WO2023116170A1 - 一种反应萃取制备生物柴油的方法及生物柴油 - Google Patents

一种反应萃取制备生物柴油的方法及生物柴油 Download PDF

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WO2023116170A1
WO2023116170A1 PCT/CN2022/126745 CN2022126745W WO2023116170A1 WO 2023116170 A1 WO2023116170 A1 WO 2023116170A1 CN 2022126745 W CN2022126745 W CN 2022126745W WO 2023116170 A1 WO2023116170 A1 WO 2023116170A1
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oil
reaction
biodiesel
animal
tower reactor
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PCT/CN2022/126745
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English (en)
French (fr)
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张家仁
张佳
王旻烜
李金�
何皓
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中国石油天然气股份有限公司
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Publication of WO2023116170A1 publication Critical patent/WO2023116170A1/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
    • C11C3/04—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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • 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
    • C11C3/02—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with glycerol
    • 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
    • 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

Definitions

  • the invention relates to a method for preparing biodiesel by reaction extraction and biodiesel, in particular to a method for reacting animal and vegetable oils with short-chain monohydric fatty alcohols or their carbonates and obtaining fatty acid monoalkyl esters through extraction, which belongs to biomass field of energy technology.
  • Biodiesel is a mixed fatty acid monoalkyl ester prepared by reacting animal and vegetable oils with short-chain monohydric fatty alcohols (such as methanol or ethanol, etc.). Because methanol has high reactivity and is cheap, fatty acid methyl ester is the most typical. Animal and vegetable oils and fats usually contain both fatty acid glycerides and partially hydrolyzed free fatty acids.
  • the esterification of fatty acids with fatty alcohols and the transesterification of fatty acid glycerides with fatty alcohols are two basic reactions for the production of biodiesel. Since the reaction conditions of the esterification reaction and the transesterification reaction are quite different, and even restrict each other, the process of preparing biodiesel from animal and vegetable oils and fats is relatively complicated.
  • the main components of refined animal and vegetable oils with low acid value are fatty acid glycerides.
  • the transesterification reaction of fatty acid glycerides and fatty alcohols is a reversible reaction, and the conversion rate of glycerides is limited by the chemical reaction equilibrium.
  • refined oils and fatty alcohols usually undergo multi-stage (such as two or three) transesterification reactions, and glycerol is separated in the middle to break the chemical reaction balance limit, thereby increasing the conversion rate of fatty acid glycerides .
  • the staged reaction can make full use of the oil raw materials and directly prepare biodiesel products with glyceride content meeting the industry requirements.
  • Alkaline catalysts can efficiently catalyze the transesterification of fatty acid glycerides and fatty alcohols, but the fatty acids in oils will neutralize the alkaline catalysts, causing catalyst poisoning and emulsification. Therefore, the base-catalyzed reaction requires the refining of oil raw materials, strict control of the content of fatty acids and other components, and even requires the acid value of oil raw materials to be reduced to below 0.2mgKOH/g, which not only increases the cost of refining oil raw materials, but more importantly, it will cause fatty acids Raw material loss. Moreover, oil raw materials with higher acid value are generally cheaper in price. Converting both free fatty acids and fatty acid glycerides into biodiesel products is an important method to improve the competitiveness of biodiesel.
  • the preparation of biodiesel from low-quality oil raw materials with high acid value mainly involves the separation of free fatty acids or pre-esterification to reduce the acid value, and then transesterification.
  • Chinese patents CN101050399A and CN105001983A disclose methods for methyl esterification of oils with high acid value. It uses methanol as an extractant to extract and separate free fatty acids in oil raw materials, and then reacts free fatty acids and fatty acid glycerides with methanol respectively, so as to improve the utilization rate of oil raw materials.
  • Another example is the two-step method for preparing biodiesel from high acid value oils disclosed in Chinese patents CN101016474A and CN1840612A.
  • the esterification reaction of fatty acid and fatty alcohol is a reversible equilibrium reaction, and the conversion rate of fatty acid is limited by the chemical reaction equilibrium. Improving the conversion rate of fatty acid can improve the utilization rate of raw materials and simplify the follow-up process. Increasing the number of esterification reactions or increasing the amount of fatty alcohol can increase the conversion rate of fatty acid, but it will significantly increase the recovery load of fatty alcohol and increase the production cost. It is an effective method to improve the conversion rate of fatty acids by continuously separating the by-product water generated by the reaction to pull the balance of chemical reactions. Currently, several methods for separating the by-product water of the esterification reaction to improve the conversion of fatty acids have been reported.
  • adsorbents to adsorb and separate by-product water is a simple method.
  • the reaction temperature is increased to vaporize methanol and by-product water.
  • the water in it is adsorbed and separated by adsorbents such as 3A molecular sieves, and the methanol is returned to the reaction system to realize continuous reaction, adsorption and separation of by-product water, and improve the conversion rate of oleic acid.
  • the molar ratio of methanol to oleic acid is 3:1, and the conversion rate of oleic acid is close to 100% after reacting at 100°C for 80 minutes.
  • the use of adsorbents to absorb and separate water, in large-scale production is usually limited by the adsorption capacity of the adsorbents for water, requiring frequent regeneration of the adsorbents, which increases operating costs.
  • the water in the reaction system can also be separated by using the water selective separation membrane to improve the conversion rate of fatty acid.
  • the method disclosed in Chinese patent CN106554276A to improve the yield of propyl gallate is to utilize membrane separation technology to separate by-product water.
  • the price, lifetime and membrane flux of selective separation membranes usually limit the application of this technology in the field of industrial production of bulk products.
  • Reactive distillation is another method for separating water, a by-product of the esterification reaction, to increase fatty acid conversion and reduce energy consumption.
  • the fatty acid is fed from the upper part of the reactive distillation column, and the fatty alcohol is fed from the lower part of the reactive distillation column, and reacts countercurrently with the fatty acid in the form of vapor, or simultaneously adds an entrainer (such as 2-ethylhexanol, Comput.Chem.Eng. 2009, 33:743-750).
  • the by-product water and low-carbon alcohols generated by the esterification reaction are separated from the top of the tower. Using reactive distillation technology, fatty acid ester products with extremely low acid value can be directly obtained.
  • Reactive distillation separates water, and simultaneous condensation and reboiling increases energy consumption.
  • vaporizing water generally means that the concentration of fatty alcohols in the liquid phase reaction system is lower, and the cycle load is significantly increased.
  • a complex water separation system is required to realize the recycling of fatty alcohols.
  • Reactive distillation can also realize esterification and transesterification at the same time.
  • the biodiesel integrated production process and special device disclosed in Chinese patent CN101294093A in this method, the reaction tower is filled with 25-50nm solid catalyst, and the temperature is controlled at 65-95 °C, the pressure is greater than atmospheric pressure 25-45mmHg, the methanol vapor is in countercurrent contact with the raw oil, after the glycerol is continuously separated in each reaction tower, the crude ester enters the next reaction tower, and the oil undergoes multiple reactions and multiple separations of glycerin to achieve higher conversion rate.
  • the object of the present invention is to provide a method for preparing biodiesel by reactive extraction and biodiesel.
  • the method for preparing biodiesel by reaction extraction provided by the invention has the advantages of short process flow, simple process, low cost, strong adaptability to the acid value of oil raw materials, etc., and can realize high-efficiency preparation of biodiesel.
  • the present invention provides a method for preparing biodiesel by reactive extraction, wherein, the method comprises: making animal and vegetable fats and monohydric fatty alcohols or their carbonates add or not add catalysts Carry out esterification reaction and/or transesterification reaction, and extract the water generated by the reaction with a polar extractant at the same time during the reaction process.
  • the main components of the animal and vegetable oils are fatty acids and fatty acid glycerides, wherein the carbon chain length is C 12 -C 24 fatty acid content is greater than 90wt%;
  • the animal and vegetable oil raw materials used in the present invention should be filtered to remove particulate matter through refining treatment before use, and the content of components such as phospholipids, metals and unsaponifiable substances in animal and vegetable oils should be appropriately reduced.
  • the animal and vegetable oil raw materials The content of phospholipid is less than 0.4wt%, the content of metal is less than 0.1wt%, and the content of unsaponifiable matter is less than 1wt%.
  • the animal and vegetable oils and fats can be obviously not suitable for directly carrying out alkali-catalyzed transesterification reaction, the animal and vegetable oils and fats with higher content of fatty acid components, including acid value greater than 0.5mgKOH /g of vegetable oil raw materials to reduce raw material costs and improve technical advantages.
  • animal and vegetable oils include various animal and vegetable oil raw materials, such as animal fats such as tallow, lard, chicken oil, duck oil, fish oil, peanut oil, soybean oil, etc. , rapeseed oil, palm oil, cottonseed oil, corn oil, sunflower oil, rice bran oil, jatropha fruit oil, microalgae oil, jatropha seed oil and other vegetable oils, as well as the acidified oil produced in the oil refining process, after other One or a combination of frying oil and catering industry waste oil whose main structure has not changed after use.
  • animal fats such as tallow, lard, chicken oil, duck oil, fish oil, peanut oil, soybean oil, etc.
  • rapeseed oil palm oil
  • cottonseed oil corn oil, sunflower oil, rice bran oil
  • jatropha fruit oil microalgae oil
  • jatropha seed oil and other vegetable oils
  • the monohydric fatty alcohol or its carbonate includes one or a combination of C 1 -C 6 monohydric fatty alcohol or its carbonate.
  • the monohydric fatty alcohol or its carbonate includes methanol, ethanol, propanol, isopropanol, butanol, isopropanol, One or a combination of butanol, pentanol, hexanol or their carbonates.
  • the reaction rate decreases, and the carbonate reaction rate is usually lower, and the by-product glycerol is simultaneously converted to glycerol carbonate. Therefore, as a specific embodiment of the method described above in the present invention, wherein, the monohydric fatty alcohol or its carbonate comprises one or more of methanol, ethanol, propanol, dimethyl carbonate and diethyl carbonate The combination.
  • the density of the polar extractant is greater than 1 g/cm 3 , and its saturated concentration in the animal and vegetable oil is less than 1 wt%.
  • the water content of the polyhydroxy compound is less than 1 wt%.
  • the polyhydroxy compound includes one or a combination of ethylene glycol, propylene glycol, glycerol, sorbitol, and glucose.
  • the polyhydroxy compound includes one or more combinations of ethylene glycol, propylene glycol, glycerol, sorbitol, glucose and dimethyl sulfoxide .
  • the catalyst when the catalyst is added, includes one or a combination of homogeneous or heterogeneous acid catalysts, homogeneous or heterogeneous base catalysts.
  • suitable acid and base catalysts can be added to carry out homogeneous or heterogeneous catalytic reactions, or non-catalytic reactions.
  • the homogeneous acid catalyst includes one or more combinations of sulfuric acid, phosphoric acid, and toluenesulfonic acid;
  • the heterogeneous acid catalyst includes acidic zeolite molecular sieve, tungsten One or more combinations of molybdenum metal oxides and cationic resins;
  • homogeneous alkali catalysts include alkali metal hydroxides or alkoxides thereof;
  • heterogeneous alkali catalysts include alkali metal or One or a combination of alkaline earth metal oxides and anion resins.
  • the alkali metal may be Na, K, etc., for example.
  • the added catalyst when it is a homogeneous acid catalyst, it can be mixed into a polar extractant for use.
  • sulfuric acid when sulfuric acid is added as a homogeneous acid catalyst, sulfuric acid can be mixed into the glycerol extractant for use.
  • the added catalyst when it is a homogeneous base catalyst, it can be mixed into monohydric fatty alcohol or its carbonate for use.
  • potassium hydroxide when potassium hydroxide is added as a homogeneous base catalyst, potassium hydroxide can be mixed into methanol for use.
  • animal and vegetable fats and oils can carry out esterification reaction and/or transesterification reaction continuously, and the reaction that takes place comprises the esterification reaction of fatty acid and fatty alcohol, the transesterification reaction of fatty acid glyceride and fatty alcohol , and transesterification reactions of fatty acids and fatty acid glycerides with carbonates of monohydric fatty alcohols.
  • the conditions of the reaction are: temperature 160-260° C., pressure 0.3-6 MPa.
  • the reaction rate may be slow; while the reaction temperature is high, the reaction conditions are usually harsh and equipment investment is increased. If the space velocity of animal and vegetable oil raw materials is too low, the utilization rate of equipment will be reduced, and if the space velocity is too high, the conversion rate of raw materials may be insufficient.
  • the method for preparing biodiesel by reactive extraction provided by the invention can be continuous or intermittent, preferably continuous. Wherein, those skilled in the art can select a suitable reactor according to the actual operation mode of the method, for example, the present invention preferably uses a continuous tower reactor.
  • the tower reactors used in the present invention include tower reactors such as oscillating flow reactors, packed towers, sieve tray towers, bubble cap towers, and valve towers.
  • suitable separators need to be equipped for the target tower reactors.
  • the tower reactor has at least two inlets and two outlets up and down, the grease inlet is below (as below the side wall of the tower reactor), and the extraction agent inlet position is above the grease inlet; The top discharge port is discharged, while the extractant is discharged from the bottom discharge port.
  • the method is a method for continuously producing biodiesel in a tower reactor, and its process specifically includes:
  • animal and vegetable oils are continuously esterified and/or transesterified in a tower reactor and extracted to prepare biodiesel.
  • the extractant inlet is positioned above the grease inlet, and the distance between the extractant inlet and the grease inlet is proportional to the diameter (inner diameter) of the tower reactor. ) ratio greater than 3 to ensure adequate extraction separation.
  • the extractant inlet is positioned above the grease inlet, and the distance between the extractant inlet and the grease inlet is proportional to the diameter (inner diameter) of the tower reactor. ) ratio is 5-80.
  • animal and vegetable oil raw materials can be converted efficiently, and biodiesel, ie fatty acid alkyl ester, can be directly prepared.
  • the present invention also provides a kind of biodiesel, wherein, the biodiesel is produced by the method for preparing biodiesel by reactive extraction mentioned above.
  • the acid value of the biodiesel is less than 0.5 mgKOH/g, and the fatty acid ester content is greater than 96 wt%.
  • the resulting biodiesel product can continue to react, or be separated, refined or purified by means of flash distillation to separate low-boiling point compounds, sedimentation to separate polar compounds, or vacuum distillation to separate high-boiling point compounds.
  • the method has strong adaptability to the acid value of animal and vegetable oil raw materials, and can directly process animal and vegetable oil raw materials with higher acid value;
  • the polar extractant used in this method is cheap and easy to get, it is immiscible with the animal and vegetable oil reaction system, and the density difference is large, and the separation is simple; by using the polar extractant to continuously extract the by-product water of the separation reaction, it can significantly Improve the conversion rate of fatty acids;
  • the method has a short technological process and a simple process, which can significantly reduce equipment investment;
  • the method can maintain the liquid phase reaction, avoid energy consumption of vaporization, and can increase the concentration of fatty alcohol in the liquid phase, thereby increasing the reaction rate and conversion rate.
  • ranges are given in terms of lower limits and upper limits. There can be one or more lower bounds, and one or more upper bounds, respectively.
  • a given range is defined by selecting a lower limit and an upper limit. Selected lower and upper limits define the boundaries of a particular range. All ranges defined in this manner are combinable, ie, any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for a particular parameter, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Additionally, if the minimum range values listed are 1 and 2, and the maximum range values listed are 3, 4, and 5, the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “0-5" indicates that all real numbers between "0-5" have been listed in the present invention, and "0-5" is only an abbreviated representation of these numerical combinations.
  • This embodiment provides a method for preparing biodiesel through continuous reaction and extraction of grease in a tower reactor, wherein the tower reactor has an inner diameter (diameter) of 50 mm and a height of 6 m, and the lower inlet, namely the grease inlet and The upper inlet, that is, the distance between the extraction agent inlets is 4m, and a 5mm ⁇ 5mm ⁇ ring is filled between the lower inlet and the upper inlet;
  • the method comprises the following specific steps:
  • the acidified oil (acid value 165mgKOH/g) that rapeseed oil refinement produces is mixed with methanol (containing 10wt% ethanol) by mass ratio after being sent in the tower reactor from the lower inlet, and makes it Flow from bottom to top in the type reactor, carry out esterification reaction and/or transesterification reaction with methanol and ethanol continuously, so that the propylene glycol extractant (the mass ratio of acidified oil is 1:1) is sent into the tower reaction from the upper inlet In the container, and make it flow from top to bottom in the tower reactor, and extract the acidified oil system countercurrently to extract the water generated by the reaction;
  • the volumetric space velocity of the acidified oil is 4h -1
  • the reaction conditions are: temperature 260°C, pressure 8MPa.
  • the extractant is continuously discharged from the bottom of the tower reactor, and the mixed fatty acid esters produced by the reaction are continuously discharged from the top of the tower reactor.
  • the fatty acid and fatty acid glyceride in the acidified oil are fully converted, and the conversion rate is close to 100%.
  • the mixture discharged from the top of the tower is distilled to separate mixed alcohols, settled to separate polar compounds, and further distilled under reduced pressure to obtain refined fatty acid esters with an acid value of less than 0.2 mgKOH/g, wherein the content of fatty acid esters is greater than 98.5 wt%.
  • This embodiment provides a method for preparing biodiesel through continuous reaction and extraction of grease in a tower reactor, wherein the tower reactor has an inner diameter (diameter) of 50 mm and a height of 6 m, and the lower inlet, namely the grease inlet and The upper inlet, that is, the distance between the extractant inlets is 2m, and Amberlyst 15 sulfonic acid resin and A-8XMP solid basic resin are filled between the lower inlet and the upper inlet (wherein Amberlyst 15 sulfonic acid resin and A-8XMP solid
  • the basic resins are cationic resin and anionic resin respectively, the mass ratio of the two is 1:1, and the total volume of Amberlyst 15 sulfonic acid resin and A-8XMP solid basic resin is 30% of theta ring volume) 3mm ⁇ 3mm theta ring ;
  • the method comprises the following specific steps:
  • tertiary soybean oil (acid value 0.9mgKOH/g) and methyl alcohol (containing 20wt% dimethyl carbonate) be that 1:0.2 is mixed by mass ratio and then sent in the tower reactor from lower inlet, and make it in the tower reactor In the type reactor, flow from bottom to top, carry out esterification reaction and/or transesterification reaction continuously with methanol and dimethyl carbonate, make glycerol extractant (with the mass ratio of tertiary soybean oil be 0.1:1) from The upper inlet is sent into the tower reactor, and it flows from top to bottom in the tower reactor, and it is extracted countercurrently with the three-stage soybean oil system to extract the water generated by the reaction;
  • the strictly controlled reaction conditions are: the volumetric space velocity of soybean oil is 0.4h -1 , the reaction temperature is 120°C, and the pressure is 0.4MPa.
  • the extractant is continuously discharged from the bottom of the tower reactor, and the mixed fatty acid esters produced by the reaction are continuously discharged from the top of the tower reactor.
  • the fatty acid and fatty acid glyceride in the tertiary soybean oil are fully converted, and the conversion rate is close to 100%.
  • the mixture discharged from the top of the tower is distilled to separate methanol and dimethyl carbonate, and the polar compound is separated by sedimentation to obtain fatty acid methyl esters with an acid value of less than 0.1 mgKOH/g, wherein the content of fatty acid methyl esters is greater than 99.0 wt%.
  • This embodiment provides a method for preparing biodiesel through continuous reaction and extraction of grease in a tower reactor, wherein the tower reactor has an inner diameter (diameter) of 50 mm and a height of 6 m, and the lower inlet, namely the grease inlet and The upper inlet, that is, the distance between the extraction agent inlets is 5m, and a 5mm ⁇ 5mm ⁇ ring is filled between the lower inlet and the upper inlet;
  • the method comprises the following specific steps:
  • the oil recovered from the catering industry (acid value 84mgKOH/g) is mixed with methanol at a mass ratio of 1:0.3, and then sent into the tower reactor from the lower inlet, and made to flow from bottom to top in the tower reactor, and Methyl alcohol carries out esterification reaction and/or transesterification reaction continuously, has mixed the glycerin extractant of 3wt% sulfuric acid (the mass ratio with catering industry recovery oil is 0.6:1) is sent in the tower reactor from upper entrance, and Make it flow from top to bottom in the tower reactor for countercurrent extraction with the recovery oil system of the catering industry to extract the water generated by the reaction;
  • the reaction conditions are strictly controlled as follows: the volume space velocity of recovered oil in the catering industry is 3h -1 , the reaction temperature is 180°C, and the pressure is 5MPa.
  • the extractant is continuously discharged from the bottom of the tower reactor, and the mixed fatty acid esters produced by the reaction are continuously discharged from the top of the tower reactor.
  • the fatty acids and fatty acid glycerides in the oil recovered from the catering industry are fully converted, and the conversion rate is close to 100%.
  • the mixture discharged from the top of the tower is distilled to separate methanol, and polar compounds are separated by settling, and further vacuum distillation is obtained to obtain refined fatty acid methyl esters with an acid value of less than 0.2 mgKOH/g, wherein the content of fatty acid methyl esters is greater than 97.5 wt%.
  • This embodiment provides a method for preparing biodiesel through continuous reaction and extraction of grease in a tower reactor, wherein the tower reactor has an inner diameter (diameter) of 50 mm and a height of 6 m, and the lower inlet, namely the grease inlet and The upper inlet, that is, the distance between the extractant inlets is 5m, and between the lower inlet and the upper inlet, ZSM-5 and magnesium aluminum hydrotalcite oxide (wherein, magnesium aluminum hydrotalcite oxide is mixed in the heterogeneous base catalyst) are filled.
  • the solid base catalyst, the mass ratio of ZSM-5 and magnesium aluminum hydrotalcite oxide is 1:1, and the total volume of ZSM-5 and magnesium aluminum hydrotalcite oxide is 30% of theta ring volume) 3mm ⁇ 3mm theta ring;
  • the method comprises the following specific steps:
  • Jatropha seed oil (acid value 31mgKOH/g) and methyl alcohol mix by mass ratio 1:0.7 and send in the tower reactor from lower entrance, and make it flow from bottom to top in tower reactor, and Methyl alcohol is carried out esterification reaction and/or transesterification reaction continuously, the sorbitol extractant (with the mass ratio of Jatropha jatropha seed oil being 0.4:1) that contains 10wt% glucose is sent in the tower reactor from upper inlet, and makes It flows from top to bottom in the tower reactor, and is extracted countercurrently with the jatropha seed oil system to extract the water generated by the reaction;
  • the reaction conditions are strictly controlled: the volumetric space velocity of Jatropha seed oil is 2h -1 , the reaction temperature is 240°C, and the pressure is 6MPa.
  • the extractant is continuously discharged from the bottom of the tower reactor, and the mixed fatty acid methyl esters generated by the reaction are discharged from the top of the tower reactor.
  • the fatty acid and fatty acid glyceride in the tung tree oil are fully converted, and the conversion rate is close to 100%.
  • the mixture discharged from the top of the tower is distilled to separate methanol, settling to separate polar compounds, and distilled under reduced pressure to obtain fatty acid methyl esters with an acid value of less than 0.2 mgKOH/g, wherein the content of fatty acid methyl esters is greater than 97.5 wt%.
  • This embodiment provides a method for preparing biodiesel through continuous reaction and extraction of grease in a tower reactor, wherein the tower reactor has an inner diameter of 50mm and a height of 6m, and the lower inlet, that is, the grease inlet and the upper inlet, That is, the distance between the extraction agent inlets is 5m, and a 5mm ⁇ 5mm theta ring mixed with nano-magnesia is filled between the lower inlet and the upper inlet, and the total volume of nano-magnesia is 30% of the volume of theta ring;
  • the method comprises the following specific steps:
  • the strictly controlled reaction conditions are: the volume space velocity of cottonseed oil is 1h -1 , the temperature is 190°C, and the pressure is 4MPa.
  • the extractant is continuously discharged from the bottom of the tower reactor, and the mixed fatty acid methyl esters generated by the reaction are continuously discharged from the top of the tower reactor.
  • the fatty acid and fatty acid glyceride in the cottonseed oil are fully converted, and the conversion rate is close to 100%.
  • the mixture discharged from the top of the tower is distilled to separate methanol to obtain fatty acid methyl esters with an acid value of less than 0.1 mgKOH/g, wherein the content of fatty acid methyl esters is greater than 98.2 wt%.
  • This embodiment provides a method for preparing biodiesel through continuous reaction and extraction of grease in a tower reactor, wherein the tower reactor has an inner diameter of 50mm and a height of 6m, and the lower inlet, that is, the grease inlet and the upper inlet, That is, the distance between the extraction agent inlets is 5m, and a 5mm ⁇ 5mm ⁇ ring is filled between the lower inlet and the upper inlet;
  • the method comprises the following specific steps:
  • the reaction conditions are strictly controlled as follows: the volume space velocity of the refined cottonseed oil is 0.5h -1 , the temperature is 180°C, and the pressure is 3MPa.
  • the extractant is continuously discharged from the bottom of the tower reactor, and the mixed fatty acid methyl esters generated by the reaction are continuously discharged from the top of the tower reactor.
  • the fatty acid and fatty acid glyceride in the refined cottonseed oil are fully converted, and the conversion rate is close to 100%.
  • the mixture discharged from the tower top is distilled to separate methanol, settled to separate glycerin, and distilled under reduced pressure to obtain fatty acid methyl esters with an acid value of less than 0.1 mgKOH/g, wherein the content of fatty acid methyl esters is greater than 98.5 wt%.
  • This comparative example provides a kind of method that fats and oils prepare biodiesel through continuous reaction in tubular reactor, wherein, described method comprises the following specific steps:
  • the reaction conditions are strictly controlled as follows: the volume space velocity of recovered oil in the catering industry is 3h -1 , the reaction temperature is 180°C, and the pressure is 5MPa.
  • the mixed fatty acid esters produced by the reaction are continuously discharged from the top of the tubular reactor.
  • the conversion rate of fatty acids and fatty acid glycerides in oil recovered by the catering industry is only about 82%.
  • the mixture continuously discharged from the top of the tubular reactor is distilled to separate methanol, and polar compounds are separated by settling, and further vacuum distillation is obtained to obtain refined fatty acid methyl esters with an acid value of about 10.6mgKOH/g, wherein the fatty acid methyl ester content is greater than 93.5wt%.
  • Example 3 the recovered oil from the catering industry is prepared in a tower reactor through continuous reaction extraction to prepare biodiesel, and the fatty acids and fatty acid glycerides in the recovered oil from the catering industry are fully converted, and the conversion rate is close to 100%, and the acid value of the resulting refined fatty acid methyl ester is less than 0.2mgKOH/g, wherein the content of fatty acid methyl ester is greater than 97.5wt%; and in comparative example 1, the same catering industry recovery oil is prepared through continuous reaction in a tubular reactor Biodiesel, the conversion rate of fatty acids and fatty acid glycerides in recovered oil from the catering industry is only about 82%, and the acid value of the obtained refined fatty acid methyl esters is obviously high, and the content of fatty acid methyl esters is low.
  • the method of preparing biodiesel through continuous reaction and extraction of oils and fats provided in the embodiments of the present invention can not only significantly improve the conversion rate of fatty acids and fatty acid glycerides, but also significantly reduce the acidity of the resulting refined fatty acid methyl esters. value.

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Abstract

一种反应萃取制备生物柴油的方法及生物柴油，其中，所述方法包括：使动植物油脂与一元脂肪醇或其碳酸酯在加入或不加入催化剂的条件下进行酯化反应和/或酯交换反应，并于反应过程中同时以极性萃取剂萃取反应所生成的水。所述反应萃取制备生物柴油的方法具有工艺流程短、过程简单、成本低廉、油脂原料酸值适应性强等优势，可实现高效制备生物柴油。

Description

一种反应萃取制备生物柴油的方法及生物柴油 技术领域
本发明涉及一种反应萃取制备生物柴油的方法及生物柴油，具体涉及一种动植物油脂与短链单羟基脂肪醇或其碳酸酯反应并经萃取得到脂肪酸单烷基酯的方法，属于生物质能源技术领域。
背景技术
随着人们对环境和健康问题的日益重视，生物柴油作为低碳、清洁、绿色和可再生的燃料，逐渐发展成为石化柴油的重要补充。生物柴油是动植物油脂与短链单羟基脂肪醇(如甲醇或乙醇等)反应制备的混合脂肪酸单烷基酯。因为甲醇的反应活性高，价格便宜，所以最典型的是脂肪酸甲酯。动植物油脂原料中通常同时含有脂肪酸甘油酯和部分水解的游离脂肪酸。脂肪酸与脂肪醇的酯化反应，以及脂肪酸甘油酯与脂肪醇的酯交换反应，是制备生物柴油的两个基本反应。由于酯化反应和酯交换反应的反应条件存在较大差异，甚至存在相互制约的情况，从而导致以动植物油脂原料制备生物柴油的工艺相对复杂。
酸值较低的精炼动植物油脂的主要成分是脂肪酸甘油酯。脂肪酸甘油酯与脂肪醇的酯交换反应是可逆反应，甘油酯的转化率受化学反应平衡限制。为了提高生物柴油产率、简化精炼工艺，精炼油脂与脂肪醇通常经过多段(如两段或三段)酯交换反应，中间分离甘油，以打破化学反应平衡限制，从而提高脂肪酸甘油酯的转化率。分段反应能充分利用油脂原料，直接制备甘油酯含量达到行业要求的生物柴油产品，是目前应用较为广泛的方法，如德国Lurgi公司和Cimbria Sket公司的均相碱催化酯交换工艺，及法国石油研究院开发的基于非均相碱催化的Esterfip-H工艺。针对精炼油脂制备生物柴油技术，中国专利CN 102824881A公开了一种生物柴油的制备方法及其专用反应器，其是使酸值小于4mgKOH/g的动植物油脂，在温度低于180℃、压力低于2MPa的条件下连续反应，油脂转化率可接近100％。
碱性催化剂能够高效催化脂肪酸甘油酯与脂肪醇发生酯交换反应，但是油脂中的脂肪酸会中和碱性催化剂，使催化剂中毒、产生乳化等问题。因此，碱催化反应要求油脂原料精炼，严格控制脂肪酸等组分的含量，甚至要求将油脂原料的酸值降低至0.2mgKOH/g以下，这不仅增加油脂原料精炼成本，更重要的是会造成脂肪酸原料损失。 而且酸值较高的油脂原料通常价格较低，将游离脂肪酸和脂肪酸甘油酯都转化为生物柴油产品，是提高生物柴油竞争力的重要方法。
在较高的温度和压力下，甚至超临界脂肪醇条件下，酯化和酯交换反应能够同时进行。例如中国专利CN1844319A、CN101070480A和CN101104812A等所公开的生物柴油制备方法，油脂与脂肪醇在较高的温度和压力下反应，然后蒸去脂肪醇、分离甘油并减压蒸馏，得到生物柴油。该方法原料酸值适应性强，但是反应条件相对苛刻，较高的反应温度(约300℃)和压力(约10MPa)会增加投资。而且，因为蒸馏后的残渣一般不再循环进入反应体系，油脂转化率直接影响生物柴油产率。
目前，以酸值较高的劣质油脂原料制备生物柴油，主要是将游离脂肪酸先分离或预酯化反应降低酸值，然后再进行酯交换反应。例如，中国专利CN101050399A和CN105001983A公开的高酸值油脂甲酯化方法。其用甲醇作为萃取剂，萃取分离油脂原料中的游离脂肪酸，然后游离脂肪酸和脂肪酸甘油酯分别与甲醇反应，以此来提高油脂原料的利用率。再比如中国专利CN101016474A和CN1840612A等公开的高酸值油脂制备生物柴油的两步法。各种酸值较高的油脂与脂肪醇在酸性催化剂作用下完成酯化反应，然后回收脂肪醇并分离副产物水，得到酸值较低的粗酯在碱性催化剂作用下酯交换反应，最后再精制得到生物柴油产品。由于碱催化酯交换反应需要严格控制酸值，这就要求预酯化反应有足够的转化率。
脂肪酸与脂肪醇酯化反应是可逆平衡反应，脂肪酸的转化率受化学反应平衡限制。提高脂肪酸转化率，可以提高原料利用率，简化后续工艺。增加酯化反应次数或者增加脂肪醇用量，都可以提高脂肪酸的转化率，但是会显著增加脂肪醇的回收负荷、增加生产成本。通过连续分离反应生成的副产物水，拉动化学反应平衡，是提高脂肪酸转化率的有效方法。当前，已经报道了几种分离酯化反应的副产物水来提高脂肪酸转化率的方法。
使用吸附剂吸附分离副产物水，是一种简单的方法。对于油酸与甲醇酯化反应(Ind.Eng.Chem.Res.2008,47:6885-6889)，提高反应温度使甲醇和副产物水汽化。蒸汽冷凝后经过3A分子筛等吸附剂吸附分离其中的水，而甲醇回流到反应体系，实现连续反应吸附分离副产物水，提高油酸的转化率。甲醇与油酸摩尔比为3:1，在100℃反应80min，油酸转化率接近100％。但是采用吸附剂吸附分离水，在规模化生产中，通常受吸附剂对水的吸附能力限制，需要对吸附剂频繁再生，增加操作费用。
利用水选择性分离膜，也能分离反应体系中的水，提高脂肪酸的转化率。中国专利CN106554276A公开的提高没食子酸丙酯化收率的方法，就是利用膜分离技术分离副产 物水。没食子酸与正丙醇酯化反应，通过水醇选择性透过膜分离水、醇，并回流醇，可以显著缩短反应时间、提高没食子酸丙酯的产率和质量。然而选择性分离膜的价格、寿命和膜通量等问题通常限制了该技术应用于大宗产品工业生产领域。
反应蒸馏是另一种分离酯化反应副产物水来提高脂肪酸转化率并降低能耗的方法。脂肪酸从反应蒸馏塔上部进料，而脂肪醇从反应蒸馏塔下部进料，并以蒸汽形式与脂肪酸对流反应，或者同时加入了夹带剂(如2-乙基己醇，Comput.Chem.Eng.2009,33:743-750)。酯化反应生成的副产物水与低碳醇从塔顶分离。利用反应蒸馏技术，可以直接得到酸值极低的脂肪酸酯产品。根据估算，在投资成本不增加的前提下，通过热集成，脂肪酸酯的能耗能够降低至108.8kWh/吨(Fuel Process.Technol.2011,92(7):1288-1296)。分离副产物水，拉动化学反应平衡，提高脂肪酸的转化率，在半连续的反应釜中也得到验证(Fuel,2012,93(1):373-380)。在反应釜中加入860g棕榈酸，甲醇进料流速为2.4g/min，棕榈油脂肪酸与甲醇在290℃、0.85MPa条件下反应180min，酸值从191.4mgKOH/g降低至0.36mgKOH/g。反应蒸馏分离水，同时冷凝和再沸会增加能耗。对于沸点比水低的脂肪醇，例如甲醇，使水汽化，通常意味着脂肪醇在液相反应体系中的浓度更低，循环负荷明显增加。而对于与水形成共沸物的脂肪醇，例如乙醇，需要复杂的水分离系统实现脂肪醇循环回收。
反应蒸馏也可以同时实现酯化和酯交换反应，例如中国专利CN101294093A公开的生物柴油一体化生产工艺及专用装置，该方法中反应塔内装填有25-50nm的固体催化剂，温度控制在65-95℃，压力大于大气压25-45mmHg，甲醇蒸汽与原料油脂逆流接触，在每个反应塔连续分离甘油后，粗酯进入下一个反应塔，油脂经过多次反应，多次分离甘油，才能实现较高的转化率。
针对动植物油脂制备生物柴油的问题，特别是酸值较高的油脂原料高效转化利用的问题，提供一种新型的反应萃取制备生物柴油的方法及生物柴油已经成为本领域亟需解决的技术问题。
发明内容
为了解决上述的缺点和不足，本发明的目的在于提供一种反应萃取制备生物柴油的方法及生物柴油。本发明所提供的反应萃取制备生物柴油的方法具有工艺流程短、过程简单、成本低廉、对油脂原料酸值适应性强等优势，可实现高效制备生物柴油。
为了实现以上目的，一方面，本发明提供了一种反应萃取制备生物柴油的方法，其中，所述方法包括：使动植物油脂与一元脂肪醇或其碳酸酯在加入或不加入催化剂的条 件下进行酯化反应和/或酯交换反应，并于反应过程中同时以极性萃取剂萃取反应所生成的水。
作为本发明以上所述方法的一具体实施方式，其中，所述动植物油脂的主要成分是脂肪酸和脂肪酸甘油酯，其中碳链长度为C 12-C 24的脂肪酸含量大于90wt％；另外，对于本发明所使用的动植物油脂原料，使用前应当通过精制处理过滤脱除颗粒物，适当降低动植物油脂中磷脂、金属和不皂化物等组分的含量，优选地，所述动植物油脂原料中磷脂的含量小于0.4wt％，金属含量小于0.1wt％，不皂化物的含量小于1wt％。
作为本发明以上所述方法的一具体实施方式，其中，所述动植物油脂可以是明显不适宜直接进行碱催化酯交换反应，脂肪酸组分含量较高的动植物油脂，包括酸值大于0.5mgKOH/g的植物油脂原料，以降低原料成本并提高技术优势。
作为本发明以上所述方法的一具体实施方式，其中，所述动植物油脂包括各种动植物油脂原料，如牛油、猪油、鸡油、鸭油、鱼油等动物油脂，花生油、大豆油、菜籽油、棕榈油、棉籽油、玉米油、向日葵油、米糠油、麻风树果油、微藻油、小桐籽油等植物油脂，以及油脂炼制过程中产生的酸化油，经过其它用途后主要结构未发生改变的煎炸油、餐饮业废油等中的一种或者几种的组合。
作为本发明以上所述方法的一具体实施方式，其中，所述一元脂肪醇或其碳酸酯包括C 1-C 6的单羟基脂肪醇或其碳酸酯中的一种或几种的组合。
为了提高转化率或改善产品的性质，作为本发明以上所述方法的一具体实施方式，其中，所述一元脂肪醇或其碳酸酯包括甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇、戊醇、己醇或其碳酸酯等中的一种或几种的组合。
通常情况下，随着脂肪醇分子量增加，反应速率会下降，并且碳酸酯反应速率通常会更低，而且副产物甘油也会同步转化为甘油碳酸酯。因此，作为本发明以上所述方法的一具体实施方式，其中，所述一元脂肪醇或其碳酸酯包括甲醇、乙醇、丙醇、碳酸二甲酯和碳酸二乙酯中的一种或几种的组合。
作为本发明以上所述方法的一具体实施方式，其中，所述一元脂肪醇或其碳酸酯与动植物油脂的质量比为0.1-1:1。
作为本发明以上所述方法的一具体实施方式，其中，所述一元脂肪醇或其碳酸酯与动植物油脂的质量比为0.2-0.7:1。
作为本发明以上所述方法的一具体实施方式，其中，所述极性萃取剂与动植物油脂的质量比为0.05-1.2:1。
作为本发明以上所述方法的一具体实施方式，其中，所述极性萃取剂与动植物油脂 的质量比为0.1-1:1。
在本发明所提供的以上方法中，若极性萃取剂和一元脂肪醇或其碳酸酯的用量过少，动植物油脂原料的转化率会下降，而增加其用量会增加分离回收负荷。
作为本发明以上所述方法的一具体实施方式，其中，所述极性萃取剂的密度大于1g/cm 3，且其在所述动植物油脂中的饱和溶解浓度小于1wt％。
萃取剂选择应充分考虑副产物使用，作为本发明以上所述方法的一具体实施方式，其中，所述极性萃取剂包括多羟基化合物和/或二甲基亚砜。
作为本发明以上所述方法的一具体实施方式，其中，所述多羟基化合物的水含量小于1wt％。
作为本发明以上所述方法的一具体实施方式，其中，所述多羟基化合物包括乙二醇、丙二醇、丙三醇、山梨醇、葡萄糖中的一种或几种的组合。
作为本发明以上所述方法的一具体实施方式，其中，所述多羟基化合物包括乙二醇、丙二醇、丙三醇、山梨醇、葡萄糖及二甲基亚砜中的一种或几种的组合。
作为本发明以上所述方法的一具体实施方式，其中，加入催化剂时，所述催化剂包括均相或非均相酸催化剂，均相或非均相碱催化剂中的一种或几种的组合。
在本发明所提供的以上方法中，可以加入合适的酸、碱催化剂，进行均相或非均相催化反应，也可以是非催化反应。
作为本发明以上所述方法的一具体实施方式，其中，均相酸催化剂包括硫酸、磷酸、甲基苯磺酸中的一种或几种的组合；非均相酸催化剂包括酸性沸石分子筛、钨钼金属氧化物、阳离子树脂中的一种或几种的组合；均相碱催化剂包括碱金属氢氧化物或其醇盐中的一种或几种的组合；非均相碱催化剂包括碱金属或碱土金属的氧化物、阴离子树脂中的一种或几种的组合。
在本发明的一些实施例中，所述碱金属例如可为Na、K等。
作为本发明以上所述方法的一具体实施方式，其中，当所加入的催化剂为均相酸催化剂时，可将其混合到极性萃取剂中使用。例如在本发明一具体实施例中，当加入硫酸作为均相酸催化剂时，可将硫酸混合到丙三醇萃取剂中使用。
作为本发明以上所述方法的一具体实施方式，其中，当所加入的催化剂为均相碱催化剂时，可将其混合到一元脂肪醇或其碳酸酯中使用。例如在本发明一具体实施例中，当加入氢氧化钾作为均相碱催化剂时，可将氢氧化钾混合到甲醇中使用。
在本发明所提供的以上方法中，动植物油脂可连续进行酯化反应和/或酯交换反应，所发生的反应包括脂肪酸与脂肪醇的酯化反应，脂肪酸甘油酯与脂肪醇的酯交换反应， 以及脂肪酸和脂肪酸甘油酯与一元脂肪醇的碳酸酯所进行的酯交换反应。
作为本发明以上所述方法的一具体实施方式，其中，所述反应的条件为：温度80-280℃、压力0.1-8MPa、动植物油脂的体积空速为0.4-4h -1。
作为本发明以上所述方法的一具体实施方式，其中，所述反应的条件为：温度160-260℃、压力0.3-6MPa。
在本发明所提供的以上方法中，若反应温度过低，可能会导致反应速率较慢；而反应温度较高，通常会导致反应条件苛刻，增加设备投资。而若动植物油脂原料的空速过低，会降低设备利用率，而空速过高，可能会造成原料转化率的不足。
本发明提供的反应萃取制备生物柴油的方法可以是连续的，也可以是间歇的，优选连续方式。其中，本领域技术人员可以根据该方法的实际作业方式选择合适的反应器，例如本发明优选使用连续塔式反应器。
本发明所使用的塔式反应器包括振荡流反应器、填料塔、筛板塔、泡罩塔、浮阀塔等塔式反应器，另外还需要针对目标塔式反应器配备合适的分离器。其中，塔式反应器至少有上下两个进料口和两个出料口，油脂入口在下方(如塔式反应器的侧壁下方)，萃取剂入口位置在油脂入口的上方；酯相从顶出料口排出，而萃取剂从底出料口排出。
作为本发明以上所述方法的一具体实施方式，其中，所述方法为在塔式反应器内连续生产生物柴油的方法，其过程具体包括：
1)使动植物油脂从塔式反应器的油脂入口进入塔式反应器并使其在塔式反应器中从下往上流动，与一元脂肪醇或其碳酸酯连续进行酯化反应和/或酯交换反应；
2)使极性萃取剂从塔式反应器的萃取剂入口进入塔式反应器并使其在塔式反应器中从上向下流动，以与动植物油脂逆流萃取；
3)使反应所得到的酯相从塔式反应器的顶部排出；
4)使极性萃取剂从塔式反应器的底部排出。
从总体效果看，动植物油脂在塔式反应器内连续酯化和/或酯交换反应并经萃取制备生物柴油。
作为本发明以上所述方法的一具体实施方式，其中，所述萃取剂入口位于所述油脂入口的上方，且萃取剂入口与油脂入口之间的距离与所述塔式反应器的直径(内径)的比值大于3，以确保充分萃取分离。
作为本发明以上所述方法的一具体实施方式，其中，所述萃取剂入口位于所述油脂入口的上方，且萃取剂入口与油脂入口之间的距离与所述塔式反应器的直径(内径)的比值为5-80。
在本发明所提供的以上方法中，在塔式反应器内经过连续酯化和/或酯交换反应，动植物油脂原料可以高效转化，直接制备得到生物柴油，即脂肪酸烷基酯。
另一方面，本发明还提供了一种生物柴油，其中，所述生物柴油是由以上所述的反应萃取制备生物柴油的方法制得。
作为本发明以上所述生物柴油的一具体实施方式，其中，生物柴油的酸值小于0.5mgKOH/g，脂肪酸酯含量大于96wt％。
在有必要的情况下，所得生物柴油产物还可以继续进行反应，或经过闪蒸分离低沸点化合物、沉降分离极性化合物或减压蒸馏分离高沸点化合物等方式进行分离精炼或提纯。
本发明提供的动植物油脂原料经反应萃取制备生物柴油的方法具有以下优势：
1、该方法对动植物油脂原料酸值适应性强，可以直接加工酸值较高的动植物油脂原料；
2、该方法中所使用的极性萃取剂廉价易得，与动植物油脂反应体系不互溶，而且密度差大，分离简单；通过使用极性萃取剂连续萃取分离反应的副产物水，可以显著提高脂肪酸的转化率；
3、该方法的工艺流程短、过程简单，可显著减少设备投资；
4、该方法可以保持液相反应，避免汽化能耗，并且可以提高脂肪醇在液相中的浓度，从而提高反应速率和转化率。
具体实施方式
需要说明的是，本发明的说明书和权利要求书中的术语“包括”以及其任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、系统、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。
本发明所公开的“范围”以下限和上限的形式给出。可以分别为一个或多个下限，和一个或多个上限。给定的范围是通过选定一个下限和一个上限进行限定的。选定的下限和上限限定了特别范围的边界。所有以这种方式进行限定的范围是可组合的，即任何下限可以与任何上限组合形成一个范围。例如，针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是可以预料到的。此外，如果列出的最小范围值为1和2，列出的最大范围值为3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。
在本发明中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本发明中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。
在本发明中，如果没有特别的说明，本发明所提到的所有实施方式以及优选实施方式可以相互组合形成新的技术方案。
在本发明中，如果没有特别的说明，本发明所提到的所有技术特征以及优选特征可以相互组合形成新的技术方案。
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。下列所描述的实施例是本发明一部分实施例，而不是全部的实施例，仅用于说明本发明，而不应视为限制本发明的范围。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。实施例中所使用的实验方法如无特殊说明，均为常规方法。
实施例1
本实施例提供了一种油脂于塔式反应器内经连续反应萃取制备生物柴油的方法，其中，所述塔式反应器的内径(直径)为50mm、高为6m，下入口，即油脂入口和上入口，即萃取剂入口之间的距离为4m，在下入口和上入口之间装填5mm×5mmθ环；
所述方法包括以下具体步骤：
使菜籽油精炼产生的酸化油(酸值为165mgKOH/g)与甲醇(含10wt％乙醇)按质量比为1:0.5混合后从下入口送入塔式反应器中，并使其在塔式反应器中从下往上流动，与甲醇和乙醇连续进行酯化反应和/或酯交换反应，使丙二醇萃取剂(与酸化油的质量比为1:1)从上入口送入塔式反应器中，并使其在塔式反应器中从上向下流动，与酸化油体系逆流萃取，以萃取反应所生成的水；
其中，酸化油的体积空速为4h -1，反应的条件为：温度260℃、压力8MPa。萃取剂从塔式反应器的底部连续排出，反应生成的混合脂肪酸酯从塔式反应器的顶部连续排出。
反应后，酸化油中脂肪酸和脂肪酸甘油酯充分转化，转化率接近100％。塔顶排出的混合物经过蒸馏分离混合醇、沉降分离极性化合物，并进一步减压蒸馏得到酸值小于0.2mgKOH/g的精炼脂肪酸酯，其中脂肪酸酯的含量大于98.5wt％。
实施例2
本实施例提供了一种油脂于塔式反应器内经连续反应萃取制备生物柴油的方法，其中，所述塔式反应器的内径(直径)为50mm、高为6m，下入口，即油脂入口和上入口，即萃取剂入口之间的距离为2m，在下入口和上入口之间装填混合了Amberlyst 15磺酸树脂和A-8XMP固体碱性树脂(其中，Amberlyst 15磺酸树脂和A-8XMP固体碱性树脂分别为阳离子树脂和阴离子树脂，二者质量比为1:1，且Amberlyst 15磺酸树脂和A-8XMP固体碱性树脂的总体积为θ环体积的30％)的3mm×3mmθ环；
所述方法包括以下具体步骤：
使三级大豆油(酸值为0.9mgKOH/g)与甲醇(含20wt％碳酸二甲酯)按质量比为1:0.2混合后从下入口送入塔式反应器中，并使其在塔式反应器中从下往上流动，与甲醇和碳酸二甲酯连续进行酯化反应和/或酯交换反应，使丙三醇萃取剂(与三级大豆油的质量比为0.1:1)从上入口送入塔式反应器中，并使其在塔式反应器中从上向下流动，与三级大豆油体系逆流萃取，以萃取反应所生成的水；
其中，严格控制反应条件为：大豆油的体积空速0.4h -1，反应温度120℃，压力0.4MPa。萃取剂从塔式反应器底部连续排出，反应生成的混合脂肪酸酯从塔式反应器顶部连续排出。
反应后，三级大豆油中的脂肪酸和脂肪酸甘油酯充分转化，转化率接近100％。塔顶排出的混合物经过蒸馏分离甲醇和碳酸二甲酯，沉降分离极性化合物，得到酸值小于0.1mgKOH/g的脂肪酸甲酯，其中脂肪酸甲酯的含量大于99.0wt％。
实施例3
本实施例提供了一种油脂于塔式反应器内经连续反应萃取制备生物柴油的方法，其中，所述塔式反应器的内径(直径)为50mm、高为6m，下入口，即油脂入口和上入口，即萃取剂入口之间的距离为5m，在下入口和上入口之间装填5mm×5mmθ环；
所述方法包括以下具体步骤：
使餐饮业回收油(酸值为84mgKOH/g)与甲醇按质量比1:0.3混合后从下入口送入塔式反应器中，并使其在塔式反应器中从下往上流动，与甲醇连续进行酯化反应和/或酯交换反应，混合了3wt％硫酸的丙三醇萃取剂(与餐饮业回收油的质量比为0.6:1)从上入口送入塔式反应器中，并使其在塔式反应器中从上向下流动，以与餐饮业回收油体系逆流萃取，以萃取反应所生成的水；
其中，严格控制反应条件为：餐饮业回收油的体积空速3h -1，反应温度为180℃，压力5MPa。萃取剂从塔式反应器底部连续排出，反应生成的混合脂肪酸酯从塔式反应器顶部连续排出。
反应后，餐饮业回收油中的脂肪酸和脂肪酸甘油酯充分转化，转化率接近100％。塔顶排出的混合物经过蒸馏分离甲醇，沉降分离极性化合物，并进一步减压蒸馏得到酸值小于0.2mgKOH/g的精炼脂肪酸甲酯，其中脂肪酸甲酯的含量大于97.5wt％。
实施例4
本实施例提供了一种油脂于塔式反应器内经连续反应萃取制备生物柴油的方法，其中，所述塔式反应器的内径(直径)为50mm、高为6m，下入口，即油脂入口和上入口，即萃取剂入口之间的距离是5m，在下入口和上入口之间装填混合了ZSM-5和镁铝水滑石氧化物(其中，镁铝水滑石氧化物为非均相碱催化剂中的固体碱催化剂，ZSM-5和镁铝水滑石氧化物二者的质量比为1:1，且ZSM-5和镁铝水滑石氧化物的总体积为θ环体积的30％)的3mm×3mmθ环；
所述方法包括以下具体步骤：
使小桐籽油(酸值为31mgKOH/g)与甲醇按质量比1:0.7混合后从下入口送入塔式反应器中，并使其在塔式反应器中从下往上流动，与甲醇连续进行酯化反应和/或酯交换反应，使含10wt％葡萄糖的山梨醇萃取剂(与小桐籽油的质量比为0.4:1)从上入口送入塔式反应器中，并使其在塔式反应器中从上向下流动，与小桐籽油体系逆流萃取，以萃取反应所生成的水；
其中，严格控制反应条件：小桐籽油的体积空速2h -1，反应温度240℃，压力6MPa。萃取剂从塔式反应器底部连续排出，反应生成的混合脂肪酸甲酯从塔式反应器顶部排出。
反应后，小桐籽油中的脂肪酸和脂肪酸甘油酯充分转化，转化率接近100％。塔顶排出的混合物经过蒸馏分离甲醇，沉降分离极性化合物，并减压蒸馏得到酸值小于0.2mgKOH/g的脂肪酸甲酯，其中脂肪酸甲酯的含量大于97.5wt％。
实施例5
本实施例提供了一种油脂于塔式反应器内经连续反应萃取制备生物柴油的方法，其中，所述塔式反应器的内径为50mm、高为6m，下入口，即油脂入口和上入口，即萃取剂入口之间的距离为5m，在下入口和上入口之间装填混有纳米氧化镁的5mm×5mmθ环，且纳米氧化镁的总体积为θ环体积的30％；
所述方法包括以下具体步骤：
使粗棉籽油(酸值为12mgKOH/g)与甲醇按质量比1:0.2混合后从下入口送入塔式反应器中，并使其在塔式反应器中从下往上流动，与甲醇连续进行酯化反应和/或酯交换反应，使甘油萃取剂(与棉籽油的质量比为0.4:1)从上入口送入塔式反应器中，并使其 在塔式反应器中从上向下流动，与粗棉籽油逆流萃取，以萃取反应所生成的水；
其中，严格控制反应条件为：棉籽油的体积空速1h -1，温度190℃，压力4MPa。萃取剂从塔式反应器底部连续排出，反应生成的混合脂肪酸甲酯从塔式反应器顶部连续排出。
反应后，棉籽油中的脂肪酸和脂肪酸甘油酯充分转化，转化率接近100％。塔顶排出的混合物经过蒸馏分离甲醇，得到酸值小于0.1mgKOH/g的脂肪酸甲酯，其中脂肪酸甲酯的含量大于98.2wt％。
实施例6
本实施例提供了一种油脂于塔式反应器内经连续反应萃取制备生物柴油的方法，其中，所述塔式反应器的内径为50mm、高为6m，下入口，即油脂入口和上入口，即萃取剂入口之间的距离为5m，在下入口和上入口之间装填5mm×5mmθ环；
所述方法包括以下具体步骤：
使精炼棉籽油(酸值为0.5mgKOH/g)与甲醇(含1wt％氢氧化钾)按质量比为1:0.2混合后从下入口送入塔式反应器中，并使其在塔式反应器中从下往上流动，与甲醇连续进行酯化反应和/或酯交换反应，使甘油萃取剂(与棉籽油的质量比为0.3:1)从上入口送入塔式反应器中，并使其在塔式反应器中从上向下流动，与精炼棉籽油逆流萃取，以萃取反应所生成的水；
其中，严格控制反应条件为：精炼棉籽油的体积空速0.5h -1，温度180℃，压力3MPa。萃取剂从塔式反应器底部连续排出，反应生成的混合脂肪酸甲酯从塔式反应器顶部连续排出。
反应后，精炼棉籽油中的脂肪酸和脂肪酸甘油酯充分转化，转化率接近100％。塔顶排出的混合物经过蒸馏分离甲醇，沉降分离甘油，减压蒸馏得到酸值小于0.1mgKOH/g的脂肪酸甲酯，其中脂肪酸甲酯的含量大于98.5wt％。
对比例1
本对比例提供了一种油脂于管式反应器内经连续反应制备生物柴油的方法，其中，所述方法包括以下具体步骤：
使餐饮业回收油(酸值为84mgKOH/g)与甲醇按质量比1:0.3混合后一并从下入口送入与实施例3所使用的塔式反应器等体积的管式反应器中，并加入与实施例3中等量的硫酸催化剂(约为餐饮业回收油质量的1.8％)；
其中，严格控制反应条件为：餐饮业回收油的体积空速3h -1，反应温度为180℃，压力5MPa。反应生成的混合脂肪酸酯从管式反应器顶部连续排出。
反应后，餐饮业回收油中脂肪酸和脂肪酸甘油酯转化率仅约为82％。管式反应器顶部连续排出的混合物经过蒸馏分离甲醇，沉降分离极性化合物，并进一步减压蒸馏得到酸值约为10.6mgKOH/g的精炼脂肪酸甲酯，其中脂肪酸甲酯含量大于93.5wt％。
对比实施例3以及对比例1后可知，实施例3中使餐饮业回收油于塔式反应器内经连续反应萃取制备生物柴油，餐饮业回收油中的脂肪酸和脂肪酸甘油酯充分转化，转化率接近100％，并且所得精炼脂肪酸甲酯的酸值小于0.2mgKOH/g，其中脂肪酸甲酯的含量大于97.5wt％；而对比例1中使相同的餐饮业回收油于管式反应器内经连续反应制备生物柴油，餐饮业回收油中脂肪酸和脂肪酸甘油酯的转化率仅约为82％，并且所得精炼脂肪酸甲酯的酸值明显偏高，脂肪酸甲酯含量偏低。
由此可知，本发明实施例所提供的油脂于塔式反应器内经连续反应萃取制备生物柴油的方法不但可以显著提高脂肪酸和脂肪酸甘油酯的转化率，还可以显著降低所得精炼脂肪酸甲酯的酸值。
以上所述，仅为本发明的具体实施例，不能以其限定发明实施的范围，所以其等同组件的置换，或依本发明专利保护范围所作的等同变化与修饰，都应仍属于本专利涵盖的范畴。另外，本发明中的技术特征与技术特征之间、技术特征与技术发明之间、技术发明与技术发明之间均可以自由组合使用。

Claims (24)

  1. 一种反应萃取制备生物柴油的方法，其中，所述方法包括：使动植物油脂与一元脂肪醇或其碳酸酯在加入或不加入催化剂的条件下进行酯化反应和/或酯交换反应，并于反应过程中同时以极性萃取剂萃取反应所生成的水。
  2. 根据权利要求1所述的方法，其中，所述动植物油脂中，碳链长度为C 12-C 24的脂肪酸含量大于90wt％。
  3. 根据权利要求1所述的方法，其中，所述动植物油脂的酸值大于0.5mgKOH/g。
  4. 根据权利要求1-3任一项所述的方法，其中，所述动植物油脂包括牛油、猪油、鸡油、鸭油、鱼油、花生油、大豆油、菜籽油、棕榈油、棉籽油、玉米油、向日葵油、米糠油、麻风树果油、微藻油、小桐籽油以及油脂炼制过程中产生的酸化油，经过其它用途后主要结构未发生改变的煎炸油、餐饮业废油中的一种或者几种的组合。
  5. 根据权利要求1所述的方法，其中，所述一元脂肪醇或其碳酸酯包括C 1-C 6的单羟基脂肪醇或其碳酸酯中的一种或几种的组合。
  6. 根据权利要求5所述的方法，其中，所述一元脂肪醇或其碳酸酯包括甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇、戊醇、己醇或其碳酸酯中的一种或几种的组合。
  7. 根据权利要求6所述的方法，其中，所述一元脂肪醇或其碳酸酯包括甲醇、乙醇、丙醇、碳酸二甲酯和碳酸二乙酯中的一种或几种的组合。
  8. 根据权利要求1，5-7任一项所述的方法，其中，所述一元脂肪醇或其碳酸酯与动植物油脂的质量比为0.1-1:1。
  9. 根据权利要求8所述的方法，其中，所述一元脂肪醇或其碳酸酯与动植物油脂的质量比为0.2-0.7:1。
  10. 根据权利要求1所述的方法，其中，所述极性萃取剂与动植物油脂的质量比为0.05-1.2:1。
  11. 根据权利要求10所述的方法，其中，所述极性萃取剂与动植物油脂的质量比为0.1-1:1。
  12. 根据权利要求1，10-11任一项所述的方法，其中，所述极性萃取剂的密度大于1g/cm 3，且其在所述动植物油脂中的饱和溶解浓度小于1wt％。
  13. 根据权利要求12所述的方法，其中，所述极性萃取剂包括多羟基化合物和/或二甲基亚砜。
  14. 根据权利要求13所述的方法，其中，所述多羟基化合物的水含量小于1wt％。
  15. 根据权利要求13或14所述的方法，其中，所述多羟基化合物包括乙二醇、丙 二醇、丙三醇、山梨醇、葡萄糖中的一种或几种的组合。
  16. 根据权利要求1所述的方法，其中，加入催化剂时，所述催化剂包括均相或非均相酸催化剂，均相或非均相碱催化剂中的一种或几种的组合。
  17. 根据权利要求16所述的方法，其中，均相酸催化剂包括硫酸、磷酸、甲基苯磺酸中的一种或几种的组合；非均相酸催化剂包括酸性沸石分子筛、钨钼金属氧化物、阳离子树脂中的一种或几种的组合；均相碱催化剂包括碱金属氢氧化物或其醇盐中的一种或几种的组合；非均相碱催化剂包括碱金属或碱土金属的氧化物、阴离子树脂中的一种或几种的组合。
  18. 根据权利要求1所述的方法，其中，所述反应的条件为：温度80-280℃、压力0.1-8MPa、动植物油脂的体积空速为0.4-4h -1。
  19. 根据权利要求18所述的方法，其中，所述反应的条件为：温度160-260℃、压力0.3-6MPa。
  20. 根据权利要求1所述的方法，其中，所述方法为连续生产生物柴油的方法，其过程具体包括：
    1)使动植物油脂从塔式反应器的油脂入口进入塔式反应器并使其在塔式反应器中从下往上流动，与一元脂肪醇或其碳酸酯连续进行酯化反应和/或酯交换反应；
    2)使极性萃取剂从塔式反应器的萃取剂入口进入塔式反应器并使其在塔式反应器中从上向下流动，以与动植物油脂逆流萃取；
    3)使反应所得到的酯相从塔式反应器的顶部排出；
    4)使极性萃取剂从塔式反应器的底部排出。
  21. 根据权利要求20所述的方法，其中，所述萃取剂入口位于所述油脂入口的上方，且萃取剂入口与油脂入口之间的距离与所述塔式反应器的直径的比值大于3。
  22. 根据权利要求20或21所述的方法，其中，所述萃取剂入口位于所述油脂入口的上方，且萃取剂入口与油脂入口之间的距离与所述塔式反应器的直径的比值为5-80。
  23. 一种生物柴油，其中，所述生物柴油是由权利要求1-22任一项所述的反应萃取制备生物柴油的方法制得。
  24. 根据权利要求23所述的生物柴油，其中，生物柴油的酸值小于0.5mgKOH/g，脂肪酸酯含量大于96wt％。
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