CN103074389A - Method for preparing biodiesel by using biological enzyme - Google Patents
Method for preparing biodiesel by using biological enzyme Download PDFInfo
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- CN103074389A CN103074389A CN2013100449552A CN201310044955A CN103074389A CN 103074389 A CN103074389 A CN 103074389A CN 2013100449552 A CN2013100449552 A CN 2013100449552A CN 201310044955 A CN201310044955 A CN 201310044955A CN 103074389 A CN103074389 A CN 103074389A
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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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Abstract
The invention provides a method for preparing biodiesel by using a biological enzyme. The method comprises the following steps of: (1) raw material mixing: uniformly mixing raw oil and glycerin into a solution A, mixing sec-butyl acetate and lipase into a solution B, and mixing the solution A and the solution B in an enzyme esterification reactor for further performing a complete esterification reaction and a complete ester exchange reaction; (2) product filtration: precisely filtering crude diesel generated by the esterification reaction, separating and recovering an enzyme from the crude diesel, centrifugally separating the crude diesel from which lipase is separated, and removing foreign residues; and (3) product purification: performing normal-pressure distillation on the centrifugally separated crude diesel, separating excessive sec-butyl acetate and water generated by reacting, and rectifying under a reduced pressure of 0.002MPa to obtain biodiesel and plant asphalt. The biodiesel prepared with the method has high kinematic viscosity, a high cetane number and a high grease transformation ratio during production.
Description
Technical field
The invention belongs to field of grease chemical technology, relate in particular to a kind of method of utilizing biological enzyme to prepare biofuel.
Background technology
Biofuel is a kind of of biomass energy, and it is the mono alkyl ester that biomass are utilized a kind of longer chain fatty acid that the technology such as thermo-cracking obtain.Biofuel is the mixture of the high complicated organic composition of oxygen level, and these mixtures mainly are the large organism of number molecular weight, almost comprises the oxygen-bearing organic matter of all kinds.Biofuel is not sulfur-bearing and aromatic hydrocarbons substantially, and cetane value is higher, biodegradable, nontoxic, environmental sound.Thereby its height contains the trouble-free burning reduction tail gas discharge of poisonous waste that oxygen CN value extremely is conducive to compressing ignition engine, so be called as low-pollution fuel.
Biofuel mainly is to produce with chemical method, namely use animal and plant grease and the low-carbon alcohol such as methyl alcohol or ethanol under acid or basic catalyst and high temperature (230～250 ℃), to carry out transesterification, generate corresponding fatty acid methyl ester or ethyl ester, be drying to obtain biofuel through washing.Methyl alcohol or ethanol can be recycled in process of production, and production unit is identical with general liquefaction equipment, can produce the byproduct glycerine about 10% in the production process.
The problem that produces for solving chemosynthesis, people utilize the biological enzyme biodiesel synthesis, namely carry out transesterification with animal grease and low-carbon alcohol by lipase, prepare corresponding fatty acid methyl ester and ethyl ester.Enzymatic Synthesis of Biodiesel has mild condition, and pure consumption is little, the advantage of non-pollution discharge.But technology generally only is 40%～60% to the low conversion rate of methyl alcohol and ethanol at present, because lipase is effective to esterification or the transesterificationization of long chain aliphatic alcohol at present, and to low conversion rates such as short chain fatty alcohol such as methyl alcohol or ethanol.And short chain alcohol has certain toxicity to enzyme, the weak point in work-ing life of enzyme.By-product glycerin and shipwreck not only form product and suppress in recovery, and the existence of the pure and mild glycerine of short-chain fat all affects reactive behavior and the stability of enzyme, and greatly shortened the work-ing life of solidifying enzyme.
Summary of the invention
The present invention is directed to the short and problem such as transformation efficiency is not high when using in biological enzyme work-ing life, the method for kind utilizing biological enzyme to prepare biofuel is provided, the problem such as catalytic effect is undesirable when having solved biological enzyme and using, and work-ing life is short, and transformation efficiency is not high.For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of method of utilizing biological enzyme to prepare biofuel comprises following preparation process:
(1) raw material mixes: first stock oil and glycerine are mixed into A liquid and evenly mix, again sec-butyl acetate and lipase are mixed into B liquid and mix, again A liquid and B liquid are mixed in further abundant esterification and transesterification reaction in the enzyme esterifier.
(2) product filters: the gas oil that esterification is generated carries out secondary filter, and with the enzyme Separation and Recovery in the gas oil, the gas oil behind the separating out fat enzyme carries out centrifugation, removes the impurity removal slag.
(3) purification of products: will carry out air distillation through centrifugation gas oil later, and isolate the water that excessive sec-butyl acetate and reaction produce, the rectification under vacuum through 0.002MPa air pressure goes out biofuel and plant asphalt again.
Preferred scheme, the acid of described stock oil fat is 1:0.13-0.76 with the mol ratio of glycerine, described sec-butyl acetate and the sour mol ratio of stock oil fat are 1.2-2.5:1.
Preferred scheme, described lipase are the composite curing enzyme that contains in the lipase that pseudomonas, yeast and animal pancreas produce one or more, and described lipase accounts for the 8%-15% of total mixture quality.
Preferred scheme, described stock oil are that one or more that use oil are discarded in just oil expression of plant or the food and drink of plam oil, soybean oil, rapeseed oil, and the acid number of described stock oil is 25-150mgKOH/g.
Preferred scheme, the temperature of described A liquid and B liquid hybrid reaction is 45-58 ℃, the reaction times is 4-24h.
Preferred scheme adopts 1 μ m filter paper filtering during described secondary filter, described when centrifugal rotating speed be 5500rpm.
The invention has the beneficial effects as follows: according to aforesaid method, utilized the lipase of multiple different sources to carry out compound, form compound curing enzyme and carry out catalyzed reaction, the characteristics of solidifying enzyme are to be beneficial to reclaim and can fully contact with substrate, for the preference of different lipase for the catalysis different carbon chain, increased speed of reaction and improved transformation efficiency; Utilize sec-butyl acetate can effectively promote the carrying out of transesterification reaction, can effectively promote simultaneously the catalytic efficiency of biological enzyme as a kind of organic solvent, reduce glycerine to the shielding effect on biological enzyme surface, so that biological enzyme can better contact with reaction substrate, so that the carrying out of the better catalyzed reaction of endonuclease capable, glycerine and sec-butyl acetate can be so that enzyme do not lost simultaneously, so endonuclease capable carries out repeatedly catalysis and recovery, increase the utilization ratio of enzyme, effectively reduced cost; The biofuel of present method preparation has good kinematic viscosity and higher cetane value, can meet the indices of conventional diesel oil, and lower sulphur content is than more environmental protection of ordinary diesel oil, and present method also has very high transformation efficiency.
Description of drawings
Fig. 1 is a kind of method simple process figure that utilizes biological enzyme to prepare biofuel.
Embodiment
Following examples are used for explanation the present invention, but do not limit the scope of the invention.
Following examples material therefor is material that sell the market.Wherein the stock oil quality is 256.42 calculating according to the palmitinic acid relative molecular weight.
Embodiment 1
(1) be first that plam oil and the 13.7kg glycerine of 25mgKOH/g is mixed into A liquid with its acid number of 1000kg, and mix at 53 ℃, lipase with 341.25kg sec-butyl acetate and total mass 8% is mixed into B liquid again, and 53 ℃ of mixing, after treating that lipase fully activates, again A liquid and B liquid are mixed in the enzyme esterifier with 53 ℃ of abundant reaction 4h of constant temperature.
(2) gas oil that esterification is generated carries out secondary filter, with the enzyme Separation and Recovery in the gas oil, enters whizzer behind the separating out fat enzyme and separates the impurity removal slag with rotating speed 5500rpm.
(3) will carry out air distillation through centrifugation gas oil later, and isolate the water that excessive sec-butyl acetate and reaction produce, rectification under vacuum gently reaches mutually heavy phase with it and goes out biofuel and plant asphalt through 0.002MPa again.
Embodiment 2
(1) be first that soybean oil and the 27.3kg glycerine of 50mgKOH/g is mixed into A liquid with its acid number of 1000kg, and mix at 55 ℃, lipase with 273.12kg sec-butyl acetate and total mass 10% is mixed into B liquid again, and 55 ℃ of mixing, after treating that lipase fully activates, again A liquid and B liquid are mixed in the enzyme esterifier with 55 ℃ of abundant reaction 8h of constant temperature.
(2) gas oil that esterification is generated carries out secondary filter, with the enzyme Separation and Recovery in the gas oil, enters whizzer behind the separating out fat enzyme and separates the impurity removal slag with rotating speed 5500rpm.
(3) will carry out air distillation through centrifugation gas oil later, and isolate the water that excessive sec-butyl acetate and reaction produce, rectification under vacuum gently reaches mutually heavy phase with it and goes out biofuel and plant asphalt through 0.002MPa again.
Embodiment 3
(1) be first that rapeseed oil and the 54.7kg glycerine of 100mgKOH/g is mixed into A liquid with its acid number of 1000kg, and mix at 45 ℃, lipase with 204.8kg sec-butyl acetate and total mass 11% is mixed into B liquid again, and 45 ℃ of mixing, after treating that lipase fully activates, again A liquid and B liquid are mixed in the enzyme esterifier with 45 ℃ of abundant reaction 16h of constant temperature.
(2) gas oil that esterification is generated carries out secondary filter, with the enzyme Separation and Recovery in the gas oil, enters whizzer behind the separating out fat enzyme and separates the impurity removal slag with rotating speed 5500rpm.
(3) will carry out air distillation through centrifugation gas oil later, and isolate the water that excessive sec-butyl acetate and reaction produce, rectification under vacuum gently reaches mutually heavy phase with it and goes out biofuel and plant asphalt through 0.002MPa again.
Embodiment 4
(1) be first that sewer oil and the 82kg glycerine of 150mgKOH/g is mixed into A liquid with its acid number of 1000kg, and mix at 58 ℃, lipase with 163.8kg sec-butyl acetate and total mass 15% is mixed into B liquid again, and 58 ℃ of mixing, after treating that lipase fully activates, again A liquid and B liquid are mixed in the enzyme esterifier with 58 ℃ of abundant reaction 24h of constant temperature.
(2) gas oil that esterification is generated carries out secondary filter, with the enzyme Separation and Recovery in the gas oil, enters whizzer behind the separating out fat enzyme and separates the impurity removal slag with rotating speed 5500rpm.
(3) will carry out air distillation through centrifugation gas oil later, and isolate the water that excessive sec-butyl acetate and reaction produce, rectification under vacuum gently reaches mutually heavy phase with it and goes out biofuel and plant pitch through 0.002MPa again.
Each component proportion among table 1. embodiment
Obtain biofuel among each embodiment of table 2. and detect data
Show that according to table 1 data enzyme is 55 ℃ of activity that left and right sides Shi You is higher, the glycerine that consumes when the stock oil acid number raises increases and the sec-butyl acetate minimizing, and glycerine and sec-butyl acetate consumption are inversely proportional to.Can find out that according to table 2 data its character of the prepared biofuel of this method is relatively stable, have good cetane value and physico-chemical property preferably, can meet the standard of ordinary diesel oil, and than more environmental protection of ordinary diesel oil.
The above is not that technical scope of the present invention is imposed any restrictions, all according to the technology of the present invention essence to any modification, equivalent variations and modification that above embodiment does, all still belong in the scope of technical scheme of the present invention.
Claims (6)
1. method of utilizing biological enzyme to prepare biofuel is characterized in that comprising following preparation process:
(1) raw material mixes: first stock oil and glycerine are mixed into A liquid and evenly mix, again sec-butyl acetate and lipase are mixed into B liquid and mix, again A liquid and B liquid are mixed in further abundant esterification and transesterification reaction in the enzyme esterifier;
(2) product filters: the gas oil that esterification is generated carries out secondary filter, and with the enzyme Separation and Recovery in the gas oil, the gas oil behind the separating out fat enzyme carries out centrifugation, removes the impurity removal slag;
(3) purification of products: will carry out air distillation through centrifugation gas oil later, and isolate the water that excessive sec-butyl acetate and reaction produce, rectification under vacuum goes out biofuel and plant asphalt through the 0.002MPa normal atmosphere again.
2. a kind of method of utilizing biological enzyme to prepare biofuel according to claim 1 is characterized in that: the acid of described stock oil fat is 1:0.13-0.76 with the mol ratio of glycerine, and described sec-butyl acetate is 1.2-2.5:1 with the fatty sour mol ratio of stock oil.
3. a kind of method of utilizing biological enzyme to prepare biofuel according to claim 1, it is characterized in that: described lipase is the composite curing enzyme that contains in the lipase that pseudomonas, yeast and animal pancreatic produce one or more, and described lipase accounts for the 8%-15% of total mixture quality.
4. a kind of method of utilizing biological enzyme to prepare biofuel according to claim 1, it is characterized in that: described stock oil is that one or more that use oil are discarded in just oil expression of plant or the food and drink of plam oil, soybean oil, rapeseed oil, and the acid number of described stock oil is 25-150mgKOH/g.
5. a kind of method of utilizing biological enzyme to prepare biofuel according to claim 1, it is characterized in that: the temperature of described A liquid and B liquid hybrid reaction is 45-58 ℃, and the reaction times is 4-24h.
6. a kind of method of utilizing biological enzyme to prepare biofuel according to claim 1 is characterized in that: adopt 1 μ m filter paper filtering during described secondary filter, described when centrifugal rotating speed be 5500rpm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103710158A (en) * | 2014-01-02 | 2014-04-09 | 华南农业大学 | Method for producing biodiesel by using kitchen wastes |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103710158A (en) * | 2014-01-02 | 2014-04-09 | 华南农业大学 | Method for producing biodiesel by using kitchen wastes |
| CN103710158B (en) * | 2014-01-02 | 2015-01-21 | 华南农业大学 | Method for producing biodiesel by using kitchen wastes |
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Application publication date: 20130501 |