WO2011109945A1 - 一种生物柴油及其制备方法 - Google Patents

一种生物柴油及其制备方法 Download PDF

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Publication number
WO2011109945A1
WO2011109945A1 PCT/CN2010/071076 CN2010071076W WO2011109945A1 WO 2011109945 A1 WO2011109945 A1 WO 2011109945A1 CN 2010071076 W CN2010071076 W CN 2010071076W WO 2011109945 A1 WO2011109945 A1 WO 2011109945A1
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Prior art keywords
oil
acid value
biodiesel
preparation
insect
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PCT/CN2010/071076
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English (en)
French (fr)
Inventor
杨得坡
黄妙玲
梁冬
厉倬学
杨文哲
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中山大学
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Priority claimed from CN2010101228233A external-priority patent/CN101812378B/zh
Priority claimed from CN2010101228375A external-priority patent/CN101805672B/zh
Application filed by 中山大学 filed Critical 中山大学
Priority to US13/390,876 priority Critical patent/US20120144732A1/en
Priority to EP10847204.4A priority patent/EP2479250B1/en
Publication of WO2011109945A1 publication Critical patent/WO2011109945A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B1/00—Production of fats or fatty oils from raw materials
    • C11B1/10—Production of fats or fatty oils from raw materials by extracting
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/10—Refining fats or fatty oils by adsorption
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/12—Refining fats or fatty oils by distillation
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes

Definitions

  • the invention relates to the field of renewable energy technologies, in particular to a biodiesel and a preparation method thereof. Background technique
  • Biodiesel also known as biodiesel, refers to long-chain fatty acid methyl esters or ethyl esters produced by transesterification processes using vegetable oils such as oil plants and engineering microalgae, as well as animal fats and catering waste oils.
  • biodiesel has continuous regenerability and excellent environmental characteristics. It has high oxygen content in biodiesel, free of sulfur and aromatic terpene hydrocarbons, and carbon monoxide and sulfur dioxide in the exhaust gas produced by combustion. The amount of sulphide is also reduced.
  • the biodegradability of biodiesel is also significantly higher than that of petrochemical diesel.
  • biodiesel raw materials are mainly plant oils, such as peanut oil, soybean oil, rapeseed oil, coconut oil, palm oil, jatropha oil, and engineering seaweed oil, food waste oil, animal oil, such as waste lard, fish oil and the like.
  • plant oils such as peanut oil, soybean oil, rapeseed oil, coconut oil, palm oil, jatropha oil, and engineering seaweed oil, food waste oil, animal oil, such as waste lard, fish oil and the like.
  • the present invention relates to the preparation of biodiesel using larvae and cockroaches of fully metamorphic insects, such as: barley larvae and cockroaches, larvae of larvae and cockroaches, moth larvae and cockroaches, larvae of larvae and cockroaches. Insects are divided into two categories: incomplete metamorphosis and complete metamorphosis.
  • the life history of completely metamorphic insects includes egg (Egg), larva (Larva), pupa (Pupa), adult (Adult). In four stages, the eggs hatch into larvae, and the larvae become cockroaches after a series of molting and other minor changes, and finally become adults.
  • This patent relates to the use and method of converting larvae of fully metamorphic insects and oils extracted from earthworms into biodiesel.
  • the fully metamorphic insect wording operation is very simple, the medium is widely sourced and the cost is low.
  • the fly is a typical fully metamorphic insect, and the maggot is the larva of the Cyclorrhapha genus Maggot.
  • the fly has a physiological characteristic of mating for life, and has a strong reproductive ability.
  • the entire life cycle is 28 days.
  • Female flies can lay eggs 5-6 times in a lifetime, and the number of eggs laid is about 100-150 each time. From eggs to hatching insects 3-4 days, insects can be propagated for 10-12 generations within one year.
  • the breeding cost of fly maggots is low, the feeding operation is convenient, and the equipment is simple.
  • the breeding can be carried out indoors or outdoors.
  • the medium has a wide range of sources, such as wheat bran, rice bran, distiller's grains, bean dregs and other agricultural and sideline products, and livestock manure. Head
  • the pre-flies large-scale aquaculture technology has matured, and it has also achieved mechanization and scale in developed countries such as the United States. For example, a large amount of cheap maggot oil can be used to produce biodiesel, which can greatly reduce its production cost.
  • the yellow mealworm Uenebrio s P p. belongs to the coleoptera, which takes about three months from egg hatching to adult emergence, and the barley larvae are cylinders. Type, about 7 cm long, about 0.5 cm wide, about 3-4 times that of Tenebrio molitor larvae. Both larvae are rich in protein (40 ⁇ 50%), fat (30 ⁇ 40%) and other nutrients. It is often used as a good bait for breeding rare animals such as arowana, ornamental birds, crickets, and snakes.
  • Moth is also a typical fully metamorphic insect, belonging to Lepidoptem, which is the largest group of Lepidoptera, accounting for about 90% of Lepidoptera species, including Gelechiidae and Noctuidae. (Noctuidae;), Saturniidae and Hepialidae, etc., their individual development through the four stages of eggs, larvae, pupa and adults, lasting more than a month, the moth larvae have higher fat content The crude fat content of the bat moth larvae is as high as 77.16%.
  • Antheraea spp. is a larva of the Lepidoptera moth, which has a fat content of more than 30%.
  • the silkworm cocoons are edible and the residue can be used as feed for fish, livestock and poultry.
  • the honeybee belongs to the Hymenoptera family (Apidae), and its individual development is also in four stages.
  • the queen bee lays eggs in the bee house, hatches into larvae, and after 7 days of development, enters the flood season. At this time, the bee body is a bee sting, and the peak is rich in protein and fat.
  • the development and application of bees at home and abroad mainly focus on health products and foods such as royal jelly, honey, and bee pollen.
  • Insects are rich in fat. Many insects have a fat content of 10%-20% and a dry product fat content of 20%-50%. According to the research, the factors affecting the fat content of insects mainly include the following three aspects: 1 The insect species, the species has different lipid content; 2 The fat content of the same species is higher in the larvae, larvae and wintering insects; Changes in the life history of insects also lead to changes in fat content. Direct or indirect effects of hormones or neurohormones in the body lead to changes in the metabolic balance between lipid synthesis and utilization, such as development, migration, diapause, reproduction, flight, etc. under endocrine control. The process affects the metabolism of lipids. Most of the insects containing high fat belong to the completely metamorphic insects. Therefore, this patent relates to the preparation of biodiesel from the larvae of the fully metamorphic insects of the insect family and the fats and oils of the cockroaches. The insects have relatively high oil content and short growth period. And reproductive ability.
  • Insect oils and fats have different characteristics from vegetable oils and fats. Plant oils and fats are present in plant oil cells or in free form such as oil droplets, and the extraction method is relatively easy. Insects and oils exist in insects in the following three ways: First, the hydrocarbon groups of monoesters such as glycerides and cholesteryl esters form weak non-covalent bonds between van der Waals bonds or hydrophobic bonds and hydrophobic bonds of other lipids and proteins.
  • Bonding in this way, there are fat, albumin, fatty acid-complex in adipose tissue; polar lipids such as diphospholipids and cholesterol are present in biofilms such as morphological membranes, mitochondria, and small cell bodies; In the serum nuclear protein complex, hydrogen bonds, ionic bonds, and hydrophobic bonds are often formed with proteins; the third is covalent bonds in the form of ester bonds, amide bonds, glycosidic bonds, etc., such as fatty acids, hydroxy fatty acids, complex In branched fatty acids. Insect The presence, solubility, and combination with other components of the oil in the above organisms are the main basis for formulating the extraction method.
  • insects hydrolyze oil to produce a large amount of unsaturated fatty acids, and the role of oxygen in the air, in the same state, insect oils are more susceptible to rancidity than vegetable oils, causing the acid price to rise and further affecting subsequent Biodiesel preparation reaction.
  • Insect oils are rich in unsaturated fatty acids, and the ratio of saturated fatty acids to unsaturated fatty acids is less than 0.4, which is close to the fatty acid composition of fish oil.
  • the saturated fatty acids of insects are mostly palmitic acid (C16:0), the content of stearic acid (C18:0) is low, and the monounsaturated fatty acids are mostly composed of oleic acid (C18: ln-9).
  • insects contain more polyunsaturated fatty acids, among which linoleic acid (C18:2n-6) and ⁇ -linolenic acid (C18:3n-3) are more prominent.
  • Insect oils and fats have odd carbon fatty acids that are rare in nature. Among them, fifteen carbonic acid and heptadecanoic acid are more common. Odd carbon fatty acids have unique physiologically active functions such as strong anticancer activity.
  • the content of linoleic acid in Coleoptera is higher, while the content of linolenic acid in Lepidoptera is higher. Studies have shown that the fatty acid composition of insect oil is related to its species, growth and development, nutritional status, environment or vocabulary. Summary of the invention
  • One of the objects of the present invention is to select a new biodiesel raw material and a method for producing the same, which have the advantages of low production cost, recyclable raw materials, and the like.
  • a method of preparing biodiesel comprising the following steps -
  • (1) Preparation of insect oil After drying and pulverizing the larvae of the fully metamorphic insects and/or insects, add 1 ⁇ 10 times the weight of the solvent, leaching at room temperature for 1 ⁇ 48 hours, filtering to obtain the extract I, and recovering the solvent after the filtrate is recovered. Obtaining a low acid value insect oil of acid value 2 or a high acid value insect oil of (acid value >2). When the acid value of the insect oil is >2, pre-esterification is carried out to obtain a low acid value of an acid value of 3 ⁇ 4 ⁇ 2.
  • the treatment conditions are: the acid value of > 2 insect oil and methanol or ethanol molar ratio of 1: 6-1: 13 , 0.5% ⁇ 5% of the weight of insect oil acid catalyst, the reaction temperature is 40 ° C ⁇ 90 ° C, the reaction time is 0.5 to 4 hours;
  • Transesterification transesterification of low acid value insect oil with methanol or ethanol under the following conditions: molar ratio of low acid value insect oil to methanol or ethanol is 1: 4-1: 9, added insect oil weight 0.5 ⁇ 2.5% basic catalyst, the reaction temperature is 40 ° C ⁇ 90 ° C, the reaction time is 10 60 minutes;
  • Phase separation After the end of transesterification, the reactants are allowed to stand for stratification, the upper liquid is crude ester, and the lower liquid is glycerin, water, methanol or ethanol and catalyst, etc., neutralized by dilute hydrochloric acid, centrifugally separated and vacuum distilled. After that, the by-product glycerin is obtained; (4) Refining treatment: The upper liquid hot water of the step (3) is washed 2 to 3 times, and the adsorption weight is 1% to 10%.
  • the process conditions are as follows: a vacuum degree of 10-0.
  • step (2) can be directly purified by molecular distillation techniques: including secondary: I. Molecular distillation separates glycerin and methanol or ethanol from the reactants under the following conditions: vacuum degree 100-10Pa, distillation The temperature is 80-160 ° C; II, molecular distillation to separate biodiesel, the process conditions are: vacuum degree is 10-0.
  • the process conditions are: a vacuum of 10-0. lPa, a distillation temperature of 100-200 ° C.
  • the single or complex organic solvent refers to a single lipophilic organic solvent or a mixed solvent of any one or several of a lipophilic and hydrophilic organic solvent
  • the lipophilic organic solvent includes but is not limited to: ⁇ , cyclohexanthene, petroleum ether, diethyl ether, ethyl acetate, chloroform, benzene
  • hydrophilic organic solvents include, but are not limited to: methanol, ethanol, propanol, acetone.
  • the completely metamorphosis insects are flies, mealworms, barley worms, silkworms, bees, moths and the like.
  • the acidic catalyst refers to concentrated sulfuric acid or p-toluenesulfonic acid.
  • the room temperature leaching may be carried out under the protection of nitrogen or without nitrogen gas, preferably under nitrogen protection.
  • the basic catalyst described in the above step (2) may be NaOH, KOH, sodium alkoxide or an alkali metal.
  • NaOH or KOH is used as a catalyst, the solid is first dissolved in methanol or ethanol to prepare an alkali concentration of 4 to 8% by weight. Alcohol solution.
  • adsorbents include, but are not limited to: activated clay, diatomaceous earth, attapulgite (Attapul g ite), activated carbon, magnesium silicate, alumina, or any of more than one.
  • Extract I is identified as a crude protein mixture by analysis and can be used directly as a feed or as a raw material for preparing chitosan.
  • Extract II, extract III and extract IV are identified as phospholipids, alcohols, pigments and the like, and can be used in the fields of chemical industry, medicine, cosmetics and the like.
  • Another object of the invention is to provide a biodiesel.
  • the biodiesel is prepared according to the method described above.
  • the method for preparing biodiesel according to the present invention using larvae of fully metamorphic insects and insect oil extracted from cockroaches As a raw material for preparing biodiesel, it has a wide range of raw materials and low cost of breeding.
  • the insect oil of the present patent refers to an oily liquid obtained by extracting (for example, a solvent method) a larva or/and a cockroach of a completely metamorphic insect, and the main component of the insect oil is a saturated fatty acid and an unsaturated fatty acid, such as: maggot oil, maggot Oil, barley insect oil, yellow meal oil, moth oil, silkworm oil, silkworm cocoon oil, etc.
  • the method of preparing biodiesel using insect oil as a raw material is somewhat different from the traditional method of converting vegetable oil, such as:
  • the present invention uses a single organic solvent or a complex solvent such as ethanol-ethyl ether to destroy the oil-binding bond in the insect to extract the whole lipid, and also acts to destroy the lipolytic enzyme activity in the insect and inhibit the acid value from increasing.
  • a single organic solvent or a complex solvent such as ethanol-ethyl ether
  • the adsorbent refers to a solid substance capable of efficiently adsorbing certain components in a gas or a liquid, and the adsorbed substance is adsorbed by intermolecular attraction (van der Waals force;), chemical reaction to form a chemical bond, and ion exchange.
  • adsorbents include activated carbon, diatomaceous earth, attapulgite, activated clay, silica gel, zeolite, wood chips, slag, humic acid, etc.
  • the most commonly used is activated carbon, which has high adsorption capacity due to its large specific surface area. .
  • the application of the adsorbent is mainly to achieve the purpose of deep purification, such as: removal of a small amount of heavy metal ions, harmful bio-degradable organic matter, decolorization and deodorization, etc.; crude biodiesel after adsorption operation can also be treated by freezing (low temperature) separation technology. Further processing makes the product more thorough.
  • the cryo-separation technique refers to a technique of separating the solidification points of different substances in a certain low temperature range, and has the advantages of no solvent pollution, simple operation, low cost, and high separation efficiency.
  • Molecular Distillation also known as short-path distillation, is a new type of liquid-liquid separation technology. It works by separating it at very high vacuum levels, depending on the mean free path difference of the molecular motion of the mixture, at temperatures well below its boiling point. Molecular distillation has the advantages unmatched by conventional distillation, and its separation efficiency is high, product yield is high, and the product quality is good due to low heating temperature and short time.
  • the technical solution of the present invention adopts the combination of adsorption clarification technology and molecular distillation technology or adsorption clarification-molecular distillation technology to remove by-products of the reaction, catalysts and impurities not participating in the reaction, thereby obtaining a stable and reliable biodiesel product.
  • crude glycerin is the main by-product in the preparation of biodiesel.
  • the yield of glycerol can also indicate the conversion rate of biodiesel.
  • High-purity glycerin is widely used in the fields of fine chemicals, food, medicine, etc.
  • Increasing the overall utilization of glycerol to increase the added value of the product reduces the production cost of biodiesel is also another aspect of the present invention.
  • the process of the present invention also provides other by-products, such as extract I (crude protein mixture), which can be used directly as a material or as a raw material for the preparation of chitosan. Extracts II, III and IV (phosphorus, sterols, pigments, etc.) can be used in the chemical, pharmaceutical, cosmetic and other fields.
  • FIG. 1 is a flow chart of the preparation method of the present invention. detailed description
  • the invention uses the larva or cockroach of the completely metamorphic insect as a raw material, and extracts the oil in the insect by a solvent method under the protection of nitrogen or without nitrogen, and the obtained low acid value (acid value ⁇ ⁇ 2) or high acid value (acid value) 2)
  • the insect oil is subjected to transesterification or pre-esterification-transesterification reaction to obtain crude biodiesel, and finally the crude oil is purified by adsorption clarification technology, molecular distillation technology or freezing (low temperature) separation technology to obtain refined oil.
  • Biodiesel see Figure 1 for details.
  • the composition of the obtained biodiesel can be seen in Table 1.
  • the insect refers to a larva or cockroach of a completely metamorphic insect, which is collected from various artificial farms, scientific research sites, and the like.
  • the maggots were collected from the Guangzhou flower and bird market, washed, treated with lime water, dried at 90 ° C, pulverized, added with 10 times the weight of petroleum ether, leached at room temperature for 48 hours under nitrogen atmosphere, and filtered to obtain extract I. It can be used directly as a feed, or as a raw material for preparing chitosan (the same as in the following examples), and the filtrate is distilled under reduced pressure to obtain a low acid value fly oil (insect oil).
  • insect oil low acid value fly oil
  • the obtained fly maggot oil is mixed with methanol in a molar ratio of 1:9, and 2.5% by weight of NaOH is added.
  • the solid is dissolved in alcohol to form an alcohol solution having an alkali concentration of 4 to 8 wt%.
  • the layer was allowed to stand, and the lower layer liquid was neutralized by dilute hydrochloric acid, centrifuged and distilled under reduced pressure to obtain by-product glycerin, and the upper layer liquid was washed with hot water for 2 to 3 times, and added.
  • the filter cake was eluted with ethyl acetate, and the solvent was recovered from the eluent to obtain the extract ⁇ .
  • the extract II was analyzed to contain phospholipids, sterols, and pigments, and was used in chemical, pharmaceutical, cosmetic, etc. In the field (same as in the following examples), the filtrate is the product biodiesel.
  • maggots are collected from the garbage dump, washed, and treated with hot water, dried at 60 ° C, pulverized, added with 1 times the weight of hexamidine, leached at room temperature for 24 hours under nitrogen atmosphere, filtered, and the filtrate is distilled under reduced pressure. The solvent is recovered to obtain a low acid value maggot oil.
  • the obtained fly maggot oil is mixed with methanol in a molar ratio of 1:6, and KOH is added in an amount of 2.5% by weight, heated and refluxed at 60 ° C for 30 minutes, and then allowed to stand for stratification, and the upper liquid is refined by molecular distillation technique.
  • the process conditions are: a vacuum of 10 Pa, a distillation temperature of 200 ° C, separation of biodiesel, the residue is an unsaponifiable matter, that is, extract III, wherein extract III is analyzed to contain phospholipids, alcohols, pigments, and the like In chemical, pharmaceutical, cosmetics And other fields (the same as the following examples).
  • the maggots were collected from rural households in Panyu, washed, and treated with hot water. They were naturally dried, pulverized, and added with petroleum ether-ethyl acetate-propanol at a weight of 3 times, leached at room temperature for 36 hours, filtered, and the filtrate was distilled under reduced pressure. The solvent is recovered to obtain a high acid value fly oil. The obtained oil was mixed with methanol at a molar ratio of 1:13, heated under reflux at 70 ° C, and 4% by weight of p-toluenesulfonic acid was added thereto, stirred, and reacted for 3 hours to obtain a low acid value fly magnolia oil.
  • the obtained fly maggot oil was mixed with methanol in a molar ratio of 1:7, and 0.5% sodium methoxide was added thereto, and heated under reflux at 65 ° C for 40 minutes, and then allowed to stand for stratification, and the lower liquid was neutralized by dilute hydrochloric acid and centrifuged. After the distillation under reduced pressure, the by-product glycerin is obtained.
  • the upper liquid is washed with hot water for 2 ⁇ 3 times, cooled, placed in a 0 °C cold storage, frozen for 24 hours, suction filtered, and the filter cake is extracted IV, wherein the extract IV is analyzed. Containing phospholipids, alcohols, and pigments, it can be used in the fields of medicine, cosmetics, etc. (the same applies in the following examples), and the filtrate is the product biodiesel.
  • the maggots were collected from the Institute of Entomology, Sun Yat-sen University, washed, treated with lime water, naturally dried, pulverized, added with 5 times the weight of n-hexane-methanol, leached at room temperature for 2 hours, filtered, and the filtrate was distilled under reduced pressure to obtain a solvent.
  • High acid value fly maggot oil The obtained fly maggot oil was mixed with methanol at a molar ratio of 1:9, heated under reflux at 50 ° C, and concentrated sulfuric acid of 2% by weight was added thereto, stirred, and reacted for 2.5 hours to obtain a low acid value fly maggot oil.
  • the obtained low acid value maggot oil was mixed with methanol in a molar ratio of 1:5, and KOH was added in an amount of 2.5% by weight of oil, and heated under reflux at 50 ° C for 50 minutes, and then allowed to stand for stratification, and the lower liquid was neutralized by dilute hydrochloric acid. After the centrifugal separation and vacuum distillation, the by-product glycerin was obtained. The upper liquid was washed with hot water for 2 to 3 times, cooled, placed in a refrigerator at 10 ° C, frozen for 120 hours, and filtered, and the filtrate was the product biodiesel.
  • the maggots were collected from rural households in Panyu, washed, and treated with hot water. They were naturally dried, pulverized, and added with petroleum ether-ethyl acetate-propanol at a weight of 3 times, leached at room temperature for 36 hours, filtered, and the filtrate was distilled under reduced pressure. The solvent is recovered to obtain a high acid value fly oil. The obtained oil was mixed with methanol at a molar ratio of 1:13, heated under reflux at 70 ° C, and 4% by weight of p-toluenesulfonic acid was added thereto, stirred, and reacted for 3 hours to obtain a low acid value fly magnolia oil.
  • the obtained fly maggot oil was mixed with methanol in a molar ratio of 1:7, and 0.5% sodium methoxide was added thereto, and heated under reflux at 65 ° C for 40 minutes, and then allowed to stand for stratification, and the lower liquid was neutralized by dilute hydrochloric acid and centrifuged. And distilled under reduced pressure
  • the by-product glycerin, the upper liquid is washed with hot water for 2 to 3 times, added with 5% by weight of magnesium silicate-activated carbon, heated to 85 ° C, stirred for 40 minutes, and suction filtered, and the filtrate is the product biodiesel.
  • the maggots were collected from a Guangdong pig farm. After treatment with lime water, they were dried at 90 ° C, pulverized, added with 10 times the weight of diethyl ether-ethanol, leached at room temperature for 30 hours, filtered, and the filtrate was distilled under reduced pressure to obtain a solvent.
  • High acid value fly maggot oil The obtained oil and ethanol were mixed at a molar ratio of 1:10, heated at 70 ° C under reflux, and 5% by weight of p-toluenesulfonic acid was added thereto, stirred, and reacted for 0.5 hour, and then ethanol was recovered by atmospheric distillation, and the mixture was allowed to stand. Layer, the lower layer of liquid is poured out to obtain low acid value maggot oil.
  • the low-acid fly maggot oil is mixed with ethanol in a molar ratio of 1:6, and the weight of the oil is 1.5% KOH.
  • the reactants are separated and purified by molecular distillation techniques, including two stages:
  • the molecular distillation process conditions are as follows: vacuum degree is 10Pa, distillation temperature is 80 °C, glycerol and ethanol are separated, and the second-stage molecular distillation process conditions are: vacuum degree is 0.1Pa, steaming temperature is 110 °C, and the organism is separated. Diesel.
  • the maggots were collected from the Institute of Economic Insects of Sun Yat-sen University, washed, lime water treated, naturally dried, pulverized, added with 8 times the weight of chloroform-methanol, leached at room temperature for 5 hours, filtered, and the filtrate was distilled under reduced pressure to obtain a solvent.
  • High acid value fly maggot oil The obtained oil was mixed with methanol at a molar ratio of 1:10, heated under reflux at 60 ° C, and concentrated sulfuric acid of 2% by weight was added thereto, stirred, and reacted for 3 hours to obtain a low acid value fly larvae oil.
  • the obtained fly maggot oil is mixed with methanol in a molar ratio of 1:7, and the weight of the oil is 2.5% NaOH, and the mixture is heated and refluxed at 60 ° C for 10 minutes, and then the reactant is separated and purified by molecular distillation technology, including three stages: I molecular distillation to separate methanol, the process conditions are: vacuum degree of 100Pa, distillation temperature of 60 ° C, II grade molecular distillation separation of glycerol, process conditions: vacuum degree of 100Pa, distillation temperature of 200 ° C; The distillation process conditions were as follows: a vacuum of 10 Pa and a distillation temperature of 200 ° C to separate biodiesel.
  • the maggots were collected from Panyu rural area, treated with lime water, dried at 90 ° C, pulverized, added with 10 times the weight of diethyl ether-ethanol, leached at room temperature for 30 hours, filtered, and the filtrate was distilled under reduced pressure to obtain a high solvent.
  • Acidic fly maggot oil The obtained oil and ethanol were mixed at a molar ratio of 1:10, heated at 70 ° C under reflux, and 5% by weight of p-toluenesulfonic acid was added thereto, stirred, and reacted for 0.5 hour, and then ethanol was recovered by atmospheric distillation, and the mixture was allowed to stand. Layer, pour the lower liquid Out, get low acid value maggot oil.
  • the obtained fly maggot oil is mixed with ethanol in a molar ratio of 1:6, and 2% of NaOH by weight of oil is added, and the mixture is heated and refluxed at 80 ° C for 30 minutes, and then the reactant is separated and purified by molecular distillation technology, including two stages:
  • the molecular distillation process conditions are as follows: vacuum degree is 30Pa, distillation temperature is 110 °C, glycerol and ethanol are separated, and the second-stage molecular distillation process conditions are: vacuum degree is 0.1Pa, distillation temperature is 100°C, and biodiesel is separated. .
  • the fly maggots were collected from the farmer's chicken farm in Panyu, Guangzhou. After washing with lime water, they were dried at 40 ° C, pulverized, and added with 1 times the weight of petroleum ether. The mixture was leached at room temperature for 10 hours under nitrogen atmosphere, filtered, and the filtrate was filtered. The solvent was distilled off under reduced pressure to obtain a low acid value fly oil.
  • the obtained fly maggot oil and methanol are mixed at a molar ratio of 1:5, 1.5% by weight of NaOH is added, and heated at 40 ° C for 60 minutes, and then allowed to stand for stratification, and the upper liquid is refined by molecular distillation technique.
  • the process conditions were as follows: a vacuum of 0.1 Pa and a distillation temperature of 100 ° C to separate biodiesel.
  • fly maggots were pulverized from the Institute of Entomology, Sun Yat-sen University, and added with cyclohexane-acetone, which was 5 times the weight, and immersed for 2 hours at room temperature.
  • the filtrate was filtered under reduced pressure to obtain a high acid value fly maggot oil.
  • the resulting fly maggot oil was mixed with methanol at a molar ratio of 1:9, heated to reflux at 50 ° C, and concentrated sulfuric acid of 2% by weight was added thereto, stirred, and reacted for 2.5 hours to obtain a low acid value fly maggot oil.
  • the obtained low acid value fly maggot oil is mixed with methanol in a molar ratio of 1:5, and an oil weight of 2.5% KOH is added.
  • Silkworm larvae were collected from the Guangdong Academy of Agricultural Sciences, washed, treated with hot water, dried at 70 ° C, pulverized, added with 10 times the weight of n-hexane, leached at room temperature for 6 hours under nitrogen protection, filtered, filtrate reduced The solvent was recovered by pressure distillation to obtain a low acid value silkworm oil.
  • the obtained silkworm oil and ethanol were mixed at a molar ratio of 1:7, and the metal sodium of 0.5% by weight of silkworm oil was added, and the mixture was heated and refluxed at 70 ° C for 40 minutes, and then allowed to stand for stratification, and the lower liquid was neutralized by dilute hydrochloric acid and centrifuged. And distilled under reduced pressure
  • the by-product glycerin, the upper liquid is washed with hot water for 2 to 3 times, added to the attapulgite having a weight of 1%, heated to 30 ° C, stirred for 60 minutes, and suction filtered, and the filtrate is the product biodiesel.
  • maggots were collected from the Institute of Entomology, Sun Yat-sen University. After washing, hot water treatment, drying at 10CTC, pulverizing, adding 1 times the weight of ether solvent, leaching at room temperature for 8 hours under nitrogen protection, filtering, decompression of the filtrate The solvent was distilled off to obtain a low acid value fly maggot oil.
  • the obtained fly maggot oil is mixed with methanol in a molar ratio of 1:4, added with 1% by weight of NaOH, heated and refluxed at 60 ° C for 10 minutes, and then allowed to stand for stratification, and the upper liquid is refined by molecular distillation technique.
  • the process conditions were as follows: a vacuum of 5 Pa and a distillation temperature of 150 ° C to separate biodiesel.
  • Tenebrio molitor larvae were collected from the genus Tenebrio molitor breeding base in Huizhou, Guangdong province. They were washed, hot-treated, naturally dried, pulverized, added with 10 times the weight of ethyl acetate, leached at room temperature for 25 hours, filtered, and the filtrate was distilled under reduced pressure to recover the solvent. , get high acid value yellow meal oil.
  • the obtained oil and methanol were mixed at a molar ratio of 1:10, heated under reflux at 80 ° C, and 5% by weight of p-toluenesulfonic acid was added thereto, and stirred for 0.5 hour to obtain a low acid value mealworm oil.
  • the low acid value mealworm oil is mixed with methanol in a molar ratio of 1:7, added with 2% KOH of oil weight, heated and refluxed at 65 ° C for 30 minutes, and then allowed to stand for stratification, and the upper liquid is refined by molecular distillation technology.
  • the process conditions were as follows: a vacuum of 10 Pa and a distillation temperature of 160 ° C to separate biodiesel.
  • Tenebrio molitor larvae were collected from Yangjiang City, Guangdong province, washed, washed with lime water, naturally dried, pulverized, added with 1 times the weight of n-hexane-ethanol, leached at room temperature for 40 hours, filtered, and the filtrate was distilled under reduced pressure to obtain the solvent.
  • the obtained oil was mixed with methanol at a molar ratio of 1:6, heated under reflux at 70 ° C, and concentrated sulfuric acid having a weight of 0.5% was added thereto, stirred, and reacted for 2 hours to obtain a low acid value mealworm oil.
  • the low acid value mealworm oil and methanol are mixed at a molar ratio of 1:9, added with 1.5% by weight of NaOH, heated and refluxed at 70 ° C for 60 minutes, and then allowed to stand for stratification, and the lower liquid is neutralized by dilute hydrochloric acid, centrifuged and Distillation was carried out under reduced pressure to obtain by-product glycerin.
  • the upper liquid was washed with hot water for 2 to 3 times, and 5% by weight of attapulgite-activated carbon was added thereto, heated to 60 ° C, stirred for 30 minutes, and filtered, and the filtrate was the product biodiesel.
  • Example 15 The preparation method of the biodiesel according to the embodiment includes the following steps:
  • the larvae of Tenebrio molitor were collected from the artificial farm of Panyu, Guangzhou. They were washed, hot-treated, naturally dried, pulverized, added with 10 times the weight of petroleum ether-methanol, leached at room temperature for 36 hours, filtered, and the filtrate was distilled under reduced pressure to recover the solvent.
  • a high acid value mealworm oil is obtained.
  • the obtained oil was mixed with methanol at a molar ratio of 1:9, heated under reflux at 55 ° C, and concentrated sulfuric acid having a weight of 1.5% was added thereto, stirred, and reacted for 1.5 hours to obtain a low acid value mealworm oil.
  • the low acid value mealworm oil and methanol are mixed at a molar ratio of 1:7, and the oil weight is 1.5% KOH, and the mixture is heated and refluxed at 60 ° C for 30 minutes, and then allowed to stand for stratification, and the lower liquid is neutralized by dilute hydrochloric acid, centrifuged and Distilled by vacuum distillation to obtain by-product glycerin, the upper layer of liquid was washed with hot water 2 to 3 times, added with 5% by weight of activated carbon, heated to 80 ° C, stirred for 30 minutes, cooled, placed in a refrigerator at 5 ° C, frozen for 72 hours , suction filtration, the filtrate is the product biodiesel.
  • Tenebrio molitor larvae were purchased from Guangzhou Fangcun Flower and Bird Market. After lime water treatment, they were dried at 10CTC, pulverized, added with 8 times the weight of hexamethylene-methanol, leached at room temperature for 25 hours, filtered, and the filtrate was distilled under reduced pressure to obtain the solvent. High acid value yellow meal oil. The obtained oil and ethanol were mixed at a molar ratio of 1:10, heated under reflux at 80 ° C, and 5% by weight of p-toluenesulfonic acid was added thereto, stirred, and reacted for 0.5 hour, and then ethanol was recovered by atmospheric distillation, and the mixture was allowed to stand. Layer, the lower layer of liquid is poured out to obtain low acid value mealworm oil.
  • the low acid value mealworm oil and ethanol are mixed at a molar ratio of 1:6, and the oil weight is 1.5% KOH, and the mixture is heated and refluxed at 80 ° C for 30 minutes, and then the reactant is separated and purified by molecular distillation technology, including two stages:
  • the molecular distillation process conditions are as follows: vacuum degree is 100 Pa, distillation temperature is 160 ° C, glycerol and ethanol are separated, and the second-stage molecular distillation process conditions are: vacuum degree is 10 Pa, distillation temperature is 200 ° C, and biodiesel is separated.
  • Tenebrio molitor was collected from Guangzhou Tenebrio molitor farm, washed, dried by lime water, naturally pulverized, added with 5-fold weight of n-hexane-ethanol, leached at room temperature for 24 hours under nitrogen protection, filtered, and the filtrate was distilled under reduced pressure. The solvent is recovered to obtain a low acid value eucalyptus oil.
  • the obtained eucalyptus oil and methanol are mixed at a molar ratio of 1:8, 1.5% by weight of NaOH is added, and the mixture is heated and refluxed at 60 ° C for 50 minutes, and then allowed to stand for stratification, and the upper liquid is refined by molecular distillation technology.
  • the conditions were: a vacuum of 5 Pa and a distillation temperature of 150 °C.
  • the preparation method of the biodiesel according to the embodiment includes the following steps: The moth was collected from the Institute of Entomology, Sun Yat-sen University, washed, treated with lime water, dried at 80 ° C, pulverized, added with 10 times its weight of hexamidine, leached at room temperature for 20 hours under nitrogen atmosphere, filtered, and filtrated. The solvent was distilled off under reduced pressure to obtain a low acid moth oil.
  • the obtained moth oil was mixed with methanol in a molar ratio of 1:7, and 1.5% by weight of NaOH was added thereto, and the mixture was heated and refluxed at 70 ° C for 60 minutes, and then allowed to stand for stratification, and the lower liquid was neutralized by dilute hydrochloric acid, centrifuged and separated. Distillation was carried out under reduced pressure to obtain by-product glycerin.
  • the upper liquid was washed with hot water for 2 to 3 times, and 5% by weight of attapulgite-activated carbon was added thereto, heated to 80 ° C, stirred for 30 minutes, and filtered, and the filtrate was the product biodiesel.
  • the barley larvae were purchased from Guangzhou Fangcun Flower and Bird Market, washed, naturally dried and pulverized. Add 5 times of cyclohexane-acetone, leaching for 2 hours at room temperature, filtered, and the filtrate was distilled under reduced pressure to obtain high acid value barley. Insect oil. The obtained oil was mixed with methanol at a molar ratio of 1:8, heated under reflux at 55 ° C, and concentrated sulfuric acid of 0.5% by weight was added thereto, stirred, and reacted for 2.5 hours to obtain a low acid value barley insect oil.
  • the low acid value barley insect oil and methanol are mixed at a molar ratio of 1:9, added with 2.5% by weight of NaOH, heated and refluxed at 50 ° C for 60 minutes, then allowed to stand for stratification, and the lower liquid is neutralized by dilute hydrochloric acid, centrifuged and After the distillation under reduced pressure, the by-product glycerin was obtained.
  • the upper liquid was washed with hot water for 2 to 3 times, added with 5% by weight of alumina, heated to 60 ° C, stirred for 40 minutes, and suction filtered, and the filtrate was the product biodiesel.
  • the barley larvae are collected from the Fangfang flower and bird market in Guangzhou. After washing and hot water treatment, they are naturally dried, pulverized, added with 5-fold weight of benzene-ethanol, leached at room temperature for 15 hours, filtered, and the filtrate is distilled under reduced pressure to obtain a high acid.
  • Value barley insect oil The obtained oil was mixed with methanol at a molar ratio of 1:11, heated to reflux at 65 ° C, and 3% by weight of p-toluenesulfonic acid was added thereto, stirred, and reacted for 4 hours to obtain a low acid value barley insect oil.
  • the low acid value barley insect oil and methanol are mixed at a molar ratio of 1:5, and 1% sodium metal by weight of oil is added, and the mixture is heated and refluxed at 65 ° C for 20 minutes, and then allowed to stand for stratification, and the lower liquid is neutralized by dilute hydrochloric acid and centrifuged. After the distillation under reduced pressure, the by-product glycerin is obtained.
  • the upper liquid is washed with hot water for 2 to 3 times, and 1% by weight of magnesium silicate is added thereto, heated to 70 ° C, stirred for 10 minutes, and filtered, and the filtrate is the product biodiesel.
  • the barley larvae were collected from the Institute of Entomology, Sun Yat-sen University, pulverized, and added to the petroleum ether-chloroform-acetone, which is 3 times the weight. The mixture was leached at room temperature for 24 hours, filtered, and the filtrate was distilled under reduced pressure to obtain a high acid value barley insect oil.
  • the obtained oil and ethanol were mixed at a molar ratio of 1:6, heated at 85 ° C under reflux, and 5% by weight of p-toluenesulfonic acid was added thereto, stirred, and reacted for 2.5 hours, and then ethanol was recovered by atmospheric distillation, and the mixture was allowed to stand. Layer, the lower layer of liquid is poured out to obtain low acid value barley insect oil.
  • the reactants were separated and purified by molecular distillation technique, including three stages: I molecular distillation to separate ethanol, the process conditions are: vacuum degree of 3000Pa, distillation temperature of 70 ° C, class II The glycerol was separated by molecular distillation.
  • the process conditions were as follows: vacuum degree was 50 Pa, and distillation temperature was 110 ° C ; Class III molecular distillation process conditions were: vacuum degree was 1 Pa, distillation temperature was 140 ° C, and biodiesel was separated.
  • the barley worm was collected from the Dongguan farm. It was washed and dried naturally, and then pulverized. It was added with 5 times the weight of hexamidine-acetone. It was leached at room temperature for 2 hours, filtered, and the filtrate was evaporated under reduced pressure to recover the solvent to obtain a high acid value barley worm. oil. The obtained oil was mixed with methanol at a molar ratio of 1:9, heated under reflux at 60 ° C, and concentrated sulfuric acid of 2% by weight was added thereto, stirred, and reacted for 2.5 hours to obtain a low acid value barley worm oil.
  • the low acid value barley worm oil and methanol are mixed at a molar ratio of 1:10, added with 2.5% by weight of NaOH, heated and refluxed at 50 ° C for 60 minutes, then allowed to stand for stratification, and the lower liquid is neutralized by dilute hydrochloric acid and centrifuged. After the distillation under reduced pressure, the by-product glycerin is obtained.
  • the upper liquid is washed with hot water for 2 to 3 times, and the activated carbon having a weight of 5% is added thereto, heated to 100 ° C, stirred for 40 minutes, and suction filtered, and the filtrate is the product biodiesel.
  • the moth was collected from the Panyu farm in Guangzhou, washed, treated with lime water, dried at 70 ° C, pulverized, added with 5 times the weight of petroleum ether-acetone, and leached at room temperature for 15 hours under nitrogen atmosphere.
  • the filtrate was distilled under reduced pressure to recover a solvent to obtain a low acid moth oil.
  • the obtained moth oil was mixed with methanol in a molar ratio of 1:8, and 1.5% by weight of NaOH was added thereto, and the mixture was heated and refluxed at 60 ° C for 50 minutes, and then allowed to stand for stratification, and the upper liquid was purified by molecular distillation technique.
  • the process conditions were as follows: a vacuum of 2 Pa and a distillation temperature of 120 ° C to separate biodiesel.
  • the moth larvae were collected from the Guangdong Academy of Agricultural Sciences, washed, naturally dried and pulverized, and added to the weight of acetic acid The ester was leached at room temperature for 36 hours under nitrogen atmosphere, filtered, and the filtrate was distilled under reduced pressure to obtain a low acid moth larvae oil.
  • the obtained moth larvae oil was mixed with methanol in a molar ratio of 1:9, KOH was added in an amount of 2.5% by weight, heated and refluxed at 70 ° C for 40 minutes, and then allowed to stand for stratification, and the lower liquid was neutralized by dilute hydrochloric acid, centrifuged and After the distillation under reduced pressure, the by-product glycerin was obtained.
  • the upper liquid was washed with hot water for 2 to 3 times, and 5% by weight of activated carbon-magnesium silicate was added thereto, heated to 70 ° C, stirred for 30 minutes, and suction filtered, and the filtrate was the product biodiesel.
  • the moth larvae were collected from the Institute of Economic Insects of Sun Yat-sen University, washed, dried by hot water, pulverized, added with 8 times the weight of ethyl acetate, leached at room temperature for 30 hours, filtered, and the filtrate was distilled under reduced pressure to obtain a high solvent.
  • Acid moth larvae oil The obtained oil was mixed with methanol at a molar ratio of 1:10, heated under reflux at 80 ° C, and p-toluenesulfonic acid having an oil weight of 5% was added thereto, stirred, and reacted for 3.5 hours to obtain a low acid moth larvae oil.
  • the obtained moth larvae oil was mixed with methanol in a molar ratio of 1:7, and KOH was added in an amount of 2% by weight, heated and refluxed at 65 ° C for 30 minutes, and then allowed to stand for stratification, and the upper liquid was purified by molecular distillation technique.
  • the process conditions were as follows: a vacuum of 10 Pa and a distillation temperature of 160 ° C to separate biodiesel.
  • Silkworm larvae were collected from Guangdong Tianqin Sericulture Co., Ltd., washed, treated with lime water, dried at 80 ° C, pulverized, added with 1 times the weight of benzene, leached at room temperature for 12 hours under nitrogen protection, filtered, filtrate The solvent was distilled off under reduced pressure to obtain a low acid value silkworm oil.
  • the obtained silkworm oil and ethanol are mixed at a molar ratio of 1:9, and the KOH is added with 1.5% by weight of silkworm oil.
  • the reactants are separated and purified by molecular distillation techniques, including two stages: I molecular distillation process conditions are: vacuum degree of 10Pa, distillation temperature of 80 ° C, separation of glycerol and ethanol, the second-stage molecular distillation process conditions are: vacuum degree of O. lPa, distillation temperature of 100 ° C, separation of organisms Diesel.
  • the silkworm cocoon was collected from Guangdong Tianqin Sericulture Co., Ltd., washed, treated with lime water, dried at 80 Torr, pulverized, added with 10 times the weight of diethyl ether, leached at room temperature for 10 hours under nitrogen atmosphere, filtered, and the filtrate was distilled under reduced pressure. The solvent is recovered to obtain a low acid value silkworm oil.
  • the obtained silkworm pupa oil and methanol are mixed at a molar ratio of 1:5, and the weight of the oil is 2.5% sodium methoxide, 70 ° C plus After hot reflux for 30 minutes, the mixture was allowed to stand for stratification, and the lower liquid was neutralized by dilute hydrochloric acid, centrifuged, and distilled under reduced pressure to obtain by-product glycerin. The upper liquid was washed with hot water for 2 to 3 times, and 6% of the attapulgite was added. Soil-magnesium silicate, heated to 60 ° C, stirred for 30 minutes, suction filtered, the filtrate is the product biodiesel.
  • the silkworm cocoon was collected from the Guangdong Academy of Agricultural Sciences, washed, and treated with hot water. It was dried at 50 ° C, pulverized, and added to the weight of cyclohexanone. It was leached at room temperature for 15 hours under nitrogen atmosphere, filtered, and the filtrate was reduced. The distillation was carried out by pressure distillation to obtain a low acid value silkworm cocoon oil.
  • the obtained silkworm pupa oil is mixed with methanol in a molar ratio of 1:6, added with 2% by weight of NaOH, heated and refluxed at 70 ° C for 30 minutes, and then allowed to stand for stratification, and the upper liquid is refined by molecular distillation technology.
  • the conditions were as follows: a vacuum of 8 Pa and a distillation temperature of 130 ° C to separate biodiesel.
  • the bee stings were collected from Guangzhou Baiyunshan bee house, washed, treated with lime water, dried at 80 ° C, pulverized, added with 10 times weight of chloroform, leached at room temperature for 20 hours under nitrogen atmosphere, filtered, filtrate The solvent is distilled off under reduced pressure to obtain a low acid value bee oyster oil.
  • the obtained bee eucalyptus oil was mixed with methanol in a molar ratio of 1:9, and 1.5% by weight of NaOH was added thereto, and the mixture was heated and refluxed at 70 ° C for 60 minutes, and then allowed to stand for stratification, and the lower liquid was neutralized by dilute hydrochloric acid, centrifuged and separated. After the distillation under reduced pressure, the by-product glycerin was obtained. The upper liquid was washed with hot water for 2 to 3 times, and the activated clay-activated carbon having a weight of 5% was added thereto, heated to 80 ° C, stirred for 20 minutes, and suction filtered, and the filtrate was the product biodiesel.
  • the bee stings were collected from the South China Botanical Garden, washed, naturally dried and pulverized. The ethyl acetate was added in 1 time by weight, and leached at room temperature for 36 hours under nitrogen atmosphere. The filtrate was filtered under reduced pressure to obtain a low acid value bee sting. oil.
  • the obtained bee eucalyptus oil was mixed with methanol in a molar ratio of 1:9, and sodium methoxide having a weight of 0.5% was added thereto, and the mixture was heated and refluxed at 70 ° C for 40 minutes, and then allowed to stand for stratification, and the lower liquid was neutralized by dilute hydrochloric acid and centrifuged. After the distillation under reduced pressure, the by-product glycerin is obtained. The upper liquid is washed with hot water for 2 to 3 times, and the activated carbon-alumina having a weight of 5% is added thereto, heated to 40 ° C, stirred for 20 minutes, and suction filtered, and the filtrate is the product biodiesel.

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Description

一种生物柴油及其制备方法 技术领域
本发明涉及可再生能源技术领域， 尤其涉及一种生物柴油及其制备方法。 背景技术
生物柴油， 又称生化柴油， 是指以油料植物与工程微藻等植物油脂以及动物油脂、 餐饮废油等为原料， 通过酯交换工艺生成的长链脂肪酸甲酯或乙酯。 生物柴油除与石化 柴油相近的性能外， 还具有持续的可再生性能， 以及优良的环保特性， 生物柴油中氧含 量高， 不含硫和芳香族垸烃， 燃烧产生的废气中一氧化碳、 二氧化硫、 硫化物量也减低 了， 此外， 生物柴油的可降解性也明显高于石化柴油。
目前制备生物柴油原料主要为植物油脂， 如花生油、 大豆油、 菜籽油、 椰子油、 棕 榈油、 小桐子油， 以及工程海藻油脂、 餐饮废油、 动物油， 如废猪油、 鱼油等。 釆用上 述原料制备生物柴油都存在一些缺点，一方面与食用油争夺原料，挤占粮食耕作的空间， 加剧我国粮食紧缺问题， 另一方面是原料如花生油和大豆油本身价格高， 使得生物柴油 的成本随之变高。据统计， 生物柴油成本的 75%为原料成本， 因此寻找新的廉价原料从 而降低成本是实现生物柴油产业化的关键。
本发明涉及到一种利用完全变态昆虫的幼虫及蛹的油脂制备生物柴油，这里的昆虫 包括： 如大麦虫幼虫及蛹、 黄粉虫幼虫及蛹、 蛾幼虫及蛹、 蝇幼虫及蛹等。 昆虫分为不 完全变态昆虫 (incomplete metamorphosis) 禾口完全变态昆虫 ( complete metamorphosis) 两大类，完全变态昆虫的生活史包括卵（Egg)、幼虫（Larva)、蛹（Pupa)、成虫（Adult) 四个阶段， 卵孵化成幼虫， 幼虫经一系列蜕皮以及其他较小变化后变成蛹， 最后变为成 虫。本专利涉及利用完全变态昆虫的幼虫及蛹中提取的油脂转化成生物柴油的用途和方 法。 完全变态昆虫词养操作十分简便， 培养基来源广泛且成本低廉， 蝇属于典型的完全 变态昆虫， 蝇蛆即为环裂亚目 （Cyclorrhapha)各科下蝇的幼虫（Maggot)。 蝇具有一次 交配可终身产卵的生理特点， 繁殖能力极强， 整个生命周期为 28天。 雌蝇一生可产卵 5-6次，每次产卵数约 100-150粒， 从卵到孵出昆虫 3-4天即可，一年内可繁殖昆虫 10-12 代。 蝇蛆的养殖成本低、 饲养操作方便、 设备简单， 其饲养可在室内或室外进行， 培养 基来源广泛、 低廉， 如麦麸、 米糠、 酒糟、 豆渣等农副产品的下脚料、 牲畜粪便等。 目 前蝇蛆规模化养殖技术已臻成熟， 在美国等发达国家也实现了机械化与规模化， 如可采 用大量廉价蝇蛆油生产生物柴油， 可大幅度减低其生产成本。 大麦虫 Zophobas spp. 和黄粉虫 Uenebrio sPp.、, 根据昆虫分类学， 均属于鞘翅目 （Coleoptera), 其从卵孵 化到成虫羽化大约需要三个多月的时间， 大麦虫幼虫呈圆筒型， 长约 7厘米， 虫体宽约 0.5厘米，为黄粉虫幼虫的 3-4倍，两者幼虫体内均富含蛋白质 (40~50%)、脂肪（30~40%) 及其他营养成分， 常被作为养殖各种龙鱼、 观赏鸟、 鳖、 蛇等稀有动物的绝佳饵料。 蛾 (Moth)也是典型的完全变态昆虫， 属鳞翅目 （Lepidoptem) , 是鳞翅目中最大的类群， 占 到鳞翅目种类的 90%左右， 包括麦蛾科 (Gelechiidae)、 夜蛾科 (Noctuidae；)、 大蚕蛾科 (； Saturniidae)和蝙蝠蛾科 (Hepialidae)等，其个体发育要经过卵、幼虫、蛹和成虫四个阶段， 历时一个多月，蛾类幼虫的脂肪含量比较高，其中蝙蝠蛾幼虫的粗脂肪含量高达 77.16%。 蚕 An theraea spp. 为鳞翅目大蚕蛾科蚕蛾的幼虫， 其干虫体中脂肪含量高达 30%以 上，蚕蛹可供食用，残渣可作鱼、畜、禽的饲料。蜜蜂（ s spp. )属膜翅目（Hymenoptera) 蜜蜂科 （Apidae) , 其个体发育也为四个阶段， 蜂王在蜂房产下卵， 孵化成幼虫， 再经 过 7天的发育， 进入蛹期， 此时的蜜蜂躯体即为蜂蛹， 峰蛹富含蛋白质和脂肪， 国内外 对蜜蜂的开发应用主要集中在蜂王浆、 蜂蜜、 蜂花粉等保健品和食品上。
昆虫的脂肪含量丰富， 许多昆虫鲜品脂肪含量为 10%-20%， 其干燥品脂肪含量为 20%-50%。 据研究， 影响昆虫脂肪含量的因素主要包括以下三个方面： ①昆虫种类， 种 类不同其脂质含量也不同； ②同种昆虫中脂肪含量以蛹、 幼虫以及处于越冬期的昆虫为 高； ③昆虫生活史变化也导致脂肪含量变化， 体内激素或神经激素的直接或间接作用导 致脂类合成和利用之间代谢平衡的变化，在内分泌控制下的如发育、迁移、滞育、繁殖、 飞行等过程都影响着脂类的新陈代谢。 含高脂肪的昆虫大部分属于完全变态型的昆虫， 因此， 本专利涉及利用昆虫纲中完全变态昆虫的幼虫和蛹中油脂为原料制备生物柴油， 该类昆虫油脂含量相对较高、 生长周期短及繁殖能力强。
昆虫油脂具有与植物油脂不相同的特性，植物的油脂因存在于植物油细胞或以油滴 等游离形式存在， 其提取方法较容易。 而昆虫油脂在昆虫体内以下三种方式存在： 其一 是甘油酯、胆 醇酯等单酯的烃基以范德华键或疏水键与其他的脂质及蛋白质的疏水键 间形成较弱的非共价键结合， 以这种方式存在有脂肪组织中的脂肪、 白蛋白、 脂肪酸一 复合体等； 其二磷脂质、 胆 醇等极性脂质存于形质膜、 线粒体、 小胞体等生体膜及血 清核蛋白质复合体中， 常与蛋白质间形成氢键、 离子键、 及疏水键； 第三种是以酯键、 酰胺键、 苷键等形式的共价键存在， 如脂肪酸、 羟基脂肪酸、 复杂支链脂肪酸中。 昆虫 油脂在上述生物体中的存在状态、溶解度及与其他成分结合方式是制定其提取方法的主 要依据。 另外昆虫体内由于解脂酶的存在作用使油脂水解产生大量的不饱和脂肪酸， 加 上空气中氧气的作用，在相同的状态下昆虫油脂较植物油脂更容易酸败致使酸价升高进 一步影响到后续的生物柴油制备反应。昆虫油脂中含有丰富的不饱和脂肪酸,其饱和脂肪 酸与不饱和脂肪酸的比值小于 0.4， 部分接近于鱼油的脂肪酸组成。 昆虫的饱和脂肪酸 大多以棕榈酸 (C16:0)为主， 硬脂酸 (C18:0)的含量较低,单不饱和脂肪酸则绝大多数以油 酸 (C18: ln-9)为绝对组成,含量多在 (30± 10)%。部分昆虫含有较多的多不饱和脂肪酸，其 中以亚油酸 (C18:2n-6)和 α -亚麻酸 (C18:3n-3)较为突出。昆虫油脂中存在着自然界较为少 见的奇数碳脂肪酸,其中以十五碳酸、十七碳酸较为多见。奇数碳脂肪酸具有独特的生理 活性功能如有较强抗癌活性。亚油酸在鞘翅目中的含量较高，而亚麻酸在鳞翅目中的含量 较高， 研究表明， 昆虫油脂脂肪酸组成与其种类、 生长发育、 营养状况、 环境或词料等 因素有关。 发明内容
本发明目的之一在于选择了一种新的生物柴油原料及其制造方法， 由该方法具有生 产成本低廉、 原料可再生得到等优点。
实现上述目的的技术方案如下：
一种制备生物柴油的方法， 包括下述步骤-
( 1 ) 昆虫油制备： 完全变态昆虫的幼虫或 /和蛹昆虫干燥粉碎后， 加入其重量 1~10 倍的溶剂， 室温浸提 1~48 小时， 过滤， 得到提取物 I， 滤液回收溶剂后得到酸值 2 的低酸值昆虫油或（酸值 >2)的高酸值昆虫油， 当昆虫油的酸值>2时， 进行预酯化处 理， 得到酸值 ¾≡2的低酸值昆虫油， 处理条件为： 将酸值 >2的昆虫油与甲醇或乙醇摩 尔比为 1 : 6-1： 13 , 昆虫油重量的 0.5%~5%的酸性催化剂， 反应温度为 40°C~90°C， 反应时间为 0.5~4小时；
(2)酯交换： 将低酸值昆虫油与甲醇或乙醇进行酯交换反应， 反应条件为： 低酸值 昆虫油与甲醇或乙醇的摩尔比为 1 : 4-1： 9，加入昆虫油重量的 0.5~2.5%的碱性催化剂， 反应温度为 40°C~90°C， 反应时间为 10 60分钟；
( 3 ) 分相： 酯交换结束后， 反应物静置分层， 上层液体为粗酯， 下层液体为甘油、 水、甲醇或乙醇和催化剂等，经过稀盐酸中和、离心分离和减压蒸馏后得到副产物甘油； (4)精制处理： 歩骤 （3 ) 的上层液体热水洗 2~3次， 加入其重量 1%~10%的吸附 齐 !J， 加热至 30°C〜100°C， 搅拌 10-60分钟， 抽滤， 滤液即产品生物柴油， 滤饼用乙酸乙 酯洗脱，洗脱液回收溶剂后，得到提取物 II；或将歩骤（3 )的上层液体水洗后，置于 0°C ~10°C冰箱 （冰库） 内， 冷冻 24 120小时， 抽滤， 滤饼为提取物 IV， 滤液即为生物柴 油； 或采用分子蒸镏技术对步骤 （3 ) 反应得到的上层液体进行精制处理， 其工艺条件 为： 真空度为 10-0. lPa， 蒸熘温度为 100-200°C， 分离出生物柴油； 也可以直接采用分 子蒸馏技术对步骤 （2) 的反应物进行精制处理： 包括二级： I、 分子蒸馏分离出反应 物中的甘油和甲醇或乙醇， 工艺条件为： 真空度为 100-10Pa， 蒸馏温度为 80-160°C ; II、 分子蒸馏分离出生物柴油， 工艺条件为： 真空度为 10-0. lPa， 蒸熘温度为 100-200 °C ;或包括三级： I、分子蒸馏分离出甲醇或乙醇，工艺条件为：真空度为 5000-lOOPa, 蒸馏温度为 60-15(TC ; II、 分子蒸馏分离出甘油， 工艺条件为： 真空度为 100-10Pa， 蒸馏温度为 100-20(TC ; III、 分子蒸馏分离出生物柴油， 馏余物为不皂化物， 即提取物
III， 工艺条件为： 真空度为 10- 0. lPa， 蒸馏温度为 100-200°C。
上述步骤 （1 ) 中： 单一或复合有机溶剂指的是单一亲脂性有机溶剂或者亲脂性和 亲水性有机溶剂的任意一种或若干种的混合溶剂， 亲脂性有机溶剂包括但不限于： 正己 垸、 环己垸、 石油醚、 乙醚、 乙酸乙酯、 氯仿、 苯； 亲水性有机溶剂包括但不限于： 甲 醇、 乙醇、 丙醇、 丙酮。
上述步骤 （1 ) 中： 所述完全变态昆虫为蝇、 黄粉虫、 大麦虫、 蚕、 蜂、 蛾等。 上述步骤 （1 ) 中： 所述酸性催化剂指的是浓硫酸或对甲苯磺酸。
上述步骤 （1 ) 中： 室温浸提可以是在氮气保护下或没有氮气保护情况下进行， 优 选为在氮气保护下浸提。
上述步骤（2)所述的碱性催化剂可为 NaOH、 KOH、 醇钠或碱金属， 采用 NaOH、 KOH作催化剂时先将其固体溶于甲醇或乙醇中制成碱浓度为 4~8%wt的醇溶液。
上述步骤（4)中： 吸附剂包括但不限于：活性白土、硅藻土、凹凸棒土（Attapulgite)、 活性炭、 硅酸镁、 氧化铝的一种或任意一种以上。
上述歩骤 （1 ) 中： 提取物 I经分析鉴定为粗蛋白混合物， 可直接作为饲料， 也可 作为制备壳聚糖的原料。 上述步骤 （4) 中： 提取物 II、 提取物 III以及提取物 IV经分析 鉴定为磷脂、 醇、 色素类等成分， 可用于化工、 医药、 化妆品等领域。
本发明的另一目的是提供一种生物柴油。
具体技术方案为： 所述生物柴油为根据以上所述方法制备得到的。
本发明所述的制备生物柴油的方法，采用完全变态昆虫的幼虫与 /和蛹提取的昆虫油 作为原料制备生物柴油的原料， 其原料来源广泛、 养殖成本低廉。
昆虫油的含量以及成分组成因为昆虫的种类、 生长环境、 营养状况以及培养条件的 不同而发生变化， 因此采用本专利技术生产的生物柴油其组成也有一些差别， 如表 1所 示： 表 1 : 昆虫生物柴油的成分分析及其相对含量
Figure imgf000007_0001
本专利的昆虫油指采用完全变态昆虫的幼虫或 /和蛹经过提取（如溶剂法）得到的油 状液体， 该昆虫油的主要成分是饱和脂肪酸与不饱和脂肪酸， 如： 蝇蛆油、 蝇蛹油、 大 麦虫油、 黄粉虫油、 蛾蛹油、 蚕油、 蚕蛹油等。 采用昆虫油为原料制备生物柴油的方法 与传统的植物油脂转化法有一些不同， 如：
( 1 ) 本发明采用单一有机溶剂或复合溶剂如乙醇一乙醚等破坏昆虫体内油脂结合 键以提取全脂质， 同时也起到破坏昆虫体内解脂酶的活性， 抑制酸价升高， 本发明研究 了在提取操作过程是否提供惰性气体（氮气）进行保护的两种情况，在充氮气的情况下， 可以更好地避免昆虫油脂的氧化。 (2) 以提取得到的昆虫油脂为原料采用脂肪酸酯交换或预酯化 -酯交换反应得到脂 肪酸垸酯和脂肪酸垸酯混合物， 混合物中含有一定的水分与脂肪酸不皂化物， 如磷脂、 甾醇、 色素类等成分， 因此我们将这一步反应后的总物质称为粗生物柴油。 当有水存在 时， 脂肪酸甲酯或脂肪酸乙酯会水解为相应的游离脂肪酸， 导致生物柴油酸值增加， 直 接影响产品的质量， 而后者在燃烧过程中， 也会导致灰分（沉淀） 的析出， 这些灰分可 附着甚至堵塞燃油过滤器（装置）或输油管道。 因此， 对粗生物柴油以精制为目的的后 处理过程是非常必要的。 吸附剂是指能有效地吸附气体或液体中某些成分的固体物 质， 其与被吸附物质之间是通过分子间引力 (范德华力；)、 发生化学作用生成化学键以及 离子交换作用而产生吸附。 常用的吸附剂有活性炭、 硅藻土、 凹凸棒土、 活性白土、 硅 胶、 沸石、 木屑、 炉渣、 腐植酸类等， 其中最为常用的是活性炭， 由于其比表面积大而 具有较高的吸附能力。 吸附剂的应用主要是达到深度净化的目的， 如： 去除少量重金属 离子、有害的生物难降解有机物以及脱色除臭等； 经过吸附操作后的粗生物柴油还可采 用冷冻（低温）分离技术对其进一步处理， 使得产品的除杂更为彻底。 冷冻分离技术是 指在一定的低温范围内根据不同物质的凝固点差异将其分离的技术， 具有无溶剂污染、 操作简便、 成本低廉、 分离效率较高等优点。
(3 ) 分子蒸馏 (Molecular Distillation), 又叫短程蒸馏， 是一种新型的液-液分离技 术。 它的工作原理是在极高真空度下， 依据混合物分子运动平均自由程差异， 在远低于 其沸点的温度下将其分离。 分子蒸馏具有常规蒸馏不可比拟的优点， 其分离效率高， 产 品收率高， 因受热温度低、 时间短， 产品品质也好。 本发明的技术方案中采用了吸附澄 清技术与分子蒸馏技术或者吸附澄清-分子蒸馏技术组合技术除去反应的副产物、 催化 剂以及未参加反应的杂质后即可得质量稳定、 可靠的生物柴油产品。
(4) 另外， 在生物柴油制备过程中粗甘油为其主要副产物， 甘油的得率也可以指 示生物柴油的转化率， 高纯度的甘油在精细化工、 食品、 医药等领域应用均很广泛， 增 加对甘油的综合利用率以提高产品的附加值降低生物柴油的生产成本也是本发明研究 的另一方面。 除甘油外， 本发明所述的方法还可以得到其它副产品， 例如提取物 I (粗 蛋白混合物）， 可直接作为词料， 也可作为制备壳聚糖的原料。 提取物 II、 III和 IV (磷 脂、 甾醇、 色素类等）， 可用于化工、 医药、 化妆品等领域。 附图说明
图 1为本发明制备方法的流程图。 具体实施方式
本发明以完全变态昆虫的幼虫或蛹为原料，在有氮气保护或没有氮气下采用溶剂法 提取昆虫中油脂， 所得到的低酸值（酸值≤≡2)或高酸值（酸值〉2)的昆虫油分别经过 酯交换或预酯化-酯交换反应后分相得到粗生物柴油， 最后采用吸附澄清技术、 分子蒸 馏技术或者冷冻（低温）分离技术对粗油进行纯化处理， 得到精制生物柴油， 具体可参 见图 1。 所得生物柴油的组成可参见表 1。 所述昆虫指的是完全变态昆虫的幼虫或蛹， 采自各类人工养殖场、 科研场所等处。
下面通过具体实施例对本发明作进一步说明。
实施例 1:
本实施例所述的生物柴油的制备方法， 包括如下步骤：
蝇蛆采自广州花鸟市场， 洗净， 石灰水处理后， 在 90Ό温度下干燥， 粉碎， 加入 其重量 10倍的石油醚， 在氮气保护下室温浸提 48小时， 过滤， 得到提取物 I， 可直接 作为饲料， 也可作为制备壳聚糖的原料 （以下实施例同）， 滤液减压蒸馏回收溶剂， 得 到低酸值蝇蛆油 （昆虫油）。
将所得的蝇蛆油与甲醇按 1 : 9的摩尔比混合， 加入油重量 2.5%的 NaOH (加入时 应先将其固体溶于醇中制成碱浓度为 4~8wt%的醇溶液， 以下实施例同）， 90°C加热回 流 10分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸馏后得到副产 物甘油， 上层液体用热水洗 2~3次， 加入其重量 10%的活性白土， 加热至 100°C， 搅拌
10 分钟， 抽滤， 滤饼用乙酸乙酯洗脱， 洗脱液回收溶剂后， 得到提取物 π， 其中提取 物 II经分析含有磷脂、 甾醇、 色素类成分， 可用于化工、 医药、 化妆品等领域（以下实 施例同）， 滤液即产品生物柴油。
实施例 2:
本实施例所述的生物柴油的制备方法， 包括如下步骤：
蝇蛆采自垃圾场， 洗净， 热水处理后， 在 60°C温度下干燥， 粉碎， 加入其重量 1 倍的正己垸， 在氮气保护下室温浸提 24小时， 过滤， 滤液减压蒸馏回收溶剂， 得到低 酸值蝇蛆油。
将所得的蝇蛆油与甲醇按 1 : 6的摩尔比混合， 加入油重量 2.5%的 KOH， 60°C加 热回流 30分钟后， 静置分层， 上层液体采用分子蒸馏技术进行精制处理， 其工艺条件 为： 真空度为 10Pa， 蒸馏温度为 200°C， 分离出生物柴油， 馏余物为不皂化物， 即提取 物 III， 其中提取物 III经分析含有磷脂、 醇、 色素类成分， 可用于化工、 医药、 化妆品 等领域 （以下实施例同）。
实施例 3:
本实施例所述的生物柴油的制备方法， 包括如下步骤：
蝇蛆采自番禹农村农户， 洗净， 热水处理后， 自然干燥， 粉碎， 加入其重量 3倍的 石油醚 -乙酸乙酯-丙醇， 室温浸提 36小时， 过滤， 滤液减压蒸馏回收溶剂， 得到高酸值 蝇蛆油。 将所得的油与甲醇以摩尔比 1 : 13的比例混合， 70°C加热回流， 并加入油重 量 4%的对甲苯磺酸， 搅拌， 反应 3小时后得到低酸值蝇蛆油。
将所得的蝇蛆油与甲醇按 1 : 7的摩尔比混合， 加入油重量 0.5%的甲醇钠， 65°C加 热回流 40分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸馏后得到 副产物甘油， 上层液体用热水洗 2~3次， 冷却， 置于 0°C冷库内， 冷冻 24小时， 抽滤， 滤饼为提取物 IV， 其中提取物 IV经分析含有磷脂、 醇、 色素类成分， 可用于医药、 化 妆品等领域 （以下实施例同）， 滤液即产品生物柴油。
实施例 4:
本实施例所述的生物柴油的制备方法， 包括如下步骤：
蝇蛆采自中山大学昆虫研究所， 洗净， 石灰水处理后， 自然干燥， 粉碎， 加入其重 量 5倍的正己烷-甲醇， 室温浸提 2小时， 过滤， 滤液减压蒸馏回收溶剂， 得到高酸值 蝇蛹油。 将所得的蝇蛹油与甲醇以摩尔比 1 : 9的比例混合， 50°C加热回流， 并加入油 重量 2%的浓硫酸， 搅拌， 反应 2.5小时后得到低酸值蝇蛹油。
将所得的低酸值蝇蛹油与甲醇按 1 : 5的摩尔比混合， 加入油重量 2.5%的 KOH， 50°C加热回流 50分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸馏 后得到副产物甘油， 上层液体用热水洗 2~3次， 冷却， 置于 10°C冰箱内， 冷冻 120小 时， 抽滤， 滤液即产品生物柴油。
实施例 5:
本实施例所述的生物柴油的制备方法， 包括如下步骤：
蝇蛆采自番禹农村农户， 洗净， 热水处理后， 自然干燥， 粉碎， 加入其重量 3倍的 石油醚 -乙酸乙酯-丙醇， 室温浸提 36小时， 过滤， 滤液减压蒸馏回收溶剂， 得到高酸值 蝇蛆油。 将所得的油与甲醇以摩尔比 1 : 13的比例混合， 70°C加热回流， 并加入油重 量 4%的对甲苯磺酸， 搅拌， 反应 3小时后得到低酸值蝇蛆油。
将所得的蝇蛆油与甲醇按 1 : 7的摩尔比混合， 加入油重量 0.5%的甲醇钠， 65°C加 热回流 40分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸馏后得到 副产物甘油，上层液体用热水洗 2〜3次，加入其重量 5%的硅酸镁-活性炭，加热至 85°C， 搅拌 40分钟， 抽滤， 滤液即产品生物柴油。
实施例 6 :
本实施例所述的生物柴油的制备方法， 包括如下步骤：
蝇蛆采自广东养猪场， 石灰水处理后， 在 90°C温度下干燥， 粉碎， 加入其重量 10 倍的乙醚-乙醇， 室温浸提 30小时， 过滤， 滤液减压蒸馏回收溶剂，得到高酸值蝇蛆油。 将所得的油与乙醇以摩尔比 1 : 10的比例混合， 70°C加热回流， 并加入油重量 5%的对 甲苯磺酸， 搅拌， 反应 0.5小时后常压蒸馏回收乙醇， 混合物静置分层， 将下层液体倒 出， 得低酸值蝇蛆油。
低酸值蝇蛆油与乙醇按 1 : 6的摩尔比混合， 加入油重量 1.5%的 KOH， 80°C加热 回流 30分钟后， 采用分子蒸馏技术对反应物进行分离纯化处理， 包括两级： I分子蒸 馏工艺条件为： 真空度为 10Pa， 蒸馏温度为 80°C， 分离出甘油和乙醇， II级分子蒸馏 工艺条件为： 真空度为 0.1Pa， 蒸熘温度为 110°C， 分离出生物柴油。
实施例 7:
本实施例所述的生物柴油制备的方法， 包括如下步骤：
蝇蛆采自中山大学经济昆虫研究所， 洗净， 石灰水处理后， 自然干燥， 粉碎， 加入 其重量 8倍的氯仿-甲醇， 室温浸提 5小时， 过滤， 滤液减压蒸馏回收溶剂， 得到高酸 值蝇蛆油。 将所得的油与甲醇以摩尔比 1 : 10的比例混合， 60°C加热回流， 并加入油 重量 2%的浓硫酸， 搅拌， 反应 3小时后得到低酸值蝇蛆油。
将所得的蝇蛆油与甲醇按 1： 7的摩尔比混合， 加入油重量 2.5%的 NaOH， 60°C加 热回流 10分钟后， 采用分子蒸馏技术对反应物进行分离纯化处理， 包括三级： I分子 蒸馏分离出甲醇， 工艺条件为： 真空度为 100Pa， 蒸馏温度为 60°C， II级分子蒸馏分离 出甘油， 工艺条件为： 真空度为 100Pa， 蒸馏温度为 200°C ; ΠΙ级分子蒸馏工艺条件为： 真空度为 10Pa， 蒸馏温度为 200°C， 分离出生物柴油。
实施例 8 :
本实施例所述的生物柴油的制备方法， 包括如下步骤：
蝇蛆采自番禹农村， 石灰水处理后， 在 90°C温度下干燥， 粉碎， 加入其重量 10倍 的乙醚-乙醇， 室温浸提 30小时， 过滤， 滤液减压蒸馏回收溶剂， 得到高酸值蝇蛆油。 将所得的油与乙醇以摩尔比 1 : 10的比例混合， 70°C加热回流， 并加入油重量 5%的对 甲苯磺酸， 搅拌， 反应 0.5小时后常压蒸馏回收乙醇， 混合物静置分层， 将下层液体倒 出， 得低酸值蝇蛆油。
将所得的蝇蛆油与乙醇按 1 : 6的摩尔比混合， 加入油重量 2%的 NaOH， 80°C加 热回流 30分钟后， 采用分子蒸馏技术对反应物进行分离纯化处理， 包括两级： I分子 蒸馏工艺条件为： 真空度为 30Pa， 蒸馏温度为 110°C， 分离出甘油和乙醇， II级分子蒸 馏工艺条件为： 真空度为 0.1Pa， 蒸馏温度为 100°C， 分离出生物柴油。
实施例 9:
本实施例所述的生物柴油的制备方法， 包括如下步骤：
蝇蛹采自广州番禺农户养鸡场， 洗净石灰水处理后， 在 40°C温度下干燥， 粉碎， 加入其重量 1倍的石油醚， 在氮气保护下室温浸提 10小时， 过滤， 滤液减压蒸馏回收 溶剂， 得到低酸值蝇蛹油。
将所得的蝇蛹油与甲醇按 1 : 5的摩尔比混合， 加入油重量 1.5%的 NaOH， 40°C加 热回流 60分钟后， 静置分层， 上层液体采用分子蒸馏技术进行精制处理， 其工艺条件 为： 真空度为 0.1Pa， 蒸熘温度为 100°C， 分离出生物柴油。
实施例 10:
本实施例所述的生物柴油的制备方法， 包括如下步骤：
干蝇蛹釆自中山大学昆虫研究所， 粉碎， 加入其重量 5倍的环己烷-丙酮， 室温浸 提 2小时， 过滤， 滤液减压蒸馏回收溶剂， 得到高酸值蝇蛹油。将所得的蝇蛹油与甲醇 以摩尔比 1 : 9的比例混合， 50°C加热回流， 并加入油重量 2%的浓硫酸， 搅拌， 反应 2.5小时后得到低酸值蝇蛹油。
将所得的低酸值蝇蛹油与甲醇按 1 : 5的摩尔比混合， 加入油重量 2.5%的 KOH，
50°C加热回流 50分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸馏 后得到副产物甘油，上层液体用热水洗 2~3次，加入其重量 7%的硅藻土，加热至 60°C， 搅拌 30分钟， 抽滤， 滤液即产品生物柴油。
实施例 11 :
本实施例所述的生物柴油的制备方法， 包括如下步骤：
蚕幼虫采自广东省农业科学院， 洗净， 热水处理后， 在 70°C温度下干燥， 粉碎， 加入其重量 10倍的正己烷， 在氮气保护下室温浸提 6小时， 过滤， 滤液减压蒸馏回收 溶剂， 得到低酸值蚕油。
将所得的蚕油与乙醇按 1 : 7的摩尔比混合， 加入蚕油重量 0.5%的金属钠， 70°C加 热回流 40分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸馏后得到 副产物甘油， 上层液体用热水洗 2〜3次， 加入其重量 1%的凹凸棒土， 加热至 30°C， 搅 拌 60分钟， 抽滤， 滤液即产品生物柴油。
实施例 12:
本实施例所述的生物柴油的制备方法， 包括如下步骤：
蝇蛹采自中山大学昆虫研究所， 洗净， 热水处理后， 在 10CTC温度下干燥， 粉碎， 加入其重量 1倍的乙醚溶剂， 在氮气保护下室温浸提 8小时， 过滤， 滤液减压蒸馏回收 溶剂， 得到低酸值蝇蛹油。
将所得的蝇蛹油与甲醇按 1 : 4的摩尔比混合， 加入油重量 1%的 NaOH， 60°C加 热回流 10分钟后， 静置分层， 上层液体采用分子蒸馏技术进行精制处理， 其工艺条件 为： 真空度为 5Pa， 蒸馏温度为 150°C， 分离出生物柴油。
实施例 13:
本实施例所述的生物柴油制备的方法， 包括如下步骤：
黄粉虫幼虫采自广东惠州圣达黄粉虫养殖基地，洗净，热水处理后自然干燥，粉碎， 加入其重量 10倍的乙酸乙酯， 室温浸提 25小时， 过滤， 滤液减压蒸馏回收溶剂， 得到 高酸值黄粉虫油。 将所得的油与甲醇以摩尔比 1 : 10的比例混合， 80°C加热回流， 并 加入油重量 5%的对甲苯磺酸， 搅拌， 反应 0.5小时后得低酸值黄粉虫油。
低酸值黄粉虫油与甲醇按 1 : 7的摩尔比混合， 加入油重量 2%的 KOH， 65°C加热 回流 30分钟后， 静置分层， 上层液体采用分子蒸馏技术进行精制处理， 其工艺条件为： 真空度为 10Pa， 蒸馏温度为 160°C， 分离出生物柴油。
实施例 14:
本实施例所述的生物柴油制备的方法， 包括如下步骤：
黄粉虫幼虫采自广东阳江市养殖场， 洗净， 石灰水处理后自然干燥， 粉碎， 加入其 重量 1倍的正己烷-乙醇， 室温浸提 40小时， 过滤， 滤液减压蒸馏回收溶剂， 得到酸值 >2的高酸值黄粉虫油。将所得的油与甲醇以摩尔比 1 : 6的比例混合， 70°C加热回流， 并加入油重量 0.5%的浓硫酸， 搅拌， 反应 2小时后得低酸值黄粉虫油。
低酸值黄粉虫油与甲醇按 1 : 9的摩尔比混合， 加入油重量 1.5%的 NaOH， 70°C加 热回流 60分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸馏后得到 副产物甘油， 上层液体用热水洗 2~3 次， 加入其重量 5%的凹凸棒土-活性炭， 加热至 60°C， 搅拌 30分钟， 抽滤， 滤液即产品生物柴油。
实施例 15: 本实施例所述的生物柴油的制备方法， 包括如下步骤：
黄粉虫幼虫采自广州番禹人工养殖场， 洗净， 热水处理后自然干燥， 粉碎， 加入其 重量 10倍的石油醚-甲醇， 室温浸提 36小时， 过滤， 滤液减压蒸馏回收溶剂， 得到高 酸值黄粉虫油。 将所得的油与甲醇以摩尔比 1 : 9的比例混合， 55°C加热回流， 并加入 油重量 1.5%的浓硫酸， 搅拌， 反应 1.5小时后得到低酸值黄粉虫油。
低酸值黄粉虫油与甲醇按 1 : 7的摩尔比混合， 加入油重量 1.5%的 KOH， 60°C加 热回流 30分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸馏后得到 副产物甘油， 上层液体用热水洗 2~3次， 加入其重量 5%的活性炭， 加热至 80°C， 搅拌 30分钟， 冷却， 置于 5°C冰箱内， 冷冻 72小时， 抽滤， 滤液即产品生物柴油。
实施例 16:
本实施例所述的生物柴油的制备方法， 包括如下步骤：
黄粉虫幼虫购自广州芳村花鸟市场， 石灰水处理后， 在 10CTC温度下干燥， 粉碎， 加入其重量 8倍的正己垸-甲醇， 室温浸提 25小时， 过滤， 滤液减压蒸馏回收溶剂， 得 到高酸值黄粉虫油。 将所得的油与乙醇以摩尔比 1 : 10的比例混合， 80°C加热回流， 并加入油重量 5%的对甲苯磺酸， 搅拌， 反应 0.5小时后常压蒸馏回收乙醇， 混合物静 置分层， 将下层液体倒出， 得低酸值黄粉虫油。
低酸值黄粉虫油与乙醇按 1 : 6的摩尔比混合， 加入油重量 1.5%的 KOH， 80°C加 热回流 30分钟后， 采用分子蒸馏技术对反应物进行分离纯化处理， 包括两级： I分子 蒸馏工艺条件为： 真空度为 100Pa， 蒸馏温度为 160°C， 分离出甘油和乙醇， II级分子 蒸馏工艺条件为： 真空度为 10Pa， 蒸馏温度为 200°C， 分离出生物柴油。
实施例 17:
本实施例所述的生物柴油的制备方法， 包括如下步骤：
黄粉虫蛹采自广州黄粉虫养殖场， 洗净， 石灰水处理后自然干燥， 粉碎， 加入其重 量 5倍的正己烷-乙醇，在氮气保护下室温浸提 24小时，过滤，滤液减压蒸馏回收溶剂， 得到低酸值蛹油。
将所得的蛹油与甲醇按 1 : 8的摩尔比混合， 加入油重量 1.5%的 NaOH， 60°C加热 回流 50分钟后， 静置分层， 上层液体采用分子蒸馏技术进行精制处理， 其工艺条件为： 真空度为 5Pa， 蒸馏温度为 150°C。
实施例 18:
本实施例所述的生物柴油的制备方法， 包括如下步骤： 蛾蛹采自中山大学昆虫研究所， 洗净， 石灰水处理后， 在 80°C温度下干燥， 粉碎， 加入其重量 10倍的正己垸， 在氮气保护下室温浸提 20小时， 过滤， 滤液减压蒸馏回收 溶剂， 得到低酸值蛾蛹油。
将所得的蛾蛹油与甲醇按 1 : 7的摩尔比混合， 加入油重量 1.5%的 NaOH， 70°C加 热回流 60分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸馏后得到 副产物甘油， 上层液体用热水洗 2~3 次， 加入其重量 5%的凹凸棒土-活性炭， 加热至 80°C， 搅拌 30分钟， 抽滤， 滤液即产品生物柴油。
实施例 19:
本实施例所述的生物柴油制备的方法， 包括如下歩骤：
大麦虫幼虫购自广州芳村花鸟市场， 洗净， 自然干燥后粉碎， 加入其重量 5倍的环 己烷-丙酮， 室温浸提 2小时， 过滤， 滤液减压蒸馏回收溶剂， 得到高酸值大麦虫油。 将所得的油与甲醇以摩尔比 1 : 8的比例混合， 55°C加热回流， 并加入油重量 0.5%的浓 硫酸， 搅拌， 反应 2.5小时后得到低酸值大麦虫油。
低酸值大麦虫油与甲醇按 1 : 9的摩尔比混合， 加入油重量 2.5%的 NaOH, 50°C加 热回流 60分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸馏后得到 副产物甘油， 上层液体用热水洗 2~3次， 加入其重量 5%的氧化铝， 加热至 60°C， 搅拌 40分钟， 抽滤， 滤液即产品生物柴油。
实施例 20:
本实施例所述的生物柴油制备的方法， 包括如下步骤：
大麦虫幼虫采广州芳村花鸟市场， 洗净， 热水处理后， 自然干燥， 粉碎， 加入其重 量 5倍的苯-乙醇， 室温浸提 15小时， 过滤， 滤液减压蒸馏回收溶剂， 得到高酸值大麦 虫油。 将所得的油与甲醇以摩尔比 1 : 11 的比例混合， 65°C加热回流， 并加入油重量 3%的对甲苯磺酸， 搅拌， 反应 4小时后得到低酸值大麦虫油。
低酸值大麦虫油与甲醇按 1 : 5的摩尔比混合， 加入油重量 1%的金属钠， 65°C加 热回流 20分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸馏后得到 副产物甘油， 上层液体用热水洗 2~3次， 加入其重量 1%的硅酸镁， 加热至 70°C， 搅拌 10分钟， 抽滤， 滤液即产品生物柴油。
实施例 21 :
本实施例所述的生物柴油制备的方法， 包括如下步骤：
大麦虫幼虫采自中山大学昆虫研究所，粉碎，加入其重量 3倍的石油醚-氯仿-丙酮， 室温浸提 24小时， 过滤， 滤液减压蒸馏回收溶剂， 得到高酸值大麦虫油。 将所得的油 与乙醇以摩尔比 1 : 6的比例混合， 85°C加热回流， 并加入油重量 5%的对甲苯磺酸， 搅拌， 反应 2.5小时后常压蒸馏回收乙醇， 混合物静置分层， 将下层液体倒出， 得低酸 值大麦虫油。
将所得到的低酸值大麦虫油与乙醇按 1 : 8的摩尔比混合，加入油重量 1%的 NaOH，
75°C加热回流 50分钟后， 采用分子蒸馏技术对反应物进行分离纯化处理， 包括三级： I分子蒸馏分离出乙醇， 工艺条件为： 真空度为 3000Pa， 蒸馏温度为 70°C， II级分子 蒸馏分离出甘油， 工艺条件为： 真空度为 50Pa， 蒸熘温度为 110°C ; III级分子蒸馏工艺 条件为： 真空度为 lPa， 蒸馏温度为 140°C， 分离出生物柴油。
实施例 22:
本实施例所述的生物柴油制备的方法， 包括如下步骤：
大麦虫蛹采自东莞养殖场， 洗净自然干燥后粉碎， 加入其重量 5倍的正己垸-丙酮， 室温浸提 2小时， 过滤， 滤液减压蒸熘回收溶剂， 得到高酸值大麦虫蛹油。 将所得的油 与甲醇以摩尔比 1 : 9的比例混合， 60°C加热回流， 并加入油重量 2%的浓硫酸， 搅拌， 反应 2.5小时后得到低酸值大麦虫蛹油。
低酸值大麦虫蛹油与甲醇按 1 : 10的摩尔比混合，加入油重量 2.5%的 NaOH， 50°C 加热回流 60分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸馏后得 到副产物甘油， 上层液体用热水洗 2〜3次， 加入其重量 5%的活性炭， 加热至 100°C， 搅拌 40分钟， 抽滤， 滤液即产品生物柴油。
实施例 23:
本实施例所述的生物柴油的制备方法， 包括如下步骤：
蛾蛹采自广州番禺养殖场， 洗净， 石灰水处理后， 在 70°C温度下干燥， 粉碎， 加 入其重量 5倍的石油醚-丙酮， 在氮气保护下室温浸提 15小时， 过滤， 滤液减压蒸馏回 收溶剂， 得到低酸值蛾蛹油。
将所得的蛾蛹油与甲醇按 1 : 8的摩尔比混合， 加入油重量 1.5%的 NaOH， 60°C加 热回流 50分钟后， 静置分层， 上层液体采用分子蒸馏技术进行精制处理， 其工艺条件 为: 真空度为 2Pa， 蒸馏温度为 120°C， 分离出生物柴油。
实施例 24:
本实施例所述的生物柴油制备的方法， 包括如下步骤：
蛾幼虫采自广东省农业科学院， 洗净， 自然干燥后粉碎， 加入其重量 3倍的乙酸乙 酯， 在氮气保护下室温浸提 36小时， 过滤， 滤液减压蒸馏回收溶剂， 得到低酸值蛾幼 虫油。
将所得的蛾幼虫油与甲醇按 1 : 9的摩尔比混合， 加入油重量 2.5%的 KOH， 70°C 加热回流 40分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸馏后得 到副产物甘油， 上层液体用热水洗 2~3 次， 加入其重量 5%的活性炭-硅酸镁， 加热至 70°C， 搅拌 30分钟， 抽滤， 滤液即产品生物柴油。
实施例 25:
本实施例所述的生物柴油制备的方法， 包括如下步骤：
蛾幼虫采自中山大学经济昆虫研究所， 洗净， 热水处理后自然干燥， 粉碎， 加入其 重量 8倍的乙酸乙酯， 室温浸提 30小时， 过滤， 滤液减压蒸馏回收溶剂， 得到高酸值 蛾幼虫油。 将所得的油与甲醇以摩尔比 1 : 10的比例混合， 80°C加热回流， 并加入油 重量 5%的对甲苯磺酸， 搅拌， 反应 3.5小时后得低酸值蛾幼虫油。
将所得的蛾幼虫油与甲醇按 1 : 7的摩尔比混合， 加入油重量 2%的 KOH, 65°C加 热回流 30分钟后， 静置分层， 上层液体采用分子蒸馏技术进行精制处理， 其工艺条件 为： 真空度为 10Pa， 蒸馏温度为 160°C， 分离出生物柴油。
实施例 26:
本实施例所述的生物柴油制备的方法， 包括如下步骤：
蚕幼虫采自广东天勤蚕业公司， 洗净， 石灰水处理后， 在 80°C温度下干燥， 粉碎， 加入其重量 1倍的苯， 在氮气保护下室温浸提 12小时， 过滤， 滤液减压蒸馏回收溶剂， 得到低酸值蚕油。
将所得的蚕油与乙醇按 1 : 9的摩尔比混合， 加入蚕油重量 1.5%的 KOH， 40°C加 热回流 40分钟后， 采用分子蒸馏技术对反应物进行分离纯化处理， 包括两级： I分子 蒸馏工艺条件为： 真空度为 10Pa， 蒸馏温度为 80°C， 分离出甘油和乙醇， II级分子蒸 馏工艺条件为： 真空度为 O. lPa, 蒸馏温度为 100°C， 分离出生物柴油。
实施例 27:
本实施例所述的生物柴油的制备方法， 包括如下步骤：
蚕蛹采自广东天勤蚕业公司， 洗净， 石灰水处理后， 在 80Ό温度下干燥， 粉碎， 加入其重量 10倍的乙醚， 在氮气保护下室温浸提 10小时， 过滤， 滤液减压蒸馏回收溶 剂， 得到低酸值蚕蛹油。
将所得的蚕蛹油与甲醇按 1 : 5的摩尔比混合， 加入油重量 2.5%的甲醇钠， 70°C加 热回流 30分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸熘后得到 副产物甘油， 上层液体用热水洗 2~3 次， 加入其重量 6%的凹凸棒土-硅酸镁， 加热至 60°C， 搅拌 30分钟， 抽滤， 滤液即产品生物柴油。
实施例 28:
本实施例所述的生物柴油的制备方法， 包括如下步骤：
蚕蛹采自广东省农业科学院， 洗净， 热水处理后， 在 50°C温度下干燥， 粉碎， 加 入其重量 1倍的环己垸， 在氮气保护下室温浸提 15小时， 过滤， 滤液减压蒸馏回收溶 齐 IJ， 得到低酸值蚕蛹油。
将所得的蚕蛹油与甲醇按 1 : 6的摩尔比混合， 加入油重量 2%的 NaOH， 70°C加 热回流 30分钟后， 静置分层， 上层液体采用分子蒸馏技术进行精制处理， 其工艺条件 为： 真空度为 8Pa， 蒸馏温度为 130°C， 分离出生物柴油。
实施例 29:
本实施例所述的生物柴油的制备方法， 包括如下步骤：
蜂蛹采自广州白云山养蜂场， 洗净， 石灰水处理后， 在 80°C温度下干燥， 粉碎， 加入其重量 10倍的氯仿， 在氮气保护下室温浸提 20小时， 过滤， 滤液减压蒸馏回收溶 齐 !]， 得到低酸值蜂蛹油。
将所得的蜂蛹油与甲醇按 1 : 9的摩尔比混合， 加入油重量 1.5%的 NaOH， 70°C加 热回流 60分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸馏后得到 副产物甘油， 上层液体用热水洗 2~3 次， 加入其重量 5%的活性白土-活性炭， 加热至 80°C， 搅拌 20分钟， 抽滤， 滤液即产品生物柴油。
实施例 30:
本实施例所述的生物柴油制备的方法， 包括如下步骤：
蜂蛹采自华南植物园， 洗净， 自然干燥后粉碎， 加入其重量 1倍的乙酸乙酯， 在氮 气保护下室温浸提 36小时， 过滤， 滤液减压蒸馏回收溶剂， 得到低酸值蜂蛹油。
将所得的蜂蛹油与甲醇按 1 : 9的摩尔比混合， 加入油重量 0.5%的甲醇钠， 70°C加 热回流 40分钟后， 静置分层， 下层液体经过稀盐酸中和、 离心分离和减压蒸馏后得到 副产物甘油，上层液体用热水洗 2~3次，加入其重量 5%的活性炭-氧化铝，加热至 40°C， 搅拌 20分钟， 抽滤， 滤液即产品生物柴油。

Claims

权 利 ^ ^
1、 一种制备生物柴油的方法， 其特征是： 主要包括以下步骤：
( 1 ) 昆虫油的制备： 完全变态昆虫的幼虫和 /或蛹干燥粉碎后， 加入其重量 1~10倍的 溶剂， 室温浸提 1~48小时， 过滤， 滤液回收溶剂后得到酸值 2的低酸值昆虫油或酸值 >2的高酸值昆虫油； 当得到的昆虫油的酸值>2时， 直接进行预酯化处理， 而得到酸 值 2的低酸值昆虫油， 处理条件为： 酸值 >2的昆虫油与甲醇或乙醇摩尔比为 1 : 6-1： 13 , 加入昆虫油重量的 0.5%〜5%的酸性催化剂， 反应温度为 40°C~90°C， 反应时间为
0.5-4小时； 所述溶剂为单一亲脂性有机溶剂或者亲脂性和亲水性有机溶剂的混合物；
(2 ) 酯交换： 将低酸值昆虫油与甲醇或乙醇进行酯交换反应， 反应条件为： 低酸值昆 虫油与甲醇或乙醇的摩尔比为 1 : 4-1： 9, 加入昆虫油重量的 0.5~2.5%的碱性催化剂， 反应温度为 40°C~90°C， 反应时间为 10 60分钟；
( 3 ) 分相： 酯交换结束后， 反应物静置分层， 上层液体为粗酯；
(4 )精制处理： 步骤 （3 ) 的上层液体热水洗后， 加入其重量 1%~10%的吸附剂， 加热 至 30°C〜100°C， 搅拌， 抽滤， 滤液即为生物柴油； 或将歩骤 （3 ) 的上层液体水洗后， 置于 0°C ~10°C， 冷冻 24 120小时， 抽滤， 滤液即为生物柴油； 或采用分子蒸馏技术对 步骤 （3 ) 反应得到的上层液体进行精制处理， 其工艺条件为： 真空度为 0.1-10Pa， 蒸 馏温度为 100-200 °C， 分离出生物柴油。
2、 根据权利要求 1所述的制备方法， 其特征是， 所述完全变态昆虫为蝇、 黄粉虫、 大 麦虫、 蚕、 蜂或蛾。 3、 根据权利要求 1所述的制备方法， 其特征是， 所述亲脂性有机溶剂为正己烷、 环己 垸、 石油醚、 乙醚、 乙酸乙酯或氯仿苯； 所述亲水性有机溶剂为甲醇、 乙醇、 丙醇或丙 酮。
4、 根据权利要求 1所述的制备方法， 其特征是， 所述室温浸提是在氮气保护下进行。
5、 根据权利要求 1所述的制备方法， 其特征是， 所述酸性催化剂是浓硫酸或对甲苯磺 酸。
6、 根据权利要求 1所述的制备方法， 其特征是， 步骤（2 )所述碱性催化剂为醇钠或碱 金属或 NaOH、 K0H。
1、 根据权利要求 1 6任一项所述的制备方法， 其特征是， 步骤 （4 ) 中所述吸附剂为 活性白土、 硅藻土、 凹凸棒土、 活性炭、 硅酸镁、 氧化铝的一种或一种以上。
8、 根据权利要求 1所述的制备方法， 其特征是， 步骤（3 )分层后的下层液体主要为甘 油、 水、 催化剂、 甲醇或乙醇的混合物， 经过稀盐酸中和、 离心分离和减压蒸馏后得到 副产物甘油。
9、 一种制备生物柴油的方法， 其特征是： 主要包括以下步骤：
( 1 ) 昆虫油制备： 完全变态昆虫的幼虫或蛹干燥粉碎后， 加入其重量 1~10倍的溶剂， 室温浸提 1~48小时， 过滤， 滤液回收溶剂后得到酸值 2的低酸值昆虫油或酸值>2的 高酸值昆虫油； 当得到的昆虫油的酸值>2 时， 进行预酯化处理， 处理条件： 酸值〉 2 的昆虫油与甲醇或乙醇摩尔比为 1 : 6-1： 13， 加入昆虫油重量的 0.5%~5%的酸性催化 剂， 反应温度为 40°C~90°C， 反应时间为 0.5 4小时， 得酸值 2的低酸值昆虫油； 所 述溶剂为单一亲脂性有机溶剂或者亲脂性和亲水性有机溶剂的混合物；
(2 ) 酯交换： 将低酸值昆虫油与甲醇或乙醇进行酯交换反应， 反应条件为： 低酸值昆 虫油与甲醇或乙醇的摩尔比为 1 : 4-1： 9， 加入昆虫油重量的 0.5~2.5%的碱性催化剂， 反应温度为 40°C~90°C， 反应时间为 10 60分钟；
( 3 )采用分子蒸馏技术对步骤（2) 的反应物进行精制处理， 包括二级： I、 分子蒸馏 分离出反应物中的甘油和甲醇或乙醇， 工艺条件为： 真空度为 100-10Pa， 蒸馏温度为 80-160°C ; II、 分子蒸馏分离出生物柴油， 工艺条件为： 真空度为 10-0.1Pa， 蒸馏温度 为 100-200°C ; 或包括三级： I、 分子蒸馏分离出甲醇或乙醇， 工艺条件为： 真空度为 5000-lOOPa, 蒸馏温度为 60-150°C ; II、 分子蒸熘分离出甘油， 工艺条件为： 真空度为 100-lOPa, 蒸馏温度为 100-200°C ; III、 分子蒸馏分离出生物柴油， 工艺条件为： 真空 度为 10-0.1Pa， 蒸馏温度为 100-200°C。
10、 根据权利要求 9所述的制备方法， 其特征是， 所述完全变态昆虫为蝇、 黄粉虫、 大 麦虫、 蚕、 蜂或蛾。
11、 根据权利要求 9所述的制备方法， 其特征是， 所述亲脂性有机溶剂为正己垸、 环己 垸、 石油醚、 乙醚、 乙酸乙酯、 氯仿或苯； 所述亲水性有机溶剂为甲醇、 乙醇、 丙醇或 丙酮。
12、 根据权利要求 9所述的制备方法， 其特征是， 所述室温浸提是在氮气保护下进行。
13、 根据权利要求 9所述的制备方法， 其特征是， 所述酸性催化剂是浓硫酸或对甲苯磺 酸。
14、 根据权利要求 9一 12任一项所述的制备方法， 其特征是， 步骤 （2)所述的碱性催 化剂为 NaOH或 KOH或醇钠或碱金属， 采用 NaOH、 KOH作催化剂时先将其固体溶于 甲醇或乙醇中制成碱浓度为 4~8wt%的醇溶液。
15、 一种由权利要求 1一 14所述方法制备得到的生物柴油。
PCT/CN2010/071076 2010-03-08 2010-03-16 一种生物柴油及其制备方法 WO2011109945A1 (zh)

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