WO2022119062A1 - Catalyseur acide solide pour la production de biodiesel, catalyseur à base solide pour la production de biodiesel, ses procédés de préparation, et procédé de production de biodiesel au moyen de ces catalyseurs - Google Patents

Catalyseur acide solide pour la production de biodiesel, catalyseur à base solide pour la production de biodiesel, ses procédés de préparation, et procédé de production de biodiesel au moyen de ces catalyseurs Download PDF

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WO2022119062A1
WO2022119062A1 PCT/KR2021/004851 KR2021004851W WO2022119062A1 WO 2022119062 A1 WO2022119062 A1 WO 2022119062A1 KR 2021004851 W KR2021004851 W KR 2021004851W WO 2022119062 A1 WO2022119062 A1 WO 2022119062A1
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oil
catalyst
biodiesel
zeolite
solid
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PCT/KR2021/004851
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English (en)
Korean (ko)
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박지연
김민철
김덕근
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한국에너지기술연구원
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • 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
    • 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
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0484—Vegetable or animal 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • Various embodiments of the present invention relate to a solid acid catalyst for biodiesel production, a solid base catalyst for biodiesel production, a method for preparing the same, and a method for producing biodiesel using the same.
  • various embodiments of the present invention relate to a solid acid catalyst for biodiesel production capable of increasing the conversion rate and yield of biodiesel, a solid base catalyst for biodiesel production, a production method thereof, and a method for producing biodiesel using the same .
  • Biodiesel is defined as methyl or ethyl ester compounds of fatty acids produced from vegetable oils or animal fats. Compared to conventional diesel, biodiesel can significantly reduce the emission of air pollutants such as carbon monoxide, fine dust, hydrocarbons, and toxic substances, making it suitable as an eco-friendly fuel for automobiles. In addition, carbon dioxide emitted from the combustion of biodiesel is absorbed and fixed again by the photosynthetic mechanism of plants, so there is almost no net carbon dioxide emission.
  • Biodiesel is an industry whose applicability is rapidly expanding by using it as an intermediate of chemical substances that replace not only fuels but also polluting petroleum products. Biodiesel is used as a raw material for manufacturing eco-friendly products such as biodegradable surfactants, synthetic lubricants and low-toxic solvents. In addition, the biodiesel plant industry has industrial characteristics such as a combined knowledge industry, a venture-type industry, a next-generation strategic industry, and an international industry.
  • biodiesel is mainly produced using vegetable oil extracted from edible crops such as soybeans and rapeseed, which has been criticized for aggravating food shortages in poor countries such as Africa and low-income groups as it causes grain prices to rise.
  • extensive rainforests or forests are being developed to produce raw materials such as palm oil in response to the increasing demand for biodiesel, which in fact promotes global warming.
  • Korea imports most of the raw materials for biodiesel (soybean oil or palm oil) from abroad, it is highly likely that supply and demand and price will depend heavily on external changes, similar to petroleum resources.
  • microalgae can be grown using water, carbon dioxide and sunlight, and can be cultivated anywhere, including wasteland, coastal areas, and the sea, so they do not compete with existing land crops in terms of land or space.
  • microalgae accumulate a large amount of oil (up to 70%) in the living body depending on the culture conditions, and the oil production per unit area is 50-100 times higher than that of conventional edible crops such as soybeans, so it has a very high potential as an alternative biological oil. . From this, interest in biodiesel production technology based on microalgae, which has excellent oil production per unit area compared to terrestrial plants, is growing (Table 1).
  • oils extracted from microalgae may be used as raw materials for functional cosmetics, or raw materials of pharmaceuticals may be extracted.
  • astaxanthin which has an antioxidant effect, can be applied as a raw material for cosmetics, food, pharmaceuticals, nutritional supplements and feed.
  • Omega-3 fatty acids including DHA (docosahexaenoic acid) and EPA (eicosapentaenoic acid) are also examples of typical oils that can be extracted from microalgae.
  • Microalgae are single-celled photosynthetic organisms that have a size of 3-30 ⁇ m and live in freshwater or seawater. It absorbs carbon dioxide and releases oxygen, and contains oils and useful substances. Compared to terrestrial plants, microalgae have a very fast growth rate, can be cultured at high concentrations in large quantities, and have the advantages of being able to grow in extreme environments. Microalgae have high fuel productivity compared to conventional crops, as the usable oil component amounts to 30-70% of biomass. Therefore, it can be said that the technology for manufacturing oil and useful substances using microalgae shows high productivity per unit area, so it is easy to secure resources and there is no competition with food resources, so it can be said that it is suitable for the domestic situation.
  • the process of producing useful substances including biofuel from microalgae is to mass-produce microalgae, harvest microalgae from which some moisture has been removed, apply various oil extraction methods to extract oil, and then biodiesel, cosmetics, or pharmaceuticals. It is used as a raw material, etc.
  • Oils extracted from microalgae generally contain triglycerides and free fatty acids at the same time.
  • the process is simplified to the base catalyst process, but when the two are mixed, free fatty acids react with the base catalyst to form soap, causing oil loss and inhibiting the separation of the biodiesel layer.
  • Bio-oil extracted from microalgae may contain other components such as chlorophyll or phospholipids in addition to free fatty acids and triglycerides, so it is necessary to apply a suitable base catalyst or acid catalyst depending on the properties.
  • a suitable base catalyst or acid catalyst instead of a homogeneous catalyst that generates waste liquid, a heterogeneous catalyst that can be recovered and reused is receiving a lot of attention from an environmental point of view.
  • the present invention provides a bio with high conversion rate through a two-step process using a solid acid catalyst and a solid base catalyst from microalgae with a very high oil production compared to conventional raw materials (soybean, rapeseed, palm, etc.) SUMMARY OF THE INVENTION
  • An object of the present invention is to provide a method for manufacturing diesel.
  • the present invention provides a solid acid catalyst for biodiesel production, a solid acid catalyst for biodiesel production that is easy to separate and reusable after recovery, in order to compensate for the disadvantage that environmental pollutants are additionally generated through a neutralization process and a water washing process when using a conventional homogeneous catalyst, and a solid for biodiesel production
  • An object of the present invention is to provide a base catalyst, a method for producing the same, and a method for producing biodiesel using the same.
  • microalgal oil prepared by solvent extraction has a dark green color and is in the form of a viscous and low fluidity liquid. Therefore, there is a need to improve the properties of microalgal oil because there is a high possibility that the biodiesel conversion rate is significantly reduced due to a decrease in catalyst activity during biodiesel production using a heterogeneous catalyst.
  • the initial acid value of microalgal oil is 5-40 mg KOH/g, and when a base catalyst is applied, it is difficult to separate biodiesel produced by the saponification reaction, and the biodiesel conversion rate is also reduced.
  • microalgal oil can be converted to biodiesel by using a large amount of a strong acid such as sulfuric acid, but in this case, the corrosion problem of the device must be considered. Therefore, the present invention uses a small amount of acid catalyst to convert free fatty acids into biodiesel, and the remaining triglyceride portion is converted to biodiesel using a base catalyst to improve the conversion rate and yield through a two-step process do.
  • a strong acid such as sulfuric acid
  • a solid acid catalyst for biodiesel production includes zeolite; and an acidic material supported on the zeolite.
  • a solid base catalyst for biodiesel production includes zeolite; and a basic material supported on the zeolite.
  • a method for preparing a solid acid catalyst for biodiesel production includes calcining a zeolite support; recovering the zeolite support after stirring using an acidic solution; and calcining the zeolite support at a temperature of 450°C to 650°C.
  • a method for preparing a solid base catalyst for biodiesel production includes calcining a zeolite support; recovering the zeolite support after stirring using a basic solution; and calcining the zeolite support at a temperature of 300 °C to 600 °C.
  • a method for producing biodiesel according to various embodiments of the present invention includes preparing at least one oil of high acid value oil and microalgal oil; reacting the oil under a solid acid catalyst to obtain a primary product; and reacting the primary product under a solid base catalyst to obtain a secondary product.
  • the present invention can produce biodiesel with a high conversion rate from microalgae, which has a very high oil production compared to conventional raw materials (soybean, rapeseed, palm, etc.), through a two-step process of a solid acid catalyst and a solid base catalyst.
  • the solid acid catalyst and the solid base catalyst of the present invention have advantages in that product separation is easy, and there is no additional energy consumption and no wastewater generation due to neutralization or water washing processes.
  • the biodiesel production method of the present invention can increase the conversion rate and yield of biodiesel by converting both the free fatty acid portion and the triglyceride portion into biodiesel through a two-step process using such a solid acid catalyst and a solid base catalyst.
  • biodiesel can contribute to the dissemination of biodiesel by converting microalgal oil into biodiesel as a new biodiesel raw material.
  • FIG. 1 is a graph confirming the FAME content according to the calcination temperature of a solid acid catalyst according to an embodiment of the present invention.
  • FIG 3 is a graph confirming the FAME content according to the calcination temperature of the solid base catalyst according to an embodiment of the present invention.
  • a solid acid catalyst for biodiesel production includes zeolite; and an acidic material supported on the zeolite.
  • the acidic material may be at least one selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and acetic acid.
  • the acidic material may be sulfuric acid.
  • Zeolite is a support for preparing a solid acid catalyst, and has a porous structure.
  • Zeolite has cation exchange properties, which means that cations located in the zeolite cavity are easily exchanged with other cations. The cations are easily exchanged even with a treatment that simply washes the zeolite with a solution of other cations.
  • it has a selective exchange property that can selectively exchange specific cations according to the size of the cavity.
  • the ion exchange properties of zeolite are being used as soil and water quality improvement agents, industrial and municipal wastewater treatment, radioactive waste treatment, etc.
  • the dehydrated zeolite can selectively adsorb inorganic and organic molecules of suitable size and shape.
  • the zeolite has the characteristic of a molecular sieve function that can separate different molecules mixed with each other. It is used as a desiccant for the purpose of dehydration of various gases by applying the adsorption and molecular sieve properties of zeolite, and the removal of impure gases from natural gas and LPG.
  • the zeolite Due to the porous structure of zeolite in which cavities large enough for molecules to adsorb regularly exist inside the crystal, the zeolite exhibits excellent surface activity and has excellent catalytic properties.
  • the catalytic properties of zeolite depend on the structure of the zeolite, the nature and structure of cations, the Si/Al content ratio, and the presence or absence of active metal elements.
  • the catalytic properties of zeolite are widely used in petroleum refining and petrochemical fields.
  • the content of water present in the cavity of the zeolite structure is sensitively changed depending on the environment such as humidity and temperature in addition to the type of zeolite and the properties of cations.
  • Endothermic and exothermic phenomena are accompanied by a change in the water content of the zeolite, that is, in the process in which water is dehydrated or absorbed in the cavity.
  • Zeolite shows high thermal stability up to about 700-800 degrees Celsius, and shows a gradual dehydration phenomenon as the temperature increases. When cooled again, reabsorption of water into the dried zeolite occurs.
  • Such dehydration and resorption properties of zeolite can be used to enhance the efficacy of various drying agents and catalysts.
  • an acidic material is supported on zeolite having these characteristics to serve as an acid catalyst suitable for the reaction of high acid value oil or microalgal oil.
  • the supported amount of the acidic material may be 2 wt% to 10 wt% compared to the solid acid catalyst.
  • the supported amount of the acidic material may be 6 wt% or more compared to the solid acid catalyst. This can improve the catalytic activity.
  • the solid acid catalyst according to various embodiments of the present invention is a heterogeneous catalyst, and can be easily recovered and reused during biodiesel production.
  • a method for preparing a solid acid catalyst for biodiesel production includes calcining a zeolite support; recovering the zeolite support after stirring using an acidic solution; and calcining the zeolite support at a temperature of 450°C to 650°C.
  • the zeolite support In the step of calcining the zeolite support, it may be prepared by calcining the zeolite support at 500° C. to 600° C. for 3 hours to 7 hours.
  • the catalyst can be recovered through a vacuum filter after stirring using an acidic solution dissolved in distilled water.
  • the recovered catalyst may be washed with distilled water.
  • the concentration of the acidic solution may be 0.2 mol/L to 6 mol/L.
  • the concentration of the acidic solution may be at least 1 mol/L. It is possible to improve the conversion rate of biodiesel when producing biodiesel from oil by using the solid acid catalyst prepared with the acidic solution of a specific concentration.
  • the firing temperature may be 450 °C to 550 °C.
  • a solid base catalyst for biodiesel production includes zeolite; and a basic material supported on the zeolite.
  • the basic material may be any one selected from the group consisting of sodium acetate, sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the basic substance may be sodium acetate.
  • a basic material is supported on the zeolite having a porous structure to serve as a base catalyst suitable for the reaction of high acid value oil or microalgal oil.
  • the amount of the basic material supported may be 2 wt% to 10 wt% compared to the solid base catalyst.
  • the supported amount of the basic material may be 6 wt% or more compared to the solid base catalyst. This can improve the catalytic activity.
  • the solid base catalyst according to various embodiments of the present invention is a heterogeneous catalyst, and can be easily recovered and reused during biodiesel production.
  • a method for preparing a solid base catalyst for biodiesel production includes calcining a zeolite support; recovering the zeolite support after stirring using a basic solution; and calcining the zeolite support at a temperature of 300 °C to 600 °C.
  • the zeolite support In the step of calcining the zeolite support, it may be prepared by calcining the zeolite support at 500° C. to 600° C. for 3 hours to 7 hours.
  • the catalyst can be recovered by using an evaporator after stirring using a basic solution dissolved in distilled water to remove the distilled water.
  • the basic solution may include an alkali metal
  • the amount of the alkali metal supported may be 5 wt% to 9 wt% compared to the zeolite.
  • the amount of alkali metal supported may be 6 wt% to 9 wt% compared to zeolite.
  • the firing temperature may be 350 °C to 550 °C.
  • a method for producing biodiesel according to various embodiments of the present invention includes preparing at least one oil of high acid value oil and microalgal oil; reacting the oil under a solid acid catalyst to obtain a primary product; and reacting the primary product under a solid base catalyst to obtain a secondary product.
  • high acid value oil or microalgal oil may be prepared.
  • soybean oil:oleic acid 9:1 (w/w) having an acid value of 20 mg KOH/g and soybean oil:oleic acid 8:2 (w/w) having an acid value of 40 mg KOH/g were prepared and used.
  • Waste cooking oil, palm sludge oil, acid oil, unrefined bio oil, microalgal oil, etc. may correspond to the high acid value oil.
  • microalgal oil it may be extracted from microalgae by one method selected from a solvent extraction method, sulfuric acid-hot water extraction method, base-solvent extraction method, acid-base-solvent extraction method.
  • the solvent extraction method is a method of separating oil from microalgae into a solvent phase using an extraction solvent capable of dissolving oil well among various components of microalgae.
  • a sulfuric acid-hot water extraction method using a sulfuric acid catalyst may be used.
  • a base-solvent extraction method and acid-base-solvent extraction method in which sodium hydroxide, potassium hydroxide, sodium hydroxide-sulfuric acid or potassium hydroxide-sulfuric acid are added during solvent extraction.
  • the microalgae may be of the genus Nanochloropsis oceanica, and the oil may be extracted using a solvent containing hexane and methanol.
  • Hexane:methanol can be 6:4 (v/v) to 8:2 (v/v).
  • hexane: methanol may be included in a volume ratio of 7:3 (v/v).
  • the solvent layer containing the oil may be recovered, and the oil may be recovered by volatilizing the solvent through vacuum evaporation. As described above, it may be extracted by reacting at least one of potassium hydroxide (KOH), sodium hydroxide (NaOH), and sulfuric acid (H 2 SO 4 ).
  • KOH potassium hydroxide
  • NaOH sodium hydroxide
  • SO 4 sulfuric acid
  • the oil can be extracted by adding 5% to 15% of potassium hydroxide compared to microalgae in addition to a solvent containing hexane and methanol.
  • potassium hydroxide compared to microalgae is added to a solvent containing hexane and methanol to react, and then sulfuric acid may be additionally added to extract the oil.
  • this oil can be reacted under a solid acid catalyst to obtain a primary product.
  • the oil may be reacted with an alcohol, and an esterification reaction may be performed using a solid acid catalyst. Since the solid acid catalyst is the same as described above, a detailed description thereof will be omitted.
  • the mass ratio of oil: alcohol may be 1:0.1 to 1:1. That is, alcohol can be used from 10% to 100% by mass compared to oil. If the amount of alcohol is less than 10%, the reaction does not occur well due to insufficient contact of the oil with the alcohol.
  • the alcohol may be methanol.
  • the mass ratio of oil:solid acid catalyst may be 1:0.05 to 1:0.2. That is, the amount of solid acid catalyst can be used from 5% to 20% compared to oil. If the catalyst amount is less than 5%, the reaction does not occur well due to insufficient contact between the oil and the catalyst. If the catalyst amount is more than 20%, the volume occupied by the catalyst in the liquid phase increases and stirring is not smooth.
  • the reaction temperature may be 100 °C to 150 °C, and the reaction time may be 1 to 6 hours.
  • the reaction temperature and reaction time can be adjusted according to the properties of the microalgae. For example, when the properties of microalgae are not good, a high reaction temperature and a long reaction time are required, and in the case of refined oil, the reaction occurs well even at a low reaction temperature and a short reaction time.
  • the primary product obtained through the above reaction may be reacted under a solid base catalyst to obtain a secondary product.
  • the primary product may be reacted with an alcohol, and a transition esterification reaction may be performed using a solid base catalyst. Since the solid base catalyst is the same as described above, a detailed description thereof will be omitted.
  • the mass ratio of the primary product: alcohol may be 1:0.1 to 1:1. That is, alcohol can be used from 10% to 100% by mass compared to the primary product. If the amount of alcohol is less than 10%, the reaction does not occur well due to insufficient contact of the oil with the alcohol.
  • the alcohol may be methanol.
  • the mass ratio of oil:solid base catalyst may be 1:0.05 to 1:0.2. That is, the amount of solid base catalyst can be used from 5% to 20% compared to oil. If the catalyst amount is less than 5%, the reaction does not occur well due to insufficient contact between the oil and the catalyst. If the catalyst amount is more than 20%, the volume occupied by the catalyst in the liquid phase increases and stirring is not smooth.
  • the reaction temperature may be 80 °C to 120 °C, and the reaction time may be 1 to 6 hours.
  • the reaction temperature and reaction time can be adjusted according to the properties of the microalgae. For example, when the properties of microalgae are not good, a high reaction temperature and a long reaction time are required, and in the case of refined oil, the reaction occurs well even at a low reaction temperature and a short reaction time.
  • the free fatty acid portion contained in the high acid value oil is converted into biodiesel by esterification with a solid acid catalyst
  • the remaining triglyceride portion It is converted into biodiesel by transesterification by this solid base catalyst.
  • saponification does not occur, the recovery of biodiesel is very easy. Therefore, in the present invention, both the yield and the conversion rate of biodiesel can be increased by converting both free fatty acids and triglycerides into biodiesel through these two-step reactions.
  • the zeolite support was prepared by calcining at 550° C. for 5 hours. After stirring using 40 mL of a sulfuric acid (H 2 SO 4 ) solution dissolved in distilled water per 1 g of the catalyst, the catalyst was recovered using a vacuum filter and further washed with distilled water. After drying sufficiently in an oven at 105 ° C., the mixture was calcined at 350, 450, 500, 550, 650, 700, and 750 ° C. for 5 hours to prepare H 2 SO 4 /HZSM-5 catalyst. The concentration of the sulfuric acid solution used was 3 mol/L.
  • the reaction was carried out at 120 °C in a batch reactor for 1 hour.
  • the biodiesel layer was separated, and the conversion rate of the recovered biodiesel was analyzed with an Agilent 7890 gas chromatograph according to a fatty acid methyl ester (FAME) standard method (EN 14103).
  • FAME fatty acid methyl ester
  • the zeolite support was prepared by calcining at 550° C. for 5 hours. After stirring using 40 mL of a sulfuric acid (H 2 SO 4 ) solution dissolved in distilled water per 1 g of the catalyst, the catalyst was recovered using a vacuum filter and further washed with distilled water. After drying sufficiently in an oven at 105 ° C. and calcining at 500 ° C. for 5 hours, H 2 SO 4 /HZSM-5 catalyst was prepared. The concentration of the sulfuric acid solution used was 0, 0.1, 0.5, 1, 3, 5 mol/L.
  • the reaction was carried out at 120 °C for 1 hour in a batch reactor.
  • the biodiesel layers were separated, and the conversion rate of the recovered biodiesel was analyzed with an Agilent 7890 gas chromatograph according to the fatty acid methyl ester (FAME) standard method (EN 14103).
  • the zeolite support was prepared by calcining at 550° C. for 5 hours. After stirring using 40 mL of sodium acetate (CH 3 COONa) solution dissolved in distilled water per 1 g of catalyst, distilled water was removed using an evaporator. After drying sufficiently in an oven at 105° C., it was calcined at 350, 450, 550, 650, and 750° C. for 5 hours to prepare a Na/HZSM-5 catalyst. The amount of sodium loaded was 6 wt% compared to the zeolite.
  • CH 3 COONa sodium acetate
  • FAME fatty acid methyl ester
  • the zeolite support was prepared by calcining at 550° C. for 5 hours. After stirring using 40 mL of sodium acetate (CH 3 COONa) solution dissolved in distilled water per 1 g of catalyst, distilled water was removed using an evaporator. After drying sufficiently in an oven at 105°C, it was calcined at 350°C for 5 hours to prepare a Na/HZSM-5 catalyst.
  • the sodium loading was 0.5, 2, 4, 6, 8 wt% compared to the zeolite.
  • FAME fatty acid methyl ester
  • Example 3 for oil biodiesel Preparation of solid acid catalyst, solid base catalyst, high acid value oil and microalgal oil for conversion catalyst activity testing
  • the zeolite support was prepared by calcining at 550° C. for 5 hours. After stirring using 40 mL of a sulfuric acid (H 2 SO 4 ) solution dissolved in distilled water per 1 g of the catalyst, distilled water was removed using an evaporator. After drying sufficiently in an oven at 105 ° C. and calcining at 500 ° C. for 5 hours, H 2 SO 4 /HZSM-5 catalyst was prepared. The amount of sulfuric acid supported was 6 wt% compared to the zeolite.
  • H 2 SO 4 sulfuric acid
  • the zeolite support was prepared by calcining at 550° C. for 5 hours. After stirring using 40 mL of sodium acetate (CH 3 COONa) solution dissolved in distilled water per 1 g of catalyst, distilled water was removed using an evaporator. After drying sufficiently in an oven at 105° C., it was calcined at 350° C. for 5 hours to prepare a Na/HZSM-5 catalyst. The amount of sodium loaded was 6 wt% compared to the zeolite.
  • CH 3 COONa sodium acetate
  • a high acid value oil was prepared by mixing soybean oil composed of triglycerides and oleic acid composed of free fatty acids.
  • a high acid value oil (HAVO-8, high acid-value oil, 8:2) having an acid value of 40 mg KOH/g was prepared by stirring soybean oil and oleic acid.
  • Oil with a solvent of hexane:methanol 7:3 (v/v) using 200 g/L wet Nanochloropsis oceanica with an oil content of 19.5% of microalgae and 35% or more of omega-3 fatty acids in the oil extracted. After sufficiently stirring at 1000 rpm for 6 hours, the solvent layer containing oil was recovered, the solvent was evaporated through vacuum evaporation, and the remaining oil (MAO, microalgal oil) was recovered.
  • MAO microalgal oil
  • Example 4 soybean oil , oleic acid, for high acid value oils biodiesel Conversion Catalyst Activity Test
  • the FMAE content increased by 90.66% more than when Na/HZSM-5 was used (3.00%), and when only H 2 SO 4 /HZSM-5 was used (12.02) %), the FAME content was increased by 81.64%.
  • the FAME content was increased by 70.73% more than when only H 2 SO 4 /HZSM-5 was used (20.55%).
  • FAME fatty acid methyl ester
  • a solid acid catalyst for biodiesel production, a solid base catalyst for biodiesel production, a method for producing the same, and a method for producing biodiesel using the same according to the present invention are conversion rates through a two-step process using a solid acid catalyst and a solid base catalyst from microalgae This high biodiesel can be produced and can contribute to the spread of biodiesel.

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Abstract

Un catalyseur acide solide pour la production de biodiesel, selon divers modes de réalisation de la présente invention, peut comprendre : de la zéolite ; et un matériau acide supporté sur la zéolite. Un catalyseur à base solide pour la production de biodiesel, selon divers modes de réalisation de la présente invention, peut comprendre : de la zéolite ; et un matériau de base supporté sur la zéolite. Un procédé de préparation d'un catalyseur acide solide pour la production de biodiesel, selon divers modes de réalisation de la présente invention, peut comprendre les étapes suivantes de : calcination d'un support de zéolite ; agitation du support de zéolite au moyen d'une solution acide, puis récupération de celui-ci ; et calcination du support de zéolite à une température de 450 à 650 °C. Un procédé de préparation d'un catalyseur à base solide pour la production de biodiesel, selon divers modes de réalisation de la présente invention, peut comprendre les étapes suivantes de : calcination d'un support de zéolite ; agitation du support de zéolite au moyen d'une solution basique, puis récupération de celui-ci ; et calcination du support de zéolite à une température de 300 à 600 °C. Un procédé de production de biodiesel, selon divers modes de réalisation de la présente invention, peut comprendre les étapes suivantes de : préparation d'au moins l'une quelconque parmi l'huile à valeur acide élevée et l'huile de microalgues ; mise en réaction de l'huile en présence d'un catalyseur acide solide pour obtenir un produit primaire ; et mise en réaction du produit primaire en présence d'un catalyseur à base solide pour obtenir un produit secondaire.
PCT/KR2021/004851 2020-12-01 2021-04-19 Catalyseur acide solide pour la production de biodiesel, catalyseur à base solide pour la production de biodiesel, ses procédés de préparation, et procédé de production de biodiesel au moyen de ces catalyseurs WO2022119062A1 (fr)

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