CN101294098B - Method for preparing biological diesel oil by using inversed micelle catalyst - Google Patents
Method for preparing biological diesel oil by using inversed micelle catalyst Download PDFInfo
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- CN101294098B CN101294098B CN200810048076.6A CN200810048076A CN101294098B CN 101294098 B CN101294098 B CN 101294098B CN 200810048076 A CN200810048076 A CN 200810048076A CN 101294098 B CN101294098 B CN 101294098B
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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 using reverse micelle catalyst is specifically suitable for the resource utilization of various waste oil such as tailings of oil plants, cooking oil, waste oil, soapstock, swill oil and so on to directly transform waste oil into the increasingly demanded diesel substitute, i.e. bio-diesel, in a reverse micelle catalysis system. The reverse micelle catalyst is composed of surfactant, water and alcohol at a proper ratio. The method comprises the following steps: adding sulfuric acid in the waste oil, introducing steam, boiling, washing with water, and separating to obtain an acidified oil layer; and adding a reverse micelle catalyst at an amount of 0.5 to 10% that of the oil and alcohol at an amount of 10 to 50% that of the acidified oil slowly, stirring at a speed of 1,500 to 3,000 rpm to form a reverse micelle catalysis reaction system, heating and reflowing for 3 to 10 h, washing with water, standing to obtain crude bio-diesel, and distilling at 200 to 250 DEG C and under 0.001 to 0.0001Mpa to obtain the pure bio-diesel with a total yield above 75%. The method has the advantages of simple and reliable process flow, high production efficiency, low energy consumption and less waste water discharge.
Description
Technical field
The present invention relates to a kind of production method of utilizing inversed micelle catalyst to prepare biofuel.This invention is specially adapted to various waste oils as the recycling of tankage, food and drink oil, sewer oil, soap stock etc., directly waste oil is converted into the substitute of diesel fuel-biofuel of growing tension in reverse micelle catalyst system.
Background technology
Energy shortage and environmental pollution are the significant challenge of facing mankind.The fossil oil that people depend on for existence is faced with exhaustion, the use of fossil oil simultaneously has also caused serious problem of environmental pollution, the for example discharge of a large amount of hydro carbons, aromatics, phenolic compound and sulfurous gas, oxynitride and greenhouse gases, has threatened the mankind's living environment.Find non-oil resource, non-petroleum-based energy production chemical product and fuel, the development renewable energy resources and related industries thereof, the Mode of Circular of establishment Sustainable development, has become the study hotspot in the current energy and environmental area.
Biofuel, comprise in a broad sense the useful biomass alternative fuel that is raw material production.The biofuel of narrow sense claims again fuel methyl esters, and biological methyl esters or esterification grease are to obtain through transesterification by take glycerolipid grease and the low-carbon alcohol that unsaturated oleic acid C18 is main component.Its raw material sources are extensive, and various edible oils and waste cooking oil, the remaining animal tallow in slaughterhouse be some oilseeds and seeds even, all contain abundant glycerin fatty acid ester class, the suitable source as biofuel.
Biofuel is mainly to prepare by the technique of transesterification.So-called transesterification is by methyl alcohol or ethanol, and the glycerine ester group of tri-glyceride is replaced to get off, and forms longer chain fatty acid methyl esters or ethyl ester.Through after transesterification, the macromole of a vegetables oil is divided into three independent fatty acid methyl esters or ethyl ester, thereby has reduced the length of carbochain, has reduced viscosity, has increased mobility, generates useful by product-glycerine simultaneously.Ester-interchange method mainly contains six kinds of methods such as acid-catalyzed transesterification, base-catalyzed transesterification, enzyme law catalysis transesterify, phase transfer system catalytic transesterification and overcritical transesterify.But these techniques are high to ingredient requirement, generally can only be applicable to vegetables oil.
The principal element that present stage is hindered China's biofuel development has two.The one, raw material is nervous, particularly as America and Europe, utilizes vegetable oil production biofuel impossible in China, and the palmitic price pressure of import is also very huge, therefore utilizes waste oil production biofuel by a lasting quite long period.The 2nd, the production technique that was originally applicable to vegetables oil has been not suitable for take the industrial production needs of the biofuel that waste oil is raw material.The complicacy of waste oil raw material guarantees the profit margin of biofuel in the urgent need to new technique.
Summary of the invention
The object of this invention is to provide a kind of production method of utilizing inversed micelle catalyst to prepare biofuel.
The object of the present invention is achieved like this: a kind of preparation method of biofuel,
The acidifying of a, waste oil
The waste oil measuring is squeezed in hydrolyzer, adding concentration is the sulfuric acid of 60-80%, sulphuric acid be waste oil heavy 1%～10%, with steam, turn over and boil 0.5-2 hour, make the complete acidifying of soap stock, after standing, emit lower floor's waste water and middle layer, with the upper part oil reservoir of salt solution washing, the salt water yield adding is a 20-40% for weight of material in pot, opens steam and turns over and boil 5-60 minute, after standing, emit lower floor's waste water, upper strata is acidification oil;
The preparation of b, reverse micelle catalysis emulsion
Tensio-active agent is mixed with water, low-carbon alcohol, and dosage of surfactant is the 0.5-10% of waste oil weight, and alcohol consumption is the 10-50% of acidification oil weight, 1500-3000 rev/min stir after, slowly add acidification oil, form reverse micelle catalysis emulsion;
C, nicellar catalysis reaction
By the reverse micelle catalysis emulsion preparing, under stirring, temperature rising reflux 3-10 hour, emits lower floor's sour water and collects after standing, saturated salt washing 2～3 times, and each amount of water is 30% of croude fatty acids amount, puts down a layer waste water; Repeat aforesaid operations, until the waste water of emitting is neutral, lower floor is the water layer that contains glycerine, and water recycles after treatment, and upper strata is biofuel crude product, sends to dehydration distillation;
D, underpressure distillation
By biofuel crude product, squeeze into distillation tower, under normal pressure, steam except moisture, under 0.0001-0.001MPa, collect 200-250 degree fraction, obtain sterling biofuel.
In the acidification step of waste oil, to turn over the time of boiling be 45 minutes to steam, and temperature is 110 ℃.
The low-carbon alcohol adopting in the preparation steps of reverse micelle catalysis emulsion is methyl alcohol or ethanol.
The production method of utilizing inversed micelle catalyst to prepare biofuel provided by the present invention, by the simple boiling to various waste oils, through technological processs such as reverse micelle, esterification, underpressure distillation, obtain refined biometric diesel oil, technique circuit is simple, reliable, production efficiency is high, and energy consumption is low, and discharge of wastewater is few.
Embodiment
Raw-material selection in the present invention:
Waste oil: from waste cooking oil, vegetable oil mill waste oil etc.
Technological operation of the present invention is as follows:
One, the acidifying of waste oil
The waste oil measuring is squeezed in hydrolyzer, how many according to water content in grease, determine the concentration of sulfuric acid, generally 70%, its add-on is 1%～10% (with grease restatement).Open steam valve, with steam, turn over and boil 1h left and right, make the complete acidifying of soap stock, then standing about 0.5 hour, emit lower floor's waste water and middle layer.With hot salt brine washing, salt solution is that sodium-chlor is water-soluble, and amount of water be 30% left and right of pot interior inventory, opens steam and turns over and boil 10min, about standing 20min, emits lower floor's waste water.The object of washing is the inorganic salt that wash away in lipid layer.Upper strata is acidification oil.
In actual production with in 45 minutes best results of 110 ℃ of boilings.
Two, the preparation of reversed phase micelle system
Now tensio-active agent is mixed with water, low-carbon alcohol, low-carbon alcohol adopts methyl alcohol or ethanol, the 0.5-10% that dosage of surfactant is oil mass.Alcohol consumption is the 10-50% of acid oil mass, 1500-3000 rev/min stir after, slowly add grease, form reverse micelle catalystic converter system.
Three, nicellar catalysis reaction
By the reverse micelle catalysis emulsion preparing, under stirring, temperature rising reflux 8h, then standing 50min, emits lower floor's sour water and collects.Saturated salt washing 2～3 times, each amount of water is 30% left and right of croude fatty acids amount, puts down a layer waste water.Repeat aforesaid operations, until the waste water of emitting is neutral.Lower floor is the water layer that contains glycerine, and water recycles after treatment.Upper strata is crude product biofuel, sends to dehydration distillation.
Four, underpressure distillation
By biofuel crude product, squeeze into distillation tower, under normal pressure, steam except moisture, under 0.001-0.0001Mpa, collect 200-250 degree fraction, obtain sterling biofuel, total recovery is more than 75%, and still implants pitch is reprocessed for highway or as fuel.
Five, the impact on biodiesel production rate such as oleyl alcohol ratio, reaction times, vitriol oil amount, inversed micelle catalyst consumption
Realize and finding, the productive rate of biofuel can be subject to the impact of the factors such as oleyl alcohol ratio, reaction times.According to the conceptual design of table 1, carry out orthogonal test, the results are shown in Table 2.
Table 1 acidification oil preparing biological diesel oil factor and water-glass
Table 2 orthogonal experiments
The degree of affecting of each factor of table 3 on acidification oil hydrolysis reaction
Each factor on the primary and secondary of acidification oil hydrolysis reaction impact is sequentially; Oleyl alcohol is than > reaction times > sulfuric acid amount > catalyst levels; Oleyl alcohol ratio and reaction times have significance effect (in Table 3) to hydrolysis reaction.
Embodiment mono-:
1 ton of sewer oil is added to 70 kilograms, 70% sulfuric acid, pass into steam and turn over and boil 2 hours under 110 degree, washing, separation obtains acid oil reservoir.
Then the cetyl trimethylammonium bromide of 70 kilograms and the 300 kilograms of methyl alcohol that slowly add oil mass, 2500 revs/min of stirrings, form after reverse micelle catalystic converter system reflux 5 hours, washing, standing, obtain biofuel crude product, under 0.008Mpa, collect 200-230 ℃ of fraction, obtain sterling biofuel, total recovery is 82.2%.
Embodiment bis-:
1 ton of Chinese honey locust oil is added to 100 kilograms, 60% sulfuric acid, pass into steam and turn over and boil 1 hour, washing, separation obtains acid oil reservoir.Then the tween 80 of 70 kilograms and polyoxyethylene glycol and the 300 kilograms of methyl alcohol that slowly add oil mass, 1500 revs/min of stirrings, form after reverse micelle catalystic converter system reflux 7 hours, washing, standing, obtain biofuel crude product, at 0.001Mpa, at 200-250 ℃ through distillation, obtain sterling biofuel, total recovery is 85.7%.
Embodiment tri-:
1 Dun You factory tankage are added to 100 kilograms, 70% sulfuric acid, pass into steam and turn over and boil 1 hour under 110 degree, washing, separation obtains acid oil reservoir.Then the Sodium palmityl sulfate of 70 kilograms and the 200 kilograms of methyl alcohol that slowly add oil mass, 3000 revs/min of stirrings, form after reverse micelle catalystic converter system reflux 8 hours, washing, standing, obtain biofuel crude product, at 0.007Mpa, at 200-230 ℃ through distillation, obtain sterling biofuel, total recovery is 78.2%.Embodiment tetra-:
1 ton of hogwash fat is added to 80 kilograms, 80% sulfuric acid, pass into steam and turn over and boil 0.5 hour under 110 degree, washing, separation obtains acid oil reservoir.Then the cetyl trimethylammonium bromide of 50 kilograms and sodium lauryl sulphate and the 400 kilograms of methyl alcohol that slowly add oil mass, 2800 revs/min of stirrings, form after reverse micelle catalystic converter system reflux 10 hours, washing, standing, obtain biofuel crude product, at 0.0001Mpa, at 200-250 ℃ through distillation, obtain sterling biofuel, total recovery is 89.3%.
In the present invention, adopt tensio-active agent, bronsted lowry acids and bases bronsted lowry can be also following material:
Tensio-active agent is cats product, anion surfactant or zwitterionics, as cetyl trimethylammonium bromide, tween 80, polyoxyethylene glycol, ammonium lauryl sulfate, dodecyl sulfate, dodecane sulfonate etc.;
Acid is various mineral acids or organic acid, example hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid or formic acid;
Alkali is various mineral alkalis or organic bases, as sodium hydroxide, calcium hydroxide, potassium hydroxide, sodium methylate, ethamine or quadrol.
Claims (3)
1. a preparation method for biofuel, is characterized in that:
The acidifying of a, waste oil
The waste oil measuring is squeezed in hydrolyzer, adding concentration is the sulfuric acid of 60-80%, sulphuric acid be waste oil heavy 1%～10%, with steam, turn over and boil 0.5-2 hour, make the complete acidifying of soap stock, after standing, emit lower floor's waste water and middle layer, with the upper part oil reservoir of salt solution washing, the salt water yield adding is a 20-40% for weight of material in pot, opens steam and turns over and boil 5-60 minute, after standing, emit lower floor's waste water, upper strata is acidification oil;
The preparation of b, reverse micelle catalysis emulsion
Tensio-active agent is mixed with water, low-carbon alcohol, and dosage of surfactant is the 0.5-10% of waste oil weight, and alcohol consumption is the 10-50% of acidification oil weight, 1500-3000 rev/min stir after, slowly add acidification oil, form reverse micelle catalysis emulsion; Described tensio-active agent is cetyl trimethylammonium bromide, tween 80 and polyoxyethylene glycol, Sodium palmityl sulfate, cetyl trimethylammonium bromide and sodium lauryl sulphate;
C, nicellar catalysis reaction
By the reverse micelle catalysis emulsion preparing, under stirring, temperature rising reflux 3-10 hour, emits lower floor's sour water and collects after standing, saturated salt washing 2～3 times, and each amount of water is 30% of croude fatty acids amount, puts down a layer waste water; Repeat aforesaid operations, until the waste water of emitting is neutral, lower floor is the water layer that contains glycerine, and water recycles after treatment, and upper strata is biofuel crude product, sends to dehydration distillation;
D, underpressure distillation
By biofuel crude product, squeeze into distillation tower, under normal pressure, steam except moisture, under 0.0001-0.001MPa, collect 200-250 ℃ of fraction, obtain sterling biofuel.
2. the preparation method of a kind of biofuel according to claim 1, is characterized in that: in the acidification step of waste oil, to turn over the time of boiling be 45 minutes to steam, and temperature is 110 ℃.
3. the preparation method of a kind of biofuel according to claim 1, is characterized in that: the low-carbon alcohol adopting in the preparation steps of reverse micelle catalysis emulsion is methyl alcohol or ethanol.
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| CN200810048076.6A CN101294098B (en) | 2008-06-16 | 2008-06-16 | Method for preparing biological diesel oil by using inversed micelle catalyst |
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| CN200810048076.6A CN101294098B (en) | 2008-06-16 | 2008-06-16 | Method for preparing biological diesel oil by using inversed micelle catalyst |
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| CN101805644B (en) * | 2010-04-30 | 2012-11-07 | 巩义市绿洲废物处理有限公司 | Method for processing liquid fuel oil by using waste oil |
| CN103571630A (en) * | 2012-07-23 | 2014-02-12 | 陕西德融新能源股份有限公司 | Pre-treatment method used for preparing biodiesel from swill oil and trench oil |
| CN102796619A (en) * | 2012-08-17 | 2012-11-28 | 西安交通大学 | Method for improving deodorizer distillate pretreatment process by supercritical methanol continuous reaction |
| CN103602523A (en) * | 2013-11-05 | 2014-02-26 | 江苏晨洁再生资源科技有限公司 | Pre-treatment technology of waste edible oil |
| CN103911216A (en) * | 2013-12-26 | 2014-07-09 | 新疆德蓝股份有限公司 | Method for preparing biodiesel by biosurfactant |
| CN103992883A (en) * | 2014-05-17 | 2014-08-20 | 浙江工商大学 | Method for preparing crude fish oil with fish oil nigre |
Citations (2)
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| CN1830949A (en) * | 2005-03-09 | 2006-09-13 | 四川古杉油脂化学有限公司 | Method for producing methyl erucate using tailing of rape oil |
| CN1865400A (en) * | 2006-06-16 | 2006-11-22 | 刘火成 | Process for preparing biological diesel oil by using waste oil of plant and animal |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830949A (en) * | 2005-03-09 | 2006-09-13 | 四川古杉油脂化学有限公司 | Method for producing methyl erucate using tailing of rape oil |
| CN1865400A (en) * | 2006-06-16 | 2006-11-22 | 刘火成 | Process for preparing biological diesel oil by using waste oil of plant and animal |
Non-Patent Citations (2)
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