CN104263527A - Preparation method of biodiesel - Google Patents
Preparation method of biodiesel Download PDFInfo
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- CN104263527A CN104263527A CN201410523777.6A CN201410523777A CN104263527A CN 104263527 A CN104263527 A CN 104263527A CN 201410523777 A CN201410523777 A CN 201410523777A CN 104263527 A CN104263527 A CN 104263527A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses a preparation method of biodiesel. The preparation method comprises the following steps: 1) carrying out transesterification on grease and fatty alcohol under the condition of ZnO/Ca(OH)2/KF, Na2SiO3/CaO/KF and KF/MMT mixture solid base; 2) steaming out the fatty alcohol from the mixture after the reaction and separating the glycerinum; 3) adding one or more nonionic surfactants in the mixture obtained in the step 2) to serve as filter aids, separating the fatty acid monoglyceride through a ceramic membrane to obtain the high-purity biodiesel. According to the preparation method, the process is simple, the adaptability of raw materials is relatively high, the problem of saponified matter accumulation is avoided, the grease utilization rate can be close to 100%, the purity of the biodiesel is high, the aftertreatment is simple, the reduced pressure distillation is avoided, the concentration of the byproduct glycerinum is high, the temperature and the pressure required by the transesterification are low, the cost is reduced, the yield of the biodiesel is high, and water-bath heating is used, so that the reaction temperature is constant.
Description
Technical field
The present invention relates to biomass energy technology field, particularly a kind of preparation method of biofuel.
Background technology
Along with people's rising steadily to the growing interest of environmental problem and oil price, biofuel, as green regenerative energy sources, becomes the important alternative fuel of petrifaction diesel.Ester-interchange method is most widely used method for producing biodiesel, and namely animal-plant oil and lower alcohol (as methyl alcohol or ethanol) obtain lipid acid low-carbon-ester by transesterification reaction.Because the reactive behavior of methyl alcohol is high, low price, so most typical biofuel is fatty acid methyl ester.
Grease, i.e. triglyceride, carry out transesterification reaction with lower alcohol, is converted into difatty acid glyceryl ester, monoglyceride successively, finally obtains lipid acid low-carbon-ester and glycerine.Because the transesterification reaction of glyceryl ester and lower alcohol is reversible reaction, the productive rate of lipid acid low-carbon-ester limits by thermodynamic(al)equilibrium, and along with the raising of grease transformation efficiency, the cost realizing unit conversion rate constantly increases.But, as the biofuel that motor spirit uses, to the concentration of unconverted grease and each intermediate product, there is strict restriction, such as, European standard EN14214 requires: monoglyceride, difatty acid glyceryl ester and triglyceride mass concentration in the product should be less than 0.8%, 0.2% and 0.2% respectively.And in mixture after the reaction, the mass concentration of monoglyceride is about 1-15%.Therefore how preparing the lipid acid low-carbon-ester of enough purity, obtain standard compliant biodiesel oil product, is a difficult problem for those skilled in the art's facing.
CN1141993C discloses the method for Acrawax under super critical condition, and the method does not use catalyzer, requires lower to glyceride stock, in the reaction times short (only needing several minutes), aftertreatment is simple, work simplification, meanwhile, by-product glycerin concentration is high, almost non-pollution discharge.But this technological reaction condition is harsh, pressure large (10-25MPa), temperature of reaction high (350-400 DEG C), makes this technology investment increase, and application is restricted.
The technique that CN101070480A describes is grease with alcohol after transesterify, and boil off alcohol, separation of glycerin, then rectification under vacuum purification, obtains the lipid acid low-carbon-ester that concentration reaches 99.0%.Because the boiling point of lipid acid low-carbon-ester is higher, about 250-400 DEG C is higher to rectifying conditional request.
US5,908,946 preparation technologies disclosing lipid acid low-carbon-ester, this technique uses the Zn Al composite oxide catalyzer with spinel structure, at higher temperature (200-250 DEG C) and pressure (being less than 10MPa), adopt two sections of fixed bed reactions, grease transformation efficiency is close to 100%.Compared with liquid caustic soda Catalytic processes, although temperature of reaction and pressure higher, without the need to acid-base neutralisation in aftertreatment, purifying products step significantly simplifies, and methyl esters productive rate is close to theoretical value, and meanwhile, qualities of glycerin concentration reaches 98%.But this technique still Shortcomings.First be that catalyst preparation process is complicated, energy consumption is higher, needs to process waste water, waste gas etc. simultaneously.And in biodiesel production method, the filling of catalyzer, inactivation and discarded, all can bring new problem.What is more important, under relatively harsh reaction conditions, grease is through two-stage reaction, and intermediate demand reduces temperature, and then the compressive reaction that heats up, and realize the productive rate of last about 10%, this makes the facility investment of this technique and energy consumption all higher.
CN101012392A discloses a kind of method removing soap and glycerine in biofuel.For the coarse biodiesel that low temperature, base-catalyzed transesterification method obtain, use microfiltration of ceramic membrane coarse biodiesel, realize being separated soap and glycerine.
Summary of the invention
The present invention is directed to Problems existing in current production of biodiesel, a kind of preparation method of biofuel is provided.
The preparation method of a kind of biofuel provided by the invention, comprising:
A preparation method for biofuel, comprising:
1) grease, fatty alcohol and solid alkali are added in reactor simultaneously and carry out transesterify, wherein solid alkali is ZnO/Ca (OH)
2/ KF, Na
2siO
3/ CaO/KF and KF/MMT mixture solid alkali are the 1-4% of oil quality, and heating in water bath makes the temperature of reaction of reactor remain on 50-80 DEG C, pressure 2-6MPa, mol ratio 8-15: 1 of fatty alcohol and grease, and reaction solution volume space velocity is 0.3-4/h;
2) mixture is after the reaction placed in the retort of taper, in steam fatty alcohol, separation of glycerin;
3) in step 2) add one or more nonionogenic tensides as flocculating aids in the mixture that obtains, by ceramic membrane separation monoglyceride, obtain high-purity biodiesel, the hydrophile-lipophile balance value of wherein said nonionogenic tenside is 3-25, nonionogenic tenside consumption is step 2) 0.1-10% of mixture quality that obtains, the propping material of wherein said ceramic membrane is pottery, film material is selected from inorganic carbon film, the mineral membrane of aluminum oxide or titanium oxide, ceramic membrane aperture is 0.02-1.4 μm, under described membrane sepn operates in the temperature of 10-120 DEG C, carry out under the condition of transmembrane pressure 0.08-0.5MPa.
Wherein reaction conditions is: temperature is 60-65 DEG C, and pressure is 2-5MPa, and mol ratio 10-11: 1 of fatty alcohol and grease, reaction volume air speed is 0.8-3/h.
Wherein said nonionogenic tenside is polyoxyethylene-type, polyether-type and/or polyol-based non-ionic surfactant.
Wherein said nonionogenic tenside is selected from one or more in fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, polyoxyethylene carboxylate, sorbitan ester and sucrose ester nonionogenic tenside.
Wherein dosage of surfactant should be step 2) 0.5-6% of mixture quality that obtains.
At 60-70 DEG C of temperature, under the condition of transmembrane pressure 0.1-0.3MPa, carry out membrane sepn operation.
Described ZnO/Ca (OH)
2the preparation method of/KF solid alkali is:
Step a: by ZnO, Ca (OH)
2and KF2H
2o is mixed into mixture, and its mol ratio is 2.0:1.0:(0.5 ~ 2.0);
Step b: add deionized water and grind, the mol ratio of itself and mixture is (2.5 ~ 3.5): 16;
Step c: drying 5 ~ 7 hours at the temperature of 70 DEG C ~ 90 DEG C;
Steps d: bake and bank up with earth 5 ~ 7 hours at the temperature of 250 DEG C ~ 500 DEG C, obtains ZnO/Ca (OH) 2/KF solid alkali.
Described Na
2siO
3the preparation method of/CaO/KF solid alkali is:
Step a: get Na
2siO
3.9H
2o, CaO and KF.2H
2o is mixed into mixture, and its mol ratio is 2.0:5.0:(1.5 ~ 6.0);
Step b: be ground to starchiness;
Step c: drying 5 ~ 7 hours at the temperature of 70 DEG C ~ 90 DEG C;
Steps d: bake and bank up with earth 3.5 ~ 4.5 hours at the temperature of 300 DEG C ~ 500 DEG C, obtain Na
2siO
3/ CaO/KF solid alkali.
The present invention has obvious advantage:
1, technical process is short, and adaptability to raw material is strong, and avoid saponified accumulation problem, Lipid use rate can close to 100%, and biofuel purity is high, and aftertreatment is simple, avoids underpressure distillation;
2, by-product glycerin concentration is high, creates condition for simplifying glycerine purifying technique;
3, ZnO/Ca (OH) is used
2/ KF, Na
2siO
3/ CaO/KF and KF/MMT mixture solid alkaline catalysts, temperature of reaction and reaction pressure low, production cost is low;
4, catalyst activity is high, improves the productive rate of biofuel;
5, heating in water bath, homo(io)thermism, the transesterification reaction in reactor is stablized, and by product is few;
6, the retort of taper, is beneficial to sweet oil separating.
Embodiment
Embodiment 1:
React production biofuel with soybean oil and methyl alcohol, processing condition, material drop into and output situation as follows:
Methyl alcohol and soybean oil are sent in tubular reactor and react, reaction conditions is: molar ratio of methanol to oil is 12: 1, is incorporated as the ZnO/Ca (OH) of soybean oil quality 2%
2/ KF, Na
2siO
3/ CaO/KF and KF/MMT mixture solid alkali, reaction solution volume space velocity is 0.5/h, and temperature of reaction is 65 DEG C, and pressure is 5MPa.Reacted material step-down, flash distillation removing methyl alcohol, then reduce temperature to 40 DEG C, centrifugation glycerine.The methyl esters obtained mutually in, methyl esters mass concentration reaches 91%, and the mass concentration of monoglyceride is 5%.Then, methyl esters mutually in be mixed into 4% Span80 (be sorbitan monooleate, hydrophile-lipophile balance value is about 4.3) after, under transmembrane pressure is 0.15MPa, via hole diameter is the ceramic membrane of 0.2 μm, carry out membrane sepn in 40 DEG C, obtain monoglyceride mass concentration lower than 0.71%, methyl esters mass concentration is about the high-purity biodiesel of 94%.The mass concentration of glycerine can reach 91%.Not by the material of film, directly as feedstock circulation to reactor, carry out second time reaction.Through circulation, grease can be converted into biodiesel oil product completely, makes biodiesel production rate reach 98%.
Embodiment 2:
Be that the Oleum Gossypii semen of 10mgKOH/g and methyl alcohol react production biofuel with acid number, processing condition, material drop into and output situation as follows:
Methyl alcohol and Oleum Gossypii semen are sent in tubular reactor and react, molar ratio of methanol to oil is 15: 1, KOH is 0.3 ‰ of soybean oil quality, is incorporated as the ZnO/Ca (OH) of soybean oil quality 3%
2/ KF, Na
2siO
3/ CaO/KF and KF/MMT mixture solid alkali, reaction solution volume space velocity is 4/h, and temperature of reactor is 75 DEG C, and pressure is 6MPa.After reaction, grease transformation efficiency is about 91%.Reacted material step-down, flash distillation removing methyl alcohol, then reduce temperature to 50 DEG C, settlement separate glycerine.Grease after separation of glycerin mutually in, the mass concentration of monoglyceride is 12%.Then, methyl esters mutually in be mixed into 1% Tween80 (polyoxyethylene 20 sorbitan monostearate, hydrophile-lipophile balance value is about 15.0) after, under transmembrane pressure is 0.2MPa, via hole diameter is the ceramic membrane of 0.5 μm, carry out membrane sepn in 30 DEG C, obtain monoglyceride mass concentration lower than 0.65%, methyl esters mass concentration be about 95% high-purity biodiesel.Biofuel is after plastic resin treatment, and free glycerin concentration is about 0.011%.Glycerine is after resin, activated carbon treatment, and concentration is about 94%.Not by the material of film, directly as feedstock circulation to reactor, carry out second time reaction.Through circulation, grease can be converted into biodiesel oil product completely, makes biodiesel production rate reach 98%.
Embodiment 3:
With plam oil, react production biofuel with methyl alcohol, processing condition, material drop into and output situation as follows:
Methyl alcohol and plam oil are sent in tubular reactor and react, molar ratio of methanol to oil is 9: 1, NaOH is 0.1 ‰ of soybean oil quality, is incorporated as the ZnO/Ca (OH) of soybean oil quality 4%
2/ KF, Na
2siO
3/ CaO/KF and KF/MMT mixture solid alkali, reaction solution volume space velocity is 1/h, and temperature of reactor is 55 DEG C, and pressure is 3MPa.After reaction, grease transformation efficiency reaches 89%.Reacted material step-down, flash distillation removing methyl alcohol, then reduce temperature to 30 DEG C, settlement separate glycerine.Grease after separation of glycerin mutually in, the mass concentration of monoglyceride is about 13%.Then, methyl esters mutually in be mixed into 2% flatly add O-25 (high-carbon fatty alcohol polyoxyethylene ether, hydrophile-lipophile balance value is about 17) after, under transmembrane pressure is 0.25MPa, via hole diameter is the ceramic membrane of 0.05 μm, carry out membrane sepn in 60 DEG C, obtain monoglyceride mass concentration lower than 0.72%, methyl acetate concentrations be about 93% biofuel.The mass concentration of glycerine can reach 89%.Not by the material of film, directly as feedstock circulation to reactor, carry out second time reaction.Through circulation, grease can be converted into biodiesel oil product completely, makes biodiesel production rate close to 97%.
Embodiment 4:
With rapeseed oil, react production biofuel with methyl alcohol, processing condition, material drop into and output situation as follows:
Methyl alcohol and rapeseed oil are sent in tubular reactor and react, molar ratio of methanol to oil is 15: 1, KOH is 0.1 ‰ of soybean oil quality, is incorporated as the ZnO/Ca (OH) of soybean oil quality 1%
2/ KF, Na
2siO
3/ CaO/KF and KF/MMT mixture solid alkali, reaction solution volume space velocity is 1/h, and temperature of reactor is 50 DEG C, and pressure is 2MPa.Reacted material step-down, flash distillation removing methyl alcohol, then reduce temperature to 50 DEG C, settlement separate glycerine, in the mixture obtained, the mass concentration of monoglyceride is about 2%, and grease transformation efficiency reaches 90%.Be mixed into 5%TX-40 (alkylphenol polyoxyethylene in the mixture, hydrophile-lipophile balance value is about 18), reduce temperature to 20 DEG C, under transmembrane pressure is 0.1MPa, via hole diameter is the ceramic membrane separation of 1.0 μm, obtain that monoglyceride mass concentration is less than 0.66%, methyl esters mass concentration close to 95% biofuel.The mass concentration of glycerine can reach 94%.Not by the material of film, directly as feedstock circulation to reactor, carry out second time reaction.Through circulation, grease can be converted into biodiesel oil product completely, makes biodiesel production rate close to 98%.
Comparative example 1:
Do not add tensio-active agent, all the other processing condition, material drop into embodiment 1.
Methyl alcohol and soybean oil are sent in tubular reactor and react, reaction conditions is: molar ratio of methanol to oil is 12: 1, is incorporated as the ZnO/Ca (OH) of soybean oil quality 2%
2/ KF, Na
2siO
3/ CaO/KF and KF/MMT mixture solid alkali, reaction solution volume space velocity is 0.5/h, and temperature of reaction is 65 DEG C, and pressure is 5MPa.Reacted material step-down, flash distillation removing methyl alcohol, then reduce temperature to 40 DEG C, centrifugation glycerine.The methyl esters obtained mutually in, methyl esters mass concentration reaches 91%, and the mass concentration of monoglyceride is about 5%.Then, under transmembrane pressure is 0.15MPa, via hole diameter is the ceramic membrane of 0.2 μm, carries out membrane sepn in 40 DEG C, and in the biofuel obtained, monoglyceride mass concentration is about 2.3%.Methyl esters mass concentration is about the high-purity biodiesel of 94%.The mass concentration of glycerine can reach 90%.Not by the material of film, directly as feedstock circulation to reactor, carry out second time reaction.Through circulation, grease can be converted into biodiesel oil product completely, makes biodiesel production rate be 96%.
Comparative example 2:
Do not add ZnO/Ca (OH)
2/ KF, Na
2siO
3/ CaO/KF and KF/MMT mixture solid alkali, all the other processing condition, material drop into embodiment 1.
Methyl alcohol and soybean oil are sent in tubular reactor and react, reaction conditions is: molar ratio of methanol to oil is 12: 1, and reaction solution volume space velocity is 0.5/h, and temperature of reaction is 65 DEG C, and pressure is 5MPa.Reacted material step-down, flash distillation removing methyl alcohol, then reduce temperature to 40 DEG C, centrifugation glycerine.The methyl esters obtained mutually in, methyl esters mass concentration is 65%, and the mass concentration of monoglyceride is 5%.Then, methyl esters mutually in be mixed into 4% Span80 (be sorbitan monooleate, hydrophile-lipophile balance value is about 4.3) after, under transmembrane pressure is 0.15MPa, via hole diameter is the ceramic membrane of 0.2 μm, carry out membrane sepn in 40 DEG C, obtain monoglyceride mass concentration lower than 0.71%, methyl esters mass concentration is about the high-purity biodiesel of 68%.The mass concentration of glycerine can reach 65%.Not by the material of film, directly as feedstock circulation to reactor, carry out second time reaction.Through circulation, grease can be converted into biodiesel oil product completely, makes biodiesel production rate be 70%.
In embodiment 1-4 and simultaneous test 1, described ZnO/Ca (OH)
2the preparation method of/KF solid alkali is:
Step a: by ZnO, Ca (OH)
2and KF2H
2o is mixed into mixture, and its mol ratio is 2.0:1.0:2.0;
Step b: add deionized water and grind, the mol ratio of itself and mixture is 3.5:16;
Step c: drying 7 hours at the temperature of 70 DEG C;
Steps d: bake and bank up with earth 7 hours at the temperature of 250 DEG C, obtains ZnO/Ca (OH) 2/KF solid alkali.
Described Na
2siO
3the preparation method of/CaO/KF solid alkali is:
Step a: get Na
2siO
3.9H
2o, CaO and KF.2H
2o is mixed into mixture, and its mol ratio is 2.0:5.0:5.0;
Step b: be ground to starchiness;
Step c: drying 5 hours at the temperature of 90 DEG C;
Steps d: bake and bank up with earth 4.5 hours at the temperature of 500 DEG C, obtain Na
2siO
3/ CaO/KF solid alkali.
Described ZnO/Ca (OH)
2/ KF, Na
2siO
3the ratio of/CaO/KF and KF/MMT is 1:1:1.
Claims (8)
1. a preparation method for biofuel, is characterized in that comprising:
1) grease, fatty alcohol and solid alkali are added in reactor simultaneously and carry out transesterify, wherein solid alkali is ZnO/Ca (OH)
2/ KF, Na
2siO
3the mixture of/CaO/KF and KF/MMT is the 1-4% of oil quality, and heating in water bath makes the temperature of reaction of reactor remain on 50-80 DEG C, pressure 2-6MPa, mol ratio 8-15: 1 of fatty alcohol and grease, and reaction solution volume space velocity is 0.3-4/h;
2) mixture is after the reaction placed in the retort of taper, in steam fatty alcohol, separation of glycerin;
3) in step 2) add one or more nonionogenic tensides as flocculating aids in the mixture that obtains, by ceramic membrane separation monoglyceride, obtain high-purity biodiesel, the hydrophile-lipophile balance value of wherein said nonionogenic tenside is 3-25, nonionogenic tenside consumption is step 2) 0.1-10% of mixture quality that obtains, the propping material of wherein said ceramic membrane is pottery, film material is selected from inorganic carbon film, the mineral membrane of aluminum oxide or titanium oxide, ceramic membrane aperture is 0.02-1.4 μm, under described membrane sepn operates in the temperature of 10-120 DEG C, carry out under the condition of transmembrane pressure 0.08-0.5MPa.
2. according to the preparation method of a kind of biofuel according to claim 1, it is characterized in that: wherein reaction conditions is: temperature is 60-65 DEG C, pressure is 2-5MPa, and mol ratio 10-11: 1 of fatty alcohol and grease, reaction volume air speed is 0.8-3/h.
3. according to the preparation method of a kind of biofuel according to claim 1, it is characterized in that: wherein said nonionogenic tenside is polyoxyethylene-type, polyether-type and/or polyol-based non-ionic surfactant.
4. according to the preparation method of a kind of biofuel according to claim 1, it is characterized in that: wherein said nonionogenic tenside is selected from one or more in fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, polyoxyethylene carboxylate, sorbitan ester and sucrose ester nonionogenic tenside.
5., according to the preparation method of a kind of biofuel according to claim 1, it is characterized in that: wherein dosage of surfactant should be step 2) 0.5-6% of mixture quality that obtains.
6. according to the preparation method of a kind of biofuel according to claim 1, it is characterized in that: at 60-70 DEG C of temperature, under the condition of transmembrane pressure 0.1-0.3MPa, carry out membrane sepn operation.
7., according to the preparation method of a kind of biofuel according to claim 1, it is characterized in that:
Described ZnO/Ca (OH)
2the preparation method of/KF solid alkali is:
Step a: by ZnO, Ca (OH)
2and KF2H
2o is mixed into mixture, and its mol ratio is 2.0:1.0:(0.5 ~ 2.0);
Step b: add deionized water and grind, the mol ratio of itself and mixture is (2.5 ~ 3.5): 16;
Step c: drying 5 ~ 7 hours at the temperature of 70 DEG C ~ 90 DEG C;
Steps d: bake and bank up with earth 5 ~ 7 hours at the temperature of 250 DEG C ~ 500 DEG C, obtains ZnO/Ca (OH) 2/KF solid alkali.
8., according to the preparation method of a kind of biofuel according to claim 1, it is characterized in that:
Described Na
2siO
3the preparation method of/CaO/KF solid alkali is:
Step a: get Na
2siO
3.9H
2o, CaO and KF.2H
2o is mixed into mixture, and its mol ratio is 2.0:5.0:(1.5 ~ 6.0);
Step b: be ground to starchiness;
Step c: drying 5 ~ 7 hours at the temperature of 70 DEG C ~ 90 DEG C;
Steps d: bake and bank up with earth 3.5 ~ 4.5 hours at the temperature of 300 DEG C ~ 500 DEG C, obtain Na
2siO
3/ CaO/KF solid alkali.
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| CN102039202A (en) * | 2010-12-15 | 2011-05-04 | 东南大学 | Solid-base monolithic catalyst with regular porous channels and preparation method of solid-base monolithic catalyst |
| CN102260597A (en) * | 2010-05-27 | 2011-11-30 | 中国石油化工股份有限公司 | Preparation method of high purity biodiesel |
| CN103894170A (en) * | 2012-12-30 | 2014-07-02 | 青岛联合创新技术服务平台有限公司 | Solid base catalyst and method for preparing biodiesel by use of solid base catalyst |
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2014
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| CN102260597A (en) * | 2010-05-27 | 2011-11-30 | 中国石油化工股份有限公司 | Preparation method of high purity biodiesel |
| CN102039202A (en) * | 2010-12-15 | 2011-05-04 | 东南大学 | Solid-base monolithic catalyst with regular porous channels and preparation method of solid-base monolithic catalyst |
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