CN102260596B - Method for preparing biodiesel by two-step process - Google Patents
Method for preparing biodiesel by two-step process Download PDFInfo
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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
The invention relates to a method for preparing biodiesel by a two-step process, which comprises the following steps: (1) supplying grease and fatty alcohol to a reactor, reacting at 190-300 DEG C under the pressure of 3-11 MPa, and separating fatty alcohol and glycerol from the crude product after reaction to obtain the crude ester phase; and (2) supplying the crude ester phase and fatty alcohol to the reactor, adding ethers, carbonates and/or carboxylates containing methoxy or oxyethyl functional groups, reacting at 190-300 DEG C under the pressure of 3-11 MPa, and collecting the biodiesel from the mixture after reaction. The invention has the advantages of simple technique, strong adaptability of raw materials, high biodiesel purity, simple after-treatment, clean production process and high concentration of the byproduct glycerol, and the grease utilization ratio approaches to 100%.
Description
Technical field
The present invention relates to the biomass energy technology field, particularly a kind of take animal-plant oil as raw material, with the technique of Fatty Alcohol(C12-C14 and C12-C18) reaction production biofuel.
Background technology
Along with people to the growing interest of environmental problem and rising steadily of oil price, biofuel as green regenerative energy sources, becomes one of important alternative fuel of petrifaction diesel.Ester-interchange method is most widely used method for producing biodiesel, and namely grease and lower alcohol (such as methyl alcohol or ethanol) obtain the lipid acid low-carbon-ester by transesterification reaction.Because the reactive behavior of methyl alcohol is high, low price is so most typical biofuel is fatty acid methyl ester.
Grease, namely triglyceride carries out transesterification reaction with lower alcohol, is converted into successively difatty acid glyceryl ester, monoglyceride, obtains at last lipid acid low-carbon-ester and glycerine.Because the transesterification reaction of glyceryl ester and lower alcohol is reversible reaction, the productive rate of lipid acid low-carbon-ester is subjected to thermodynamics equilibrium limit, along with the raising of grease transformation efficiency, realizes that the cost of unit conversion rate constantly increases.Yet, biofuel as the motor spirit use, concentration to unconverted grease and each intermediate product has strict restriction, for example, European standard EN14214 requires: monoglyceride, difatty acid glyceryl ester and the mass concentration of triglyceride in product should be respectively less than 0.8%, 0.2% and 0.2%.Therefore how preparing the lipid acid low-carbon-ester of enough purity, obtain standard compliant biofuel product, is the difficult problem of those skilled in the art's facing.
CN1141993C discloses the method for Acrawax under the super critical condition, and the method is not used catalyzer, requires lower to glyceride stock, in the reaction times short (only needing several minutes), aftertreatment is simple, work simplification, simultaneously, by-product glycerin concentration is high, almost non-pollution discharge.But this technological reaction condition is harsh, pressure large (10-25MPa), and temperature of reaction high (350-400 ℃) so that this technology investment increases, is restricted in application.
The technique that CN101070480A describes is that grease boils off alcohol with pure through after the transesterify, separation of glycerin, and then rectification under vacuum is purified, and obtains concentration and reaches 99.0% lipid acid low-carbon-ester.Because the boiling point of lipid acid low-carbon-ester is higher, about 250-400 ℃, higher to the rectifying conditional request.
US 5,908,946 disclose the preparation technology of lipid acid low-carbon-ester, this technique is used the zinc-aluminium composite oxide catalysts with spinel structure, under higher temperature (200-250 ℃) and pressure (less than 10MPa), adopt two sections fixed bed reactions, the grease transformation efficiency is near 100%.Compare with the liquid caustic soda Catalytic processes, although temperature of reaction and pressure are higher, need not acid-base neutralisation in the aftertreatment, the purifying products step is significantly simplified, and the methyl esters productive rate is near theoretical value, and simultaneously, qualities of glycerin concentration surpasses 98%.But this technique is Shortcomings still.At first be that catalyst preparation process is complicated, energy consumption is higher, needs simultaneously to process waste water, waste gas etc.And in biodiesel production method, the filling of catalyzer, inactivation and discarded all can bring new problem.
Summary of the invention
The present invention is directed to the problem that exists in the present production of biodiesel, provide a kind of two step method to prepare the novel process of biofuel.Utilize this technique, the animal-plant oil transformation efficiency can reach 100%, and fatty acid ester content obtains the by-product glycerin of high density simultaneously greater than 96% in the biofuel.
Two step method provided by the invention prepares the method for biofuel, comprising:
1) grease and Fatty Alcohol(C12-C14 and C12-C18) are offered reactor, under the pressure of 190-300 ℃ and 3-11MPa, react, from reacted crude product, tell Fatty Alcohol(C12-C14 and C12-C18) and glycerine, obtain thick ester phase;
2) thick ester phase and Fatty Alcohol(C12-C14 and C12-C18) are offered reactor, add and be selected from ether, carbonic ether and/or the carboxylic acid ester compound that contains methoxy or ethoxy functional group, under 190-300 ℃ and 3-11MPa pressure, react collection of biological diesel oil from reacted mixture.
Step 1) in, described grease comprises various animal-plant oil and little algae oil, and its main component is triglyceride.For product is met the requirements of the standard, preferably reduce as far as possible the content of unsaponifiables and free fatty acids in the grease, make the content of unsaponifiables less than 1%, the acid number of grease is less than 40mgKOH/g, preferably less than 28mgKOH/g.
Described Fatty Alcohol(C12-C14 and C12-C18) is selected from the single hydroxyl alcohol of C1-C12, the single hydroxyl alcohol of preferred C1-C5, such as methyl alcohol, ethanol etc., can use mixed Fatty Alcohol(C12-C14 and C12-C18), for example carbonatoms is the single hydroxyl alcohol of 1-5 and the alcohol mixture of hexanol, octanol, 2-Ethylhexyl Alcohol and lauryl alcohol, and the mass concentration of particular methanol is no less than 80%.
Described reactor can be reactor or tubular reactor.Reaction conditions is: temperature is 190-300 ℃, and pressure is 3-11MPa, and molar ratio of methanol to oil is 4-60: 1, and reaction solution volume air speed is 0.1-15h
-1Optimum condition is: temperature is 200-280 ℃, and pressure is 4-8MPa, and molar ratio of methanol to oil is 6-40: 1, and reaction solution volume air speed is 0.4-10h
-1Under such condition, reaction mixture is in supercritical state, can not be supercritical state also.
Can also can add a small amount of alkaline catalysts not with alkaline catalysts in the reaction, consumption is the 0-0.1% of oil quality, is preferably the 0.002-0.08% of oil quality.Alkaline catalysts can be selected from oxyhydroxide, alcoholate, oxide compound, carbonate, supercarbonate, the C10-C24 soap of I A in the periodic table of elements, II A element.In preferred sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium oleate, potassium oleate, sodium stearate, the potassium stearate etc. one or more.
For step 1) reacted mixture, can be less than 160 ℃, Distillation recovery Fatty Alcohol(C12-C14 and C12-C18) under normal pressure or the reduced pressure; Being lower than under 100 ℃ the condition, by fibre bed, or leave standstill, or centrifugation glycerine, obtain thick ester phase.
Step 2) in, thick ester phase and Fatty Alcohol(C12-C14 and C12-C18) are offered reactor, add auxiliary agent, described auxiliary agent is selected from ether, carbonic ether and/or the carboxylic acid ester compound that contains methoxy or ethoxy functional group, preferred molecular weight is less than 150, such as in dme, methyl ethyl ether, diethyl ether, methyl tertiary butyl ether, methylcarbonate, diethyl carbonate, methyl acetate, the ethyl acetate etc. one or more.Auxiliary dosage is 0.5～15% of oil quality, is preferably 1～10% of oil quality.
Reaction conditions is: temperature is 190-300 ℃, and pressure is 3-11MPa, and molar ratio of methanol to oil is 4-60: 1, and reaction solution volume air speed is 0.1-15h
-1Optimum condition is: temperature is 200-280 ℃, and pressure is 4-8MPa, and molar ratio of methanol to oil is 6-40: 1, and reaction solution volume air speed is 0.4-10h
-1Under such condition, reaction mixture is in supercritical state, can not be supercritical state also.
For step 2) reacted mixture can be less than 160 ℃, Distillation recovery Fatty Alcohol(C12-C14 and C12-C18) under normal pressure or the reduced pressure; Or also being lower than under 100 ℃ the condition, by fibre bed, or leave standstill, or centrifugation glycerine, obtain biofuel; For the micro-glycerine that dissolves in the biofuel, can also can pass through the sorbent materials such as resin, silica gel and atlapulgite through washing, biofuel is further purified.
The present invention has obvious advantage:
1, technique is simple, and adaptability to raw material is stronger, and speed of reaction is fast, and the Lipid use rate can be near 100%, and biofuel purity is high, and aftertreatment is simple, the production process cleaning;
2, by-product glycerin concentration is high.
Embodiment
Embodiment 1:
Fatty acid methyl ester and glycerine are produced in soybean oil and methyl alcohol reaction, and processing condition, material input and output situation are as follows:
With methyl alcohol and soybean oil blend, send in the tubular reactor and react, wherein, molar ratio of methanol to oil is 12: 1, and potassium stearate is 0.08% of soybean oil quality, and reaction solution volume air speed is 0.4h
-1, temperature of reaction is 280 ℃, pressure is 8MPa.Behind the first set reaction, the grease transformation efficiency surpasses 96%.Reaction mixture directly reduces pressure to normal pressure, and methyl alcohol is reclaimed in flash distillation, then reduces temperature to 50 ℃, leaves standstill 4h, separation of glycerin.With the thick ester phase after the separation of glycerin, with the methyl alcohol that replenishes, send in the tubular reactor and react, wherein, molar ratio of methanol to oil is 12: 1, and methylcarbonate and potassium stearate are respectively 1% and 0.08% of soybean oil quality, temperature is that 280 ℃, pressure are the 8MPa reaction, and air speed is 0.4h
-1Methyl alcohol is reclaimed in reacted mixture air distillation, and the mass concentration of fatty acid methyl ester is about 99% in the biofuel.Wherein the mass concentration of monoglyceride, difatty acid glyceryl ester, triglyceride and free glycerol is about respectively: 0.65%, 0.08%, 0.06% and 0.006%.Through two-step reaction, the Lipid use rate is about 100%.Collect the by-product glycerin that twice standing separation obtains, behind the Distillation recovery methyl alcohol, mass concentration is about 95%.
Embodiment 2:
Oleum Gossypii semen and the reaction of mixed Fatty Alcohol(C12-C14 and C12-C18), production biofuel and glycerine, processing condition, material input and output situation are as follows:
Mixed Fatty Alcohol(C12-C14 and C12-C18) is the methanol solution that contains 20wt% ethanol.With Oleum Gossypii semen and fatty alcohol mixture, send in the tubular reactor and react, wherein, molar ratio of methanol to oil is 40: 1, and KOH is 0.05% of Oleum Gossypii semen quality, and temperature of reaction is 250 ℃, and pressure is 6MPa, reaction solution volume air speed is 10h
-1Behind the first set reaction, the grease transformation efficiency is about 98%.Reacted mixture is depressurized to a normal atmosphere, and Fatty Alcohol(C12-C14 and C12-C18) is reclaimed in flash distillation, then reduces temperature to 60 ℃, at 4000rpm centrifugation glycerine.With the thick ester phase after the separation of glycerin and the Fatty Alcohol(C12-C14 and C12-C18) that replenishes, send in the tubular reactor and react, wherein, molar ratio of methanol to oil is 40: 1, and ethyl acetate and KOH are respectively 5% and 0.05% of Oleum Gossypii semen quality, and temperature is 250 ℃, and pressure is 6MPa, air speed is 10h
-1Fatty Alcohol(C12-C14 and C12-C18) is reclaimed in reacted mixture air distillation, and the mass concentration that directly obtains monoglyceride, difatty acid glyceryl ester, triglyceride and free glycerol after the separation of glycerin is respectively: 0.3%, 0.02%, 0.01% and 0.017% biofuel product.Further purify through the BD10Dry polymeric adsorbent, the mass concentration of free glycerol can be reduced to 0.002% again.Collect two times centrifugal and separate the by-product glycerin that obtains, concentration surpasses 93%.
Embodiment 3:
Fatty acid methyl ester and glycerine are produced in rapeseed oil and methyl alcohol reaction, and processing condition, material input and output situation are as follows:
With rapeseed oil and methyl alcohol, pressed molar ratio of methanol to oil 15: 1, send in the tubular reactor and react, wherein, NaOH is 0.03% of rapeseed oil quality, reaction solution volume air speed is 2h
-1, temperature of reactor is 200 ℃, pressure is 4MPa.Behind the first set reaction, grease transformation efficiency about 85%.Reaction mixture reduces pressure, and atmospheric flashing reclaims methyl alcohol, then reduces temperature to 50 ℃, leaves standstill 4h, separation of glycerin.With the thick ester phase after the separation of glycerin, with the methyl alcohol that replenishes, send in the tubular reactor and react, wherein, molar ratio of methanol to oil is 30: 1, and dme and NaOH are respectively 10% and 0.03% of rapeseed oil quality, temperature of reaction is that 200 ℃, pressure are the 4MPa reaction, and air speed is 2h
-1Reacted mixture, methyl alcohol is reclaimed in air distillation, then at 50 ℃, leaves standstill the 4h separation of glycerin.The mass concentration that obtains monoglyceride, difatty acid glyceryl ester, triglyceride and free glycerol after the separation of glycerin is about respectively: 0.74%, 0.11%, 0.07% and 0.026%, and the mass concentration of fatty acid methyl ester is near 99% biofuel product.Further purify through the BD10Dry polymeric adsorbent, the mass concentration of free glycerol is about 0.007%.Collect the by-product glycerin that twice standing separation obtains, mass concentration surpasses 96%.
Embodiment 4:
Oleum Gossypii semen and the reaction of mixed Fatty Alcohol(C12-C14 and C12-C18), production biofuel and glycerine, processing condition, material input and output situation are as follows:
Mixed Fatty Alcohol(C12-C14 and C12-C18) is the methanol solution that contains 20wt% ethanol.With Oleum Gossypii semen and fatty alcohol mixture, send in the tubular reactor and react, wherein, molar ratio of methanol to oil is 40: 1, and KOH is 0.05% of Oleum Gossypii semen quality, and temperature of reaction is 250 ℃, and pressure is 6MPa, reaction solution volume air speed is 10h
-1Behind the first set reaction, the grease transformation efficiency is about 98%.Reacted mixture is depressurized to a normal atmosphere, and Fatty Alcohol(C12-C14 and C12-C18) is reclaimed in flash distillation, then reduces temperature to 60 ℃, at 4000rpm centrifugation glycerine.With the thick ester phase after the separation of glycerin and the Fatty Alcohol(C12-C14 and C12-C18) that replenishes, send in the tubular reactor and react, wherein, molar ratio of methanol to oil is 40: 1, and diethyl carbonate and KOH are respectively 10% and 0.05% of Oleum Gossypii semen quality, and temperature is 250 ℃, and pressure is 6MPa, air speed is 10h
-1Fatty Alcohol(C12-C14 and C12-C18) is reclaimed in reacted mixture air distillation, and the mass concentration that directly obtains monoglyceride, difatty acid glyceryl ester, triglyceride and free glycerol is respectively: 0.2%, 0.02%, 0.01% and 0.006% biofuel product.Collect two times centrifugal and separate the by-product glycerin that obtains, concentration surpasses 93%.
Embodiment 5:
Fatty acid methyl ester and glycerine are produced in rapeseed oil and methyl alcohol reaction, and processing condition, material input and output situation are as follows:
With rapeseed oil and methyl alcohol, pressed molar ratio of methanol to oil 15: 1, send in the tubular reactor and react, wherein, NaOH is 0.03% of rapeseed oil quality, reaction solution volume air speed is 2h
-1, temperature of reactor is 230 ℃, pressure is 4MPa.Behind the first set reaction, grease transformation efficiency about 97%.Reaction mixture reduces pressure, and atmospheric flashing reclaims methyl alcohol, then reduces temperature to 50 ℃, leaves standstill 4h, separation of glycerin.With the thick ester phase after the separation of glycerin, with the methyl alcohol that replenishes, send in the tubular reactor and react, wherein, molar ratio of methanol to oil is 30: 1, and methylcarbonate and NaOH are respectively 10% and 0.03% of rapeseed oil quality, temperature of reaction is that 230 ℃, pressure are the 4MPa reaction, and air speed is 2h
-1Reacted mixture, methyl alcohol is reclaimed in air distillation, the mass concentration that directly obtains monoglyceride, difatty acid glyceryl ester, triglyceride and free glycerol is respectively: 0.54%, 0.07%, 0.04% and 0.009%, and the mass concentration of fatty acid methyl ester is near 99% biofuel product.Collect the by-product glycerin that twice standing separation obtains, mass concentration surpasses 96%.
Claims (10)
1. two step method prepares the method for biofuel, comprising:
1) grease and Fatty Alcohol(C12-C14 and C12-C18) are offered reactor, react under the pressure of 190-300 ℃ and 3-11MPa, tell Fatty Alcohol(C12-C14 and C12-C18) and glycerine from reacted crude product, obtain thick ester phase, wherein, molar ratio of methanol to oil is 4-60: 1, and reaction solution volume air speed is 0.1-15h
-1
2) thick ester phase and Fatty Alcohol(C12-C14 and C12-C18) are offered reactor, add the auxiliary agent that is selected from the ether, carbonic ether and/or the carboxylic acid ester compound that contain methoxy or ethoxy functional group, under 190-300 ℃ and 3-11MPa pressure, react, collection of biological diesel oil from reacted mixture, wherein, molar ratio of methanol to oil is 4-60: 1, and reaction solution volume air speed is 0.1-15h
-1, described auxiliary agent molecular weight is less than 150, and auxiliary dosage is 0.5～15% of oil quality.
2. in accordance with the method for claim 1, the mass concentration of methyl alcohol is no less than 80% in the described Fatty Alcohol(C12-C14 and C12-C18).
3. in accordance with the method for claim 1, step 1) reaction conditions comprises temperature 200-280 ℃, pressure 4-8MPa, and molar ratio of methanol to oil 6-40: 1, reaction solution volume air speed 0.4-10h
-1
4. in accordance with the method for claim 1, the alkaline catalysts consumption is the 0-0.1% of oil quality in the reaction.
5. in accordance with the method for claim 1, the alkaline catalysts consumption is the 0.002-0.08% of oil quality in the reaction.
6. in accordance with the method for claim 1, alkaline catalysts is selected from I A, the oxyhydroxide of II A element, alcoholate, oxide compound, carbonate, supercarbonate, C10-C24 soap.
7. in accordance with the method for claim 1, alkaline catalysts is selected from one or more in sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium oleate, potassium oleate, sodium stearate, the potassium stearate.
8. in accordance with the method for claim 1, described auxiliary agent is selected from one or more in dme, methyl ethyl ether, diethyl ether, methyl tertiary butyl ether, methylcarbonate, diethyl carbonate, methyl acetate, the ethyl acetate.
9. in accordance with the method for claim 1, auxiliary dosage is 1～10% of oil quality.
10. in accordance with the method for claim 1, step 2) in, reaction conditions comprises: temperature 200-280 ℃, and pressure 4-8MPa, molar ratio of methanol to oil 6-40: 1, reaction solution volume air speed 0.4-10h
-1
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Families Citing this family (5)
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| CN102533442B (en) * | 2011-12-31 | 2014-03-12 | 临沂实能德环保燃料化工有限责任公司 | Method for purifying biodiesel |
| CN103374462B (en) * | 2012-04-26 | 2014-10-29 | 中国石油化工股份有限公司 | Preparation method of biodiesel |
| CN104212498A (en) * | 2013-05-31 | 2014-12-17 | 北京艾比蒂生物科技有限公司 | Method for preparing biodiesel by using ansu apricot oil |
| CN104004596B (en) * | 2014-06-18 | 2016-01-20 | 刘火成 | A kind of method utilizing high acid value propagation waste oil production biofuel |
| CN105695111A (en) * | 2016-03-10 | 2016-06-22 | 中国人民解放军第二炮兵工程大学 | Ethyl ester type biological diesel prepared from prickly ash seeds and preparation method of biological diesel |
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| CN1923959A (en) * | 2005-08-31 | 2007-03-07 | 中国石油化工股份有限公司 | Method of preparing organism diesel oil from mixing plant oil |
| CN1840612A (en) * | 2005-11-07 | 2006-10-04 | 清华大学 | Process for preparing bio- diesel oil by two-step catalysis of acid-containing fat |
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