CN101294096B - Process for producing biological diesel oil - Google Patents
Process for producing biological diesel oil Download PDFInfo
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- CN101294096B CN101294096B CN2008100115743A CN200810011574A CN101294096B CN 101294096 B CN101294096 B CN 101294096B CN 2008100115743 A CN2008100115743 A CN 2008100115743A CN 200810011574 A CN200810011574 A CN 200810011574A CN 101294096 B CN101294096 B CN 101294096B
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- biofuel
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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
Abstract
A preparation method of bio-diesel for solving the problems such as complex post-treatment and environmental pollution existing in the conventional method comprises the following steps: mixing animal and plant oil or waste grease with methanol or ethanol in the presence of nanometer crystal whisker catalyst with an amount of 0.1 to 5% the weight of the raw material oil and an alcohol/oil molar ratio of 4:1 to 10:1, carrying out ultrasonic transesterification reaction, standing the reactive mixture to obtain an upper layer containing the mixture liquid of glycerol and residual methanol or ethanol and a lower layer containing crude product, and pump-filtering the lower crude product layer to obtain the bio-diesel. The preparation method of the invention is efficient, safe and pollution-free and is conducive to industrial production, and meets the requirement of people for the environment. The yield of the bio-diesel prepared by the method is above 97%. The method has the advantages of simple operation, less consumption of catalyst, short time, greatly simplified post-treatment process, no environmental pollution, safe and reliable operation, and low production cost, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of biofuel.
Background technology
Transesterify is used wider aspect oil modification, organic intermediate synthetic.In recent years, along with serious day by day global energy shortage and environmental degradation, the control motor vehicle exhaust, the human physical environment of depending on for existence of protection becomes present human urgent problem.The energy research personnel of countries in the world try to explore to develop alternative fuel and renewable energy source from the angle of environment protection and resource strategy, and biofuel is exactly wherein a kind of, and transesterify then is the important technology of preparation biofuel.The chemical catalysts that adopt in the tradition ester exchange process more, as sodium hydroxide, potassium hydroxide, sodium methylate or the vitriol oil etc., these catalyzer require raw material is carried out pre-treatment, anhydrous as far as possible, no free acid, reaction finish needs neutralization, washing, complex process, environmental pollution is serious, and catalyzer can not reclaim.Advantage such as be easy to separate, can be recycled and nano whisker has reaction conditions gentleness, product, can be eco-friendly catalytic material of new generation.Yet when carrying out the stearic exchange with nano whisker, catalyzer and reactant are heterogeneous in the reaction system, need high-speed stirring, equipment is complicated, and also longer with the reaction time, this makes the advantage of nano-crystal whisker catalysis agent be not fully utilized in actual production.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of biofuel, it is complicated as the aftertreatment that catalyzer brings to solve traditional paddling process and traditional liquid acid, alkali, problems such as contaminate environment, adopt nano whisker and intensified by ultrasonic wave technology, the productive rate height is applicable to suitability for industrialized production, and production cost is low, wide, the easily storage of raw material sources, safety non-pollution.
The technical scheme that the present invention takes is as follows:
Under the condition of nano-crystal whisker catalysis agent, animal-plant oil or waste grease are mixed with methyl alcohol or ethanol, wherein catalyst levels accounts for the 0.1%-5% of stock oil weight, alcohol oil mole proportioning is 4: 1-10: 1, carry out transesterification reaction with ultrasonic wave, ultrasonic frequency is 25KHz-120KHz, and the reaction times is 3min-60min, and temperature is 15 ℃-75 ℃; After reacting completely, reaction mixture sat is two-layer about being divided into, and the upper strata is glycerine and residue methyl alcohol or alcoholic acid mixed solution, and lower floor is a coarse products; To get biofuel behind lower floor's coarse products process vacuum pump suction filtration at last.
The preparation method of above-mentioned biofuel reclaims catalyzer in lower floor's coarse products simultaneously through behind the suction filtration.
The preparation method of above-mentioned biofuel with the distillation of upper strata mixed solution, obtains the glycerin by-products that purity is 80%-95%.
The preparation method of above-mentioned biofuel, distillation is reclaimed simultaneously and is obtained methyl alcohol or ethanol.
The preparation method of above-mentioned biofuel, described nano-crystal whisker catalysis agent is calcium sulfate crystal whiskers, nano-calcium carbonate calcium pyroborate or nano-oxide whisker.
The preparation method of above-mentioned biofuel, described animal-plant oil is rapeseed oil, soybean oil, barbadosnut seed oil, peanut oil, lard or sheep oil.
The preparation method of above-mentioned biofuel, described waste grease is a waste cooking oil.
The preparation method of above-mentioned biofuel recycles in the catalyzer input reaction of recovery.
The preparation method of above-mentioned biofuel recycles in the methyl alcohol of recovery or the reaction of ethanol input.
The preparation method of above-mentioned biofuel, described nanometer vitriol whisker is nanometer calcium sulfate whisker or nanometer magnesium sulfate crystal whisker, and the nano-carbonate whisker is nano-calcium carbonate calcium pyroborate or nano-calcium carbonate magnesium whisker, and the nano-oxide whisker is a nano zinc oxide crystal whisker.
Beneficial effect of the present invention:
Carry out transesterification reaction owing to adopt ultrasonic wave, can greatly improve the speed of inhomogeneous reaction, realize that the homogeneous media between the inhomogeneous reaction thing is mixed the diffusion process of accelerated reaction thing and product, promote the generation of solid cenotype, control particulate size and distribution.Ultrasonic wave has remarkable advantages and distinctive feature comparing with traditional method aspect the mass transfer of strengthening between the heterogeneous interface.Nano whisker and ultrasonic wave are used to prepare biofuel simultaneously, are a kind of preparation methods of very efficient, safety non-pollution, have both met people for environment requirement, also help suitability for industrialized production.Adopt preparation method of the present invention, the productive rate of preparation biofuel can reach more than 97%, and method is simple, uses catalytic amount few, consuming time few; Last handling process is simplified greatly, and whole process does not have any pollution substance and occurs, and does not pollute the environment, and is safe and reliable; The catalyzer and methyl alcohol or the ethanol that reclaim can drop in the reaction and recycles, and production cost is low, is applicable to suitability for industrialized production.
Embodiment
Under the condition of nano-crystal whisker catalysis agent, animal-plant oil or waste grease are mixed with methyl alcohol or ethanol, the nano-crystal whisker catalysis agent is calcium sulfate crystal whiskers or nano-calcium carbonate calcium pyroborate or nano-oxide whisker, be specially: nanometer vitriol whisker is nanometer calcium sulfate whisker or nanometer magnesium sulfate crystal whisker, the nano-carbonate whisker is nano-calcium carbonate calcium pyroborate or nano-calcium carbonate magnesium whisker, and the nano-oxide whisker is a nano zinc oxide crystal whisker.And catalyst levels accounts for the 0.1%-5% of stock oil weight; Described animal-plant oil is one of in rapeseed oil, soybean oil, barbadosnut seed oil, peanut oil, lard, the sheep oil; Described waste grease is a waste cooking oil.Alcohol oil mole proportioning is 4: 1-10: 1, carry out transesterification reaction with ultrasonic wave, and ultrasonic frequency is 15KHz-120KHz, and the reaction times is 3min-60min, and temperature is 15 ℃-75 ℃; After reacting completely,, be divided into two-layer up and down with reaction mixture sat.The upper strata is glycerine and residue methyl alcohol or alcoholic acid mixed solution, and lower floor is a coarse products.With the distillation of upper strata mixed solution, obtain the glycerin by-products that purity is 80%-95%; Reclaim methyl alcohol or ethanol simultaneously, recycle in the methyl alcohol of recovery or the reaction of ethanol input.After lower floor's coarse products is through the vacuum pump suction filtration, reclaim catalyzer simultaneously, recycle in the catalyzer input reaction of recovery.To get biofuel behind lower floor's coarse products process vacuum pump suction filtration at last.
Be used for further describing the present invention with the test example by the following examples:
Embodiment 1
10ml rapeseed oil and 60ml methyl alcohol are put into the Erlenmeyer flask of 100ml, add 0.17g nanometer calcium sulfate whisker, temperature is set to 60 ℃, reacts 20min under the ultrasonic wave of 30KHz.After reaction is finished, reaction solution is poured in the separating funnel, left standstill, be divided into two-layer up and down.
Behind lower floor's coarse products process vacuum pump suction filtration, promptly get biofuel m=9.43g, productive rate can reach 98.07%.Reclaim the catalyzer on the filter paper behind the suction filtration simultaneously; The upper strata mixed solution is carried out air distillation, reclaim methyl alcohol, and to obtain purity be 88% glycerin by-products.
Embodiment 2
10ml soybean oil and 40ml ethanol are put into the Erlenmeyer flask of 100ml, add 0.09g nanometer magnesium sulfate crystal whisker, temperature is set to 65 ℃, reacts 40min under the ultrasonic wave of 30KHz.After reaction is finished, reaction solution is poured in the separating funnel, left standstill, be divided into two-layer up and down.
Behind lower floor's coarse products process vacuum pump suction filtration, promptly get biofuel m=9.21g, productive rate can reach 98.35%.Reclaim the catalyzer on the filter paper behind the suction filtration simultaneously; The upper strata mixed solution is carried out air distillation, reclaim methyl alcohol, and to obtain purity be 89% glycerin by-products.
Embodiment 3
10ml barbadosnut seed oil and 60ml ethanol are put into the Erlenmeyer flask of 100ml, add 0.13g nano-calcium carbonate calcium pyroborate or nano-calcium carbonate magnesium whisker, temperature is set to 55 ℃, reacts 30min under the ultrasonic wave of 25KHz.After reaction is finished, reaction solution is poured in the separating funnel, left standstill, be divided into two-layer up and down.
Behind lower floor's coarse products process vacuum pump suction filtration, promptly get biofuel m=9.06g, productive rate can reach 97.56%.Reclaim the catalyzer on the filter paper behind the suction filtration simultaneously; The upper strata mixed solution is carried out air distillation, reclaim methyl alcohol, and to obtain purity be 86% glycerin by-products.
Embodiment 4
10ml peanut oil and 50ml methyl alcohol are put into the Erlenmeyer flask of 100ml, add the 0.16g nano zinc oxide crystal whisker, temperature is set to 60 ℃, reacts 40min under the ultrasonic wave of 35KHz.After reaction is finished, reaction solution is poured in the separating funnel, left standstill, be divided into two-layer up and down.
Behind lower floor's coarse products process vacuum pump suction filtration, promptly get biofuel m=8.97g, productive rate can reach 97.12%.Reclaim the catalyzer on the filter paper behind the suction filtration simultaneously; The upper strata mixed solution is carried out air distillation, reclaim methyl alcohol, and to obtain purity be 90% glycerin by-products.
Embodiment 5
Get a certain amount of lard, heating is got the Erlenmeyer flask that 10m lard and 50ml methyl alcohol are put into 100ml with its liquefaction, adds 0.10g nanometer calcium sulfate whisker, and temperature is set to 75 ℃, reacts 30min under the ultrasonic wave of 25KHz.After reaction is finished, reaction solution is poured in the separating funnel, left standstill, be divided into two-layer up and down.
Promptly get biofuel m=8.89g with reaching behind lower floor's coarse products process vacuum pump suction filtration, productive rate can reach 97.25%.Reclaim the catalyzer on the filter paper behind the suction filtration simultaneously; The upper strata mixed solution is carried out air distillation, reclaim methyl alcohol, and to obtain purity be 87% glycerin by-products.
Embodiment 6
Get a certain amount of waste cooking oil, filter (filter screen order number is respectively 60 orders, 80 orders, 100 orders) through 3 steps, will filter back waste oil heating, 105 ℃-110 ℃ dewater, till not having bubble to emerge.
10ml waste cooking oil and 70ml ethanol are put into the Erlenmeyer flask of 100ml, add 0.10g nanometer calcium sulfate whisker, temperature is set to 65 ℃, reacts 30min under the ultrasonic wave of 30KHz.After reaction is finished, reaction solution is poured in the separating funnel, left standstill, be divided into two-layer up and down.
Behind lower floor's coarse products process vacuum pump suction filtration, promptly get biofuel m=8.98g, productive rate can reach 97.06%.Reclaim the catalyzer on the filter paper behind the suction filtration simultaneously; The upper strata mixed solution is carried out air distillation, reclaim methyl alcohol, and to obtain purity be 92% glycerin by-products.
Part physicochemical property to the biofuel that obtains after the esterification is tested, and the results are shown in following table 1.
The quality index of table 1 biofuel product
| Sequence number | Quality index | Desired value |
| 1 | Density (g/cm 3，15℃) | 0.879 |
| 2 | Viscosity (mm 2/s，40℃) | 3.87 |
| 3 | Open flash point (℃) | 156 |
| 4 | Sulphur content (%) | 0.0043 |
| 5 | Cetane value | 52 |
| 6 | Ash content (%) | 0.015 |
| 7 | Moisture (%) | 237 |
| 8 | Corrosion usefulness to copper | 1 |
| 9 | Total glycerine (%) | 0.23 |
Claims (10)
1. the preparation method of a biofuel, it is characterized in that: under the condition of nano-crystal whisker catalysis agent, animal-plant oil or waste grease are mixed with methyl alcohol or ethanol, wherein catalyst levels accounts for the 0.1%-5% of stock oil weight, alcohol oil mole proportioning is 4: 1-10: 1, carry out transesterification reaction with ultrasonic wave, and ultrasonic frequency is 25KHz-120KHz, reaction times is 3min-60min, and temperature is 15 ℃-75 ℃; After reacting completely, reaction mixture sat is two-layer about being divided into, and the upper strata is glycerine and residue methyl alcohol or alcoholic acid mixed solution, and lower floor is a coarse products; To get biofuel behind lower floor's coarse products process suction filtration at last.
2. the preparation method of biofuel as claimed in claim 1 is characterized in that: reclaim catalyzer in lower floor's coarse products simultaneously through behind the suction filtration.
3. the preparation method of biofuel as claimed in claim 1 is characterized in that: the upper strata mixed solution is distilled, obtain the glycerin by-products that purity is 80%-95%.
4. the preparation method of biofuel as claimed in claim 3 is characterized in that: distill and reclaim methyl alcohol or ethanol simultaneously.
5. the preparation method of biofuel as claimed in claim 1, it is characterized in that: described nano-crystal whisker catalysis agent is nanometer vitriol whisker, nano-carbonate whisker or nano-oxide whisker.
6. the preparation method of biofuel as claimed in claim 1, it is characterized in that: described animal-plant oil is rapeseed oil, soybean oil, barbadosnut seed oil, peanut oil, lard or sheep oil.
7. the preparation method of biofuel as claimed in claim 1, it is characterized in that: described waste grease is a waste cooking oil.
8. the preparation method of biofuel as claimed in claim 2 is characterized in that: recycle in the catalyzer input reaction of recovery.
9. the preparation method of biofuel as claimed in claim 4 is characterized in that: recycle in the methyl alcohol of recovery or the reaction of ethanol input.
10. the preparation method of biofuel as claimed in claim 5, it is characterized in that: described nanometer vitriol whisker is nanometer calcium sulfate whisker or nanometer magnesium sulfate crystal whisker, the nano-carbonate whisker is nano-calcium carbonate calcium pyroborate or nano-calcium carbonate magnesium whisker, and the nano-oxide whisker is a nano zinc oxide crystal whisker.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100115743A CN101294096B (en) | 2008-05-22 | 2008-05-22 | Process for producing biological diesel oil |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100115743A CN101294096B (en) | 2008-05-22 | 2008-05-22 | Process for producing biological diesel oil |
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| Publication Number | Publication Date |
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| CN101294096A CN101294096A (en) | 2008-10-29 |
| CN101294096B true CN101294096B (en) | 2011-04-20 |
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| CN2008100115743A Expired - Fee Related CN101294096B (en) | 2008-05-22 | 2008-05-22 | Process for producing biological diesel oil |
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| CN111115579B (en) * | 2020-01-12 | 2021-12-17 | 浙江博瑞电子科技有限公司 | Reactive ultrasonic rectification purification method for HCL electronic gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1858160A (en) * | 2006-06-02 | 2006-11-08 | 中国农业科学院油料作物研究所 | Method for preparing biological diesel oil using nano solid acid or alkali catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1858160A (en) * | 2006-06-02 | 2006-11-08 | 中国农业科学院油料作物研究所 | Method for preparing biological diesel oil using nano solid acid or alkali catalyst |
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Granted publication date: 20110420 Termination date: 20120522 |