CN100569912C - A kind of processing method for preparing biofuel - Google Patents
A kind of processing method for preparing biofuel Download PDFInfo
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- CN100569912C CN100569912C CNB2006100807020A CN200610080702A CN100569912C CN 100569912 C CN100569912 C CN 100569912C CN B2006100807020 A CNB2006100807020 A CN B2006100807020A CN 200610080702 A CN200610080702 A CN 200610080702A CN 100569912 C CN100569912 C CN 100569912C
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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
A kind of processing method for preparing biofuel may further comprise the steps in order: (A) with grease and alcohol extracting supply response device, carry out transesterification reaction; (B) steam monohydroxy-alcohol from reacted crude product; (C) mixed ester is separated with glycerine mutually; (D) mixed ester phase and glycerine are obtained high purity fatty acid ester and glycerine by distillation respectively.According to method provided by the invention, reaction conversion ratio can reach 100%, and through the rectifying of rectification under vacuum tower, cat head fatty acid monoester purity can reach more than 99.0%.Also can obtain the higher mono-glycerides cut of content, use as additive.Technology of the present invention has universality to various refining oils and non-refining oil, and basic three-waste free discharge, is an eco-friendly friendly process.
Description
Technical field
The present invention relates to a kind of method by grease and monohydroxy-alcohol prepared in reaction fatty acid ester.
Background technology
Biofuel can be carried out transesterification reaction by grease and methyl alcohol and be made, and it (generally is low-carbon alcohol, as C with another kind of alcohol that transesterification reaction refers to triglyceride level
1-C
8Monohydroxy-alcohol) reaction carried out.In its reaction product fatty acid 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, enzyme catalysis method and supercritical methanol technology.
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, carries out according to the operation of raw material dehydration, esterification and transesterify, phase-splitting, decolouring as catalyzer with sulfuric acid, raw material is earlier at 60-100 ℃, dewater under the vacuum, 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, usually contain free fatty acids, 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 acid 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 pre-esterification treatment, use acid catalyst, normal pressure, 50～120 ℃, free fatty acids and alcohol are carried out esterification, add the acid catalyst that the pre-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 remove acid, basic catalyst from reaction process and product, need can produce a large amount of waste water with a large amount of washing water.By-product glycerin concentration is low, reclaims difficulty.
US5713965A discloses a kind of method, and in the presence of lipase, hexane is made solvent, grease and pure prepared in reaction fatty acid methyl ester, i.e. diesel-fuel.Though adopt the enzyme catalyst reaction conditions to relax, having deficiency is that long reaction time, efficient are lower, needs solvent, enzyme more expensive and in high purity methanol easy inactivation.
PCT/JP99/0543 discloses the method for a kind of grease and monohydroxy-alcohol prepared in reaction fatty acid 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 invention provides a kind of processing method for preparing biofuel, reaction conversion ratio can reach 100%, and fatty acid monoester purity can reach more than 99.0%, can obtain the higher mono-glycerides cut of content simultaneously, uses as additive.
The processing method of preparation biofuel provided by the invention may further comprise the steps in order:
(A) provide reactor with grease and alcohol, carry out transesterification reaction;
(B) steam monohydroxy-alcohol from reacted crude product;
(C) mixed ester is separated with glycerine mutually;
(D) mixed ester phase and glycerine are obtained high purity fatty acid ester and glycerine by distillation respectively.
Said grease is a tri-glyceride, is mainly derived from animal oil or vegetables oil, the refined plant oil of preferred soybean oil, rapeseed oil, Oleum Gossypii semen, Oleum Cocois, palm wet goods, and acid number also can change in the larger context, for example, can be 0-130mgKOH/g.
Said monohydroxy-alcohol is meant that carbon number is 1～6 Fatty Alcohol(C12-C14 and C12-C18), 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 ethanol.
In step (A), the preferred tubular reactor of said reactor.Grease and alcohol can offer reactor separately, or with offering reactor after their pre-mixings, before offering reactor, available preheater also can directly enter reactor, like this with the material preheating, reactor had both played the effect of preheater, also played the effect of reactor.As adopt preheater, preheating together after can or mixing grease and alcohol difference preheating.
Temperature of reactor 200-350 ℃, preferably 260-320 ℃, pressure 6.0-12MPa, best 8-11MPa, alcohol/molar equivalent is 3-60: 1, be preferably 4-12: 1.Liquid hourly space velocity is 0.1～20h
-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.
Temperature raises and to help improving reaction conversion ratio, but temperature is when too high, and reaction product is black, has burnt matter to produce.Therefore, temperature remains on 200-350 ℃, preferably is advisable for 260-320 ℃.
Pressure is high more favourable more to reaction, but pressure is too high, makes the investment of device and process cost raising more, so pressure should be at 6.0-12MPa, preferably 7-11MPa is advisable.
The reaction that generates fatty acid ester is reversible balanced reaction, for improving the transformation efficiency of grease, suitably improve alcohol/molar equivalent, balance is moved to the product direction, but improving alcohol/molar equivalent shortens material residence time in reactor, transformation efficiency descends, and plant energy consumption and process cost are increased, and usage ratio of equipment is descended.So alcohol/molar equivalent remains on 3-60: 1, best 4-12: 1.
Can also optionally add basic cpd and carry out to promote reaction in step (A), 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 as 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 weigh % for the 0.005-2 of grease weight, the heavy % of preferred 0.005-0.05.
In step (B), the reacting coarse product from step (A) obtains by flash distillation, steams monohydroxy-alcohol at＜150 ℃, and flash distillation can be carried out under greater than the condition of normal atmosphere, normal pressure or a vacuum.
In step (C), mixture behind the flash distillation monohydroxy-alcohol that step (B) is obtained carries out mixed ester mutually and the separating of glycerine phase, preferably carry out sharp separation by the fibrous bundle separator, separation condition is temperature 20-150 ℃, 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 finish, thereby significantly improve velocity of separation and production efficiency.
In step (D), light phase (mixed methyl phase) and glycerine that step (C) is obtained distill respectively, preferably by 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 ℃.
Method provided by the invention can also be passed through mono-glycerides and the two sweet esters in further separating step (D) the still raffinate of step (E).If obtain the higher cut of content of monoglyceride, can adopt the rectifying of secondary molecule, the still raffinate that obtains from step (D) enters the molecule rectifier unit, at pressure less than 5Pa, preferably less than 3Pa, be more preferably less than or equal under the 1Pa pressure, 170-220 ℃ of hot face temperature under the preferred 180-200 ℃ of condition, can obtain the higher mono-glycerides cut of content, last running can enter second stage molecule rectifying, at above-mentioned pressure, 200-250 ℃ of hot face temperature under the preferred 220-250 ℃ of condition, steams two sweet esters, these two sweet esters can be used as raw material and are circulated to reactor inlet again, carry out secondary reaction.If do not need to obtain the higher mono-glycerides cut of content, the rectifying of available one-level molecule directly steams mono-glycerides and two sweet esters, and they are circulated to reactor inlet, carries out secondary reaction.And heavy residue can be used as fuel.Molecule rectifying is to reach the purpose of separating a plurality of components also can adopt multistage.
Technology of the present invention has universality to various refining oils and non-refining oil.Even with the very high non-refining oil of acid number is raw material, also capable of direct processing, save the numerous and diverse pre-treatment of operation, energy consumption, facility investment are descended.In addition, contain the higher organic substance of boiling point in the various non-refining oil plants, be difficult for separating with mono-glycerides, two sweet esters, triglyceride level separates, use the inventive method, the higher organic substance of they and boiling point is effectively separated, the composition that can become fatty acid methyl ester in the non-refining oil is utilized.
According to method provided by the invention, reaction conversion ratio can reach 100%, and fatty acid monoester purity can reach more than 99.0%.Also can obtain the higher mono-glycerides cut of by-product content, use as additive.Control according to processing condition of the present invention, glycerine can not reduce.
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 below by example, but the present invention is not limited to this.
" product yield " is defined as follows among the embodiment:
Product yield=(product weight/oil plant weight) * 100%
Buy and execute example 1
With content of triglyceride is 72m%, and the not refined vegetable oil of acid number 52mgKOH/g and methyl alcohol are respectively with 600 Grams Per Hours, and the speed of 152 Grams Per Hours is provided in the preheater, liquid hourly space velocity 1.2h
-1200 ℃ of preheater temperature, continuously be provided to the material after the preheating in the tubular reactor, temperature is 270 ℃ in the reactor, pressure 7MPa, reaction conversion ratio is nearly 100%, outflow reactor material flow 752 Grams Per Hours, reacting coarse product enters flashing tower, removes methyl alcohol and methyl alcohol is reclaimed, reuses at＜150 ℃.Leftover materials are entered the separator that contains fibrous bundle, at 52 ℃ of temperature, liquid hourly space velocity 10h
-1Divide the ester output phase, ester enters the rectification under vacuum tower mutually, at vacuum tightness 8mmHg, and 289 ℃ of tower stills, under 0.7: 1 the condition of reflux ratio, cat head obtains fatty acid methyl ester, purity＞99.0%, and the still raffinate enters the molecule rectifier unit, at residual voltage 5-6Pa, under 190 ℃ of the hot faces, obtain the higher lighting end of content of monoglyceride, will remain high boiler material and enter the rectifying of secondary molecule, at residual voltage 2 ± 1Pa, under 240～250 ℃ of the hot faces, obtain lighting end, this part lighting end can be used as raw material and is circulated to the reactor feed mouth, carry out secondary reaction, product yield can reach 95.3%.
Embodiment 2
With content of triglyceride is 93m%, and the not refined vegetable oil of acid number 9mgKOH/g and methyl alcohol are respectively with 600 Grams Per Hours, and the speed of 200 Grams Per Hours is provided in the preheater, liquid hourly space velocity 1.2h
-1200 ℃ of preheater temperature, continuously be provided to the material after the preheating in the tubular reactor, temperature is 290 ℃ in the reactor, pressure 10MPa, reaction conversion ratio is nearly 100%, outflow reactor material flow 800 Grams Per Hours, reacting coarse product enters flashing tower, removes methyl alcohol and methyl alcohol is reclaimed, reuses at＜150 ℃.Leftover materials are entered the fibrous bundle separator, at 40 ℃ of temperature, liquid hourly space velocity 5h
-1, tell the mixed ester phase, mixed ester enters thin-film evaporator mutually, at vacuum tightness 7mmHg, under the condition that temperature is 242 ℃, steam fatty acid methyl ester, purity＞99.0%, the still raffinate enters the molecule rectifier unit, at residual voltage 2 ± 1Pa, under 240～250 ℃ of the hot faces, topping processing, this part material can be used as raw material and is circulated to the reactor feed mouth, carries out secondary reaction, and product yield can reach 94.6%.
Embodiment 3
With content of triglyceride is 77m%, and the oil plant of acid number 42mgKOH/g and methyl alcohol are provided in the preheater with the speed of 600 Grams Per Hours and 239 Grams Per Hours respectively, and adds the KOH of oil plant weight 0.01%, liquid hourly space velocity 1.2h
-1, 200 ℃ of preheater temperature continuously are provided to the material after the preheating in the tubular reactor, temperature is 260 ℃ in the reactor, pressure 9MPa, reaction conversion ratio 100%, the crude product of outflow reactor enters flashing tower, removes methyl alcohol and methyl alcohol is reclaimed, reuses at＜150 ℃.Leftover materials are entered 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, mixed ester enters 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%, the still raffinate enters the molecule rectifier unit, at residual voltage 4Pa, under 190 ℃ of the hot faces, obtain the higher lighting end of content of monoglyceride, will remain high boiler material and enter the rectifying of secondary molecule, at residual voltage 2 ± 1Pa, under 240～250 ℃ of the hot faces, topping processing, this part material can be used as raw material and is circulated to the reactor feed mouth, carries out secondary reaction.Product yield can reach 96%.The composition that can become fatty acid methyl ester in the raw material almost all is 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 100 Grams Per Hours respectively, and add the NaOH of oil plant weight 0.02%, liquid hourly space velocity 4.6h
-1200 ℃ of preheater temperature, continuously be provided to the material after the preheating in the tubular reactor, temperature is 260 ℃ in the reactor, pressure 7MPa, reaction conversion ratio 100%, outflow reactor material flow 700 Grams Per Hours, the crude product of outflow reactor enters flashing tower, removes methyl alcohol and methyl alcohol is reclaimed, reuses at＜150 ℃.Leftover materials enter the fibre bed that contains fibrous bundle, at 25 ℃ of temperature, liquid hourly space velocity 9h
-1Under the condition, divide continuously ester output mutually with glycerine mutually, mixed ester enters thin-film evaporator mutually, at vacuum tightness 20mmHg, under the condition that temperature is 255 ℃, steam fatty acid methyl ester, purity＞99.0%, the still raffinate is circulated to the reactor feed mouth as raw material, carries out secondary reaction, and the composition that can become fatty acid methyl ester in the raw material almost all is converted to required product.
Claims (15)
1. processing method for preparing biofuel may further comprise the steps in order:
(A) grease and monohydroxy-alcohol are offered tubular reactor, add basic cpd and carry out transesterification reaction, temperature of reaction is 200-350 ℃, and reaction pressure is 7-11MPa, and the consumption of basic cpd is the 0.005-0.05% of grease weight; Wherein basic cpd is selected from alcoholate, carbonate or the C of sodium or potassium
12～C
24In the soap one or more;
(B) from reacted crude product, steam monohydroxy-alcohol;
(C) mixed ester is separated with glycerine mutually;
(D) mixed ester phase and glycerine are obtained high purity fatty acid ester and glycerine by distillation respectively.
2. in accordance with the method for claim 1, it is characterized in that said grease is a tri-glyceride.
3. in accordance with the method for claim 1, it is characterized in that said monohydroxy-alcohol is the Fatty Alcohol(C12-C14 and C12-C18) of carbon number 1～6.
4. in accordance with the method for claim 1, it is characterized in that said monohydroxy-alcohol is methyl alcohol or ethanol.
5. in accordance with the method for claim 1, it is characterized in that temperature of reaction is 260-320 ℃.
6. in accordance with the method for claim 1, it is characterized in that alcohol/molar equivalent is 3-60: 1, liquid hourly space velocity is 0.1～20h
-1
7. in accordance with the method for claim 1, it is characterized in that alcohol/molar equivalent is 4-12: 1.
8. in accordance with the method for claim 1, it is characterized in that, in step (B), flash vaporization point＜150 ℃.
9. in accordance with the method for claim 1, it is characterized in that in step (C), the mixed ester in the mixture that steams monohydroxy-alcohol that step (B) is obtained separates by the fibrous bundle separator with glycerine mutually.
10. in accordance with the method for claim 9, it is characterized in that separation condition is temperature 20-150 ℃, air speed 0.1-10h
-1
11. in accordance with the method for claim 9, it is characterized in that separation condition is temperature 40-100 ℃, air speed 1-4h
-1
12. in accordance with the method for claim 1, it is characterized in that in step (D), mixed methyl phase and glycerine that step (C) is obtained distill by rectification under vacuum tower or thin-film evaporator respectively.
13. in accordance with the method for claim 12, it is characterized in that rectifying tower pressure is less than 0.1MPa, reflux ratio 0.1-10: 1.
14. in accordance with the method for claim 12, it is characterized in that rectifying Tata still or thin film evaporation actuator temperature are 100-300 ℃.
15. in accordance with the method for claim 1, it is characterized in that, also comprise step (E), promptly by mono-glycerides and two sweet esters in the further separating step of molecule rectifying (D) the still raffinate.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5380523B2 (en) * | 2008-04-01 | 2014-01-08 | エスケー ケミカルズ カンパニー リミテッド | Method for producing fatty acid alkyl ester using fatty acid |
| CN102477357A (en) * | 2010-11-25 | 2012-05-30 | 中国石油化工股份有限公司 | Method for preparing biodiesel |
| CN102559393B (en) * | 2010-12-23 | 2015-02-25 | 中国石油化工股份有限公司 | Method for preparing biodiesel with low acid value |
| CN102824881B (en) * | 2011-06-14 | 2015-01-14 | 北京大学 | Preparation method of biodiesel and special reactor for same |
| CN102586032B (en) * | 2012-02-17 | 2013-07-10 | 临沂实能德环保燃料化工有限责任公司 | Production method for biodiesel |
| CN102649920B (en) * | 2012-05-07 | 2013-04-03 | 唐山金利海生物柴油股份有限公司 | Device and method for continuously preparing biodiesel under intermediate-temperature and medium-pressure condition |
| 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 |
| 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 |
| CN105647655B (en) * | 2014-11-26 | 2023-03-10 | 中国石油化工股份有限公司 | Method for preparing 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 |
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