CN103113993B - Method for preparing lubricant from biodiesel - Google Patents
Method for preparing lubricant from biodiesel Download PDFInfo
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- CN103113993B CN103113993B CN201310013843.0A CN201310013843A CN103113993B CN 103113993 B CN103113993 B CN 103113993B CN 201310013843 A CN201310013843 A CN 201310013843A CN 103113993 B CN103113993 B CN 103113993B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses an epoxidation, isomerization and esterification process for preparing lubricant from biodiesel and relates to a process for preparing alcohol-ester-type environment-friendly lubricant base oil by using solid acid as a catalyst, and belongs to the technical field of lubricant modification processes. According to the process, the biodiesel (fatty-acid methyl ester) is subjected to epoxidation by using hydrogen peroxide, formic acid and the solid-acid catalyst, and thus, double bonds are saturated; and long-chain fatty acid is adopted to carry out isomerization and esterification reaction under the participation of the solid-acid catalyst, unstable epoxy bonds are opened, and thus, isomerized biodiesel grease monoester is obtained. The solid-acid catalyst used by the process has the characteristics of good stability, easiness in separation, and environment friendliness.
Description
Technical field
The invention belongs to biofuel modified technique technical field, particularly a kind of epoxy biofuel, by high materialization modification, is prepared the method for lubricant base.
Background technology
The whole world approximately has 5,000,000～1,000 ten thousand t petroleum base chemical to enter biosphere every year according to statistics, even in the reclaim of lubricant utilization ratio country of high (being greater than 60%), still have 4%～10% lubricant entered environment, only the European Community just has 600,000 t lubricating oil entered environments every year.The oil product that causes these problems is hydraulic efficiency oil and the disposable lubricating oil passing through of the recycle system, as lubricants such as chain saw oil, two stroke engine oil, railroad track lubricant, exposed gear oil and steel wire lubricating esters.Lubricant severe contamination land, rivers and the lake of entered environment, also serious harm ecotope and the eubiosis, reaches 100 years as mineral oil to the pollution of underground water, and the life-span that the mineral oil of 0.1 μ g/g can reduce marine shrimp reaches 20%.
Along with the continuous reinforcement of mankind's environmental consciousness and environmental protection legislation, caused pollution problem that people have started to note and research lubricating oil scatters and disappears in environment.Many petroleum chemical enterprises have started to drop into the petrochemicals of the friendly excellent performance of a large amount of research effort development environments, the environmental problem of being brought being widely used in process to solve lubricating oil in the world.The biodegradable lubricating oil that research and development meet environmental requirement has become the important subject in lubricating oil field since the nineties in 20th century.Along with scientific and technical development, industrial lubricant demand growth amplitude is larger simultaneously, and European and American countries is to future developments such as long lifetime, biodegradable (comprising the blended oil with vegetables oil), ucon oils now.Thus, the demand of synthetic oil, vegetables oil, II/III class base oil will increase by a fairly big margin.
Biofuel will be the reproducible environment-friendly type energy that can partly replace oil, if but do not improve its oxidative stability and can't serve as modern lubricating oil.Adopting biofuel to carry out the synthetic high-quality lubricating oil of upgrading, is a kind of approach of indirect utilization bioenergy and sun power, by exploring effective way and the principle that can obtain a biofuel chemical modification and become industrial lubricants.Under the situation that petroleum resources are in short supply now; along with the raising of people's living standard and the enhancing of environmental protection consciousness; development and exploitation have moving biofuel ester " green " lubricant base of improvement of regenerative power; not only there is the meaning of environmental protection Sustainable development, and there is great society and economic implications.
Modern machinery and equipment to the requirement of lubricating oil is: (1) is environmentally friendly, nontoxic, biodegradable; (2) there is higher oxidation-resistance, have longer work-ing life; (3) require that pour point is low, viscosity index is high, can adapt to the special occasions of severe cold and high temperature operating mode; (4) be convenient to the oil product of synthetic different viscosity grade.
Biofuel is carried out to chemical modification, and by saturated two keys, catalytic isomerization esterification can produce one and has good in oxidation resistance, high low temperature adaptability is good, biodegradable high-quality ucon oil.
In prior art, conventionally adopt liquid acid, the such as vitriol oil, strong phosphoric acid etc., or resene catalyzer, such as D001 resin, D002, DH, CR and 732 etc., carry out the catalyst system of chemical modification as biofuel, when but liquid acid is used as catalyzer, can increase on the one hand the difficulty of discharge and the aftertreatment of waste water, on the other hand, water-content can affect the balance of reaction, and then the transformation efficiency of impact reaction; And while using resene catalyzer, if there is metal ion in reaction system, metal ion just may carry out chelating with resin, reduce acidic site and the acid active centre of resin catalyst, equally also can make catalyst activity reduction, reaction shows as level of response and reduces, and transformation efficiency is not high (in prior art, press oxirane value transformation efficiency and calculate, epoxy diesel oil is prepared the transformation efficiency of lubricating oil in 87.5% left and right).
Summary of the invention
Technical problem to be solved by this invention is: in prior art, utilize biofuel, prepare in the method for lubricant base, while using liquid acid as catalyzer, can increase on the one hand the difficulty of discharge and the aftertreatment of waste water, on the other hand, water-content can affect the balance of reaction, and then the transformation efficiency of impact reaction; And while using resene catalyzer, if there is metal ion in reaction system, metal ion just may carry out chelating with resin, makes catalyst activity reduction, the transformation efficiency of reaction is not high.
For solving this technical problem, technical scheme provided by the invention is:
The invention provides one and utilize biofuel, prepare the method for lubricant base, this preparation method is that, under catalyzer condition, first by biofuel, epoxidation modification, is prepared into epoxy biofuel; Taking epoxy biofuel and longer chain fatty acid as raw material, under catalyzer condition, carry out the reaction of open loop isomery esterification modification again, obtain alcohol ester type lubricating oil,
As preferably: biofuel is vegetable fatty acid esters, is selected from methyl soyate, rapeseed oil fatty acid methyl esters or Castor Oil Fatty Acid methyl esters;
As preferably: the catalyzer of epoxidation and ring-opening reaction, be solid acid catalyst, be selected from 3A type zeolite molecular sieve K
2oAl
2o
32SiO
24.5H
2o, Y zeolite NaO
2al
2o
34.9SiO
29.4H2O, ZSM type molecular sieve ZSM-5-H, ZSM-5-Na, mordenite Na
2oAl
2o
310SiO
26H
2one in O solid acid catalyst;
As preferably: longer chain fatty acid is the organic acid of a chain length 2-10 carbon atom, be selected from the one in acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid or capric acid;
The concrete steps of above-mentioned reaction method are:
(1) epoxidation reaction: take biofuel, solid acid catalyst and formic acid, be put in the there-necked flask with condenser and agitator, the constant pressure funnel that hydrogen peroxide is housed is inserted in bottleneck one end, be preheated to 40 DEG C, stir, drip hydrogen peroxide, maintain the temperature between 40-60 DEG C, within one hour, dropwise; Keep temperature in 60-65 DEG C, then at this temperature, continue stirring reaction 3-4h, after completion of the reaction, reaction mixture is cooled to room temperature, pour in separating funnel, leave standstill, isolate lower floor's water and solid acid catalyst; Then upper organic phase is washed to PH=6, leaves standstill, lower floor's water is poured out, organic phase is distilled at 100 DEG C, obtain epoxidation biodiesel,
As preferably: the mass ratio of biofuel, hydrogen peroxide, formic acid, solid catalyst is 100:40-45:6-8:2-3,
(2) isomery esterification ring-opening reaction: take longer chain fatty acid and solid acid catalyst and be put in the there-necked flask with condenser and agitator, stirring, reflux, be heated to temperature is 70-100 DEG C, then add the epoxy biofuel making in step (1), ring-opening reaction 6-15h; In reaction process, from there-necked flask, got one time sample every 2 hours, after NaOH solution washing that institute's sample thief is 0.05% through solute massfraction, washing, reclaim under reduced pressure lipid acid, measure its oxirane value, when oxirane value is tending towards 0, and no longer change, be reaction end; In the time that reaction reaches terminal, stopped reaction, is cooled to room temperature by reaction mixture, pours in separating funnel, isolates lower floor's water and solid acid catalyst; Then upper organic phase washing is extremely neutral, then through rotary evaporation 2h, finally obtain alcohol ester type lubricating oil,
As preferably: the mass ratio of epoxy biofuel, lipid acid, solid acid catalyst is 10:10-100:0.1-1;
As preferably: the washing of upper organic phase is first to use the NaHCO of solute massfraction 5%
3solution washing 3 times, then use the salt water washing 3 times of solute massfraction 5%, finally use hot distilled water wash;
As preferably: when rotary evaporation operation, set vacuum tightness-0.07MPa, temperature is 97 DEG C.
The invention has the beneficial effects as follows: the present invention, in preparation process, uses solid acid catalyst to replace liquid acid catalyst, has avoided in reaction process, produces acid waste water and pollution on the environment; Solid acid catalyst has replaced resene catalyzer, has avoided metal ion in reaction system and the chelating of resin catalyst, and the decline of the catalyst activity causing; Molecular sieve catalyst is than other strongly-acid solid acid catalysts, and its acid intensity is moderate, little to equipment corrosion.When method of the present invention is prepared alcohol ester type lubricating oil, transformation efficiency (pressing oxirane value transformation efficiency calculates) is more than 96%.
Embodiment
Embodiment 1:
(1) take the methyl soyate of 50g, 1g solid acid catalyst ZSM-5-H type molecular sieve and 3.5g formic acid are put in the there-necked flask with condenser and agitator, the constant pressure funnel that 21g hydrogen peroxide is housed is inserted in bottleneck one end, be preheated to 40 DEG C, stir, drip, maintain the temperature between 40-60 DEG C, drip hydrogen peroxide, within one hour, dropwise, keep temperature in 60-65 DEG C, then at this temperature, continue reaction 3.5h, after completion of the reaction, reaction mixture is cooled to room temperature, pour in separating funnel, leave standstill, isolate lower floor's water and solid acid catalyst, then upper oil phase (organic phase) is first used to 5%(solute massfraction) NaHCO
3solution washing 3 times, each 50mL, use again 5%(solute massfraction) NaCl solution washing 3 times, each 30mL, finally use hot distilled water (70 DEG C) washing 3 times, each 50mL, PH=6 after washing, leaves standstill, and lower floor's water is poured out, and oil phase is distilled at 100 DEG C, obtains epoxidation biodiesel, and recording its oxirane value is 5.92.
(2) Glacial acetic acid and the 1.3g ZSM-5-H type molecular sieve catalyst that take 30g are put in the there-necked flask with condenser and agitator, stir, reflux, being heated to temperature is 80 DEG C, then add 30g epoxy biofuel (epoxy soybean oil fatty acid methyl ester), ring-opening reaction, in reaction process, sample once from there-necked flask every 2h, institute's sample thief is through 0.05%(solute massfraction) NaOH solution washing, distillation washing washing, decompression (vacuum tightness-0.07MPa, 100 DEG C of temperature) reclaim after lipid acid, measure its oxirane value, when oxirane value is tending towards 0, and no longer change (t=6h), be reaction end.In the time that reaction reaches terminal, stopped reaction, reaction mixture is cooled to room temperature, pours in separating funnel, isolates lower floor's water and solid acid catalyst; Then by the upper organic phase washing of reaction product, first use 5%(solute massfraction) NaHCO
3solution washing 3 times, each 50mL, then use 5%(solute massfraction) NaCl solution washing 3 times, each 30mL, finally uses hot distilled water (70 DEG C) washing 3 times, each 50mL, after washing, PH equals 7; Final reaction product upper organic phase product is through rotary evaporation (vacuum tightness-0.07MPa, 97 DEG C of temperature) 2h, steam water and low-boiling-point organic compound, make product concentrated, obtain alcohol ester type (acetic acid isomery ester) lubricating oil, when the method for the present embodiment is prepared alcohol ester type lubricating oil, transformation efficiency (calculating by oxirane value transformation efficiency) is 98%.
Above-mentioned oxirane value is measured and is carried out with reference to the mensuration (hydrochloric acid-acetone method) of GB1677-81 softening agent oxirane value,
Oxirane value X calculation formula is: X={[V-(V
1-V
2÷ G × W)] × N × 0.016 × 100}/W,
In formula: V-blank test consumes the milliliter number of standard solution of sodium hydroxide; V
1-specimen test consumes the milliliter number of standard solution of sodium hydroxide; V
2in-sample, measure the milliliter number that acid number consumes standard solution of sodium hydroxide; The equivalent concentration of N-standard solution of sodium hydroxide; W-sample weight, gram; The quality of sample when G-mensuration acid number, gram; The milligramequivalent of 0.016-oxygen; Sample acid number is less than at 0.5 o'clock, (V
2÷ G × W) can ignore.
Embodiment 2:
(1) take the rapeseed oil fatty acid methyl esters of 50g, 1.5g solid acid catalyst ZSM-5-Na type molecular sieve and 4g formic acid are put in the there-necked flask with condenser and agitator, the constant pressure funnel that 20g hydrogen peroxide is housed is inserted in bottleneck one end, be preheated to 40 DEG C, stir, drip, maintain the temperature between 40-60 DEG C, drip hydrogen peroxide, within one hour, dropwise, keep temperature in 60-65 DEG C, then at this temperature, continue reaction 4h, after completion of the reaction, reaction mixture is cooled to room temperature, pour in separating funnel, leave standstill, isolate lower floor's water and solid acid catalyst, then upper oil phase (organic phase) is first used to 5%(solute massfraction) NaHCO
3solution washing 3 times, each 50mL, use again 5%(solute massfraction) NaCl solution washing 3 times, each 30mL, finally use hot distilled water (70 DEG C) washing 3 times, each 50mL, PH=6 after washing, leaves standstill, and lower floor's water is poured out, and oil phase is distilled at 100 DEG C, obtains epoxidation biodiesel, recording its oxirane value is the mensuration reference example 1 of 5.36(oxirane value).
(2) butyric acid and the 1.1g ZSM-5-Na type molecular sieve catalyst that take 30g are put in the there-necked flask with condenser and agitator, stir, reflux, being heated to temperature is 85 DEG C, then add 30g epoxy biofuel (epoxy rapeseed oil fatty acid methyl ester), ring-opening reaction, in reaction process, from there-necked flask, get one time sample every 2h, institute's sample thief is through 0.05%(solute massfraction) NaOH solution washing, distillation washing washing, decompression (vacuum tightness-0.07MPa, 110 DEG C of temperature) reclaim after lipid acid, measure its oxirane value (the mensuration reference example 1 of oxirane value), when oxirane value is tending towards 0, and no longer change (t=9h), be reaction end.In the time that reaction reaches terminal, stopped reaction, reaction mixture is cooled to room temperature, pours in separating funnel, isolates lower floor's water and solid acid catalyst; Then by the upper organic phase washing of reaction product, first use 5%(solute massfraction) NaHCO
3solution washing 3 times, each 50mL, then use 5%(solute massfraction) NaCl solution washing 3 times, each 30mL, finally uses hot distilled water (70 DEG C) washing 3 times, each 50mL, after washing, PH equals 7; Final reaction product upper organic phase product is through rotary evaporation (vacuum tightness-0.07MPa, 97 DEG C of temperature) 2h, steam water and low-boiling-point organic compound, make product concentrated, obtain alcohol ester type (butyric acid isomery ester) lubricating oil, when the method for the present embodiment is prepared alcohol ester type lubricating oil, transformation efficiency (calculating by oxirane value transformation efficiency) is 97%.
Embodiment 3:
(1) take methyl soyate, the 1.5g solid acid catalyst Y zeolite NaO of 50g
2al
2o
34.9SiO
29.4H
2o and 3.5g formic acid are put in the there-necked flask with condenser and agitator, and the constant pressure funnel that 20.5g hydrogen peroxide is housed is inserted in bottleneck one end, is preheated to 40 DEG C, stir, drip, maintain the temperature between 40-60 DEG C, drip hydrogen peroxide, within one hour, dropwise, keep temperature in 60-65 DEG C, then at this temperature, continue reaction 3.5h, after completion of the reaction, reaction mixture is cooled to room temperature, pours in separating funnel, leave standstill, isolate lower floor's water and solid acid catalyst; Then upper oil phase (organic phase) is first used to 5%(solute massfraction) NaHCO
3solution washing 3 times, each 50mL; Use again 5%(solute massfraction) NaCl solution washing 3 times, each 30mL; Finally use hot distilled water (70 DEG C) washing 3 times, each 50mL, PH=6 after washing, leave standstill, lower floor's water is poured out, oil phase is distilled at 100 DEG C, obtain epoxidised soybean oil fatty acid methyl ester, recording its oxirane value is the mensuration reference example 1 of 5.70(oxirane value).
(2) take valeric acid and the 1.5g Y zeolite NaO of 60g
2al
2o
34.9SiO
29.4H
2o catalyzer is put in the there-necked flask with condenser and agitator, stirring, reflux, be heated to temperature is 90 DEG C, then add 30g epoxy soybean oil fatty acid methyl ester, ring-opening reaction, in reaction process, from there-necked flask, get one time sample every 2h, institute's sample thief is through 0.05%(solute massfraction) NaOH solution washing, distilled water wash, decompression (vacuum tightness-0.07MPa, 110 DEG C of temperature) reclaim after lipid acid, measure its oxirane value (the mensuration reference example 1 of oxirane value), when oxirane value is tending towards 0, and no longer change (t=10h), be reaction end.In the time that reaction reaches terminal, stopped reaction, reaction mixture is cooled to room temperature, pours in separating funnel, isolates lower floor's water and solid acid catalyst; Then by the upper organic phase washing of reaction product, first use 5%(solute massfraction) NaHCO
3solution washing 3 times, each 50mL, then use 5%(solute massfraction) NaCl solution washing 3 times, each 30mL, finally uses hot distilled water (70 DEG C) washing 3 times, each 50mL, after washing, PH equals 7; Final reaction product upper organic phase product is through rotary evaporation (vacuum tightness-0.07MPa, 97 DEG C of temperature) 2h, steam water and low-boiling-point organic compound, make product concentrated, obtain alcohol ester type (valeric acid isomery ester) lubricating oil, when the method for the present embodiment is prepared alcohol ester type lubricating oil, transformation efficiency (calculating by oxirane value transformation efficiency) is 96%.
Embodiment 4:
(1) take Castor Oil Fatty Acid methyl esters, the 1.5g solid acid catalyst 3A type zeolite molecular sieve K of 50g
2oAl
2o
32SiO
24.5H
2o and 3g formic acid are put in the there-necked flask with condenser and agitator, and the constant pressure funnel that 22.5 hydrogen peroxide are housed is inserted in bottleneck one end, is preheated to 40 DEG C, stir, drip, maintain the temperature between 40-60 DEG C, drip hydrogen peroxide, within one hour, dropwise, keep temperature in 60-65 DEG C, then at this temperature, continue reaction 4h, after completion of the reaction, reaction mixture is cooled to room temperature, pours in separating funnel, leave standstill, isolate lower floor's water and solid acid catalyst; Then upper oil phase (organic phase) is first used to 5%(solute massfraction) NaHCO
3solution washing 3 times, each 50mL; Use again 5%(solute massfraction) NaCl solution washing 3 times, each 30mL; Finally use hot distilled water (70 DEG C) washing 3 times, each 50mL, PH=6 after washing, leaves standstill, and lower floor's water is poured out, and oil phase is distilled at 100 DEG C, obtains epoxidation biodiesel, recording its oxirane value is the mensuration reference example 1 of 6.11(oxirane value).
(2) take caproic acid and the 1.8g3A type zeolite molecular sieve K of 90g
2oAl
2o
32SiO
24.5H
2o catalyzer is put in the there-necked flask with condenser and agitator, stir, reflux, being heated to temperature is 85 DEG C, then add 30g epoxy biofuel (epoxy castor oil fatty acid methyl ester), ring-opening reaction, in reaction process, from there-necked flask, get one time sample every 2h, institute's sample thief is through 0.05%(solute massfraction) NaOH solution washing, distillation washing washing, decompression (vacuum tightness-0.07MPa, 120 DEG C of temperature) reclaim after lipid acid, measure its oxirane value (the mensuration reference example 1 of oxirane value), when oxirane value is tending towards 0, and no longer change (t=12h), be reaction end.In the time that reaction reaches terminal, stopped reaction, reaction mixture is cooled to room temperature, pours in separating funnel, isolates lower floor's water and solid acid catalyst; Then by the upper organic phase washing of reaction product, first use 5%(solute massfraction) NaHCO
3solution washing 3 times, each 50mL, then use 5%(solute massfraction) NaCl solution washing 3 times, each 30mL, finally uses hot distilled water (70 DEG C) washing 3 times, each 50mL, after washing, PH equals 7; Final reaction product upper organic phase product is through rotary evaporation (vacuum tightness-0.07MPa, 97 DEG C of temperature) 2h, steam water and low-boiling-point organic compound, make product concentrated, obtain alcohol ester type (caproic acid isomery ester) lubricating oil, when the method for the present embodiment is prepared alcohol ester type lubricating oil, transformation efficiency (calculating by oxirane value transformation efficiency) is 97%.
Embodiment 5:
(1) take the methyl soyate of 50g, 1.5g solid acid catalyst ZSM-5-H type molecular sieve and 3g formic acid are put in the there-necked flask with condenser and agitator, the constant pressure funnel that 22g hydrogen peroxide is housed is inserted in bottleneck one end, be preheated to 40 DEG C, stir, drip, maintain the temperature between 40-60 DEG C, drip hydrogen peroxide, within one hour, dropwise, keep temperature in 60-65 DEG C, then at this temperature, continue reaction 4h, after completion of the reaction, reaction mixture is cooled to room temperature, pour in separating funnel, leave standstill, isolate lower floor's water and solid acid catalyst, then upper oil phase (organic phase) is first used to 5%(solute massfraction) NaHCO
3solution washing 3 times, each 50mL, use again 5%(solute massfraction) NaCl solution washing 3 times, each 30mL, finally use hot distilled water (70 DEG C) washing 3 times, each 50mL, PH=6 after washing, leaves standstill, and lower floor's water is poured out, and oil phase is distilled at 100 DEG C, obtains epoxidation biodiesel, recording its oxirane value is the mensuration reference example 1 of 5.96(oxirane value).
(2) taking the sad of 90g and 1.8g ZSM-5-H type molecular sieve catalyst is put in the there-necked flask with condenser and agitator, stir, reflux, being heated to temperature is 85 DEG C, then add 30g epoxy biofuel (epoxy soybean oil fatty acid methyl ester), ring-opening reaction, in reaction process, from there-necked flask, get one time sample every 2h, institute's sample thief is through 0.05%(solute massfraction) NaOH solution washing, distillation washing washing, decompression (vacuum tightness-0.07MPa, 120 DEG C of temperature) reclaim after lipid acid, measure its oxirane value (the mensuration reference example 1 of oxirane value), when oxirane value is tending towards 0, and no longer change (t=13h), be reaction end.In the time that reaction reaches terminal, stopped reaction, reaction mixture is cooled to room temperature, pours in separating funnel, isolates lower floor's water and solid acid catalyst; Then by the upper organic phase washing of reaction product, first use 5%(solute massfraction) NaHCO
3solution washing 3 times, each 50mL, then use 5%(solute massfraction) NaCl solution washing 3 times, each 30mL, finally uses hot distilled water wash 3 times, each 50mL, after washing, PH equals 7; Final reaction product upper organic phase product is through rotary evaporation (vacuum tightness-0.07MPa, 97 DEG C of temperature) 2h, steam water and low-boiling-point organic compound, make product concentrated, obtain alcohol ester type (sad isomery ester) lubricating oil, when the method for the present embodiment is prepared alcohol ester type lubricating oil, transformation efficiency (calculating by oxirane value transformation efficiency) is 96%.
Embodiment 6
(1) take rapeseed oil fatty acid methyl esters, the 1.5g solid acid catalyst mordenite Na of 50g
2oAl
2o
310SiO
26H
2o and 3g formic acid are put in the there-necked flask with condenser and agitator, and the constant pressure funnel that 22g hydrogen peroxide is housed is inserted in bottleneck one end, is preheated to 40 DEG C, stir, drip, maintain the temperature between 40-60 DEG C, drip hydrogen peroxide, within one hour, dropwise, keep temperature in 60-65 DEG C, then at this temperature, continue reaction 4h, after completion of the reaction, reaction mixture is cooled to room temperature, pours in separating funnel, leave standstill, isolate lower floor's water and solid acid catalyst; Then upper oil phase (organic phase) is first used to 5%(solute massfraction) NaHCO
3solution washing 3 times, each 50mL; Use again 5%(solute massfraction) NaCl solution washing 3 times, each 30mL; Finally use hot distilled water (70 DEG C) washing 3 times, each 50mL, PH=6 after washing, leaves standstill, and lower floor's water is poured out, and oil phase is distilled at 100 DEG C, obtains epoxidation biodiesel, recording its oxirane value is the mensuration reference example 1 of 5.52(oxirane value).
(2) take 120 capric acid and 1.8g mordenite Na
2oAl
2o
310SiO
26H
2o catalyzer is put in the there-necked flask with condenser and agitator, stir, reflux, being heated to temperature is 85 DEG C, then add 30g epoxy biofuel (epoxy rapeseed oil fatty acid methyl ester), ring-opening reaction, in reaction process, from there-necked flask, get one time sample every 2h, institute's sample thief is through 0.05%(solute massfraction) NaOH solution washing, distillation washing washing, decompression (vacuum tightness-0.07MPa, 130 DEG C of temperature) reclaim after lipid acid, measure its oxirane value (the mensuration reference example 1 of oxirane value), when oxirane value is tending towards 0, and no longer change (t=13h), be reaction end.In the time that reaction reaches terminal, stopped reaction, reaction mixture is cooled to room temperature, pours in separating funnel, isolates lower floor's water and solid acid catalyst; Then by the upper organic phase washing of reaction product, first use 5%(solute massfraction) NaHCO
3solution washing 3 times, each 50mL, then use 5%(solute massfraction) NaCl solution washing 3 times, each 30mL, finally uses hot distilled water wash 3 times, each 50mL, after washing, PH equals 7; Final reaction product upper organic phase product is through rotary evaporation (vacuum tightness-0.07MPa, 97 DEG C of temperature) 2h, steam water and low-boiling-point organic compound, make product concentrated, obtain alcohol ester type (capric acid isomery ester) lubricating oil, when the method for the present embodiment is prepared alcohol ester type lubricating oil, transformation efficiency (calculating by oxirane value transformation efficiency) is 97%.
The performance comparison of table one epoxidation isomery of the present invention esterification modification biofuel and biofuel
Note: viscosity adopts special capillary viscosimeter (Φ=1.5 and 3.0, viscous modulus is respectively 0.289 and 7.448) to measure according to standard GB/T/T265-88;
Viscosity index is tabled look-up according to formula VI=[(L-U by standard GB/T/T1995-1998 according to the viscosity that records)/(L-H)] × 100 calculate,
In formula: 100 DEG C of kinematic viscosity of L-and sample are identical, the kinematic viscosity of the oil product that viscosity index is 0 in the time of 40 DEG C, mm
2/ s; Kinematic viscosity when H-with 100 DEG C, sample is identical, the kinematic viscosity of the oil product that viscosity index is 100 in the time of 40 DEG C, mm
2/ s; Kinematic viscosity when 40 DEG C, U-sample, mm
2/ s;
The pour point of chemical modification biofuel is measured according to standard GB/T/T3535-2006 with the SYD-510F multifunctional low-temperature tester that Shanghai Peng Pu refrigerator factory produces;
Adopt four ball formula friction wear testing machines to measure the last non seizure load (P of modification biological diesel oil according to the standard of GB/T3142-1982
b) and wear scar diameter (WSD), the test condition of wear scar diameter is: load 392N, and rotating speed 1455r/min, under room temperature condition, long time consuming 30min, steel ball used is that diameter is the GCr15 standard rolling bearing steel ball of 12.7mm, hardness is 60 ~ 63HRC;
Oxidation induction period adopts rotary oxygen bomb method to measure according to national petroleum chemical industry standard SH/T0193-2008.
Biological degradability is to be CEC L-33-T-82 according to the CEC L-33-A-93(predecessor of the European Community) experimental technique, the lubricating oil specifying according to German blue angels environmental mark passes through standard.
In upper table, data show, the ultrasonic auxiliary lower isomery esterification modification epoxy biofuel of the present invention is compared with epoxy biofuel with biofuel, has the following advantages:
(1) frictional behaviour excellence: four-ball tester frictional experiment, using wear scar diameter as index, long mill 30min under 392N pressure, the biofuel wear scar diameter of epoxidation isomery esterification modification is 0.46mm to the maximum, biofuel is 0.63mm, and isomery esterification modification biofuel frictional behaviour is better than biofuel.Epoxidation isomery esterification modification biofuel P
bvalue is all greater than the 509N of biofuel.
(2) low temperature rheology better performances: the pour point of epoxidation isomery esterification modification biofuel declines to a great extent than the pour point of biofuel and epoxy biofuel, biofuel is-3 DEG C, epoxy biofuel is 0 DEG C, and the pour point of the biofuel of epoxidation isomery esterification modification is all lower than-6 DEG C; The viscosity of epoxidation isomery esterification modification biofuel is all higher than biofuel and epoxy biofuel, taking epoxidation isomery esterification modification biofuel as base oil, carries out compositely with low viscosity oil plant, can modulate the lube stock of a series of viscosity grades.
(3) oxidative stability significantly improves: through rotary oxygen bomb method (140 DEG C) test, the oxidation induction period of biofuel is 60min, and the oxidation induction period of alcohol ester type lubricant after epoxidation isomery esterification modification is all greater than 100min.
(4) biological degradability improves: be CEC L-33-T-82 according to the CEC L-33-A-93(predecessor of the European Community) the lubricating oil that specifies according to German blue angels environmental mark of experimental technique pass through standard, record 21 days biological degradation rates 95% of biofuel, and the biological degradation rate of epoxidation isomery esterification modification biofuel is all greater than 96%, meeting the lubricating oil that German blue angels environmental mark specifies is that in 21 days, biological degradability is not less than 70% by standard, therefore be environmental friendly lubricant.
Therefore, the performance of lubricant base prepared by method of the present invention, meets the requirement of modern machinery and equipment to lubricating oil.
Claims (5)
1. biofuel is prepared a method for lubricating oil, it is characterized in that: described preparation method, and concrete steps are,
(1) epoxidation reaction: by biofuel, molecular sieve solid acid catalyst and formic acid, be put in the there-necked flask with condenser and agitator, the constant pressure funnel that hydrogen peroxide is housed is inserted in bottleneck one end, be preheated to 40 DEG C, stir, drip hydrogen peroxide, maintain the temperature between 40-60 DEG C, within one hour, dropwise; Keep temperature in 60-65 DEG C, then at this temperature, continue stirring reaction 3-4h, after completion of the reaction, reaction mixture is cooled to room temperature, pour in separating funnel, leave standstill, isolate lower floor's water and molecular sieve solid acid catalyst; Then upper organic phase is washed to PH=6, leaves standstill, lower floor's water is poured out, organic phase is distilled at 100 DEG C, obtain epoxidation biodiesel,
Wherein, the mass ratio of biofuel, hydrogen peroxide, formic acid, molecular sieve solid acid catalyst is 100:40-45:6-8:2-3;
(2) isomery esterification ring-opening reaction: will
short chain or medium chain fatty acidbe put in the there-necked flask with condenser and agitator with molecular sieve solid acid catalyst, stirring, reflux, be heated to temperature is 70-100 DEG C, then adds the epoxy biofuel making in step (1), ring-opening reaction 6-15h; In reaction process, from there-necked flask, got one time sample every 2 hours, after NaOH solution washing that institute's sample thief is 0.05% through solute massfraction, washing, reclaim under reduced pressure lipid acid, measure its oxirane value, when oxirane value is tending towards 0, and no longer change, be reaction end; In the time that reaction reaches terminal, stopped reaction, is cooled to room temperature by reaction mixture, pours in separating funnel, isolates lower floor's water and molecular sieve solid acid catalyst; Then upper organic phase washing is extremely neutral, then through rotary evaporation 2h, finally obtain alcohol ester type lubricating oil,
Wherein,
short chain or medium chain fatty acidfor acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid or capric acid,
And the mass ratio of epoxy biofuel, lipid acid, molecular sieve solid acid catalyst is 10:10-100:0.1-1.
2. biofuel as claimed in claim 1 is prepared the method for lubricating oil, it is characterized in that: in step (2), the washing of described upper organic phase is, the NaHCO that is first 5% with solute massfraction
3solution washing 3 times, then the salt water washing that is 5% with solute massfraction 3 times, finally use hot distilled water wash.
3. biofuel as claimed in claim 1 is prepared the method for lubricating oil, it is characterized in that: in step (2), when described rotary evaporation operates, set vacuum tightness-0.07MPa, temperature is 97 DEG C.
4. biofuel as claimed in claim 1 is prepared the method for lubricating oil, it is characterized in that: described molecular sieve solid acid catalyst is 3A type zeolite molecular sieve K
2oAl
2o
32SiO
24.5H
2o, Y zeolite NaO
2al
2o
34.9SiO
29.4H
2o, ZSM type molecular sieve ZSM-5-H, ZSM-5-Na, mordenite Na
2oAl
2o
310SiO
26H
2one in O solid acid catalyst.
5. biofuel as claimed in claim 1 is prepared the method for lubricating oil, it is characterized in that: in step (1), described biofuel is methyl soyate, rapeseed oil fatty acid methyl esters or Castor Oil Fatty Acid methyl esters.
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| CN103113221B (en) * | 2013-01-25 | 2016-01-13 | 江苏高科石化股份有限公司 | A kind of alcohol ester type environment lubricant base, preparation method and its usage |
| CN103601703B (en) * | 2013-07-11 | 2016-01-13 | 中南林业科技大学 | The method of epoxidation methyl eleostearate is prepared by tung oil |
| CN103497839B (en) * | 2013-09-03 | 2015-09-02 | 常州大学 | A kind of epoxy biodiesel prepares the method for Biolubrication oil base oil |
| CN103666770B (en) * | 2013-12-03 | 2015-02-04 | 中国林业科学研究院林产化学工业研究所 | Preparation method of epoxy modified castor oil |
| CA2853848C (en) * | 2014-06-09 | 2021-05-18 | Ajay Kumar Dalai | Process for producing a lubricant from an epoxy-triglyceride |
| CN104450104B (en) * | 2014-12-27 | 2016-08-24 | 安耐驰河北石油化工股份有限公司 | A kind of preparation method of biodegradable lubricating oil |
| US10093636B2 (en) | 2016-08-05 | 2018-10-09 | Cpc Corporation, Taiwan | Method for synthesizing bio-plasticizers using acidic ionic liquids as catalysts |
| CN107338082A (en) * | 2017-07-03 | 2017-11-10 | 湖南德邦生物润滑油有限公司 | The method that epoxidised fatty acid glycerol three ester opened loop compound prepares lubricating oil biological basis oil with epoxy fatty acid monoester opened loop compound |
| CN107384509A (en) * | 2017-07-03 | 2017-11-24 | 湖南德邦生物润滑油有限公司 | Epoxidised fatty acid glycerol three ester mixes the method that ring-opening reaction prepares biological lubricant with epoxy fatty acid monoester |
| CN109401821A (en) * | 2018-09-06 | 2019-03-01 | 绵阳环亚电子商务有限公司 | A kind of castor bean machine oil and its production method |
| CN109913300B (en) * | 2019-03-28 | 2022-12-16 | 乐福思健康用品有限公司 | Biodegradable environment-friendly lubricant and preparation method thereof |
| CN112552989A (en) * | 2021-01-20 | 2021-03-26 | 安徽联亚新材料有限公司 | Biodegradable plant-based anti-wear lubricating oil and preparation method thereof |
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