CN101113349A - Method for producing biodiesel with convenient post-treatment - Google Patents
Method for producing biodiesel with convenient post-treatment Download PDFInfo
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- CN101113349A CN101113349A CNA2006100294477A CN200610029447A CN101113349A CN 101113349 A CN101113349 A CN 101113349A CN A2006100294477 A CNA2006100294477 A CN A2006100294477A CN 200610029447 A CN200610029447 A CN 200610029447A CN 101113349 A CN101113349 A CN 101113349A
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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 invention relates to the technical field of a production method of the bio-diesel. The production method of the bio-diesel with convenient post-treatment is that: the invention adopts activated solid alkali catalyst to perform transesterification under the circumstance of 4:1-25:1 molar ratio between alcohols, such as methanol, ethanol, butanol, etc. and plants oils; the addition amount of the catalyst is 0.01-3 percent, after reaction, residual methanol are steamed out, the reaction liquid phase is filtered when still being hot, the catalyst is separated, then the filtrate is stood overnight to layer and the products at the upper layer is the bio-diesel.
Description
Technical field
The present invention relates to a kind of production method technical field of biofuel.
Background technology
With vegetables oil, animal oil, waste edible oil etc. is that raw material carries out transesterification reaction with alcohol (methyl alcohol, ethanol, propyl carbinol etc.), and product is biofuel (fatty acid ester), and byproduct is a glycerine.Traditional transesterification reaction adopts homogeneous catalyst, as NaOH, KOH, sodium methylate etc., consumption is about about 1% (oil is heavy), temperature of reaction generally is the boiling point of methyl alcohol, and speed of response is fast, transformation efficiency height (more than 95%), but also exist significant disadvantages simultaneously, product need neutralize washing and bring a large amount of trade effluents, causes environmental pollution, the aftertreatment complexity.Carry out transesterification reaction with overcritical on-catalytic method, the reaction times is short, and transformation efficiency can reach more than 95%, product does not need washing, and aftertreatment is simple, but the molar ratio of methanol to oil height, temperature of reaction and pressure surpass the critical temperature and the emergent pressure of methyl alcohol, and production technique is to the equipment requirements height; Lipase is used for transesterification reaction product separation and convenient post-treatment, and no waste water produces, and temperature of reaction is a room temperature, but the reaction times reach a couple of days, lipase immobilization, activity and price are crucial.In the existing document, Wu Guoying etc. vegetables oil prepares biofuel. Jiangsu Petrochemical Engineering College journal .2002,14 (13): 8～11, it uses liquid base rather than solid alkali, as preparation biofuel such as KOH, NaOH, sodium methylates, exist significant disadvantages, the biofuel product need neutralize washing and bring a large amount of trade effluents, cause environmental pollution, the aftertreatment complexity.
Summary of the invention
The present invention seeks to overcome above-mentioned preparation method's deficiency, a kind of aftertreatment production method of bio-diesel oil very easily is provided.Solid base catalyst is used for transesterification reaction, and it is neutral that product biofuel and byproduct are, the washing that therefore need not neutralize, and last handling process is convenient, and no waste water produces, and catalyzer can repeatedly repeat or disposable use.
The technical solution used in the present invention is:
A kind of production method of biofuel of convenient post-treatment, this method is: the solid base catalyst that adopts activated processing, under 4: 1～25: 1 the condition of mol ratio of alcohol such as methyl alcohol or ethanol, propyl carbinol and vegetables oil, carry out transesterification reaction, the catalyzer add-on is 0.01%～3%, distill out unnecessary methyl alcohol after the reaction, reaction liquid phase filtered while hot is isolated catalyzer, with the filtrate standing stay-over demixion, the upper strata product is biofuel then.
Described solid base catalyst is alkali or alkaline earth metal oxide, loading type alkali metal and oxyhydroxide, and it comprises: alkalimetal oxide Rb20, alkaline earth metal oxide and oxyhydroxide MgO, CaO, SrO, BaO, MgO-NaOH, MgO-Na, Mg-Al composite oxides etc., loading type alkali metal and oxyhydroxide y-Al2O3-NaOH-Na, Y-Al2O3-KOH-K etc.
Alkali or alkaline earth metal oxide only need activation treatment simply promptly can become the catalyzer of this transesterification reaction; Loading type alkali metal and oxyhydroxide are to flood NaOH, KOH etc. on Y-Al2O3 roasting load Na, K etc. make again.
Alkalimetal oxide Rb20, alkaline earth metal oxide and oxyhydroxide MgO, CaO, Sr (), BaO, MgO-NaOH, MgO-Na, Mg-Al composite oxides etc., loading type alkali metal and oxyhydroxide are as the catalyst for ester exchange reaction of vegetables oil with alcohol, it is neutral that product biofuel and byproduct glycerine are, therefore do not need processes such as neutralization washing, thereby can not produce a large amount of trade effluents and cause environmental pollution, the product convenient post-treatment.
The invention has the beneficial effects as follows:
Adopt the solid base catalyst vegetables oil similar to homogeneous catalyst NaOH, KOH, sodium methylate etc., the same main performance index that meets 0 filial piety diesel oil of biofuel that product biofuel and homogeneous catalyst prepare to the transesterification reaction transformation efficiency of methyl alcohol.Great advantage is: solid alkali is as the catalyst for ester exchange reaction of vegetables oil with alcohol, and it is neutral that product biofuel and byproduct glycerine are, and do not need processes such as neutralization washing, thereby can not produce a large amount of trade effluents causes environmental pollution, the product convenient post-treatment.
Embodiment
Be used for further describing the present invention with the test example by the following examples.
Embodiment 1
In the 500mL four-hole boiling flask, according to molar ratio of methanol to oil is to add that the soybean oil 275.1 that drying handled restrains, ethanol 83 restrains at 6: 1, after stirring heating reaches the about 800c of alcohol reflux, adding ready weight is oily heavy 2%BaO 5.5 grams, 3.5 hours afterreactions of reaction finish under 80 ~ C, distill out unnecessary alcohol, reaction liquid phase filtered while hot, isolate catalyzer, then filtrate is poured into standing stay-over demixion in the separating funnel.The upper strata product is a biofuel, and lower floor is the byproduct glycerin layer, and the pH value of byproduct glycerin layer is 7.
Upper strata biofuel product pH value is 7, and product need not aftertreatment, and this has been avoided processes such as pickling that the homogeneous catalysis method need carry out, washing, has prevented the generation of industrial sewage effectively.The fatty-acid ethyl ester content of chromatogram detection of biological diesel oil is 95.1%, and bio-diesel yield is up to 99.5%.The biofuel product meets 0# diesel oil leading indicator.
Embodiment 2
In the 500mL four-hole boiling flask, according to molar ratio of methanol to oil is to add that the Oleum Gossypii semen 281.2 that drying handled restrains, methyl alcohol 57.8 restrains at 6: 1, the weight that adds the cosolvent normal hexane again weighs 15% 42.1 gram for oil, stirring heating reaches methyl alcohol and normal hexane and refluxes after about 70 ℃, adding ready weight is oily heavy 0.8%y-Al2O3-NaOH-Na meter 2.3 grams, keep 1.5 hours afterreactions of back flow reaction to finish, distill out cosolvent 5 normal hexanes and unnecessary methyl alcohol.Reaction liquid phase filtered while hot is isolated catalyzer, then filtrate is poured into standing stay-over demixion in the separating funnel.The upper strata product is a biofuel, and lower floor is the byproduct glycerin layer, and the pH value of byproduct glycerin layer is 7.
Upper strata biofuel product pH value is 7, and product need not aftertreatment, and this has been avoided processes such as pickling that the homogeneous catalysis method need carry out, washing, has prevented the generation of industrial sewage effectively.The fatty acid methyl ester of chromatogram detection of biological diesel oil is 96.5%, and bio-diesel yield is up to 99.5%.The biofuel product meets 0 deaf diesel oil leading indicator.
Embodiment 3
In the 1L autoclave, according to molar ratio of methanol to oil is that to add former press for extracting juice rapeseed oil, propyl carbinol, the catalyzer y-Al2O3-KOH-K that drying handled at 25: 1 be 0.05% of former press for extracting juice rapeseed oil, reaction is 10 minutes under about 280 ℃, 4.7MPa, and reaction distills out unnecessary propyl carbinol after finishing.Reaction liquid phase filtered while hot is isolated catalyzer, then filtrate is poured into standing stay-over demixion in the separating funnel.The upper strata product is a biofuel, and lower floor is the byproduct glycerin layer, and the pH value of byproduct glycerin layer is 7.
Upper strata biofuel product pH value is 7, and product need not aftertreatment, and this has been avoided processes such as pickling that the homogeneous catalysis method need carry out, washing, has prevented the generation of industrial sewage effectively.The fatty acid butyl ester content of chromatogram detection of biological diesel oil is 93.9%, and bio-diesel yield reaches 97.8%.The biofuel product meets 0 filial piety diesel oil leading indicator.
Claims (2)
1. the production method of the biofuel of a convenient post-treatment, this method is: the solid base catalyst that adopts activated processing, under 4: 1～25: 1 the condition of mol ratio of alcohol such as methyl alcohol or ethanol, propyl carbinol and vegetables oil, carry out transesterification reaction, the catalyzer add-on is 0.01%～3%, distill out unnecessary methyl alcohol after the reaction, reaction liquid phase filtered while hot is isolated catalyzer, with the filtrate standing stay-over demixion, the upper strata product is biofuel then.
2. the production method of the biofuel of convenient post-treatment as claimed in claim 1, it is characterized in that: solid base catalyst is alkali or alkaline earth metal oxide, loading type alkali metal and oxyhydroxide, and it comprises: alkalimetal oxide Rb2O, alkaline earth metal oxide and oxyhydroxide MgO, CaO, SrO, BaO, MgO-NaOH, MgO-Na, Mg-Al composite oxides etc., loading type alkali metal and oxyhydroxide y-Al2O3-NaOH-Na, Y-Al2O3-KOH-K.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2006100294477A CN101113349A (en) | 2006-07-27 | 2006-07-27 | Method for producing biodiesel with convenient post-treatment |
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| CNA2006100294477A CN101113349A (en) | 2006-07-27 | 2006-07-27 | Method for producing biodiesel with convenient post-treatment |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851560A (en) * | 2010-05-21 | 2010-10-06 | 中国林业科学研究院林产化学工业研究所 | Method for improving quality of bio-oil through ozonization-esterification |
| WO2012111023A1 (en) | 2011-02-14 | 2012-08-23 | Council Of Scientific & Industrial Research (An Indian Registered Body Incorporated Under The Registration Of Societies Act (Act Xxxi Of 1860) | Improved process for the preparation of fatty acid alkyl esters (biodiesel) from triglyceride oils using eco-friendly solid base catalysts |
| CN108295835A (en) * | 2017-11-22 | 2018-07-20 | 黎明职业大学 | A kind of preparation method and its catalyzed transesterification method of tin oxide |
| CN109503654A (en) * | 2018-12-28 | 2019-03-22 | 山东泰和水处理科技股份有限公司 | The separation method of catalyst in a kind of esterification system |
-
2006
- 2006-07-27 CN CNA2006100294477A patent/CN101113349A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851560A (en) * | 2010-05-21 | 2010-10-06 | 中国林业科学研究院林产化学工业研究所 | Method for improving quality of bio-oil through ozonization-esterification |
| CN101851560B (en) * | 2010-05-21 | 2012-07-18 | 中国林业科学研究院林产化学工业研究所 | Method for improving quality of bio-oil through ozonization-esterification |
| WO2012111023A1 (en) | 2011-02-14 | 2012-08-23 | Council Of Scientific & Industrial Research (An Indian Registered Body Incorporated Under The Registration Of Societies Act (Act Xxxi Of 1860) | Improved process for the preparation of fatty acid alkyl esters (biodiesel) from triglyceride oils using eco-friendly solid base catalysts |
| US9029583B2 (en) | 2011-02-14 | 2015-05-12 | Council Of Scientific & Industrial Research | Process for the preparation of fatty acid alkyl esters (biodiesel) from triglyceride oils using eco-friendly solid base catalysts |
| CN108295835A (en) * | 2017-11-22 | 2018-07-20 | 黎明职业大学 | A kind of preparation method and its catalyzed transesterification method of tin oxide |
| CN109503654A (en) * | 2018-12-28 | 2019-03-22 | 山东泰和水处理科技股份有限公司 | The separation method of catalyst in a kind of esterification system |
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Application publication date: 20080130 |