C to 70°C, wherein the third mixture is stirred vigorously throughout the duration at a speed ranging between 600 rpm to 800 rpm until a fine dispersion of oil was obtained; v. transferring the oil into a separating unit to obtain two layers, wherein the top layer is aqueous layer containing acetic acid, water and traces of sulphuric acid and wherein the bottom layer is organic layer containing epoxidized fatty acid methyl ester and acids; vi. isolating and treating the organic layer distilled water to obtain acid-free organic layer; and vii. passing the acid-free organic layer through a bed of anhydrous sodium sulphate, anhydrous calcium chloride preferably anhydrous sodium sulphate to remove water and obtain moisture-free organic layer; and viii. removing the hexane from the moisture-free organic layer using evaporator unit to obtain solvent-free epoxidized fatty acid methyl ester; ix. adding 2-ethyl hexanol and sulphamic acid one after another into the solvent-free epoxidized fatty acid methyl ester while heating at a temperature ranging between 100°C to 105°C to obtain a fourth mixture and the reaction is continued for a time period ranging between 3 hours to 6 hours while vigorously stirring throughout the duration at a speed ranging between 600 rpm to 800 rpm until reaction mixture was obtained, wherein for every 100 grams of the solvent-free epoxidized fatty acid methyl ester 2 to 4 moles of 2-ethyl hexanol is used and wherein the sulphamic acid is used in an amount of 2% by weight of the solvent-free epoxidized fatty acid methyl ester; x. transferring the reaction mixture into a separating unit to obtain two layers, wherein the top layer is aqueous layer containing traces of sulphamic acid and wherein the bottom layer is organic layer containing solvent and ring-opened fatty acid methyl ester with acid traces; xi. isolating and treating the organic layer with distilled water to obtain acid-free organic layer; xii. passing the acid-free organic layer through a bed of anhydrous sodium sulphate to remove traces of water and obtain moisture-free organic layer; and xiii. removing the ethanol from the moisture-free organic layer using evaporator unit to obtain solvent-free bio-lubricant of the present invention.
With reference to step (iv), the vigorous stirring is necessary to avoid formation of high peroxide concentration zones that could result in producing explosive mixtures. Meanwhile, 2 ml of samples were withdrawn at definite time intervals from the third mixture to determine the completion of reaction. It is important to recognize that the reactions from steps (i) to (vi) are carried out in-situ.
For the purpose of the present invention, the term “acid-free organic layer” may include insignificant and/or traces amount of the acid. For the purpose of the present invention, the term “moisture-free organic layer” may include insignificant and/or traces amount of moisture. For the purpose of the present invention, the term “solvent-free epoxidized fatty acid methyl ester” may include insignificant and/or traces amount of solvent.
The step (ix) is representing a ring-opening and simultaneous partial esterification of the epoxidized fatty acid ester process. For the purpose of the present invention, the term “solvent-free bio-lubricant” may include insignificant and/or traces amount of solvent. The biolubricant was analysed for iodine value (IV), epoxy oxirane oxygen content (OOC), epoxy equivalent weight (EEW), and hydroxyl value (HV), outcome of which is observable from Table 3.
The third aspect of the present invention discusses the method of producing bio-lubricant using the epoxidized fatty acid methyl ester. The method of producing bio-lubricant using epoxidized fatty acid methyl ester comprises the steps of: i. adding 2-ethyl hexanol and sulphamic acid one after another into the epoxidized fatty acid methyl ester while heating at a temperature ranging between 100°C to 105°C to obtain a mixture and the reaction is continued for a time period ranging between 3 hours to 6 hours while vigorously stirring throughout the duration at a speed ranging between 600 rpm to 800 rpm until reaction mixture was obtained, wherein for every 100 grams of the epoxidized fatty acid methyl ester 2 to 4 moles of 2-ethyl hexanol is used and wherein the sulphamic acid is used in an amount of 2% by weight of the epoxidized fatty acid methyl ester; ii. transferring the reaction mixture into a separating unit to obtain two layers, wherein the top layer is aqueous layer containing traces of sulphamic acid and wherein the bottom layer is organic layer containing solvent and ring-opened fatty acid methyl ester with acid traces; iii. isolating and treating the organic layer with distilled water to obtain acid-free organic layer; iv. passing the acid-free organic layer through a bed of anhydrous sodium sulphate to remove traces of water and obtain moisture-free organic layer; and v. removing the ethanol from the moisture-free organic layer using evaporator unit to obtain solvent-free bio-lubricant of the present invention.
For the purpose of the present invention, the term “acid-free organic layer” may include insignificant and/or traces amount of the acid. For the purpose of the present invention, the term “moisture-free organic layer” may include insignificant and/or traces amount of moisture. For the purpose of the present invention, the term “solvent-free bio-lubricant” may include insignificant and/or traces amount of solvent. The step (i) is representing a ringopening and simultaneous partial esterification of the epoxidized fatty acid ester process. For the purpose of the present invention, the term “bio-lubricant of the present invention” refers to bio-lubricant without additive.
The following example is constructed to illustrate the present invention in a non-limiting sense. Example 1
Epoxidized fatty acid methyl ester (bio-plasticizer) of the present invention
The epoxidized fatty acid methyl ester (bio-plasticizer) of the present invention is prepared by adopting a method as described in the first aspect of the present invention.
Test results for the epoxidized fatty acid methyl ester (bio-plasticizer) of the present invention
The epoxidized fatty acid methyl ester (bio-plasticizer) of the present invention was tested for chemical properties such as iodine value (IV), oxirane oxygen content (OOC), epoxy equivalent weight (EEW) and hydroxyl value (HV).
The chemical properties of the epoxidized fatty acid methyl ester (bio-plasticizer) of the present invention is summarized in Table 1 .
Table 1 : Chemical properties of the epoxidized fatty acid methyl ester (bio-plasticizer) of the present invention
Based on the results obtained it is evident that all the three epoxidized fatty acid methyl ester (bio-plasticizer) of the present invention namely C1875 ME, PME and C1898 ME share similar chemical properties.
The epoxidized fatty acid methyl ester (bio-plasticizer) of the present invention was further tested for mechanical properties such as tensile strength, tensile modulus, dart impact, and hardness.
The mechanical properties of the epoxidized fatty acid methyl ester (bio-plasticizer) of the present invention and conventional plasticizer are summarized in Table 2. Table 2: Mechanical properties of the epoxidized fatty acid methyl ester (bio-plasticizer) of the present invention and conventional plasticizer
The results showed that the epoxidized fatty acid methyl ester (bio-plasticizer) of the present invention has comparable mechanical properties with conventional plasticizer; in particular, the epoxidized fatty acid methyl ester (bio-plasticizer) of the present invention has improved tensile modulus in comparison with a conventional plasticizer.
Example 2
Bio-lubricant of the present invention
The bio-lubricant of the present invention produced using epoxidized fatty acid methyl ester (bio-plasticizer) of the present invention by adopting a method as described in the second aspect and third aspect of the present invention.
Test results for the bio-lubricant of the present invention
The bio-lubricant of the present invention was tested for chemical properties such as oxirane oxygen content (OOC) and epoxy equivalent weight (EEW).
The chemical properties of the bio-lubricant of the present invention and conventional biolubricant are summarized in Table 3.
Table 3: Chemical properties of the bio-lubricant of the present invention
The bio-lubricant of the present invention with additive and bio-lubricant of the present invention without additive was further tested for physiochemical properties such as pour point and flash point.
The physiochemical properties of the bio-lubricant of the present invention (with and without additive) and conventional bio-lubricant are summarized in Table 4.
Table 4: Physiochemical properties of the bio-lubricant of the present invention and conventional bio-lubricant
Table 4 shows that the bio-lubricant of the present invention without additive exhibit similar physicochemical properties which is an indicate that the bio-lubricant of the present invention is efficient even without using any conventional additive.
The bio-lubricant of the present invention finds application in the field of machining i.e. hydraulic fluids, turbine fluids, compressor, chain saws and metal working i.e. gears, greases but not limited thereto.
As a whole, the results obtained in the present invention shows that the the fatty acid methyl ester of the present invention which is palm-based methyl ester has the potential to produce bio-plasticizer and bio-lubricant. The bio-plasticizer and bio-lubricant of the present invention which is produced by using palm-based methyl ester has improved characteristics such as lower pour point and a higher flash point even without use of any conventional additives in comparison with conventional bio-plasticizer and bio-lubricant. The latter is important, specifically for transportation to prevent easy combustion.
The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting. As used herein, the singular forms "a", "an" and "the" may be intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms "comprises", "comprising", “including” and “having” are inclusive and therefore specify the presence of stated features, integers, steps, operations, elements and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components and/or groups therefrom.
The method, steps, processes and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated, unless specifically identified as an order of performance. It is also to be understood that additional or alternative steps may be employed. The use of the expression “at least” or “at least one” suggests the use of one or more elements, as the use may be in one of the embodiments to achieve one or more of the desired objects or results.
Next Patent: AN ELECTRIC MACHINE AND METHOD OF USE