CN102477357A - Method for preparing biodiesel - Google Patents
Method for preparing biodiesel Download PDFInfo
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- CN102477357A CN102477357A CN2010105586393A CN201010558639A CN102477357A CN 102477357 A CN102477357 A CN 102477357A CN 2010105586393 A CN2010105586393 A CN 2010105586393A CN 201010558639 A CN201010558639 A CN 201010558639A CN 102477357 A CN102477357 A CN 102477357A
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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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Abstract
The invention provides a method for preparing biodiesel, which includes the steps: (A) providing oil and monohydric alcohol to a reactor for transesterification, (B) obtaining monohydric alcohol from reacted crude products by means of flash distillation, wherein the products include mixed esters and glycerin or water, (C) separating the mixed esters from the glycerin or the water, (D) returning parts of mixed esters to an inlet of the reactor to be mixed with oil serving as raw materials prior to entering the rector, and (E) respectively distilling residual mixed esters and the glycerin or the water to obtain high-purity aliphatic esters and glycerin. By the aid of the method, the biodiesel with a lower acid value can be obtained in high yield.
Description
Technical field
The present invention relates to a kind of preparation method of bio-diesel oil.
Background technology
Biofuel can be carried out transesterification reaction through grease and single hydroxyl alcohol and made.Transesterification reaction refers to triglyceride level and single hydroxyl alcohol (generally is a low-carbon alcohol, like C
1-C
8Monohydroxy-alcohol) reaction carried out.In its reaction product fatty ester is arranged, promptly biofuel, mono-glycerides, two sweet esters, glycerine, pure and mild triglyceride level are raw material.Its preparation method can be divided into acid catalyzed process, base catalysis method, supercritical methanol technology etc.
CN1412278A discloses a kind of acid catalyzed process, with the method for preparing biological diesel oil from high acid value waste animal and plant oil, it with sulfuric acid as catalyzer; Operation according to raw material dehydration, esterification and transesterify, phase-splitting, decolouring is carried out, and raw material dewaters under the vacuum earlier at 60～100 ℃; Then, under 40～85 ℃, sulfuric acid add-on 2～6%; Carried out esterification and transesterification reaction 6 hours, and told the fatty acid methyl ester phase, with atlapulgite 90～125 ℃ of decolourings get final product biofuel.
It is raw material that CN1473907A adopts the tankage of vegetable oil refining and edible refiltered oil; Catalyzer is inorganic and organic acid is composite forms by sulfuric acid, hydrochloric acid, tosic acid, Witco 1298 Soft Acid, naphthene sulfonic acid etc.; Produce through operations such as acidifying removal of impurities, continous vacuum dehydration, esterification, layering, underpressure distillation, the vacuum tightness-0.08 of continous vacuum dehydration～-0.09Mpa, 60～95 ℃ of temperature; Dewater to water-content below 0.2%; Esterif iotacation step catalyzer add-on 1～3%, 60～80 ℃ of esterification temperatures, 6 hours reaction times.Reaction after product neutralization is earlier removed catalyzer, and then, layering removes and anhydrates, and the after product that anhydrates obtains biofuel through underpressure distillation.
Acid catalysis existing problems speed of response is slow more than base catalysis, in addition, has a large amount of spent acid, waste water generation.
In the natural fats and oils, contain free fatty acids usually, under the more situation of free fatty acids, as directly using the base catalysis method; Use base metal catalysts, can produce fatty acid soaps, base metal catalysts is wanted excessive and the fatty ester layer is separated with glycerin layer to become difficulty like this; For avoiding these problems, DE3444893 discloses a kind of method, at first; Oil plant is carried out preparatory esterification treatment,, free fatty acids and alcohol are carried out esterification with acid catalyst, normal pressure, 50～120 ℃; Add the acid catalyst that the preparatory esterification of neutralization earlier of excessive base metal catalysts is left over then, carry out transesterification reaction again, the requirement of base metal catalysts has bigger increase.Adopt that the pre-esterifying process existing problems are that technical process is long, step is many, facility investment, energy consumption significantly rise, and in addition, needs from reaction process and product, remove acid, basic catalyst, need can produce great amount of wastewater with a large amount of washing water.By-product glycerin concentration is low, reclaims difficulty.
PCT/JP99/0543 discloses the method for a kind of grease and monohydroxy-alcohol prepared in reaction fatty ester; At 270～280 ℃, under 11～12MPa, methyl alcohol is reacted with oil plant; The fatty acid methyl ester production rate is 55～60%, the separation scheme of the not open reaction of this patent back crude product.
Summary of the invention
The present invention provides a kind of process method for preparing biofuel, reaction yield >=95%, and fatty acid monoester purity can reach more than 99.0%, can obtain the lower biofuel of acid number by high yield.
The process method of preparation biofuel provided by the invention may further comprise the steps in order:
(A) grease and monohydroxy-alcohol are offered reactor drum, carry out transesterification reaction;
(B) steam monohydroxy-alcohol from reacted crude product, product be divided into mixed ester mutually with glycerine mutually or water;
(C) with mixed ester and glycerine or aqueous phase separation;
(D) partially mixed ester is back to reactor inlet and mixes entering reactor drum in back with raw oil material;
(E) residue mixed ester and glycerine or water distill respectively, obtain high purity fatty acid ester and glycerine.
Said grease is a tri-glyceride, is mainly derived from animal oil or vegetables oil, for example VT 18, rapeseed oil, Oleum Gossypii semen, Oleum Cocois, palm wet goods; Can be to make with extra care to plant oil, also can be unpurified crude oil or waste oil, and acid number can change in the larger context; For example; Can be 0～200mgKOH/g, preferred 5～140mgKOH/g, more preferably 30～100mgKOH/g.
Said monohydroxy-alcohol is that carbon number is 1～6 monohydric aliphatic alcohols, can be single Fatty Alcohol(C12-C14 and C12-C18), also can be the mixture of one or more Fatty Alcohol(C12-C14 and C12-C18), particular methanol and/or ethanol.
In step (A), the preferred tubular reactor of said reactor drum.Grease and alcohol can offer reactor drum separately, or with offering reactor drum after their pre-mixings, before offering reactor drum; Available preheater also can directly get into reactor drum, like this with the material preheating; Reactor drum had both played the effect of preheater, also played the effect of reactor drum.As adopt preheater, preheating together after can or mixing grease and alcohol difference preheating.
Temperature of reaction is 100～340 ℃, preferred 160～280 ℃, and more preferably 240～270 ℃, pressure 0.1～12Mpa, preferred 0.5～8Mpa, 2～6Mpa most preferably, alcohol/molar equivalent is 3-60: 1, be preferably 4-12: 1.Liquid hourly space velocity is 0.1～20h
-1, preferred 0.5～5h
-1Under these conditions, a kind of material in whole system or grease and the alcohol can be in supercritical state, also can not be in supercritical state.
In step (A), can also optionally add basic cpd and carry out to promote reaction, basic cpd is selected from oxyhydroxide, alcoholate, oxide compound, carbonate, supercarbonate, the C of I A in the periodictable, II A element
12～C
24Soap, preferred sodium, potassium, caesium, magnesium, calcium, the oxyhydroxide of barium, alcoholate, oxide compound, carbonate, supercarbonate, soap are like NaOH, CsOH, Ca (OH)
2, KOH, Na
2O, K
2O, Na
2CO
3, K
2CO
3Deng, more preferably following compound: the oxyhydroxide of sodium, potassium, magnesium, oxide compound, alcoholate or C
12～C
24Soap.The basic cpd consumption can be 0.005～2 heavy % of grease weight, the heavy % of preferred 0.005-0.05.
In step (B); The reacting coarse product that obtains from step (A); Steam monohydroxy-alcohol through flash distillation (flash vaporization point＜150 ℃), obtain mixed ester mutually with glycerine mutually or water, mixed ester generally contains fatty acid methyl ester, mono-glycerides, two sweet esters, triglyceride, lipid acid etc. in mutually.Flash distillation can be carried out under greater than the condition of normal atmosphere, normal pressure or a vacuum.
In step (C), the mixed ester that step (B) is obtained is separated with glycerine.Can separate through settling process, preferably carry out sharp separation through the fibrous bundle separator, separation condition is 20～150 ℃ of temperature, preferred 40～100 ℃, pressure greater than a normal atmosphere or normal pressure all can, air speed 0.1～10h
-1, preferred 1～4h
-1For the serious reacting coarse product of emulsification, reach good minute phase effect, adopt settling process generally need place and spend the night, and adopt the fibrous bundle separator in very short time, to accomplish, thereby significantly improve velocity of separation and production efficiency.
In step (D), partially mixed ester is back to reactor inlet mixes with raw oil material.The mixed ester that returns accounts for 1～80%, preferred 10～60% of whole mixed ester phases (weight) mutually.
In step (E), light phase (mixed ester phase) that step (C) is obtained and glycerine or water distill respectively, preferably through rectification under vacuum tower or thin-film evaporator distillation; Pressure is less than 0.1MPa; Preferably less than 0.04MPa, reflux ratio 0.1～10 in the rectifying tower: 1, preferred 1～6: 1; Tower still or thin film evaporation actuator temperature are 100～300 ℃, preferably less than 280 ℃.
Technology of the present invention can make reaction conversion ratio higher, and the product acid number is lower.Present method has universality to various refining oils and non-refining oil; Both, also, capable of direct processing to the non-refining oil that acid number is very high applicable to the very high non-refining oil of acid number applicable to the refining oil that consists of triglyceride level; Save the numerous and diverse pre-treatment of operation, energy consumption, facility investment are descended.
According to method provided by the invention, reaction yield can reach >=and 95%, fatty acid monoester purity can reach more than 99%, can obtain the lower biofuel of acid number by high yield.
The basic three-waste free discharge of this technology is an eco-friendly friendly process, and is favourable to environment protection.
Embodiment
Further specify the present invention through instance below, but the present invention is not limited to this.
Embodiment 1
Respectively with 600 Grams Per Hours, the speed of 140 Grams Per Hours is provided in the preheater, liquid hourly space velocity 1.2h with the acidifying of acid number 187mgKOH/g oil and methyl alcohol
-1200 ℃ of preheater temperature continuously are provided to the material after the preheating in the tubular reactor, and temperature is 260 ℃ in the reactor drum; Pressure 6Mpa; Outflow reactor material flow 740 Grams Per Hours, reacting coarse product get into flashing tower, remove methyl alcohol and methyl alcohol is reclaimed, reuses at＜150 ℃.Leftover materials are got into the separator that contains fibrous bundle, at 52 ℃ of temperature, liquid hourly space velocity 10h
-1, tell the mixed ester phase, wherein the mixed ester of 50% weight is back to reactor inlet and the laggard reactor drum of acidifying oil raw materials mix mutually, reaction yield 95.1%, circulation back ester phase acid number 2mgKOH/g.Other 50% mixed ester gets into the rectification under vacuum tower mutually, at vacuum tightness 8mmHg, and 280 ℃ of tower stills, under 0.7: 1 the condition of reflux ratio, cat head obtains fatty acid methyl ester, purity＞99.0%.
Comparative example 1
Mixed ester does not return inlet mutually, and other reaction is all identical with embodiment 1 with the separating technology condition, and reaction back mixed ester phase acid number is 7.4mgKOH/g.
Embodiment 2
Respectively with 600 Grams Per Hours, the speed of 170 Grams Per Hours is provided in the preheater, liquid hourly space velocity 1.2h with the acidifying of acid number 187mgKOH/g oil and methyl alcohol
-1200 ℃ of preheater temperature continuously are provided to the material after the preheating in the tubular reactor, and temperature is 250 ℃ in the reactor drum; Pressure 2.5Mpa; Outflow reactor material flow 770 Grams Per Hours, reacting coarse product get into flashing tower, remove methyl alcohol and methyl alcohol is reclaimed, reuses at＜150 ℃.Leftover materials are got into the fibrous bundle separator, at 40 ℃ of temperature, liquid hourly space velocity 5h
-1, tell the mixed ester phase, wherein; 20% weight mixed ester is back to reactor inlet and the laggard reactor drum of acidifying oil raw materials mix mutually, reaction yield 87.7%, circulation back mixed ester phase acid number 3.4mgKOH/g; Other 80% mixed ester gets into thin-film evaporator mutually, at vacuum tightness 7mmHg, under the condition that temperature is 242 ℃; Steam fatty acid methyl ester, purity＞99.0%.
Embodiment 3
Oil plant and the methyl alcohol of acid number 93mgKOH/g are provided in the preheater with the speed of 600 Grams Per Hours and 129 Grams Per Hours respectively, and add the KOH of oil plant weight 0.01%, liquid hourly space velocity 1h
-1, 200 ℃ of preheater temperature continuously are provided to the material after the preheating in the tubular reactor; Temperature is 250 ℃ in the reactor drum; Pressure 7Mpa, the crude product of outflow reactor gets into flashing tower, removes methyl alcohol and methyl alcohol is reclaimed, reuses at＜150 ℃.Leftover materials are got into the fibre bed that contains fibrous bundle, at 20 ℃ of temperature, liquid hourly space velocity 10h
-1Under the condition, tell continuously mixed ester mutually with glycerine mutually, wherein 10% weight mixed ester is back to reactor inlet and the laggard reactor drum of the oily raw materials mix of acidifying mutually; Reaction yield 95%, circulation back mixed ester phase acid number 1.9mgKOH/g, other 90% mixed ester gets into the rectification under vacuum tower mutually; At vacuum tightness 10mmHg, 280 ℃ of tower stills are under 3: 1 the condition of reflux ratio; Cat head steams fatty acid methyl ester, purity>=99.5%.Make the composition that can become fatty acid methyl ester in the raw material almost all be converted to required product.
Embodiment 4
Refined vegetable oil and methyl alcohol are provided in the preheater with the speed of 600 Grams Per Hours and 107 Grams Per Hours respectively, and add the NaOH of oil plant weight 0.01%, liquid hourly space velocity 1h
-1200 ℃ of preheater temperature continuously are provided to the material after the preheating in the tubular reactor, and temperature is 210 ℃ in the reactor drum; Pressure 2.5Mpa; Outflow reactor material flow 700 Grams Per Hours, the crude product of outflow reactor gets into flashing tower, removes methyl alcohol and methyl alcohol is reclaimed, reuses at＜150 ℃.Leftover materials get into the fibre bed that contains fibrous bundle, at 25 ℃ of temperature, liquid hourly space velocity 9h
-1Under the condition, tell continuously mixed ester mutually with glycerine mutually, wherein 15% weight mixed ester is back to reactor inlet and the laggard reactor drum of the oily raw materials mix of acidifying mutually; Reaction yield 95.3%, circulation back mixed ester phase acid number 0.6mgKOH/g, other 85% mixed ester gets into the rectification under vacuum tower mutually; Mixed ester gets into thin-film evaporator mutually; At vacuum tightness 20mmHg, under the condition that temperature is 255 ℃, steam fatty acid methyl ester; Purity＞99.0%, the composition that can become fatty acid methyl ester in the raw material almost all is converted to required product.
Claims (12)
1. one kind prepares method of bio-diesel oil, may further comprise the steps in order:
(A) grease and monohydroxy-alcohol are offered reactor drum, carry out transesterification reaction;
(B) steam monohydroxy-alcohol from reacted crude product, product be divided into mixed ester mutually with glycerine mutually or water;
(C) mutually or aqueous phase separation with mixed ester and glycerine;
(D) partially mixed ester is back to reactor inlet and mixes entering reactor drum in back with raw oil material;
(E) will remain mixed ester and glycerine mutually or water distill respectively, obtain high purity fatty acid ester and glycerine.
2. according to the described method of claim 1, wherein said acid value of oil and fat is 0～210mgKOH/g.
3. according to the described method of claim 1, said monohydroxy-alcohol is that carbon number is 1～6 monohydric aliphatic alcohols.
4. according to the described method of claim 1, said monohydroxy-alcohol is methyl alcohol and/or ethanol.
5. according to the described method of claim 1, in step (A), temperature of reaction is 100～340 ℃, pressure 0.1～12Mpa.
6. according to the described method of claim 1, in step (A), temperature of reaction is 160～280 ℃, pressure 0.5～8Mpa.
7. according to the described method of claim 1, in step (A), temperature of reaction is 240～270 ℃, pressure 2～6Mpa.
8. according to the described method of claim 1, in step (A), alcohol/molar equivalent is 3-60: 1, and liquid hourly space velocity is 0.1～20h
-1
9. according to the described method of claim 1, in step (A), alcohol/molar equivalent is 4-12: 1, and liquid hourly space velocity is 0.5～5h
-1
10. according to the described method of claim 1, in step (A), also add basic cpd, the basic cpd consumption is 0.005～2 heavy % of grease weight.
11. according to the described method of claim 1, in step (D), the mixed ester that returns accounts for 2～80 weight % of whole mixed ester phases mutually.
12. according to the described method of claim 1, in step (D), the mixed ester that returns accounts for 10～60 weight % of whole mixed ester phases mutually.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105586393A CN102477357A (en) | 2010-11-25 | 2010-11-25 | Method for preparing biodiesel |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105586393A CN102477357A (en) | 2010-11-25 | 2010-11-25 | Method for preparing biodiesel |
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| CN102477357A true CN102477357A (en) | 2012-05-30 |
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| CN2010105586393A Pending CN102477357A (en) | 2010-11-25 | 2010-11-25 | Method for preparing biodiesel |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103509583A (en) * | 2012-06-25 | 2014-01-15 | 中国石油化工股份有限公司 | Refining method of biodiesel |
| CN104774694A (en) * | 2015-04-08 | 2015-07-15 | 郑州凯山生化工程有限公司 | Method for synchronously preparing biodiesel and glycerol from high-acid-value vegetable oil |
| CN106479683A (en) * | 2015-08-25 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of apparatus and method preparing biodiesel |
| CN109852459A (en) * | 2019-03-22 | 2019-06-07 | 合肥学院 | A kind of synthetic method containing molybdenum disulfide/spent bleaching clay compound lubricant dispersion system lubricating oil in esters |
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|---|---|---|---|---|
| CN1724613A (en) * | 2005-02-03 | 2006-01-25 | 云南师范大学 | Technology of preparing biological diesel oil from animal and vegetable oil |
| CN1970694A (en) * | 2006-12-07 | 2007-05-30 | 张以光 | Production process of biological diesel oil |
| CN101070480A (en) * | 2006-05-12 | 2007-11-14 | 中国石油化工股份有限公司 | Process for preparing biological diesel oil |
| CN101230288A (en) * | 2007-01-24 | 2008-07-30 | 新疆协力新能源有限责任公司 | Method for producing biological diesel oil |
-
2010
- 2010-11-25 CN CN2010105586393A patent/CN102477357A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724613A (en) * | 2005-02-03 | 2006-01-25 | 云南师范大学 | Technology of preparing biological diesel oil from animal and vegetable oil |
| CN101070480A (en) * | 2006-05-12 | 2007-11-14 | 中国石油化工股份有限公司 | Process for preparing biological diesel oil |
| CN1970694A (en) * | 2006-12-07 | 2007-05-30 | 张以光 | Production process of biological diesel oil |
| CN101230288A (en) * | 2007-01-24 | 2008-07-30 | 新疆协力新能源有限责任公司 | Method for producing biological diesel oil |
Non-Patent Citations (1)
| Title |
|---|
| 苏有勇等: "生物柴油副产物粗甘油精制工艺的研究", 《中国油脂》, no. 12, 20 December 2008 (2008-12-20), pages 58 - 60 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103509583A (en) * | 2012-06-25 | 2014-01-15 | 中国石油化工股份有限公司 | Refining method of biodiesel |
| CN103509583B (en) * | 2012-06-25 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of process for purification of biofuel |
| CN104774694A (en) * | 2015-04-08 | 2015-07-15 | 郑州凯山生化工程有限公司 | Method for synchronously preparing biodiesel and glycerol from high-acid-value vegetable oil |
| CN106479683A (en) * | 2015-08-25 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of apparatus and method preparing biodiesel |
| CN109852459A (en) * | 2019-03-22 | 2019-06-07 | 合肥学院 | A kind of synthetic method containing molybdenum disulfide/spent bleaching clay compound lubricant dispersion system lubricating oil in esters |
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Application publication date: 20120530 |