CN105950674A - Method for improving quality of biodiesel - Google Patents
Method for improving quality of biodiesel Download PDFInfo
- Publication number
- CN105950674A CN105950674A CN201610527969.3A CN201610527969A CN105950674A CN 105950674 A CN105950674 A CN 105950674A CN 201610527969 A CN201610527969 A CN 201610527969A CN 105950674 A CN105950674 A CN 105950674A
- Authority
- CN
- China
- Prior art keywords
- enzyme
- biodiesel
- fats
- lipase
- oils
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/649—Biodiesel, i.e. fatty acid alkyl esters
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Fats And Perfumes (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention provides a method for improving the quality of biodiesel. The method comprises the following steps: 1, reacting oil, short-chain alcohol, water and liquid lipase in a one-stage or multi-stage enzyme reactor, separating a reaction solution into a heavy phase and a light phase, and recycling enzymes in the heavy phase, the light phase being used for subsequent immobilized enzyme transformation; 2, causing the light phase obtained in step 1 to flow into a one-stage or multi-stage reactor with immobilized lipase, adding short-chain alcohol for reaction, and performing online dehydration in a reaction process; 3, causing a reaction solution obtained in step 2 to flow into an enzyme reactor of the next stage to be reacted with dimethyl carbonate or diethyl carbonate, and performing online hydration in a reaction process to further implement complete transformation of the oil to biodiesel, wherein the yield of the biodiesel exceeds 98 percent, and the total glycerin content is lower than 0.2 percent. According to the method, low-quality non-edible oil can be transformed into high-quality biodiesel, a subsequent separation and purification process is greatly simplified, and good economic benefits and social benefits are achieved.
Description
Technical field
The present invention relates to biodiesel synthesis technical field, specifically, relate to a kind of method improving biodiesel quality.
Background technology
Biodiesel is the long-chain fatty acid esters material generated by ester exchange reaction by bio-oil raw material, is a kind of novel non-pollution renewable energy, has broad application prospects in oil prodution industry.Biodiesel is mainly produced by chemical method at present, i.e. carries out ester exchange reaction by animal and plant fat and some low-carbon alcohols (methanol or ethanol) under alkali or acidic catalyst effect, generates corresponding fatty acid methyl ester or ethyl ester.Chemical method is prepared biodiesel and is had the disadvantage in that the free fatty in 1. glyceride stock and water have a strong impact on the carrying out of reaction；2. methanol dissolubility in oils and fats is poor, is easily formed emulsion, adds the difficulty of subsequent treatment；3. whole set process requires that methanol usage substantially exceeds reaction mol ratio, and the recovery of excessive methanol adds energy consumption.
Biological enzyme biodiesel synthesis is utilized to have reaction condition gentle, non-pollutant discharge and there is the advantages such as the glyceride stock suitability widely, meet the developing direction of Green Chemistry, thus be increasingly subject to the attention of people.But there is problems with in the preparation utilizing the normal fat enzyme catalysis technique low-quality unedible oil fat raw material of conversion to carry out biodiesel, total glycerol content in biodiesel oil product is often beyond American-European relevant standard, follow-up mostly need to be through multiple working procedures such as loaded down with trivial details washing, distillations, process energy consumption is high, product yield is low, in the urgent need to developing new technology to improve the quality of biodiesel.
Summary of the invention
It is an object of the invention to provide a kind of method improving biodiesel quality.
In order to realize the object of the invention, a kind of method improving biodiesel quality that the present invention provides, comprise the following steps:
S1, oils and fats, short chain alcohol, water and liquid aliphatic enzyme are reacted in one or more levels enzyme reactor, then reactant liquor is separated into heavy phase and light phase, enzyme in recycling heavy phase, light phase (coarse biodiesel phase) converts for follow-up immobilized enzyme；
S2, by the light phase inflow that obtains in S1 equipped with in one or more levels enzyme reactor of immobilized-lipase, and add short chain alcohol and react, containing biodiesel crude product in gained reactant liquor, course of reaction carries out the online dehydration of gentleness；
S3, S2 gained reactant liquor is flowed in next stage enzyme reactor, unreacted glyceride completely and fatty acid in reactant liquor is made enzymatically to react with dimethyl carbonate or diethyl carbonate, that carries out gentleness in course of reaction is dehydrated the water byproduct to generate in removing course of reaction, and then realization fully converting from oils and fats to biodiesel online.
Aforesaid method, S1 is to add oils and fats, the short chain alcohol of oils and fats molal quantity 4-8 times, the water of oil quality 2%-20% and the liquid aliphatic enzyme of unit of living based on 200-2000 standard enzyme of oil quality in one or more levels enzyme reactor, reacts 3-8 hour in 30 DEG C-55 DEG C.
Aforesaid method, by S1 gained reactant liquor by centrifugation or after static layering, reclaims the pheron in heavy phase with membrance separation.The film of separation and recovery pheron includes metal film, organic membrane, inoranic membrane or ceramic membrane etc..Such as, the organic membrane selecting molecular cut off to be 15000Da carries out the recovery of above-mentioned lipase, and the response rate of pheron is up to 95%, and in the enzyme liquid of recovery, the residual quantity of by-product glycerin is less than 5%, and the enzyme of recovery can be reused.
During S2 in preceding method particularly as follows: flow into one or more levels enzyme reactor equipped with immobilized-lipase based on 200-1000 enzyme of oil quality unit alive by the short chain alcohol of light phase and oils and fats molal quantity 1-3 times obtained in S1, react 0.5-3 hour in 20 DEG C-55 DEG C.
S3 in preceding method is particularly as follows: load in the enzyme reactor presetting immobilized-lipase by S2 gained reactant liquor and dimethyl carbonate based on total oils and fats molal quantity 0.1-3 times or diethyl carbonate, the consumption of lipase is based on 200-1000 enzyme of oil quality unit alive, reacts 3-10 hour in 20 DEG C-55 DEG C.Course of reaction uses gentle online dehydration.Effectively glyceride stock is converted into the yield of biodiesel more than 98%, and total glycerol content of biodiesel finished product is less than 0.2%, and acid value is less than 05mg KOH/g.Fig. 1 is shown in by course of reaction schematic diagram.
The online dehydration of heretofore described gentleness refers to utilize film, molecular sieve or air stripping.Film used by online dehydration is organic membrane, inoranic membrane or ceramic membrane etc.；Molecular sieve used by online dehydration isOrMolecular sieve etc.；Described air stripping is directly to be connected with the tank body equipped with anhydrous short chain alcohol or dimethyl carbonate or diethyl carbonate reactor side, and the temperature of air stripping liquid is 20-40 DEG C, and the opposite side of reactor is connected with vacuum pump, and then vacuum pump is connected with condenser；Vacuum control in reactor is 0-15 DEG C at 10-100Mpa, condenser temperature；Described short chain alcohol includes methanol, ethanol etc..
Heretofore described lipase includes the lipase deriving from yeast, mycete, antibacterial or other microorganism；Lipase is single lipase or the combination of multiple lipase.Such as, at least one during described lipase derives from antarctic candida (Candida antarctica), thermophilic hyphomycete (Thermomyces lanuginosus), aspergillus niger (Aspergillus niger), aspergillus oryzae (Aspergillus oryzae), rhizomucor miehei (Rhizomucor miehei) and Rhizopus oryzae (Rhizopus oryzae) etc..
Heretofore described oils and fats is the bio-oil containing polybasic unsaturated fatty acid, including Vegetable oil lipoprotein, animal oil, waste edible oil, acidification oil, the concise leftover bits and pieces of oils and fats and microbial grease etc..Wherein, described Vegetable oil lipoprotein is Oleum Ricini, Petiolus Trachycarpi oil, Oleum Brassicae campestris, soybean oil, Oleum Arachidis hypogaeae semen, Semen Maydis oil, Oleum Gossypii semen, Testa oryzae oil, curcas oil, shinyleaf yellowhorn oil or Jatropha curcas oil etc.；Described animal oil is fish oil, Adeps Bovis seu Bubali, Adeps Sus domestica or Adeps Caprae seu ovis etc.；Described microbial grease is yeast oils and fats or microalgae oils and fats etc..Described waste edible oil is hogwash fat or waste oil etc.；Described oil and fat refining leftover bits and pieces is acidification oil etc..
The present invention uses the biodiesel oil preparing process that liquid aliphatic enzyme and immobilized-lipase combine, and in liquid enzymatic leading portion course of reaction, it is not necessary to glyceride stock is carried out any pretreatment, oils and fats can be made to reach more than 90% to the conversion ratio of biodiesel.Next stage fixed lipase catalyzed during, during overall process or partial reaction, introduce online dehydration technique.For reducing total glycerol content in product further; introduce the 3rd step enzymatic conversion reaction; using dimethyl carbonate or diethyl carbonate as acyl acceptor; in overall process, introduce online dehydration simultaneously; bio-diesel yield finally can be made more than 98%; product acid value is less than 0.5mg KOH/g, and total glycerol content is less than 0.2%.Low-quality unedible oil fat can be changed into high-quality biological diesel oil by the present invention, enormously simplify follow-up separation purifying technique, has extraordinary economic benefit and social benefit.
Accompanying drawing explanation
Fig. 1 is the process chart that the method that the present invention uses liquid aliphatic enzyme and immobilized-lipase to combine prepares biodiesel.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.If not specializing, the conventional means that technological means used in embodiment is well known to those skilled in the art, raw materials used it is commercial goods.
Embodiment 1
By 10g waste oil, water based on oil quality 10% and the liquid aliphatic enzyme deriving from antarctic candida (Candida antarctica) of live based on 200 standard enzyme of unit oil quality (200U/g soybean oil), it is placed in and is suitable in one or more levels enzyme reactor enzymatic.Temperature control 35 DEG C, then at the uniform velocity will add in 3 hours based on the ethanol that oils and fats mol ratio is 4.5:1.After reacting 6 hours, the conversion ratio of effective oils and fats to biodiesel is 90%, then carries out reactant liquor standing split-phase, isolates the heavy phase containing enzyme and light phase.Heavy phase reclaims pheron further with membrance separation, choose the organic membrane that molecular cut off is 15000Da and carry out the recovery of above-mentioned lipase, the response rate of pheron is up to 95%, and in the enzyme liquid of recovery, the remaining quantity of by-product glycerin is less than 5%, and the enzyme of recovery can be reused.Light phase flow into immobilized enzyme reactor (immobilized-lipase deriving from aspergillus oryzae Aspergillus oryzae equipped with living based on 200 standard enzyme of unit oil quality) again, being simultaneously introduced based on coarse biodiesel mol ratio is the methanol of 1:1, react, temperature control 20 DEG C, methanol at the uniform velocity added in 1 hour.In this course of reaction, (film including organic membrane, inoranic membrane or ceramic membrane is dehydrated device and includes to carry out online dehydration as shown in Figure 1OrMolecular sieve is at interior water absorber).Reacting 4 hours, in system, effective oils and fats is 97% to the conversion ratio of biodiesel.Further coarse biodiesel is flowed into mutually again immobilized enzyme reactor (immobilized-lipase deriving from aspergillus oryzae Aspergillus oryzae equipped with living based on 200 standard enzyme of unit oil quality), being simultaneously introduced based on coarse biodiesel mol ratio is the dimethyl carbonate of 1:1, react, temperature control 20 DEG C.In this course of reaction, (film including organic membrane, inoranic membrane or ceramic membrane is dehydrated device and includes to carry out online dehydration as shown in Figure 1OrMolecular sieve is at interior water absorber).Reacting 0.5 hour, in system, effective oils and fats is 98.5% to the conversion ratio of biodiesel, and total glycerol content is 0.18%, and acid value is 0.3mg KOH/g.
Embodiment 2
By 10g Adeps Sus domestica, water based on oil quality 4% and enter the liquid aliphatic enzyme deriving from aspergillus oryzae (Aspergillus oryzae) lived based on 300 standard enzyme of unit oil quality, it is placed in and is suitable in one or more levels enzyme reactor enzymatic.Temperature control 40 DEG C, then at the uniform velocity will add in 4 hours based on the methanol that oils and fats mol ratio is 5:1.After reacting 8 hours, the conversion ratio of effective oils and fats to biodiesel is 91%.Then it is centrifuged reactant liquor separating, isolates the heavy phase containing enzyme and contain the light phase of coarse biodiesel.Heavy phase reclaims pheron further with membrance separation, choose the organic membrane that molecular cut off is 15000Da and carry out the recovery of above-mentioned lipase, the response rate of pheron is up to 95%, and in the enzyme liquid of recovery, the remaining quantity of by-product glycerin is less than 5%, and the enzyme of recovery can be reused.The light phase enzyme reactor (immobilized-lipase deriving from aspergillus oryzae Aspergillus oryzae equipped with living based on 200 standard enzyme of unit oil quality) flowed into again equipped with immobilized enzyme, being simultaneously introduced based on coarse biodiesel mol ratio is the methanol of 2:1, reacts.Temperature control 20 DEG C, methanol added in 1 hour.In this course of reaction, carry out online dehydration (including the water absorber of organic membrane) as shown in Figure 1.Reacting 4 hours, in system, effective oils and fats is 98% to the conversion ratio of biodiesel.Further, coarse biodiesel flows into the enzyme reactor (immobilized-lipase deriving from aspergillus oryzae Aspergillus oryzae equipped with living based on 200 standard enzyme of unit oil quality) equipped with immobilized enzyme mutually again, being simultaneously introduced based on coarse biodiesel mol ratio is the dimethyl carbonate of 0.2:1, reacts.Temperature control 20 DEG C.In this course of reaction, carry out online dehydration (including the water absorber of organic membrane) as shown in Figure 1.Reacting 1 hour, in system, effective oils and fats is 98.8% to the conversion ratio of biodiesel, and total glycerol is 0.12%, and acid value is 0.3mg KOH/g.
Embodiment 3
By 10g palmitoleic acid, water based on oil quality 5% and the liquid aliphatic enzyme deriving from thermophilic hyphomycete (Thermomyces lanuginosus) lived based on 200 standard enzyme of unit oil quality and the liquid aliphatic enzyme deriving from aspergillus oryzae (Aspergillus oryzae) lived based on 400 standard enzyme of unit oil quality, be placed in and be suitable in one or more levels enzyme reactor enzymatic.Temperature control 45 DEG C, then at the uniform velocity will add in 2 hours based on the ethanol that oils and fats mol ratio is 6:1.Reacting 5 hours, the conversion ratio of effective oils and fats to biodiesel is 92%, is then centrifuged reactant liquor separating, and isolates the heavy phase containing enzyme and contains the light phase of coarse biodiesel.Heavy phase reclaims pheron further with membrance separation, choose the inoranic membrane that molecular cut off is 15000 and carry out the recovery of above-mentioned lipase, the response rate of pheron is up to 95%, and in the enzyme liquid of recovery, the remaining quantity of by-product glycerin is less than 5%, and the enzyme of recovery can be reused.Isolated light phase enter back into immobilized enzyme reactor (immobilized-lipase deriving from aspergillus oryzae Aspergillus oryzae equipped with living) based on 200 standard enzyme of unit oil quality, being simultaneously introduced based on coarse biodiesel mol ratio is the ethanol of 1:1, reacts.Temperature control 20 DEG C, ethanol at the uniform velocity added in 1 hour.In this course of reaction, carry out air stripping as shown in Figure 1 and be dehydrated online.Reacting 5 hours, in system, effective oils and fats is 97.8% to the conversion ratio of biodiesel.Coarse biodiesel enters back into immobilized enzyme reactor (immobilized-lipase deriving from antarctic candida Candida antarctica equipped with living based on 200 standard enzyme of unit oil quality) mutually further, is simultaneously introduced the diethyl carbonate based on coarse biodiesel mol ratio is 1:1 and reacts.In this course of reaction, carry out online dehydration as shown in Figure 1.So-called air stripping is dehydrated online and refers to that enzyme reactor side connects dehydrated alcohol tank, opposite side connects vacuum pump and condenser, vacuum in control system is 15MPa, condenser temperature is 2 DEG C, and enzyme reactor temperature is 30 DEG C, reacts 1 hour, in system, the yield of fatty acid short-chain ester is 98.6%, total glycerol content is 0.1%, acid value is 0.4mg KOH/g..
Embodiment 4
By 10g yeast oils and fats, water based on oil quality 3% and the liquid aliphatic enzyme deriving from antarctic candida (Candida antarctica) lived based on 100 standard enzyme of unit oil quality and the liquid aliphatic enzyme deriving from thermophilic hyphomycete (Thermomyces lanuginosus) lived based on 300 standard enzyme of unit oil quality, it is placed in and is suitable in one or more levels enzyme reactor enzymatic.Temperature control 50 DEG C, then at the uniform velocity will add in 2 hours based on the methanol that oils and fats mol ratio is 4:1.Reacting 5 hours, the conversion ratio of effective oils and fats to biodiesel is 92%.Then carry out reactant liquor standing split-phase, isolate the heavy phase containing enzyme and contain the light phase of coarse biodiesel.Heavy phase reclaims pheron further with membrance separation, choose the ceramic membrane that molecular cut off is 15000 and carry out the recovery of above-mentioned lipase, the response rate of pheron is up to 95%, and in the enzyme liquid of recovery, the remaining quantity of by-product glycerin is less than 5%, and the enzyme of recovery can be reused.Isolated light phase enter back into immobilized enzyme reactor (immobilized-lipase deriving from aspergillus oryzae Aspergillus oryzae equipped with living) based on 200 standard enzyme of unit oil quality, being simultaneously introduced based on coarse biodiesel mol ratio is the methanol of 2:1, reacts.Temperature control 25 DEG C, methanol at the uniform velocity added in 1 hour.In this course of reaction, carry out air stripping as shown in Figure 1 and be dehydrated online.Reacting 4 hours, in system, effective oils and fats is 98.0% to the conversion ratio of biodiesel.Coarse biodiesel enters back into immobilized enzyme reactor (immobilized-lipase deriving from Aspergillus oryzae equipped with living based on 200 standard enzyme of unit oil quality) mutually further, is simultaneously introduced the diethyl carbonate based on coarse biodiesel mol ratio is 1:1 and reacts.Online dehydration as shown in Figure 1 is realized in this course of reaction.So-called air stripping is dehydrated online and refers to that enzyme reactor side connects dehydrated alcohol tank, opposite side connects vacuum pump and condenser, vacuum in control system is 15MPa, condenser temperature is 2 DEG C, enzyme reactor temperature is 30 DEG C, reacts 1.4 hours, and in system, the yield of fatty acid short-chain ester is 98.6%, total glycerol content is 0.13%, and acid value is 0.2mg KOH/g.
Embodiment 5
By little for 10g Oleum Verniciae fordii, water based on oil quality 8% and the liquid aliphatic enzyme deriving from antarctic candida (Candida antarctica) lived based on 800 standard enzyme of unit oil quality, it is placed in and is suitable in one or more levels enzyme reactor enzymatic.Temperature control 40 DEG C, then at the uniform velocity will add in 2 hours based on the ethanol that oils and fats mol ratio is 6:1.Reacting 5 hours, the conversion ratio of effective oils and fats to biodiesel is 91%.Then it is centrifuged reactant liquor separating, isolates the heavy phase containing enzyme and contain the light phase of coarse biodiesel.Heavy phase reclaims pheron further with membrance separation, choose the organic membrane that molecular cut off is 15000Da and carry out the recovery of above-mentioned lipase, the response rate of pheron is up to 95%, and in the enzyme liquid of recovery, the remaining quantity of by-product glycerin is less than 5%, and the enzyme of recovery can be reused.That separates light phase enters back into immobilized enzyme reactor (equipped with the immobilized-lipase deriving from thermophilic hyphomycete Thermomyces lanuginosus lived based on 200 standard enzyme of unit oil quality and the immobilized-lipase deriving from antarctic candida Candida antarctica lived based on 50 standard enzyme of unit oil quality), being simultaneously introduced based on coarse biodiesel mol ratio is the methanol of 1:1, reacts.Temperature control 30 DEG C, methanol added in 1 hour.In this course of reaction, carry out air stripping as shown in Figure 1 and be dehydrated online.Reacting 5 hours, in system, effective oils and fats is 97.3% to the conversion ratio of biodiesel.Coarse biodiesel enters back into immobilized enzyme reactor (immobilized-lipase deriving from Aspergillus oryzae equipped with living based on 500 standard enzyme of unit oil quality) mutually further, is simultaneously introduced the diethyl carbonate based on coarse biodiesel mol ratio is 1:1 and reacts.In this course of reaction, realize air stripping as shown in Figure 1 be dehydrated online.So-called air stripping is dehydrated online and refers to that enzyme reactor side connects absolute methanol tank, opposite side connects vacuum pump and condenser, vacuum in control system is 15MPa, condenser temperature is 4 DEG C, enzyme reactor temperature is 30 DEG C, reacts 1 hour, and in system, the yield of fatty acid short-chain ester is 98.6%, total glycerol content is 0.15%, and acid value is 0.45mg KOH/g.
Embodiment 6
By 10g fish oil, water based on oil quality 10% and the liquid aliphatic enzyme deriving from rhizomucor miehei (Rhizomucor miehei) lived based on 500 standard enzyme of unit oil quality, it is placed in and is suitable in one or more levels enzyme reactor enzymatic.Temperature control 55 DEG C, then at the uniform velocity will add in 3 hours based on the ethanol that oils and fats mol ratio is 6:1.Reacting 8 hours, the conversion ratio of effective oils and fats to biodiesel is 91%, is then centrifuged reactant liquor separating., isolate the heavy phase containing enzyme and contain the light phase of coarse biodiesel.Heavy phase reclaims pheron further with membrance separation, choose the inoranic membrane that molecular cut off is 15000 and carry out the recovery of above-mentioned lipase, the response rate of pheron is up to 95%, and in the enzyme liquid of recovery, the remaining quantity of by-product glycerin is less than 5%, and the enzyme of recovery can be reused.That separates light phase enters back into immobilized enzyme reactor (immobilized-lipase deriving from aspergillus oryzae Aspergillus oryzae equipped with living) based on 400 standard enzyme of unit oil quality, being simultaneously introduced based on coarse biodiesel mol ratio is the methanol of 1.5:1, reacts.Temperature control 25 DEG C, methanol at the uniform velocity added in 1 hour.In this course of reaction, carry out online dehydration as shown in Figure 1.Reacting 5 hours, in system, effective oils and fats is 97.2% to the conversion ratio of biodiesel.Further, coarse biodiesel enters back into immobilized enzyme reactor (immobilized-lipase deriving from Thermomyces lanuginosus equipped with living based on 300 standard enzyme of unit oil quality) mutually, is simultaneously introduced the diethyl carbonate based on coarse biodiesel mol ratio is 1:1 and reacts.In this course of reaction, carry out air stripping as shown in Figure 1 and be dehydrated online.Air stripping is dehydrated online and refers to that enzyme reactor side connects Carbon Dioxide dimethyl ester tank, opposite side connects vacuum pump and condenser, vacuum in control system is 15MPa, condenser temperature is 2 DEG C, enzyme reactor temperature is 30 DEG C, reacts 1 hour, and in system, the yield of fatty acid short-chain ester is 98.6%, total glycerol content is 0.08%, and acid value is 0.5mg KOH/g.
Embodiment 7
By 10g hogwash fat, water based on oil quality 8% and the liquid aliphatic enzyme deriving from rhizomucor miehei (Rhizomucor miehei) lived based on 500 standard enzyme of unit oil quality, it is placed in and is suitable in one or more levels enzyme reactor enzymatic.Temperature control 35 DEG C, then at the uniform velocity will add in 4 hours based on the ethanol that oils and fats mol ratio is 5:1.Reacting 8 hours, the conversion ratio of effective oils and fats to biodiesel is 92%.Then it is centrifuged reactant liquor separating, isolates the heavy phase containing enzyme and contain the light phase of coarse biodiesel.Heavy phase reclaims pheron further with membrance separation, choose the ceramic membrane that molecular cut off is 15000 and carry out the recovery of above-mentioned lipase, the response rate of pheron is up to 95%, and in the enzyme liquid of recovery, the remaining quantity of by-product glycerin is less than 5%, and the enzyme of recovery can be reused.That separates light phase enters back into immobilized enzyme reactor (equipped with the immobilized-lipase deriving from aspergillus oryzae Aspergillus oryzae lived based on 100 standard enzyme of unit oil quality and the immobilized-lipase deriving from antarctic candida Candida antarctica lived based on 100 standard enzyme of unit oil quality), being simultaneously introduced based on coarse biodiesel mol ratio is the ethanol of 1:1, reacts.Temperature control 25 DEG C, ethanol at the uniform velocity added in 2 hours.In this course of reaction, carry out air stripping as shown in Figure 1 and be dehydrated online.Reacting 4 hours, in system, effective oils and fats is 97.3% to the conversion ratio of biodiesel.Coarse biodiesel enters back into immobilized enzyme reactor (immobilized-lipase deriving from antarctic candida Candida antarctica equipped with living based on 200 standard enzyme of unit oil quality) mutually further, is simultaneously introduced the dimethyl carbonate based on coarse biodiesel mol ratio is 1:1 and reacts.In this course of reaction, carry out air stripping as shown in Figure 1 and be dehydrated online.So-called air stripping is dehydrated online and refers to that enzyme reactor side connects absolute methanol tank, opposite side connects vacuum pump and condenser, vacuum in control system is 15MPa, condenser temperature is 2 DEG C, enzyme reactor temperature is 30 DEG C, reacts 0.8 hour, and in system, the yield of fatty acid short-chain ester is 98.6%, total glycerol content is 0.15%, and acid value is 0.3mg KOH/g.
Embodiment 8
By 10g acidification oil, water based on oil quality 6% and the liquid aliphatic enzyme deriving from aspergillus oryzae (Aspergillus oryzae) lived based on 500 standard enzyme of unit oil quality, it is placed in and is suitable in one or more levels enzyme reactor enzymatic.Temperature control 40 DEG C, then at the uniform velocity will add in 3 hours based on the propanol that oils and fats mol ratio is 5:1.Reacting 8 hours, the conversion ratio of effective oils and fats to biodiesel is 93%, is then centrifuged reactant liquor separating, and isolates the heavy phase containing enzyme and contains the light phase of coarse biodiesel.Heavy phase reclaims pheron further with membrance separation, choose the organic membrane that molecular cut off is 15000Da and carry out the recovery of above-mentioned lipase, the response rate of pheron is up to 95%, and in the enzyme liquid of recovery, the remaining quantity of by-product glycerin is less than 5%, and the enzyme of recovery can be reused.Isolated light phase enter back into immobilized enzyme reactor (immobilized-lipase deriving from aspergillus oryzae Aspergillus oryzae equipped with living) based on 600 standard enzyme of unit oil quality, being simultaneously introduced based on coarse biodiesel mol ratio is the methanol of 2:1, reacts.Temperature control 35 DEG C, methanol at the uniform velocity added in 1 hour.In this course of reaction, carry out online dehydration as shown in Figure 1.Reacting 4 hours, in system, effective oils and fats is 97.1% to the conversion ratio of biodiesel.Coarse biodiesel enters back into immobilized enzyme reactor (immobilized-lipase deriving from antarctic candida Candida antarctica equipped with living based on 300 standard enzyme of unit oil quality) mutually further, is simultaneously introduced the dimethyl carbonate based on coarse biodiesel mol ratio is 1:1 and reacts.In this course of reaction, carry out air stripping as shown in Figure 1 and be dehydrated online.So-called air stripping is dehydrated online and refers to that enzyme reactor side connects absolute methanol tank, opposite side connects vacuum pump and condenser, vacuum in control system is 15MPa, condenser temperature is 2 DEG C, enzyme reactor temperature is 30 DEG C, reacts 1 hour, and in system, the yield of fatty acid short-chain ester is 98.7%, total glycerol content is 0.14%, and acid value is 0.25mg KOH/g.
Embodiment 9
By 10g Oleum Ricini, water based on oil quality 5% and the liquid aliphatic enzyme deriving from antarctic candida (Candida antarctica) lived based on 800 standard enzyme of unit oil quality, it is placed in and is suitable in one or more levels enzyme reactor enzymatic.Temperature control 45 DEG C, then at the uniform velocity will add in 3 hours based on the ethanol that oils and fats mol ratio is 6:1.Reacting 6 hours, the conversion ratio of effective oils and fats to biodiesel is 91%, is then centrifuged reactant liquor separating, and isolates the heavy phase containing enzyme and contains the light phase of coarse biodiesel.Heavy phase reclaims pheron further with membrance separation, choose the organic membrane that molecular cut off is 15000Da and carry out the recovery of above-mentioned lipase, the response rate of pheron is up to 95%, and in the enzyme liquid of recovery, the remaining quantity of by-product glycerin is less than 5%, and the enzyme of recovery can be reused.Isolated coarse biodiesel enters back into immobilized enzyme reactor (immobilized-lipase deriving from antarctic candida Candida antarctica equipped with living based on 200 standard enzyme of unit oil quality) mutually, being simultaneously introduced based on coarse biodiesel mol ratio is the methanol of 1:1, reacts.Temperature control 20 DEG C, ethanol added in 2 hours.In this course of reaction, carry out online dehydration as shown in Figure 1.Reacting 3 hours, in system, effective oils and fats is 97.4% to the conversion ratio of biodiesel.Coarse biodiesel enters back into immobilized enzyme reactor (immobilized-lipase deriving from antarctic candida Candida antarctica equipped with living based on 500 standard enzyme of unit oil quality) mutually further, is simultaneously introduced the dimethyl carbonate based on coarse biodiesel mol ratio is 0.5:1 and reacts.In this course of reaction, carry out air stripping as shown in Figure 1 and be dehydrated online.So-called air stripping is dehydrated online and refers to that enzyme reactor side connects Carbon Dioxide dimethyl ester tank, opposite side connects vacuum pump and condenser, vacuum in control system is 20MPa, condenser temperature is 0 DEG C, enzyme reactor temperature is 35 DEG C, reacts 1.5 hours, and in system, the yield of fatty acid short-chain ester is 98.8%, total glycerol content is 0.12%, and acid value is 0.4mg KOH/g.
Embodiment 10
By 10g waste oil, water based on oil quality 8% and the liquid aliphatic enzyme deriving from aspergillus oryzae (Aspergillus oryzae) lived based on 2000 standard enzyme of unit oil quality, it is placed in and is suitable in one or more levels enzyme reactor enzymatic.Temperature control 35 DEG C, then at the uniform velocity will add in 2 hours based on the methanol that oils and fats mol ratio is 5:1.Reacting 5 hours, the conversion ratio of effective oils and fats to biodiesel is 93%, is then centrifuged reactant liquor separating, and isolates the heavy phase containing enzyme and contains the light phase of coarse biodiesel.Heavy phase reclaims pheron further with membrance separation, choose the inoranic membrane that molecular cut off is 15000 and carry out the recovery of above-mentioned lipase, the response rate of pheron is up to 95%, and in the enzyme liquid of recovery, the remaining quantity of by-product glycerin is less than 5%, and the enzyme of recovery can be reused.Isolated coarse biodiesel enters back into immobilized enzyme reactor (immobilized-lipase deriving from antarctic candida Candida antarctica equipped with living based on 200 standard enzyme of unit oil quality) mutually, it is simultaneously introduced ethanol based on coarse biodiesel 2:1, reacts.Temperature control 30 DEG C, ethanol added in 2 hours.In this course of reaction, carry out online dehydration as shown in Figure 1.Reacting 3 hours, in system, effective oils and fats is 97.4% to the conversion ratio of biodiesel.Coarse biodiesel enters back into immobilized enzyme reactor (immobilized-lipase deriving from antarctic candida Candida antarctica equipped with living based on 500 standard enzyme of unit oil quality) mutually further, is simultaneously introduced the dimethyl carbonate based on coarse biodiesel mol ratio is 0.5:1 and reacts.In this course of reaction, carry out air stripping as shown in Figure 1 to be dehydrated online, so-called air stripping is dehydrated online and refers to that enzyme reactor side connects Carbon Dioxide dimethyl ester tank, and opposite side connects vacuum pump and condenser, and the vacuum in control system is 20MPa, condenser temperature is 0 DEG C, enzyme reactor temperature is 35 DEG C, reacts 1.5 hours, and in system, the yield of fatty acid short-chain ester is 98.8%, total glycerol content is 0.12%, and acid value is 0.35mg KOH/g.
Embodiment 11
By 10g hogwash fat, water based on oil quality 10% and the liquid aliphatic enzyme deriving from aspergillus niger (Aspergillus niger) lived based on 500 standard enzyme of unit oil quality, it is placed in and is suitable in one or more levels enzyme reactor enzymatic.Temperature control 35 DEG C, then at the uniform velocity will add in 3 hours based on the methanol that oils and fats mol ratio is 6:1.Reacting 6 hours, the conversion ratio of effective oils and fats to biodiesel is 92%, then carries out standing or centrifugation by reactant liquor, isolates the heavy phase containing enzyme and contains the light phase of coarse biodiesel.Heavy phase reclaims pheron further with membrance separation, choose the organic membrane that molecular cut off is 15000Da and carry out the recovery of above-mentioned lipase, the response rate of pheron is up to 95%, and in the enzyme liquid of recovery, the remaining quantity of by-product glycerin is less than 5%, and the enzyme of recovery can be reused.Isolated light phase enter back into immobilized enzyme reactor (immobilized-lipase deriving from rhizomucor miehei Rhizomucor miehei equipped with living) based on 200 standard enzyme of unit oil quality, being simultaneously introduced based on coarse biodiesel mol ratio is the methanol of 2:1, reacts.Temperature control 20 DEG C, methanol added in 2 hours.In this course of reaction, carry out online dehydration as shown in Figure 1.Reacting 4 hours, in system, effective oils and fats is 97.5% to the conversion ratio of biodiesel.Coarse biodiesel enters back into immobilized enzyme reactor (immobilized-lipase deriving from antarctic candida Candida antarctica equipped with living based on 600 standard enzyme of unit oil quality) mutually further, is simultaneously introduced the diethyl carbonate based on coarse biodiesel mol ratio is 1:1 and reacts.In this course of reaction, realize air stripping as shown in Figure 1 to be dehydrated online, so-called air stripping is dehydrated online and refers to that enzyme reactor side connects dehydrated alcohol tank, and opposite side connects vacuum pump and condenser, and the vacuum in control system is 20MPa, condenser temperature is 0 DEG C, enzyme reactor temperature is 35 DEG C, reacts 1.5 hours, and in system, the yield of fatty acid short-chain ester is 98.6%, total glycerol content is 0.15%, and acid value is 0.35mg KOH/g.
Embodiment 12
By little for 10g Oleum Verniciae fordii, water based on oil quality 8% and the liquid aliphatic enzyme deriving from thermophilic hyphomycete (Thermomyces lanuginosus) lived based on 500 standard enzyme of unit oil quality, it is placed in and is suitable in one or more levels enzyme reactor enzymatic.Temperature control 45 DEG C, then at the uniform velocity will add in 4 hours based on the ethanol that oils and fats mol ratio is 6:1.Reacting 6 hours, the conversion ratio of effective oils and fats to biodiesel is 92%, is then centrifuged reactant liquor separating, and isolates the heavy phase containing enzyme and contains the light phase of coarse biodiesel.Heavy phase reclaims pheron further with membrance separation, choose the organic membrane that molecular cut off is 15000Da and carry out the recovery of above-mentioned lipase, the response rate of pheron is up to 95%, and in the enzyme liquid of recovery, the remaining quantity of by-product glycerin is less than 5%, and the enzyme of recovery can be reused.Isolated light phase enter back into immobilized enzyme reactor (immobilized-lipase deriving from antarctic candida Candida antarctica equipped with living based on 200 standard enzyme of unit oil quality), be simultaneously introduced the ethanol based on coarse biodiesel mol ratio is 1:1 and react.Temperature control 25 DEG C, ethanol added in 1 hour.In this course of reaction, carry out online dehydration as shown in Figure 1.Reacting 3 hours, in system, effective oils and fats is 97.4% to the conversion ratio of biodiesel.Coarse biodiesel enters back into immobilized enzyme reactor (immobilized-lipase deriving from antarctic candida Candida antarctica equipped with living based on 800 standard enzyme of unit oil quality) mutually further, is simultaneously introduced the dimethyl carbonate based on coarse biodiesel mol ratio is 1.5:1 and reacts.In this course of reaction, carry out air stripping as shown in Figure 1 to be dehydrated online, so-called air stripping is dehydrated online and refers to that enzyme reactor side connects Carbon Dioxide dimethyl ester tank, and opposite side connects vacuum pump and condenser, and the vacuum in control system is 20MPa, condenser temperature is 0 DEG C, enzyme reactor temperature is 35 DEG C, reacts 1.5 hours, and in system, the yield of fatty acid short-chain ester is 98.8%, total glycerol content is 0.16%, and acid value is 0.4mg KOH/g.
Embodiment 13
By 10g algae oils and fats, water based on oil quality 12% and the liquid aliphatic enzyme deriving from antarctic candida (Candida antarctica) lived based on 600 standard enzyme of unit oil quality, it is placed in and is suitable in one or more levels enzyme reactor enzymatic.Temperature control 45 DEG C, then will add based on the ethanol speed change that oils and fats mol ratio is 6:1.The ethanol of 40% at the uniform velocity adds before the reaction for 2 hours, and the ethanol of remaining 60% at the uniform velocity added in ensuing 2 hours.Reacting 8 hours, in system, effective oils and fats is 90% to the conversion ratio of biodiesel.Then it is centrifuged reactant liquor separating, isolates the heavy phase containing enzyme and contain the light phase of coarse biodiesel.Heavy phase reclaims pheron further with membrance separation, choose the ceramic membrane that molecular cut off is 15000 and carry out the recovery of above-mentioned lipase, the response rate of pheron is up to 95%, and in the enzyme liquid of recovery, the remaining quantity of by-product glycerin is less than 5%, and the enzyme of recovery can be reused.Isolated light phase enter back into immobilized enzyme reactor (equipped with the immobilized-lipase deriving from antarctic candida Candida antarctica lived based on 100 standard enzyme of unit oil quality and the immobilized-lipase deriving from rhizomucor miehei Rhizomucor miehei lived based on 100 standard enzyme of unit oil quality), being simultaneously introduced based on coarse biodiesel mol ratio is the methanol of 1:1, reacts.Temperature control 25 DEG C, methanol added in 1 hour.In this course of reaction, carry out online dehydration as shown in Figure 1.Reacting 3 hours, in system, effective oils and fats is 97.4% to the conversion ratio of biodiesel.Coarse biodiesel enters back into immobilized enzyme reactor (immobilized-lipase deriving from antarctic candida Candida antarctica equipped with living based on 500 standard enzyme of unit oil quality) mutually further, is simultaneously introduced the dimethyl carbonate based on coarse biodiesel mol ratio is 1:1 and reacts.In this course of reaction, carry out air stripping as shown in Figure 1 to be dehydrated online, so-called air stripping is dehydrated online and refers to that enzyme reactor side connects Carbon Dioxide dimethyl ester tank, and opposite side connects vacuum pump and condenser, and the vacuum in control system is 20MPa, condenser temperature is 0 DEG C, enzyme reactor temperature is 35 DEG C, reacts 1.5 hours, and in system, the yield of fatty acid short-chain ester is 98.6%, total glycerol content is 0.14%, and acid value is 0.45mg KOH/g.
Although, the present invention is described in detail the most with a general description of the specific embodiments, but on the basis of the present invention, can make some modifications or improvements it, and this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention.
Claims (9)
1. the method improving biodiesel quality, it is characterised in that comprise the following steps:
S1, by oils and fats, short chain alcohol, water and liquid aliphatic enzyme in one or more levels enzyme reactor
React, then reactant liquor is separated into heavy phase and light phase, the enzyme in recycling heavy phase,
Light phase for follow-up immobilized enzyme conversion；
S2, by anti-equipped with one or more levels enzyme of immobilized-lipase for the light phase inflow that obtains in S1
Answer in device, and add short chain alcohol and react, containing biodiesel crude product in gained reactant liquor,
Course of reaction is dehydrated online；
S3, S2 gained reactant liquor is flowed in next stage enzyme reactor, make in reactant liquor the most anti-
Should glyceride and fatty acid enzymatically send out with dimethyl carbonate or diethyl carbonate completely
Raw reaction, carries out online dehydration to remove the by-product generated in course of reaction in course of reaction
Water, and then realize the conversion from oils and fats to biodiesel.
Method the most according to claim 1, it is characterised in that S1 is to one or more levels
Enzyme reactor adds oils and fats, the short chain alcohol of oils and fats molal quantity 4-8 times, oil quality 2%-20%
Water and the liquid aliphatic enzyme of unit of living based on 200-2000 standard enzyme of oil quality, in 30
DEG C-55 DEG C react 3-8 hour.
Method the most according to claim 1 and 2, it is characterised in that S1 gained is reacted
Liquid by centrifugation or after static layering, reclaims the pheron in heavy phase with membrance separation；Separation and recovery enzyme
The film of albumen includes metal film, organic membrane, inoranic membrane or ceramic membrane.
4. according to the method described in any one of claim 1-3, it is characterised in that S2 particularly as follows:
The short chain alcohol of light phase and oils and fats molal quantity 1-3 times obtained in S1 is flowed into equipped with based on oils and fats matter
In one or more levels enzyme reactor of the immobilized-lipase measuring 200-1000 enzyme unit alive, in
20 DEG C-55 DEG C are reacted 0.5-3 hour.
5. according to the method described in any one of claim 1-4, it is characterised in that S3 particularly as follows:
By S2 gained reactant liquor and dimethyl carbonate based on total oils and fats molal quantity 0.1-3 times or carbonic acid two
Ethyl ester loads in the enzyme reactor presetting immobilized-lipase, and the consumption of lipase is based on oil
Lipid amount 200-1000 enzyme unit alive, reacts 3-10 hour in 20 DEG C-55 DEG C.
6. according to the method described in any one of claim 1-5, it is characterised in that described online
Dehydration refers to utilize film, molecular sieve or air stripping.
Method the most according to claim 6, it is characterised in that the film used by online dehydration
For organic membrane, inoranic membrane or ceramic membrane；Molecular sieve used by online dehydration isOrMolecule
Sieve；Described air stripping be by reactor side directly with equipped with anhydrous short chain alcohol or dimethyl carbonate or
The tank body of diethyl carbonate is connected, and the temperature of air stripping liquid is 20-40 DEG C, another of reactor
Side is connected with vacuum pump, and then vacuum pump is connected with condenser；Vacuum control in reactor is existed
10-100Mpa, condenser temperature is 0-15 DEG C；Described short chain alcohol includes methanol, ethanol.
8. according to the method described in any one of claim 1-7, it is characterised in that described fat
Enzyme includes the lipase deriving from yeast, mycete, antibacterial or other microorganism；Lipase is single
Plant lipase or the combination of multiple lipase.
9. according to the method described in any one of claim 1-8, it is characterised in that described oils and fats
For the bio-oil containing polybasic unsaturated fatty acid, including Vegetable oil lipoprotein, animal oil, give up
The concise leftover bits and pieces of edible oil, acidification oil, oils and fats and microbial grease.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610527969.3A CN105950674A (en) | 2016-07-06 | 2016-07-06 | Method for improving quality of biodiesel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610527969.3A CN105950674A (en) | 2016-07-06 | 2016-07-06 | Method for improving quality of biodiesel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105950674A true CN105950674A (en) | 2016-09-21 |
Family
ID=56900393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610527969.3A Pending CN105950674A (en) | 2016-07-06 | 2016-07-06 | Method for improving quality of biodiesel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105950674A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108103116A (en) * | 2017-12-25 | 2018-06-01 | 东莞深圳清华大学研究院创新中心 | A kind of technique of enzymatic preparing biodiesel from lipid |
| CN111411129A (en) * | 2019-01-04 | 2020-07-14 | 清华大学 | Process for improving enzymatic grease preparation biodiesel by adding decomposable ammonium salt |
| CN114657062A (en) * | 2022-04-25 | 2022-06-24 | 广州市朗坤环境科技有限公司 | Reactor and method for preparing biodiesel by lipase catalysis for deacidification |
| WO2022227123A1 (en) * | 2021-04-26 | 2022-11-03 | 东莞深圳清华大学研究院创新中心 | Technological method for co-production of l-ascorbic acid palmitate and biodiesel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676304B (en) * | 2011-03-15 | 2013-06-19 | 清华大学 | Preparation method for biodiesel fuel |
| CN105420298A (en) * | 2014-09-18 | 2016-03-23 | 清华大学 | Online dehydration and acid reduction process used in biodiesel preparation process adopting enzymatic oil and fat |
-
2016
- 2016-07-06 CN CN201610527969.3A patent/CN105950674A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676304B (en) * | 2011-03-15 | 2013-06-19 | 清华大学 | Preparation method for biodiesel fuel |
| CN105420298A (en) * | 2014-09-18 | 2016-03-23 | 清华大学 | Online dehydration and acid reduction process used in biodiesel preparation process adopting enzymatic oil and fat |
Non-Patent Citations (3)
| Title |
|---|
| A-RA GOA ET AL: "Enzymatic coproduction of biodiesel and glycerol carbonate from soybean oil in solvent-free system", 《ENZYME AND MICROBIAL TECHNOLOGY》 * |
| ER-ZHENG SU ET AL: "Lipase-catalyzed irreversible transesterification of vegetable oils for fatty acid methyl esters production with dimethyl carbonate as the acyl acceptor", 《BIOCHEMICAL ENGINEERING JOURNAL》 * |
| JI YOUNG MIN ET AL: "Lipase-catalyzed simultaneous biosynthesis of biodiesel and glycerol carbonate from corn oil in dimethyl carbonate", 《BIOTECHNOL LETT》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108103116A (en) * | 2017-12-25 | 2018-06-01 | 东莞深圳清华大学研究院创新中心 | A kind of technique of enzymatic preparing biodiesel from lipid |
| CN111411129A (en) * | 2019-01-04 | 2020-07-14 | 清华大学 | Process for improving enzymatic grease preparation biodiesel by adding decomposable ammonium salt |
| CN111411129B (en) * | 2019-01-04 | 2021-10-01 | 清华大学 | Process for improving enzymatic grease preparation biodiesel by adding decomposable ammonium salt |
| WO2022227123A1 (en) * | 2021-04-26 | 2022-11-03 | 东莞深圳清华大学研究院创新中心 | Technological method for co-production of l-ascorbic acid palmitate and biodiesel |
| CN114657062A (en) * | 2022-04-25 | 2022-06-24 | 广州市朗坤环境科技有限公司 | Reactor and method for preparing biodiesel by lipase catalysis for deacidification |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Moazeni et al. | Enzymatic transesterification for biodiesel production from used cooking oil, a review | |
| EP2636747B1 (en) | Process for preparing biodiesel with lipase and separate online dehydration | |
| EP2687588B1 (en) | Method for preparing biodiesel | |
| Pinzi et al. | Latest trends in feedstocks for biodiesel production | |
| He et al. | Cost-effective biodiesel production from wet microalgal biomass by a novel two-step enzymatic process | |
| CN101284998A (en) | Process for preparing biodiesel by coupling catalytic reaction and separation process | |
| CN105950674A (en) | Method for improving quality of biodiesel | |
| US11034984B2 (en) | Method for improving yield of enzymatic preparation of biodiesel from greases | |
| CN105420298B (en) | Online dehydration and deacidification technique during enzymatic preparing biodiesel from lipid | |
| CN105925628A (en) | Coupling process for producing biodiesel with enzymic method and enriching polyunsaturated fatty acid ester | |
| KR101244469B1 (en) | Method and Device for Producing Bio-Diesel and Fermentation Material by Culturing Microalgae | |
| CN106399406A (en) | Coupling process for preparing biodiesel and enriching polyunsaturated fatty acid esters | |
| Arous et al. | Oleaginous microorganisms for simultaneous biodiesel production and wastewater treatment: a review | |
| Al Makishah | Bioenergy: Microbial Biofuel Production Advancement. | |
| CN103882069A (en) | Preparation method of long chain fatty acid ester | |
| Ozsoy et al. | Fungal oil production from oleaginous fungi Mucor circinelloides and Aspergillus oryzae cultivated on sugar beet pulp | |
| CN106118888A (en) | Different acyl receptor combination prepares the new technology of biodiesel | |
| KR102411079B1 (en) | Method for preparing of bio-diesel and fatty acid using microalgae oil | |
| Paes et al. | Omics in biofuel production: a sustainable approach | |
| CN107034243A (en) | The preparation technology of fatty acid short-chain ester | |
| CN101381614A (en) | Technique for preparing biodiesel by catalyzing oil using recovery of non-immobilized lipase | |
| Antunes et al. | Microbial Biotechnology for Renewable and Sustainable Energy: The Current Status of Biogas, Biodiesel, and Bioethanol in Brazil | |
| CN108103116A (en) | A kind of technique of enzymatic preparing biodiesel from lipid | |
| CN102676305A (en) | Method for preparing biodiesel by oil | |
| Takara et al. | Sustainable bioenergy from biofuel residues and wastes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160921 |