CN101381614A - Technique for preparing biodiesel by catalyzing oil using recovery of non-immobilized lipase - Google Patents
Technique for preparing biodiesel by catalyzing oil using recovery of non-immobilized lipase Download PDFInfo
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- CN101381614A CN101381614A CNA2008102243159A CN200810224315A CN101381614A CN 101381614 A CN101381614 A CN 101381614A CN A2008102243159 A CNA2008102243159 A CN A2008102243159A CN 200810224315 A CN200810224315 A CN 200810224315A CN 101381614 A CN101381614 A CN 101381614A
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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
Abstract
The invention provides a process for preparing biological diesel oil by recovering non-immobilization lipase catalyzed grease, which belongs to the field of biological fuel synthesis. The process is as follows: 4 to 9mol of short-chain alcohol based on the grease, 1 to 20 percent of water based on the weight of the grease, and 20 to 200 non-immobilization lipases of the enzyme live unit based on the mass of the unit grease are added in a biochemical reactor to react at a temperature of between 30 and 65 DEG C for 5 and 15 hours, and the yield of grease raw materials converted into the biological diesel oil reaches more than 95 percent; after the reaction, the mixture is subjected to centrifugation to remove the middle emulsion layer, and pheron in the lower-layer water phase is extracted out by utilizing the upper-layer oil phase or grease of reaction raw materials; during the extraction, a new emulsion layer is formed, and the new emulsion layer is recovered until the recovery rate of the pheron reaches more than 95 percent; and the emulsion layers are combined, and the recovered emulsion layer can be directly used for the next catalysis. The process has the advantages of effectively reducing the enzyme loss and achieving the aim of the repeated use of the lipase.
Description
Technical field
The invention belongs to the synthetic field of biofuel, be particularly related to a kind of recovery non-immobilized lipase technique for preparing biodiesel by catalyzing oil using, utilize non-immobilized lipase catalysis of renewable glyceride stock to prepare in the biofuel process, reclaiming the technology that non-immobilized lipase is used for biodiesel manufacture.
Background technology
Biofuel is the long chain fatty acid ester class material that is generated by transesterification reaction by the bio-oil raw material, and as a kind of recyclable organism fuel of cleaning, the research of biofuel and application have been subjected to widely to be paid close attention to.
Biofuel mainly is to use chemical method production at present, promptly uses animal-plant oil and some low-carbon alcohol (methyl alcohol or ethanol) to carry out transesterification reaction under alkali or an acidic catalyst effect, generates corresponding fatty acid methyl ester or ethyl ester.Chemical method prepares biofuel and has the following inevitable shortcoming: 1. free fatty acids in the glyceride stock and water have a strong impact on the carrying out of reaction; 2. methyl alcohol solvability in grease is bad, thereby easily causes the formation of emulsion to make the subsequent processes complexity; 3. the processing requirement methanol usage substantially exceeds the reaction mol ratio, the evaporation backflow increase process energy consumption of excessive methanol.
Because free fatty acids and the less water of utilizing the biological enzyme biodiesel synthesis to have in reaction conditions gentleness, non-pollutant discharge, the glyceride stock do not influence advantages such as enzymatic reaction, meet the developing direction of Green Chemistry, thereby are subject to people's attention day by day.But compare with chemical method, the cost of biological enzyme is too high, and this has become the main bottleneck of restriction enzyme process industrialization production biofuel.
Immobilized lipase can be reused, and this can reduce the use cost of enzyme to a certain extent.But the preparation cost of immobilized enzyme is very high, and wherein most costs ascribe the downstream process running cost of enzyme, the i.e. separation of enzyme, purifying and immobilization to.So directly utilize non-immobilized lipase (as liquid aliphatic enzyme and resolvase powder) as catalyzer, then can effectively save the separation of enzyme, purifying and immobilization supervisor can reduce the preparation cost of enzyme significantly.Yet, utilizing non-immobilized lipase to prepare in the process of biofuel as catalyzer conversion renewable oils fat raw material, can the repeatedly reuse that realize these non-immobilized lipases be the keys that reduce the enzyme cost, also are the main restricting factors that can non-immobilized lipase finally be applied to diesel preparation field.
The present invention proposes utilizing non-immobilized lipase (comprising liquid aliphatic enzyme and on-fixed enzyme powder) to prepare in the process of biofuel as catalyzer conversion renewable oils fat raw material, utilize abstraction technique that above-mentioned non-immobilized lipase is reclaimed, the lipase after the recovery can continue on for the catalyzed reaction of next batch.This invention can effectively solve the reuse of non-immobilized lipase, reduces the use cost of non-immobilized lipase greatly.This technology has very important application prospect in diesel preparation field.
Summary of the invention
The object of the present invention is to provide a kind of recovery non-immobilized lipase technique for preparing biodiesel by catalyzing oil using, utilizing non-immobilized lipase (comprising liquid aliphatic enzyme and lipase powder) conversion renewable oils fat raw material to prepare in the process of biofuel, after a collection of secondary response in front finishes, utilize abstraction technique that non-immobilized lipase is reclaimed.Oil phase (being mainly biofuel) and reaction raw materials (animal-plant oil) that extraction phase in the extraction process generates for the reaction back.This invention efficiently solves the reuse problem of non-immobilized lipase in catalysis preparing biological diesel oil by animal plant lipid process, can reduce the production cost of process for preparing biodiesel by enzyme significantly, has important prospects for commercial application.
The present invention is as the reaction acyl acceptor with the short chain alcohol roh; utilize non-immobilized lipase to carry out the transesterification reaction biodiesel synthesis as catalyst glyceride stock and above-mentioned short chain alcohol; after reaction finishes; centrifugal; acceleration comprises that the same oil phase of the water of lipase (is mainly biofuel; also have a little intermediate product and unreacted grease completely) separation; emulsion layer (zymoprotein more than 70% concentrates on emulsion layer) in the middle of taking away; also have the zymoprotein of 25-30% to be distributed in lower floor's water; and then with upper oil phase or utilize the reaction raw materials grease to remove to extract the zymoprotein of lower floor's aqueous phase; form new emulsion layer in the extraction process; wherein most of enzyme is distributed in new emulsion layer again, can repeatedly repeat this extraction step as required and reach more than 95% until the rate of recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.This process can be carried out the efficient recovery of lipase, has reached the purpose that repeats reuse lipase.
Technology of the present invention is: the short chain alcohol that adds based on grease 4-9 mole (can be taked the mode that repeatedly add intermittence in batches or Continuous Flow adds, guarantee that the single add-on is no more than 3 moles and get final product), adding is based on the water of oil quality 1%-20%, and based on the live non-immobilized lipase of unit of the oil quality 20-200 of unit enzyme, the lipase of different sources can be used in combination, pack into and be suitable in any biochemical reactor of enzyme reaction, temperature is controlled at 30 ℃～65 ℃, react after 5-15 hours, glyceride stock transforms the yield that generates biofuel and surpasses 95%.After reaction finishes, centrifugal, emulsion layer (zymoprotein more than 70% concentrates on emulsion layer) in the middle of taking away, also have the zymoprotein of 25-30% to be distributed in lower floor's water, and then with upper oil phase or utilize the reaction raw materials grease to remove to extract the zymoprotein of lower floor's aqueous phase, oil phase is with the 0.1-4 that is in a ratio of of water, form new emulsion layer in the extraction process, then this emulsion layer is reclaimed, can repeatedly repeat this extraction step as required again, reach more than 95% until the rate of recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.This process can be carried out the efficient recovery of lipase, has reached the purpose that repeats reuse lipase.
Lipase of the present invention is non-immobilized lipase, comprises deriving from yeast cell fungal cell, the liquid aliphatic enzyme of bacterium or other microorganism or the free-fat enzyme of other form such as enzyme powder.
Grease of the present invention is that bio-oil comprises Vegetable oil lipoprotein, animal grease, waste edible oil, the concise tankage of grease and microbial oil.
Vegetable oil lipoprotein of the present invention is Viscotrol C, rapeseed oil, soybean oil, peanut oil, Semen Maydis oil, oleum gossypii seminis, Rice pollard oil, curcas oil, shinyleaf yellowhorn oil, Jatropha curcas oil.
Animal grease of the present invention is fish oil, lard.
Microbial oil of the present invention is the yeast grease, the microalgae grease.
R is the alkyl with 1-5 carbon atom in the short chain alcohol roh of the present invention.
Short chain alcohol of the present invention is methyl alcohol, ethanol, propyl alcohol, butanols or amylalcohol.
Of the present inventionly be a little, effectively reduced the loss of enzyme, reached the purpose that repeats reuse lipase.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1
With mol ratio is methyl alcohol and the rapeseed oil (rapeseed oil 9.65g) of 4:1, adding is based on the water of oil quality 1%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, adding is based on the liquid aliphatic enzyme that derives from Aspergillus oryzae of 40 enzymes of unit oil quality unit alive, the reaction rotating speed is controlled at 600rpm, and methyl alcohol at the uniform velocity added in 6 hours, and bio-diesel yield was 85% in 8 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away, and then remove to extract the zymoprotein of lower floor's aqueous phase with upper oil phase, oil phase is in a ratio of 0.5 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed, can repeatedly repeat this extraction step as required, reach more than 95% until the rate of recovery of zymoprotein.Merge each emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 2
With mol ratio is methyl alcohol and the lard (lard 9.65g) of 9:1, adding is based on the water of oil quality 10%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 70 ℃ after, adding is based on the lipase powder that derives from Aspergillus oryzae of 70 enzymes of unit oil quality unit alive, the reaction rotating speed is controlled at 500rpm, and methyl alcohol at the uniform velocity added in 8 hours, and bio-diesel yield was 98% in 10 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away, and then remove to extract the zymoprotein of lower floor's aqueous phase with upper oil phase, oil phase is in a ratio of 1 with water, forms new emulsion layer in the extraction process, this emulsion layer is reclaimed again, can repeatedly repeat this extraction step as required, reach more than 95% until the rate of recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 3
With mol ratio is methyl alcohol and the hogwash fat (hogwash fat 9.65g) of 6:1, adding is based on the water of oil quality 15%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 50 ℃ after, the liquid aliphatic enzyme that derives from Aspergillus oryzae that adds 100 enzymes of unit oil quality unit alive, the reaction rotating speed is controlled at 800rpm, methyl alcohol is non-in 8 hours at the uniform velocity to add, and (addition manner was in preceding 3 hours: 0 hour adding 2 mole, of methanol, react and add 1 mole again after 1 hour, adding 2 moles after 2 hours again, add 1 mole again after 4 hours) bio-diesel yield was 95% 8 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away, and then remove to extract the zymoprotein of lower floor's aqueous phase with upper oil phase, oil phase is in a ratio of 2 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed, can repeatedly repeat this extraction step as required again, reach more than 95% until the rate of recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 4
With mol ratio is methyl alcohol and the curcas oil (curcas oil 9.65g) of 4:1, adding is based on the water of oil quality 2%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, the lipase powder that derives from Candida antarctica that adds 40 enzymes of unit oil quality unit alive, the reaction rotating speed is controlled at 1000rpm, and methyl alcohol at the uniform velocity added in 3 hours, and bio-diesel yield was 85% in 6 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away, and then remove to extract the zymoprotein of lower floor's aqueous phase with upper oil phase, oil phase is in a ratio of 5 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed, can repeatedly repeat this extraction step as required again, reach more than 95% until the rate of recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 5
With mol ratio is ethanol and the algae grease (algae grease 9.65g) of 9:1, adding is based on the water of oil quality 8%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 30 ℃ after, the liquid aliphatic enzyme that derives from Candida antarctica that adds 20 enzymes of unit oil quality unit alive, the reaction rotating speed is controlled at 400rpm, and methyl alcohol is non-in 10 hours at the uniform velocity to add, and bio-diesel yield was 93% in 15 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away, and then remove to extract the zymoprotein of lower floor's aqueous phase with the reaction raw materials grease, oil phase is in a ratio of 0.1 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed, can repeatedly repeat this extraction step as required again, reach more than 95% until the rate of recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 6
With mol ratio is ethanol and the hogwash fat (hogwash fat 9.65g) of 6:1, adding is based on the water of oil quality 10%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 50 ℃ after, the liquid aliphatic enzyme that derives from Candida antarctica that adds 100 enzymes of unit oil quality unit alive, the reaction rotating speed is controlled at 300rpm, and methyl alcohol at the uniform velocity added in 8 hours, and bio-diesel yield was 95% in 10 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away, and then remove to extract the zymoprotein of lower floor's aqueous phase with the reaction raw materials grease, oil phase is in a ratio of 1 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed, can repeatedly repeat this extraction step as required again, reach more than 95% until the rate of recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 7
With mol ratio is methyl alcohol and the hogwash fat (hogwash fat 9.65g) of 8:1, adding is based on the water of oil quality 16%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 50 ℃ after, add the liquid aliphatic enzyme that derives from Rhizomucor miehei of 300 enzymes of unit oil quality unit alive and the liquid aliphatic enzyme that derives from Rhizopus oryzae of 40 enzyme units alive, the reaction rotating speed is controlled at 500rpm, methyl alcohol at the uniform velocity added in 10 hours, and bio-diesel yield was 95% in 12 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away, and then remove to extract the zymoprotein of lower floor's aqueous phase with the reaction raw materials grease, oil phase is in a ratio of 2 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed, can repeatedly repeat this extraction step as required again, reach more than 95% until the rate of recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 8
With mol ratio is methyl alcohol and the hogwash fat (hogwash fat 9.65g) of 9:1, adding is based on the water of oil quality 20%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 60 ℃ after, the liquid aliphatic enzyme that derives from Thermomyces lanuginosus that adds 200 enzymes of unit oil quality unit alive, the reaction rotating speed is controlled at 1000rpm, and methyl alcohol at the uniform velocity added in 12 hours, and bio-diesel yield was 95% in 14 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away, and then remove to extract the zymoprotein of lower floor's aqueous phase with the reaction raw materials grease, oil phase is in a ratio of 3 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed, can repeatedly repeat this extraction step as required again, reach more than 95% until the rate of recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 9
With mol ratio is methyl alcohol and the hogwash fat (hogwash fat 9.65g) of 7:1, adding is based on the water of oil quality 10%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 60 ℃ after, the liquid aliphatic enzyme that derives from Rhizopus oryzae that adds 200 enzymes of unit oil quality unit alive, the reaction rotating speed is controlled at 1500rpm, and methyl alcohol at the uniform velocity added in 3 hours, and bio-diesel yield was 95% in 5 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away, and then remove to extract the zymoprotein of lower floor's aqueous phase with the reaction raw materials grease, oil phase is in a ratio of 5 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed, can repeatedly repeat this extraction step as required again, reach more than 95% until the rate of recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 10
With mol ratio is methyl alcohol and the hogwash fat (hogwash fat 9.65g) of 7:1, adding is based on the water of oil quality 15%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 50 ℃ after, add the liquid aliphatic enzyme that derives from Aspergillus oryzae of 30 enzymes of unit oil quality unit alive and the enzyme powder that derives from Candida antarctica of 20 enzyme units alive, the reaction rotating speed is controlled at 800rpm, methyl alcohol is non-in 8 hours at the uniform velocity to add, and (addition manner was in preceding 3 hours: 0 hour adding 2 mole, of methanol, react and add 1 mole again after 1 hour, adding 2 moles after 2 hours again, add 1 mole again after 4 hours) bio-diesel yield was 95% 8 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away, and then remove to extract the zymoprotein of lower floor's aqueous phase with the reaction raw materials grease, oil phase is in a ratio of 4 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed, can repeatedly repeat this extraction step as required again, reach more than 95% until the rate of recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 11
With mol ratio is methyl alcohol and the hogwash fat (hogwash fat 9.65g) of 7:1, adding is based on the water of oil quality 10%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 60 ℃ after, add the lipase that reclaims among the embodiment 9, the reaction rotating speed is controlled at 1500rpm, and methyl alcohol at the uniform velocity added in 3 hours, and bio-diesel yield was 94% in 5 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away, and then remove to extract the zymoprotein of lower floor's aqueous phase with the reaction raw materials grease, oil phase is in a ratio of 3 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed, can repeatedly repeat this extraction step as required again, reach more than 95% until the rate of recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
According to the foregoing description; this technology is as the reaction acyl acceptor with the short chain alcohol roh; utilize non-immobilized lipase to carry out the transesterification reaction biodiesel synthesis as catalyst glyceride stock and above-mentioned short chain alcohol; after reaction finishes; centrifugal; acceleration comprises that the same oil phase of the water of lipase (is mainly biofuel; also have a little intermediate product and unreacted grease completely) separation; emulsion layer (zymoprotein more than 70% concentrates on emulsion layer) in the middle of taking away; also have the zymoprotein of 25-30% to be distributed in lower floor's water; and then with upper oil phase or utilize the reaction raw materials grease to remove to extract the zymoprotein of lower floor's aqueous phase; form new emulsion layer in the extraction process; this emulsion layer is reclaimed, can repeatedly repeat this extraction step as required again, reach more than 95% until the rate of recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.This process can be carried out the efficient recovery of lipase, has reached the purpose that repeats reuse lipase.It is characterized in that: the short chain alcohol that adds based on grease 4-9 mole (can be taked the mode that repeatedly add intermittence in batches or Continuous Flow adds, guarantee that the single add-on is no more than 3 moles and get final product), adding is based on the water of oil quality 1%-20%, and based on the live non-immobilized lipase of unit of the oil quality 20-200 of unit enzyme, the lipase of different sources can be used in combination, pack into and be suitable in any biochemical reactor of enzyme reaction, temperature is controlled at 30 ℃～65 ℃, react after 5-15 hours, glyceride stock transforms the yield that generates biofuel and surpasses 95%.After reaction finishes, centrifugal, emulsion layer (zymoprotein more than 70% concentrates on emulsion layer) in the middle of taking away, also have the zymoprotein of 25-30% to be distributed in lower floor's water, and then with upper oil phase or utilize the reaction raw materials grease to remove to extract the zymoprotein of lower floor's aqueous phase, oil phase is with the 0.5-4 that is in a ratio of of water, form new emulsion layer in the extraction process, this emulsion layer is reclaimed, can repeatedly repeat this extraction step as required again, reach more than 95% until the rate of recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.This process can be carried out the efficient recovery of lipase, has reached the purpose that repeats reuse lipase.
Claims (10)
1. one kind is reclaimed the non-immobilized lipase technique for preparing biodiesel by catalyzing oil using, it is characterized in that: add short chain alcohol roh based on grease 4-9 mole, adding is based on the water of oil quality 1%-20%, and based on the live non-immobilized lipase of unit of the oil quality 20-200 of unit enzyme, the lipase of different sources is used alone or in combination, pack into and be suitable in any biochemical reactor of enzyme reaction, temperature is controlled at 30 ℃～65 ℃, react after 5-15 hours, glyceride stock transforms the yield that generates biofuel and surpasses 95%; After reaction finishes, centrifugal, emulsion layer in the middle of taking away, and then with upper oil phase or utilize the reaction raw materials grease to remove to extract the zymoprotein of lower floor's aqueous phase, oil phase forms new emulsion layer with the 0.1-4 that is in a ratio of of water in the extraction process, this emulsion layer is reclaimed again, repeatedly repeat this extraction step as required, reach more than 95% until the rate of recovery of zymoprotein; Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch.
2. method according to claim 1 is characterized in that, described lipase is non-immobilized lipase, and non-immobilized lipase comprises liquid aliphatic enzyme or lipase enzyme powder.
3, method according to claim 1 is characterized in that, described lipase derives from yeast, mould, the lipase of bacterium or other microorganism.
4, according to claim 1 or 3 described methods, it is characterized in that described lipase derives from Candidaantarctica, Rhizomucor miehe, the lipase of Thermomyces lanuginosus or Aspergillus oryzae.
5. method according to claim 1 is characterized in that, the addition manner of short chain alcohol is taked the mode that repeatedly add intermittence in batches or Continuous Flow adds.
6. method according to claim 1 is characterized in that, described glyceride stock is a bio-oil, and bio-oil comprises Vegetable oil lipoprotein, animal grease, waste edible oil, the concise tankage of grease or microbial oil.
7. method according to claim 6 is characterized in that, described Vegetable oil lipoprotein is Viscotrol C, rapeseed oil, soybean oil, peanut oil, Semen Maydis oil, oleum gossypii seminis, Rice pollard oil, curcas oil, shinyleaf yellowhorn oil or Jatropha curcas oil; Described animal grease is fish oil or lard.
8. method according to claim 6 is characterized in that, described microbial oil is yeast grease or microalgae grease.
9. method according to claim 1 is characterized in that, R is the alkyl with 1-5 carbon atom in the described short chain alcohol roh.
10. method according to claim 1 is characterized in that, described short chain alcohol is methyl alcohol, ethanol, propyl alcohol or butanols or amylalcohol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676305A (en) * | 2011-03-15 | 2012-09-19 | 清华大学 | Method for preparing biodiesel by oil |
| WO2012122826A1 (en) * | 2011-03-15 | 2012-09-20 | 清华大学 | Method for preparing biodiesel |
| CN105821018A (en) * | 2016-05-15 | 2016-08-03 | 江南大学 | Method for recovering liquid lipase |
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| JP2668187B2 (en) * | 1993-09-17 | 1997-10-27 | 日清製油株式会社 | Transesterification method using lipase powder |
| DK1270734T3 (en) * | 2001-06-21 | 2008-05-05 | T & T Oleochemie Gmbh | Process for enzymatic cleavage of oils and fats |
| CN101250424A (en) * | 2008-03-31 | 2008-08-27 | 清华大学 | Enzyme method technique for improving bio-diesel yield by adding short-chain alcohol in organic medium |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676305A (en) * | 2011-03-15 | 2012-09-19 | 清华大学 | Method for preparing biodiesel by oil |
| WO2012122826A1 (en) * | 2011-03-15 | 2012-09-20 | 清华大学 | Method for preparing biodiesel |
| US10246644B2 (en) | 2011-03-15 | 2019-04-02 | Tsinghua University | Method for preparing biodiesel |
| CN105821018A (en) * | 2016-05-15 | 2016-08-03 | 江南大学 | Method for recovering liquid lipase |
| CN105821018B (en) * | 2016-05-15 | 2019-11-19 | 江南大学 | A kind of method of withdrawal liquid lipase |
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