CN104342215A - Method for preparing biodiesel with alcoholysis one-step method - Google Patents

Method for preparing biodiesel with alcoholysis one-step method Download PDF

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Publication number
CN104342215A
CN104342215A CN201310338099.1A CN201310338099A CN104342215A CN 104342215 A CN104342215 A CN 104342215A CN 201310338099 A CN201310338099 A CN 201310338099A CN 104342215 A CN104342215 A CN 104342215A
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Prior art keywords
alcoholysis
reaction
cooh
biofuel
oil
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CN201310338099.1A
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吴如明
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SHANGHAI DINGYUAN PETROLEUM CHEMICAL Co Ltd
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SHANGHAI DINGYUAN PETROLEUM CHEMICAL Co Ltd
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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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  • Fats And Perfumes (AREA)

Abstract

The invention discloses a method for preparing biodiesel with an alcoholysis one-step method. According to the invention, raw material oil is subjected to pretreatment, hydrolysis, gas-phase alcoholysis, flash evaporation, and reduced-pressure distillation, such that the finished product biodiesel is obtained. The reaction conditions of gas-phase alcoholysis are controlled as the following: reaction temperature is 150-200 DEG C; and reaction pressure is 1.0-1.5MPa. The molar amount of methanol is higher than the molar amount of the raw material oil, and excessive methanol can be recycled and processed. The method has the following advantages: raw material oil treatment is simple; high-acid-value and high-water oil can be normally used; when multiple raw materials are used, switching is convenient; catalyst is not used, such that subsequent treatment processes are simplified; and basically no acid, alkali or other sewage is discharged. Methanol produced after the alcoholysis reaction can be recycled after separation, such that environment can be protected, and cost can be saved. Product quality is stable and reliable, and meets national standards.

Description

A kind of method utilizing alcoholysis single stage method to manufacture biofuel
Technical field
The present invention relates to biofuel and manufacture field, be specifically related to a kind of method utilizing alcoholysis single stage method to manufacture biofuel.
Background technology
Biofuel (Biodiesel) refers to the waterplant greases such as oil crops, Wild oil plant and engineering microalgae and animal grease, food garbage wet goods to be the reproducibility diesel oil fuel of the replaced petrifaction diesel that stock oil is made by ester exchange process.Biofuel is the one of biomass energy, and it is the mono alkyl ester of a kind of longer chain fatty acid that the technology such as biomass economy thermo-cracking obtain.Biofuel is the mixture of the high complicated organic composition of oxygen level, and these mixtures organism that mainly number molecular weight is large, almost comprises the oxygen-bearing organic matter of all kinds, as: ether, aldehyde, ketone, phenol, organic acid, alcohol etc.Composite biodiesel is with the byproduct of discarded vegetable and animals oils, used oil and refinery for raw material, then adds catalyzer, through specific equipment and special process synthesis.In recent years, by the impact of crude oil price, environmental protection pressure, Biodiesel is in widespread attention.
The manufacture method of biofuel can be divided into Physical and chemical method two class.Physical comprises direct mixing method and mini-emulsion process, and chemical method comprises cracking process, esterification process and ester-interchange method.
1, direct mixing method
Also known as dilution method.At the biofuel research initial stage, people once imagined and are mixed with diesel oil, ethanol etc. to reduce its viscosity by grease, improved volatility, but often after life-time service occur that vegetables oil is rotten, polymerization and incomplete combustion phenomenon.Have and mixed respectively with Stoddard solvent (48 paraffin and 52 cycloalkanes) with diesel oil, soybean oil with diesel oil, Thistle oil by sunflower seed oil, although viscosity declines to some extent, life-time service still can make intake valve carbon distribution, and adheres on cylinder head and steel loop.
2, mini-emulsion process
Animal-plant oil and solvent etc. being mixed and made into microemulsion is also solve a kind of high method of vegetable and animals oils viscosity.Microemulsion can comprise petrifaction diesel, vegetables oil, alcohol, tensio-active agent and a kind of cetane number improver.Microemulsion is placed not stratified for a long time, and the boiling point of its composition is low, can improve atomization characteristics during flash distillation, is that its calorific value and cetane value are slightly low; But viscosity is still higher than standard.After life-time service microemulsion, oil nozzle and tail gas valve also can produce carbon distribution.Therefore physical mixed method can not do qualified biofuel.
3, cracking process
Thermal cracking products mainly alkane, alkene, diolefine, aromatic hydrocarbon and the carboxylic acid etc. of fatty acid triglycercide.Different types of vegetables oil split product very different.Owing to reacting complicated, so product structure is also complicated, it has been generally acknowledged that reaction is the chain reaction caused by free radical or carbonium ion.Sulphur content, moisture and copper corrosion conformance with standard, but carbon residue, ash content and pour point are then unsatisfactory.
4, esterification process
Esterification process makes lipid acid and methyl alcohol or ethanol under acid catalysis, esterification occurs and makes resin acid first (second) ester.Because lipid acid price is higher, generally need not, and be raw material with the acidification oil produced in course of oil processing, wherein both containing lipid acid, again containing glycerin fatty acid ester.Reaction is generally carried out under the reflux temperature of methyl alcohol, also can carry out in pressurized reactor, the methyl esters generated in reaction process is easy to be separated with sulfuric acid with water, but transform due to triglyceride can not be made simultaneously, when therefore adopting acidification oil as raw material production biofuel, generally also transesterification reaction will be proceeded.
5, transesterify (alcoholysis) method
Ester-interchange method adopts animal-plant oil and alcohol (particularly methyl alcohol) to carry out transesterification reaction at catalyst-free or under acid catalyst, alkaline catalysts or enzyme exist, and generate fatty acid methyl ester and glycerine, wherein base catalysis is the most general.One of main drawback of base catalysis is that it is higher to the purity requirement of reactant, be subject to the impact of moisture and free fatty acids, so, first must carry out vegetables oil pre-treatment, catalyzer drying and methanol dehydration, which limits the use of waste oil, because biodiesel Free Fat acid content is often beyond 2%.The acid catalyzed reaction times is longer than base catalysis, and productive rate is low, thus studies less.
Enzyme catalysis causes increasing concern, and enzyme catalysis is the same with acid catalysis, by free fatty acids and moisture effects few.Enzyme can also generate methyl esters by catalysis Esterification of Free Fat Acid while catalytic transesterification.The shortcoming of enzyme process is that the methyl alcohol of high density can make enzyme deactivation, the price of enzyme more expensive and be difficult to recycle, for these shortcomings, take immobilized candida sp.lipase as catalyzer, in reaction process, methyl alcohol is added in segmentation, and transformation efficiency can reach 95%, and enzyme uses 100 days still non-inactivations.Enzymatic Synthesis of Biodiesel has mild condition, alcohol consumption is few, the advantages such as non-pollutant discharge, but due to low-carbon alcohol toxic to enzyme, cause enzymatic conversion method rate low (lower than 90%), not yet industrialization at present.
Summary of the invention
The object of the invention is in order to provide a kind of simple to operate, productive rate is high and the free of contamination alcoholysis single stage method that utilizes manufactures the method for biofuel.
In order to reach object of the present invention, technical scheme is as follows:
Utilize alcoholysis single stage method to manufacture a method for biofuel, comprise the following steps:
1), be hydrolyzed:
By stock oil clear water or steam hydrolysis, reaction formula is as follows:
R 1COO-CH 2-CH（R 2COO）-CH 2-OOCR 3+3H 2O
=R 1COOH+R 2COOH+R 3COOH+CH 2OHCHOHCH 2OH
Obtain lipid acid and glycerine sugar water after stock oil hydrolysis, lipid acid enters next step operation, and glycerine sugar water directly carries out sewage disposal.
2), gas phase alcoholysis:
By methanol gasifying, the temperature controlling methanol steam is 110 DEG C ~ 180 DEG C, and methanol steam pressure is 1.0MPa ~ 1.5MPa, and is passed into by the methanol steam after gasification in the lipid acid of described step 1) generation, and carry out alcoholysis, reaction formula is as follows:
R 1COOH+CH 3OH=R 1COOCH 3+H 2O
R 2COOH+CH 3OH=R 2COOCH 3+H 2O
R 3COOH+CH 3OH=R 3COOCH 3+H 2O
Temperature and pressure has larger impact to speed of response, and the too low then speed of response of temperature is just very slow.Controlling temperature of reaction is 150 DEG C ~ 200 DEG C, and reaction pressure is 1.0MPa ~ 1.5MPa, and preferably, temperature of reaction is 180 DEG C, and reaction pressure is 1.3MPa, and the reaction times is 3 ~ 6 hours.
Reaction mechanism is: sour dehydroxylation alcohol dehydrogenase, remove-OH in RCOOH, R ' OH removes H, then connects together.Acid has a hydroxyl-COOH, and hydroxyl is connected on carbon, and during participation esterification, hydroxyl and carbon disconnect.Alcohol is then that the hydrogen on hydroxyl is sloughed, and the hydrogen then sloughed and hydroxyl generate water, and then RCO-and-OR ' link together and generate RCOOR '.
The mol ratio controlling methyl alcohol and stock oil is 1.1:1 ~ 1.6:1, preferably 1.3:1.Obtain the thick product of ester compound after alcoholysis, and enter next step operation.Excessive methyl alcohol then recycles, and can give over to and reuse.
3), flash distillation:
By described step 2) in the thick product material of reacted ester class carry out flash distillation, flash distillation is exactly that the saturated liquid of high pressure enters after in the container comparing low pressure because the unexpected reduction of pressure makes these saturated liquids become saturated vapo(u)r under the container pressure of a part and saturated solution.Obtain Primary product and remaining methyl alcohol after flash distillation, remaining methyl alcohol is with above-mentioned steps 2), recycle, can give over to and reuse.Primary product continues next step.
4), underpressure distillation:
The Primary product obtained in described step 3) is carried out underpressure distillation, different according to component boiling point each in Primary product, light constituent, plant asphalt, middle carbon diesel oil and high-carbon diesel oil can be obtained.Middle carbon diesel oil and high-carbon diesel oil depending on amount of carbon atom, the biofuel that middle carbon diesel oil and high-carbon diesel oil namely finally obtain.
The beneficial effect that the present invention has:
Stock oil process is simple, and high acid value, high water grease can normally use, and when adopting plurality of raw materials, switches also very convenient.And do not use catalyzer, simplify subsequent treatment process, the sewage discharges such as basic anacidity, alkali.The methyl alcohol generated after alcoholysis reaction is recoverable after being separated, not only environmental protection but also cost-saving.Stable and reliable product quality, can reach every quality index of BD100 standard completely.
Methyl alcohol under gas phase condition with fatty acid esterification, simultaneously produce alcoholysis to reach the object of transesterify with grease, working pressure is low, process stabilizing is ripe, to equipment without particular requirement, quality product and yield guaranteed, avoid the unfavourable condition of soda acid and the particular requirement of High Temperature High Pressure.By controlling the temperature and pressure of methanol steam, can Reaction time shorten, can ensure again to react completely.
Accompanying drawing explanation
Fig. 1 is the schema of manufacture method of the present invention.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not only confined to embodiment.
As shown in Figure 1, a kind of method utilizing alcoholysis single stage method to manufacture biofuel, step is as follows:
1), be hydrolyzed:
Be hydrolyzed by stock oil clear water, reaction formula is as follows:
R 1COO-CH 2-CH（R 2COO）-CH 2-OOCR 3+3H 2O
=R 1COOH+R 2COOH+R 3COOH+CH 2OHCHOHCH 2OH
Obtain lipid acid and glycerine sugar water after stock oil hydrolysis, lipid acid enters next step operation, and glycerine sugar water directly carries out sewage disposal.
2), gas phase alcoholysis:
By methanol gasifying, controlling the temperature of methanol steam is 110 DEG C, and methanol steam pressure is 1.2MPa, and the methanol steam after gasification is passed into above-mentioned steps 1) in the lipid acid that produces, carry out alcoholysis, reaction formula is as follows:
R 1COOH+CH 3OH=R 1COOCH 3+H 2O
R 2COOH+CH 3OH=R 2COOCH 3+H 2O
R 3COOH+CH 3OH=R 3COOCH 3+H 2O
Controlling temperature of reaction is 180 DEG C, and reaction pressure is 1.3MPa, and the reaction times is 5 hours, and the mol ratio of methyl alcohol and stock oil is 1.3:1.
Obtain the thick product of ester compound after alcoholysis, and enter next step operation.Excessive methyl alcohol then recycles, and can give over to and reuse.The waste water produced after Methanol Recovery etc. then carry out sewage disposal.
3), flash distillation:
By above-mentioned steps 2) in reacted ester class thick product material pass in the lower container of pressure, namely carry out flash distillation.Obtain Primary product and remaining methyl alcohol after flash distillation, remaining methyl alcohol is with above-mentioned steps 2), recycle, can give over to and reuse.Primary product continues next step.
4), underpressure distillation:
By above-mentioned steps 3) in the Primary product that obtains carry out underpressure distillation, different according to component boiling point each in Primary product, light constituent, plant asphalt, middle carbon diesel oil and high-carbon diesel oil can be obtained.Middle carbon diesel oil and high-carbon diesel oil depending on amount of carbon atom, the biofuel that middle carbon diesel oil and high-carbon diesel oil namely finally obtain.
Detect the biofuel that the present embodiment produces, examination criteria is with reference to GB/T1884-2000, GB/T265-1988, GB/T261-2008, GB/T6536-2010, SH/T0694-2000, SH/T0246-1992, SH/T0689-2000, GB/T508-1985.Detected result is as shown in table 1,
As known from Table 1, the biofuel produced by the present invention, indices is conformance with standard all.
The every Data Detection result of table 1
Last it is noted that above embodiment only in order to illustrate the present invention and and unrestricted technical scheme described in the invention, therefore, although this specification sheets with reference to each above-mentioned embodiment to present invention has been detailed description, but, those of ordinary skill in the art is to be understood that, still can modify to the present invention or equivalent replacement, and all do not depart from technical scheme and the improvement thereof of the spirit and scope of the present invention, it all should be encompassed in right of the present invention.

Claims (4)

1. utilize alcoholysis single stage method to manufacture a method for biofuel, it is characterized in that, comprise the following steps:
1), be hydrolyzed:
Be hydrolyzed by stock oil clear water, obtain lipid acid and glycerine sugar water, reaction formula is as follows:
R 1COO-CH 2-CH（R 2COO）-CH 2-OOCR 3+3H 2O
=R 1COOH+R 2COOH+R 3COOH+CH 2OHCHOHCH 2OH
2), gas phase alcoholysis:
By methanol gasifying, the temperature controlling methanol steam is 110 DEG C ~ 180 DEG C, and methanol steam pressure is 1.0MPa ~ 1.5MPa, and is passed into by the methanol steam after gasification in the lipid acid of described step 1) generation, and carry out alcoholysis, reaction formula is as follows:
R 1COOH+CH 3OH=R 1COOCH 3+H 2O
R 2COOH+CH 3OH=R 2COOCH 3+H 2O
R 3COOH+CH 3OH=R 3COOCH 3+H 2O
Controlling temperature of reaction is 150 DEG C ~ 200 DEG C, and reaction pressure is 1.0MPa ~ 1.5MPa, and the reaction times is 3 ~ 6 hours,
3), flash distillation:
By described step 2) in reacted material carry out flash distillation, obtain Primary product and remaining methyl alcohol,
4), underpressure distillation:
The Primary product obtained in described step 3) is carried out underpressure distillation, obtains biofuel.
2. the method utilizing alcoholysis single stage method to manufacture biofuel according to claim 1, it is characterized in that, the mol ratio of described methyl alcohol and described stock oil is 1.1:1 ~ 1.6:1.
3. the method utilizing alcoholysis single stage method to manufacture biofuel according to claim 2, it is characterized in that, the mol ratio of described methyl alcohol and described stock oil is 1.3:1.
4. the alcoholysis single stage method that utilizes according to claim 1 manufactures the method for biofuel, it is characterized in that, described step 2) in control temperature of reaction be 180 DEG C, reaction pressure is 1.3MPa.
CN201310338099.1A 2013-08-05 2013-08-05 Method for preparing biodiesel with alcoholysis one-step method Pending CN104342215A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1827742A (en) * 2006-04-06 2006-09-06 河南省商丘油脂化学厂 Application of selective hydrolysis process in bio-diesel oil production
CN1900224A (en) * 2005-06-15 2007-01-24 中国石油化工股份有限公司 Process for preparing biological diesel oil
CN101195572A (en) * 2006-12-08 2008-06-11 四川古杉油脂化学有限公司 Method for synthesizing fatty acid methyl ester
CN102382716A (en) * 2010-09-03 2012-03-21 陕西渭力生物能源有限公司 Method and equipment for preparing biodiesel with high-acid-value waste oil

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1900224A (en) * 2005-06-15 2007-01-24 中国石油化工股份有限公司 Process for preparing biological diesel oil
CN1827742A (en) * 2006-04-06 2006-09-06 河南省商丘油脂化学厂 Application of selective hydrolysis process in bio-diesel oil production
CN101195572A (en) * 2006-12-08 2008-06-11 四川古杉油脂化学有限公司 Method for synthesizing fatty acid methyl ester
CN102382716A (en) * 2010-09-03 2012-03-21 陕西渭力生物能源有限公司 Method and equipment for preparing biodiesel with high-acid-value waste oil

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张立新: "《传质分离技术》", 31 August 2009, 化学工业出版社 *

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Application publication date: 20150211