CN1810931A - Microwave process to prepare biological diesel oil - Google Patents
Microwave process to prepare biological diesel oil Download PDFInfo
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- CN1810931A CN1810931A CNA2006100551673A CN200610055167A CN1810931A CN 1810931 A CN1810931 A CN 1810931A CN A2006100551673 A CNA2006100551673 A CN A2006100551673A CN 200610055167 A CN200610055167 A CN 200610055167A CN 1810931 A CN1810931 A CN 1810931A
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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 relates to microwave process to prepare biological diesel oil, and belongs to the field of grease chemical technology. The present invention features that after animal or plant grease, plant oil leftover, recovered waste oil or their mixture in 1000 weight portions, methanol in 150-200 weight portions, and acid catalyst comprising sulfuric acid, hydrochloric acid, phosphoric acid, organic acid or solid acid in 5-30 weight portions are mixed in a reactor, the reactor is set inside a 200-1000 W power microwave generator for heating reflux of 4-60 min, and through further evaporation out of un-reacted methanol, stilling for 12 hr to separate out crude biological diesel oil product, neutralization, washing and continuous vacuum distillation, biological diesel oil product is produced. The present invention has the advantages of wide material source, easy embodiment, fast reaction and high production efficiency.
Description
Technical field
The present invention relates to a kind of microwave method and prepare method of bio-diesel oil, belong to field of grease chemical technology.
Background technology
Biofuel is meant with oil crops such as soybean, Semen Brassicae campestris, oil-yielding shrubs such as oil palm and Chinese pistache fruit, oil plant waterplant and animal grease such as engineering microalgae, the food and drink wet goods that gives up are raw material, the organic fatty acid esters class A fuel A that obtains through transesterification, it has high hexadecane value, do not have sulphur and do not have the advantageous characteristic of arene compound, biodegradable, nontoxic, environmental sound, and flash-point more helps transporting safely and storing than the petrifaction diesel height.The aggravation of energy shortage in recent years, mineral substance energy worsening shortages, the development substitutability energy has become inexorable trend, and the reproducible green energy resource of environment amenable cleaning---biofuel becomes the focus of people's research gradually.
Biodiesel raw material consists of the alcohols and the tri-glyceride of short chain.Its main preparation methods has direct use and hybrid system, micro emulsion method, pyrolysis method and ester-interchange method.Preceding two kinds of methods are because oil viscosity is high and easy volatile not, cause problems such as the stuck and deposition of carbon of engine nozzle coking, piston ring in various degree; Vegetables oil and animal tallow cracked shortcoming are at high temperature to carry out, and need catalyzer, and reaction is difficult to control and apparatus expensive; And ester-interchange method mainly changes into full-bodied vegetables oil or animal grease by transesterification the fatty acid ester of low-viscosity.The biofuel that adopts ester-interchange method to prepare have viscosity low, need not to consume remarkable advantage such as lot of energy, grease directly carries out the standard production method that transesterify is the biofuel used of US and European with methyl alcohol.
The transesterify process that is used to prepare biofuel roughly is divided into homogeneous catalysis transesterify process, heterogeneous catalyst transesterify process, enzyme catalysis transesterify process, homogeneous system catalytic transesterification process and overcritical transesterify process.Wherein, homogeneous catalysis transesterify process mainly comprises acid-catalyzed transesterification process and base-catalyzed transesterification process.
The waste and old grease that reclaims with market has the double environmental protection meaning as the raw material of biofuel.American I daho National E ﹠amp; E Laboratory carried out the test of frying oil production biofuel, and the Kowloon bus uses to utilize and reclaims the biofuel that waste cooking oil is produced, and domestic also have a lot of enterprises to adopt the waste oil system of recovery biofuel.Reclaim waste oil because oxidative rancidity and reclaim after acidification, greasy acid value is often very high, even up to more than the 100mg/g.Have a large amount of free fatty acidies in the waste oil, when adopting waste oil to produce thing diesel oil next life, free fatty acids can be directly and basic catalyst generation soap, therefore, can not directly use alkaline catalysts, can only use acid-catalyzed transesterification.Acid-catalyzed transesterification process catalyzer commonly used has the vitriol oil, Phenylsulfonic acid and phosphoric acid etc., acid-catalyzed transesterification process productive rate height, but speed of reaction is slow.Studies show that at 95 ℃, methyl alcohol is 40: 1 with plam oil amount of substance ratio, 5%H as Crabbe etc.
2SO
4Under the condition, the fatty acid methyl ester productive rate reaches 97% needs 9h; And under 80 ℃ and the same terms, obtain same productive rate need 24h (CrabbeE, Nolasco-Hipolito C, Kobayashi G, et al, Process Biochemistry, 2001:65-71); The transesterification reaction kinetics of research such as Freedman soybean oil finds that at 65 ℃, methyl alcohol is 30: 1 with soybean oil amount of substance ratio, 1%H
2SO
4Under the condition, the fatty acid methyl ester productive rate reach 99% need 50h (Freedman B, Butterfield RO, Pryde E H.J.Am.Oil Chem.Soc., 1986,63:1375-1380); Usefulness sulfuric acid such as Obibuzor utilize grease (free fatty acids in the pericarp as catalyst recovery, 25%～26%), the amount of alcohol oil substances was than 35: 1,68 ℃ of temperature, reaction times is at 12h, fatty acid ester productive rate about 97% (Obibuzor J U.Abigor R D, Okiy D A.J.Am.OilChem.Soc., 2003,80 (1): 77-80).
1986, Canadian Gedye and co-worker thereof have studied the esterification of carrying out in microwave oven, make microwave in organic synthesis, use (Gedye R as a kind of new technology, Smith F, Westaway K, et al.The uses of microwave ovens for rapid organic synthesis.Tetrahedron Lett, 1986,27 (3): 279-282.).From 1986 so far, organic synthesis under the microwave radiation, owing to can improve speed of reaction several times even thousands of times, have easy and simple to handle, by product is few, the productive rate height, easy purifying and advantages of environment protection, bring once leap to organic synthesis, developing into a very noticeable frontier-MORE chemistry (Microwave induced Organic ReactionsEnhancement Chemistry) is that microwave promotes organic chemistry, also can be called microwave induction catalytic organic reaction chemistry.
Microwave heating is that electric field energy is deep into material inside, directly acting on material molecule makes it to move and generate heat, this internal heating is different with the traditional heating method, the latter is realized by thermal conduction and thermal convection, be called outer heating. it is fast that internal heating has rate of heating, only needs the time of the 1/10-1/100 of outer heating method to finish, have be quick on the draw, characteristics [Zhang Hualian such as inertialess and lag-effect, the system temperature that is heated are even, thermo-efficiency height, Hu Ximing, Lai Shengli.Microwave is to the principle of dynamics research of chemical reaction effect.South China Science ﹠ Engineering University's journal, 1997,25 (9): 46-50.].This internal heating mode might make some can not be activated under the normal reflux condition fully and can't carry out or the reaction that is difficult to carry out is taken place.This has just showed wide prospect for microwave promotes organic chemistry research.
Summary of the invention
At present acid-catalyzed transesterification production biofuel long reaction time, shortcoming that production efficiency is low, the present invention proposes a kind of novel method for preparing biofuel with microwave technology at short notice, not only production technique is simple, and is safe and reliable, and the production efficiency height.
The present invention utilizes microwave method to prepare method of bio-diesel oil and comprises the steps:
1, by mass ratio 1000 parts of greases, methyl alcohol 150-200 part, catalyzer 5-30 part are mixed in reaction vessel after, place the microwave generator of power 200-1000w, reflux 4-60 minute
2, be warming up between 60-100 ℃ and steam unreacted methanol, leave standstill and tell upper strata crude product biofuel after 12 hours.
3, with containing 10%Na
2CO
3Saturated aqueous common salt in and washing crude product biofuel, neutral crude product biofuel.
4, further adopt continous vacuum distillatory way, the cut between collecting 220-320 ℃ under the vacuum 5mmHg obtains refined biometric diesel oil.
Grease of the present invention is meant the natural animal-plant grease, plant oil leftover or recovery waste oil, or above-mentioned several mixture.
Catalyzer of the present invention is meant sulfuric acid, hydrochloric acid, phosphoric acid, organic acid and solid acid an acidic catalyst.
Advantage of the present invention is:
1, the reaction times is short, preparation efficiency is high;
2, raw material sources are wide;
3, methanol usage is few, has alleviated the pressure that reclaims alcohol.
Embodiment
The following examples can make the professional and technical personnel more understand the present invention, but do not limit claim of the present invention in any form.
Embodiment 1
The various animal oil of input, vegetables oil mix naturally in the reactor of 1000 milliliters tool reflux condensate devices sewer oil 600g, vitriol oil 5g, methyl alcohol 110g, after mixing, place microwave oven (WP700J17-G, Galanz) in, microwave heating backflow 4min under power 400w.Sampling and measuring acid number≤5mgKOH/g, lipid acid triglyceride content are less than 3%, and then the explanation reaction is finished.
Stop microwave heating reaction, will remain methyl alcohol and steam,, reaction product left standstill tell lower floor's dilute sulphuric acid and glycerol liquor after 12 hours, obtain the crude product biofuel in 98 ℃ of gas phase temperatures collection unreacted methanol down.
With containing 10%Na
2CO
3Saturated aqueous common salt in and washing crude product biofuel, neutral crude product biofuel.
Neutral crude product biofuel is carried out continous vacuum distillation, and the cut under vacuum tightness＜5mmHg between 30-190 ℃ of the collection is refined biometric diesel oil.
Embodiment 2
In the reactor of 1000 milliliters tool reflux condensate devices, drop into unpurified rapeseed oil 600g, phosphatase 11 5g, methyl alcohol 120g, after mixing, place microwave oven (WP700J17-G, Galanz) in, microwave heating backflow 35min under power 400w.Sampling and measuring acid number≤5mgKOH/g, lipid acid triglyceride content are less than 3%, and then the explanation reaction is finished.
Stop microwave heating reaction, will remain ethanol and steam,, reaction product left standstill tell lower floor's dilute sulphuric acid and glycerol liquor after 12 hours, obtain the crude product biofuel in 98 ℃ of gas phase temperatures collection unreacted methanol down.
With containing 10%Na
2CO
3Saturated aqueous common salt in and washing crude product biofuel, neutral crude product biofuel.
Neutral crude product biofuel is carried out continous vacuum distillation, and the cut under vacuum tightness＜5mmHg between 30-190 ℃ of the collection is refined biometric diesel oil.
Embodiment 3
In the reactor of 1000 milliliters tool reflux condensate devices, drop into unpurified soya-bean oil 600g, tosic acid 10g, methyl alcohol 100g, after mixing, place microwave oven (WP700J17-G, Galanz) in, microwave heating backflow 58min under power 800w.Sampling and measuring acid number≤5mgKOH/g, lipid acid triglyceride content are less than 3%, and then the explanation reaction is finished.
Stop microwave heating reaction, will remain Virahol and steam,, reaction product left standstill tell lower floor's dilute sulphuric acid and glycerol liquor after 12 hours, obtain the crude product biofuel in 90 ℃ of gas phase temperatures collection unreacted methanol down.
With containing 10%Na
2CO
3Saturated aqueous common salt in and washing crude product biofuel, neutral crude product biofuel.
Neutral crude product biofuel is carried out continous vacuum distillation, and the cut under vacuum tightness＜5mmHg between 30-190 ℃ of the collection is refined biometric diesel oil.
Embodiment 4
In the reactor of 1000 milliliters tool reflux condensate devices, drop into acidifying oil 600g, tosic acid 10g, methyl alcohol 110g, after mixing, place microwave oven (WP700J17-G, Galanz) in, microwave heating backflow 10min under power 800w.Sampling and measuring acid number≤5mgKOH/g, lipid acid triglyceride content are less than 3%, and then the explanation reaction is finished.
Stop microwave heating reaction, will remain Virahol and steam,, reaction product left standstill tell lower floor's dilute sulphuric acid and glycerol liquor after 12 hours, obtain the crude product biofuel in 98 ℃ of gas phase temperatures collection unreacted methanol down.
With containing 10%Na
2CO
3Saturated aqueous common salt in and washing crude product biofuel, neutral crude product biofuel.
Neutral crude product biofuel is carried out continous vacuum distillation, and the cut under vacuum tightness＜5mmHg between 130-190 ℃ of the collection is refined biometric diesel oil.
Claims (4)
1, a kind of microwave method prepares the production method of bio-diesel oil, after it is characterized in that 1000 parts of greases, methyl alcohol 150-200 part, catalyzer 5-30 part being mixed in reaction vessel by mass ratio, it is that the microwave generator reflux of 200-1000W is after 4-60 minute that reactor is placed power, steam unreacted methanol, leave standstill separate after 12 hours the crude product biofuel, the neutralization washing, the continous vacuum distillation gets finished diesel fuel.
2, microwave method according to claim 1 prepares the biofuel method, it is characterized in that described grease comprises the natural animal-plant grease, plant oil leftover or recovery waste oil, or above-mentioned several mixture.
3, microwave method according to claim 1 prepares the biofuel method, it is characterized in that described catalyzer comprises sulfuric acid, hydrochloric acid, phosphoric acid, organic acid and solid acid an acidic catalyst.
4, microwave method according to claim 1 prepares the biofuel method, it is characterized in that described employing continous vacuum distillatory method, is meant the biofuel cut collect 130-190 ℃ under vacuum tightness＜5mmHg between.
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| CNA2006100551673A CN1810931A (en) | 2006-02-22 | 2006-02-22 | Microwave process to prepare biological diesel oil |
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| CNA2006100551673A CN1810931A (en) | 2006-02-22 | 2006-02-22 | Microwave process to prepare biological diesel oil |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100510008C (en) * | 2006-10-23 | 2009-07-08 | 西北农林科技大学 | Method for preparing biodiesel by microwave-assisted Lewis base catalysis |
| CN101126029B (en) * | 2006-08-15 | 2011-08-17 | 广西师范大学 | Technique for preparing biological diesel oil by microwave catalyzing and film separating method |
| CN101407747B (en) * | 2007-10-11 | 2012-02-22 | 中国石油化工股份有限公司 | Microwave modified vegetable oil |
| CN102676242A (en) * | 2012-06-04 | 2012-09-19 | 昆明理工大学 | Method for preparing biodiesel fuel by conducting supercritical methanol microwave pyrolysis and solid acid catalysis on agriculture and forestry waste |
| CN102676308A (en) * | 2012-06-04 | 2012-09-19 | 昆明理工大学 | Method for preparing biodiesel fuel with kitchen waste |
| CN103663853A (en) * | 2012-09-18 | 2014-03-26 | 苏州克莱尔环保科技有限公司 | Food residue collection and transportation treatment management system |
| CN111778075A (en) * | 2020-07-10 | 2020-10-16 | 江苏海森电气科技有限公司 | Environment-friendly biomass diesel oil green production process |
-
2006
- 2006-02-22 CN CNA2006100551673A patent/CN1810931A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101126029B (en) * | 2006-08-15 | 2011-08-17 | 广西师范大学 | Technique for preparing biological diesel oil by microwave catalyzing and film separating method |
| CN100510008C (en) * | 2006-10-23 | 2009-07-08 | 西北农林科技大学 | Method for preparing biodiesel by microwave-assisted Lewis base catalysis |
| CN101407747B (en) * | 2007-10-11 | 2012-02-22 | 中国石油化工股份有限公司 | Microwave modified vegetable oil |
| CN102676242A (en) * | 2012-06-04 | 2012-09-19 | 昆明理工大学 | Method for preparing biodiesel fuel by conducting supercritical methanol microwave pyrolysis and solid acid catalysis on agriculture and forestry waste |
| CN102676308A (en) * | 2012-06-04 | 2012-09-19 | 昆明理工大学 | Method for preparing biodiesel fuel with kitchen waste |
| CN102676308B (en) * | 2012-06-04 | 2014-04-02 | 昆明理工大学 | Method for preparing biodiesel fuel with kitchen waste |
| CN102676242B (en) * | 2012-06-04 | 2015-05-13 | 昆明理工大学 | Method for preparing biodiesel fuel by conducting supercritical methanol microwave pyrolysis and solid acid catalysis on agriculture and forestry waste |
| CN103663853A (en) * | 2012-09-18 | 2014-03-26 | 苏州克莱尔环保科技有限公司 | Food residue collection and transportation treatment management system |
| CN103663853B (en) * | 2012-09-18 | 2017-05-31 | 苏州克莱尔环保科技有限公司 | A kind of Food residue collection and transportation treatment management system |
| CN111778075A (en) * | 2020-07-10 | 2020-10-16 | 江苏海森电气科技有限公司 | Environment-friendly biomass diesel oil green production process |
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