CN101126032A - Method for preparing biological diesel oil by using solid acid base double-function catalyst - Google Patents

Method for preparing biological diesel oil by using solid acid base double-function catalyst Download PDF

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Publication number
CN101126032A
CN101126032A CNA2007100534244A CN200710053424A CN101126032A CN 101126032 A CN101126032 A CN 101126032A CN A2007100534244 A CNA2007100534244 A CN A2007100534244A CN 200710053424 A CN200710053424 A CN 200710053424A CN 101126032 A CN101126032 A CN 101126032A
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zno
sio
kcl
nacl
solid acid
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王承明
翟龙霞
吴谋成
高洁芬
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Huazhong Agricultural University
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Huazhong Agricultural University
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Priority to CNA2007100534244A priority Critical patent/CN101126032A/en
Publication of CN101126032A publication Critical patent/CN101126032A/en
Priority to CN2008801093152A priority patent/CN101861372B/en
Priority to PCT/CN2008/001691 priority patent/WO2009046636A1/en
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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
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Abstract

The invention discloses a bio-diesel oil preparation method made by solid acid and base bifunctional catalyst. The molar ratio of low carbon alcohol and raw material oil is 3:1-40:1; then the raw reaction material is prepared according to that the solid and base bifunctional catalyst is of 0.1-20 percent of raw material oil, and the reaction material is then sent into a reaction device with 25 MPa of pressure and 300 DEG C to be stirred and fully reacted; thereafter, the low carbon alcohol is distilled and the solid acid and base bifunctional catalyst is separated out. Finally, the bio-diesel oil and glycerin are made. The solid acid and base bifunctional catalyst has high activity, is easy to be separated and recycled, can be reused, has convenient operation, easy control, low cost, simple sequential treatment to obtained production, high transformation rate, good industrialization application prospect and is environment-friendly.

Description

A kind of method that biodiesel is prepared with solid acid-base bifunctional catalyst
Technical field
The present invention relates to a kind of method that biodiesel is prepared with solid acid-base bifunctional catalyst, belong to bioenergy and catalysis technique prepares the technical field of biodiesel.
Background technology
Biodiesel is a kind of green regenerative energy sources, can as high-quality petrifaction diesel substitute.It using vegetable oil, animal oil, waste cooking oils is that raw material and alcohols carry out ester exchange reaction under certain condition that it, which is, and product is biodiesel, and byproduct is glycerine.Traditional ester exchange reaction uses homogeneous catalyst, such as NaOH, KOH, sodium methoxide or the concentrated sulfuric acid, according to liquid alkali as a catalyst, feedstock oil and methanol must be strictly dehydrated, otherwise the free fatty easily formed in milk, and feedstock oil has very big infringement to the activity of alkalescence.Reaction temperature is usually the boiling point of methanol, and reaction speed is fast, high conversion rate, but simultaneously there is also obvious shortcoming, product needs to neutralize the substantial amounts of industrial wastewater that washing is brought, and causes environmental pollution, post-processes extremely complex.Biodiesel is prepared under conditions of liquid acid catalyst presence, although liquid acid catalyst is to the moisture of feedstock oil and the content of free fatty without what particular/special requirement, but liquid acid has corrosivity, it is high to equipment requirement, and it is difficult separation that reaction, which terminates rear methanol and by-product glycerin, last handling process is complicated, production cost is increased.In addition, using liquid acid or liquid alkali as a catalyst, large amount of sewage being discharged in last handling process, environmental pollution is caused.
At present, the research of solid catalyst conversion biodiesel is more and more, using common solid acid (such as number of patent application：Or solid base (such as number of patent application 200410038292.4)：200510037862.2) method of biodiesel, preparation technology can be simplified, pollution to environment is avoided, but solid base is easily limited by conditions such as the moisture and acid number of raw material, and the reaction temperature of solid acid is higher, and solid acid or solid base catalyst Reusability performance are the problem of needing to consider.Therefore, in the urgent need to the good solid catalyst of exploitation catalytic activity height, raw material wide adaptation range, Reusability performance.
The content of the invention
To overcome the deficiencies in the prior art, the present invention provides a kind of method that biodiesel is prepared with solid acid-base bifunctional catalyst, solid acid-base bifunctional catalyst is not easy coking and deactivation in the reaction, and long service life can be repeatedly used, and the biodiesel produced and byproduct glycerine are into neutrality, washing need not be neutralized, not etching apparatus, save washing step, produced without waste water, subsequent processes are convenient.
Realize technical scheme that the object of the invention uses for：A kind of method that biodiesel is prepared with solid acid-base bifunctional catalyst, it is 3: 1~40: 1 by low-carbon alcohols and the mol ratio of feedstock oil, solid acid-base bifunctional catalyst is equipped with reaction raw materials for the 0.1~20% of raw material weight of oil, reaction raw materials are placed in normal pressure~25Mpa, in the reaction unit of room temperature~300 DEG C, then stirring steams low-carbon alcohols and isolates solid acid-base bifunctional catalyst to abundant reaction, biodiesel and glycerine are obtained, described solid acid-base bifunctional catalyst is：Cs-Ba-P-O/SiO2、Cu-ZnO-Al2O3、Cu-CoO-ZnO-Al2O3、Cu-ZnO-CoO-Al2O3-TiO2、Cu-ZnO-CoO-Al2O3-ZrO2、Cu-ZnO-CoO-Al2O3-TiO2-ZrO2、ZnO-Al2O3-SiO2-NaZSM-5、ZnO-Al2O3-SiO2-WO2-MnO2、ZnO-Al2O3-SiO2-WO2-FeO、ZnO-Al2O3-SiO2-WO2-CoO、ZnO-Al2O3-SiO2-WO2-NiO、ZnO-Al2O3-SiO2-WO2-CuO、ZnO-HZSM-5、K2O-B2O3-TiO2-ZrO2、MxOy-Na2CO3、MxOy-Na2O、MxOy-K2CO3、MxOy-K2O、MxOy-SiO2-Na2CO3、MxOy-SiO2-Na2O、MxOy-SiO2-K2CO3、MxOy-SiO2-K2O、MxOy-SiO2-MgO、CuSO4-ZrO2-MxOy、CuSO4-La2O3-ZrO2、CuSO4-La2O3-MxOy、CuO-ZnO-MxOy、CuO-ZnO-ZrO2、Na2CO3-NaCl-AO、Na2O-NaCl-AO、Na2CO3-KCl-AO、Na2O-KCl-AO、K2CO3-KCl-AO、K2O-KCl-AO、K2CO3-NaCl-AO、K2O-NaCl-AO、Na2CO3-KCl-AO、Na2O-KCl-AO、Na2O-K2O-AO、Na2CO3-AO、Na2O-AO、K2CO3-AO、K2O-AO、K2CO3-KCl-MxOy、K2O-KCl-MxOy、K2CO3-NaCl-MxOy、K2O-NaCl-MxOy、Na2CO3-NaCl-MxOy、Na2O-NaCl-MxOy、Na2CO3-KCl-MxOy、Na2O-KCl-MxOy、Na2O-K2O-MxOy、Na2CO3-K2O-MxOy、K2CO3-K2O-MxOy、MxOy-AO-Na2CO3、MxOy-AO-Na2O、MxOy-AO-K2CO3、MxOy-AO-K2O、Na2CO3-KCl-ZnO、Na2CO3-K2O-ZnO、K2CO3-KCl-ZnO、K2CO3-K2O-ZnO、Na2CO3-NaCl-ZnO、Na2O-NaCl-ZnO、K2CO3-NaCl-ZnO、K2CO3-KCl-ZnO、K2O-KCl-ZnO、K2O-NaCl-ZnO、Na2O-KCl-ZnO、Na2O-K2-ZnO、K2CO3-KCl-SiO2、K2CO3-NaCl-SiO2、Na2CO3-NaCl-SiO2、Na2CO3-KCl-SiO2、K2O-KCl-SiO2、K2O-NaCl-SiO2、Na2O-NaCl-SiO2、Na2O-KCl-SiO2、Na2O-K2O-SiO2、CuO-ZnO-MxOy、Na2O-MxOy-TiO2-ZrO2、K2O-MxOy-TiO2-ZrO2、Na2CO3-MxOy-TiO2-ZrO2、K2CO3-MxOy-TiO2-ZrO2、NaCl-MxOy-TiO2-ZrO2、KCl-MxOy-TiO2-ZrO2、Pt-SiO2-MxOy、NaCl-CuCl2-MxOy、KCl-CuCl2-MxOy、Na2O-CuCl2-MxOy、K2O-CuCl2-MxOy、Na2O-CuO-MxOy、K2O-CuO-MxOy、MxOy-Pd-SiO2、Fe2O3-Cr2O3、Co-MoO3-MxOy、CoMo-ZrO2-MxOyWherein A is ii major element in the periodic table of elements, M is ii I major elements, rare earth metal, Si, Ge, Sn, Pb, Mn, Zn, P, Sb, Se, Te, Po or Bi in the periodic table of elements, X is 1 or 2, Y is 1,2,3,4,5,6 or 7, and atlapulgite, granular carclazyte, aluminum oxide, molecular sieve, magnetic Fe can also be used in above-mentioned solid catalyst2O3, magnetic Fe3O4、Co2O3、Ni2O3One or more of mixtures be used as carrier.In order to shorten the reaction time for preparing biodiesel, the diameter of particle size of solid acid-base bifunctional catalyst is nano-scale.
Described low-carbon alcohols are methanol, ethanol or the mixture of the two.
Described feedstock oil is any one or a few the mixture in animal and plant fat, microbial fermentation grease, microalgae oil, grease deodorized distillate, the oil of one or more of compositions containing monoglyceride, diglyceride, triglycerides and free fatty, acidification oil, including the waste oil containing animal and plant fat, food and drink abandoned oil, waste grease, oil foot, oil-containing crops, oil plant, low-grade leaching oil.
In order to reduce the time of vegetable oil and low-carbon alcohols reaction under solid acid-base bifunctional catalyst, in reaction raw materials can the cosolvent containing above-mentioned raw materials oil quality 0~80%, cosolvent is one or more of mixtures of tetrahydrofuran, the tert-butyl alcohol, toluene, hexane, hexamethylene, diisopropyl ether, No. 6 solvents, petroleum ether or dioxane.
The low-carbon alcohols steamed and the solid acid-base bifunctional catalyst isolated are reusable.
Because feedstock oil can be catalyzed by acids and can be alkali catalyzed when being converted into biodiesel, solid acid-base bifunctional catalyst is in same catalyst, not only there is acid centre but also there is basic center, the acid point and alkali point of its surface of solids act synergistically and manifest very high catalytic activity and selectivity simultaneously, and having very long service life, this is due to the acid site and alkali center of solid acid-base bifunctional catalyst to making reactant molecule have appropriate orientation.Simultaneously because the catalytic action point of solid acid-base bifunctional catalyst acts synergistically while being acid point and alkali point, it is different from the strong acid catalyst of solid acid or the strong base catalyst of solid base：On the one hand it is that catalytic mechanism is different, solid acid or solid base are the catalysis of single strong acid or highly basic, and the catalytic action of solid acid-base bifunctional catalyst point acts synergistically while be acid point and alkali point；Another aspect solid acid-base bifunctional catalyst is different from the ingredient requirement and catalytic effect of solid acid or the catalytic reaction of solid base, solid base is easily limited by conditions such as the moisture and acid number of raw material, it is only suitable for preparing biodiesel by ester exchange reaction in low moisture content and the glyceride stock of low acid value, when preparing biodiesel by ester exchange reaction for higher moisture content and/or the glyceride stock of higher acid value, grease is occurred saponification side reaction or the presence due to the free fatty in raw material makes solid base occur acid poisoning and inactivate, and catalytic efficiency declines；And the reaction temperature of solid acid is higher or the reaction time is longer.When preparing biodiesel using solid acid-base bifunctional catalyst fcc raw material oil, even if the water content of feedstock oil is higher and/or acid value of feedstock oil is higher, the efficiency that it prepares biodiesel is still higher.In addition, solid acid or solid base catalyst easy coking and deactivation during the course of the reaction, solid acid or solid base catalyst Reusability performance are also the problem of needing to consider, and the catalytic action point of solid acid-base bifunctional catalyst be acid point and while alkali point concerted catalysis act on, it is not easy coking and deactivation, thus long service life, can be repeatedly used.
Compared with prior art, the present invention has the advantage that：
1. prepare biodiesel using solid acid-base bifunctional catalyst fcc raw material oil, even if the water content of feedstock oil is higher and/or acid value of feedstock oil is higher, its efficiency for preparing biodiesel can reach more than 99%.Solid acid-base bifunctional catalyst fcc raw material oil preparation biodiesel is wider to the scope of application of feedstock oil, and the requirement to raw material W/O part content and acid value is looser, with preferable practicality, and can comprehensively utilize some abandoned oils, reduce environmental pollution.
2. being catalyzed animal and plant fat raw material ester exchange reaction using solid acid-base bifunctional catalyst, biodiesel conversion rate reaches more than 99%, and technical target of the product meets ASTMD6751-02 standards.
3. compared with existing solid acid or solid base catalyst, the Reusability of difunction catalyst is greatly enhanced, by simple activation process, reusable 100 times, conversion ratio keeps constant.
4. using catalyst of the solid bifunctional catalyst as vegetable and animals oils and alcohols ester exchange reaction, obtained product is into neutrality, the subsequent treatments such as washing need not be neutralized, not etching apparatus, without sewage discharge, solve conventional homogeneous acid or base catalyst prepare present in biodiesel to the corrosivity of equipment, subsequent treatment is extremely complex, byproduct glycerine hardly possible is purified the problems such as.
Embodiment
Embodiment 1
In 500ml there-necked flasks, in the ratio that molar ratio of methanol to oil is 40: 1, add under the methanol of 100.00g crude rapeseed oils and requirement, mechanical agitation when temperature reaches 65 DEG C, add the Al that quality is crude rapeseed oil 20%2O3-K2CO3Catalyst 20.0g, at 60~65 DEG C, reacts 10 hours under normal pressure, then filters, isolate solid catalyst Al2O3-K2CO3, methanol is reclaimed after liquid phase is distilled, liquid phase is retransferred into separatory funnel, stood, upper strata is coarse biodiesel, and lower floor is byproduct glycerine.Composition through gas phase analysis coarse biodiesel, the content of fatty acid methyl ester is 98.1%.
Embodiment 2
In 500ml there-necked flasks, in the ratio that molar ratio of methanol to oil is 3: 1,5% Al for adding that quality is feedstock oil is added under the methanol of 100.00g animal and plant fats, waste oil, food and drink abandoned oil, waste grease, oil-containing crops, oil plant, microbial fermentation grease, microalgae oil, grease deodorized distillate, oil foot, any one or a few the mixture in acidification oil and requirement, mechanical agitation2O3-K2CO3Catalyst 5.0g, adds tetrahydrofuran 30mL, under 25Mpa pressure, 300 DEG C of reaction temperature, reacts 0.5 hour.Reaction is filtered while hot after terminating, and isolates solid catalyst Al2O3-K2CO3, methanol is reclaimed after liquid phase is distilled, transfer liquid phase is stood, upper strata is coarse biodiesel, and lower floor is byproduct glycerine into separatory funnel.Constituted through gas phase analysis mixture, the content of fatty acid methyl ester is more than 85.0% (content of fatty acid methyl ester is 87.5% when wherein feedstock oil uses crude rapeseed oil) in coarse biodiesel.
Embodiment 3
In 500ml there-necked flasks, in the ratio that molar ratio of methanol to oil is 15: 1, add the methanol of 100.00g crude rapeseed oils and requirement, when temperature reaches 65 DEG C under mechanical agitation, add the 0.1% bifunctional catalyst 0.1g that quality is feedstock oil, it is 60~65 DEG C, 4 hours normal pressure lower reaction time in reaction temperature.Reaction is filtered while hot after terminating, and isolates solid catalyst, and methanol is reclaimed in liquid phase redistillation, and transfer liquid phase is stood, upper strata is coarse biodiesel, and lower floor is byproduct glycerine into separatory funnel.Constituted through gas phase analysis mixture, the content of fatty acid methyl ester is more than 90.0% (wherein using bifunctional catalyst Al in coarse biodiesel2O3-SiO292.1%) content of fatty acid methyl ester is during-KCl.
Above-mentioned bifunctional catalyst is Cs-Ba-P-O/SiO2、Cu-ZnO-Al2O3、Cu-CoO-ZnO-Al2O3、Cu-0.ZnO-CoO-Al2O3-TiO2、Cu-ZnO-CoO-Al2O3-ZrO2、Cu-ZnO-CoO-Al2O3-TiO2-ZrO2、ZnO-Al2O3-SiO2-NaZSM-5、ZnO-Al2O3-SiO2-WO2-MnO2、ZnO-Al2O3-SiO2-WO2-FeO、ZnO-Al2O3-SiO2-WO2-CoO、ZnO-Al2O3-SiO2-WO2-NiO、ZnO-Al2O3-SiO2-WO2-CuO、ZnO-HZSM-5、K2O-B2O3-TiO2-ZrO2、MxOy-Na2CO3、MxOy-Na2O、MxOy-K2CO3、MxOy-K2O、MxOy-SiO2-Na2CO3、MxOy-SiO2-Na2O、MxOy-SiO2-K2CO3、MxOy-SiO2-K2O、MxOy-SiO2-MgO、CuSO4-ZrO2-MxOy、CuSO4-La2O3-ZrO2、CuSO4-La2O3-MxOy、CuO-ZnO-MxOy、CuO-ZnO-ZrO2、Na2CO3-NaCl-AO、Na2O-NaCl-AO、Na2CO3-KCl-AO、Na2O-KCl-AO、K2CO3-KCl-AO、K2O-KCl-AO、K2CO3-NaCl-AO、K2O-NaCl-AO、Na2CO3-KCl-AO、Na2O-KCl-AO、Na2O-K2O-AO、Na2CO3-AO、Na2O-AO、K2CO3-AO、K2O-AO、K2CO3-KCl-MxOy、K2O-KCl-MxOy、K2CO3-NaCl-MxOy、K2O-NaCl-MxOy、Na2CO3-NaCl-MxOy、Na2O-NaCl-MxOy、Na2CO3-KCl-MxOy、Na2O-KCl-MxOy、Na2O-K2O-MxOy、Na2CO3-K2O-MxOy、K2CO3-K2O-MxOy、MxOy-AO-Na2CO3、MxOy-AO-Na2O、MxOy-AO-K2CO3、MxOy-AO-K2O、Na2CO3-KCl-ZnO、Na2CO3-K2O-ZnO、K2CO3-KCl-ZnO、K2CO3-K2O-ZnO、Na2CO3-NaCl-ZnO、Na2O-NaCl-ZnO、K2CO3-NaCl-ZnO、K2CO3-KCl-ZnO、K2O-KCl-ZnO、K2O-NaCl-ZnO、Na2O-KCl-ZnO、Na2O-K2-ZnO、K2CO3-KCl-SiO2、K2CO3-NaCl-SiO2、Na2CO3-NaCl-SiO2、Na2CO3-KCl-SiO2、K2O-KCl-SiO2、K2O-NaCl-SiO2、Na2O-NaCl-SiO2、Na2O-KCl-SiO2、Na2O-K2O-SiO2、CuO-ZnO-MxOy、Na2O-MxOy-TiO2-ZrO2、K2O-MxOy-TiO2-ZrO2、Na2CO3-MxOy-TiO2-ZrO2、K2CO3-MxOy-TiO2-ZrO2、NaCl-MxOy-TiO2-ZrO2、KCl-MxOy-TiO2-ZrO2、Pt-SiO2-MxOy、NaCl-CuCl2-MxOy、KCl-CuCl2-MxOy、Na2O-CuCl2-MxOy、K2O-CuCl2-MxOy、Na2O-CuO-MxOy、K2O-CuO-MxOy、MxOy-Pd-SiO2、Fe2O3-Cr2O3、Co-MoO3-MxOy、CoMo-ZrO2-MxOyWherein A is ii major element in the periodic table of elements, M is ii I major elements, rare earth metal, Si, Ge, Sn, Pb, Mn, Zn, P, Sb, Se, Te, Po or Bi in the periodic table of elements, X is 1 or 2, Y is 1,2,3,4,5,6 or 7, and atlapulgite, granular carclazyte, aluminum oxide, molecular sieve, magnetic Fe can also be used in above-mentioned solid catalyst2O3, magnetic Fe3O4、Co2O3、Ni2O3One or more of mixtures be used as carrier.
Embodiment 4
In 500ml there-necked flasks, in the ratio that molar ratio of methanol to oil is 15: 1, add under the methanol of 100.00g crude rapeseed oils and requirement, mechanical agitation when temperature reaches 65 DEG C, add the Al that quality is crude rapeseed oil 5%2O3-SiO2-K2O catalyst 5.0g, in 60~65 DEG C, 4 hours normal pressure lower reaction time.Reaction is filtered while hot after terminating, and isolates solid catalyst, and methanol is reclaimed in liquid phase redistillation, liquid phase is shifted into separatory funnel, is stood, upper strata is coarse biodiesel, lower floor is byproduct glycerine, is constituted through gas phase analysis mixture, and the content of fatty acid methyl ester is 95.8% in coarse biodiesel.
Embodiment 5
In 500ml there-necked flasks, in the ratio that molar ratio of methanol to oil is 15: 1, add under the methanol of 100.00g crude rapeseed oils and requirement, mechanical agitation when temperature reaches 65 DEG C, add the Al that quality is crude rapeseed oil 5%2O3-SiO2-K2O catalyst 5.0g, and the cosolvent tetrahydrofuran that weight is weight of oil 5%~20% is added, in 40~85 DEG C, synthesis under normal pressure 2~3 hours.Reaction is filtered while hot after terminating, and isolates solid catalyst, and methanol is reclaimed in liquid phase redistillation, and transfer liquid phase is stood, upper strata is coarse biodiesel, and lower floor is byproduct glycerine into separatory funnel.Constituted through gas phase analysis mixture, the content of fatty acid methyl ester is 98.0% in coarse biodiesel.
Embodiment 6
In 500ml there-necked flasks, in the ratio that molar ratio of methanol to oil is 15: 1, add under the methanol of 100.00g crude rapeseed oils and requirement, mechanical agitation when temperature reaches 65 DEG C, add 20% Al that quality is raw material weight of oil2O3-SiO2-K2O catalyst 20g, add 80g cosolvent tetrahydrofuran, the tert-butyl alcohol, toluene, hexane, hexamethylene, diisopropyl ether, No. 6 solvents, petroleum ether or dioxane, in 45~85 DEG C, synthesis under normal pressure 2~3 hours.Reaction is filtered while hot after terminating, and isolates solid catalyst；Methanol is reclaimed in liquid phase redistillation, and transfer liquid phase is stood into separatory funnel, and upper strata is coarse biodiesel, and lower floor is byproduct glycerine.Constituted through gas phase analysis mixture, the content of fatty acid methyl ester is more than 98.5% in coarse biodiesel.
Embodiment 7
In 500ml there-necked flasks, in the ratio that molar ratio of methanol to oil is 40: 1, add under the methanol of 100.00g crude rapeseed oils and requirement, mechanical agitation when temperature reaches 65 DEG C, add the Al that quality is crude rapeseed oil 20%2O3-K2CO3Catalyst (particle diameter 10nm) 20.0g, at 60~65 DEG C, reacts 3 hours under normal pressure, then filters, isolate solid catalyst Al2O3-K2CO3, methanol is reclaimed after liquid phase is distilled, liquid phase is retransferred into separatory funnel, stood, upper strata is coarse biodiesel, and lower floor is byproduct glycerine.Composition through gas phase analysis coarse biodiesel, the content of fatty acid methyl ester is 98.7%.

Claims (8)

1. a kind of method that biodiesel is prepared with solid acid-base bifunctional catalyst, it is characterised in that：It is 3: 1~40: 1 by low-carbon alcohols and the mol ratio of feedstock oil, solid acid-base bifunctional catalyst is equipped with reaction raw materials for the 0.1~20% of raw material oil quality, reaction raw materials are placed in normal pressure~25Mpa, in the reaction unit of room temperature~300 DEG C, stirring is reacted to abundant, then low-carbon alcohols are steamed and solid acid-base bifunctional catalyst is isolated, biodiesel and glycerine is obtained, described solid acid-base bifunctional catalyst is：Cs-Ba-P-O/SiO2、Cu-ZnO-Al2O3、Cu-CoO-ZnO-Al2O3、Cu-ZnO-CoO-Al2O3-TiO2、Cu-ZnO-CoO-Al2O3-ZrO2、Cu-ZnO-CoO-Al2O3-TiO2-ZrO2、ZnO-Al2O3-SiO2-NaZSM-5、ZnO-Al2O3-SiO2-WO2-MnO2、ZnO-Al2O3-SiO2-WO2-FeO、ZnO-Al2O3-SiO2-WO2-CoO、ZnO-Al2O3-SiO2-WO2-NiO、ZnO-Al2O3-SiO2-WO2-CuO、ZnO-HZSM-5、K2O-B2O3-TiO2-ZrO2、MxOy-Na2CO3、MxOy-Na2O、MxOy-K2CO3、MxOy-K2O、MxOy-SiO2-Na2CO3、MxOy-SiO2-Na2O、MxOy-SiO2-K2CO3、MxOy-SiO2-K2O、MxOy-SiO2-MgO、CuSO4-ZrO2-MxOy、CuSO4-La2O3-ZrO2、CuSO4-La2O3-MxOy、CuO-ZnO-MxOy、CuO-ZnO-ZrO2、Na2CO3-NaCl-AO、Na2O-NaCl-AO、Na2CO3-KCl-AO、Na2O-KCl-AO、K2CO3-KCl-AO、K2O-KCl-AO、K2CO3-NaCl-AO、K2O-NaCl-AO、Na2CO3-KCl-AO、Na2O-KCl-AO、Na2O-K2O-AO、Na2CO3-AO、Na2O-AO、K2CO3-AO、K2O-AO、K2CO3-KCl-MxOy、K2O-KCl-MxOy、K2CO3-NaCl-MxOy、K2O-NaCl-MxOy、Na2CO3-NaCl-MxOy、Na2O-NaCl-MxOy、Na2CO3-KCl-MxOy、Na2O-KCl-MxOy、Na2O-K2O-MxOy、Na2CO3-K2O-MxOy、K2CO3-K2O-MxOy、MxOy-AO-Na2CO3、MxOy-AO-Na2O、MxOy-AO-K2CO3、MxOy-AO-K2O、Na2CO3-KCl-ZnO、Na2CO3-K2O-ZnO、K2CO3-KCl-ZnO、K2CO3-K2O-ZnO、Na2CO3-NaCl-ZnO、Na2O-NaCl-ZnO、K2CO3-NaCl-ZnO、K2CO3-KCl-ZnO、K2O-KCl-ZnO、K2O-NaCl-ZnO、Na2O-KCl-ZnO、Na2O-K2-ZnO、K2CO3-KCl-SiO2、K2CO3-NaCl-SiO2、Na2CO3-NaCl-SiO2、Na2CO3-KCl-SiO2、K2O-KCl-SiO2、K2O-NaCl-SiO2、Na2O-NaCl-SiO2、Na2O-KCl-SiO2、Na2O-K2O-SiO2、CuO-ZnO-MxOy、Na2O-MxOy-TiO2-ZrO2、K2O-MxOy-TiO2-ZrO2、Na2CO3-MxOy-TiO2-ZrO2、K2CO3-MxOy-TiO2-ZrO2、NaCl-MxOy-TiO2-ZrO2、KCl-MxOy-TiO2-ZrO2、Pt-SiO2-MxOy、NaCl-CuCl2-MxOy、KCl-CuCl2-MxOy、Na2O-CuCl2-MxOy、K2O-CuCl2-MxOy、Na2O-CuO-MxOy、K2O-CuO-MxOy、MxOy-Pd-SiO2、Fe2O3-Cr2O3、Co-MoO3-MxOy、CoMo-ZrO2-MxOy, wherein A is ii major element in the periodic table of elements, and M is ii I major elements, rare earth metal, Si, Ge, Sn, Pb, Mn, Zn, P, As, Sb, Se, Te, Po or Bi in the periodic table of elements, and X is 1 or 2, Y are 1,2,3,4,5,6 or 7.
2. the method for biodiesel is prepared with solid acid-base bifunctional catalyst according to claim 1, it is characterised in that：Solid acid-base bifunctional catalyst uses atlapulgite, granular carclazyte, aluminum oxide, molecular sieve, magnetic Fe2O3, magnetic Fe3O4、Co2O3Or Ni2O3In one or more of mixtures be used as carrier.
3. the method for biodiesel is prepared with solid acid-base bifunctional catalyst according to claim 1, it is characterised in that：The diameter of particle size of solid acid-base bifunctional catalyst is nano-scale.
4. the method for biodiesel is prepared with solid acid-base bifunctional catalyst according to claim 1, it is characterised in that：Low-carbon alcohols are methanol, ethanol or the mixture of the two.
5. the method for biodiesel is prepared with solid acid-base bifunctional catalyst according to claim 1, it is characterised in that：Feedstock oil is any one or a few the mixture in animal and plant fat, microbial fermentation grease, microalgae oil, grease deodorized distillate.
6. the method for biodiesel is prepared with solid acid-base bifunctional catalyst according to claim 1, it is characterised in that：Feedstock oil is any one or a few the mixture in the oily of one or more of compositions containing monoglyceride, diglyceride, triglycerides and free fatty, acidification oil.
7. the method for biodiesel is prepared with solid acid-base bifunctional catalyst according to claim 1, it is characterised in that：Add the cosolvent of raw material oil quality 0~80% in reaction raw materials, cosolvent is one or more of mixtures of tetrahydrofuran, the tert-butyl alcohol, toluene, hexane, hexamethylene, diisopropyl ether, No. 6 solvents, petroleum ether or dioxane.
8. the method for biodiesel is prepared with solid acid-base bifunctional catalyst according to claim 1, it is characterised in that：Recycle the low-carbon alcohols steamed and the solid acid-base bifunctional catalyst isolated.
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