JP5721152B2 - Biodiesel fuel production method and apparatus, and fat and oil decarboxylation catalyst used in the method - Google Patents

Description

  The present invention relates to a method for efficiently producing a high-quality biodiesel fuel from fats and oils and a raw material for oil extraction and a production apparatus therefor. The present invention also relates to an oil and fat decarboxylation catalyst having excellent efficiency used in the production method and production apparatus.

Biodiesel fuel is an extremely important technology for reducing the emissions of greenhouse gases and air pollutants and for building an energy recycling society. As a method for producing this biodiesel fuel, a fatty acid methyl ester (FAME) method has been widely introduced. In the fatty acid methyl esterification method, a diesel engine fuel is obtained by a transesterification reaction between a raw oil and fat and a lower alcohol (subsidiary raw material) (Non-patent Document 1).
As a technique relating to the fatty acid methyl esterification method, (Patent Document 1) discloses “a method for producing a fatty acid alkyl ester by reacting oil and fat with a lower alcohol in the presence of a calcium-based solid catalyst”. Yes.
Further, (Patent Document 2) states that “in the process A and the process A in which the raw oil and fat are reacted with alcohol in the presence of a solid acid catalyst, and the free fatty acid present in the raw oil and fat is converted into a fatty acid alkyl ester. Step B for removing moisture from the obtained reaction mixture, and the liquid obtained in Step B and the alcohol are reacted in the presence of a solid base catalyst to transesterify triacylglyceride, which is the main component of the raw oil and fat. And a process C for converting it into a fatty acid alkyl ester, and a method for producing a biodiesel oil.

As another method for producing biodiesel fuel, a hydrotreatment method described in (Non-patent Document 1) is known. The hydrotreating method is a method that applies the hydrotreating technology that is a conventional petroleum refining process, and by hydrotreating under high pressure such as 10 MPa, oxygen in the raw material fat is mainly removed as water and lightened. A unsaturated oil-derived unsaturated bond is saturated to obtain a hydrocarbon oil having a boiling point range of light oil.
In addition, (Patent Document 3) states that “a fluidized catalytic cracking apparatus having a reaction zone, a separation zone, a stripping zone, and a regeneration zone is used, and in a reaction zone at an outlet temperature of 480 to 540 ° C., a raw material oil containing biomass is added. In addition, a biomass processing method is disclosed in which a gasoline base material, a diesel fuel base material, or the like is obtained by contacting with a solid acid catalyst such as ultrastable Y-type zeolite or silica alumina for 1 to 3 seconds.
Further, (Patent Document 4) states that “a solid acid catalyst is heated to a temperature range of 350 to 450 ° C. in a reaction vessel, and liquid oil is contacted with the solid acid catalyst to remove oxygen-containing components from the oil. , A method for catalytic cracking of fats and oils that synthesizes a hydrocarbon mixture mainly composed of olefins and paraffins having 9 to 24 carbon atoms.

JP 2008-143983 A JP 2008-1856 A JP 2007-177193 A Japanese Patent Application No. 2008-086034

ENEOS Technical Review Vol. 49, No. 2 (June 2007)

However, the above conventional techniques have the following problems.
(1) The fatty acid methyl esterification method disclosed in Non-Patent Document 1, Patent Document 1 and Patent Document 2 requires a large amount of lower alcohol, and thus has a problem of requiring high running costs. . In addition, impurities (such as dienes, hydroxyl groups, peroxides, etc.) in the raw oil and fat are likely to remain in the product oil, so that the product oil is unstable to air and has a problem of lacking storage stability. It was. In order to solve this problem, a process of adsorbing impurities such as peroxide by using an adsorbent such as activated clay and removing it from the produced oil is required, which has a problem that the processing process becomes complicated.
(2) In the fatty acid methyl esterification method, since an alkali catalyst is used as described in Non-Patent Document 1, there arises a problem that fatty acid soap is by-produced. This is because when the amount of fatty acid soap by-product increases, it becomes difficult to separate the fatty acid ester layer and the glycerin layer, and the fatty acid ester is mixed into the glycerin layer, resulting in a decrease in the yield of the fatty acid ester. Moreover, since the alkali catalyst (caustic soda etc.) is melt | dissolving in the glycerin byproduced, this process is a problem. Establishment of processing technology for glycerin, a by-product, is indispensable for establishing technology for fatty acid methyl esterification, but no effective processing technology has been established yet.
(3) In the fatty acid methyl esterification method described in Patent Document 1, by-product of fatty acid soap can be kept low by using a calcium-based solid catalyst, but as another problem, free fatty acid contained in the raw material triglyceride This causes a problem of reducing the activity of the solid catalyst. As a result, a large amount of solid catalyst must be used, a large amount of spent catalyst is generated, and reactivation treatment of the spent catalyst is required. It had the subject that a property fell.
(4) In order to suppress a decrease in the activity of the solid base catalyst due to free fatty acids, Patent Document 2 discloses a technique for removing free fatty acids from raw material fats and oils by treating the free fatty acids in the presence of a solid acid catalyst as a previous step. Is disclosed. The technique disclosed in Patent Document 2 requires a plurality of steps in order to treat a free fatty acid in the presence of a solid acid catalyst in Step A and then react the alcohol in the presence of a solid base catalyst in Step C. The problem is that the processing steps become complicated.
(5) The hydrotreating method described in Non-Patent Document 1 has a problem that the resulting hydrocarbon oil has a high freezing point of + 20 ° C. and poor fluidity. Moreover, glycerin mixed in the obtained hydrocarbon oil, and had the subject that it lacked stability. The high freezing point of hydrocarbon oils is problematic especially when used in cold regions, and is currently only used as a mixture with light oil at 5% or less.
(6) The technique disclosed in Patent Document 3 is a technique for obtaining a gasoline base material or the like from fats and oils using a fluid catalytic cracking apparatus having a reaction zone, a separation zone, a stripping zone and a regeneration zone. In this technology, it is necessary to transport the collected raw material fats and oils to a site where a large-scale fluid catalytic cracking apparatus is present for processing. However, plant-based biomass, which is a raw material for fats and oils, has a problem in that it requires a great deal of cost for collection and transportation to a fluid catalytic cracking device because it is a distributed production resource based on a vast land. Also, in order to reduce transportation costs, constructing a large-scale fluid catalytic cracker at the plant biomass production base simply for the purpose of producing biodiesel fuel has problems such as increased running costs. Had. In addition, when the raw oil / fat comes into contact with the solid acid catalyst in the reaction zone having an outlet temperature of 480 to 540 ° C., the bonds between the carbons of the alkyl groups are easily cleaved, resulting in a low molecular weight product and an increase in the production amount of gasoline fuel base materials. In addition, the production amount of the diesel fuel base material has been reduced. In addition, since the reaction of the solid acid catalyst generates a lot of aromatics, the amount of coke (carbide produced on the catalyst for treating hydrocarbons such as coke and petroleum, also called coke) is large, and the surface of the solid acid catalyst This causes a problem that the activity of the catalyst is lowered at an early stage and a problem that a plurality of catalysts are combined and agglomerated, resulting in a decrease in yield and difficulty in operation. Further, when the activity of the catalyst is lowered, the decarboxylation ability is lowered, and impurities such as carboxylic acid (free fatty acid) are easily produced as by-products, resulting in a problem that the produced oil turns black or has a bad odor. There was a problem that the product oil with many acids, many aromatics and low cetane number is not suitable for actual use.
(7) The technology disclosed in Patent Document 4 is a fuel for a diesel engine having a heated solid acid catalyst and fats and oils as a main component, and mainly containing olefins and paraffins having 9 to 24 carbon atoms from the fats and oils by catalytic cracking. This is a technique for obtaining a hydrocarbon mixture. Although a solid acid catalyst is used, the reaction temperature is lower by using a reaction temperature lower than that of Patent Document 3, and the carbon-to-carbon cleavage ratio of the alkyl group is low. However, since the reaction is still a solid acid catalyst, there are problems in that the amount of coke produced is large, the yield of kerosene / light oil is lowered, and the activity of the catalyst tends to be lowered. Further, when the activity of the catalyst is lowered, the decarboxylation ability is lowered, and impurities such as carboxylic acid (free fatty acid) are easily produced as by-products, resulting in a problem that the produced oil turns black or has a bad odor.

  The present invention solves the above-mentioned conventional problems, does not require alcohol (subsidiary raw material), does not by-produce glycerin, and is a product of impurities such as dienes, hydroxyl groups, and peroxides in the raw oil and fat Residual in the interior, low coke production, low pour point, and impurities such as carboxylic acids (free fatty acids) are hardly produced as a by-product. In addition, it is difficult to cause a problem that the activity of the catalyst decreases due to the free fatty acid produced as a by-product.Therefore, incidental operations such as treatment and reactivation of the used catalyst greatly reduce running costs and increase productivity. In addition, pretreatment for removing free fatty acids from raw oils and fats is unnecessary, and the reaction can be carried out under normal pressure, which simplifies the production process and simplifies the reaction apparatus. Can build distributed energy supply system for supplying the energy needed in a place, and an object thereof is to provide a method for producing a good bio-diesel fuels yield in many raw materials that unsaturated fatty acids. Moreover, it aims at providing the manufacturing apparatus of the biodiesel fuel which can obtain a good-quality biodiesel fuel with high yield from oil extraction raw material and fats and oils. Further, the present invention provides an oil and fat decarboxylation catalyst for use in a method for producing biodiesel fuel that can efficiently obtain a good quality biodiesel fuel from fat and oil by advancing the decarboxylation decomposition reaction while suppressing the breakage of the double bond of the oil and fat. For the purpose.

In order to solve the above conventional problems, the biodiesel fuel production method of the present invention has the following configuration.
In the method for producing biodiesel fuel according to claim 1 of the present invention, at 350 ° C. to 475 ° C., the fat and oil decarboxylation decomposition catalyst and the fat contact with each other in the reaction vessel and ) To produce mainly C8-C24 hydrocarbons, and the fat and oil decarboxylation catalyst is an FCC waste whose acid sites are poisoned by one or more of silica, alkali metal and alkaline earth metal. One or more of the catalyst and the mixture composed of the composites include a composition coated with a weak alkaline compound composed of any one or more of magnesium hydroxide, oxide, and carbonate. Yes.

With this configuration, the following effects can be obtained.
(1) At 350 ° C. to 475 ° C., when the fat and oil decarboxylation decomposition catalyst and the fat and oil are brought into contact with each other, the ester bond portion of glycerin is cleaved by the action of the fat and fat decarboxylation decomposition catalyst, and the decarboxylation decomposition shown in (Chemical Formula 1) occurs. The cracked gas (hydrocarbon) used as biodiesel fuel can be obtained. In addition, depending on the kind of fat and oil decarboxylation decomposition catalyst, it is also considered that de-CO occurs preferentially. As apparent from the reaction shown in (Chemical Formula 1), since glycerin is not by-produced, establishment of processing technology for glycerin, processing man-hours, and the like are not required. Moreover, since a gaseous compound of propane, methane, ethane, and butane is obtained as a by-product, it can be used as a gaseous fuel, and can also be used as a fuel for heating an oil and fat decarboxylation decomposition catalyst.
(2) Since this decarboxylation is carried out under conditions where alcohol is not substantially present, the running cost can be greatly reduced, and unstable impurities such as dienes and peroxides in the raw oil and fat can be removed. Since it is easily decomposed on the surface of the carbonic acid decomposition catalyst, it is difficult to remain in the product, and impurities such as carboxylic acid (free fatty acid) are also hardly produced as a by-product. Biodiesel fuel excellent in storage stability which is difficult can be obtained. In addition, a process for adsorbing and removing impurities such as peroxide using an adsorbent is not required, which is economical. Furthermore, since the amount of coke produced is small, it is difficult to cause problems such as a decrease in the activity of the fat decarboxylation catalyst due to precipitation of coke on the surface of the catalyst, and a problem that the fat decarboxylation decomposition catalyst binds and agglomerates, resulting in a high yield. With this, stable operation is possible.
(3) Although free fatty acids are present in the raw material, impurities such as carboxylic acids (free fatty acids) are hardly produced as a by-product due to cleavage of the ester bond portion of glycerin such as fat and oil and the removal of CO _2. Even if free fatty acids are by-produced, they are easily decomposed into hydrocarbons and carbon dioxide gas, so that the problem that the activity of the catalyst decreases due to the by-produced carboxylic acid (free fatty acids) hardly occurs. For this reason, it is not necessary to use a large amount of catalyst in anticipation of a decrease in activity, and there is no increase in running cost or productivity due to incidental work such as treatment or reactivation of the used catalyst. . Oils and fats with many unsaturated bonds (such as Jatropha oil) are very effective because they contain many free fatty acids due to oxidative degradation.
(4) takes place de CO ₂ or removing CO glycerin in decarboxylation decomposition using oil decarboxylation decomposition catalyst, by collecting the remaining carbon chain, mostly the freezing point as the hydrocarbon having from 8 to 24 carbon atoms - A biodiesel fuel excellent in fluidity around 20 ° C. can be obtained.
(5) Pre-treatment for removing free fatty acids from raw oils and fats to prevent a decrease in the activity of fat and oil decarboxylation cracking catalyst is not necessary, and the catalytic cracking process can be carried out under normal pressure, thus producing biodiesel fuel. The process and the reaction apparatus can be simplified, the productivity is excellent, and the biodiesel fuel can be produced at a low cost. For this reason, the reaction apparatus can be constructed at a low cost at a plant biomass production base or a required place, and a distributed energy supply system that supplies necessary energy at a required place can be constructed.
(6) Since the fat and oil decarboxylation decomposition catalyst is heated to 350 to 475 ° C., the reaction rate of decarboxylation decomposition is large, and the biodiesel fuel mainly composed of olefins and paraffins having 8 to 24 carbon atoms with high productivity. Can be manufactured.
(7) At 350 to 475 ° C., the oil is in a liquid state and hardly evaporates. Therefore, only the product is led out as gas from the reaction vessel.
(8) Fats and oils hardly thermally decompose at 350 to 475 ° C. Therefore, most of the fats and oils are decarboxylated, so that the double bond portion is prevented from being thermally cut and reduced in molecular weight.
(9) Since the product is derived as a gas, phosphoric acid in the raw material is deposited on the oil and fat decarboxylation cracking catalyst and hardly transfers to the cracked oil. Therefore, there is no performance degradation or damage caused by engine phosphoric acid, and cracked oil can be used safely. This is particularly effective when the raw material is jatropha, fish salmon (or fish oil), soybeans or the like having a high phosphoric acid content.
(10) FCC waste catalyst whose acid sites are poisoned by one or more of silica, magnesium oxide, alkali metal and alkaline earth metal, and a mixture of these composites hardly reduces the molecular weight of mineral oil, When a mixture of the raw material for oil extraction and mineral oil is used as the raw material, the mineral oil can act as an extractant for the oil remaining in the raw material for oil extraction and the residue, and the efficiency can be further increased.
(11) The acid point is poisoned by one or more of alkali metal and alkaline earth metal and the acid point is weakened, so that the cleavage of the double bond portion in the oil and fat is suppressed, and decarboxylation is efficiently performed. Occur. Moreover, the production | generation of a fatty acid is also suppressed. Therefore, the production yield of fuel is increased.
(12) Generation of coke is suppressed, equipment maintenance is reduced, and catalyst deterioration is delayed.
(13) Since the FCC catalyst widely used in the fluid catalytic cracking of petroleum can be used, it is easy to obtain the catalyst.
(14) FCC in which acid sites are poisoned by at least one of silica, alkali metal and alkaline earth metal coated with a weak alkaline compound consisting of at least one of magnesium hydroxide, oxide and carbonate Since the waste catalyst hardly reduces the molecular weight of mineral oil, the use of a mixture of fats and oils and a raw material of mineral oil and mineral oil as raw materials increases the extraction efficiency of the fats and oils, and can increase the yield of cracked oil.

Here, oils and fats include rapeseed oil, palm oil, palm kernel oil, olive oil, soybean oil, sesame oil, castor oil, jatropha oil, corn oil and other vegetable oils, terpenes, fish oil, pork fat, and beef tallow Oils and fats collected from certain types of algae such as animal fats and the like, and mixtures thereof can be used. Moreover, waste cooking oils, such as tempura oil, can also be used. Oils and fats such as lard and beef tallow that solidify at room temperature are melted and liquefied by a heated catalyst or preheating, so that the oils and fats can be either liquid or solid.
The fats and oils can be reacted by bringing one or more kinds of mixtures into contact with the catalyst. In addition, the oil / fat can be preheated at a temperature of 475 ° C. or lower before being brought into contact with the catalyst. The reason is to increase the decomposition efficiency by heating quickly after contact with the catalyst.
Oils and fats are triacylglycerols (three acyl groups esterified to glycerin), but phospholipids, glycolipids, fatty acids, and the like can also be used as the raw material of the present invention.

The oil and fat decarboxylation catalyst is preferably weakly alkaline, neutral, or weakly acidic. Specifically, at least one of solid catalyst silica and alkali-poisoned solid acid catalyst is used. Many ceramics can also be used as catalysts.
More specifically, at least one of a mixture of silica, an FCC waste catalyst whose acid sites are poisoned by one or more of alkali metals and alkaline earth metals, and a composite thereof is magnesium hydroxide. Including those coated with a weak alkaline compound consisting of at least one of an oxide, a carbonate, and an alkaline earth metal oxide such as MgO, CaO, SrO, BaO, La ₂ O ₃ , Th ₂ Lanthanoids such as O ₃ , oxides of actinides, metal oxides such as ZrO ₂ and TiO ₂ , metal carbonates such as alkaline earth metals, composite oxides such as SiO ₂ —MgO and SiO ₂ —CaO, Rb and Cs Such as zeolite exchanged with alkali metal ions or alkaline earth metal ions, alkali metal compounds or alkaline earth metal compounds, and partially or fully The FCC catalyst and FCC waste catalyst, Na, Na / MgO the alkali metal is deposited in K such, K / metal deposition metal oxides such as _{MgO, KF / Al 2 O 3} , LiCO 3 / alkali metal such as SiO ₂ A mixture such as a salt or a support (for example, a support in which a solid base is supported on silica, coke, or the like) can be used. Also, a mineral such as dolomite that becomes a mixture of MgO and CaO when heated can be suitably used.
These ammonia temperature increase and desorption temperatures are 50 to 250 ° C for alumina, 30 to 200 ° C for silica gel, 200 to 600 ° C for zeolite, and 0 to 100 ° C for activated carbon. The FCC catalyst poisoned with Na is 30 to 200 ° C., the silicon oxide supporting magnesium oxide is 0 to 60 ° C., and the activated carbon supporting magnesium oxide is 0 to 70 ° C. Those with a temperature rise and desorption temperature higher than 400 ° C are very strong acid catalysts, and the product easily reduces the molecular weight of the alkyl group in fats and oils by breaking the carbon-carbon bond, and attacks the carbon-carbon double bond. As a result, the production of coke increases because more aromatics are produced. For this reason, the yield of the product oil is lowered, and further, the increased coke accelerates the decrease in the activity of the catalyst, the decarboxylation ability is lowered, the production of carboxylic acid is increased, and the quality of the product oil is lowered. When the one having a temperature rise and desorption temperature higher than 400 ° C. is used, since there are many aromatics in the produced oil, the cetane number is low and the quality is low and the quality is low, so it is unsuitable for actual use as a diesel fuel. In addition, when using a catalyst with a temperature rising / leaving temperature of ammonia of 100 ° C. or less, such as activated carbon and activated coke, a mixture of fats and oils and mineral oil can be used as a raw material. This is because catalysts such as activated carbon and activated coke hardly reduce the molecular weight of mineral oil. Mineral oil includes atmospheric residual oil obtained by distilling crude oil, vacuum gas oil obtained by further distillation of atmospheric residue under reduced pressure, vacuum residue, hydrotreated oil, or pyrolysis oil, and Of the mixture. Moreover, the hydrocarbon produced | generated by decarboxylation decomposition of fats and oils can also be used. These mineral oils can function as an extractant for the oils and fats remaining in the residue and can further increase efficiency.

The acid point poisoning is 50% or more, more preferably 90% or more. If the acid point poisoning is less than 50%, the production of coke and light gas increases, which is not preferable.
As the acid sites are poisoned, the temperature rise and desorption temperature of ammonia decreases. The ammonia temperature rise and desorption temperature is preferably less than 400 ° C, more preferably less than 200 ° C, and even more preferably less than 100 ° C due to poisoning. When the temperature is 400 ° C. or higher, the product tends to have a low molecular weight, and a large amount of aromatics is formed to become coke, and the catalytic activity tends to decrease. When the temperature is lower than 100 ° C., the carbon-carbon bond is hardly broken, so that it can be used for raw materials in which mineral oil or the like is mixed.

The FCC catalyst is a synthetic zeolitic solid acid catalyst granulated into 40 to 80 μm particles used in a fluid catalytic cracking process of petroleum. Various methods can be used for poisoning the FCC catalyst with an alkali metal. For example, a method in which the FCC catalyst is poisoned by immersing the FCC catalyst in an aqueous alkali metal salt solution can be used.
Moreover, the FCC waste catalyst currently processed as industrial waste can also be used as a FCC catalyst. The FCC waste catalyst is discharged from the fluid catalytic cracking process of petroleum. In the fluid catalytic cracking process of petroleum, coke accumulates on the catalyst surface and the catalytic activity gradually decreases. Therefore, although the fluid catalytic cracking process of petroleum has a step of regenerating the catalyst by heating and incinerating the coke, it has a step of adding a new catalyst and a step of extracting the old catalyst in order to keep the catalyst activity constant. This extracted old catalyst is an FCC waste catalyst, and many are treated as industrial waste. The FCC waste catalyst still has sufficient catalytic activity and can be obtained at a very low cost. When coke accumulates on the FCC waste catalyst surface and the catalyst function is lowered, the catalyst is heated in an oxygen atmosphere to incinerate the coke on the catalyst surface and regenerate the catalyst.

  When the heating temperature of the oil and fat decarboxylation decomposition catalyst is lower than 350 ° C., the progress of the decarbonation decomposition reaction is slowed, and the oil and fat is polymerized and solidified, and the hydrocarbon productivity tends to decrease. Moreover, when it becomes higher than 475 degreeC, the production | generation amount of the light gas and coke of 4 or less carbon atoms will increase, and the production | generation amount of the product which has a C8-C24 olefin and paraffin as a main component will be seen. Therefore, neither is preferable.

As a reaction apparatus for producing biodiesel fuel, for example, an apparatus equipped with a reaction vessel in which an oil decarboxylation catalyst is accommodated and a heating device for heating the oil decarboxylation decomposition catalyst in the reaction vessel is used. As the reaction vessel, a fixed bed method, a fluidized bed method, a rotary kiln method, a stirring method, or the like can be used. Of these, the stirring method is preferable. If the reaction conditions deteriorate during operation, decomposition products (aromatic compounds, etc.) such as fat and oil are polymerized and adhered to the surface of the fat decarboxylation and decomposition catalyst, and a plurality of fat and oil decarboxylation decomposition catalysts are bonded by the polymer. This is because the agglomeration in the reaction vessel may result in the inability to operate, but the agglomeration can be prevented mechanically by stirring to prevent agglomeration.
In the decarbonation process, when the fat and oil decarbonization catalyst is heated and the catalyst reaches the reaction temperature, the raw material and fat are introduced into the reaction vessel by spraying, spraying, dripping, spraying, etc., and contacted with the fat and decarbonization catalyst. Let Processing can be performed continuously or batchwise. Oils and fats are decomposed in contact with a heated oil and fat decarboxylation decomposition catalyst, and have a vapor pressure as a combustible gas. By introducing an inert gas such as nitrogen gas or helium gas or a flow gas such as water vapor continuously or intermittently, the generated combustible gas can be discharged out of the system. The discharged combustible gas is cooled to become biodiesel fuel oil. By using water vapor as a flow gas, a water-soluble component can be dissolved in water vapor to obtain a cleaning effect of combustible gas. When a catalyst such as CaO is used, a decrease in the activity of the catalyst can be prevented as described later.
The deactivated fat decarboxylation catalyst can also be regenerated as needed in the reaction vessel or after being extracted from the reaction vessel.

As an example of a reaction of a fat or oil in contact with the oil and fat decarboxylation decomposition catalyst, MgO (catalyst) is combined with CO ₂ fat decomposing oil and fat, and magnesium carbonate. Since magnesium carbonate decomposes at 350 to 450 ° C. and decarboxylation occurs, MgO after decarboxylation repeatedly contributes to the decomposition of fats and oils.
In addition, CaO (catalyst) combines with CO ₂ of fats and oils in the presence of moisture to decompose the fats and oils to become calcium hydrogen carbonate. Since calcium carbonate is decomposed and decarboxylated at around 300 ° C., CaO after decarboxylation repeatedly contributes to the decomposition of fats and oils.

  The pressure in the reaction vessel is preferably maintained at atmospheric pressure or positive pressure. Combustible gases such as light oil and kerosene are generated by decarboxylation and decomposition of fats and oils, so if the pressure is negative, air may be introduced into the reaction vessel, and the generated combustible gas may ignite and explode. Because.

  In the decarbonation and decomposition step, the liquid space velocity indicating the input amount (volume) per hour with respect to the fat and oil decarboxylation / decomposition catalyst (volume) is 0.05 / h to 2.0 / h, preferably 0.3. / H to 1.0 / h is preferably used. If the liquid space velocity is less than 0.05 / h, the treatment efficiency is low, and the product oil becomes light gas due to secondary decomposition, and the yield of lamp / light oil decreases, which is not preferable. On the other hand, if it exceeds 2.0 / h, the contact time between the catalyst and the oil and fat is shortened and the oil decomposition rate is lowered, which is not preferable.

Invention of Claim 2 of this invention is a manufacturing method of the biodiesel fuel of Claim 1, Comprising: Either one or both of the said fats and oils decarboxylation decomposition catalyst and the said fats and oils contacts and desorbs. It has the structure heated to 350 to 475 degreeC before performing a carbonic acid decomposition reaction.
With this configuration, in addition to the operation obtained in the first aspect, the following operation can be obtained.
(1) Either one or both of the heated fat decarbonation catalyst and / or the heated fat serves as a heat medium, and the temperature of the portion in contact with the fat on the surface of the fat decarbonization catalyst increases, so that the fat decarbonization catalyst Due to the action, the reaction of cleaving the ester bond portion of glycerin proceeds smoothly.

  Here, it is preferable to heat both the fat decarbonation catalyst and the fat at the start of operation because the temperature in the reaction vessel is kept uniform and the reaction proceeds smoothly. After the reaction is stabilized, energy consumption can be reduced by heating one side.

Invention of Claim 3 of this invention is a manufacturing method of the biodiesel fuel of Claim 1 or 2, Comprising: It has the structure by which an oil extraction raw material is used instead of the said fats and oils.
With this configuration, in addition to the operation obtained in the first or second aspect, the following operation can be obtained.
(1) When the raw material for oil extraction comes into contact with the fat and oil decarboxylation and decomposition catalyst at 350 ° C. to 475 ° C., cellulose such as shells in the raw material for oil extraction is carbonized, and the oil and fat component of the raw material for oil extraction elutes and the oil and fat decarboxylation and decomposition catalyst The ester bond portion of the oil / fat component is cleaved by contact with the gas, and de-CO ₂ or de-CO shown in (Chemical Formula 1) occurs, so that cracked gas (hydrocarbon) serving as biodiesel fuel can be obtained.
(2) Since the raw material for oil extraction generates water vapor when heated and decomposed, it is suitable when using an oil decarboxylation and decomposition catalyst that functions well in the presence of moisture, such as CaO.

Here, the raw materials for oil extraction include oil palm pulp and seeds, coconut endosperm, rapeseed, olive fruits, seeds such as sesame seeds and castor sesame seeds, and berries and seeds of plants before oil extraction, such as seeds of oilseed burdock (Yatrofa) and kohjiju Etc. can be used. In addition, certain types of algae are known to store oils and fats in cells, and the algae obtained by dehydrating and concentrating the algae can also be used. It is preferable to use the raw material for oil extraction after drying. This is to remove moisture and increase heating efficiency. In addition, in order to increase the decomposition efficiency of the fat and oil decarboxylation decomposition catalyst, it is preferable to use a material that has a large surface area by pulverization or crushing. An oil raw material after being oiled by pressing or the like can also be used. It is known that many oils and fats still remain after oil extraction.
In addition, since cellulose, such as a shell of the raw material for oil extraction, is carbonized and remains in the reaction vessel, the remaining carbide may be extracted from the reaction vessel as necessary.

As a mixture of fats and oils or a raw material for extraction and mineral oil, a raw material for extraction after thermally extracting with a mineral oil such as hexane can be used. It is known that many oils and fats still remain after oil extraction.
In addition, alkaline oil candy, fish bream, and livestock shark (internal organs) discharged from the oil refining process are rich in oil and fat and can be used as raw materials.

The fat and oil decarboxylation catalyst can be regenerated by heating to 500 ° C. to 600 ° C. and exposing to an atmosphere containing oxygen. The coke adhering to the surface of the fat decarboxylation catalyst is burned out and regenerated simply by aeration while heating the fat decarbonation decomposition catalyst whose activity has been lowered due to adhesion of coke, etc., and is excellent in resource saving.
The reaction vessel can be used as it is for the regeneration of the fat and oil decarboxylation catalyst. The heating temperature for regeneration is preferably 500 ° C to 600 ° C. If it is less than 500 ° C., regeneration takes time and it is not practical. If the temperature exceeds 600 ° C., the structure of the ceramics may be changed and the fat decarboxylation / decomposition catalyst may be modified and the activity may be lowered.

  The organic acid contained in the raw oil and fat or the raw material for oil extraction has a problem that it becomes a catalyst poison and lowers the activity of the catalyst, but the organic acid is easily decomposed into hydrocarbons and carbon dioxide by the fat and oil decarboxylation decomposition catalyst. The problem that the activity of the catalyst decreases is unlikely to occur. For this reason, it is not necessary to use a large amount of catalyst in anticipation of a decrease in activity, and there is no increase in running cost or productivity due to incidental work such as treatment or reactivation of the used catalyst. .

Invention of Claim 4 of this invention is the manufacturing method of the biodiesel fuel of Claim 3, Comprising: The said oil-fat decarboxylation decomposition | disassembly catalyst is the carbide | carbonized_material derived from the said extraction raw material which remained after manufacture of biodiesel fuel. It has a configuration containing carbon that has been activated by heating in an oxygen atmosphere.
With this configuration, in addition to the operation obtained in the third aspect, the following operation can be obtained.
(1) By heating in an oxygen atmosphere, the coke accumulated on the surface of the fat and oil decarboxylation decomposition catalyst in the reaction vessel is burned, and the fat and oil decarboxylation decomposition catalyst is regenerated.
(2) Cellulose such as shells of raw material for oil extraction is carbonized and remains in the reaction vessel. Therefore, it is necessary to extract and discard it appropriately. However, since it is changed to activated carbon, it can be effectively used as a catalyst and must be discarded. Disappear.
(3) Even in areas where industrialization and transportation network development are not progressing, it is possible to easily procure an oil decarboxylation catalyst.

  Here, the reaction vessel can be used as it is for the activation of the carbide derived from the oil extraction raw material. The heating temperature for regeneration is preferably 500 ° C to 600 ° C. Below 500 ° C., it takes time to regenerate the catalyst and activate carbon, which is not practical. If the temperature exceeds 600 ° C., the structure of the ceramics may be changed and the fat decarboxylation / decomposition catalyst may be modified and the activity may be lowered.

The method for producing biodiesel fuel according to claim 5 of the present invention is the method for producing biodiesel fuel according to any one of claims 1 to 4, wherein the molar ratio in the decarboxylation decomposition reaction is 1 / 10 to 10/1 (H ₂ O / oil / fat) water vapor coexists.
With this configuration, in addition to the actions obtained in claims 1 to 4, the following actions are obtained.
(1) Since steam promotes hydrolysis of ester bonds, the decomposition efficiency of fats and oils is improved.

Here, in the decarboxylation decomposition reaction of fats and oils in the present invention, water is always generated as a side reaction, so that the reaction proceeds without adding water vapor. Therefore, when the amount of water vapor is 1/10 or less, the promoting effect is not clear.
If the water content in the raw material exceeds 10/1 in the molar ratio, the water content in the produced oil increases and the quality deteriorates. Therefore, it is necessary to remove (dry) the water from the raw material stage or from the produced oil. This corresponds to the case of using raw material for oil extraction or fish cake. This is the reason why there are many water components as shown in Table 3 in the case of soybean of Example 6 described later. However, if a process of removing the water component from the produced oil is added to the subsequent stage, no particular problem occurs.

A biodiesel fuel production apparatus according to a sixth aspect of the present invention is a biodiesel fuel production apparatus used in the biodiesel fuel production method according to any one of the first to fifth aspects, wherein the oil or fat is used. A first reaction vessel having a decarboxylation decomposition catalyst therein, a heating unit that heats the fat decarboxylation decomposition catalyst or the fat or oil extraction raw material, and an input for charging the oil extraction raw material or the oil into the first reaction vessel And a first gas deriving unit for deriving the generated gas mixture from the first reaction vessel.
With this configuration, the following effects can be obtained.
(1) Since the decarboxylation decomposition reaction proceeds at the same time that the oil-decompressing raw material and oil are heated by the heated oil decarboxylation decomposition catalyst, there is little generation of coke, etc., heat efficiency is good, and high yield fuel production can be performed. .
(2) Continuous operation can be performed by heating and supplying the raw material fat or oiled raw material, and the structure of the reaction vessel becomes simple and easy to manage.

Here, the first reaction vessel can be provided with a stirring device. In particular, when using an oil-extracted raw material, it is preferable to provide a stirring device so that the catalyst in the reaction vessel and the oil-extracted raw material can sufficiently come into contact with each other.
In the decarbonation process, when the fat and oil decarbonization catalyst is heated and the catalyst reaches the reaction temperature, the raw material and fat are put into the reaction vessel by spraying, spraying, dripping, spraying, etc., and contacted with the fat and decarboxylation catalyst. Let The fats and oil extraction raw materials can be charged continuously or batchwise. Oils and fats are decomposed in contact with a heated oil and fat decarboxylation decomposition catalyst, and have a vapor pressure as a combustible gas. By introducing an inert gas such as nitrogen gas or helium gas or a flow gas such as water vapor continuously or intermittently, the generated combustible gas can be discharged out of the system. The discharged combustible gas is cooled to become biodiesel fuel oil.

The amount of the oil and fat decarboxylation catalyst is preferably 5% by volume or more, more preferably 20% by volume or more. If the amount of the fat decarboxylation catalyst is less than 5% by volume, the ratio of fats and oils that can come into contact with the catalyst is reduced, and the ratio of fats and oils that are thermally decomposed by heating is increased. Absent. In addition, when the oil extraction raw material is added, if it exceeds 60% by volume, it is not preferable because the raw material to be heated without increasing contact with the catalyst increases when the raw material having a large volume such as the oil extraction raw material is supplied and the discharge frequency of the residue increases. .
More preferably, the amount of the oil / fatty acid decarboxylation / decomposition catalyst is 50% by volume or less when the raw material is input.

  When decomposing by heating oil extraction raw materials and fats and oils, when they reach the reaction temperature, the oil extraction raw materials and oils and fats are put into the reaction vessel by spraying, spraying, dripping, spraying, etc., and brought into contact with the oil decarboxylation decomposition catalyst . Since the catalyst is heated by heated oil or the like, continuous treatment can be performed. In the case of processing in a batch system, it is preferable to heat the oil extraction raw material and fats or oils in consideration of the amount of heat necessary for heating the catalyst, or to preheat the catalyst.

The invention according to claim 7 of the present invention is the biodiesel fuel production apparatus according to claim 6, wherein the second reaction is connected to the first gas lead-out part and filled with the fat decarboxylation catalyst. A container, a gas introduction part for introducing the product gas mixture of the first reaction vessel into the second reaction vessel, and a gas mixture decarboxylated and decomposed by the oil decarboxylation catalyst of the second reaction vessel The second gas deriving unit is provided.
With this configuration, in addition to the operation obtained in the sixth aspect, the following operation can be obtained.
(1) A second reaction vessel for introducing the gas mixture produced from the first reaction vessel is filled with the oil decarboxylation catalyst, and the organic acid in the gas produced from the first reaction vessel is second. Since it is decarboxylated and decomposed by the fat and oil decarboxylation catalyst in the reaction vessel, the acid in the product is further reduced and the quality is improved.
(2) Even if the organic acid generated in the first reaction vessel or the organic acid contained in the raw oil / fat is led out together with the gas generated in the first reactor without touching the catalyst through the upper part of the first reactor. Since the carbonic acid is decomposed by the second reaction vessel, the organic acid in the product is reduced and the high quality is maintained.
(3) When the apparatus is operated for a long time and the function of the catalyst is lowered, the reaction becomes incomplete in the first reaction vessel, and the organic acid that could not be reacted is mixed in the generated gas mixture, Product quality is reduced. Since this deterioration in quality is suppressed, the device can be operated for a longer time, and the operating efficiency is increased.

  Here, the fat decarboxylation catalyst used in the first reaction vessel and the second reaction vessel is not necessarily the same. Further, since the gas mixture led out from the first reaction vessel and introduced into the second reaction vessel is at a high temperature, it is not always necessary to warm the fat decarboxylation decomposition catalyst in the second reaction vessel. However, when the temperature of the fat and oil decarboxylation decomposition catalyst in the second reaction vessel during operation is lower than 350 ° C., a heating device for heating the fat and oil decarboxylation decomposition catalyst in the second reaction vessel is required. As the second reaction vessel, a single tube or a packed bed reactor such as a radial flow type is used.

The invention according to claim 8 of the present invention is used in the biodiesel fuel production method according to any one of claims 1 to 5 or the biodiesel fuel production apparatus according to claim 6 or 7. An oil and fat decarboxylation decomposition catalyst, wherein at least one of silica, an FCC waste catalyst whose acid sites are poisoned by one or more of alkali metal and alkaline earth metal, and a mixture of these composites is magnesium. In other words, it has a configuration including a material coated with a weak alkaline compound consisting of at least one of hydroxide, oxide, and carbonate.
With this configuration, the following effects can be obtained.
(1) FCC in which acid sites are poisoned by at least one of silica, alkali metal and alkaline earth metal coated with a weak alkaline compound consisting of one or more of magnesium hydroxide, oxide and carbonate Since the mixture of waste catalyst and their composites hardly reduces the molecular weight of mineral oil, the use of a mixture of oil and fat or compressed raw material and mineral oil as raw materials increases the extraction efficiency of the oil and fat and increases the yield of cracked oil. Can be raised.
(2) The acid point is poisoned by one or more of alkali metal and alkaline earth metal and the acid point is weakened, so that the cleavage of the double bond portion in the oil and fat is suppressed, and the decarboxylation decomposition is efficiently performed. Occur. Moreover, the production | generation of a fatty acid is also suppressed. Therefore, the production yield of fuel is increased.
(3) Generation of coke is suppressed, equipment maintenance is reduced, and catalyst deterioration is delayed.
(4) Since an FCC catalyst widely used in fluid catalytic cracking of petroleum can be used, it is easy to obtain a catalyst.

As described above, according to the method for producing biodiesel fuel of the present invention, the following advantageous effects can be obtained.
According to the invention of claim 1,
(1) Unlike the conventional FAME method, since no secondary raw material alcohol is required, the running cost can be greatly reduced, and impurities such as dienes and hydroxyl groups in the raw oil and fat hardly remain in the product. Since the amount of coke produced is small and impurities such as carboxylic acids (free fatty acids) are hardly produced as by-products, it is stable against air and has excellent storage stability with no blackening or off-flavor, and has a freezing point of around −20 ° C. It is possible to provide a method for producing a biodiesel fuel from which a biodiesel fuel excellent in fluidity can be obtained.
(2) Unlike conventional FAME methods, glycerin is not produced as a by-product, so it is not necessary to establish glycerin processing technology or processing man-hours, and to adsorb and remove impurities such as peroxide using an adsorbent. Production of biodiesel fuel that eliminates the need for a process and that does not cause problems such as reduced catalyst activity due to coke depositing on the surface of the catalyst and that the catalyst binds and agglomerates, enabling stable operation at a high yield. Can provide a method.
(3) Although free fatty acids are present in the raw material, impurities such as carboxylic acids (free fatty acids) are hardly produced as a by-product due to cleavage of the ester bond portion of glycerin such as fat and oil and the removal of CO _2. Even if free fatty acids are produced as by-products, they are easily decomposed into hydrocarbons and carbon dioxide gas, so that the problem that the activity of the catalyst is lowered due to the by-produced carboxylic acid (free fatty acids) is unlikely to occur. Because there is no need to use a large amount of catalyst at the same time, there is no increase in running cost or productivity due to incidental work such as treatment and reactivation of the used catalyst. An excellent method for producing biodiesel fuel can be provided.
(4) Pretreatment for removing free fatty acids from raw oils and fats is not necessary, and the reaction can be carried out under normal pressure, thus simplifying the biodiesel fuel production process and reactor, and improving productivity It is possible to provide a method for producing biodiesel fuel that is excellent and that can produce biodiesel fuel at a low cost and can construct a distributed energy supply system that supplies necessary energy at a necessary place.
(5) Since thermal decomposition is suppressed, the yield is improved, the concentration of fatty acid in the product is lowered, and a method for producing biodiesel fuel that can be used as a fuel with confidence can be provided.
(6) Since the catalyst maintains stable activity, it can be used repeatedly, and a method for producing a high-quality biodiesel fuel at a low cost can be provided.
(7) Since the acid point has been weakened, the cleavage of the double bond portion in the oil and fat is suppressed, and the decarboxylation decomposition occurs efficiently. Moreover, the production of organic acids can be suppressed. Therefore, an oil decarboxylation catalyst having a high production yield of fuel can be provided.
(8) The generation of coke is suppressed, the maintenance of the apparatus is reduced, and an oil and fat decarboxylation decomposition catalyst with a slow catalyst deterioration can be provided.
(9) Since a widely used FCC catalyst can be used with a simple operation, it is easy to implement. In addition, since the FCC catalyst can be easily regenerated even if the catalytic function is lowered, a large regenerator is not required. Moreover, since the processing method is established even if it processes without reproducing | regenerating, the fat-and-oil decarboxylation decomposition | disassembly catalyst which can carry out a facility operation safely can be provided.
(10) Since the FCC waste catalyst processed as waste can also be used, an oil decarboxylation catalyst that can be operated at a very low cost can be provided.
(11) Since silica hardly reduces the molecular weight of mineral oil, when a mixture of oil and fat or oiled raw material and mineral oil is used as a raw material, the mineral oil functions as an oil extractant, and a highly efficient method for producing biodiesel fuel. Can be provided.
(12) Silica coated with a weakly alkaline compound consisting of one or more of magnesium hydroxide, oxide, and carbonate hardly reduces the molecular weight of mineral oil, so a mixture of fats and oils and raw material and mineral oil When used as a raw material, the extraction efficiency of fats and oils is increased, and a method for producing biodiesel fuel with a high yield of cracked oil can be provided.

According to invention of Claim 2, in addition to the effect of Claim 1,
(1) Either the heated fat decarbonation catalyst or the heated fat becomes a heat medium, and the temperature of the part in contact with the fat on the surface of the fat decarbonization catalyst rises. Since the reaction of cleaving the ester bond portion of glycerin proceeds smoothly, it is possible to provide a method for producing biodiesel fuel that can reduce energy consumption for heating.
(2) By heating both the oil and fat decarboxylation catalyst and the oil and fat at the start of operation, it is possible to provide a method for producing biodiesel fuel in which the temperature in the reaction vessel is kept uniform and the reaction proceeds smoothly.

According to invention of Claim 3, in addition to the effect of Claim 1 or 2,
(1) When the raw material for oil extraction comes into contact with the fat and oil decarboxylation and decomposition catalyst at 350 ° C. to 475 ° C., cellulose such as shells in the raw material for oil extraction is carbonized, and the oil and fat component of the raw material for oil extraction elutes and the oil and fat decarboxylation and decomposition catalyst The ester bond portion of the oil and fat component is cleaved by contact with the oil, and the de-CO ₂ or de-CO shown in (Chemical Formula 1) occurs, and a cracked gas (hydrocarbon) that becomes a biodiesel fuel can be obtained. It is possible to provide a method for producing biodiesel fuel that can be used as a raw material simply by drying organic matter containing a large amount of oil and fat.
(2) Since the oil extraction raw material generates water vapor when heated and decomposed, it is suitable when using an oil decarboxylation and decomposition catalyst that functions well in the presence of moisture such as CaO. A method for producing biodiesel fuel with higher efficiency using raw materials can be provided.

According to invention of Claim 4, in addition to the effect of Claim 3,
(1) By heating in an oxygen atmosphere, coke accumulated on the surface of the fat and oil decarboxylation catalyst in the reaction vessel is burned and the fat and oil decarboxylation catalyst is regenerated. A manufacturing method can be provided.
(2) Cellulose such as shells of raw material for oil extraction is carbonized and remains in the reaction vessel. Therefore, it is necessary to extract and discard it appropriately. However, since it is changed to activated carbon, it can be effectively used as a catalyst and must be discarded. Therefore, a method for producing biodiesel fuel capable of continuous operation can be provided.
(3) Since an oil and fat decarboxylation catalyst that can be continuously operated can be procured even in an area where industrialization has not progressed, a method for producing a biodiesel fuel that can be easily introduced regardless of the area can be provided.

According to the invention of claim 5, in addition to the effects of claims 1 to 4,
(1) Since steam promotes hydrolysis of ester bonds, it is possible to provide a method for producing biodiesel fuel that improves the decomposition efficiency of fats and oils.

According to the invention of claim 6,
(1) Biodiesel fuel with low yield of coke, good thermal efficiency and good yield, because decarbonation and decomposition reactions proceed at the same time that the oil extraction raw materials and fats come into contact with the fat and oil decarboxylation cracking catalyst at 350 to 475 ° C. Manufacturing equipment can be provided.
(2) It is possible to provide a biodiesel fuel production apparatus that is easy to manage by being heated and charged with raw material fat or oiled raw material, being easily operated continuously, having good thermal efficiency.

According to invention of Claim 7, in addition to the effect of Claim 6,
(1) A second reaction vessel for introducing the gas mixture produced from the first reaction is filled with the oil / fatty acid decarboxylation catalyst, and the organic acid in the gas produced from the first reaction vessel is subjected to the second reaction. Since it is decarboxylated and decomposed by the fat and oil decarboxylation catalyst in the container, it is possible to provide an apparatus for producing biodiesel fuel in which the acid in the product is further reduced and the quality of the product oil is good.
(2) Even if the organic acid generated in the first reaction vessel or the organic acid contained in the raw oil / fat is led out together with the gas generated in the first reactor without touching the catalyst through the upper part of the first reactor. Since the carbon dioxide is decomposed by the second reactor, an organic acid in the product is reduced, and a biodiesel fuel production apparatus that maintains the high quality of the produced oil can be provided.
(3) When the apparatus is operated for a long time and the function of the catalyst decreases, the reaction becomes incomplete in the first reaction vessel, the organic acid in the generated gas mixture increases, and the quality of the product oil is increased. Go down. Since this deterioration in quality is suppressed, the apparatus can be operated for a longer time, and a biodiesel fuel production apparatus with high operating efficiency can be provided.

According to the invention described in claim 8,
(1) Silica coated with a weak alkaline compound consisting of any one or more of magnesium hydroxide, oxide and carbonate, non-acidic zeolite modified with alkali, and a mixture of these composites is a mineral oil Therefore, when a mixture of fats and oils or compressed raw materials and mineral oil is used as a raw material, the extraction efficiency of the fats and oils can be improved, and a fat and oil decarboxylation cracking catalyst with a high yield of cracked oil can be provided.
(2) Since the acid point is weakened, the cleavage of the double bond portion in the fat and oil is suppressed, and decarboxylation decomposition occurs efficiently. Moreover, the production of organic acids can be suppressed. Therefore, an oil decarboxylation catalyst having a high production yield of fuel can be provided.
(3) The generation of coke can be suppressed, the maintenance of the apparatus can be reduced, and the fat and oil decarboxylation cracking catalyst with a slow catalyst deterioration can be provided.
(4) Since a widely used FCC catalyst can be used with a simple operation, it is easy to implement. In addition, since the FCC catalyst can be easily regenerated even if the catalytic function is lowered, a large regenerator is not required. Moreover, since the processing method is established even if it processes without reproducing | regenerating, the fat-and-oil decarboxylation decomposition | disassembly catalyst which can carry out a facility operation safely can be provided.
(5) Since the FCC waste catalyst currently processed as a waste can also be utilized, the fat decarboxylation decomposition catalyst which becomes very cheap in operating cost can be provided.

Configuration diagram of the reactor according to Embodiment 1 Configuration diagram of reactor of embodiment 2 Configuration diagram of reactor of embodiment 3 The figure which shows carbon number distribution of the cracked oil obtained in Example 2 The figure which shows carbon number distribution of the cracked oil obtained in Example 7 The figure which shows carbon number distribution of the cracked oil obtained in Example 8 The figure which shows carbon number distribution of the cracked oil obtained in Example 9 The figure which shows carbon number distribution of the cracked oil obtained in Example 10

Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples.
(Embodiment 1)
First, the reactor used in Examples 1 to 7 and Examples 9 to 14 will be described.
FIG. 1 is a configuration diagram of the reactor according to the first embodiment.
In the figure, 1 is the reaction apparatus of Embodiment 1 used in the examples of the present invention, 2 is a reaction vessel, 3 is granular silica contained in the reaction vessel 2, activated carbon, solid base, Fat decarbonation cracking catalyst such as poisoned FCC catalyst, 4 is a heater for heating the catalyst 3 accommodated in the reaction vessel 2 to 350 to 475 ° C., 5 is spraying, dripping and spraying the fat and oil extraction raw material to the reaction vessel 2 The raw material input unit 6 is supplied by, for example, a flow gas introduction unit 6 for introducing an inert gas such as nitrogen gas or a flow gas such as water vapor into the reaction vessel 2, 7 is a stirring device for stirring the catalyst 3, and 8 is the reaction vessel 2. A first outlet pipe for entraining the product generated in the flow gas to the outside of the reaction vessel 2 and 9 is connected to the first outlet tube 8 and has a boiling point of 0 ° C. to the temperature of the reaction vessel. A cracked oil reservoir for storing a cracked product (hereinafter referred to as cracked oil) of 0 is a discharge pipe whose one end is connected to the cracked oil reservoir 9, 11 is a cooling pipe which is disposed in the discharge pipe 10 and cools the discharge pipe 10 to 0 ° C. to liquefy cracked oil in the product, and 12 is a discharge pipe 10 is connected to the other end of the cooling trap device for storing a liquefied decomposition product (hereinafter referred to as light oil) having a boiling point of −80 to 0 ° C. It is a connected gas exhaust pipe.

(Embodiment 2)
Next, the reactor of Embodiment 2 used in Example 8 will be described.
FIG. 2 is a configuration diagram of the reactor according to the second embodiment.
In the figure, 21 is the reaction apparatus of the second embodiment. Portions common to those in FIG. 1 are denoted by the same reference numerals and description thereof is omitted. Reference numeral 22 denotes a heating unit that heats the raw oil and fat and the raw material for oil extraction. Reference numeral 23 denotes an auxiliary heating unit for heating when the temperature of the catalyst 3 is low, such as at the start of operation.

(Embodiment 3)
Next, the reactor of Embodiment 3 used in Example 15 will be described.
FIG. 3 is a block diagram of the reactor according to the third embodiment.
In the figure, reference numeral 31 denotes a reactor according to the third embodiment. Portions common to those in FIG. 1 are denoted by the same reference numerals and description thereof is omitted. Reference numeral 32 denotes a first reaction vessel according to Embodiment 3, which corresponds to the reaction vessel 2 of FIG. 33 is an oil and fat decarboxylation catalyst A such as granular silica contained in the first reaction vessel 32, and 8 is a product produced in the first reaction vessel 32 accompanied by a flow gas to the outside of the first reaction vessel 32. 1 is a first outlet pipe, 34 is a second reaction vessel, 35 is an oil decarboxylation cracking catalyst B such as granular silica, activated carbon, solid base, etc. accommodated in the second reaction vessel 34, Reference numeral 38 denotes a second outlet pipe for leading the gas decarboxylated and decomposed in the second reaction vessel 34.

Example 1
The oil and fat decarboxylation / decomposition catalyst (hereinafter abbreviated as catalyst) 3 is a catalyst silica (manufactured by Fuji Silysia Chemical Co., Ltd., trade name: Caractect Q-15, particle size 1.18 to 2.36 mm). 50 mL of the catalyst was accommodated in the reaction container 2 having an internal volume of 150 mL, and heated to 420 ° C. while being stirred by the stirring device 7 (50 rpm). The heating temperature of the catalyst 3 was measured by bringing a thermocouple (not shown) placed in the reaction vessel 2 into contact with the catalyst 3.
After confirming that the catalyst 3 had risen to the reaction temperature of 420 ° C., palm oil (oil and fat) was dropped from the raw material charging unit 5 into the reaction vessel 2 under atmospheric pressure and charged. The amount of oil and fat charged was 0.25 mL / min, and the amount of flow gas (nitrogen gas) introduced from the flow gas inlet 6 was 50 mL / min.
A product was obtained by adding a total of 75 g of fats and oils. Component analysis of the cracked oil stored in the cracked oil storage unit 9 and the gas substances (carbon monoxide, carbon dioxide, and light hydrocarbon gas) discharged from the gas discharge pipe 13 was performed. Analysis of cracked oil was performed using GC-MS. Among gas substances, analysis of carbon monoxide and carbon dioxide was performed using GC-TCD, and analysis of light hydrocarbon gas was performed using GC-FID. . Moreover, the catalyst after experiment was analyzed by TG-DTA.

(Example 2)
The same procedure as in Example 1 was performed except that a catalyst in which MgO was supported on the catalyst silica used in Example 1 was used and the reaction temperature was 410 ° C.
The catalyst in which MgO is supported on silica is magnesium nitrate (Mg (NO ₃ ) ₂ .6H ₂ O) in an amount corresponding to 10% by mass as metal magnesium with respect to the catalyst silica used in Example 1. The aqueous solution was impregnated in silica by the Incipient Wetness method, dried at 120 ° C. after the impregnation, and then calcined in the air at 500 ° C. for 3 hours.

(Example 3)
The same procedure as in Example 1 was performed except that active coke (manufactured by Mitsui Mining Co., Ltd., particle size after crushing: 1.18 to 2.36 mm) was used as the fat and carbonic acid decomposition catalyst, and the reaction temperature was 400 ° C.

Example 4
The same procedure as in Example 1 was performed except that a catalyst in which MgO was supported on the active coke used in Example 3 was used and the reaction temperature was 400 ° C.
The catalyst in which MgO was supported on active coke was magnesium nitrate (Mg (NO ₃ ) ₂ .6H ₂ O) in an amount corresponding to 10% by mass as metal magnesium with respect to the active coke used in Example 3. The aqueous solution was impregnated into activated coke by the Incipient Wetness method, dried at 120 ° C. after impregnation, and then calcined at 350 ° C. for 3 hours in a nitrogen atmosphere.

(Comparative Example 1)
The same procedure as in Example 1 was conducted, except that an FCC waste catalyst was used as the catalyst and the reaction temperature was 420 ° C.
The FCC waste catalyst is obtained by regenerating a solid zeolite catalyst based on a synthetic zeolite granulated into 40 to 80 μm particles used in a fluid catalytic cracking (FCC) process of petroleum.

The analysis results of the products in the above examples and comparative examples will be described.
Table 1 shows the amount of product and the yield of cracked oil in Examples 1 to 4 and Comparative Example 1.

From Table 1, it was found that the cracked oil yields of Examples 1 to 4 were all 50% or more, and Comparative Example 1 was 46%. The residue was less in Examples 1 to 4 than in Comparative Example 1. Therefore, this residue is examined.
From the TG-DTA analysis results of the catalyst after the experiment, about 9% of coke remained in the catalysts of Examples 1 to 4, but about 30% of coke remained in the catalyst of Comparative Example 1 (FCC waste catalyst). It was found that it remained. Further, from the analysis result of the cracked oil by GC-MS, the cracked oil of Comparative Example 1 contains about 50% paraffin, about 20% olefin, and about 20% aromatic compound. Examples 1-4 It was found that about 50 to 60% paraffin and about 30 to 40% olefin were present in the cracked oil, but there were almost no aromatic compounds. From this result, it was surmised that the residue was mainly coke, and the coke was a polymer of an olefin-derived aromatic compound produced by the acid point of the catalyst (FCC waste catalyst). In Examples 1-4, since neutral silica or a solid base is used as a catalyst, it is presumed that almost no aromatic compound was produced, and therefore, the production of coke was small and the amount of residue produced was reduced. It was.

  In Comparative Example 1, a small amount of alcohol and fatty acid were detected as oxygen-containing substances in the cracked oil, but in Examples 1 to 4, they were not detected, and ketones were mainly produced. The cracked oil of Comparative Example 1 had a strange odor and turned black so that it could be visually confirmed when left for about a week. However, the cracked oils of Examples 1 to 4 did not turn black or have a bad odor and were stored. It was found to be excellent in stability. This cause was presumed to be the influence of impurities such as carboxylic acid (fatty acid) contained in the cracked oil of Comparative Example 1.

FIG. 4 is a graph showing the carbon number distribution of the cracked oil obtained in Example 2. On the other hand, the fatty acid composition of the fats and oils (palm oil) used in the experiment is as follows: lauric acid (C12) 0.2%, myristic acid (C14) 1.1%, palmitic acid (C16) 44.0%, stearic acid (C18) ) 4.5%, oleic acid (C18: 1) 39.2%, linoleic acid (C18: 2) 10.1%, linolenic acid (C18: 3) 0.4%. From FIG. 4, it was found that in Example 2, paraffins or olefins having a carbon number corresponding to the fatty acids contained in the fats and oils were mainly generated. The other examples had the same tendency.
It was -12.5 degreeC when the pour point of the obtained cracked oil was measured based on JISK2269 (The pour point of crude oil and a petroleum product, and a petroleum product cloud point test method). Since the pour point of commercially available general light oil is -7 ° C, it was found that a cracked oil having a pour point as low as that of general light oil can be produced.
Table 2 shows the amount of carbon monoxide and carbon dioxide generated in Examples 1 to 4 and Comparative Example 1.
When the amount of carbon dioxide was compared, it turned out that it is increasing in order of the comparative example 1, Example 1, and Examples 2-4. Since the catalyst of Comparative Example 1 is a solid acid, the catalyst of Example 1 is silica (neutral), and the catalysts of Examples 2 to 4 are solid bases, the silica or solid base is catalyzed as in Examples 1 to 4. As a result, it was confirmed that CO ₂ can be selectively recovered.
From the results of Table 2 and FIG. 4, the decomposition mechanism of fats and oils is inferred as follows. Glycerin is removed from the oil contacted with the heated oil decarboxylation decomposition catalyst, and fatty acid is produced. In the produced fatty acid, the carboxyl group portion is removed as CO ₂ and the remaining carbon chain is recovered as cracked oil. The glycerin group is recovered as a light hydrocarbon gas such as propane.

By the above examples, since the amount of coke produced is small and impurities such as carboxylic acid (free fatty acid) are hardly produced as by-products, it is stable against air etc. It was clarified that a biodiesel fuel excellent in low-point fluidity can be obtained.
In Example 3, similar results were obtained when activated carbon was used instead of the activated coke as the catalyst.

(Example 5)
Using a catalyst in which MgO is supported on silica for catalyst (same catalyst as in Example 2), waste edible oil (75 g of soybean oil and rapeseed oil) actually used for one week in a university cafeteria is reacted under atmospheric pressure. The procedure was the same as in Example 1 except that it was dropped into the container (0.25 mL / min) and He gas (50 mL / min) was used as the flow gas.

(Example 6)
An experiment was conducted in which cracked oil was produced from the raw material for oil extraction, using commercially available soybeans (dried soybeans, produced in Hokkaido) as the raw material for oil extraction. Soybeans were crushed to approximately half the size to facilitate degradation. Using a catalyst in which MgO is supported on catalyst silica (the same catalyst as in Example 2), the reaction temperature is set to 410 ° C., and soybean crushed material (500 g) is put in a reaction vessel under atmospheric pressure little by little with a microfeeder. The procedure was the same as Example 1 except for the addition.

(Example 7)
Using rice bran discharged from a rice mill as a raw material fat, an experiment was conducted to produce cracked oil from the raw material. A catalyst in which MgO is supported on silica for catalyst (the same catalyst as in Example 2), the reaction temperature was set to 410 ° C., and rice bran (500 g) was added little by little with a microfeeder in a reaction vessel under atmospheric pressure. Was the same as in Example 1.

(Example 8)
An experiment was conducted to produce cracked oil using the reaction apparatus of Embodiment 2 using Jatropha oil, which has a large amount of unsaturated fatty acids as raw material fat and oil, and had a low recovery rate of cracked oil in the conventional method as raw material fat.
As the fat and oil decarboxylation / decomposition catalyst 3, the same catalyst in which MgO was supported on the same silica for catalyst as in Example 2 was used. 50 mL of this catalyst was accommodated in a reaction vessel 2 having an internal volume of 150 mL. The raw material fat was heated to 450 ° C. by the heating unit 22. The heating temperature of the raw material fat was measured by bringing a thermocouple (not shown) placed in the heating unit 22 into contact with the raw material fat.
After confirming that the raw material fat increased to 450 ° C. of the reaction temperature, Jatropha oil (fat) was dropped from the raw material charging unit 5 into the reaction vessel 2 under atmospheric pressure. The amount of oil and fat charged was 1.0 mL / min, and the amount of flow gas (nitrogen gas) introduced from the flow gas inlet 6 was 50 mL / min.
A product was obtained by adding a total of 75 g of fats and oils.

Example 9
An experiment was conducted to produce cracked oil from animal fats. Example 4 was the same as Example 4 except that pork fat (500 g) discharged from the meat processing plant as raw oil was heated to 80 ° C. and used in a liquid state.

(Example 10)
Example 4 was the same as Example 4 except that beef fat (500 g) discharged from a meat processing plant as a raw oil was heated to 80 ° C. and used in a liquid state.

Table 3 shows the amount of product and the yield of cracked oil in Example 5, Example 6, and Example 8.
In Example 6, oily components, aqueous components, precipitates, and suspended matters were mixed in the cracked oil. It is considered that the raw material for oil extraction contains abundant components other than fats and oils. Therefore, the cracked oil yield of Example 6 was converted from the ratio of the oily component to the input amount, unlike Examples 1 to 5, in order to exclude the influence of precipitates and the like. In Example 6, the gas substance was not analyzed. This is because the influence of components other than fats and oils is great.
In the case of using a raw material for oil extraction, when the raw material has a large amount of water, the aqueous content increases in the cracked oil produced as in Example 6. Therefore, in order to use it as a fuel, the water is removed from the raw material or from the cracked oil. A process of removing is necessary.

In Table 3, as shown in Example 5, it was confirmed that cracked oil was obtained from waste edible oil in a yield of 60% or more. This is a result almost the same as Examples 1-4 which used palm oil as raw material fats and oils. Although it is considered that waste cooking oil has a higher degree of oxidation than palm oil, it was revealed that cracked oil was obtained in a high yield according to this example.
Moreover, as shown in Example 6, it was confirmed that an oil component was obtained with a yield of 5.7% from the raw material for oil extraction (soybean). Since it is said that the content of fats and oils in domestic soybeans is about 10 wt%, the oil component yield of 5.7 wt% can be said to be a considerably high yield.

  FIG. 5 shows the carbon number distribution of cracked oil obtained from rice bran in Example 7. Production of hydrocarbons with a wide range of carbon numbers from C5 to C34 was observed. In particular, it contained a large amount of C10-C20 lamps and light oil. The cracked oil contained about 20% of C6-C13 aromatic hydrocarbons. Rice bran is rich in lipase and free fatty acids, but has an oxidation degree of 0.35 mg KOH / g and an oxidation stability of 24 h or more, and can be used as a biodiesel fuel.

Table 3 shows the results obtained from Jatropha oil in Example 8. Jatropha oil is unsaturated with palmitic acid (C16) 14.9%, stearic acid (C18) 6.9%, oleic acid (C18: 1) 41.8%, linoleic acid (C18: 2) 34.8% Although the yield of the pyrolysis method was low due to the high fatty acid ratio, the method of the present invention showed a high cracked oil recovery rate of 63.1%. FIG. 6 shows the carbon number distribution of hydrocarbons in the cracked oil obtained. It was shown that the number of carbons is distributed over a wide range but the double bonds are conserved.
Further, Jatropha oil has a high phosphoric acid content, and when it is converted into fuel by the conventional method, it remains in the fuel oil and damages the engine and the like. When the phosphoric acid concentration of the cracked oil of Example 8 and the Jatropha oil used as the raw material fat was measured by IPC, it was about 10 mg / L for the raw fat and oil, and 0.9 mg / L for the cracked oil. It was shown that the phosphoric acid in the raw material fats and oils does not migrate to the cracked oil, and a cracked oil with a low phosphoric acid content can be obtained.

  The carbon number distribution of hydrocarbons in cracked oil obtained from lard in Example 9 is shown in FIG. 7, and the carbon number distribution of hydrocarbons in cracked oil obtained from beef tallow in Example 10 is shown in FIG. Hydrocarbons having a wide range of carbon numbers from C5 to C34 from beef tallow and C5 to C31 from beef tallow were produced. Both the kerosene and light oil components in the cracked oil were approximately 65%.

  From the above examples, it was revealed that oil components can be easily collected from waste edible oil, raw material for extraction, and animal fats and oils. The biodiesel fuel production method of the present invention is extremely useful because it does not require alcohol (a secondary raw material) and does not by-produce glycerin.

(Example 11)
The same procedure as in Comparative Example 1 was performed except that a catalyst obtained by poisoning the FCC waste catalyst used in Comparative Example 1 with NaCl was used.
The catalyst obtained by poisoning the FCC waste catalyst with NaCl was prepared by adding 1.0 L of 50 g / L NaCl aqueous solution to 50 g FCC waste catalyst and treating at 50 ° C. ± 5 ° C. for 1 hour. The acid point of the catalyst obtained by this method was poisoned by approximately 90%. When the acid point of the catalyst obtained by this method was evaluated by the ammonia temperature rising desorption method, about 90% of the acid point was poisoned.

Example 12a
The same procedure as in Comparative Example 1 was performed except that silica, which is a solid acid catalyst, was used as the catalyst.

(Example 12b)
The same procedure as in Comparative Example 1 was performed except that a catalyst obtained by poisoning the silica used in Example 12a with an aqueous magnesium nitrate solution was used.
The catalyst in which silica was poisoned with an aqueous magnesium nitrate solution was prepared by adding 1.0 g of 50 g / L Mg (NO ₃ ) 2 aqueous solution to 50 g of silica and treating at 50 ° C. ± 5 ° C. for 1 hour. When the acid point of the catalyst obtained by this method was evaluated by the ammonia temperature rising desorption method, about 90% of the acid point was poisoned.

(Example 13)
The same procedure as in Comparative Example 1 was carried out except that the FCC waste catalyst used in Comparative Example 1 was poisoned with Mg and a catalyst carrying magnesium oxide was used.
The catalyst in which the FCC waste catalyst was poisoned with Mg and magnesium oxide was further supported was added at 50 ° C. ± 5 ° C. by adding 1.0 L of 50 g / L Mg (NO ₃ ) 2 aqueous solution to 50 g FCC waste catalyst. And processed for 1 hour. Here, the term “supported” refers to a state in which magnesium oxide is contained in the catalyst in excess of the acid point poisoning.

Table 4 shows the results when the acid sites are poisoned. The upper part of the table shows the amount of product and the yield of cracked oil in Comparative Example 1, Example 11, Example 12a, Example 12b and Example 13.
Alkaline poisoning of the solid acid catalyst increases the production of CO ₂ and increases the yield of cracked oil. Furthermore, by supporting magnesium oxide, the production of CO ₂ increases and the yield of cracked oil increases. The yield increases and the amount of residue decreases. The breakdown of the residue is shown at the bottom of Table 4. It is thought that the amount of coke formed as a by-product was significantly reduced compared with Comparative Examples 1 and 2 and the yield of cracked oil was increased because the cleavage of double bond parts in fats and oils was reduced by alkaline poisoning of the solid acid catalyst. It is done.

(Example 14)
Example 2 was repeated except that the reaction temperature was 350 ° C.

(Example 15)
Example 2 was repeated except that the reaction temperature was 475 ° C.
(Comparative Example 2)
Example 2 was repeated except that the reaction temperature was 300 ° C.
(Comparative Example 3)
Example 2 was repeated except that the reaction temperature was 550 ° C.

Table 5 is a table showing the influence on cracked oil yield at each temperature, and shows the amount of product and the yield of cracked oil in Comparative Example 2, Example 14, Example 2, Example 15 and Comparative Example 3. It is shown.
From this, it was shown that the temperature range of the reaction is preferably 350 ° C to 475 ° C. At 300 ° C. (Comparative Example 2), the reaction is slow and impractical. Moreover, it is considered that the residue amount increased due to the polymerization and solidification of fats and oils, and the productivity of hydrocarbons decreased. At 550 ° C. (Comparative Example 3), the yield of cracked oil is low, and the amount of residue is large. Therefore, it is considered that pyrolysis occurred and the amount of gas and coke produced increased.

(Comparative Example 4)
If the reaction is repeated many times, the activity of the catalyst gradually decreases. The same procedure as in Example 2 was performed, except that a catalyst with reduced activity was used. The carbon content of the catalyst with reduced activity was measured as a weight loss after heating at 800 ° C. for 1 hour in an air atmosphere and found to be 45% by weight.

(Example 16)
The catalyst was heated and held at 500 ° C. ± 20 ° C. for 6 hours while flowing a mixed gas of 50% air + 50% nitrogen gas at 200 ml / min into the reaction vessel containing the catalyst used in Comparative Example 4. Thereafter, the carbon content was measured in the same manner as in Comparative Example 4. During the regeneration, the stirring blade was rotated at 10 times / min and slowly stirred. Next, the same procedure as in Example 2 was performed except that the regenerated catalyst was used.

(Example 17)
The same operation as in Example 16 was performed except that the holding temperature at the time of regeneration was 550 ° C. ± 20 ° C.

(Example 18)
The same operation as in Example 16 was performed except that the holding temperature at the time of regeneration was 600 ° C. ± 20 ° C.
(Comparative Example 5)
The same procedure as in Example 16 was performed except that the heating and holding temperature of the catalyst during regeneration was 450 ° C. ± 20 ° C.
(Comparative Example 6)
The same procedure as in Example 12b was performed except that the heating and holding temperature of the catalyst during regeneration was 650 ° C. ± 20 ° C.

  Table 6 is a table showing the effects of catalyst regeneration and regeneration temperature, and shows the results of Example 2, Comparative Examples 4 to 6, and Examples 16 to 18. From this, it was shown that the catalyst can be regenerated by maintaining the temperature at 500 ° C. to 600 ° C. in an atmosphere containing oxygen. At 450 ° C. (Comparative Example 4), regeneration was slow, carbon remained, and activity was low. In addition, the activity decreased at 650 ° C., which was not preferable. The regenerated one (Examples 16-18) showed higher recovery of cracked oil than the new catalyst (Example 2). .

(Example 19)
The procedure was the same as Example 2 except that the liquid space velocity was 0.05 / h.

(Example 20)
The procedure was the same as Example 2 except that the liquid space velocity was 2.0 / h.
(Comparative Example 7)
The procedure was the same as Example 2 except that the liquid space velocity was 0.02 / h.
(Comparative Example 8)
The same as Example 2 except that the liquid space velocity was 4.0 / h.

Table 7 is a table showing the effect of liquid space velocity on cracked oil yield, showing the amount of product and cracked oil yield in Comparative Example 7, Example 19, Example 20, and Comparative Example 8. Is.
From this, it was shown that the range of liquid space velocity is preferably 0.05 / h to 2.0 / h. 0.02 / h (Comparative Example 7) is not preferable because the processing speed is low, the processing efficiency is low, and the product oil is gasified by secondary decomposition, resulting in a decrease in yield. In 4.0 / h (Comparative Example 8), the yield of cracked oil is low, and the amount of residue is large. Therefore, the contact time between the catalyst and the fat / oil is shortened, and the fat / oil decomposition rate is considered to be lowered.

(Example 21)
The same procedure as in Comparative Example 4 was performed except that the reactor according to Embodiment 3 was used. In the first reaction vessel 32 of the reactor C, silica carrying magnesium oxide was used as the fat and oil decarboxylation catalyst A33. In the second reaction vessel 34, an FCC waste catalyst poisoned with Na was used as an oil and fat decarboxylation catalyst B35.
The silica carrying magnesium oxide was prepared in the same manner as in Example 2.
The FCC waste catalyst poisoned with Na was prepared in the same manner as in Example 11.

Table 8 shows the results of Example 21 and Comparative Example 4. In Table 8, the oxidation, iodine value, and oxidation stability were measured according to the BDF standard draft of the Agency for Natural Resources and Energy.
The installation of the second reactor reduces the acid in the product.

  The present invention does not require alcohol (subsidiary raw material) from fats and oiled raw materials, does not by-produce glycerin, and impurities such as dienes and hydroxyl groups in the raw fats and oils hardly remain in the product, Since the amount of coke produced is small, the pour point of the produced oil is low, and impurities such as carboxylic acids (free fatty acids) are hardly produced as a by-product, so it is stable against air, etc. A method for producing biodiesel fuel can be provided. In addition, pretreatment and the like for removing free fatty acids from raw oils and fats are not necessary, and the reaction can be performed under normal pressure, so that the manufacturing process and the reaction apparatus can be simplified, and at the necessary place. It is possible to provide a biodiesel fuel production apparatus capable of constructing a distributed energy supply system that supplies necessary energy. Furthermore, it is difficult to cause a problem that the activity of the catalyst is reduced due to the free fatty acid produced as a by-product, so that the running cost increases or the productivity decreases due to incidental work such as treatment or reactivation of the used catalyst. The decarboxylation decomposition catalyst used for the manufacturing method of the biodiesel fuel which is excellent in production efficiency and productivity can be provided.

DESCRIPTION OF SYMBOLS 1 Reactor 2 of Embodiment 1 Reaction container 3 Fat decarbonation decomposition catalyst 4 Heater 5 Raw material input part 6 Flow gas introduction part 7 Stirrer 8 First outlet pipe 9 Decomposed oil storage part 10 Discharge pipe 11 Cooling pipe 12 Cooling trap Apparatus 13 Gas exhaust pipe 21 Reaction apparatus 22 of embodiment 2 Raw material oil heating section 23 Auxiliary heating section 31 Reaction apparatus 32 of embodiment 3 First reaction vessel 33 Oil decarboxylation decomposition catalyst A
34 Second reaction vessel 35 Fat and oil decarboxylation catalyst B
38 Second outlet tube

Claims (8)

At 350 ° C. to 475 ° C., the fat and oil decarboxylation decomposition catalyst and the fat contact with each other in the reaction vessel, and mainly the C8 to C24 hydrocarbons in the decarbonation decomposition reaction represented by (Chemical Formula 1) by the fat and oil decarboxylation decomposition catalyst. And the fat and oil decarboxylation decomposition catalyst is at least one of a mixture comprising silica, an FCC waste catalyst whose acid sites are poisoned by one or more of alkali metal and alkaline earth metal, and a mixture thereof. A method for producing biodiesel fuel, comprising a material coated with a weak alkaline compound consisting of one or more of magnesium hydroxide, oxide, and carbonate.
  2. One or both of the fat and oil decarboxylation catalyst and the fat and oil are heated to 350 ° C. to 475 ° C. before contacting and decarboxylating decomposition reaction. Of manufacturing biodiesel fuel.   3. The method for producing biodiesel fuel according to claim 1 or 2, wherein an oiled raw material is used in place of the fats and oils.   The said fat and oil decarboxylation decomposition catalyst contains what turned into activated carbon by heating the carbide | carbonized_material derived from the said oil extraction raw material which remained after manufacture of the biodiesel fuel in oxygen atmosphere. Of manufacturing biodiesel fuel. The biodiesel fuel according to any one of claims 1 to 4, wherein water vapor in a molar ratio of 1/10 to 10/1 (H ₂ O / oil) coexists in the decarboxylation decomposition reaction. Production method. An apparatus for producing a biodiesel fuel for use in the method of manufacturing biodiesel fuel according to any one of claims 1 to 5, a first reaction vessel having the oil decarboxylation decomposition catalyst therein, the An oil decarboxylation catalyst or a heating part for heating the oil or oil-squeezed raw material, an input part for introducing the oil-squeezed raw material or oil into the first reaction container, and a first gas for deriving the generated gas mixture from the first reaction container A biodiesel fuel production apparatus comprising: a deriving unit;   A second reaction vessel connected to the first gas deriving unit and filled with the fat decarboxylation catalyst, a gas introduction unit for introducing the product gas mixture of the first reaction vessel into the second reaction vessel, The biodiesel fuel production apparatus according to claim 6, further comprising a second gas deriving unit for deriving a gas mixture decarboxylated by the fat decarbonation catalyst of the second reaction vessel.   An oil and fat decarboxylation catalyst for use in the biodiesel fuel production method according to any one of claims 1 to 5 or the biodiesel fuel production apparatus according to claim 6 or 7, comprising silica, FCC waste catalyst whose acid sites are poisoned by one or more of alkali metals and alkaline earth metals, and a mixture of those composites, any one of magnesium hydroxide, oxide and carbonate An oil / fatty acid decarboxylation catalyst comprising one or more of these coated with a weak alkaline compound.