CN101805672B - Biodiesel and preparation method thereof - Google Patents
Biodiesel and preparation method thereof Download PDFInfo
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- CN101805672B CN101805672B CN2010101228375A CN201010122837A CN101805672B CN 101805672 B CN101805672 B CN 101805672B CN 2010101228375 A CN2010101228375 A CN 2010101228375A CN 201010122837 A CN201010122837 A CN 201010122837A CN 101805672 B CN101805672 B CN 101805672B
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Abstract
The invention relates to a biodiesel and a preparation method thereof. The preparation method for the biodiesel comprises the following steps: using larvas (maggots) of insecta diptera cyclorrhapha insect flies and adopting a solvent method to extract oil in the maggots to obtain maggot oil with a low acid value (the acid value is less than or equal to 2) or a high acid value (the acid value is higher than 2); respectively carrying out ester exchange or pre-esterification ester exchange reaction on the maggot oil; carrying out phase separation on the processed maggot oil to obtain crude biodiesel; and finally adopting the adsorption clarification technology or the molecular distillation technology to carry out purification treatment on the crude biodiesel to obtain the refined biodiesel. The invention has the advantages of wide raw material source, easy cultivation and low production cost. And the invention also has the advantages of opening a novel technical route for producing biodiesel and also providing a novel approach for the development and utilization of maggots.
Description
Technical field
The present invention relates to field of renewable energy technology, relate in particular to a kind of biofuel and preparation method thereof.
Background technology
Biofuel is claimed biochemical diesel oil again, is meant that with Vegetable oil lipoprotein such as oilseed plant and engineering microalgae and animal oil and fat, waste cooking oil etc. be raw material, the longer chain fatty acid methyl esters or the ethyl ester that generate through ester exchange process.Biofuel is except that the performance close with petrifaction diesel; Also have lasting renewable performance, and good environmental protection characteristic, oxygen level is high in the biofuel; Not sulfur-bearing and aromatic series alkane; Carbon monoxide, sulfurous gas, sulfide amount lower greatly in the waste gas that burning produces, and in addition, the degradability of biofuel is also apparently higher than petrifaction diesel.
The raw material of preparation biofuel is mainly Vegetable oil lipoprotein at present, like peanut oil, VT 18, rapeseed oil, Oleum Cocois, plam oil, Jatropha curcas oil, engineering marine alga grease; Waste cooking oil; Animal oil like useless lard, fish oil etc., and extracts the grease that obtains behind the plant-animal prevalent variety cultivation.This patent discloses with saueda salsa oil CN101070483 [utilizing saueda salsa oil production method of bio-diesel oil, Yang Qingli, Yu Shanlin, Zhu Feng, Qin Song, Pan Lijuan, Cao Yuliang] is that raw material is with single stage method production method of bio-diesel oil; CN101113356 [a kind ofly produces method of bio-diesel oil with sewer oil; Father-in-law's sky wave] this patent is to draw thick monoesters about the sewer oil of earlier removing colloid and impurity through purification with methyl alcohol, sodium methylate reaction, further handles the smart monoesters that obtains and alkane again and flows and section synthesize biofuel.Adopt some shortcomings of feedstock production biofuel existence described in above each raw material and the patent; On the one hand with edible oil contention raw material; Tie up the space of grain farming; Aggravation China's grain problem in short supply is that the own price of raw material such as peanut oil and VT 18 is high on the other hand, makes the cost of biofuel uprise thereupon.Therefore according to statistics, 75% of biofuel cost is a raw materials cost, thereby seeking that new cheap raw material reduces cost is the key that realizes the biofuel industrialization.
Fly (Flies) wide material sources and quantity are huge; Be complete metamorphosis (Complete metamorphosis); Comprise ovum (Egg), larva (Maggot), pupa (Pupa), adult (Flies) four-stage its life history; Belong to typical complete metamorphosis, belong to Insecta Diptera Aristocera (Cyclorrhapha) insect kind.The fly maggot that the present invention relates to is the larva (Maggot) of fly under each section of Aristocera (Cyclorrhapha).Fly has the physilogical characteristics that a mating can be laid eggs all the life, and prolificacy is strong, and whole life is 28 days.Female fly can lay eggs 5-6 time all one's life, and each about 100-150 grain of laying to hatching fly maggot 3-4 days, can be bred fly maggot 10-12 generation in 1 year from ovum.The aquaculture cost of fly maggot is very low, raising is easy to operate, and its raising can be carried out at indoor or outdoors, and the substratum wide material sources are like the tankage of agricultural byproducts such as wheat bran, rice bran, vinasse, bean dregs, excrement of animals etc.Fly maggot large-scale cultivation technology has been attained maturation at present, has also realized mechanize and mass-producing in developed countries such as the U.S., as adopting a large amount of cheap fly maggot oil production biofuel, can lower its production cost significantly.
Chinese scholars focuses mostly at aspects such as fly maggot protein matter, chitosan, Regitex FAs about the applied research of fly maggot at present.Gross protein value is up to 60.88% in the fly maggot, and fly maggot also can be developed into related prodss such as medicine, healthcare products, biochemical preparation, agricultural chemicals and chemical industry except that doing the animal protein source.Patent CN 1415757A [a kind ofly from fly maggot, extract protein and chitin and prepare methods of chitosan with chitin with enzyme hydrolysis method, the summer Wenshui, Chen Jie builds beautiful jade ingeniously; He Jidong] relate to the enzymic hydrolysis process for extracting and the Application and Development thereof of fly maggot protein matter and chitin.New through looking into, do not see that as yet fly maggot becomes the bibliographical information of biofuel both at home and abroad at present.The bright article lipid content of fly maggot is 10%-20%, and its dry product lipid content is 20%-40%.Having with Vegetable oil lipoprotein (as: rapeseed oil) as the greasy fly maggot oil of insect has some serious differences, and the grease of plant exists because of the oil cell that is present in plant or with forms such as oil droplets, and its process for extracting is relatively easy.Having research that betel nut kind benevolence is pulverized the back and adopt single solvent ethyl acetate to extract, is 1: 10 at solid-liquid ratio, extracts 4h under 60 ℃ of bath temperature conditions; The yield of betel nut seed oil just can reach 95.01% (Zhou Wenhua, Zhang Haide, He Shuan; Deng; The research of betel oil extractive technique, tropical agriculture engineering 2008,32 (2): 1-4.); CN 1065879A [leaches the method for Viscotrol C with alcohol; Liu Dachuan; Unfold neat Yutang] this patent is about the castor-oil plant cleaning, roll embryo, steam fry after, a part of Viscotrol C is produced in squeezing earlier; Leach the residue grease in the Semen Ricini cake with alcohol then, mixing oil is handled through deposition, filtration, depickling and decolouring and is made industry or pharmaceutical Viscotrol C.And the insect grease has three kinds of existing waies in insect body: the alkyl of monoesters such as first glyceryl ester, cholesterol ester combines to form more weak non covalent bond between Van der Waals key or hydrophobic bond and other lipid and proteinic hydrophobic bond, has fat in the fatty tissue, BSA, lipid acid-complex body etc. by this way; Its two phospholipid, cholesterol isopolarity lipid are stored in plasma membrane, plastosome, endoplasmic reticulum etc. and give birth in body film and the serum nucleoprotein complex body, form hydrogen bond, ionic linkage, and hydrophobic bond between normal and protein; The third is that covalent linkage with forms such as ester bond, amido linkage, glycosidic bonds exists, in lipid acid, hydroxy fatty acid, complicated branched chain fatty acid.It is to formulate the main foundation of its process for extracting that existence, the solubleness of insect grease in above-mentioned organism reaches with other composition combinations.The existence owing to lipolytic enzyme makes fat hydrolysis produce a large amount of unsaturated fatty acidss in the fly maggot body in addition; Add the effect of oxygen in the air, fly maggot oil has influence on follow-up biodiesel manufacture reaction with other the same the becoming sour more easily than Vegetable oil lipoprotein of insect grease from face under identical state.In addition; The moity of fly maggot oil also exists difference with Vegetable oil lipoprotein with each composition relative content ratio; Saturated lipid acid is main with palmitinic acid (C16:0) in its grease; The content of Triple Pressed Stearic Acid (C18:0) is lower, also exists the comparatively rare odd-carbon fatty acid of nature simultaneously, like 15 carbonic acid.Also contain abundant unsaturated fatty acids in the fly maggot oil, wherein oleic acid (C18:1), linolic acid (C18:2), Zoomeric acid (C16:1) content are higher.Research shows, factors such as fly maggot oil lipid acid is formed with its kind, grown, nutritional status, environment or feed are relevant.
Summary of the invention
One of the object of the invention has been to find a kind of new biodiesel raw material and method of manufacture thereof, has low production cost, regenerated raw materials by this method and advantage such as obtains.
The technical scheme that realizes above-mentioned purpose is following:
A kind of preparation method of bio-diesel oil comprises the steps:
(1) fly maggot oil preparation: after the fly maggot drying and crushing, add the solvent of 1～10 times of its weight, room temperature lixiviate 1～48 hour; Filter, obtain extract I, filtrating obtains the low acid number fly maggot oil of acid number≤2 or the high acid value fly maggot oil of (acid number＞2) after reclaiming solvent; When the acid number of fly maggot oil＞2, carry out preparatory esterification treatment, obtain the low acid number fly maggot oil of acid number≤2; Treatment condition are: with the fly maggot oil of acid number＞2 and methyl alcohol or ethanol mol ratio is 1: 6～1: 13; 0.5%～5% an acidic catalyst of fly maggot oil weight, temperature of reaction is 40 ℃～90 ℃, the reaction times is 0.5～4 hour;
(2) transesterify: will hang down acid number fly maggot oil and methyl alcohol or ethanol and carry out transesterification reaction; Reaction conditions is: low acid number fly maggot oil and methyl alcohol or alcoholic acid mol ratio are 1: 4～1: 9; 0.5～2.5% the basic catalyst that adds fly maggot oil weight; Temperature of reaction is 40 ℃～90 ℃, and the reaction times is 10～60 minutes;
(3) phase-splitting: after transesterify finished, reactant standing demix, supernatant liquid were thick ester, and lower floor's liquid is glycerine, water, methyl alcohol or ethanol and catalyzer etc., through obtaining by-product glycerin after Hydrogen chloride neutralization, spinning and the underpressure distillation;
(4) refinement treatment: the supernatant liquid hot water wash of step (3) 2～3 times, add the sorbent material of its weight 1%～10%, be heated to 30 ℃～100 ℃; Stirred 10-60 minute, suction filtration, filtrating is the product biofuel; Filter cake is used eluent ethyl acetate, and elutriant obtains extract II after reclaiming solvent; Or adopting the molecular distillation technique supernatant liquid that reaction obtains to step (3) to carry out refinement treatment, its processing condition are: vacuum tightness is 0.1-10Pa, and distillation temperature is 100-200 ℃, isolates biofuel; Also can directly adopt molecular distillation technique that the reactant of step (2) is carried out refinement treatment: to comprise secondary: I, short-path distillation are isolated glycerine and methyl alcohol or the ethanol in the reactant; Processing condition are: vacuum tightness is 100-10Pa, and distillation temperature is 80-160 ℃; II, short-path distillation are isolated biofuel, and processing condition are: vacuum tightness is 10-0.1Pa, and distillation temperature is 100-200 ℃; Or comprise three grades: I, short-path distillation are isolated methyl alcohol or ethanol, and processing condition are: vacuum tightness is 5000-100Pa, and distillation temperature is 60-150 ℃; II, short-path distillation are isolated glycerine, and processing condition are: vacuum tightness is 100-10Pa, and distillation temperature is 100-200 ℃; III, short-path distillation are isolated biofuel, and heating up in a steamer excess is unsaponifiables, i.e. extract II I, and processing condition are: vacuum tightness is 10-0.1Pa, distillation temperature is 100-200 ℃.
In the above-mentioned steps (1): described solvent is the mixture of lipotropy organic solvent or lipotropy and hydrophilic organic solvent; The lipotropy organic solvent includes but not limited to: normal hexane, hexanaphthene, sherwood oil, ether, ETHYLE ACETATE, chloroform, benzene; Hydrophilic organic solvent includes but not limited to: methyl alcohol, ethanol, propyl alcohol, acetone.
In the above-mentioned steps (1): said an acidic catalyst refers to the vitriol oil or tosic acid.
In the above-mentioned steps (1): the room temperature lixiviate can be under nitrogen protection or not have to carry out under the nitrogen protection situation, preferably lixiviate under nitrogen protection.
The said basic catalyst of above-mentioned steps (2) can be NaOH, KOH, sodium alkoxide or basic metal, adopts NaOH, should earlier its solid be dissolved in when KOH makes catalyzer and process the alcoholic solution that alkali concn is 4～8wt% in methyl alcohol or the ethanol.
In the above-mentioned steps (4): sorbent material includes but not limited to: atlapulgite, zeyssatite, attapulgite (Attapulgite), gac, Magnesium Silicate q-agent, aluminum oxide a kind of or more than any one.
In the above-mentioned steps (1): extract I is the crude protein mixture through Analysis and Identification, can also can be used as the raw material of preparation chitosan, antibacterial peptide directly as feed.In the above-mentioned steps (4): extract II and extract II I are compositions such as phosphatide, sterol, pigment through Analysis and Identification, can be used for fields such as chemical industry, medicine, makeup.
Another object of the present invention provides a kind of biofuel, and concrete technical scheme is: said biofuel is for to prepare according to the above method.
Preparation method of bio-diesel oil of the present invention adopts the raw material of fly maggot oil as the feedstock production biofuel, and its raw material sources are extensive, aquaculture cost is cheap.
The content of fly maggot oil and one-tenth are grouped into because of the difference of provenance, growing environment, nutritional status and the culture condition of fly and change, and its composition of biofuel that therefore adopts patent art to produce also has some difference, and is as shown in table 1:
Table 1: the composition analysis of fly maggot biofuel and relative content thereof
The fly maggot oil of this patent refers to adopt the larva (fly maggot) of complete metamorphosis fly class through extracting the oily liquids that (like solvent method) obtains, and its staple is sfas and unsaturated fatty acids, and fly maggot oil is a kind of insect oil.Adopting fly maggot oil is that the feedstock production method of bio-diesel oil has some different with traditional Vegetable oil lipoprotein conversion method, as:
(1) the present invention adopts in single organic solvent or the destruction insect body such as double solvents such as alcohol-ether the grease associative key to extract full-cream matter; Also play simultaneously the activity of destroying lipolytic enzyme in the insect body; Suppressing acid value raises; The present invention has studied extracting the two kinds of situation whether operating process provides rare gas element (nitrogen) to protect, and under the situation of inflated with nitrogen, can avoid the oxidation of fly maggot oil better.
(2) fly maggot oil that obtains with extraction is that raw material adopts fatty ester exchange or preparatory esterification-transesterification reaction to obtain lipid acid alkane ester and lipid acid alkane ester mixture; Contain certain moisture and lipid acid unsaponifiables in the mixture; Like compositions such as phosphatide, sterol, pigments, so we are called coarse biodiesel with reacted total material of this step.When water exists; Fatty acid methyl ester or fatty-acid ethyl ester can be hydrolyzed to corresponding free fatty acids; Cause acid number of biodiesel to increase, directly influence the quality of product, and the latter is in combustion processes; Also can cause separating out of ash content (deposition), these ash contents are attached to even are blocked in oil fuel purifier (device) or oil pipeline.Therefore, to coarse biodiesel with refining be that the last handling process of purpose is very important.Sorbent material is meant the solid matter of some composition in adsorbed gas effectively or the liquid, is through intermolecular attraction (Van der Waals force) between itself and the adsorbed material, takes place that chemical action generates chemical bond and ion exchange produces absorption.Sorbent material commonly used has gac, zeyssatite, attapulgite, atlapulgite, silica gel, zeolite, wood chip, slag, humic-acid kind etc.Wherein the most commonly used is gac, owing to its specific surface area has higher adsorptive power greatly.The application of sorbent material mainly is the purpose that reaches deep purifying, as: remove a small amount of heavy metal ion, deleterious bio-refractory organism and decolouring and deodorizing etc.;
(3) (Molecular Distillation MD), is short-path distillation again to short-path distillation; It is a kind of novel liquid-liquid separation technology; Its principle of work is under the XHV degree, according to mixture molecular motion mfp difference, under far below the temperature of its boiling point with its separation.Short-path distillation has the incomparable advantage of routine distillation, and its separation efficiency is high, and product yield is high,, time weak point low because of heating temperature, and product quality because of its device particular structure form, is easy to amplify again, helps the expansion of industrially scalable.Adopted adsorption clarification technology and molecular distillation technique or adsorption clarification-molecular distillation technique combination technique to remove the by product of dereaction, catalyzer in the technical scheme of the present invention and participate in the impurity of reaction after get final product steady quality, biofuel product reliably.
(4) in addition; Raw glycerine is its main by product in the biodiesel manufacture process; The yield of glycerine also can indicator organism diesel oil transformation efficiency; Highly purified glycerine is used all very extensive in fine chemistry industry, food, medicine and other fields, the comprehensive utilization ratio that increases glycerine also is that the present invention studies on the other hand with the production cost that improves value-added content of product reduction biofuel.Except that glycerine, method of the present invention can also obtain other sub product, and for example extract I (crude protein mixture) can also can be used as the raw material of preparation chitosan, antibacterial peptide directly as feed.Extract II and III (phosphatide, sterol, pigment etc.) can be used for fields such as chemical industry, medicine, makeup.
Description of drawings
Fig. 1 is preparing method's of the present invention schema.
Embodiment
The present invention is a raw material with the fly larvae (fly maggot) of each section below the Insecta Diptera Aristocera; Nitrogen protection is being arranged or do not having to adopt under the nitrogen solvent method to extract grease in the fly maggot; The fly maggot oil of resulting low acid number (acid number≤2) or high acid value (acid number＞2) obtains coarse biodiesel through phase-splitting after transesterify or the preparatory esterification-transesterification reaction respectively; Adopt adsorption clarification technology or molecular distillation technique that thick oil is carried out purification process at last, obtain refining biodiesel, specifically can be referring to Fig. 1.The composition of gained biofuel can be referring to table 1.Said fly maggot is meant the larva of each section below the Insecta Diptera Aristocera, picks up to propagate field, human excrement, animal manure, outdoor sewage, refuse tip, laboratory and carcase etc. artificially and locate.
Through specific embodiment the present invention is described further below.
Embodiment 1:
The preparation method of the described biofuel of present embodiment comprises the steps:
Fly maggot picks up from Fanyu, Guangzhou, cleans, after liming is put to death; Dry under 40 ℃ of temperature, pulverize, add the sherwood oil of 1 times of its weight; The room temperature lixiviate is 1 hour under nitrogen protection, filters and obtains extract I, can be directly as feed; Also can be used as the raw material (following examples are identical) of preparation chitosan, antibacterial peptide, the filtrate decompression distillating recovering solvent obtains low acid number fly maggot oil.
With the mixed in molar ratio that the fly maggot oil and the methyl alcohol of gained are pressed 1: 4, add the NaOH (add fashionable should earlier its solid being dissolved in and process the alcoholic solution that alkali concn is 4～8wt% in the alcohol, following examples together) of fly maggot oil weight 0.5%; 40 ℃ of reflux are after 60 minutes, and standing demix, supernatant liquid adopt molecular distillation technique to carry out refinement treatment; Its processing condition are: vacuum tightness is 0.1Pa, and distillation temperature is 100 ℃, isolates biofuel; Heating up in a steamer excess is unsaponifiables; Be extract II I, wherein extract II I contains phosphatide, sterol, pigment composition through analysis, can be used for fields (following examples are identical) such as medicine, makeup.
Embodiment 2:
The preparation method of the described biofuel of present embodiment comprises the steps:
Fly maggot picks up from birds and flowers market, Guangzhou, cleans, and after liming was put to death, drying and crushing under 90 ℃ of temperature added the sherwood oil of 10 times of its weight, and the room temperature lixiviate is 48 hours under nitrogen protection, filters, and the filtrate decompression distillating recovering solvent obtains low acid number fly maggot oil.
With the fly maggot oil of gained and methyl alcohol mixed in molar ratio by 1: 9, add the NaOH of fly maggot oil weight 2.5%, 90 ℃ of reflux are after 10 minutes, standing demix; Lower floor liquid obtains by-product glycerin after through Hydrogen chloride neutralization, spinning and underpressure distillation, and supernatant liquid adds the atlapulgite of its weight 10% with hot water wash 2～3 times; Be heated to 100 ℃, stirred suction filtration 10 minutes; Filter cake is used eluent ethyl acetate, and elutriant obtains extract II after reclaiming solvent; Wherein extract II contains phosphatide, sterol, pigment composition through analysis, can be used for fields (following examples are identical) such as medicine, makeup, and filtrating is the product biofuel.
Embodiment 3:
The preparation method of the described biofuel of present embodiment comprises the steps:
Fly maggot picks up from the refuse tip, cleans, and is dry under 60 ℃ of temperature after the hot-water cure, pulverizes, and adds the normal hexane of 1 times of its weight, and the room temperature lixiviate is 24 hours under nitrogen protection, filters, and the filtrate decompression distillating recovering solvent obtains low acid number fly maggot oil.
With the fly maggot oil of gained and methyl alcohol mixed in molar ratio by 1: 6; The KOH that adds fly maggot oil weight 2.5%, 60 ℃ of reflux are after 30 minutes, standing demix; Supernatant liquid adopts molecular distillation technique to carry out refinement treatment; Its processing condition are: vacuum tightness is 10Pa, and distillation temperature is 200 ℃, isolates biofuel.
Embodiment 4:
The preparation method of the described biofuel of present embodiment comprises the steps:
Fly maggot picks up from pig manure, cleans, and is dry under 70 ℃ of temperature after the hot-water cure, pulverizes, and adds the normal hexane of 10 times of its weight, and the room temperature lixiviate is 6 hours under nitrogen protection, filters, and the filtrate decompression distillating recovering solvent obtains low acid number fly maggot oil.
With the mixed in molar ratio that the fly maggot oil and the ethanol of gained are pressed 1: 7, add the KOH of fly maggot oil weight 0.5%, 70 ℃ of reflux are after 40 minutes; Standing demix, lower floor liquid obtain by-product glycerin after through Hydrogen chloride neutralization, spinning and underpressure distillation, and supernatant liquid is with hot water wash 2～3 times; The attapulgite that adds its weight 1% is heated to 30 ℃, stirs 60 minutes; Suction filtration, filtrating are the product biofuel.
Embodiment 5:
The method of the described biodiesel manufacture of present embodiment comprises the steps:
Fly maggot picks up from chicken manure, cleans, and is dry under 80 ℃ of temperature after liming is handled, and pulverizes, and adds the benzene of 1 times of its weight, and the room temperature lixiviate is 12 hours under nitrogen protection, filters, and the filtrate decompression distillating recovering solvent obtains low acid number fly maggot oil.
With the mixed in molar ratio that the fly maggot oil and the ethanol of gained are pressed 1: 9, add the KOH of fly maggot oil weight 1.5%, 40 ℃ of reflux are after 40 minutes; Adopt molecular distillation technique that reactant is carried out separation and purification treatment, comprise two-stage: I short-path distillation processing condition are: vacuum tightness is 10Pa, and distillation temperature is 80 ℃; Isolate glycerine and ethanol; II level short-path distillation processing condition are: vacuum tightness is 0.1Pa, and distillation temperature is 100 ℃, isolates biofuel.
Embodiment 6:
The preparation method of the described biofuel of present embodiment comprises the steps:
The buying of dry fly maggot is grow shrimp factory from Fanyu, pulverizes, and adds the hexanaphthene-acetone of 5 times of its weight, and room temperature lixiviate 2 hours is filtered, and the filtrate decompression distillating recovering solvent obtains the high acid value fly maggot oil.With 1: 9 mixed of mol ratio, 50 ℃ of reflux, and add the vitriol oil of fly maggot oil weight 2% stir with the fly maggot oil of gained and methyl alcohol, reacts to obtain hanging down the acid number fly maggot oil after 2.5 hours.
With the mixed in molar ratio that the low acid number fly maggot oil and the methyl alcohol of gained are pressed 1: 5, add the KOH of fly maggot oil weight 2.5%, 50 ℃ of reflux are after 60 minutes; Standing demix, lower floor liquid obtain by-product glycerin after through Hydrogen chloride neutralization, spinning and underpressure distillation, and supernatant liquid is with hot water wash 2～3 times; The zeyssatite that adds its weight 5% is heated to 60 ℃, stirs 30 minutes; Suction filtration, filtrating are the product biofuel.
Embodiment 7:
The preparation method of the described biofuel of present embodiment comprises the steps:
Fly maggot picks up from insect institute of Zhongshan University, cleans, and is after the hot-water cure, dry under 100 ℃ of temperature; Pulverize, add the ether solvent of 1 times of its weight, the room temperature lixiviate is 8 hours under nitrogen protection; Filter, the filtrate decompression distillating recovering solvent obtains low acid number fly maggot oil.
With the fly maggot oil of gained and methyl alcohol mixed in molar ratio by 1: 4; The NaOH that adds fly maggot oil weight 1%, 60 ℃ of reflux are after 10 minutes, standing demix; Supernatant liquid adopts molecular distillation technique to carry out refinement treatment; Its processing condition are: vacuum tightness is 5Pa, and distillation temperature is 130 ℃, isolates biofuel.
Embodiment 8:
The preparation method of the described biofuel of present embodiment comprises the steps:
Fly maggot picks up from the park, cleans, and is dry under 80 ℃ of temperature after liming is handled, and pulverizes, and adds the ether of 10 times of its weight, and the room temperature lixiviate is 10 hours under nitrogen protection, filters, and the filtrate decompression distillating recovering solvent obtains low acid number fly maggot oil.
With the mixed in molar ratio that the fly maggot oil and the methyl alcohol of gained are pressed 1: 5, add the sodium methylate of fly maggot oil weight 2.5%, 70 ℃ of reflux are after 20 minutes; Standing demix, lower floor liquid obtain by-product glycerin after through Hydrogen chloride neutralization, spinning and underpressure distillation, and supernatant liquid is with hot water wash 2～3 times; Attapulgite-the Magnesium Silicate q-agent that adds its weight 6% is heated to 60 ℃, stirs 30 minutes; Suction filtration, filtrating are the product biofuel.
Embodiment 9:
The preparation method of the described biofuel of present embodiment comprises the steps:
Fly maggot picks up from field ight soil, cleans, and is dry under 50 ℃ of temperature after the hot-water cure, pulverizes, and adds the hexanaphthene of 1 times of its weight, and the room temperature lixiviate is 15 hours under nitrogen protection, filters, and the filtrate decompression distillating recovering solvent obtains low acid number fly maggot oil.
With the fly maggot oil of gained and methyl alcohol mixed in molar ratio by 1: 6; The NaOH that adds fly maggot oil weight 2%, 70 ℃ of reflux are after 30 minutes, standing demix; Supernatant liquid adopts molecular distillation technique to carry out refinement treatment; Its processing condition are: vacuum tightness is 8Pa, and distillation temperature is 140 ℃, isolates biofuel.
Embodiment 10:
The preparation method of the described biofuel of present embodiment comprises the steps:
Fly maggot picks up from the refuse tip, restaurant, cleans, and is dry under 80 ℃ of temperature after liming is handled, and pulverizes, and adds the chloroform of 2 times of its weight, and the room temperature lixiviate is 20 hours under nitrogen protection, filters, and the filtrate decompression distillating recovering solvent obtains low acid number fly maggot oil.
With the mixed in molar ratio that the fly maggot oil and the methyl alcohol of gained are pressed 1: 9, add the NaOH of fly maggot oil weight 1.5%, 70 ℃ of reflux are after 60 minutes; Standing demix, lower floor liquid obtain by-product glycerin after through Hydrogen chloride neutralization, spinning and underpressure distillation, and supernatant liquid is with hot water wash 2～3 times; Atlapulgite-the gac that adds its weight 5% is heated to 80 ℃, stirs 20 minutes; Suction filtration, filtrating are the product biofuel.
Embodiment 11:
The preparation method of the described biofuel of present embodiment comprises the steps:
Fly maggot picks up from home dwelling district, Fanyu, cleans, and is dry under 70 ℃ of temperature after liming is handled, and pulverizes, and adds the chloroform of 10 times of its weight, and the room temperature lixiviate is 5 hours under nitrogen protection, filters, and the filtrate decompression distillating recovering solvent obtains low acid number fly maggot oil.
With the mixed in molar ratio that the fly maggot oil and the methyl alcohol of gained are pressed 1: 8, add the NaOH of fly maggot oil weight 1.5%, 60 ℃ of reflux are after 50 minutes; Standing demix; Supernatant liquid adopts molecular distillation technique to carry out refinement treatment, and its processing condition are: vacuum tightness is 2Pa, and distillation temperature is 110 ℃.
Embodiment 12:
The method of the described biodiesel manufacture of present embodiment comprises the steps:
Fly maggot picks up from animal decomposed body place, cleans, and pulverizes after the seasoning, adds the ETHYLE ACETATE of 1 times of its weight, and the room temperature lixiviate is 36 hours under nitrogen protection, filters, and the filtrate decompression distillating recovering solvent obtains low acid number fly maggot oil.
With the mixed in molar ratio that the fly maggot oil and the methyl alcohol of gained are pressed 1: 9, add the KOH of fly maggot oil weight 1.5%, 70 ℃ of reflux are after 40 minutes; Standing demix, lower floor liquid obtain by-product glycerin after through Hydrogen chloride neutralization, spinning and underpressure distillation, and supernatant liquid is with hot water wash 2～3 times; Gac-the aluminum oxide that adds its weight 5% is heated to 80 ℃, stirs 20 minutes; Suction filtration, filtrating are the product biofuel.
Embodiment 13:
The method of the described biodiesel manufacture of present embodiment comprises the steps:
Fly maggot picks up from animal excrement, cleans, and seasoning after the hot-water cure is pulverized, and adds the ETHYLE ACETATE of 10 times of its weight, and room temperature lixiviate 25 hours is filtered, and the filtrate decompression distillating recovering solvent obtains the high acid value fly maggot oil.With 1: 10 mixed of mol ratio, 80 ℃ of reflux, and add the tosic acid of fly maggot oil weight 5% stir, and react and must hang down the acid number fly maggot oil after 0.5 hour with the fly maggot oil of gained and methyl alcohol.
Low acid number fly maggot oil and methyl alcohol are pressed 1: 7 mixed in molar ratio; The KOH that adds fly maggot oil weight 2%, 65 ℃ of reflux are after 30 minutes, standing demix; Supernatant liquid adopts molecular distillation technique to carry out refinement treatment; Its processing condition are: vacuum tightness is 10Pa, and distillation temperature is 160 ℃, isolates biofuel.
Embodiment 14:
The method of the described biodiesel manufacture of present embodiment comprises the steps:
Fly maggot picks up from Guangzhou Haizhu District peasant household lavatory, cleans, and liming is handled the back seasoning, pulverizes, and adds the normal hexane-ethanol of 1 times of its weight, and room temperature lixiviate 42 hours is filtered, and the filtrate decompression distillating recovering solvent obtains the high acid value fly maggot oil of acid number＞2.With 1: 6 mixed of mol ratio, 70 ℃ of reflux, and add the vitriol oil of fly maggot oil weight 0.5% stir, and react and must hang down the acid number fly maggot oil after 2 hours with the fly maggot oil of gained and methyl alcohol.
Low acid number fly maggot oil and methyl alcohol are pressed 1: 9 mixed in molar ratio, add the NaOH of fly maggot oil weight 1.5%, and 70 ℃ of reflux are after 60 minutes; Standing demix, lower floor liquid obtain by-product glycerin after through Hydrogen chloride neutralization, spinning and underpressure distillation, and supernatant liquid is with hot water wash 2～3 times; Attapulgite-the gac that adds its weight 5% is heated to 50 ℃, stirs 20 minutes; Suction filtration, filtrating are the product biofuel.
Embodiment 15:
The preparation method of the described biofuel of present embodiment comprises the steps:
Fly maggot picks up from the pig farm, Guangdong, cleans, and seasoning after the hot-water cure is pulverized, and adds the sherwood oil-methyl alcohol of 10 times of its weight, and room temperature lixiviate 36 hours is filtered, and the filtrate decompression distillating recovering solvent obtains the high acid value fly maggot oil.With 1: 9 mixed of mol ratio, 55 ℃ of reflux, and add the vitriol oil of fly maggot oil weight 1.5% stir with the fly maggot oil of gained and methyl alcohol, reacts to obtain hanging down the acid number fly maggot oil after 1.5 hours.
Low acid number fly maggot oil and methyl alcohol are pressed 1: 8 mixed in molar ratio, add the sodium methylate of fly maggot oil weight 2.5%, and 55 ℃ of reflux are after 50 minutes; Adopt molecular distillation technique that reactant is carried out separation and purification treatment, comprise two-stage: I short-path distillation processing condition are: vacuum tightness is 50Pa, and distillation temperature is 130 ℃; Isolate glycerine and methyl alcohol; II level short-path distillation processing condition are: vacuum tightness is 5Pa, and distillation temperature is 150 ℃, isolates biofuel.
Embodiment 16:
The method of the described biodiesel manufacture of present embodiment comprises the steps:
Fly maggot picks up from animal cultivation field, Guangzhou, cleans, and pulverizes after the seasoning, adds the hexanaphthene-acetone of 5 times of its weight, and room temperature lixiviate 2 hours is filtered, and the filtrate decompression distillating recovering solvent obtains the high acid value fly maggot oil.With 1: 9 mixed of mol ratio, 50 ℃ of reflux, and add the vitriol oil of fly maggot oil weight 0.5% stir with the fly maggot oil of gained and methyl alcohol, reacts to obtain hanging down the acid number fly maggot oil after 2.5 hours.
Low acid number fly maggot oil and methyl alcohol are pressed 1: 9 mixed in molar ratio, add the NaOH of fly maggot oil weight 2.5%, and 50 ℃ of reflux are after 60 minutes; Standing demix, lower floor liquid obtain by-product glycerin after through Hydrogen chloride neutralization, spinning and underpressure distillation, and supernatant liquid is with hot water wash 2～3 times; The aluminum oxide that adds its weight 5% is heated to 60 ℃, stirs 40 minutes; Suction filtration, filtrating are the product biofuel.
Embodiment 17:
The method of the described biodiesel manufacture of present embodiment comprises the steps:
Fly maggot picks up from hospital's (engineering fly maggot), cleans, and after liming was handled, seasoning was pulverized, and adds the chloroform-ethanol of 8 times of its weight, and room temperature lixiviate 5 hours is filtered, and the filtrate decompression distillating recovering solvent obtains the high acid value fly maggot oil.With 1: 10 mixed of mol ratio, 60 ℃ of reflux, and add the vitriol oil of fly maggot oil weight 2% stir with the fly maggot oil of gained and methyl alcohol, reacts to obtain hanging down the acid number fly maggot oil after 2 hours.
Low acid number fly maggot oil and methyl alcohol are pressed 1: 4 mixed in molar ratio, add the NaOH of fly maggot oil weight 1%, and 60 ℃ of reflux are after 10 minutes; Adopt molecular distillation technique that reactant is carried out separation and purification treatment, comprise three grades: the I short-path distillation is isolated methyl alcohol, and processing condition are: vacuum tightness is 100Pa; Distillation temperature is 60 ℃; II level short-path distillation is isolated glycerine, and processing condition are: vacuum tightness is 100Pa, and distillation temperature is 200 ℃; III level short-path distillation processing condition are: vacuum tightness is 10Pa, and distillation temperature is 200 ℃, isolates biofuel.
Embodiment 18:
The method of the described biodiesel manufacture of present embodiment comprises the steps:
Fly maggot picks up from putrid food, cleans, and after the hot-water cure, seasoning is pulverized, and adds the benzene-methyl alcohol of 5 times of its weight, and room temperature lixiviate 15 hours is filtered, and the filtrate decompression distillating recovering solvent obtains the high acid value fly maggot oil.With 1: 11 mixed of mol ratio, 65 ℃ of reflux, and add the tosic acid of fly maggot oil weight 3% stir with the fly maggot oil of gained and methyl alcohol, reacts to obtain hanging down the acid number fly maggot oil after 4 hours.
Low acid number fly maggot oil and methyl alcohol are pressed 1: 5 mixed in molar ratio, add the sodium Metal 99.5 of fly maggot oil weight 1%, and 65 ℃ of reflux are after 20 minutes; Standing demix, lower floor liquid obtain by-product glycerin after through Hydrogen chloride neutralization, spinning and underpressure distillation, and supernatant liquid is with hot water wash 2～3 times; The Magnesium Silicate q-agent that adds its weight 1% is heated to 70 ℃, stirs 10 minutes; Suction filtration, filtrating are the product biofuel.
Embodiment 19:
The preparation method of the described biofuel of present embodiment comprises the steps:
Fly maggot picks up from kind Yu rural area peasant household, cleans, and after the hot-water cure, seasoning is pulverized, and adds the petroleum ether-ethyl acetate-propyl alcohol of 2 times of its weight, and room temperature lixiviate 40 hours is filtered, and the filtrate decompression distillating recovering solvent obtains the high acid value fly maggot oil.With 1: 13 mixed of mol ratio, 70 ℃ of reflux, and add the tosic acid of fly maggot oil weight 4% stir with the fly maggot oil of gained and methyl alcohol, reacts to obtain hanging down the acid number fly maggot oil after 3 hours.
Low acid number fly maggot oil and methyl alcohol are pressed 1: 7 mixed in molar ratio, add the sodium methylate of fly maggot oil weight 0.5%, and 60 ℃ of reflux are after 40 minutes; Standing demix, lower floor liquid obtain by-product glycerin after through Hydrogen chloride neutralization, spinning and underpressure distillation, and supernatant liquid is with hot water wash 2～3 times; Magnesium Silicate q-agent-the gac that adds its weight 5% is heated to 80 ℃, stirs 50 minutes; Suction filtration, filtrating are the product biofuel.
Embodiment 20:
The method of the described biodiesel manufacture of present embodiment comprises the steps:
Fly maggot picks up from economic insects institute of Zhongshan University, pulverizes, and adds the sherwood oil-chloroform-acetone of 3 times of its weight, and room temperature lixiviate 28 hours is filtered, and the filtrate decompression distillating recovering solvent obtains the high acid value fly maggot oil.With the fly maggot oil of gained and ethanol with 1: 6 mixed of mol ratio, 75 ℃ of reflux, and add the tosic acid of fly maggot oil weight 5%; Stir, react air distillation recovery ethanol after 2.5 hours, the mixture standing demix; Lower floor's liquid is poured out, must be hanged down the acid number fly maggot oil.
With resulting low acid number fly maggot oil and ethanol mixed in molar ratio by 1: 8, add the sodium Metal 99.5 of fly maggot oil weight 1%, 75 ℃ of reflux are after 50 minutes; Adopt molecular distillation technique that reactant is carried out separation and purification treatment, comprise three grades: the I short-path distillation is isolated ethanol, and processing condition are: vacuum tightness is 3000Pa; Distillation temperature is 70 ℃; II level short-path distillation is isolated glycerine, and processing condition are: vacuum tightness is 50Pa, and distillation temperature is 110 ℃; III level short-path distillation processing condition are: vacuum tightness is 1Pa, and distillation temperature is 140 ℃, isolates biofuel.
Embodiment 21:
The preparation method of the described biofuel of present embodiment comprises the steps:
Fly maggot picks up from propagates the field artificially, dry under 90 ℃ of temperature after liming is handled, and pulverizes, and adds the ether-ethanol of 7 times of its weight, and room temperature lixiviate 25 hours is filtered, and the filtrate decompression distillating recovering solvent obtains the high acid value fly maggot oil.With the fly maggot oil of gained and ethanol with 1: 10 mixed of mol ratio, 80 ℃ of reflux, and add the tosic acid of fly maggot oil weight 5%; Stir, react air distillation recovery ethanol after 0.5 hour, the mixture standing demix; Lower floor's liquid is poured out, must be hanged down the acid number fly maggot oil.
Low acid number fly maggot oil and ethanol are pressed 1: 6 mixed in molar ratio, add the KOH of fly maggot oil weight 1.5%, and 80 ℃ of reflux are after 30 minutes; Adopt molecular distillation technique that reactant is carried out separation and purification treatment, comprise two-stage: I short-path distillation processing condition are: vacuum tightness is 10Pa, and distillation temperature is 80 ℃; Isolate glycerine and ethanol; II level short-path distillation processing condition are: vacuum tightness is 0.1Pa, and distillation temperature is 100 ℃, isolates biofuel.
Embodiment 22:
The preparation method of the described biofuel of present embodiment comprises the steps:
Fly maggot picks up from Guangdong peasant household poulty house, and is dry under 90 ℃ of temperature after liming is handled, and pulverizes, and adds the normal hexane-methyl alcohol of 7 times of its weight, and room temperature lixiviate 25 hours is filtered, and the filtrate decompression distillating recovering solvent obtains the high acid value fly maggot oil.With the fly maggot oil of gained and ethanol with 1: 10 mixed of mol ratio, 80 ℃ of reflux, and add the tosic acid of fly maggot oil weight 5%; Stir, react air distillation recovery ethanol after 0.5 hour, the mixture standing demix; Lower floor's liquid is poured out, must be hanged down the acid number fly maggot oil.
Low acid number fly maggot oil and ethanol are pressed 1: 6 mixed in molar ratio, add the KOH of fly maggot oil weight 1.5%, and 80 ℃ of reflux are after 30 minutes; Adopt molecular distillation technique that reactant is carried out separation and purification treatment, comprise two-stage: I short-path distillation processing condition are: vacuum tightness is 100Pa, and distillation temperature is 160 ℃; Isolate glycerine and ethanol; II level short-path distillation processing condition are: vacuum tightness is 10Pa, and distillation temperature is 200 ℃, isolates biofuel.
Claims (13)
1. one kind prepares method of bio-diesel oil, it is characterized in that: mainly may further comprise the steps:
(1) preparation of fly maggot oil: after the fly maggot drying and crushing, add the solvent of 1～10 times of its weight, room temperature lixiviate 1～48 hour is filtered, and filtrating obtains the low acid number fly maggot oil of acid number≤2 or the high acid value fly maggot oil of acid number＞2 after reclaiming solvent; When the acid number of the fly maggot oil that obtains＞2; Carry out preparatory esterification treatment; Thereby obtain the low acid number fly maggot oil of acid number≤2, treatment condition are: the fly maggot oil of acid number＞2 and methyl alcohol or ethanol mol ratio are 1: 6～1: 13, add 0.5%～5% an acidic catalyst of fly maggot oil weight; Temperature of reaction is 40 ℃～90 ℃, and the reaction times is 0.5～4 hour; Said solvent is the mixture of lipotropy organic solvent or lipotropy and hydrophilic organic solvent;
(2) transesterify: will hang down acid number fly maggot oil and methyl alcohol or ethanol and carry out transesterification reaction; Reaction conditions is: low acid number fly maggot oil and methyl alcohol or alcoholic acid mol ratio are 1: 4～1: 9; 0.5～2.5% the basic catalyst that adds fly maggot oil weight; Temperature of reaction is 40 ℃～90 ℃, and the reaction times is 10～60 minutes;
(3) phase-splitting: after transesterify finished, reactant standing demix, supernatant liquid were thick ester;
(4) refinement treatment: after the supernatant liquid hot water wash of step (3), add the sorbent material of its weight 1%～10%, be heated to 30 ℃～100 ℃, stir, suction filtration, filtrating is biofuel; Or adopting the molecular distillation technique supernatant liquid that reaction obtains to step (3) to carry out refinement treatment, its processing condition are: vacuum tightness is 10-0.1Pa, and distillation temperature is 100-200 ℃, isolates biofuel.
2. preparation method according to claim 1 is characterized in that, said lipotropy organic solvent is normal hexane, hexanaphthene, sherwood oil, ether, ETHYLE ACETATE, chloroform or benzene; Said hydrophilic organic solvent is methyl alcohol, ethanol, propyl alcohol or acetone.
3. preparation method according to claim 1 is characterized in that, said room temperature lixiviate is under nitrogen protection, to carry out.
4. preparation method according to claim 1 is characterized in that, said an acidic catalyst is the vitriol oil or tosic acid.
5. preparation method according to claim 1; It is characterized in that; The said basic catalyst of step (2) is sodium alkoxide or basic metal or NaOH or KOH, earlier its solid is dissolved in when adopting NaOH or KOH to make catalyzer and processes the alcoholic solution that alkali concn is 4～8wt% in methyl alcohol or the ethanol.
6. according to each described preparation method of claim 1-5, it is characterized in that sorbent material described in the step (4) is one or more of atlapulgite, zeyssatite, attapulgite, gac, Magnesium Silicate q-agent, aluminum oxide.
7. preparation method according to claim 1 is characterized in that, the lower floor's liquid in the step (3) after the layering is mainly glycerine, water, catalyzer, methyl alcohol or alcoholic acid mixture, through obtaining by-product glycerin after Hydrogen chloride neutralization, spinning and the underpressure distillation.
8. one kind prepares method of bio-diesel oil, it is characterized in that: mainly may further comprise the steps:
(1) fly maggot oil preparation: after the fly maggot drying and crushing, add the solvent of 1～10 times of its weight, room temperature lixiviate 1～48 hour is filtered, and filtrating obtains the low acid number fly maggot oil of acid number≤2 or the high acid value fly maggot oil of acid number＞2 after reclaiming solvent; When the acid number of the fly maggot oil that obtains＞2; Carry out preparatory esterification treatment; Treatment condition are: the fly maggot oil of acid number＞2 and methyl alcohol or ethanol mol ratio are 1: 6～1: 13, add 0.5%～5% an acidic catalyst of fly maggot oil weight, and temperature of reaction is 40 ℃～90 ℃; Reaction times is 0.5～4 hour, gets the low acid number fly maggot oil of acid number≤2; Said solvent is the mixture of lipotropy organic solvent or lipotropy and hydrophilic organic solvent;
(2) transesterify: will hang down acid number fly maggot oil and methyl alcohol or ethanol and carry out transesterification reaction; Reaction conditions is: low acid number fly maggot oil and methyl alcohol or alcoholic acid mol ratio are 1: 4～1: 9; 0.5～2.5% the basic catalyst that adds fly maggot oil weight; Temperature of reaction is 40 ℃～90 ℃, and the reaction times is 10～60 minutes;
(3) adopt molecular distillation technique that the reactant of step (2) is carried out refinement treatment, comprise secondary: I, short-path distillation are isolated glycerine and methyl alcohol or the ethanol in the reactant, and processing condition are: vacuum tightness is 100-10Pa, and distillation temperature is 80-160 ℃; II, short-path distillation are isolated biofuel, and processing condition are: vacuum tightness is 10-0.1Pa, and distillation temperature is 100-200 ℃; Or comprise three grades: I, short-path distillation are isolated methyl alcohol or ethanol, and processing condition are: vacuum tightness is 5000-100Pa, and distillation temperature is 60-150 ℃; II, short-path distillation are isolated glycerine, and processing condition are: vacuum tightness is 100-10Pa, and distillation temperature is 100-200 ℃; III, short-path distillation are isolated biofuel, and processing condition are: vacuum tightness is 10-0.1Pa, and distillation temperature is 100-200 ℃.
9. preparation method according to claim 8 is characterized in that, said lipotropy organic solvent is normal hexane, hexanaphthene, sherwood oil, ether, ETHYLE ACETATE, chloroform or benzene; Said hydrophilic organic solvent is methyl alcohol, ethanol, propyl alcohol or acetone.
10. preparation method according to claim 8 is characterized in that, said room temperature lixiviate is under nitrogen protection, to carry out.
11. preparation method according to claim 8 is characterized in that, said an acidic catalyst is the vitriol oil or tosic acid.
12. each described preparation method according to Claim 8-11; It is characterized in that; The described basic catalyst of step (2) is NaOH, KOH, sodium alkoxide or basic metal, adopts NaOH, earlier its solid is dissolved in when KOH makes catalyzer and processes the alcoholic solution that alkali concn is 4～8wt% in methyl alcohol or the ethanol.
13. biofuel for preparing by each said method of claim 1-12.
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| CN2010101228375A CN101805672B (en) | 2010-03-08 | 2010-03-08 | Biodiesel and preparation method thereof |
| US13/390,876 US20120144732A1 (en) | 2010-03-08 | 2010-03-16 | Biodiesel and Preparation Method Thereof |
| EP10847204.4A EP2479250B1 (en) | 2010-03-08 | 2010-03-16 | Biodiesel and preparation method thereof |
| PCT/CN2010/071076 WO2011109945A1 (en) | 2010-03-08 | 2010-03-16 | Biodiesel and preparation method thereof |
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| IT1401796B1 (en) * | 2010-09-03 | 2013-08-28 | Caprio | PLANT AND METHOD FOR THE BIO-CONVERSION OF ORGANIC WASTE AND THE BIOSTABILIZATION OF INDIFFERENTIAL URBAN SOLID WASTE |
| CN102358866A (en) * | 2011-09-15 | 2012-02-22 | 宁守俭 | Method for distillation synthesis of biodiesel by acid-catalyzed reaction |
| CN102660383B (en) * | 2012-06-02 | 2013-04-24 | 哈尔滨工业大学 | Separation process of essential oil in toad maggots |
| CN102660382B (en) * | 2012-06-02 | 2013-05-01 | 哈尔滨工业大学 | Separation process of essential oil in toad maggots |
| CN103343048B (en) * | 2013-07-09 | 2014-11-05 | 四川国为制药有限公司 | Method for reducing anisidine value of high-content fish oil |
| CN103725423A (en) * | 2013-12-25 | 2014-04-16 | 济南开发区星火科学技术研究院 | Method for producing biodiesel by utilizing swill-cooked dirty oil |
| CN104845595B (en) * | 2015-05-13 | 2018-01-23 | 北京中德汇诚石油技术有限公司 | A kind of automobile engine water-free cooling composition |
| CN105132122A (en) * | 2015-09-11 | 2015-12-09 | 江苏锦宇环境工程有限公司 | Method of preparing biodiesel by utilizing grass carp visceral fat |
| CN105754726A (en) * | 2016-02-17 | 2016-07-13 | 中山大学 | Bio lubricant base oil based on fly maggot oil and preparation method thereof |
| CN105670808A (en) * | 2016-04-01 | 2016-06-15 | 任春山 | Method for preparing green biodiesel by using artificially cultured base material |
| CN106336673B (en) * | 2016-08-25 | 2019-02-01 | 深圳市市政设计研究院有限公司 | A kind of bio oil compounding nano diatomite modified pitch and preparation method thereof |
| AU2019262044B2 (en) * | 2018-05-03 | 2024-05-30 | Renewable Energy Group, Inc. | Methods and devices for producing biodiesel, diesel-range hydrocarbons, and products obtained therefrom |
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