CN100999681A - Process of preparing biodiesel by acid-containing greasy - Google Patents
Process of preparing biodiesel by acid-containing greasy Download PDFInfo
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- CN100999681A CN100999681A CNA2007100781025A CN200710078102A CN100999681A CN 100999681 A CN100999681 A CN 100999681A CN A2007100781025 A CNA2007100781025 A CN A2007100781025A CN 200710078102 A CN200710078102 A CN 200710078102A CN 100999681 A CN100999681 A CN 100999681A
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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 process of preparing biodiesel oil with acid-containing grease as material includes the following steps: the esterification reaction of free fatty acid in animal and vegetable grease material and methanol in the presence of active carbon carried acid catalyst to lower the acid value of the material grease; the further esterification reaction of triglyceride in animal and vegetable grease material and methanol in the presence of alkali catalyst to prepare biodiesel oil; standing after reaction to delaminate into the upper layer of coarse biodiesel oil and the lower layer of glycerin, soap and alkali catalyst mixture; distilling the coarse biodiesel oil to recover methanol, water washing and vacuum distilling to obtain refined biodiesel oil; and distilling the mixture to recover methanol for reuse, water washing and vacuum distilling to obtain feed level glycerin. The present invention has the advantages of cheap and reusable catalyst, environment friendship, low cost, etc.
Description
Technical field
The present invention relates to a kind of is raw material with the acid-containing oil, and the production technique that adopts immobilized an acidic catalyst of gac and two steps of base catalysis to combine prepares method of bio-diesel oil.
Background technology
Fossil fuel is the main energy sources that current mankind is used, but people have to face the exhausted day by day serious situation of the disposable energy, simultaneously because using without restraint of fossil fuel caused serious Greenhouse effect and problem of environmental pollution, therefore, biofuel is taken as the green substitute of fossil fuel, has become the focus that many countries research and develop energetically.
Biofuel is called sunlight fuel again, and it is meant that grease and low-carbon (LC) alcohols material are through esterification, transesterification reaction and the long chain fatty acid ester that obtains has environmental protection, reproducible characteristics.Compare with petrifaction diesel, biofuel can significantly reduce the discharging of pollutents such as greenhouse gases, ring benzene class carcinogens and black smoke.The preparation method of bio-diesel oil mainly is a chemical method at present, comprises acid-catalyzed transesterification method and base-catalyzed transesterification method.Acid-catalyzed transesterification method productive rate height wherein, but speed of reaction is slow, and product separation is difficult and easily produce the three wastes, and the base-catalyzed transesterification method is strict to stock oil, suitability is not strong.
It is the raw material production biofuel that present American-European developed country adopts refined plant oil, edible oil mostly, so production cost is very high, has limited its business-like development greatly.For China, because populous, refined plant oil must at first satisfy edible demand.But annual 500000 tons of the acidifying oil that approximately produce of China, 1,000,000 tons in city waste oil utilizes these waste oil production biofuel that epochmaking meaning is arranged.
Chinese patent CN200610044926.6A discloses a kind of method of vitriol oil two-step catalysis biodiesel synthesis.This method has shortened the reaction times, but owing to all use the vitriol oil as catalyzer in the two-step reaction process, product is difficult to separate in last handling process.And the vitriol oil has the intensive corrosive nature to equipment, exists very big potential safety hazard aborning, therefore is unfavorable for industrialization promotion.
Chinese patent CN1743417A discloses a kind of two-step approach of utilizing solid sulphuric acid iron and sodium hydroxide as the Catalyst Production biofuel, and overall yield has reached 93%.But ferric sulfate is dissolved in pure and mild oil hardly, so the catalyzer contact area is little, needs to adopt than fine powder, has so just brought trouble to product separation, and also reclaiming to glycerine has increased difficulty.
Chinese patent CN200610200554.1A discloses a kind of two-step approach of utilizing solid iron trichloride and sodium hydroxide as the Catalyst Production biofuel, and overall yield reaches more than 85%.Because iron trichloride is soluble in methyl alcohol and ethanol and itself and has color, therefore after finishing, the first step reaction needs product to be cleaned with methyl alcohol or ethanol, otherwise the aftertreatment difficulty, but this certainly will increase cost.
Aftertreatment complicated is one of major obstacle of restriction biofuel suitability for industrialized production in the biodiesel manufacture process.Road how to seek a simple possible, low cost and free of contamination biodiesel manufacture is the target that the various countries scientific research personnel seek assiduously.The present invention adopts the immobilized an acidic catalyst of gac, has remarkable advantages in production technique: granular active carbon has abundant space, high-specific surface area, and therefore catalytic efficiency significantly improves in reaction process; In reaction process, need not to stir, not only simple to operate and energy-conservation; Catalyst separating is simple and recyclable utilizes economy and environmental protection again.
Summary of the invention
The purpose of this invention is to provide a kind of technology that adopts cheap raw material production biofuel, its cost is low, technology is simple.
Technical scheme of the present invention is to be raw material with the acid-containing oil, and the two-step approach production technique that adopts immobilized an acidic catalyst of gac and base catalysis to combine prepares the high-quality biofuel, and its concrete steps are as follows:
1) the immobilized an acidic catalyst of gac is made up of carrier granule shaped activated carbon and loaded article ferric sulfate, and wherein gac content is 59.3%～74.1%, and loaded article content is 25.9%～40.7%;
2) in reactor, add a certain amount of stock oil, the immobilized an acidic catalyst of gac and methyl alcohol, the immobilized an acidic catalyst of gac that adds is pressed the loaded article metering and is 2%～3% of stock oil weight, the methyl alcohol that adds and the mol ratio of stock oil were 10: 1～15: 1,85～95 ℃ of following heating reflux reactions 4～7 hours;
3) after reaction finished, air distillation was reclaimed methyl alcohol and while hot reactant is carried out suction filtration, and filter residue is the immobilized an acidic catalyst of gac, can reuse;
4) with the filtrate standing demix that obtains, and separate and remove a spot of glycerine of sub-cloud, supernatant liquid is preheated to 40～70 ℃, add potassium hydroxide and methyl alcohol, the potassium hydroxide consumption is 1% of a stock oil weight, the methyl alcohol that adds and the mol ratio of stock oil were 3: 1～9: 1,40～70 ℃ of following stirring reactions 0.5～2 hour;
5) after reaction finishes, standing over night, the upper strata is biofuel and methyl alcohol, lower floor is glycerine, potassium hydroxide, soap and methyl alcohol, supernatant liquid is washed to washing lotion with 65～95 ℃ of hot water is neutral after methyl alcohol is reclaimed in the normal pressure distillation, can obtain the refining biodiesel product through underpressure distillation again, lower floor can obtain feed grade glycerine through washing and underpressure distillation again after methyl alcohol is reclaimed in the normal pressure distillation.
Embodiment
Embodiment one:
In the 250ml there-necked flask, add the refining rapeseed oil of 45.26g, 9.56g oleic acid (acid number is 34.71), 27ml methyl alcohol, 4.23g the immobilized an acidic catalyst of gac (ferric sulfate content is 25.9%) is heated to 95 ℃ with water-bath, makes methanol eddy, and need not to stir, react after 4 hours, the reaction solution acid number reduces to 1.31, and esterification yied is 96.22%.Suction filtration was removed catalyzer after methyl alcohol was reclaimed in air distillation, and the filtrate standing demix is removed a small amount of glycerine that sub-cloud is produced by partial glycerol three ester generation transesterification reactions.Supernatant liquid is joined in the 250ml there-necked flask, be preheated to 65 ℃, add 0.55g potassium hydroxide, 17ml methyl alcohol, behind the stirring reaction 1 hour, standing over night, reaction solution is divided into two-layer, the upper strata is biofuel and methyl alcohol, lower floor is methyl alcohol, glycerine, soap and potassium hydroxide, and upper oil phase after methyl alcohol is reclaimed in the normal pressure distillation, is neutral with 65 ℃ hot washes to washing lotion, can obtain the refining biodiesel product through underpressure distillation again, the reaction total yield is 93.06%.
Embodiment two:
In the 250ml there-necked flask, add the refining rapeseed oil of 31.79g, 5.73g oleic acid (acid number is 30.35), 19ml methyl alcohol, 1.85g the immobilized an acidic catalyst of gac (ferric sulfate content is 40.7%) is heated to 95 ℃ with water-bath, makes methanol eddy, and need not to stir, react after 4 hours, the reaction solution acid number reduces to 1.75, and esterification yied is 94.23%.Suction filtration was removed catalyzer after methyl alcohol was reclaimed in air distillation, and the filtrate standing demix is removed a small amount of glycerine that sub-cloud is produced by partial glycerol three ester generation transesterification reactions.Supernatant liquid is joined in the 250ml there-necked flask, be preheated to 65 ℃, add 0.38g potassium hydroxide, 17ml methyl alcohol, behind the stirring reaction 0.5 hour, standing over night, reaction solution is divided into two-layer, the upper strata is biofuel and methyl alcohol, lower floor is methyl alcohol, glycerine, soap and potassium hydroxide, and upper oil phase after methyl alcohol is reclaimed in the normal pressure distillation, is neutral with 75 ℃ hot washes to washing lotion, can obtain the refining biodiesel product through underpressure distillation again, the reaction total yield is 89.93%.
Embodiment three:
In the 250ml there-necked flask, add the refining rapeseed oil of 46.07g, 9.74g oleic acid (acid number is 34.31), 27ml methyl alcohol, 6.48g the immobilized an acidic catalyst of gac (ferric sulfate content is 25.9%) is heated to 85 ℃ with water-bath, makes methanol eddy, and need not to stir, react after 6 hours, the reaction solution acid number reduces to 1.57, and esterification yied is 95.42%.Suction filtration was removed catalyzer after methyl alcohol was reclaimed in air distillation, and the filtrate standing demix is removed a small amount of glycerine that sub-cloud is produced by partial glycerol three ester generation transesterification reactions.Supernatant liquid is joined in the 250ml there-necked flask, be preheated to 65 ℃, add 0.55g potassium hydroxide, 17ml methyl alcohol, behind the stirring reaction 1 hour, standing over night, reaction solution is divided into two-layer, the upper strata is biofuel and methyl alcohol, lower floor is methyl alcohol, glycerine, soap and potassium hydroxide, and upper oil phase after methyl alcohol is reclaimed in the normal pressure distillation, is neutral with 85 ℃ hot washes to washing lotion, can obtain the refining biodiesel product through underpressure distillation again, the reaction total yield is 83.35%.
Embodiment four:
In the 250ml there-necked flask, add the useless rapeseed oil (acid number is 38.92) of 52.89g high acid value, 40ml methyl alcohol, 4.04g the immobilized an acidic catalyst of gac (ferric sulfate content is 25.9%), be heated to 85 ℃ with water-bath, make methanol eddy, and need not to stir, react after 5 hours, the reaction solution acid number reduces to 1.82, and esterification yied is 95.32%.Suction filtration was removed catalyzer after methyl alcohol was reclaimed in air distillation, and the filtrate standing demix is removed a small amount of glycerine that sub-cloud is produced by partial glycerol three ester generation transesterification reactions.Supernatant liquid is joined in the 250ml there-necked flask, be preheated to 65 ℃, add 0.53g potassium hydroxide, 16ml methyl alcohol, behind the stirring reaction 1 hour, standing over night, reaction solution is divided into two-layer, the upper strata is biofuel and methyl alcohol, lower floor is methyl alcohol, glycerine, soap and potassium hydroxide, and upper oil phase after methyl alcohol is reclaimed in the normal pressure distillation, is neutral with 95 ℃ hot washes to washing lotion, can obtain the refining biodiesel product through underpressure distillation again, the reaction total yield is 89.50%.
Embodiment five:
In the 250ml there-necked flask, add 50.87g sewer oil (acid number is 38.52), 25ml methyl alcohol, 4.03g through the immobilized an acidic catalyst of used gac (the original content of ferric sulfate is 25.9%) once, and do not do any processing, be heated to 95 ℃, make methanol eddy with water-bath, and need not to stir, react after 7 hours, the reaction solution acid number reduces to 1.98, and esterification yied is 94.86%.Suction filtration was removed catalyzer after methyl alcohol was reclaimed in air distillation, and the filtrate standing demix is removed a small amount of glycerine that sub-cloud is produced by partial glycerol three ester generation transesterification reactions.Supernatant liquid is joined in the 250ml there-necked flask, be preheated to 70 ℃, add 0.51g potassium hydroxide, 16ml methyl alcohol, behind the stirring reaction 1 hour, standing over night, reaction solution is divided into two-layer, the upper strata is biofuel and methyl alcohol, lower floor is methyl alcohol, glycerine, soap and potassium hydroxide, and upper oil phase after methyl alcohol is reclaimed in the normal pressure distillation, is neutral with 95 ℃ hot washes to washing lotion, can obtain the refining biodiesel product through underpressure distillation again, the reaction total yield is 84.72%.
Claims (2)
1, a kind of method of preparing biodiesel by acid-containing greasy is characterized in that step is as follows:
1) the immobilized an acidic catalyst of gac is made up of carrier granule shaped activated carbon and loaded article ferric sulfate, and wherein gac content is 59.3%～74.1%, and loaded article content is 25.9%～40.7%;
2) in reactor, add a certain amount of stock oil, the immobilized an acidic catalyst of gac and methyl alcohol, the immobilized an acidic catalyst of gac that adds is pressed the loaded article metering and is 2%～3% of stock oil weight, the methyl alcohol that adds and the mol ratio of stock oil were 10: 1～15: 1,85～95 ℃ of following heating reflux reactions 4～7 hours;
3) after reaction finished, air distillation was reclaimed methyl alcohol and while hot reactant is carried out suction filtration, and filter residue is the immobilized an acidic catalyst of gac, can reuse;
4) with the filtrate standing demix that obtains, and separate and remove a spot of glycerine of sub-cloud, supernatant liquid is preheated to 40～70 ℃, add potassium hydroxide and methyl alcohol, the potassium hydroxide consumption is 1% of a stock oil weight, the methyl alcohol that adds and the mol ratio of stock oil were 3: 1～9: 1,40～70 ℃ of following stirring reactions 0.5～2 hour;
5) after reaction finishes, standing over night, the upper strata is biofuel and methyl alcohol, lower floor is glycerine, potassium hydroxide, soap and methyl alcohol, supernatant liquid is washed to washing lotion with 65～95 ℃ of hot water is neutral after methyl alcohol is reclaimed in the normal pressure distillation, can obtain the refining biodiesel product through underpressure distillation again, lower floor can obtain feed grade glycerine through washing and underpressure distillation again after methyl alcohol is reclaimed in the normal pressure distillation.
2, method according to claim 1 is characterized in that step 2) described in stock oil can be high acid value animal and vegetable oil or sewer oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100781025A CN100427569C (en) | 2007-01-05 | 2007-01-05 | Process of preparing biodiesel by acid-containing greasy |
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| CNB2007100781025A CN100427569C (en) | 2007-01-05 | 2007-01-05 | Process of preparing biodiesel by acid-containing greasy |
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| CN100999681A true CN100999681A (en) | 2007-07-18 |
| CN100427569C CN100427569C (en) | 2008-10-22 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011109945A1 (en) * | 2010-03-08 | 2011-09-15 | 中山大学 | Biodiesel and preparation method thereof |
| CN101338214B (en) * | 2008-08-08 | 2012-05-09 | 贵州大学 | Method for preparing biodiesel using acidizing oil as raw material under normal pressure |
| CN102517155A (en) * | 2011-12-14 | 2012-06-27 | 清华大学 | Method for combined production of cracked biodiesel and activated carbon |
| CN103396883A (en) * | 2013-06-27 | 2013-11-20 | 黄耀江 | Method for preparing biodiesel by utilizing oil plant |
| CN105670789A (en) * | 2015-12-31 | 2016-06-15 | 界首市强梦生物科技有限公司 | Apparatus and method for separating animal oil components from illegally recycled waste cooking oil |
| CN110055136A (en) * | 2019-05-09 | 2019-07-26 | 河南农业大学 | A method of with non-strong dead livestock and poultry preparing biodiesel from lipid |
| CN113462422A (en) * | 2021-07-09 | 2021-10-01 | 中国林业科学研究院林产化学工业研究所 | One-step preparation process of biodiesel by bifunctional catalysis of high-acid-value grease and continuous device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6712867B1 (en) * | 1999-08-18 | 2004-03-30 | Biox Corporation | Process for production of fatty acid methyl esters from fatty acid triglycerides |
| CN1303187C (en) * | 2005-10-08 | 2007-03-07 | 暨南大学 | Method for synthesizing biodiesel utilizing swill water oil |
| CN100386407C (en) * | 2006-06-12 | 2008-05-07 | 大连理工大学 | Process of producing biological diesel by high acid waste oil |
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2007
- 2007-01-05 CN CNB2007100781025A patent/CN100427569C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338214B (en) * | 2008-08-08 | 2012-05-09 | 贵州大学 | Method for preparing biodiesel using acidizing oil as raw material under normal pressure |
| WO2011109945A1 (en) * | 2010-03-08 | 2011-09-15 | 中山大学 | Biodiesel and preparation method thereof |
| US20120144732A1 (en) * | 2010-03-08 | 2012-06-14 | Sun Yat-Sen University | Biodiesel and Preparation Method Thereof |
| CN102517155A (en) * | 2011-12-14 | 2012-06-27 | 清华大学 | Method for combined production of cracked biodiesel and activated carbon |
| CN103396883A (en) * | 2013-06-27 | 2013-11-20 | 黄耀江 | Method for preparing biodiesel by utilizing oil plant |
| CN103396883B (en) * | 2013-06-27 | 2015-03-04 | 黄耀江 | Method for preparing biodiesel by utilizing oil plant |
| CN105670789A (en) * | 2015-12-31 | 2016-06-15 | 界首市强梦生物科技有限公司 | Apparatus and method for separating animal oil components from illegally recycled waste cooking oil |
| CN110055136A (en) * | 2019-05-09 | 2019-07-26 | 河南农业大学 | A method of with non-strong dead livestock and poultry preparing biodiesel from lipid |
| CN113462422A (en) * | 2021-07-09 | 2021-10-01 | 中国林业科学研究院林产化学工业研究所 | One-step preparation process of biodiesel by bifunctional catalysis of high-acid-value grease and continuous device |
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| CN100427569C (en) | 2008-10-22 |
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Granted publication date: 20081022 Termination date: 20120105 |