CN101134904B - New process for preparing biodiesel - Google Patents
New process for preparing biodiesel Download PDFInfo
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- CN101134904B CN101134904B CN2007101337370A CN200710133737A CN101134904B CN 101134904 B CN101134904 B CN 101134904B CN 2007101337370 A CN2007101337370 A CN 2007101337370A CN 200710133737 A CN200710133737 A CN 200710133737A CN 101134904 B CN101134904 B CN 101134904B
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- Prior art keywords
- heat shock
- shock protein
- hsp
- lypase
- immobilized enzyme
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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 present invention belongs to the field of biodiesel oil technology, and is especially one new biodiesel oil preparing process. Lipase and heat shock protein as enzyme stabilizer are first well mixed and then mixed with carrier to prepare immobilized enzyme reactor, and the mixed liquid of oil, grease and methanol or ethanol is made to pass through the immobilized enzyme reactor to produce ester converting reaction producing methyl fatty ester or ethyl fatty ester, i. e., biodiesel oil. The existence of heat shock protein raises the reaction activity and stability of lipase, prolongs the service life of immobilized enzyme, raises the converting rate to biodiesel oil and lowers the production cost of biodiesel oil.
Description
Technical field
The invention belongs to field of biodiesel oil, be specifically related to a kind of novel process for preparing biofuel.
Background technology
The production of biofuel is to adopt grease and methyl alcohol or ethanol to carry out transesterification through lypase, prepares corresponding fatty acid methyl ester and ethyl ester, also is biofuel.
It is big to utilize the biological enzyme biodiesel synthesis to remove output, outside the quality height, also has advantages such as reaction conditions gentleness, pure consumption are little, non-pollutant discharge, has preferable environment friendly, thereby receives people's attention day by day.But utilize biological enzyme to prepare biofuel at present and exist some problem demanding prompt solutions: lypase is effective to the esterification or the transesterificationization of long chain aliphatic alcohol; And it is lower to short chain fatty alcohol (like methyl alcohol or ethanol etc.) transformation efficiency; Generally being merely
methyl alcohol and ethanol has certain toxicity to enzyme, makes enzyme deactivation easily; By-product glycerin and water recovery difficult are big, and cost is high, and is not only influential to the efficient of whole process of production, and glycerine is also toxic to enzyme; The existence of the pure and mild glycerine of short-chain fat all influences the reactive behavior and the stability of enzyme, and shortened the work-ing life of immobilized enzyme greatly, and the problems referred to above are main bottlenecks of biological enzyme suitability for industrialized production biofuel.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can effectively improve lypase reactive behavior and stability, reduce production costs and improve the novel process of the preparation biofuel of transformation efficiency.
For realizing above-mentioned purpose, the present invention has adopted following technical scheme: a kind of novel process for preparing biofuel, and it may further comprise the steps:
Carrier after a, the present invention provide a kind of mixed solution that lypase and heat shock protein(HSP) are obtained after by 1: 1 weight ratio thorough mixing and a kind of to clean up with clean-out system;
B, with carrier and above-mentioned mixed solution weight ratio thorough mixing by 1: 20, can get immobilized enzyme reactor;
Described lypase is with after heat shock protein(HSP) mixes mutually, fully is dissolved in earlier in the buffering liquid 1 hour, discard last liquid after, again with the carrier thorough mixing;
Described buffering liquid also has multiple choices, like phosphate buffered saline buffer, acetate buffer solution, carbonic acid buffer, citrate buffer solution, tris buffer;
C, with edible oil and methyl alcohol or ethanol by 1: 7.5 mol ratio mix mutually the oleyl alcohol mixture;
D, be under 20～45 ℃ the condition, gained oleyl alcohol mixture to be placed in the immobilized enzyme reactor in temperature, after reaction biofuel.
Because the present invention has introduced heat shock protein(HSP) in reaction process; And through lypase and heat shock protein(HSP) co-absorbed are made immobilized enzyme reactor on carrier; Thereby improved lypase reactive behavior and stability greatly, and lypase is significantly improved the transformation efficiency of short chain fatty alcohol (like methyl alcohol or ethanol etc.), and prolonged the work-ing life of immobilized enzyme; Thereby reduced the production cost of biofuel, improved production efficiency.
Summary of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
As shown in Figure 1, the carrier after the present invention provides a kind of mixed solution that lypase and heat shock protein(HSP) are obtained after by 1: 1 weight ratio thorough mixing and a kind of to clean up with clean-out system.
Described lypase has multiple available; Such as psychrophilic bacteria lypase such as pseudomonas, pseudomonas pseudoalcaligenes lypase, Aspergillus lypase, yeast fat enzyme, Mucor lypase etc.; As preferred version of the present invention; Described lypase is that lipase from candida sp or false unit cell belong to lypase, and because of these two kinds of lypase can make the transformation efficiency of whole transesterification higher, output is bigger and the unit output cost is lower.
Learn when organism is exposed to pyritous, will synthesize heat shock protein(HSP) (HSPs) with protection organism self by thermal excitation, and many heat shock protein(HSP)s to have chaperone activity according to research.
Can be learnt that by above-mentioned the character of heat shock protein(HSP) itself has determined it can improve the reactive behavior or the stability of enzyme effectively, as preferred version of the present invention, described heat shock protein(HSP) is small molecules heat shock protein(HSP) (SHSPs).The distribution of small molecules heat shock protein(HSP) is very extensive, and the gene of small molecules heat shock protein(HSP) is all arranged in the genome from the bacterium to people, thereby its source is abundant, is convenient to gather materials on the spot, and cost is less.
As the present invention's preferred version further, described small molecules heat shock protein(HSP) comes from extreme hyperthermophilic archaeon strain.Small molecules heat shock protein(HSP) in the extreme hyperthermophilic archaeon strain has multiple function, comprises giving multiple lypase thermotolerance with opposing high temperature, to prevent protein aggregation, reduces methyl alcohol and the ethanol toxicity to enzyme as Chaperones Molecular, improves the stable and active of enzyme.Because the small molecules heat shock protein(HSP) in the extreme hyperthermophilic archaeon strain has this special specific aim for lypase, makes it can in invention, bring into play bigger effect.
After carrier cleaned up with clean-out system, with carrier and above-mentioned mixed solution thorough mixing, can get immobilized enzyme reactor by 1: 20 weight ratio.
Carrier can have multiple choices; Like strong-basicity styrene resin anion(R.A), strong-basicity styrene resin cation(R.C.), CMC 99.5, Win 40350, calcium phosphate etc.; As preferred version of the present invention, described carrier is Vilaterm anionite-exchange resin or Vilaterm Zeo-karb, because of enriching in these two kinds of resin sources; And price is lower, is beneficial to large-scale production and application.
When carrier is cleaned; Clean-out system also has multiple choices; Like 0.1 mole hydrochloride, 0.1 molar sodium hydroxide and clear water, can be earlier to clean with 0.1 mole hydrochloride of 2 times of volumes of carrier, the back is washed with the clear water of 5 times of volumes; And then, wash with 5 times of volume clear water again with the washing of 0.1 molar sodium hydroxide of 2 times of volumes.
As preferred version of the present invention, described clean-out system is a pure water.Use pure water not only can reach cleaning performance preferably, and can simplify cleaning step, reduce and clean cost.
As another kind of preferred version of the present invention,, can the gained mixed solution fully be dissolved in earlier in the buffering liquid 1 hour with after heat shock protein(HSP) mixes mutually at described lypase, discard last liquid after, again with the carrier thorough mixing.
Earlier fully be dissolved in the buffering liquid lypase and heat shock protein(HSP); Can improve the degree of mixing of lypase and heat shock protein(HSP) effectively; Both can combine better to make them; Further the function of performance heat shock protein(HSP) improves the performance that lypase tolerates various bad conditions, strengthens its biological activity and stability.
Described buffering liquid also has multiple choices; Like phosphate buffered saline buffer, acetate buffer solution, carbonic acid buffer, citrate buffer solution, tris buffer etc.; As the present invention's preferred version further; Described buffering liquid is that the pH value is that 7.8 phosphoric acid salt or pH value are 5.0 acetate buffer liquid, and these two kinds of buffering liquids are comparatively common, and it is low to be convenient to preparation and cost.
As preferred version of the present invention; Described mixed solution and the carrier thorough mixing of being made up of lypase and heat shock protein(HSP) can get immobilized enzyme reactor after 1 hour; Described oleyl alcohol mixture obtains biofuel after being placed on and reacting half a hour in the immobilized enzyme reactor, and the gained biofuel is used the separation and purification of biofuel separating machine.
In the above-mentioned reaction times, can obtain preferable immobilized enzyme reactor; And make the fine biofuel; Gained diesel oil is after using the separation and purification of biofuel separating machine; Can the water in the former product, glycerine and by product and removing residues such as methyl alcohol or ethanol further be obtained the biofuel that technical indicator meets national biofuel standard and satisfies No. 0 excellent diesel oil standard of China.
As the present invention's preferred version further, mixed solution that described lypase and heat shock protein(HSP) are formed and carrier thorough mixing also evenly stir, and described oleyl alcohol mixture is placed on when reacting in the immobilized enzyme reactor and evenly stirs.Through evenly stirring, can accelerate reaction process, shorten the reaction times, reach the technique effect of enhancing productivity.
Through embodiment the present invention is further described below:
Embodiment 1, get 200 milligrams in Vilaterm anionite-exchange resin, put into 1000 ml beakers, with twice back of 1000 milliliters of pure water washings airing.Simultaneously by 1: 1 weight ratio, restraining the small molecules heat shock protein(HSP)s to 2 gram lypase and 2, fully to be dissolved in 250 milliliters, the pH value of 20mm be in 7.8 the phosphate-buffered liquid, at room temperature placed one hour, discards last liquid.Above-mentioned carrier and lypase and small molecules heat shock protein(HSP) and Vilaterm anionite-exchange resin thorough mixing and stirred one hour, be prepared into immobilized enzyme reactor.With the edible corn oil is raw material; When temperature is 40 ℃; Oil is mixed with 1: 7.5 mol ratio with alcohol mutually; Totally 1000 milliliters, to put into the said fixing enzyme reactor and stir half a hour, grease and triglyceride level transformation efficiency reach
.After immobilized enzyme reactor used 100 times repeatedly, grease and triglyceride level transformation efficiency reached
.As contrast; When being prepared into immobilized enzyme reactor; Do not add the stablizer small molecules heat shock protein(HSP) of enzyme; Grease and triglyceride level transformation efficiency have only
; After practical repeatedly 100 times, grease and triglyceride level transformation efficiency reach
.
Embodiment 2, be carrier, be that 5.0 acetic acid is that buffering liquid prepares immobilized enzyme reactor with the Vilaterm Zeo-karb with the pH value by instance 1 said method; With the edible rapeseed oil is raw material; When temperature is 40 ℃; Oil is mixed with 1: 7.5 mol ratio with alcohol mutually; Totally 1000 milliliters, to put into the said fixing enzyme reactor and stir half a hour, grease and triglyceride level transformation efficiency reach
.After using 100 times repeatedly, grease and triglyceride level transformation efficiency reach
.As contrast; When being prepared into immobilized enzyme reactor; Do not add the stablizer small molecules heat shock protein(HSP) of enzyme; Grease and triglyceride level transformation efficiency have only
; After using 100 times repeatedly, grease and triglyceride level transformation efficiency reach
.
Embodiment 3, be the preparing carriers immobilized enzyme reactor with the strong-basicity styrene resin anion(R.A) by instance 1 said method; With the edible peanut oil is raw material; When temperature is 40 ℃; Oil is mixed with 1: 7.5 mol ratio with alcohol mutually; Totally 1000 milliliters, to put into the said fixing enzyme reactor and stir half a hour, grease and triglyceride level transformation efficiency reach
.After using 100 times repeatedly, grease and triglyceride level transformation efficiency reach
.As contrast; When being prepared into immobilized enzyme reactor; Do not add the stablizer small molecules heat shock protein(HSP) of enzyme; Grease and triglyceride level transformation efficiency have only
; After using 100 times repeatedly, grease and triglyceride level transformation efficiency reach
.
Embodiment 4, be carrier, be that 5.0 acetic acid is that buffering liquid prepares immobilized enzyme reactor with the strong-basicity styrene resin cation(R.C.) with the pH value by instance 1 said method; With the plam oil is raw material; When temperature is 40 ℃; Oil is mixed with 1: 7.5 mol ratio with alcohol mutually; Totally 1000 milliliters, to put into the said fixing enzyme reactor and stir half a hour, grease and triglyceride level transformation efficiency reach
.After using 100 times repeatedly, grease and triglyceride level transformation efficiency reach
.As contrast; When being prepared into immobilized enzyme reactor; Do not add the stablizer small molecules heat shock protein(HSP) of enzyme; Grease and triglyceride level transformation efficiency have only
; After using 100 times repeatedly, grease and triglyceride level transformation efficiency reach
.
Embodiment 5, with the CMC 99.5 preparing carriers immobilized enzyme reactor by instance 1 said method; With the curcas oil is raw material; When temperature is 40 ℃; Oil is mixed with 1: 7.5 mol ratio with alcohol mutually; Totally 1000 milliliters, to put into the said fixing enzyme reactor and stir half a hour, grease and triglyceride level transformation efficiency reach
.After using 100 times repeatedly, grease and triglyceride level transformation efficiency reach
.As contrast; When being prepared into immobilized enzyme reactor; Do not add the stablizer small molecules heat shock protein(HSP) of enzyme; Grease and triglyceride level transformation efficiency have only
; After using 100 times repeatedly, grease and triglyceride level transformation efficiency reach
.
Embodiment 6, be carrier with the Win 40350, be that 5.0 acetic acid is that buffering liquid prepares immobilized enzyme reactor with the pH value by instance 1 said method.With the edible corn oil is raw material; When temperature is 40 ℃; Oil is mixed with 1: 7.5 mol ratio with alcohol mutually; Totally 1000 milliliters, to put into the said fixing enzyme reactor and stir half a hour, grease and triglyceride level transformation efficiency reach
.After using 100 times repeatedly, grease and triglyceride level transformation efficiency reach
.As contrast; When being prepared into immobilized enzyme reactor; Do not add the stablizer small molecules heat shock protein(HSP) of enzyme; Grease and triglyceride level transformation efficiency have only
; After using 100 times repeatedly, grease and triglyceride level transformation efficiency reach
.
Embodiment 7, with calcium phosphate the preparing carriers immobilized enzyme reactor by instance 1 said method; With the edible rapeseed oil is raw material; When temperature is 40 ℃; Oil is mixed with 1: 7.5 mol ratio with alcohol mutually; Totally 1000 milliliters, to put into the said fixing enzyme reactor and stir half a hour, grease and triglyceride level transformation efficiency reach
.After using 100 times repeatedly, grease and triglyceride level transformation efficiency reach
.As contrast; When being prepared into immobilized enzyme reactor; Do not add the stablizer small molecules heat shock protein(HSP) of enzyme; Grease and triglyceride level transformation efficiency have only
; After using 100 times repeatedly, grease and triglyceride level transformation efficiency reach
.
Claims (9)
1. novel process for preparing biofuel is characterized in that may further comprise the steps:
Carrier after a, the present invention provide a kind of mixed solution that lypase and heat shock protein(HSP) are obtained after by 1: 1 weight ratio thorough mixing and a kind of to clean up with clean-out system;
B, with carrier and above-mentioned mixed solution weight ratio thorough mixing by 1: 20, can get immobilized enzyme reactor;
Described lypase is with after heat shock protein(HSP) mixes mutually, fully is dissolved in earlier in the buffering liquid 1 hour, discard last liquid after, again with the carrier thorough mixing;
Described buffering liquid also has multiple choices, like phosphate buffered saline buffer, acetate buffer solution, carbonic acid buffer, citrate buffer solution, tris buffer;
C, with edible oil and methyl alcohol or ethanol by 1: 7.5 mol ratio mix mutually the oleyl alcohol mixture;
D, be under 20～45 ℃ the condition, gained oleyl alcohol mixture to be placed in the immobilized enzyme reactor in temperature, after reaction biofuel.
2. the novel process of preparation biofuel according to claim 1 is characterized in that: described lypase is that lipase from candida sp or false unit cell belong to lypase.
3. the novel process of preparation biofuel according to claim 1 is characterized in that: described heat shock protein(HSP) is the small molecules heat shock protein(HSP).
4. the novel process of preparation biofuel according to claim 1 is characterized in that: described carrier is Vilaterm anionite-exchange resin or Vilaterm Zeo-karb.
5. the novel process of preparation biofuel according to claim 1 is characterized in that: described clean-out system is a pure water.
6. the novel process of preparation biofuel according to claim 1; It is characterized in that: described mixed solution and the carrier thorough mixing of being made up of lypase and heat shock protein(HSP) can get immobilized enzyme reactor after 1 hour; Described oleyl alcohol mixture obtains biofuel after being placed on and reacting half a hour in the immobilized enzyme reactor, and the gained biofuel is used the separation and purification of biofuel separating machine.
7. the novel process of preparation biofuel according to claim 3 is characterized in that: described small molecules heat shock protein(HSP) comes from extreme hyperthermophilic archaeon strain.
8. the novel process of preparation biofuel according to claim 1 is characterized in that: described buffering liquid is that the pH value is that 7.8 phosphoric acid salt or pH value are 5.0 acetate buffer liquid.
9. the novel process of preparation biofuel according to claim 1; It is characterized in that: mixed solution that described lypase and heat shock protein(HSP) are formed and carrier thorough mixing also evenly stir, and described oleyl alcohol mixture is placed on when reacting in the immobilized enzyme reactor and evenly stirs.
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| CN2007101337370A CN101134904B (en) | 2007-09-29 | 2007-09-29 | New process for preparing biodiesel |
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|---|---|---|---|
| CN2007101337370A CN101134904B (en) | 2007-09-29 | 2007-09-29 | New process for preparing biodiesel |
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| CN101134904A CN101134904A (en) | 2008-03-05 |
| CN101134904B true CN101134904B (en) | 2012-01-25 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101353587B (en) * | 2008-08-28 | 2011-12-07 | 大连海事大学 | Method for improving lipase-catalyzed production biodiesel production rate |
| CN101898199B (en) * | 2009-05-27 | 2012-06-27 | 中国科学院沈阳应用生态研究所 | Eluent for removing polycyclic aromatic hydrocarbon pollutant in soil and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1453332A (en) * | 2003-04-24 | 2003-11-05 | 华南理工大学 | Biologically catalystic process of converting fat into ester to produce biological diesel oil |
| CN1640991A (en) * | 2004-12-06 | 2005-07-20 | 华中科技大学 | Method for producing biological diesel using lipase |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1453332A (en) * | 2003-04-24 | 2003-11-05 | 华南理工大学 | Biologically catalystic process of converting fat into ester to produce biological diesel oil |
| CN1640991A (en) * | 2004-12-06 | 2005-07-20 | 华中科技大学 | Method for producing biological diesel using lipase |
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