CN100365100C - Method of preparing biological diesel oil by methanol critical low alkali process - Google Patents
Method of preparing biological diesel oil by methanol critical low alkali process Download PDFInfo
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- CN100365100C CN100365100C CNB2005100412676A CN200510041267A CN100365100C CN 100365100 C CN100365100 C CN 100365100C CN B2005100412676 A CNB2005100412676 A CN B2005100412676A CN 200510041267 A CN200510041267 A CN 200510041267A CN 100365100 C CN100365100 C CN 100365100C
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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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- 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
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Abstract
The present invention belongs to a new technology for preparation bioenergy. The ester exchange reaction is carried out on vegetable oil and critical methanol under the catalysis of micro alkali of which the addition is from 0.05% to 0.1% to make crude product biologic diesel oil and by product glycerol present neutral. Thereby, the neutralizing washing procedure is not needed, and the post processing procedure is greatly simplified. No waste water is discharged, and therefore, the pollution can not be created on the environment. Because the reaction temperature and the pressure are decreased to be 240(+/-)5 DEG C and 6.9 to 7MPa, the molar ratio of methanol to oil is from 42 to 21:1 in the critical state of methanol; the reaction time is lasted for about 100 to 120 minutes, the energy consumption is lower than that of a supercritical method, and the temperature-resistant and pressure-resistant requirements on reacting equipment are reduced, but the yield of methyl ester can reach 99 to 97%.
Description
Technical field
The invention belongs to the bioenergy new preparation process, refer in particular to a kind of method of preparing biological diesel oil by methanol critical low alkali process.
Background technology
Biofuel is a kind of alternative petrifaction diesel, reproducible clean fuel.Available vegetable and animals oils, waste edible oil etc. carry out transesterification reaction for alcohol such as raw material and methyl alcohol, ethanol, and product is fatty acid methyl ester (back abbreviation methyl esters), and byproduct is a glycerine.Traditional transesterification reaction adopts homogeneous catalyst, as NaOH, KOH, sodium methylate etc., is about 1% in the vegetables oil consumption, temperature of reaction generally is the boiling point of methyl alcohol, in 1 hour reaction times, the transformation efficiency height reaches more than 95%, but also exist significant disadvantages simultaneously, though the base catalysis method reacts easy usually, in order to remove alkaline catalysts, the aftertreatment of reaction solution is very cumbersome, product need neutralize washing and bring a large amount of trade effluents, causes environmental pollution.Yuichiro W. is at " Yuichiro Warabi, DadanKusdiana, Shiro Saka, Bioresource Technology 91 (2004) 283-287 " lipid acid and the reaction of triglyceride level in supercritical alcohols in the research rape seed oil in the article, propose to carry out transesterification reaction with overcritical on-catalytic method, reaction times is short, transformation efficiency can reach more than 95%, and product does not need washing, and aftertreatment is simple, but molar ratio of methanol to oil reaches 42/1, temperature of reaction is 350 ℃, and pressure is 20MPa.Surpass the critical temperature and the emergent pressure of methyl alcohol, production technique is to the equipment requirements height.Transesterification reaction prepares the biodiesel processes report under the another kind of catalyst-free, M.Diasakou etc. are at (M.Diasakou, A.Louloudi, N.Papayannakos, Fuel 1998 vol.77.No.12 pp.1297-1302) point out during the kinetics of research soya-bean oil transesterification reaction under catalyst-free in the article: when methyl alcohol and soya-bean oil mol ratio are 27/1, in 10 hours reaction times, the content of methyl esters reaches 65% during 220 ℃ of temperature of reaction; When methyl alcohol and soya-bean oil mol ratio are 27/1, in 10 hours reaction times, the content of methyl esters reaches 85% during 235 ℃ of temperature of reaction.This work also has supercritical methanol technology aftertreatment characteristic of simple, and molar ratio of methanol to oil and temperature of reaction and pressure ratio supercritical methanol technology are low, but the reaction times is longer, and the content of methyl esters is lower.
Summary of the invention
The purpose of this invention is to provide a kind of critical little base catalysis legal system of on base catalysis method and supercritical methanol technology basis, developing and be equipped with biofuel, this method is because there is micro-base catalysis, both had overcritical aftertreatment characteristic of simple, the product aftertreatment of reaction back need not neutralization washing, environmentally safe, low because of temperature of reaction and pressure ratio supercritical methanol technology again, heat-up time is shorter, and the content of methyl esters is higher, and energy consumption is low, the technology that operation is simple, cost is low is easier to the advantage of industrialization.
The technical scheme that realizes above-mentioned purpose is:
Little or low alkaline catalysts is an alkali metal hydroxide, as: NaOH, KOH, sodium methylate etc. are dissolved in the little alkaline solution of preparation in 2～3ml methyl alcohol, add-on 0.1～0.05% (weight with vegetables oil is standard metering).At 240 ± 5 ℃ of temperature of reaction, pressure is 6.9～7.0 Mpa, methyl alcohol: the vegetables oil mol ratio is under 42～21: 1 the condition, to add alkaline solution in a subtle way, in the autoclave pressure that band stirs, carry out transesterification reaction after 100～120 minutes, steam unreacted methanol, quiescent settling divides two-layer up and down then.Lower floor is a coarse biodiesel, sampling analysis methyl esters content; The upper strata is a raw glycerine, and sampling analysis glycerol content, the transformation efficiency of transesterification reaction are 99～97%.The biofuel product that makes meets 0# diesel oil main performance index.
The invention has the beneficial effects as follows:
(1) low alkaline catalysts adds, and reaction product two layers of solution up and down is that thick product biofuel and byproduct glycerine pH 6～7 are neutral, thus need not the neutralization washing, without sewage discharge, subsequent disposal is simplified greatly, and is the same with supercritical methanol technology;
(2) temperature of reaction is 240 ± 5 ℃, and pressure is 6.9～7.0Mpa, at the methanol critical state, molar ratio of methanol to oil is reduced to 42～21: 1, and all low than supercritical methanol technology, energy consumption reduces simultaneously, the withstand voltage heatproof of conversion unit is required to reduce, and yield 99～97% easier industrialization of methyl esters.
(3) glycerol content of upper strata raw glycerine is than base catalysis method and supercritical methanol technology height, and the content of glycerine makes separating and the simplification greatly of purifying of methyl esters and glycerine up to more than 91%.
Description of drawings
Fig. 1 is the process flow diagram of the low alkaline process of critical methanol
Embodiment
Embodiment 1
In 1L band magnetic agitation autoclave pressure, add thick rapeseed oil 100.0 grams, industrial grade benzenemethanol 146.7 grams respectively, molar ratio of methanol to oil is 42: 1, (in rapeseed oil) alkaline catalysts 0.05%, be that 0.05gKOH is dissolved in 3ml methyl alcohol, stirring heating reaches 240 ± 5 ℃, after pressure was 6.9MPa, 120 minutes afterreactions of clock reaction finished, and distill out unnecessary methyl alcohol, reacting liquor while hot is poured standing demix in the separating funnel into, lower floor is a coarse biodiesel, and the upper strata is the byproduct raw glycerine, and the pH value of levels is 6～7, and sampling respectively, analytical results is listed in the following table.
Levels reacting coarse product pH value is 6～7, so need not aftertreatment, has avoided common base catalysis method need add processes such as acid neutralization, washing, has prevented the generation of industrial sewage effectively.It is 96.3% that chromatogram detects methyl esters content, and bio-diesel yield reaches 99.7%; Glycerol content is 91.0%, and yield is up to 96.5%.
Embodiment 2
Change alkaline catalysts add-on in the foregoing description 1 into 0.1%, other condition is identical, and test-results is listed in the table.Upper strata byproduct of reaction raw glycerine pH value is 7～8, and following reaction product layer coarse biodiesel pH value is 6～7, need not aftertreatment.It is 99.1% that chromatogram detects methyl esters content, and bio-diesel yield is up to 99.7%.
Embodiment 3
The molar ratio of methanol to oil of the foregoing description 1 is reduced to 21: 1, and other condition is identical, and test-results is listed in the table.Levels reacting coarse product pH value is 6～7, still need not aftertreatment.It is 95.1% that chromatogram detects methyl esters content, and bio-diesel yield is up to 97.3%.
Embodiment 4
Change alkaline catalysts in the foregoing description 1 into NaOH, other condition is identical with embodiment 1, and test-results is listed in the table.Levels reacting coarse product pH value is 6～7, still need not aftertreatment.It is 98.1% that chromatogram detects methyl esters content, and bio-diesel yield is up to 98.3%.
Embodiment 5 is a comparative experimental example 1
Do not add base catalysis in the foregoing description 1, other condition is identical with embodiment 1, and test-results is listed in the table.The yield of chromatogram detection of biological diesel oil is 46.1%, and the yield of glycerine is 16.5%.Obviously do not have little base catalysis, just prepare biofuel under the methanol critical condition, the yield of methyl esters is very low.
Embodiment 6 is a comparative experimental example 2
Under condition of normal pressure, temperature of reaction is 60 ℃, and other condition is identical with embodiment 2, and test-results is listed in the table.The yield of chromatogram detection of biological diesel oil is 0%.Obviously in the little base catalysis of normal pressure, not to prepare biofuel under the methanol critical condition, transesterification reaction takes place hardly.
Embodiment 7 is a comparative experimental example 3
Conventional base catalysis legal system is equipped with biofuel, and test-results is listed in the table.
Watch test condition and result
| Instance number | Temperature of reaction ℃ | Reaction pressure MPa | The alcohol oil rate mole | Alkali add-on % | Bio-diesel yield % | Glycerine yield % | Reacting liquid pH value |
| One | 245 | ?6.9 | ?42∶1 | ?0.05 | ?99.7 | 96.5 | 6～7 |
| Two | 245 | ?6.9 | ?42∶1 | ?0.1 | ?99.7 | Do not survey | 7～8 |
| Three | 245 | ?6.1 | ?21∶1 | ?0.05 | ?97.3 | Do not survey | 6～7 |
| Four | 245 | ?6.9 | ?42∶1 | ?0.05 | ?98.3 | Do not survey | 6～7 |
| Five | 245 | ?6.9 | ?42∶1 | ?0 | ?46.1 | 16.5 | 6 |
| Six | 60 | Normal pressure | ?42∶1 | ?0.1 | ?0 | Do not survey | 7～8 |
| Seven | 60 | Normal pressure | ?42∶1 | ?1 | ?91.2 | Do not survey | 9～10 |
Claims (3)
1. the method for preparing biological diesel oil by methanol critical low alkali process, it is characterized in that taking little or low amount alkaline catalysts is that alkali metal hydroxide is dissolved in 2～3ml methyl alcohol, add-on counts 0.1～0.05% to account for the vegetables oil mass fraction, 240 ± 5 ℃ of temperature of reaction, pressure is 6.9～7.0Mpa, then at methyl alcohol: the vegetables oil mol ratio is under 42～21: 1 the condition, the little alkaline solution that adds above-mentioned preparation, transesterification reaction in the autoclave pressure that band stirs, steam unreacted methanol, quiescent settling then, two-layer about dividing, promptly lower floor is a coarse biodiesel, and the upper strata is a raw glycerine.
2. the method for preparing biological diesel oil by methanol critical low alkali process according to claim 1 is characterized in that described alkali metal hydroxide is NaOH or KOH or sodium methylate.
3. the method for preparing biological diesel oil by methanol critical low alkali process according to claim 1 is characterized in that the described transesterification reaction time is: when reacting liquid temperature arrives 240 ± 5 ℃, pick up counting, reacted 100～120 minutes.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100412676A CN100365100C (en) | 2005-08-01 | 2005-08-01 | Method of preparing biological diesel oil by methanol critical low alkali process |
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| CNB2005100412676A CN100365100C (en) | 2005-08-01 | 2005-08-01 | Method of preparing biological diesel oil by methanol critical low alkali process |
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| CN100365100C true CN100365100C (en) | 2008-01-30 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200649B (en) * | 2006-12-13 | 2012-01-25 | 中国石油化工股份有限公司 | Preparation method of biological diesel fuel |
| WO2008071040A1 (en) * | 2006-12-15 | 2008-06-19 | China Petroleum & Chemical Corporation | A procss for preparing biodiesel |
| US8500828B2 (en) * | 2006-12-15 | 2013-08-06 | China Petroleum & Chemical Corporation | Process for preparing a bio-diesel |
| CN101429469B (en) * | 2007-11-08 | 2012-01-25 | 中国石油化工股份有限公司 | Chemical processing method for lipid |
| CN103131541A (en) * | 2013-03-11 | 2013-06-05 | 贵州大学 | Method for preparing biodiesel from Xanthium strumarium |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039423A (en) * | 1975-03-10 | 1977-08-02 | Gulf Oil Canada Limited | Preparation of petroleum pitch |
| CN1556174A (en) * | 2003-12-31 | 2004-12-22 | 中国农业科学院油料作物研究所 | Production method of biodiesel oil using high acid ralue animal and vegetable grease |
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- 2005-08-01 CN CNB2005100412676A patent/CN100365100C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039423A (en) * | 1975-03-10 | 1977-08-02 | Gulf Oil Canada Limited | Preparation of petroleum pitch |
| CN1556174A (en) * | 2003-12-31 | 2004-12-22 | 中国农业科学院油料作物研究所 | Production method of biodiesel oil using high acid ralue animal and vegetable grease |
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Assignee: Jiangsu Kate Petroleum New Energy Co., Ltd. Assignor: Jiangsu Polytechnic University Contract fulfillment period: 2008.8.28 to 2013.8.28 contract change Contract record no.: 2008320000867 Denomination of invention: Method of preparing biological diesel oil by methanol critical low alkali process Granted publication date: 20080130 License type: Exclusive license Record date: 20081013 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.8.28 TO 2013.8.28; CHANGE OF CONTRACT Name of requester: JIANGSU KATE PETROLEUM NEW ENERGY CO., LTD. Effective date: 20081013 |
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