CN1640991A - Method for producing biological diesel using lipase - Google Patents
Method for producing biological diesel using lipase Download PDFInfo
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- CN1640991A CN1640991A CNA2004100612803A CN200410061280A CN1640991A CN 1640991 A CN1640991 A CN 1640991A CN A2004100612803 A CNA2004100612803 A CN A2004100612803A CN 200410061280 A CN200410061280 A CN 200410061280A CN 1640991 A CN1640991 A CN 1640991A
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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 present invention discloses one kind of biological diesel oil producing process with lipase. Animal and plant oil material after filtering and emulsifying treatment is mixed with methanol or ethanol; at temperature of 15-45 deg.c and inside sealed container, immobilized lipase is utilized to catalyze ester exchange reaction in the oil-water interface for 4-18 hr; through separation of product and lipase, centrifugal laminating and letting stand, the coarse glycerin in the lower layer is separated out; and the upper layer liquid is distilled to obtain biological diesel oil product while recovering organic solvent. The said process has the features of short reaction period, high production efficiency, circular use of lipase, low temperature of reaction, simple production process, no pollution, etc.
Description
Technical field
The invention belongs to the bioenergy technical field, be specifically related to a kind of production method of bio-diesel oil.
Background technology
Along with traditional mineral products energy such as oil are exhausted day by day, and the problem of environmental pollution that burning mineral products fuel produces is serious day by day, force people to begin to seek the energy of cleaning, sustainable use, simultaneously, clean fuel is also called in the Sustainable development of highly developed automotive industry.Through the exploration of many decades, biofuel is progressively accepted by people.Biofuel comprises prosene and animal diesel oil, compare with other alternative fuel, its advantage clearly, it is not sulfur-bearing and aromatic hydrocarbons substantially, the cetane value height, biodegradable, nontoxic, environmental sound, biofuel still are that first Fitness Testing that satisfies " 1990 clean air bill " requires the alternative fuel kind.Compare with using petroleum diesel, its unit calorific value is the highest in all substitute energys, and can be suitable for existing diesel motor use, can obviously reduce uncombusted hydrocarbon, carbon monoxide and particle content simultaneously.But at present biofuel substantially all adopts chemical process production industrial, promptly use animal and plant grease and 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 again.Disclosing a kind of as CN1412278A is catalyzer with methyl alcohol and sulfuric acid, utilizes high acid value and waste animal vegetable oil production method of bio-diesel oil.But the chemical method biodiesel synthesis has following shortcoming: complex process, alcohol must be excessive, and subsequent technique must have corresponding pure retrieving arrangement, energy consumption height; Because unsaturated fatty acids is at high temperature apt to deteriorate in the fat, color and luster is dark; Esterification products is difficult to reclaim the cost height; Generative process has waste lye discharging, contaminate environment.
People begin to attempt adopting the enzyme process catalyzed production biodiesel at present, promptly utilize microbial lipase replacing acid alkaline catalysts catalysis transesterification.A kind of biocatalysis grease transesterification production method of bio-diesel oil is disclosed as CN1453332A.Realized the simplification technical process, the problem of non-pollutant discharge.But it is long also to exist the reaction times in actual production, and the problem that the catalytic efficiency of enzyme is low is restricting the process of Production by Enzymes biofuel industrialization.
Summary of the invention
The objective of the invention is to overcome the above-mentioned shortcoming that exists in present chemical process and the biological enzyme production biofuel process, a kind of lipase production method of bio-diesel oil of utilizing is provided.The reaction times of this method is short, work simplification, and the transformation efficiency height of biofuel, and this method also has, and energy consumption is low, product is easy to characteristics such as recovery and non-pollutant discharge.
A kind of lipase production method of bio-diesel oil of utilizing provided by the invention, its step comprises:
(1) pre-treatment of stock oil: bio-oil is removed by filter impurity, carry out stirring and emulsifying then;
(2) reinforced and transesterification reaction: with mol ratio is that 1: 1～1: 2 grease and methyl alcohol or ethanol join in the container, and adding immobilized lipase and organic solvent, wherein, the mass ratio of immobilized lipase and stock oil is 1: 10～25, and the mass ratio of organic solvent and stock oil is 1: 0.5～1.5; Under 30 ℃ ± 15 ℃ temperature condition, with the airtight hybrid reaction 4～18h of mentioned component, in reaction process, secondary adds methyl alcohol or ethanol, and each methyl alcohol that adds or ethanol and greasy mol ratio are 1: 1～2: 1.
(3) separate, filter: reaction is separated enzyme after finishing from reaction product, again reaction product is carried out centrifugal layering, isolates the raw glycerine of lower floor after leaving standstill, and organic solvent is reclaimed in liquid distillation in upper strata, obtains refined biometric diesel oil simultaneously.
The present invention adopts immobilized lipase catalyzed transesterification on the organic solvent oil-water interface then by stock oil is carried out pre-treatment.Particularly, the present invention has following characteristics:
1, the method that adds with gradation stream has improved the transformation efficiency of biofuel greatly, reaches as high as 94%.
2, adopt specific immobilized lipase repeatedly to recycle, and loss of enzyme activity is very little, thereby has further reduced production cost.
3, enzymatic reaction temperature is low, issuable other by product under the consumption of the minimizing energy and the hot conditions.
4, production technique is simple, and discharge is pollution-free.
5, superior product quality.The biofuel performance of producing reaches 2 of foreign biomolecule diesel oil (DIN V 51.606) and China
#Diesel oil standard.Compare with using petroleum diesel, its unit calorific value is the highest in all substitute energys, and can be suitable for existing diesel motor use, can obviously reduce uncombusted hydrocarbon, carbon monoxide and particle content simultaneously.
Embodiment
The present invention is the transesterification reaction of finishing on the organic solvent oil-water interface, and the synthetic esterification yield of transesterify can reach 85-94%, and its reaction principle is:
R wherein
1, R
2, R
3Be C
7-17Alkyl or alkylene.
The grease that uses among the present invention is various raw material animals and plants or microbial oil, as rapeseed oil, soybean oil, Oleum Gossypii semen, peanut oil, Semen Maydis oil and lard etc.
The lipase that uses among the present invention is to adopt the present lipase of suitability for industrialized production or the lipase of this laboratory short run fermentative production, adopts immobilization to handle then and comes into operation.The lipase immobilization method is: in certain pH damping fluid, add the enzyme powder, stirring is fully dissolved it, and a certain amount of diatomite is added in the enzyme liquid, and behind the constant temperature vibration certain hour, centrifugal collection solid is washed fixation support 3-5 time with acetone.Carrier granule is disperseed, with distillation washing 3-5 time, acetone is washed off again, i.e. being fixed lipase after the lyophilize.
The organic solvent that uses among the present invention is sherwood oil, octane-iso, normal hexane, normal heptane, hexanaphthene and trichloromethane etc.
In process of production, employed immobilized lipase is reusable, and the organic solvent that is evaporated and a small amount of methyl alcohol that does not utilize or ethanol reclaim multiplexing through condensation.Methyl alcohol or ethanol divide three equivalent to add, better effects if during each 4～6h at interval.
The present invention is further detailed explanation below in conjunction with example.
The stock oil that is used for following embodiment is the pretreated bio-oil of process.Preprocessing process is earlier bio-oil to be removed by filter impurity, carries out stirring and emulsifying again.In the stirring and emulsifying process, stirring velocity is preferably 5000-10000rpm, and the stirring and emulsifying time is preferably 5-10min.
Embodiment 1
With 3.00g pretreated rapeseed oil of process and 0.11g methyl alcohol (oleyl alcohol mol ratio 1: 1), 1.50g sherwood oil, 0.12g immobilized lipase mixes 45 ℃ of airtight oscillatory reaction 4h in the 50ml tool plug Erlenmeyer flask of packing into, add 0.11g methyl alcohol again and continue reaction 4h, add methyl alcohol 0.11g at last for the third time and continue reaction 4h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 87%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.87; Flash-point (℃) 115; Viscosity (cst) 6.6; Calorific value (kJ/g) 34.6; Acid number (mgKOH/g) 0.14.
Embodiment 2
With 3.00g pretreated rapeseed oil of process and 0.16g methyl alcohol (oleyl alcohol mol ratio 1: 1.5), 3.00g sherwood oil, 0.15g immobilized lipase mixes 35 ℃ of airtight oscillatory reaction 4h in the 50ml tool plug Erlenmeyer flask of packing into, add 0.16g methyl alcohol again and continue reaction 5h, add methyl alcohol 0.16g at last for the third time and continue reaction 6h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 92%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.87; Flash-point (℃) 115; Viscosity (cst) 6.6; Calorific value (kJ/g) 34.6; Acid number (mgKOH/g) 0.14.
Embodiment 3
With 3.00g pretreated rapeseed oil of process and 0.21g methyl alcohol (oleyl alcohol mol ratio 1: 2), 4.50g sherwood oil, 0.30g immobilized lipase mixes 25 ℃ of airtight oscillatory reaction 5h in the 50ml tool plug Erlenmeyer flask of packing into, add 0.21g methyl alcohol again and continue reaction 5h, add methyl alcohol 0.21g at last for the third time and continue reaction 5h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 94%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.87; Flash-point (℃) 115; Viscosity (cst) 6.6; Calorific value (kJ/g) 34.6; Acid number (mgKOH/g) 0.14.
Embodiment 4
With 3.00g pretreated this laboratory gained microbial oil of process and 0.21g methyl alcohol (oleyl alcohol mol ratio 1: 2), 4.50g sherwood oil, 0.30g immobilized lipase mixes 25 ℃ of airtight oscillatory reaction 5h in the 50ml tool plug Erlenmeyer flask of packing into, add 0.21g methyl alcohol again and continue reaction 5h, add methyl alcohol 0.21g at last for the third time and continue reaction 5h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 91%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.87; Flash-point (℃) 117; Viscosity (cst) 6.5; Calorific value (kJ/g) 34.6; Acid number (mgKOH/g) 0.14.
Embodiment 5
With 4.00g pretreated fish oil of process and 0.14g methyl alcohol (oleyl alcohol mol ratio 1: 1), 2.00g sherwood oil, 0.20g immobilized lipase mixes 25 ℃ of airtight oscillatory reaction 4h in the 50ml tool plug Erlenmeyer flask of packing into, add 0.14g methyl alcohol again and continue reaction 4h, add methyl alcohol 0.14g at last for the third time and continue reaction 4h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 89%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.88; Flash-point (℃) 113; Viscosity (cst) 6.7; Calorific value (kJ/g) 34.7; Acid number (mgKOH/g) 0.13.
Embodiment 6
With 5.00g pretreated lard of process and 0.17g methyl alcohol (oleyl alcohol mol ratio 1: 1), 7.50g sherwood oil, 0.25g immobilized lipase mixes 45 ℃ of airtight oscillatory reaction 6h in the 50ml tool plug Erlenmeyer flask of packing into, add 0.17g methyl alcohol again and continue reaction 5h, add methyl alcohol 0.17g at last for the third time and continue reaction 4h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 91%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.89; Flash-point (℃) 117; Viscosity (cst) 6.8; Calorific value (kJ/g) 34.8; Acid number (mgKOH/g) 0.15.
Embodiment 7
With 6.00g pretreated Semen Maydis oil of process and 0.25g methyl alcohol (oleyl alcohol mol ratio 1: 1.2), 6.00g normal heptane, 0.30g immobilized lipase mixes 45 ℃ of airtight oscillatory reaction 5h in the 100ml tool plug Erlenmeyer flask of packing into, add 0.25g methyl alcohol again and continue reaction 5h, add methyl alcohol 0.25g at last for the third time and continue reaction 5h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 90%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.89; Flash-point (℃) 112; Viscosity (cst) 6.7; Calorific value (kJ/g) 34.6; Acid number (mgKOH/g) 0.14.
Embodiment 8
With 6.00g pretreated Semen Maydis oil of process and 0.21g methyl alcohol (oleyl alcohol mol ratio 1: 1), 6.00g normal heptane, 0.60g immobilized lipase mixes 30 ℃ of airtight oscillatory reaction 6h in the 100ml tool plug Erlenmeyer flask of packing into, add 0.21g methyl alcohol again and continue reaction 6h, add methyl alcohol 0.21g at last for the third time and continue reaction 6h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 93%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.89; Flash-point (℃) 112; Viscosity (cst) 6.7; Calorific value (kJ/g) 34.6; Acid number (mgKOH/g) 0.14.
Embodiment 9
With 10.00g pretreated Semen Maydis oil of process and 0.50g ethanol (oleyl alcohol mol ratio 1: 1), 10.00g normal heptane, 0.50g immobilized lipase mixes 15 ℃ of airtight oscillatory reaction 4h in the 100ml tool plug Erlenmeyer flask of packing into, add 0.50g ethanol again and continue reaction 4h, add ethanol 0.50g at last for the third time and continue reaction 4h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 85%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.91; Flash-point (℃) 118; Viscosity (cst) 6.8; Calorific value (kJ/g) 34.7; Acid number (mgKOH/g) 0.14.
Embodiment 10
With 16.00g pretreated Oleum Gossypii semen of process and 0.56g methyl alcohol (oleyl alcohol mol ratio 1: 1), 16.00g octane-iso, 0.80g immobilized lipase mixes 45 ℃ of airtight oscillatory reaction 5h in the 250ml tool plug Erlenmeyer flask of packing into, add 0.56g methyl alcohol again and continue reaction 5h, add methyl alcohol 0.56g at last for the third time and continue reaction 5h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 89%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.88; Flash-point (℃) 112; Viscosity (cst) 6.7; Calorific value (kJ/g) 34.6; Acid number (mgKOH/g) 0.14.
Embodiment 11
With 16.00g pretreated Oleum Gossypii semen of process and 0.84g methyl alcohol (oleyl alcohol mol ratio 1: 1.5), 24.00g octane-iso, 1.6g immobilized lipase mixes 40 ℃ of airtight oscillatory reaction 6h in the 250ml tool plug Erlenmeyer flask of packing into, add 0.84g methyl alcohol again and continue reaction 6h, add methyl alcohol 0.84g at last for the third time and continue reaction 6h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 93%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.88; Flash-point (℃) 112; Viscosity (cst) 6.7; Calorific value (kJ/g) 34.6; Acid number (mgKOH/g) 0.14.
Embodiment 12
With 16.00g pretreated Oleum Gossypii semen of process and 1.60g ethanol (oleyl alcohol mol ratio 1: 2), 16.00g trichloromethane, 0.80g immobilized lipase mixes 25 ℃ of airtight oscillatory reaction 4h in the 250ml tool plug Erlenmeyer flask of packing into, add 1.60g ethanol again and continue reaction 5h, add ethanol 1.60g at last for the third time and continue reaction 6h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 87%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.88; Flash-point (℃) 112; Viscosity (cst) 6.7; Calorific value (kJ/g) 34.6; Acid number (mgKOH/g) 0.14.
Embodiment 13
With 32.00g pretreated peanut oil of process and 1.11g methyl alcohol (oleyl alcohol mol ratio 1: 1), 32.00g hexanaphthene, 1.60g immobilized lipase mixes 45 ℃ of airtight oscillatory reaction 5h in the 500ml tool plug Erlenmeyer flask of packing into, add 1.11g methyl alcohol again and continue reaction 5h, add methyl alcohol 1.11g at last for the third time and continue reaction 5h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 91%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.89; Flash-point (℃) 112; Viscosity (cst) 6.7; Calorific value (kJ/g) 34.6; Acid number (mgKOH/g) 0.14.
Embodiment 14
With 32.00g pretreated peanut oil of process and 1.33g methyl alcohol (oleyl alcohol mol ratio 1: 1.2), 32.00g hexanaphthene, 1.60g immobilized lipase mixes 35 ℃ of airtight oscillatory reaction 5h in the 500ml tool plug Erlenmeyer flask of packing into, add 1.33g methyl alcohol again and continue reaction 5h, add methyl alcohol 1.33g at last for the third time and continue reaction 5h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 94%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.89; Flash-point (℃) 112; Viscosity (cst) 6.7; Calorific value (kJ/g) 34.6; Acid number (mgKOH/g) 0.14.
Embodiment 15
With 32.00g pretreated peanut oil of process and 1.11g methyl alcohol (oleyl alcohol mol ratio 1: 1), 32.00g trichloromethane, 1.60g immobilized lipase mixes 15 ℃ of airtight oscillatory reaction 5h in the 500ml tool plug Erlenmeyer flask of packing into, add 1.11g methyl alcohol again and continue reaction 5h, add methyl alcohol 1.11g at last for the third time and continue reaction 5h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 86%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.89; Flash-point (℃) 112; Viscosity (cst) 6.7; Calorific value (kJ/g) 34.6; Acid number (mgKOH/g) 0.14.
Embodiment 16
With 65.00g pretreated soybean oil of process and 2.25g methyl alcohol (oleyl alcohol mol ratio 1: 1), 97.50g normal hexane, 3.25g immobilized lipase mixes 45 ℃ of airtight oscillatory reaction 6h in the 1000ml tool plug Erlenmeyer flask of packing into, add 2.25g methyl alcohol again and continue reaction 6h, add methyl alcohol 2.25g at last for the third time and continue reaction 6h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 90%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.89; Flash-point (℃) 112; Viscosity (cst) 6.7; Calorific value (kJ/g) 34.6; Acid number (mgKOH/g) 0.14.
Embodiment 17
With 65.00g pretreated soybean oil of process and 2.93g methyl alcohol (oleyl alcohol mol ratio 1: 1.3), 97.50g normal hexane, 3.25g immobilized lipase mixes 35 ℃ of airtight oscillatory reaction 5h in the 1000ml tool plug Erlenmeyer flask of packing into, add 2.93g methyl alcohol again and continue reaction 5h, add methyl alcohol 2.93g at last for the third time and continue reaction 5h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 92%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.89; Flash-point (℃) 112; Viscosity (cst) 6.7; Calorific value (kJ/g) 34.6; Acid number (mgKOH/g) 0.14.
Embodiment 18
With 600.00g pretreated soybean oil of process and 20.78g methyl alcohol (oleyl alcohol mol ratio 1: 1), 600.00g normal hexane, 30.00g immobilized lipase mixes in the 10L fermentor tank of packing into, 35 ℃ of airtight stirring reaction 5h, add 20.78g methyl alcohol again and continue reaction 5h, add methyl alcohol 20.78g at last for the third time and continue reaction 5h, with product with after enzyme separates, centrifugal layering, organic solvent is reclaimed in final evaporation, obtains refined biometric diesel oil simultaneously.Ester conversion rate finally reaches 91%.Its property analysis of thing diesel oil result that produces is: density (g/cm
3) 0.89; Flash-point (℃) 112; Viscosity (cst) 6.7; Calorific value (kJ/g) 34.6; Acid number (mgKOH/g) 0.14.
According to above embodiment, utilize immobilized lipase production biofuel, through filtering and the raw oil material of emulsification utilizes fixed lipase catalyzed transesterification reaction under suitable temperature condition, different raw oil materials can both effectively be transformed the generation biofuel. the thing diesel oil that produces after testing its performance reach 2 of foreign biomolecule diesel oil (DIN V 51.606) and China
#Diesel oil standard.Have industrialization and enlarge the potentiality of producing.
Claims (5)
1, a kind of lipase production method of bio-diesel oil of utilizing, its step comprises:
(1) pre-treatment of stock oil: bio-oil is removed by filter impurity, carry out stirring and emulsifying then;
(2) reinforced and transesterification reaction: with mol ratio is that 1: 1～1: 2 grease and methyl alcohol or ethanol join in the container, and adding immobilized lipase and organic solvent, wherein, the mass ratio of immobilized lipase and stock oil is 1: 10～25, and the mass ratio of organic solvent and stock oil is 1: 0.5～1.5; Under 30 ℃ ± 15 ℃ temperature condition, with the airtight hybrid reaction 4～18h of mentioned component, in reaction process, secondary adds methyl alcohol or ethanol, and each methyl alcohol that adds or ethanol and greasy mol ratio are 1: 1～2: 1.
(3) separate, filter: reaction is separated enzyme after finishing from reaction product, again reaction product is carried out centrifugal layering, isolates the raw glycerine of lower floor after leaving standstill, and organic solvent is reclaimed in liquid distillation in upper strata, obtains refined biometric diesel oil simultaneously.
2, method according to claim 1 is characterized in that: in the step (2), methyl alcohol or ethanol divide three equivalent to add, each 4～6h at interval.
3, method according to claim 1 is characterized in that: employed organic solvent is sherwood oil, octane-iso, normal hexane, normal heptane, hexanaphthene and trichloromethane in the step (2).
4, method according to claim 1 is characterized in that: in the step (2), optimal reaction temperature is 30 ℃-40 ℃.
5, method according to claim 1 is characterized in that: the stock oil that uses be rapeseed oil, soybean oil, Oleum Gossypii semen, peanut oil, Semen Maydis oil, lard and fish oil and microbial oil.
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| CNB2004100612803A CN1295301C (en) | 2004-12-06 | 2004-12-06 | Method for producing biological diesel using lipase |
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| CNB2004100612803A CN1295301C (en) | 2004-12-06 | 2004-12-06 | Method for producing biological diesel using lipase |
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| CN1295301C CN1295301C (en) | 2007-01-17 |
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Cited By (13)
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| CN100375781C (en) * | 2005-11-09 | 2008-03-19 | 中国科学院广州能源研究所 | Production of biological diesel oil by fixed enzyme method |
| CN100400621C (en) * | 2006-08-22 | 2008-07-09 | 南京九康科技发展有限公司 | Novel chinaberry biologic diesel oil and method for preparing the same |
| CN100404643C (en) * | 2006-07-07 | 2008-07-23 | 清华大学 | Process for transferring grease for producing biodiesel oil using microorganism cell conversion in organic medium reaction system |
| CN102021207A (en) * | 2010-11-04 | 2011-04-20 | 清华大学 | On-line dehydration process for preparing biodiesel from renewable grease through catalysis of lipase |
| CN102177244A (en) * | 2007-09-21 | 2011-09-07 | 斯塔特伊公司 | Biodiesel |
| CN101134904B (en) * | 2007-09-29 | 2012-01-25 | 安徽格林生物能源股份有限公司 | New process for preparing biodiesel |
| CN102492560A (en) * | 2011-11-28 | 2012-06-13 | 华南理工大学 | Production device and production method for distribution type plant oil transesterification |
| CN102634548A (en) * | 2012-04-25 | 2012-08-15 | 云南师范大学 | Method for producing biodiesel by using low-temperature active lipase catalytic oil |
| CN102676304A (en) * | 2011-03-15 | 2012-09-19 | 清华大学 | Preparation method for biodiesel fuel |
| WO2012122827A1 (en) * | 2011-03-15 | 2012-09-20 | 清华大学 | Method for preparing biodiesel using feedstock oil |
| CN102864164A (en) * | 2011-07-04 | 2013-01-09 | 深圳市绿微康生物工程有限公司 | Expansion of application of penicillium lipase in biodiesel preparation |
| CN104148073A (en) * | 2014-08-14 | 2014-11-19 | 上海第二工业大学 | Preparation method and application of iron-oxide-loading nitrogen-carbon nano-tube (FeOx/CNx) catalyst |
| CN112094700A (en) * | 2020-09-16 | 2020-12-18 | 上海理工大学 | Method for preparing biodiesel by ultrasonic-assisted deep eutectic solvent enzymatic method |
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| JPH11263750A (en) * | 1998-03-16 | 1999-09-28 | Osaka City | Long-chain unsaturated fatty acid menthol ester and its production by enzyme method |
| JP3837466B2 (en) * | 2001-02-06 | 2006-10-25 | 独立行政法人酒類総合研究所 | Method for producing biodiesel (monoalkyl ester) |
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