CN103468414A - Method for preparing biodiesel by using composite solid acid catalyst - Google Patents
Method for preparing biodiesel by using composite solid acid catalyst Download PDFInfo
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- CN103468414A CN103468414A CN2013104536386A CN201310453638A CN103468414A CN 103468414 A CN103468414 A CN 103468414A CN 2013104536386 A CN2013104536386 A CN 2013104536386A CN 201310453638 A CN201310453638 A CN 201310453638A CN 103468414 A CN103468414 A CN 103468414A
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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
- 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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Abstract
A method for preparing biodiesel by using a composite solid acid catalyst comprises the following steps of (1) biomass raw materials and methyl alcohol are mixed in a reaction vessel, the composite solid acid catalyst is added, and reaction is carried out between room temperature to the boiling point of reacting liquid to obtain reaction liquid, wherein the boiling point of the reacting liquid is the boiling point of the mixed liquid at corresponding pressure, and the reacting time is 10 minutes to 24 hours; (2) after the reaction is finished, the solid acid catalyst is separated through a filtration method or a centrifugal separation method, the liquid phase is poured into a separating funnel, the upper layer liquid is extracted after the liquid is layered through still standing, and the biodiesel can be obtained after the methyl alcohol is obtained through distillation. The method for preparing the biodiesel by using the composite solid acid catalyst has the advantages that reacting conditions are mild, the catalyst is high in activity and selectivity and easy to separate and recycle, the environment is not polluted, and the method for preparing the biodiesel by using the composite solid acid catalyst is beneficial to industrialized popularization.
Description
Technical field
The present invention relates to use the reutilization technology of biomass resource and abandoned biomass resource, particularly a kind of method of using composite solid-acid catalyst to prepare biofuel.
Background technology
In recent years, the fast development of world economy makes the energy consumption sharp increase, and the whole world all is faced with problem of energy crisis.Biofuel is as a kind of typical " green energy resource ", because of biodegradable, renewable, nontoxic, advantages of environment protection, be expected to substitute existing mineral diesel fuel, greatly develop biofuel to sustainable economic development, alleviate environmental stress and control the everyways such as topsoil and there is very important strategic importance.At present, in the world particularly developed country all be devoted to develop efficient, free of contamination biomass energy utilization technologies.Wherein, the countries such as the U.S., Italy, France build up the tens of seats of biodiesel production apparatus in succession, and Europe has become the main grown place of global biochemical diesel oil.
Vegetable oil lipoprotein comprises soya-bean oil, peanut oil, rapeseed oil, sesame oil, corn wet goods, is one of optimal raw material of preparation biofuel.Ester-interchange method is the most frequently used biodiesel oil preparing process, and its catalyzer can be divided into homogeneous catalyst and heterogeneous catalyst.Although homogeneous phase alkaline catalysts, as KOH, NaOH etc., industrial, be widely used, but when in reactant, fatty acid content is higher, alkaline catalysts and lipid acid generation saponification and severe attrition occurs, referring to: Helwani etc., Appl Catal A:Gen, 2009,363:1-10, when the sewer oil of particularly take is that main waste grease is as raw material, the homogeneous phase alkaline catalysts is very limited aborning, referring to: Zhang etc., Resources Conservation and Recycling, 2012,60:20-37.In addition, the homogeneous catalysis method needs neutralization to remove catalyzer and dry except moisture in producing, and treating processes has increased energy consumption and sewage output.Heterogeneous catalyst possesses and is insoluble to reactant, the advantage that reproducible, reaction preference is high, transformation efficiency is high and product yield is high, as alkalimetal oxide, alkaline earth metal oxide, transition metal oxide, ion exchange resin, carbon base catalyst and enzyme catalyst etc.But, being subject to the impact of free fatty acids, the easy inactivation of solid base catalyst, be unfavorable for industrial production.The heterogeneous acid catalysis method has the advantage of the anti-high FFA content of homogeneous acid catalysis method and high catalytic activity concurrently, but there is no the shortcoming of the separation of homogeneous acid catalysate, pollution level, etching apparatus, will become the most important approach of preparation biofuel.In solid acid, because of a little less than acidic zeolite, temperature of reaction is higher, and heteropolyacid is unfavorable for separating because of easy lipid acid, sulfonic acid ion exchange resin, referring to: Kiss etc., Adv Synth Catal, 2006,348:75-81, sulfonic group modified mesoporous SiO
2, referring to: Melero etc., Green Chem, 2009,11:1285-1308; Mbaraka etc., Am Oil Chem Soc, 2006,83:79-91, sulfonation charcoal are catalyst based, referring to: Lou etc., Bioresour Technol, 2008,99:8752-8758, all have stronger acidity, catalytic activity is high, but has the problem that selectivity is poor, be easy to carbon deposit.2012, we once disclosed a kind of preparation and application of the composite solid-acid catalyst for condensation reaction, application number: 201210246953.7, now find, this catalyzer has high activity and selectivity equally for transesterification reaction, can be for the preparation of biofuel, and the product excellent performance of anti-lipid acid.
Summary of the invention
The object of the invention is to the problem existed for production of biodiesel, a kind of method of using composite solid-acid catalyst to prepare biofuel is provided, the method is simple to operate, aftertreatment is easy, the environmental friendliness degree is high, also can be widely used in other transesterification reactions.
Technical scheme of the present invention:
A kind of method of using composite solid-acid catalyst to prepare biofuel, step is as follows:
1) biomass material and methyl alcohol are mixed in reaction vessel, adding composite solid-acid catalyst, is that room temperature-reaction solution boiling point is reacted in temperature, and the reaction solution boiling point refers to the boiling point under the mixed solution corresponding pressure, reaction times is 10min-24 hour, obtains reaction solution;
2) after completion of the reaction, by filter method or centrifugal separation method, isolate solid acid catalyst, liquid phase is poured separating funnel into, after stratification, takes out supernatant liquid, after Distillation recovery methyl alcohol, can obtain biofuel.
Described biomass material is natural animal-plant grease or waste grease, comprises soybean oil, rapeseed oil, sesame oil, peanut oil, sewer oil, Semen Maydis oil and methyl benzoate, and the volume ratio of biomass material and methyl alcohol is 1:1-10.
Described composite solid-acid catalyst is according to the described method preparation of patent 201210246953.7, the 0.1-50% of the total mass that the add-on of composite solid-acid catalyst is biomass material and methyl alcohol.
Advantage of the present invention is: this preparation method's reaction conditions gentleness, catalyst activity and selectivity is high, be easy to Separation and Recovery, free from environmental pollution, is conducive to industrialization promotion.
Embodiment
Followingly the present invention is further elaborated in conjunction with the embodiments, but does not limit content of the present invention.In embodiment, the preparation method of composite solid-acid catalyst used is shown in patent 201210246953.7.
embodiment 1:
A kind of method of using composite solid-acid catalyst to prepare biofuel, step is as follows:
1) soybean oil of 5mL and 10mL methyl alcohol are mixed in there-necked flask, add 1g silica gel base composite solid-acid catalyst (aluminum chloride modified), under stirring, oil bath is heated to reflux state, and isothermal reaction 2h, obtain reaction solution;
2) naturally cool to after completion of the reaction room temperature, then reaction solution is transferred in centrifuge tube, centrifugal 5min in whizzer, incline and liquid, with methanol wash pipe inner catalyst, recentrifuge separates, and inclines and washing lotion and merge in previous liquid phase, puts into the standing 2h of separating funnel, separate supernatant liquid, methyl alcohol is reclaimed in underpressure distillation, can make biofuel, viscosity 4.12mm
2/ s, productive rate 93%.
Infrared spectra (KBr compressing tablet) measurement result is: 2961 cm
-1.
embodiment 2:
A kind of method of using composite solid-acid catalyst to prepare biofuel, step is as follows:
1) 1 mixes the sewer oil of 5mL and 15mL methyl alcohol in there-necked flask, adds 1.2g silica gel base composite solid-acid catalyst (aluminum chloride modified), and under stirring, oil bath is heated to reflux state, and isothermal reaction 3h, obtain reaction solution;
2) naturally cool to after completion of the reaction room temperature, by the reaction solution decompress filter and with the catalyzer on methanol wash filter paper, pour gained washing lotion and filtrate merging into separating funnel, after stratification, take out supernatant liquid, Distillation recovery methyl alcohol, can make biofuel, viscosity 4.35mm
2/ s, productive rate 90%.
Infrared spectra (KBr compressing tablet) measurement result is: 2935 cm
-1.
embodiment 3:
A kind of method of using composite solid-acid catalyst to prepare biofuel, step is as follows:
1) 1 adds the methyl alcohol of the Semen Maydis oil of 1mL and 2mL in the stainless steel pressure still and mixes, and adds 0.2g alumina base composite solid-acid catalyst (aluminum chloride modified), and after sealing, oil bath temperature is controlled at 120 ℃, and insulation reaction 30min, obtain reaction solution;
2) naturally cool to after completion of the reaction room temperature, by the reaction solution decompress filter and with the catalyzer on methanol wash filter paper, pour gained washing lotion and filtrate merging into separating funnel, after stratification, take out supernatant liquid, Distillation recovery methyl alcohol, can make biofuel, viscosity 4.16 mm
2/ s, productive rate 95%.
Infrared spectra (KBr compressing tablet) measurement result is: 2875 cm
-1.
embodiment 4:
A kind of method of using composite solid-acid catalyst to prepare biofuel, step is as follows:
1) 1 mixes the methyl alcohol of the methyl benzoate of 2mL and 3mL in there-necked flask, adds 0.5g silica gel base composite solid-acid catalyst (aluminum chloride modified), and under stirring, oil bath is heated to reflux state, and isothermal reaction 3h, obtain reaction solution;
2) naturally cool to after completion of the reaction room temperature, by the reaction solution decompress filter and with the catalyzer on propyl carbinol washing filter paper, gained washing lotion and filtrate merging are poured in matrass, remove methyl alcohol and propyl carbinol under reduced pressure, obtain butyl benzoate, productive rate 98%.
Infrared spectra (KBr compressing tablet) measurement result is: 1722cm
-1.
Claims (3)
1. a method of using composite solid-acid catalyst to prepare biofuel is characterized in that step is as follows:
1) biomass material and methyl alcohol are mixed in reaction vessel, adding composite solid-acid catalyst, is that room temperature-reaction solution boiling point is reacted in temperature, and the reaction solution boiling point refers to the boiling point under the mixed solution corresponding pressure, reaction times is 10min-24 hour, obtains reaction solution;
2) after completion of the reaction, by filter method or centrifugal separation method, isolate solid acid catalyst, liquid phase is poured separating funnel into, after stratification, takes out supernatant liquid, after Distillation recovery methyl alcohol, can obtain biofuel.
2. use according to claim 1 composite solid-acid catalyst to prepare the method for biofuel, it is characterized in that: described biomass material is natural animal-plant grease or waste grease, comprise soybean oil, rapeseed oil, sesame oil, peanut oil, sewer oil, Semen Maydis oil and methyl benzoate, the volume ratio of biomass material and methyl alcohol is 1:1-10.
3. use according to claim 1 composite solid-acid catalyst to prepare the method for biofuel, it is characterized in that: described composite solid-acid catalyst is according to the described method preparation of patent 201210246953.7, the 0.1-50% of the total mass that the add-on of composite solid-acid catalyst is biomass material and methyl alcohol.
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| CN2013104536386A CN103468414A (en) | 2013-09-29 | 2013-09-29 | Method for preparing biodiesel by using composite solid acid catalyst |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338215A (en) * | 2008-08-25 | 2009-01-07 | 清华大学 | Method for preparing biodiesel by catalyzing oil or fatty acid with solid |
| CN102755901A (en) * | 2012-07-17 | 2012-10-31 | 天津理工大学 | Preparation and application of composite solid acid catalyst used for condensation reaction |
| CN102824928A (en) * | 2012-09-14 | 2012-12-19 | 聊城大学 | Solid acid catalyst for preparing biodiesel and preparation method as well as application of solid acid catalyst |
| CN102965203A (en) * | 2012-10-31 | 2013-03-13 | 潍坊金信达生物化工有限公司 | Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst |
| CN103319341A (en) * | 2013-06-28 | 2013-09-25 | 华东师范大学 | Method for synthesizing methyl oleate |
-
2013
- 2013-09-29 CN CN2013104536386A patent/CN103468414A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338215A (en) * | 2008-08-25 | 2009-01-07 | 清华大学 | Method for preparing biodiesel by catalyzing oil or fatty acid with solid |
| CN102755901A (en) * | 2012-07-17 | 2012-10-31 | 天津理工大学 | Preparation and application of composite solid acid catalyst used for condensation reaction |
| CN102824928A (en) * | 2012-09-14 | 2012-12-19 | 聊城大学 | Solid acid catalyst for preparing biodiesel and preparation method as well as application of solid acid catalyst |
| CN102965203A (en) * | 2012-10-31 | 2013-03-13 | 潍坊金信达生物化工有限公司 | Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst |
| CN103319341A (en) * | 2013-06-28 | 2013-09-25 | 华东师范大学 | Method for synthesizing methyl oleate |
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Application publication date: 20131225 |