CN102978011A - Method for preparing low-pour-point lubricant additive from low-priced cotton seed oil - Google Patents
Method for preparing low-pour-point lubricant additive from low-priced cotton seed oil Download PDFInfo
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Abstract
The invention discloses a method for preparing a low-pour-point lubricant additive from low-priced cotton seed oil. The method comprises the following steps: mixing cotton seed oil, methanol and potassium hydroxide so as to prepare fatty acid methyl esters, uniformly mixing the fatty acid methyl esters, formic acid and petroleum ethers at room temperature, stirring and heating the obtained mixture, dripping a mixture of hydrogen peroxide and phosphoric acid into the obtained mixture, standing the obtained product to carry out delamination, separating a water layer, washing an oil layer by using water until the oil layer is neutral, and carrying out reduced pressure distillation to obtain colorless transparent oily epoxidized fatty acid methyl esters, wherein the epoxy value is greater than 4-7, the iodine value is less than 2-0, the acid value is less than 1, and the yield is 90-94%; adding calcium carbonate into a residual formic acid solution after reaction so as to obtain calcium formate which can be recycled; and carrying out esterification reaction on the epoxidized fatty acid methyl esters so as to obtain epoxidized fatty acid methyl ester mixed fatty acid esters. According to the method disclosed by the invention, atalyst application amount is low, the process is clean, the implementation conditions are simple, and the mass production can be implemented conveniently.
Description
Technical field
The present invention relates to the method that a kind of hydrogen peroxide oxidation process prepares the epoxy cottonseed oil methyl esters.
Background technology
Vegetables oil has good oilness, degradability, sticking warm nature and wide material sources, the condition such as renewable, becomes a kind of base oil with degradable lubricant of very strong competitive power.But contain a large amount of unsaturated link(age)s in the vegetables oil molecule, oxidation stability is poor, thereby has limited the use of vegetables oil as lubricant base oil.After vegetables oil carried out modification and functional changing, can make vegetables oil have the advantages such as good oxidation-resistance, extreme pressure and antiwear behavior, improve the performance that vegetables oil uses as lubricant base or additive.
The low price vegetables oil, as Oleum Gossypii semen, peanut oil, vegetable seed wet goods, and domestic a large amount of trench main body of oil is vegetables oil, this class oil more and more is used to the production biofuel or is directly discarded at present, cause environmental pollution, its output is huge, and is with low cost.How to transform these low price vegetables oil and be high value added product, turn waste into wealth, become urgent problem.
Xinjiang is the main producing region of Cotton in China, and is also very huge as the output of the byproduct Oleum Gossypii semen of producing cotton.According to incompletely statistics, the present output of cotton in Xinjiang is calculated with this about 2,700,000 tons, and the output of Xinjiang Oleum Gossypii semen reaches about 500,000 tons.In the course of processing of Oleum Gossypii semen, produce the oil foot material of 5%-10%, most of cotton oil source mill has all abandoned the oil foot material as waste, whenever be only Xinjiang just up to 60,000 to 70,000 tons, has formed huge pollution and waste.
Be used to refine biofuel for cheap vegetables oil major part at present, although effectively solved the re-using of waste and old resource, its added value is lower, can bring the problems such as oil dilution, machine oil wear out when using this class biofuel.If the cheap vegetables oil of this class is converted into the plant oil lubricating oil additive, not only be conducive to the re-using of resource, increased added value of product, reduce the environmental pollution that this class low price vegetables oil brings, the plant oil based lubricating oil additive of this class also has good consistency with lubricant base oil simultaneously, can reduce the poor impact of consistency that lubricating oil brings in using the additive process, have additive to open up new approach for producing novel lubricating.
Except mainly containing the triglyceride level, also have a large amount of free lipid acid in the cheap vegetables oil, partial glycerol three esters are decomposed cause lipid acid free out.This project is to cottonseed oil foot, the cheap vegetables oil employing of trench wet goods physical method is purified after the acidifying, adopt the pre-esterification techniques of polyvalent alcohol, free fatty acids in this cheap vegetables oil is carried out esterification treatment, recycling epoxidation reaction technology, two keys in the vegetables oil of esterification treatment are carried out epoxidation, then epoxidised vegetables oil is introduced function group, vegetables oil is carried out functional modification, make it have extreme-pressure anti-wear and the characteristic such as anti-oxidant, can use as lubricating oil additive, realize on this basis the pilot scale industrial scale of 500 tons lubricating oil additive.
Oleum Gossypii semen, soybean oil is rich in an alkene in flax wet goods polyunsaturated long-chain fatty acids grease, diene, the active key species such as triolefin, but equal initial ring oxidizing reaction are expanded its Application Areas.Use the epoxidation product of biodegradable vegetables oil and derivative thereof to be widely used in softening agent, lubricating oil additive, (European patent EP 89709 (1983) and EP437 in the middle of the industry such as macromolecule polyester and makeup, 764 (1991), Japanese Patent JP06025681 (1994) JP07138586 (1995), JP59053777 (1984), JP2000095662 (2000) etc. all has relevant report).
Alkene and other unsaturated hydrocarbons contain active intermediate, and these species can generate the useful organic chemicals of difference in functionality after by epoxidation, and very deep meaning is arranged in Synthetic Organic Chemistry.Epoxidizing method is because of the difference of its raw material and catalyzer difference to some extent.More common method has: (1) uses peroxy acid to be oxygenant, take acid or biological enzyme as catalyzer; (2) be that oxygenant adopts transition metal-catalyzed method with the organic or inorganic peroxy acid; (3) by halohydrin (halohydrines); (4) come (the James.Kener Functionlization of oleyl carbonate by epoxidation such as epoxidation with molecular oxygen, the idation of cottonseed oil by aqueous hydrogen peroxide catalysed by liquid inorganic acids such as JAOCS (2007) 84:457-461 and Srikanta Dinda, Bioresourse echnology, 99 (2008): 3737-3744. is for cottonseed oil foot, peanut oil foot, waste vegetable oil and the trench oil handling such as rapeseed oil residue, domestic existing technology basic ideas: behind its remove impurity make use of physics methods, be hydrolyzed, plant main body of oil triglyceride level is changed into free fatty acids, then free fatty acids is carried out esterification, obtain biofuel.
For plant oil modified investigative technique as lubricating oil, mainly comprise chemical modification, add oxidation inhibitor and biologic modified method.Chemic modified method comprises, epoxidation, hydrogenation, transesterify etc.Wherein the vegetables oil epoxidation can improve vegetables oil as resistance of oxidation and extreme pressure and antiwear behavior that lubricating oil uses, generally adopts Peracetic Acid and hydrogen peroxide under the solid catalyst effect, makes the two keys in the vegetables oil molecule generate the epoxy product; Ester-interchange method adopts polyvalent alcohol and fatty acid methyl ester to carry out transesterification reaction under suitable catalyst, with this structure that changes vegetables oil, reaches the requirement that improves the lubricating oil use properties.Research for vegetables oil ucon oil additive is reported seldom at present.
Summary of the invention
The object of the invention is, a kind of method for preparing the low pour point lubricating oil additive from low price oleum gossypii seminis is provided, the method is take Oleum Gossypii semen, methyl alcohol as raw material, prepare fatty acid methyl ester take potassium hydroxide as catalyzer, fatty acid methyl ester, formic acid, sherwood oil are at room temperature mixed, stir and heat up, drip the mixture of hydrogen peroxide and phosphoric acid, standing demix, branch vibration layer, oil reservoir washes with water to neutrality, underpressure distillation can obtain water white transparency oily thing epoxy aliphatic acid methyl ester, wherein oxirane value＞4～7, iodine number＜2～0, acid number＜1, yield 90-94%.In remaining aqueous formic acid, add calcium carbonate or calcium oxide after the reaction, obtain calcium formiate and reclaim; Then epoxy aliphatic acid methyl ester is carried out esterification and obtain the epoxy aliphatic acid methyl ester mixed aliphatic ester.Its acid number＜0.5-～2,40 ℃ of viscosity 100-350 of temperature, temperature takes 100 ℃ of viscosity 10-40, viscosity index 120～160, flash-point 230～240, pour point-15～-30.The present invention uses catalytic amount very little, and technique cleans, implementation condition is simple, safe, easy and simple to handle, can realize effective utilization of lower concentration hydrogen peroxide, is convenient to carry out large-scale production.
Of the present inventionly a kind ofly prepare the method for low pour point lubricating oil additive from low price oleum gossypii seminis, follow these steps to carry out:
A, take Oleum Gossypii semen, methyl alcohol as raw material, prepare fatty acid methyl ester take potassium hydroxide as catalyzer, temperature of reaction 70-80 ℃, reaction times 1-3h;
B, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation obtains fatty acid methyl ester;
C, with fatty acid methyl ester, the mixture of formic acid and sherwood oil places in three mouthfuls of reaction flasks, mixes, and under agitation is warming up to 20-50 ℃, dripping concentration is the mixture of 20-30% hydrogen peroxide and phosphoric acid;
The mixture of d, hydrogen peroxide and phosphoric acid dropwise and temperature steadily after, system temperature is transferred to 30 ℃-65 ℃ of temperature of reaction, reaction times 3-7h;
E, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation gets light yellow oil and is epoxy aliphatic acid methyl ester;
F, add mass percent 5-15% calcium oxide or the calcium carbonate of raw material after will reacting in the remaining aqueous formic acid, can obtain calcium formiate, reclaim;
G, mixed fatty acid is heated to temperature 100-130 ℃, again step e epoxy aliphatic acid methyl ester is slowly joined in the mixed fatty acid, reaction 5-8h;
Decompression steams unreacted mixed fatty acid after h, the reaction, can obtain light yellow transparent oily matter epoxy aliphatic acid methyl ester mixed aliphatic ester.
The mass ratio of Oleum Gossypii semen, methyl alcohol and potassium hydroxide is 1:0.2-0.3:0.05-0.07 among the step a.
Concentration is 30% hydrogen peroxide among the step c.
The mass ratio of step c fatty acid methyl ester, formic acid and sherwood oil is 1:0.25:0.5.
The mass ratio of step c hydrogen peroxide and phosphoric acid is 1.3:0.005.
The mass ratio of step g epoxy aliphatic acid methyl ester and mixed fatty acid is 1:0.3-0.7.
Of the present inventionly a kind ofly prepare the method for low pour point lubricating oil additive, the oxirane value of the epoxy aliphatic acid methyl ester that the method steps d obtains＞4～7, iodine number＜2～0, acid number＜1, yield 90-94% from low price oleum gossypii seminis.
Working concentration is preferably 30% hydrogen peroxide in the reaction process, can realize effective utilization of lower concentration hydrogen peroxide.
Prepare in the method for epoxy aliphatic acid methyl ester at hydrogen peroxide method, select formic acid to cook epoxidizing agent, obviously be better than acetic acid and dichloro acetic acid.
The acid number of the light yellow transparent oily matter epoxy aliphatic acid methyl ester mixed aliphatic ester that step f obtains＜0.5～2,40 ℃ of viscosity 100-350 of temperature, 100 ℃ of viscosity 10-40 of temperature, viscosity index 120-160, flash-point 230-240, pour point-15～-30.
Method of the present invention, the method characteristics are: adopting peroxyformic acid and hydrogen peroxide under the relatively mild condition under catalyst action, making the two keys in the fatty acid methyl ester generate the epoxy product; Then epoxide and mixed fatty acid carry out the partial esterification reaction under suitable reaction conditions, with this structure that changes fatty acid methyl ester, reach the requirement that improves the lubricating oil use properties.Simultaneously, react remaining aqueous formic acid and just can obtain a kind of new product---calcium formiate through the alkaline purification of routine, thus Atom economy that fully can realization response, and used reaction mass is industry raw material commonly used, makes things convenient for, is easy to get, inexpensive.
Not only can obtain epoxy aliphatic acid methyl ester and the mixed aliphatic ester of high yield and higher degree by the method, and can get rid of and use the operation unsafe factor of high-strength hydrogen peroxide in suitability for industrialized production, realize the greenization of synthesis technique and the Atom economy of whole reaction.Technique cleaning therefore of the present invention, environmental friendliness need not high-pressure and high-temperature device, and implementation condition is simple, is convenient to carry out mass-producing and produces continuously.
Compare with existing technique, the method for preparing the epoxy aliphatic acid methyl ester mixed aliphatic ester among the present invention has obvious difference:
1. the present invention uses the 20-30% hydrogen peroxide in reaction process, has realized effective utilization of lower concentration hydrogen peroxide, has greatly reduced industrial production cost, has saved resource;
2. no matter the epoxy aliphatic acid methyl ester that obtains by the method for the invention has reached higher level on product yield and purity;
3. the present invention adopts esterification techniques that epoxidised fatty acid methyl ester is gone on foot esterification and obtains extreme-pressure anti-wear and oxidation resistant lubricating oil additive;
4. the used raw material of the present invention is the industrial goods commonly used that are easy to get, and all can effectively transform in the reaction, has realized taking full advantage of of reaction raw materials.
Embodiment
The invention will be further described below by specific embodiment:
Embodiment 1
A, with the 50g Oleum Gossypii semen, the mixture of 16g methyl alcohol and 0.2g potassium hydroxide places in three mouthfuls of reaction flasks, mixes, and under agitation rises to temperature 70 C, reaction times 1h;
B, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation obtains fatty acid methyl ester, wherein, and acid number 0.5, yield 96 %;
C, the mixture that will make with extra care 50g fatty acid methyl ester, 12.5g formic acid and 25g sherwood oil place three mouthfuls of reaction flasks with electric stirring, dropping funnel, prolong, and be placed on water bath with thermostatic control, mix under the rear stirring and rise to temperature 45 C, dripping mass ratio is the hydrogen peroxide of 1.3:0.005 and the mixture of phosphoric acid;
The mixture of d, hydrogen peroxide and phosphoric acid dropwise and temperature steadily after, system temperature is transferred to 50 ℃ of temperature of reaction, reaction times 3h;
E, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation obtains epoxy aliphatic acid methyl ester, and wherein oxirane value 4.9, iodine number 1, acid number 0.3, yield 91 %;
F, add mass percent 5% calcium carbonate of raw material after will reacting in the remaining aqueous formic acid, can obtain calcium formiate, reclaim;
G, mixed fatty acid is heated to 100 ℃ of temperature, again step e epoxy aliphatic acid methyl ester is slowly joined in the mixed fatty acid, reaction 5h, the mass ratio of epoxy aliphatic acid methyl ester and mixed fatty acid is 1:0.3;
Decompression steams unreacted mixed fatty acid after h, the reaction, gets final product to get light yellow transparent oily matter epoxy aliphatic acid methyl ester mixed aliphatic ester, and the product pour point is-21.
Embodiment 2
A, with the 50g Oleum Gossypii semen, the mixture of 18g methyl alcohol and 0.25g potassium hydroxide places in three mouthfuls of reaction flasks, mixes, and under agitation rises to 76 ℃ of temperature, the reaction 2h;
B, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation obtains fatty acid methyl ester, wherein, and acid number 0.4, yield 97 %;
C, the mixture that will make with extra care 50g fatty acid methyl ester, 12.5g formic acid and 25g sherwood oil place three mouthfuls of reaction flasks with electric stirring, dropping funnel, prolong, and be placed on water bath with thermostatic control, mix under the rear stirring and rise to temperature 50 C, dripping mass ratio is the hydrogen peroxide of 1.3:0.005 and the mixture of phosphoric acid;
The mixture of d, hydrogen peroxide and phosphoric acid dropwise and temperature steadily after, system temperature is transferred to 50 ℃ of temperature of reaction, reaction times 4h;
E, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation obtains epoxy aliphatic acid methyl ester, and wherein oxirane value 5.2, iodine number 0.7, and acid number 0.3, yield can reach 93 %;
Add mass percent 5% calcium oxide of raw material after f, the reaction in the remaining aqueous formic acid, can obtain calcium formiate, reclaim;
G, mixed fatty acid is heated to 100 ℃ of temperature, again step c epoxy epoxy aliphatic acid methyl ester is slowly joined in the mixed fatty acid, reaction 6h, the mass ratio of epoxy aliphatic acid methyl ester and mixed fatty acid is 1:0.3;
Decompression steams unreacted mixed fatty acid after h, the reaction, gets final product to get light yellow transparent oily matter epoxy aliphatic acid methyl ester mixed aliphatic ester, and the product pour point is-23.
Embodiment 3
A, with the 50g Oleum Gossypii semen, the mixture of 20g methyl alcohol and 0.2g potassium hydroxide places in three mouthfuls of reaction flasks, mixes, under agitation rise to the temperature 78 ℃, the reaction 2h;
B, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation obtains fatty acid methyl ester, wherein, and acid number 0.6, yield 94 %;
C, the mixture that will make with extra care 50g fatty acid methyl ester, 12.5g formic acid and 25g sherwood oil place with three mouthfuls of reaction flasks of electric stirring, dropping funnel, prolong and are placed on water bath with thermostatic control, mix and rise to 55 ℃ of temperature under the rear stirring, dripping mass ratio is the hydrogen peroxide of 1.3:0.005 and the mixture of phosphoric acid;
The mixture of d, hydrogen peroxide and phosphoric acid dropwise and temperature steadily after, system temperature is transferred to 55 ℃ of temperature of reaction, reaction times 7h;
E, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation obtains epoxy aliphatic acid methyl ester, and wherein oxirane value 5.47, iodine number 0.5, acid number 0.2, yield 95%;
Add mass percent 5% calcium oxide of raw material after f, the reaction in the remaining aqueous formic acid, can obtain calcium formiate, reclaim;
G, mixed fatty acid is heated to 100 ℃ of temperature, again step e epoxy epoxy aliphatic acid methyl ester is slowly joined in the lipid acid, reaction 6h, the mass ratio of epoxy aliphatic acid methyl ester and mixed fatty acid is 1:0.3;
Decompression steams unreacted mixed fatty acid after h, the reaction, gets final product to get light yellow transparent oily matter epoxy aliphatic acid methyl ester mixed aliphatic ester, and the product pour point is-25.
Embodiment 4
A, with the 50g Oleum Gossypii semen, the mixture of 18g methyl alcohol and 0.3g potassium hydroxide places in three mouthfuls of reaction flasks, mixes, under agitation degree of rising to is 80 ℃, the reaction 3h;
B, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation obtains fatty acid methyl ester, wherein, and acid number 0.2, yield 93 %;
C, the mixture that will make with extra care 50g fatty acid methyl ester, 12.5g formic acid and 25g sherwood oil place with three mouthfuls of reaction flasks of electric stirring, dropping funnel, prolong and are placed on water bath with thermostatic control, mix and rise to 55 ℃ of temperature under the rear stirring, dripping mass ratio is the hydrogen peroxide of 1.3:0.005 and the mixture of phosphoric acid;
The mixture of d, hydrogen peroxide and phosphoric acid dropwise and temperature steadily after, system temperature is transferred to 55 ℃ of temperature of reaction, reaction times 7h;
E, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation obtains epoxy aliphatic acid methyl ester, and wherein oxirane value 5.8, iodine number 0.2, acid number 0.3, yield 96%;
F, add mass percent 5% calcium carbonate of raw material after will reacting in the remaining aqueous formic acid, can obtain calcium formiate, reclaim;
G, mixed fatty acid is heated to 100 ℃ of temperature, again step c epoxy epoxy aliphatic acid methyl ester is slowly joined in the mixed fatty acid, reaction 8h, the mass ratio of epoxy aliphatic acid methyl ester and mixed fatty acid is 1:0.3;
Decompression steams unreacted mixed fatty acid after h, the reaction, gets final product to get light yellow transparent oily matter epoxy aliphatic acid methyl ester mixed aliphatic ester, and the product pour point is-26.
Embodiment 5
A, with the 50g Oleum Gossypii semen, the mixture of 18g methyl alcohol and 0.3g potassium hydroxide places in three mouthfuls of reaction flasks, mixes, under agitation rise to the temperature 78 ℃, the reaction 3h;
B, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation obtains fatty acid methyl ester, wherein, and acid number 0.2, yield 96 %;
C, the mixture that will make with extra care 50g fatty acid methyl ester, 12.5g formic acid and 25g sherwood oil place with three mouthfuls of reaction flasks of electric stirring, dropping funnel, prolong and are placed on water bath with thermostatic control, mix and rise to 55 ℃ of temperature under the rear stirring, dripping mass ratio is the hydrogen peroxide of 1.3:0.005 and the mixture of phosphoric acid;
The mixture of d, hydrogen peroxide and phosphoric acid dropwise and temperature steadily after, system temperature is transferred to 55 ℃ of temperature of reaction, reaction times 6h;
E, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation obtains the epoxy polyisobutene, and wherein oxirane value 6.1, iodine number 0.3, acid number 0.25, yield 95%;
F, add mass percent 5% calcium oxide of raw material after will reacting in the remaining aqueous formic acid, can obtain calcium formiate, reclaim;
G, mixed fatty acid is heated to 100 ℃ of temperature, again step e epoxy epoxy aliphatic acid methyl ester is slowly joined in the mixed fatty acid, reaction 7h, the mass ratio of epoxy aliphatic acid methyl ester and mixed fatty acid is 1:0.3;
Decompression steams unreacted mixed fatty acid after h, the reaction, gets final product to get light yellow transparent oily matter epoxy aliphatic acid methyl ester mixed aliphatic ester, and the product pour point is-28.
Embodiment 6
A, with the 50g Oleum Gossypii semen, the mixture of 22g methyl alcohol and 0.25g potassium hydroxide places in three mouthfuls of reaction flasks, mixes, and under agitation rises to 75 ℃ of temperature, the reaction 2h;
B, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation obtains fatty acid methyl ester, wherein, and acid number 0.2, yield 97 %;
C, the mixture that will make with extra care 50g fatty acid methyl ester, 12.5g formic acid and 25g sherwood oil place with three mouthfuls of reaction flasks of electric stirring, dropping funnel, prolong and are placed on water bath with thermostatic control, mix and rise to 55 ℃ of temperature under the rear stirring, dripping mass ratio is the hydrogen peroxide of 1.3:0.005 and the mixture of phosphoric acid;
The mixture of d, hydrogen peroxide and phosphoric acid dropwise and temperature steadily after, system temperature is transferred to 55 ℃ of temperature of reaction, reaction times 5h;
E, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation obtains the epoxy polyisobutene, and wherein oxirane value 6.23, iodine number 0, acid number 0.2, yield 96%;
F, add mass percent 5% calcium carbonate of raw material after will reacting in the remaining aqueous formic acid, can obtain calcium formiate, reclaim;
G, mixed fatty acid is heated to 100 ℃ of temperature, again step c epoxy epoxy aliphatic acid methyl ester is slowly joined in the mixed fatty acid, reaction 6h, the mass ratio of epoxy aliphatic acid methyl ester and mixed fatty acid is 1:0.3;
Decompression steams unreacted mixed fatty acid after h, the reaction, gets final product to get light yellow transparent oily matter epoxy aliphatic acid methyl ester mixed aliphatic ester, and the product pour point is-29.
Claims (6)
1. one kind prepares the method for low pour point lubricating oil additive from low price oleum gossypii seminis, it is characterized in that following these steps to carrying out:
A, take Oleum Gossypii semen, methyl alcohol as raw material, prepare fatty acid methyl ester take potassium hydroxide as catalyzer, temperature of reaction 70-80 ℃, reaction times 1-3h;
B, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation obtains fatty acid methyl ester;
C, with fatty acid methyl ester, the mixture of formic acid and sherwood oil places in three mouthfuls of reaction flasks, mixes, and under agitation rises to temperature 20-50 ℃, dripping concentration is the mixture of 20-30% hydrogen peroxide and phosphoric acid;
The mixture of d, hydrogen peroxide and phosphoric acid dropwises, and after temperature is steady, system temperature is transferred to 30 ℃-65 ℃ of temperature of reaction, reaction times 3-7h;
E, reaction are transferred to standing demix in the separating funnel with reaction mixture after finishing, and branch vibration layer, oil reservoir wash with water to neutrality, and underpressure distillation gets light yellow oil and is epoxy aliphatic acid methyl ester;
F, add mass percent 5-15% calcium oxide or the calcium carbonate of raw material after will reacting in the remaining aqueous formic acid, can obtain calcium formiate, reclaim;
G, mixed fatty acid is heated to temperature 100-130 ℃, again step e epoxy aliphatic acid methyl ester is slowly joined in the mixed fatty acid, reaction 5-8h;
Decompression steamed unreacted mixed fatty acid after h, reaction finished, and can obtain light yellow transparent oily matter epoxy aliphatic acid methyl ester mixed aliphatic ester.
2. method according to claim 1, the mass ratio that it is characterized in that Oleum Gossypii semen, methyl alcohol and potassium hydroxide among the step a is 1:0.2-0.3:0.05-0.07.
3. method according to claim 1, concentration is 30% hydrogen peroxide among its characterization step c.
4. method according to claim 1, the mass ratio that it is characterized in that step c fatty acid methyl ester, formic acid and sherwood oil is 1:0.25:0.5.
5. method according to claim 1, the mass ratio that it is characterized in that step c hydrogen peroxide and phosphoric acid is 1.3:0.005.
6. method according to claim 1, the mass ratio that it is characterized in that step g epoxy aliphatic acid methyl ester and mixed fatty acid is 1:0.3-0.7.
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| CN107141269A (en) * | 2017-05-19 | 2017-09-08 | 佛山市高明晟俊塑料助剂有限公司 | A kind of preparation method of epoxy aliphatic acid methyl ester |
| CN108130157A (en) * | 2017-11-15 | 2018-06-08 | 泰州市艾瑞斯克模具有限公司 | A kind of preparation method of the degradable biological matrix lubricant based on natural fat |
| CN115746939A (en) * | 2019-03-28 | 2023-03-07 | 王琰 | Preparation method of biodegradable environment-friendly lubricant |
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| CN107141269B (en) * | 2017-05-19 | 2019-07-30 | 佛山市高明晟俊塑料助剂有限公司 | A kind of preparation method of epoxy aliphatic acid methyl ester |
| CN108130157A (en) * | 2017-11-15 | 2018-06-08 | 泰州市艾瑞斯克模具有限公司 | A kind of preparation method of the degradable biological matrix lubricant based on natural fat |
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