CN102041176A - Method for preparing low temperature epoxy fatty acid branched-chain alcohol ester improver for biodiesel and application thereof - Google Patents
Method for preparing low temperature epoxy fatty acid branched-chain alcohol ester improver for biodiesel and application thereof Download PDFInfo
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- CN102041176A CN102041176A CN2011100083320A CN201110008332A CN102041176A CN 102041176 A CN102041176 A CN 102041176A CN 2011100083320 A CN2011100083320 A CN 2011100083320A CN 201110008332 A CN201110008332 A CN 201110008332A CN 102041176 A CN102041176 A CN 102041176A
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Abstract
The invention discloses a method for preparing a low temperature epoxy fatty acid branched-chain alcohol ester improver for biodiesel and application thereof. The method comprises the steps of taking natural oil and branched-chain alcohol as raw materials to react in the presence of a catalyst, and carrying out distilling, standing and layering on the product to obtain supernatant fatty acid branched-chain alcohol ester; and then mixing the fatty acid branched-chain alcohol ester with formic acid, adding an epoxidation catalyst, reacting while dropwise adding hydrogen peroxide, and carrying out standing, layering, neutralizing and dewatering on the product to obtain epoxy fatty acid branched-chain alcohol ester. The invention develops an epoxy fatty acid branched-chain alcohol ester improver aiming at the characteristics of biodiesel. The method has the following beneficial effects: by branching bonds of fatty acid ester and introducing a polar group onto the interior double bond structure of the fatty acid ester, the improver can be easily mixed with the biodiesel to form uniform solution, thus being beneficial to blocking further growth of solid crystals; and after different oil-based biodiesels and the improver are mixed, the low temperature fluidity of the biodiesels can be obviously improved, the condensation point and cold filter point can be reduced by 5-15 DEG C, the calorific value can be improved, and the viscosity can be reduced.
Description
Technical field
The invention belongs to the preparation method of biofuel pour point depressant, be specifically related to a kind of by preparing the method that epoxyfatty acid side chain alcohol ester improves biodiesel lower-temperature fluidity.
Background technology
Biofuel is a kind of important renewable and clean energy resource, generally carries out transesterify by methyl alcohol and grease or esterification makes.The performance that it is close with petrifaction diesel, good recyclability and environmental-protecting performance advantage also have been subjected to extensive concern.But because the influence of chain saturated fatty acids component and impurities, the condensation point and the cold filter clogging temperature of biofuel are higher, and low-temperature fluidity is poor, separate out the crystallization meeting and stop up engine, and it is restricted aspect practical application, and commercialization is obstructed greatly.Thereby the research that improves the biofuel low-temperature performance is very necessary.
The method of the raising biofuel low-temperature performance of using mainly contains three kinds at present: 1. winterization is handled, and can remove high melting point component, but can lose 13～20% product, and productive rate is lower, serious waste of resources;
Sneak into a certain amount of refined diesel oil, can significantly reduce the condensation point of biofuel, but little, and still can not break away from dependence the mineral substance oil to the cold filter clogging temperature and the viscosity influence of mixture;
Adding pour point depressant, mainly is to add diesel pour inhibitor and the low temperature improvers that is fit to different biofuel.Diesel pour inhibitor has the effect that reduces the biofuel condensation point to a certain extent, but to almost not influence of cold filter clogging temperature, the pour point depression effect similar to petrifaction diesel do not occur.And, develop one of research direction that the improving agent that is fit to different biofuel is this area and focus at the biodiesel fuel component constructional feature.According to biofuel self structure character, there is the investigator to adopt the method for on the long linear of fatty acid ester, introducing side chain and utilizing biofuel internal double bonds structure to carry out the selectivity addition to come pour point depression.The former utilizes the difference of space structure, makes the polarization of molecule asymmetry, and the latter makes system and biofuel structural similitude by introducing polar group, is easy to mix, and the blocking-up solid crystal increases, thereby improves the biodiesel lower-temperature fluidity energy.The research report of existing American scholar points out that Virahol and sec-butyl alcohol have reduced by 7～11 ℃ and 12～14 ℃ respectively than corresponding methyl esters Tc.The domestic pour point depression performance that also has research to report the rapeseed oil epoxy aliphatic acid methyl ester, utilize biofuel to contain the characteristics of double bond structure, on the biofuel structure, introduce the polar group of some amount, to increase the polarity of biofuel self, reach the purpose that reduces biofuel cold filter clogging temperature and zero pour.The result shows that rapeseed oil biofuel cold filter clogging temperature has reduced by 3 ℃, but to not influence of zero pour.
Summary of the invention
In order to solve low temperature improvers that prior art exists shortcoming to the DeGrain of the cold filter clogging temperature that reduces biofuel, the present invention provides a kind of method and application thereof for preparing epoxyfatty acid branched-chain alcoho ester biological diesel oil at low-temperature improving agent on the basis of above-mentioned technology.The polar epoxyfatty acid side chain alcohol ester improving agent of this method preparation can reduce its condensation point and cold filter clogging temperature with after the biofuel of different oil and fat preparations is miscible.
Technical scheme of the present invention is: a kind of method for preparing epoxyfatty acid branched-chain alcoho ester biological diesel oil at low-temperature improving agent, and the preparation method is:
The first step, with natural fats and oils and branched-chain alcoho is raw material, preparation lipid acid side chain alcohol ester in the presence of catalyzer, wherein, the mol ratio of natural fats and oils and branched-chain alcoho is: 1:1～10, catalyst levels accounts for 0.8～5% of natural fats and oils weight, under 45～100 ℃ of temperature, obtain lipid acid side chain alcohol ester crude product behind reaction 20～120 min, lipid acid side chain alcohol ester crude product is distilled, isolate unreacted branched-chain alcoho, remaining liquid obtains upper strata lipid acid side chain alcohol ester and lower floor's glycerine behind standing demix; Described branched-chain alcoho is a unbranched secondary alcohol type branched-chain alcoho on primary alconol type branched-chain alcoho between C3～C8 or the alpha-carbon atom;
In second step, the lipid acid side chain alcohol ester that previous step is prepared is that mix 100:5～30 with formic acid by mass ratio, adds epoxidation catalyst, and the epoxidation catalyst consumption accounts for 0.8～3% of grease weight, stirs and is warming up to 40～50 ℃; The dropping mass concentration is 25～55% hydrogen peroxide, and the mass ratio of hydrogen peroxide consumption and lipid acid side chain alcohol ester is 100:30～80, and rate of addition is 20～40mL/h, is warming up to 55～70 ℃ then, and insulation reaction 2～6 h get epoxyfatty acid side chain alcohol ester crude product; Lipid acid side chain alcohol ester crude product is left standstill phase-splitting, reclaim the formic acid of lower floor's aqueous phase; Upper oil phase promptly makes epoxyfatty acid side chain alcohol ester after moisture is removed in alkali cleaning, washing, underpressure distillation.
Described natural fats and oils comprises: any one in soybean oil, Oleum Gossypii semen, rapeseed oil, tea oil, plam oil, Chinese catalpa oil, coptis wood oil, the smooth bark oil or any several mixture, saturated fatty acid content≤20%wt in the described natural fats and oils.
Described branched-chain alcoho is Virahol, isopropylcarbinol, sec-butyl alcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, 2-amylalcohol, 3-amylalcohol, 3,3-dimethyl-1-butanols, 2,3,-dimethyl-1-butanols, 2-ethyl-1-butanols, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 2-hexanol, 3-hexanol, 2,2-dimethyl-1-amylalcohol, 3,3-dimethyl-1-amylalcohol, 2-ethyl-1-amylalcohol, 3-ethyl-1-amylalcohol, 4, any one in 4-dimethyl-2-amylalcohol, the isooctyl alcohol or any several mixture.
Used catalyzer is the alkoxide of sulfuric acid, phosphoric acid, tosic acid, alkali metal hydroxide or basic metal branched-chain alcoho in the first step; Used epoxidation catalyst is any one in sulfuric acid, phosphoric acid or the tosic acid in second step.
When the alkoxide that adopts alkali metal hydroxide or basic metal branched-chain alcoho in the first step is catalyzer, the water content≤0.5%wt of natural fats and oils, acid number is less than 10.
Used formic acid recycled during used branched-chain alcoho and second went on foot in the first step.
0.5～3% low temperature improvers and the biofuel that the present invention is made that accounts for the biofuel quality according to low temperature improvers mixes use.
Described biofuel is soybean oil biofuel, Oleum Gossypii semen biofuel, rapeseed oil biofuel, sunflower seed oil biofuel, Chinese catalpa oil biodiesel, Chinese pistache oil biodiesel, smooth bark oil biodiesel, sewer oil biofuel, KFC's abendoned oil biofuel.
Beneficial effect:
(1) the present invention introduces polar group on portion's double bond structure within it by fatty acid ester ester bond collateralization is reached, and preparation epoxyfatty acid side chain alcohol ester improving agent can mix with biofuel, helps blocking solid crystal and further increases.
(2) the epoxyfatty acid side chain alcohol ester improving agent of the present invention's preparation can make the condensation point of biofuel and cold filter clogging temperature reduce by 5 ℃～15 ℃; Calorific value rising simultaneously, viscosity reduce.
(3) the epoxyfatty acid side chain alcohol ester improving agent of the present invention's preparation can be applied to multiple fat-based biofuel.
(4) consumption of the epoxyfatty acid side chain alcohol ester improving agent of the present invention's preparation is lower than 3% of biofuel quality, and product usefulness is higher; And recyclable, the recycle of branched-chain alcoho and formic acid reduces cost, and has the higher industrial using value.
Description of drawings
The GC-MS collection of illustrative plates of Fig. 1 methyl soyate;
The GC-MS collection of illustrative plates of Fig. 2 synthetic lipid acid of the present invention isobutyl ester;
The GC-MS collection of illustrative plates of Fig. 3 synthetic fatty acid isooctyl of the present invention;
Fig. 4 synthetic epoxyfatty acid of the present invention isobutyl ester infrared spectrogram;
The different monooctyl ester infrared spectrogram of Fig. 5 synthetic epoxyfatty acid of the present invention;
Fig. 1 is pure soybean oil methyl esters, and Fig. 2-3 is the various side chain fatty acid esters with the soybean oil preparation.By contrast, can find out the distribution of various side chain fatty acid esters among Fig. 2-3.
Fig. 4-5 is the infrared spectrogram of the epoxy aliphatic acid methyl ester of side chain fatty acid ester correspondence among Fig. 2-3.910～720 cm among the figure
-1Near absorption peak shows the vibration of oxirane ring; The C-O stretching vibration of ester is at 1170 cm
-1The place absorbs; Ester carbonyl group is at 1738 cm
-1The place absorbs.
Embodiment
With unbranched secondary alcohol type branched-chain alcoho on primary alconol type branched-chain alcoho between natural fats and oils and the C3～C8 or the alpha-carbon atom is raw material, preparation lipid acid side chain alcohol ester in the presence of catalyzer.Wherein, the mol ratio of grease and branched-chain alcoho is: 1:1～10, catalyst levels account for 0.8～5% of grease weight, under 45～75 ℃ of temperature, obtain product A behind reaction 10～90min.With the A distillation, remaining product obtains upper strata lipid acid side chain alcohol ester and lower floor's glycerine behind standing demix.Lipid acid side chain alcohol ester with the previous step preparation mixes by mass ratio: 100:5～30 with formic acid again, adds epoxidation catalyst, and consumption accounts for 0.8～3% of grease weight, stirs and is warming up to 40～50 ℃; Drip 25～55% hydrogen peroxide, the mass ratio of its consumption and lipid acid side chain alcohol ester is 100:30～80, and rate of addition is 20～40mL/h, is warming up to 55～70 ℃ then, and insulation reaction 2～6 h get reaction product B.Product B is left standstill phase-splitting, reclaim lower floor's sour water phase; Upper oil phase through alkali cleaning, be washed to neutrality, remove moisture through underpressure distillation again, promptly make epoxyfatty acid side chain alcohol ester.
The epoxyfatty acid side chain alcohol ester low temperature improvers of described preparation is with after biofuel is mixed, and low temperature flowability significantly improves, and condensation point and cold filter clogging temperature reduce amplitude can reach 5～15 ℃.
The quality of used epoxyfatty acid side chain alcohol ester accounts for biofuel 0.5～3%, has the higher industrial using value.
Described natural fats and oils comprises: soybean oil, Oleum Gossypii semen, rapeseed oil, tea oil, plam oil, Chinese catalpa oil, coptis wood oil, smooth bark oil, saturated fatty acid content≤20%wt in the raw material.
Described branched-chain alcoho is:
C3 type branched-chain alcoho: Virahol;
C4 type branched-chain alcoho: isopropylcarbinol sec-butyl alcohol;
C5 type branched-chain alcoho: 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, 2-amylalcohol, 3-amylalcohol;
C6 type branched-chain alcoho: 3,3-dimethyl-1-butanols, 2,3 ,-dimethyl-1-butanols, 2-ethyl-1-butanols, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 2-hexanol, 3-hexanol;
C7 type branched-chain alcoho: 2,2-dimethyl-1-amylalcohol, 3,3-dimethyl-1-amylalcohol, 2-ethyl-1-amylalcohol, 3-ethyl-1-amylalcohol, 4,4-dimethyl-2-amylalcohol;
C8 type branched-chain alcoho: isooctyl alcohol.
The catalyzer of described preparation lipid acid side chain alcohol ester is the alkoxide of sulfuric acid, phosphoric acid, tosic acid, alkali metal hydroxide or basic metal branched-chain alcoho; Epoxidation catalyst is selected sulfuric acid, phosphoric acid and tosic acid for use.
When adopting alkaline catalyst for esterification reaction, greasy water content is lower than 0.5%, and acid number is less than 10.
Biofuel is soybean oil biofuel, Oleum Gossypii semen biofuel, rapeseed oil biofuel, sunflower seed oil biofuel, Chinese catalpa oil biodiesel, Chinese pistache oil biodiesel, smooth bark oil biodiesel, sewer oil biofuel, KFC's abendoned oil biofuel.
Branched-chain alcoho and formic acid can be recycled.
Described natural fats and oils can be one or more mixtures of soybean oil, Oleum Gossypii semen, rapeseed oil, tea oil, plam oil, Chinese catalpa oil, coptis wood oil, smooth bark oil, when adopting basic catalyst, the water content of natural fats and oils will be lower than 0.5%wt, and acid number is less than 10 mgKOH/g.Branched-chain alcoho comprises:
C3 type branched-chain alcoho: Virahol;
C4 type branched-chain alcoho: isopropylcarbinol sec-butyl alcohol;
C5 type branched-chain alcoho: 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, 2-amylalcohol, 3-amylalcohol;
C6 type branched-chain alcoho: 3,3-dimethyl-1-butanols, 2,3 ,-dimethyl-1-butanols, 2-ethyl-1-butanols, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 2-hexanol, 3-hexanol;
C7 type branched-chain alcoho: 2,2-dimethyl-1-amylalcohol, 3,3-dimethyl-1-amylalcohol, 2-ethyl-1-amylalcohol, 3-ethyl-1-amylalcohol, 4,4-dimethyl-2-amylalcohol;
C8 type branched-chain alcoho: the mixing of one or more in the isooctyl alcohol is used.
Step 2, the lipid acid side chain alcohol ester of previous step preparation is mixed with formic acid, add epoxidation catalyst, stirring is warming up to 40～50 ℃, the dropping mass concentration is 25～55% hydrogen peroxide, and rate of addition is 20～40mL/h, is warming up to 55～70 ℃ then, insulation reaction 2～6 h obtain epoxyfatty acid side chain alcohol ester.Wherein, catalyzer comprises sulfuric acid, phosphoric acid, tosic acid, and consumption accounts for 0.8～3% of grease weight; Lipid acid side chain alcohol ester and formic acid by mass ratio are: 100:5～30, the mass ratio of hydrogen peroxide and lipid acid side chain alcohol ester is 100:30～80.Crude product is left standstill phase-splitting, reclaim the in addition recycle of formic acid of lower floor's aqueous phase, upper oil phase is washed till pH with the alkali lye of 5%wt and is about 6.5, is washed till neutrality with distilled water again, leaves standstill and tells upper oil phase, moisture is removed in underpressure distillation through routine, obtains epoxyfatty acid side chain alcohol ester.
Step 3 is mixed the epoxyfatty acid side chain alcohol ester that makes with biofuel, analyze rerum natura.Wherein account for 0.5～3% of biofuel quality by epoxyfatty acid side chain alcohol ester.Described biofuel can be one or more mixtures of soybean oil biofuel, Oleum Gossypii semen biofuel, rapeseed oil biofuel, sunflower seed oil biofuel, Chinese catalpa oil biodiesel, Chinese pistache oil biodiesel, smooth bark oil biodiesel, sewer oil biofuel, KFC's abendoned oil biofuel.
Embodiment 2
Step 2 is got 50g lipid acid Virahol ester and 10g formic acid and is placed 250 mL there-necked flasks, adds the 1g vitriol oil, after stirring is warming up to 45 ℃, drips 60g 35% hydrogen peroxide, and rate of addition is 20mL/h; Be warming up to 60 ℃, insulation reaction 4h after dripping hydrogen peroxide; Thick product obtains epoxyfatty acid Virahol ester through leaving standstill phase-splitting, neutralization, processed.
Step 3 is got 1g epoxyfatty acid Virahol ester and 100g soybean oil biofuel, mixes, and surveying its 40 ℃ of kinematic viscosity is 3.8mm
2/ s, 20 ℃ of density are 825Kg/m
3, condensation point is-12 ℃, cold filter clogging temperature is-11 ℃.
Embodiment 3
Step 2 is got 50g lipid acid Virahol ester and 15g formic acid and is placed 250 mL there-necked flasks, adds the 3g vitriol oil, after stirring is warming up to 50 ℃, drips 60g 35% hydrogen peroxide, and rate of addition is 30mL/h; Be warming up to 65 ℃, insulation reaction 4h after dripping hydrogen peroxide; Thick product obtains epoxyfatty acid Virahol ester through leaving standstill phase-splitting, neutralization, processed.
Step 3 is got 1g epoxyfatty acid Virahol ester and 100g soybean oil biofuel, mixes, and surveying its 40 ℃ of kinematic viscosity is 4.0mm
2/ s, 20 ℃ of density are 830Kg/m
3, condensation point is-12 ℃, cold filter clogging temperature is-9 ℃.
Step 2 is got 50g lipid acid Virahol ester and 30g formic acid and is placed 250 mL there-necked flasks, adds the 1g vitriol oil, and after stirring was warming up to 50 ℃, Dropwise 5 0g 35% hydrogen peroxide, rate of addition were 30mL/h; Be warming up to 70 ℃, insulation reaction 4h after dripping hydrogen peroxide; Thick product obtains epoxyfatty acid Virahol ester through leaving standstill phase-splitting, neutralization, processed.
Step 3 is got 1g epoxyfatty acid Virahol ester and 100g soybean oil biofuel, mixes, and surveying its 40 ℃ of kinematic viscosity is 4.0mm
2/ s, 20 ℃ of density are 840Kg/m
3, condensation point is-9 ℃, cold filter clogging temperature is-5 ℃.
Embodiment 5
Step 2 is got 50g lipid acid sec-butyl alcohol ester and 15g formic acid and is placed 250 mL there-necked flasks, adds the 1.5g vitriol oil, and after stirring was warming up to 50 ℃, Dropwise 5 0g 35% hydrogen peroxide, rate of addition were 30mL/h; Be warming up to 60 ℃, insulation reaction 5h after dripping hydrogen peroxide; Thick product obtains epoxyfatty acid sec-butyl alcohol ester through leaving standstill phase-splitting, neutralization, processed.
Step 3 is got 2g epoxyfatty acid sec-butyl alcohol ester and 100g rapeseed oil biofuel, mixes, and surveying its 40 ℃ of kinematic viscosity is 4.0mm
2/ s, 20 ℃ of density are 835Kg/m
3, condensation point is-17 ℃, cold filter clogging temperature is-15 ℃.
Embodiment 6
Step 2 is got 50g lipid acid isobutyl alcohol ester and 30g formic acid and is placed 250 mL there-necked flasks, adds the 1.5g vitriol oil, after stirring is warming up to 50 ℃, drips 40g 35% hydrogen peroxide, and rate of addition is 30mL/h; Be warming up to 65 ℃, insulation reaction 4h after dripping hydrogen peroxide; Thick product obtains epoxyfatty acid isobutyl alcohol ester through leaving standstill phase-splitting, neutralization, processed.
Step 3 is got 1g epoxyfatty acid isobutyl alcohol ester and 100g soybean oil biofuel, mixes, and surveying its 40 ℃ of kinematic viscosity is 3.8mm
2/ s, 20 ℃ of density are 820Kg/m
3, condensation point is-14 ℃, cold filter clogging temperature is-10 ℃.
Embodiment 7
Step 2 is got 50g lipid acid isobutyl alcohol ester and 40g formic acid and is placed 250 mL there-necked flasks, adds 3g phosphoric acid, and after stirring was warming up to 50 ℃, Dropwise 5 0g 35% hydrogen peroxide, rate of addition were 25mL/h; Be warming up to 65 ℃, insulation reaction 4h after dripping hydrogen peroxide; Thick product obtains epoxyfatty acid isobutyl alcohol ester through leaving standstill phase-splitting, neutralization, processed.
Step 3 is got 3g epoxyfatty acid isobutyl alcohol ester and 100g KFC abendoned oil biofuel, mixes, and surveying its 40 ℃ of kinematic viscosity is 4.1mm
2/ s, 20 ℃ of density are 830Kg/m
3, condensation point is 2 ℃, cold filter clogging temperature is 5 ℃.
Embodiment 8
Step 2 is got 50g lipid acid 2-ethyl-1-butyl alcohol ester and 30g formic acid and is placed 250 mL there-necked flasks, adds the 2g tosic acid, after stirring is warming up to 50 ℃, drips 40g 35% hydrogen peroxide, and rate of addition is 30mL/h; Be warming up to 65 ℃, insulation reaction 4h after dripping hydrogen peroxide; Thick product obtains epoxyfatty acid 2-ethyl-1-butyl alcohol ester through leaving standstill phase-splitting, neutralization, processed.
Step 3 is got 2g epoxyfatty acid 2-ethyl-1-butyl alcohol ester and 100g sewer oil biofuel, mixes, and surveying its 40 ℃ of kinematic viscosity is 3.5mm
2/ s, 20 ℃ of density are 820Kg/m
3, condensation point is 2 ℃, cold filter clogging temperature is 2 ℃.
Embodiment 9
Step 2 is got 50g lipid acid 3-ethyl-1-amylalcohol ester and 30g formic acid and is placed 250 mL there-necked flasks, adds the 1.5g vitriol oil, after stirring is warming up to 50 ℃, drips 40g 35% hydrogen peroxide, and rate of addition is 30mL/h; Be warming up to 65 ℃, insulation reaction 4h after dripping hydrogen peroxide; Thick product obtains epoxyfatty acid 3-ethyl-1-amylalcohol ester through leaving standstill phase-splitting, neutralization, processed.
Step 3 is got 1g epoxyfatty acid 3-ethyl-1-amylalcohol ester and 100g smooth bark oil biodiesel, mixes, and surveying its 40 ℃ of kinematic viscosity is 4.2mm
2/ s, 20 ℃ of density are 840Kg/m
3, condensation point is-14 ℃, cold filter clogging temperature is-13 ℃.
Step 2 is got 50g lipid acid 2-ethyl-1-amylalcohol ester and 30g formic acid and is placed 250 mL there-necked flasks, adds the 1.5g vitriol oil, after stirring is warming up to 50 ℃, drips 40g 35% hydrogen peroxide, and rate of addition is 30mL/h; Be warming up to 65 ℃, insulation reaction 4h after dripping hydrogen peroxide; Thick product obtains epoxyfatty acid 2-ethyl-1-amylalcohol ester through leaving standstill phase-splitting, neutralization, processed.
Step 3 is got 1g epoxyfatty acid 2-ethyl-1-amylalcohol ester and 100g Chinese catalpa oil biodiesel, mixes, and surveying its 40 ℃ of kinematic viscosity is 4.0mm
2/ s, 20 ℃ of density are 826Kg/m
3, condensation point is-18 ℃, cold filter clogging temperature is-15 ℃.
Embodiment 11
Step 2 is got 50g lipid acid isooctyl alcohol ester and 40g formic acid and is placed 250 mL there-necked flasks, adds the 1.5g vitriol oil, and after stirring was warming up to 50 ℃, Dropwise 5 0g 35% hydrogen peroxide, rate of addition were 25mL/h; Be warming up to 65 ℃, insulation reaction 5h after dripping hydrogen peroxide; Thick product obtains epoxyfatty acid isooctyl alcohol ester through leaving standstill phase-splitting, neutralization, processed.
Step 3 is got 1g epoxyfatty acid isooctyl alcohol ester and 100g Chinese pistache oil biodiesel, mixes, and surveying its 40 ℃ of kinematic viscosity is 4.1mm
2/ s, 20 ℃ of density are 830Kg/m
3, condensation point is-17 ℃, cold filter clogging temperature is-16 ℃.
Embodiment 12
Step 2 is got 50g mixed fatty acid side chain alcohol ester and 25g formic acid and is placed 250 mL there-necked flasks, adds the 1g vitriol oil, after stirring is warming up to 45 ℃, drips 60g 35% hydrogen peroxide, and rate of addition is 30mL/h; Be warming up to 60 ℃, insulation reaction 4h after dripping hydrogen peroxide; Thick product obtains hybrid epoxidized fatty acid side chain alcohol ester through leaving standstill phase-splitting, neutralization, processed.
Step 3 is got 1g hybrid epoxidized fatty acid side chain alcohol ester and 100g sunflower seed oil biofuel, mixes, and surveying its 40 ℃ of kinematic viscosity is 4.0mm
2/ s, 20 ℃ of density are 828Kg/m
3, condensation point is-16 ℃, cold filter clogging temperature is-13 ℃.
Embodiment 13
Step 2 is got 50g mixed fatty acid side chain alcohol ester and 20g formic acid and is placed 250 mL there-necked flasks, adds the 1.5g vitriol oil, after stirring is warming up to 45 ℃, and Dropwise 5 0g 35%wt hydrogen peroxide, rate of addition is 25mL/h; Be warming up to 60 ℃, insulation reaction 4h after dripping hydrogen peroxide; Thick product obtains hybrid epoxidized fatty acid side chain alcohol ester through leaving standstill phase-splitting, neutralization, processed.
Step 3 is got 1g hybrid epoxidized fatty acid side chain alcohol ester and 100g soybean oil biofuel, mixes, and surveying its 40 ℃ of kinematic viscosity is 4.0mm2/s, and 20 ℃ of density are 810Kg/m3, and condensation point is-15 ℃, and cold filter clogging temperature is-14 ℃.
The part of fuel character data of the initial biofuel (fatty acid methyl ester) of table 1
| Biofuel (fatty acid methyl ester) | Condensation point (℃) | Cold filter clogging temperature (℃) | Kinematic viscosity (40 ℃) (mm 2/s) |
| The soybean oil biofuel | -2 | -1 | 4.2 |
| The Oleum Gossypii semen biofuel | 2 | 2 | 4.2 |
| The rapeseed oil biofuel | -11 | -7.5 | 4.0 |
| The sunflower seed oil biofuel | -6 | 1 | 4.3 |
| The Chinese catalpa oil biodiesel | -10 | -9 | 3.7 |
| The Chinese pistache oil biodiesel | -8 | -6 | 4.1 |
| The smooth bark oil biodiesel | 3 | 5 | 4.0 |
| The sewer oil biofuel | 8 | 11 | 4.5 |
| KFC's |
10 | 13 | 4.3 |
The oxirane value of table 2 part epoxyfatty acid side chain alcohol ester
| Title | Oxirane value (%) |
| Epoxyfatty acid Virahol ester | 4.8 |
| Epoxyfatty acid isobutyl alcohol ester | 4.3 |
| Epoxyfatty acid 2-ethyl-1-butyl alcohol ester | 4.2 |
| Epoxyfatty acid isooctyl alcohol ester | 3.9 |
The consumption of table 3 rapeseed oil basic ring oxygen lipid acid isobutyl alcohol ester is to the influence of soybean oil biofuel pour point depression effect
| The consumption (%wt) of epoxyfatty acid isobutyl alcohol ester | The biofuel condensation point (℃) | The biofuel cold filter clogging temperature (℃) |
| 0 | -2 | -1 |
| 0.5 | -12 | -9 |
| 1 | -14 | -13 |
| ? | -15 | -15 |
| 3 | -17 | -16 |
As above table can be found out, can significantly improve the condensation point and the cold filter clogging temperature of biofuel after the biofuel low temperature improvers of the present invention's preparation and biofuel mixing are used.
Add the rapeseed oil basic ring oxygen lipid acid isobutyl alcohol ester of 2%wt in various fat-based biofuel, the pour point depression result is as shown in table 4.
Table 4 rapeseed oil basic ring oxygen lipid acid isobutyl alcohol ester is to the influence of various biofuel pour point depression effects
| Biofuel (fatty acid methyl ester) | Condensation point (℃) | Cold filter clogging temperature (℃) |
| The soybean oil biofuel | -15 | -15 |
| The Oleum Gossypii semen biofuel | -8 | -7 |
| The rapeseed oil biofuel | -25 | -20 |
| The sunflower seed oil biofuel | -20 | -16 |
| The Chinese catalpa oil biodiesel | -23 | -21 |
| The Chinese pistache oil biodiesel | -21 | -18 |
| The smooth bark oil biodiesel | -9 | -9 |
| The sewer oil biofuel | -4 | -2 |
| KFC's abendoned oil biofuel | -2 | 0 |
Claims (8)
1. method for preparing epoxyfatty acid branched-chain alcoho ester biological diesel oil at low-temperature improving agent is characterized in that the preparation method is:
The first step, with natural fats and oils and branched-chain alcoho is raw material, preparation lipid acid side chain alcohol ester in the presence of catalyzer, wherein, the mol ratio of natural fats and oils and branched-chain alcoho is: 1:1～10, catalyst levels accounts for 0.8～5% of natural fats and oils weight, under 45～100 ℃ of temperature, obtain lipid acid side chain alcohol ester crude product behind reaction 20～120 min, lipid acid side chain alcohol ester crude product is distilled, isolate unreacted branched-chain alcoho, remaining liquid obtains upper strata lipid acid side chain alcohol ester and lower floor's glycerine behind standing demix; Described branched-chain alcoho is a unbranched secondary alcohol type branched-chain alcoho on primary alconol type branched-chain alcoho between C3～C8 or the alpha-carbon atom;
In second step, the lipid acid side chain alcohol ester that previous step is prepared is that mix 100:5～30 with formic acid by mass ratio, adds epoxidation catalyst, and the epoxidation catalyst consumption accounts for 0.8～3% of grease weight, stirs and is warming up to 40～50 ℃; The dropping mass concentration is 25～55% hydrogen peroxide, and the mass ratio of hydrogen peroxide consumption and lipid acid side chain alcohol ester is 100:30～80, and rate of addition is 20～40mL/h, is warming up to 55～70 ℃ then, and insulation reaction 2～6 h get epoxyfatty acid side chain alcohol ester crude product; Lipid acid side chain alcohol ester crude product is left standstill phase-splitting, reclaim the formic acid of lower floor's aqueous phase; Upper oil phase promptly makes epoxyfatty acid side chain alcohol ester after moisture is removed in alkali cleaning, washing, underpressure distillation.
2. the method for preparing epoxyfatty acid branched-chain alcoho ester biological diesel oil at low-temperature improving agent as claimed in claim 1, it is characterized in that, described natural fats and oils comprises: any one in soybean oil, Oleum Gossypii semen, rapeseed oil, tea oil, plam oil, Chinese catalpa oil, coptis wood oil, the smooth bark oil or any several mixture, saturated fatty acid content≤20%wt in the described natural fats and oils.
3. the method for preparing epoxyfatty acid branched-chain alcoho ester biological diesel oil at low-temperature improving agent as claimed in claim 1, it is characterized in that, described branched-chain alcoho is a Virahol, isopropylcarbinol, sec-butyl alcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, the 2-amylalcohol, the 3-amylalcohol, 3,3-dimethyl-1-butanols, 2,3,-dimethyl-1-butanols, 2-ethyl-1-butanols, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, the 2-hexanol, the 3-hexanol, 2,2-dimethyl-1-amylalcohol, 3,3-dimethyl-1-amylalcohol, 2-ethyl-1-amylalcohol, 3-ethyl-1-amylalcohol, 4,4-dimethyl-2-amylalcohol, in the isooctyl alcohol any one or any several mixture.
4. the method for preparing epoxyfatty acid branched-chain alcoho ester biological diesel oil at low-temperature improving agent as claimed in claim 1 is characterized in that used catalyzer is the alkoxide of sulfuric acid, phosphoric acid, tosic acid, alkali metal hydroxide or basic metal branched-chain alcoho in the first step; Used epoxidation catalyst is any one in sulfuric acid, phosphoric acid or the tosic acid in second step.
5. the method for preparing epoxyfatty acid branched-chain alcoho ester biological diesel oil at low-temperature improving agent as claimed in claim 4, it is characterized in that, when the alkoxide that adopts alkali metal hydroxide or basic metal branched-chain alcoho in the first step is catalyzer, the water content≤0.5%wt of natural fats and oils, acid number is less than 10.
6. the method for preparing epoxyfatty acid branched-chain alcoho ester biological diesel oil at low-temperature improving agent as claimed in claim 1 is characterized in that, used formic acid recycled during used branched-chain alcoho and second went on foot in the first step.
7. the using method of the biofuel low temperature improvers that obtains based on the described method for preparing epoxyfatty acid branched-chain alcoho ester biological diesel oil at low-temperature improving agent of claim 1, it is characterized in that, account for 0.5～3% of biofuel quality according to low temperature improvers low temperature improvers and biofuel mixed use.
8. the using method of low temperature improvers as claimed in claim 7, it is characterized in that described biofuel is soybean oil biofuel, Oleum Gossypii semen biofuel, rapeseed oil biofuel, sunflower seed oil biofuel, Chinese catalpa oil biodiesel, Chinese pistache oil biodiesel, smooth bark oil biodiesel, sewer oil biofuel, KFC's abendoned oil biofuel.
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| CN105694998A (en) * | 2016-04-21 | 2016-06-22 | 广西丰泰能源科技有限公司 | Low-condensation-point biological fuel for vehicles |
| CN105779034A (en) * | 2016-04-21 | 2016-07-20 | 广西丰泰能源科技有限公司 | Bio-fuel for vehicle |
| CN105779033A (en) * | 2016-04-21 | 2016-07-20 | 广西丰泰能源科技有限公司 | Vehicle biofuel |
| CN108948421A (en) * | 2018-06-20 | 2018-12-07 | 深圳立山环保材料有限公司 | A kind of epoxy plasticiser mixture and preparation method thereof |
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Application publication date: 20110504 |