CN101338216A - Method for preparing biodesel form rapeseed oil niger - Google Patents
Method for preparing biodesel form rapeseed oil niger Download PDFInfo
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- CN101338216A CN101338216A CNA2008101401244A CN200810140124A CN101338216A CN 101338216 A CN101338216 A CN 101338216A CN A2008101401244 A CNA2008101401244 A CN A2008101401244A CN 200810140124 A CN200810140124 A CN 200810140124A CN 101338216 A CN101338216 A CN 101338216A
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- ester
- rapeseed oil
- biodesel
- niger
- oil
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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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
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Abstract
A method for preparing bio-diesel by rapeseed oil soapstock includes the following steps: (1) the rapeseed oil soapstock is acidified by vitriol solution so as to obtain acidified oil; (2) a molecule distilling device is used to separate fat acid and ester substance in the acidified oil so as to respectively obtain light-component fat acid and heavy-component ester substance; (3) the light-component fat acid is added with methanol and catalyst ZrO2-TiO2/SO4<2-> and reflux reacted for 4 to 8 hours at 70 to 95 DEG C so as to obtain fat acid methyl ester, that is, the bio-diesel, in esterification reaction; (4) the heavy-component ester substance is added with methanol and sodium methanol for esterification reaction so as to obtain coarse fat acid methyl ester and is refined in the molecule distilling device so as to obtain the bio-diesel. The present invention adopts the cheap and easily obtained soapstock as the raw material, thus reducing the production cost of the bio-diesel with high production efficiency and environmental-protection production process.
Description
Technical field
The present invention relates to a kind of preparation method of bio-diesel oil, particularly relate to a kind of soap stock and prepare method of bio-diesel oil in conjunction with the solid catalysis technology.
Background technology
Biofuel (Biodiesel) is meant the cleaning alternative fuel that can be used for self-igniton engine with renewable resources productions such as animal-plant oil, and it is that low-carbon alcohol such as raw material and methyl alcohol are carried out the fatty acid monoester that transesterification reaction generates under the effect of catalyzer such as acid, alkali or enzyme.At present, the exhaustion day by day along with petroleum resources in order to alleviate the dependence to oil, reduces oil combustion simultaneously environment is caused serious pollution, and the institutes of a lot of countries in the world and factory begin the production of biofuel is launched comprehensively to research and develop.
The biofuel cost is a big bottleneck of its scale operation of restriction and application, and wherein the cost of raw material accounts for the 60%-70% of biofuel total cost greatly, and therefore research and development select for use resourceful raw material and technology to become research emphasis.And soap stock is the by product in the rapeseed oil alkali-refining deacidification process, and it accounts for 5% of rapeseed oil output, and is good and cheap, aboundresources.Wherein the composition of soap stock mainly contains: neutral oil, phosphatide, soda soap and moisture, go back some protein in addition, and materials such as carbohydrate and pigment, the content of total fatty acids reaches 40%-60%.Domestic comprehensive utilization aspect developing degree at the rapeseed oil processed side product is low at present, is used for soapmaking, lipid acid and acidifying oil more, and deficiency in economic performance also causes the wasting of resources, even contaminate environment, and the comprehensive utilization of therefore developing soap stock has great significance.
The higher grease of acid value adopts mineral acid or organic acid as catalyzer more, carries out esterification under certain conditions with low-carbon alcohol, to obtain biofuel.The carrying out of adopting sulfuric acid, phosphoric acid catalyzed reaction disclosed among the patent CN11775913A.This method is more to the consumption of low-carbon alcohol, and the catalyzed transesterification time is long, and transformation efficiency is not high comparatively speaking yet.Point out in " Preparation of biodiesel with soapstock " literary composition, soap stock obtains croude fatty acids through replenishing saponification-acidolysis-washing-drying-centrifugation method, be the catalyst esterification then with sulfuric acid and then obtain biofuel, this method soda acid consumption is big, three-waste pollution is serious, is not suitable for scale operation, and its strength of acid of the catalyzer of solid super-strong acid type is higher 10,000 times than 100% sulfuric acid, function with reactions such as catalytic esterification, alkylation and hydrolysis, " ZrO
2-TiO
2/ SO
4 2-The research of catalysis Synthesis of ethyl lactate " pointed out that lactic acid and ethanol can react in the literary composition generated ethyl lactate under the effect of this catalyzer, productive rate reaches 46.76%, and the research that replaces sulphuric acid catalysis to carry out esterification with solid acid has become one of the research focus in the synthetic field of catalysis in recent years.In addition, the technology of soap stock production biofuel is disclosed in the patent No. 200610096218.7, at first soap stock and sulfuric acid reaction are obtained acidifying oil, again by twice esterification of sulfuric acid catalysis, sodium methylate catalysis transesterification obtains biofuel then, but the acid value after the esterification often is difficult to reach the condition of follow-up base catalyzed reactions or needs comparatively complicated processing mode to reach the requirement of transesterification, and process is comparatively loaded down with trivial details, and produces corresponding waste water.
Summary of the invention
The objective of the invention is to adopt soap stock cheap and easy to get as raw material, propose a kind of rationally feasible, the higher and production method of bio-diesel oil comparatively environmental protection of efficient.
The present invention adopts high vacuum, molecular distillation technique that separation degree is high that the lipid acid in the soap stock acidifying oil is separated with Ester, utilize the solid catalysis mode to carry out esterification to lipid acid then, Ester adopts the chemical bases catalytic way to carry out transesterification, and the biofuel product is made with extra care.The molecular distillation technique ultimate principle is under high vacuum condition, because distance is less than or equal to the molecule mean motion free path of separated material between the hot face of molecular still and the condensing surface, when molecule evaporates on the liquid film surface, effusion molecule (light constituent) directly arrives the condensing surface condensation through molecular impact each other hardly, heavy constituent flow down along hot face, thereby realize the separation of material.
The present invention is a raw material with the rapeseed oil soap stock, and the concrete operations step is as follows:
(1) soap stock is obtained acidifying oil with the sulphuric acid soln acidifying;
(2) utilize molecular distillation apparatus that the lipid acid in the acidifying oil is separated with Ester, obtain light constituent lipid acid respectively, the heavy constituent Ester;
(3) catalyzer---the sulfate radical complex metal oxides (ZrO of adding methyl alcohol and solid super-strong acid type in the single port flask of light constituent lipid acid is housed
2-TiO
2/ SO
4 2-), under 70-95 ℃ on the magnetic force heating and stirring device back flow reaction 4-8h, it is biofuel that this esterification gets fatty acid methyl ester;
(4) in the heavy constituent Ester, add methyl alcohol and sodium methylate and carry out transesterification and get crude fatty acid methyl ester, then in molecular distillation apparatus to its make with extra care biofuel.In being housed, the single port flask of heavy constituent Ester adds methyl alcohol and sodium methylate, in under 50-65 ℃ on the magnetic force heating and stirring device back flow reaction 0.5-2h, this transesterification gets crude fatty acid methyl ester, then in molecular distillation apparatus to its make with extra care biofuel.
In the said process of the present invention, acidification reaction: with rapeseed oil soap stock and concentration is that 50% sulphuric acid soln carries out acidification reaction, to the pH2-3 reaction terminating, after the layering upper strata grease washing and drying is obtained acidifying oil.
Acid esters separates: utilize molecular distillation apparatus that gained acidifying oil is carried out acid esters and separate, promptly 180 ℃ of distillation temperatures, under this temperature, could make ester and lipid acid high efficiency separation, make fatty acid content in the heavy constituent satisfy the requirement of base catalysis, under working pressure 5-10Pa, feeding temperature 80-100 ℃, rotating speed 150r/min condition the lipid acid in the acidifying oil is separated with Ester, obtain light constituent---lipid acid respectively, heavy constituent---Ester.
The light constituent esterification; In the single port flask, add light constituent lipid acid, add methyl alcohol and catalyzer ZrO then
2-TiO
2/ SO
4 2-, back flow reaction 4-8h on 70-95 ℃ of lower magnetic force heating and stirring device, reaction finishes the centrifugal solid catalyst that goes out, and its solution upper strata is methyl alcohol and water, and lower floor is a biofuel for the oil phase fatty acid methyl ester.This process reaction equation:
The heavy constituent transesterification: add the heavy constituent Ester in the single port flask, add methyl alcohol and sodium methylate then, mixture is in 50-65 ℃ of back flow reaction 0.5-2h on the magnetic force heating and stirring device.Reaction finishes to place separating funnel to leave standstill, and isolates lower floor's glycerine phase, to the upper strata washing and drying, get crude fatty acid methyl ester, in molecular distillation apparatus it is made with extra care then, remove impurity such as pigment and unreacted glyceryl ester, obtaining fatty acid methyl ester is biofuel.This process reaction equation:
The invention has the advantages that:
1, the operational path of a novel soap stock production biofuel has been proposed.Carry out catalyzed reaction respectively by isolated lipid acid of molecular distillation and Ester and generate biofuel, solved acid value and too highly be difficult for adopting separately alkaline catalysts, only adopt esterification in the not high and esterification-transesterification metallization processes of acid catalyst transformation efficiency to be difficult to reach the problem of subsequent reactions requirement.
2, adopt the solid super acidic catalyst Zr O that in methyl esterification of fatty acid, does not use as yet
2-TiO
2/ SO
4 2-Problem such as avoided severe corrosive that the conventional acid catalyzer vitriol oil had, big and product is not easily separated to equipment damage, and centrifugal gained solid catalyst is not treated then can to reuse, can not pollute environment yet, belong to the environmental type catalyzer, and its catalytic esterification effect is better, and the fatty acid esterification rate reaches more than 95%.
3, transesterification gained biofuel has higher quality through after refining, and fatty acid methyl ester reaches more than 97% after by gas chromatography-mass spectrometry analysis in the product.
Description of drawings
Fig. 1 is an artwork of the present invention.
Embodiment
The method of preparing biodesel form rapeseed oil niger is as follows:
(1) acidifying
Taking by weighing 100g rapeseed oil soap stock and place the 500ml there-necked flask, in 85 ℃ of following preheatings, is that 50% sulphuric acid soln adds separating funnel with the concentration for preparing, be added drop-wise in the reaction vessel to the pH value and be 2-3, and timing 1.5h, reaction finishes standing demix, and the upper strata obtains acidifying oil through washing and drying.
(2) acid/ester separates
100g acidifying oil is joined the molecular distillation apparatus (U.S., Pope2# scraped film type molecular distillation instrument) in, 180 ℃ of distillation temperatures, working pressure 7Pa, 80 ℃ of feeding temperatures, obtain the weight component under the rotating speed 150r/min condition, reorganization is divided into lipid material 55g, mainly contains sweet three esters, sweet diester and sweet monoesters, light constituent is 45g, is mainly mixed fatty acid.
(3) esterification
100g light constituent lipid acid is added in the single port flask, and adding alcohol/sour mol ratio then is the methyl alcohol of 6:1, the ZrO of 0.5g
2-TiO
2/ SO
4 2-Catalyzer, and put into stirrer, the continuous backflow device, react 5h on 80 ℃ of lower magnetic force heating and stirring devices, reaction finishes centrifugation and goes out catalyzer, can directly be used as next catalyst for reaction, the solution upper strata is methyl alcohol and water, lower floor is an oil phase, isolates oil phase and is fatty acid methyl ester, and this process esterification yield is 95.48%.
(4) transesterification
10g heavy constituent Ester is added in the single port flask, add the methyl alcohol of 20% (v/w, ml/g oil) then, the sodium methylate of 0.05g, and put into stirrer, the continuous backflow device reacts 1h on 65 ℃ of lower magnetic force heating and stirring devices.Reaction finishes to place separating funnel to leave standstill, and isolates lower floor's glycerine phase, to the upper strata washing and drying, gets crude fatty acid methyl ester, and this process transformation efficiency is 95%.Owing to still contain pigment in the product, therefore impurity such as glyceryl ester are according to step 2) in operational condition (only distillation temperature is changed into 120 ℃, all the other conditions are constant) it is made with extra care, the finished product are by the GC-MS analyzing and testing, and the content of fatty acid methyl ester reaches 97.78%.
Claims (8)
1, a kind of method of preparing biodesel form rapeseed oil niger is characterized in that may further comprise the steps: (1) obtains acidifying oil with the rapeseed oil soap stock with the sulphuric acid soln acidifying; (2) utilize molecular distillation apparatus that the lipid acid in the acidifying oil is separated with Ester, obtain light constituent lipid acid respectively, the heavy constituent Ester; (3) in light constituent lipid acid, add methyl alcohol and catalyzer ZrO
2-TiO
2/ SO
4 2-, in 70-95 ℃ of back flow reaction 4-8h, carrying out esterification, to get fatty acid methyl ester be biofuel; (4) in the heavy constituent Ester, add methyl alcohol and sodium methylate and carry out transesterification and get crude fatty acid methyl ester, then in molecular distillation apparatus to its make with extra care biofuel.
2, according to the method for the described preparing biodesel form rapeseed oil niger of claim 1, it is characterized in that described rapeseed oil soap stock concentration is that 50% sulphuric acid soln carries out acidifying, terminal point is to pH2-3.
3, according to the method for the described preparing biodesel form rapeseed oil niger of claim 1, it is characterized in that described acidifying oil through molecular distillation apparatus 180 ℃ of distillation temperatures, working pressure 7Pa, 80 ℃ of feeding temperatures, separation of fatty acids and Ester under the rotating speed 150r/min condition.
4,, it is characterized in that the 0.5g solid super acidic catalyst Zr O that adds in the described 10g light constituent lipid acid according to the method for the described preparing biodesel form rapeseed oil niger of claim 1
2-TiO
2/ SO
4 2-
5,, it is characterized in that adding methyl alcohol, solid super acid catalyst in the described light constituent lipid acid, at 80 ℃ of following back flow reaction 5h according to the method for the described preparing biodesel form rapeseed oil niger of claim 1.
6, according to the method for the described preparing biodesel form rapeseed oil niger of claim 1, it is characterized in that described heavy constituent transesterification is meant adding heavy constituent Ester in the single port flask, add methyl alcohol and sodium methylate then, mixture is in 50-65 ℃ of back flow reaction 0.5-2h on the magnetic force heating and stirring device.Reaction finishes to place separating funnel to leave standstill, and isolates lower floor's glycerine phase, to the upper strata washing and drying, gets crude fatty acid methyl ester.
7,, it is characterized in that the 0.05g sodium methylate that adds in the described 10g heavy constituent Ester according to the method for the described preparing biodesel form rapeseed oil niger of claim 6.
8, according to the method for the described preparing biodesel form rapeseed oil niger of claim 6, it is characterized in that adding methyl alcohol, sodium methylate in the described heavy constituent Ester, mixture is in 65 ℃ of following back flow reaction 1h.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008101401244A CN101338216A (en) | 2008-08-13 | 2008-08-13 | Method for preparing biodesel form rapeseed oil niger |
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| CNA2008101401244A CN101338216A (en) | 2008-08-13 | 2008-08-13 | Method for preparing biodesel form rapeseed oil niger |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516056A (en) * | 2011-12-08 | 2012-06-27 | 河北欣奇典生物科技有限公司 | Method for reproduction of fatty acid with molecular distillation distillate of unsaturated fatty acid |
| CN104928042A (en) * | 2015-06-10 | 2015-09-23 | 华北科技学院 | Method for preparing biodiesel |
| CN105316114A (en) * | 2014-06-25 | 2016-02-10 | 金广恒环保技术（南京）有限公司 | Recycle utilization system of converting drainage oil into bio-diesel |
| CN105754726A (en) * | 2016-02-17 | 2016-07-13 | 中山大学 | Bio lubricant base oil based on fly maggot oil and preparation method thereof |
-
2008
- 2008-08-13 CN CNA2008101401244A patent/CN101338216A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516056A (en) * | 2011-12-08 | 2012-06-27 | 河北欣奇典生物科技有限公司 | Method for reproduction of fatty acid with molecular distillation distillate of unsaturated fatty acid |
| CN105316114A (en) * | 2014-06-25 | 2016-02-10 | 金广恒环保技术（南京）有限公司 | Recycle utilization system of converting drainage oil into bio-diesel |
| CN104928042A (en) * | 2015-06-10 | 2015-09-23 | 华北科技学院 | Method for preparing biodiesel |
| CN105754726A (en) * | 2016-02-17 | 2016-07-13 | 中山大学 | Bio lubricant base oil based on fly maggot oil and preparation method thereof |
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Open date: 20090107 |