KR101391221B1 - Method and apparatus for manufacturing biodiesel fuel, and decomposition catalyst for decarboxylation of fats used in the method - Google Patents

Abstract

It does not require an alcohol (subsidiary raw material), does not produce glycerin as a by-product, and is free from impurities such as dienes remaining in the product, produces a small amount of coke, has a low pour point and is stable against air, It is difficult to increase the storage stability and the running cost is increased by the auxiliary operation such as the treatment or re-activation of the used catalyst. Therefore, the production efficiency and productivity are excellent and the free fatty acid There is provided a method of manufacturing a biodiesel fuel which can simplify a manufacturing process and simplify a reaction device and can form a distributed energy supply system that supplies necessary energy at a required place. The fat decarbonation decomposition catalyst and the fat are brought into contact with each other at 350 ° C to 475 ° C and the ester bond portion is cleaved by the action of the fat decarboxylation decomposing catalyst to produce a biodegradable product mainly containing C ₈ to C ₂₄ hydrocarbons Get diesel fuel.

Description

FIELD OF THE INVENTION The present invention relates to a method for producing a biodiesel fuel, a method for producing the biodiesel fuel, an apparatus for producing the biodiesel fuel, an apparatus for producing the biodiesel fuel, a method for producing the biodiesel fuel,

TECHNICAL FIELD The present invention relates to a method and apparatus for efficiently producing high-quality biodiesel fuel from a frying or milking raw material. The present invention also relates to a method for producing the same, and more particularly to a method for producing the same.

Biodiesel fuel is a very important technology for the reduction of global warming gas and air pollutant emissions and for the establishment of an energy recycling society. As a method for producing the biodiesel fuel, a fatty acid methyl ester (FAME) method is widely used. The fatty acid methyl esterification method is to obtain a fuel for a diesel engine by transesterifying a raw material and a lower alcohol (sub ingredient) (Non-Patent Document 1).

As a technique relating to a fatty acid methyl esterification method (Patent Document 1), "a method of producing a fatty acid alkyl ester by reacting a fat with a lower alcohol in the presence of a calcium-based solid catalyst" is disclosed.

(Patent Document 2) discloses a process comprising the steps A and A of converting a free fatty acid present in a raw material oil into a fatty acid alkyl ester by reacting a raw material and an alcohol in the presence of a solid acid catalyst and removing the moisture from the reaction mixture obtained in the process A Process B and a process C for converting a triacylglyceride, which is a main component of a raw material oil, into a fatty acid alkyl ester by subjecting the liquid obtained in Step B and an alcohol in the presence of a solid base catalyst to an ester exchange reaction, thereby producing a biodiesel oil &Quot;

As a method of producing other biodiesel fuel, the hydrogenation treatment method described in Non-Patent Document 1 is known. The hydrotreating method is a method of applying hydrogenation technology which is a conventional petroleum refining process and hydrogenation treatment is carried out under a high pressure of 10 MPa to oxygenate in the raw material oil as water mainly and to be hardened and to saturate the unsaturated bonds originating from the raw material oil, Of the boiling point range.

[Patent Document 3] discloses that "a flow catalytic cracker having a reaction zone, a separation zone, a stripping zone, and a regeneration zone is used, and a feedstock containing biomass in a reaction zone at an outlet temperature of 480 to 540 ° C And a solid acid catalyst such as stable Y type zeolite or silica alumina for 1 to 3 seconds to obtain a gasoline base material or a diesel fuel base material.

(Patent Document 4) discloses that "a solid acid catalyst is heated in a reaction vessel in a temperature range of 350 to 450 占 폚, the solid acid catalyst is brought into contact with a liquid phase retainer to remove the oxygenate component from the retainer, A method for catalytic cracking of a fat-and-oil mixture in which a hydrocarbon mixture composed mainly of olefin and paraffin is synthesized ".

Japanese Patent Laid-Open No. 2008-143983 Japanese Patent Application Laid-Open No. 2008-1856 Japanese Patent Application Laid-Open No. 2007-177193 Japanese Patent Application No. 2008-086034

 ENEOS Technical Review Volume 49 Issue 2 (June 2007)

However, the above-described conventional techniques have the following problems.

(1) In the fatty acid methyl esterification method disclosed in Non-Patent Document 1, Patent Document 1 and Patent Document 2, a large amount of lower alcohol is required, and thus a large running cost is required. Further, impurities (for example, dienes, hydroxyl groups, peroxides, etc.) in the raw material retention are liable to remain in the produced oil, so that the produced oil is unstable to air and the like and has a problem that storage stability is lacking. In order to solve this problem, a process of adsorbing impurities such as peroxide by using an adsorbent such as activated clay or the like and removing from the produced flow channel is required, which has a problem that the treatment process is complicated.

(2) In the fatty acid methyl esterification method, as described in Non-Patent Document 1, there is a problem that fatty acid soap is by-produced because an alkali catalyst is used. If the fatty acid soap has a large by-product amount, it is difficult to separate the fatty acid ester layer and the glycerin layer, so that the fatty acid ester is mixed into the glycerin layer and the yield of the fatty acid ester is lowered. In addition, since the alkali catalyst (caustic soda, etc.) is dissolved in the by-produced glycerin, this treatment became a problem. Establishment of the treatment technique of glycerin, which is a by-product, is indispensable for establishing the technique of the fatty acid methyl esterification method, but the effective treatment technique has not yet been established.

(3) In the fatty acid methyl esterification method described in Patent Document 1, the byproduct of fatty acid soap can be suppressed to a low level by using a calcium-based solid catalyst. However, another problem is that free fatty acid contained in triglyceride as raw material lowers the activity of the solid catalyst There is a problem. As a result, it is necessary to use a large amount of the solid catalyst to generate a large amount of used catalyst, and the reactivation treatment of the used catalyst is also required, so that the auxiliary operation is increased and the running cost is raised, There is a problem that it is deteriorated.

(4) In order to suppress the lowering of the activity of the solid base catalyst by the free fatty acid, Patent Document 2 discloses a technique of removing free fatty acid from the raw material holding by treating the free fatty acid in the presence of a solid acid catalyst as a previous step have. The technique disclosed in Patent Document 2 requires a plurality of steps because the free fatty acid is treated in the step A in the presence of the solid acid catalyst and then reacted in the presence of the alcohol and the solid base catalyst in the step C, They had a problem of being miscellaneous goods.

(5) In the hydrotreating method described in Non-Patent Document 1, there was a problem that the solidification point of the obtained hydrocarbon oil was as high as +20 占 폚 and the fluidity was poor. Further, there is a problem that glycerin is mixed into the obtained hydrocarbon oil, resulting in lack of stability. The higher the solidifying point of the hydrocarbon oil is, in particular, a problem in the case of use in a cold paper, and is presently mixed with diesel oil in a condition of 5% or less.

(6) The technique disclosed in Patent Document 3 is a technique for obtaining a gasoline base material or the like from a fuel oil using a fluidized catalytic cracking apparatus having a reaction zone, a separation zone, a stripping zone, and a regeneration zone. In this technique, it is necessary to transport the collected raw material to a point where a large-scale flow catalytic cracking apparatus exists to perform the treatment. However, plant biomass, which is a raw material of oil, has a problem of requiring a great deal of cost for transportation to a collection and flow catalytic cracking unit because it is a distributed and computational resource having a vast land as a production base. In addition, the construction of a large-scale fluid catalytic cracking apparatus for the purpose of producing biodiesel fuel at the production base of the plant biomass in order to reduce the transportation cost had a problem such as an increase in the running cost. Further, when the raw material oil is contacted with the solid acid catalyst in the reaction zone at the outlet temperature of 480 to 540 캜, the bond between the carbon atoms of the alkyl group tends to be cleaved, resulting in a low molecular weight product, an increased production amount of the gasoline fuel, . In addition, in the reaction of the solid acid catalyst, since a large amount of aromatic is produced, the amount of produced coke (also called carbide or coke produced on the catalyst for treating hydrocarbons such as petroleum) is large and precipitates on the surface of the solid acid catalyst, There is a problem in that the activity of the catalyst is deteriorated and a problem that a plurality of catalysts are combined and become massive is caused, which lowers the yield and makes it difficult to operate the catalyst. Further, when the activity of the catalyst is lowered, the decarbonation ability is lowered, and impurities such as carboxylic acid (free fatty acid) are easily produced as a by-product, and the resulting product is blackened or odorous. There is a problem that a product oil having a lot of acids, a lot of aromatics and a low cetane number is not suitable for actual use.

(7) The technique disclosed in Patent Document 4 is a technique for obtaining a hydrocarbon mixture which becomes a fuel for a diesel engine, in which a heated solid acid catalyst is contacted with a fuel and catalytic cracking is carried out from the oil to mainly contain olefins and paraffins having 9 to 24 carbon atoms . A solid acid catalyst is used, but by using a reaction temperature lower than that in Patent Document 3, milder reaction conditions are obtained, and the rate of cleavage of the carbon atoms of the alkyl group is low. However, since the reaction is also a solid acid catalyst, there is a problem that the amount of coke produced is large, the yield of kerosene and diesel oil is lowered, and the activity of the catalyst is easily lowered. Further, when the activity of the catalyst is lowered, the decarbonation ability is lowered, and impurities such as carboxylic acid (free fatty acid) are easily produced as a by-product, and the resulting product is blackened or odorous.

Disclosure of the Invention The present invention has been made to solve the above-mentioned conventional problems, and it is an object of the present invention to provide a coke oven which does not require an alcohol (subsidiary raw material) and does not produce glycerin as a by- (Free fatty acid) is difficult to be produced as a by-product because it is stable to air and the like, so that it is difficult to generate a black color or bad odor and thus the storage stability is excellent. Further, There is no problem of lowering the activity of the used catalyst. Therefore, the running cost is greatly reduced by the auxiliary operation such as the treatment or the re-activation of the used catalyst, so that the productivity is excellent and the pretreatment for removing the free fatty acid from the raw material holding is not necessary And the reaction can be carried out under atmospheric pressure. Therefore, It is a further object of the present invention to provide a method of manufacturing a biodiesel fuel which can simplify the apparatus and can provide a distributed energy supply system that supplies necessary energy at a required place and that yields even a raw material rich in unsaturated fatty acids do. It is another object of the present invention to provide an apparatus for producing biodiesel fuel which can obtain a high-quality biodiesel fuel from a milking raw material or a fat with good yield. It is another object of the present invention to provide a decarbonate decomposing catalyst for use in a method for producing a biodiesel fuel which can efficiently obtain a high quality biodiesel fuel by advancing a decarboxylation cracking reaction by suppressing the cleavage of double bonds of the fat .

In order to solve the above-described conventional problems, the method for producing biodiesel fuel of the present invention has the following configuration.

The method for producing a biodiesel fuel according to claim 1 of the present invention is a method for producing a biodiesel fuel according to claim 1, wherein the fat decarbonation catalyst is contacted with the fat decarbonation catalyst in a reaction vessel at 350 ° C to 475 ° C, Has a constitution which mainly produces C ₈ to C ₂₄ hydrocarbons in the decomposition reaction of decarbonation.

(1)

With this configuration, the following actions are obtained.

(1) When the fat decarbonation decomposition catalyst and the fat are brought into contact with each other at 350 ° C to 475 ° C, the ester bond portion of the glycerin is cleaved (cleaved) by the action of the fat decarboxylation decomposition catalyst, (Hydrocarbons) to be the biodiesel fuel can be obtained. Also, depending on the type of the decarbonate decomposition catalyst, preferential de-CO may occur. As is evident from the reaction shown in Chemical Formula 1, since glycerin is not produced as a by-product, the establishment of the treatment technique of glycerin and the treatment process are not required. Further, since gaseous compounds of propane, methane, ethane and butane are obtained as by-products, they can be used as gaseous fuels and can be used as a fuel for heating the firing decarbonation decomposition catalyst.

(2) This decarbonation decomposition is carried out under the condition that substantially no alcohol is present, so that the running cost can be drastically reduced, and unstable impurities such as dienes and peroxides in the raw material retention can be easily It is difficult to remain in the product due to decomposition, and impurities such as carboxylic acid (free fatty acid) are also difficult to be produced as a by-product, so that it is possible to obtain a biodiesel fuel which is stable to air and is excellent in storage stability with less occurrence of blackness and odor. In addition, a step of adsorbing and removing impurities such as peroxide by using an adsorbent is unnecessary, which is excellent in economy. In addition, since the amount of coke produced is small, there is no problem that the coke is deposited on the surface of the catalyst and the deterioration of the decalboxylating decomposition catalyst due to the activation of the decomposition catalyst or the decomposition of the decalinized carbonate decomposition catalyst is difficult to occur. It becomes.

(3) Although free fatty acid is present in the raw material, impurities such as carboxylic acid (free fatty acid) are less likely to be produced as a result of cleavage of the ester bond portion of glycerin such as fat and de-CO ₂ , It is difficult to easily cause a problem that the activity of the catalyst is lowered by the by-produced carboxylic acid (free fatty acid) because it is easily decomposed into hydrocarbon and carbon dioxide gas. Therefore, it is not necessary to use a large amount of catalyst in anticipation of the decrease in activity, and there is no possibility that the running cost is increased or the productivity is lowered due to the auxiliary operation such as the treatment or re-activation of the used catalyst. Fats containing waste oils or unsaturated bonds (such as yatrope oil) are very effective because they contain more free fatty acids in oxidative deterioration.

(4) Dehydrocarbon decomposition using a decarbonated decomposition catalyst for dehydrogenation leads to de-CO ₂ or de-CO of glycerin, and the remaining carbon chains are recovered, whereby a hydrocarbon having a carbon number of 8 to 24, Biodiesel fuel can be obtained.

(5) Pre-treatment for removing free fatty acid from the raw material oil to prevent the deterioration of the activity of the decalboxylation decomposition catalyst becomes unnecessary, and since the catalytic decomposition step can be performed under atmospheric pressure, the production process of the biodiesel fuel and the reaction apparatus It is possible to simplify the fuel cell, thereby improving the productivity and manufacturing the biodiesel fuel at low cost. Therefore, the reaction device can be constructed at low cost in a production base or a necessary place of plant-based biomass, and a distributed energy supply system for supplying necessary energy at a necessary place can be constructed.

(6) Since the dehydrogenative decarbonation catalyst is heated to 350 to 475 DEG C, a biodiesel fuel having olefins and paraffins having 8 to 24 carbon atoms as the main components can be produced with a high rate of decarbonation decomposition and high productivity.

(7) At 350 to 475 ° C, the oil is liquid and hardly evaporates. Therefore, only the product from the reaction vessel is drawn out as a gas.

(8) At 350 to 475 ° C, the oil is hardly pyrolyzed. Therefore, since the fat is almost decomposed by decarboxylation, the double bond portion is thermally cut to prevent low molecular weight.

(9) Since the product is derived as a gas, the phosphoric acid in the raw material is deposited on the dehydrogenative decarboxylation catalyst for decomposition, so that the decomposition channel hardly shifts. Therefore, there is no performance degradation or damage caused by phosphoric acid in the engine, so the decomposition oil can be used safely. Especially, it is effective when yatrofana fish residue (or fish oil) and soybean which have high phosphoric acid content are used as raw materials.

Herein, as the fat, animal oils such as vegetable oils such as rapeseed oil, palm oil, palm kernel oil, olive oil, soybean oil, perilla oil, castor oil, yatropha oil and corn oil, terpenes, fish oil, lard, , Etc., or mixtures thereof, may be used. In addition, waste cooking oil such as frying oil may be used. Liquids such as lard and woji which solidify at room temperature are dissolved and liquefied by heated catalyst or preheating, so the oil can be used in both liquid and solid form.

The oil may be reacted by bringing a mixture of one or more species into contact with the catalyst. Further, the oil may be preheated at a temperature of 475 DEG C or lower before being contacted with the catalyst. So as to be rapidly heated after contacting with the catalyst to increase the decomposition efficiency.

The fat is triacylglycerol (three acyl groups are ester-bonded to glycerin), but phospholipids, glycolipids, fatty acids and the like can also be used in the raw materials of the present invention.

The sustained decarboxylation catalyst is preferably weakly alkaline, neutral or slightly acidic. Specifically, one or more of the silica of the solid catalyst, the activated carbon, the solid base, the clay mineral, and the alkali poisoned solid acid are used. Examples of activated carbon include carbides such as particulate powder and fibrous carbide treated at a high temperature of about 1000 캜. Most of the ceramics can also be used as a catalyst.

More specifically, the activated carbon (to the particular, raised from the above 500 ℃ high temperature), coke, active coke, alkaline earth metal oxides MgO, such as CaO, SrO, BaO, La ₂ O _3, Th ₂ O _3, such as the lanthanides , the solenoid actinoids oxide, ZrO ₂ and TiO _2, such as a metal oxide, an alkaline earth metal such as a metal carbonate, SiO ₂ -MgO, SiO ₂ -CaO, such as a complex oxide, Rb, or an alkali metal ion or alkaline earth metal such as Cs Ion exchanged zeolite, an FCC catalyst partially or totally poisoned by addition of an alkali metal compound or an alkaline earth metal compound, an FCC spent catalyst, a metal such as Na / MgO or K / MgO deposited with an alkali metal such as Na or K Deposited metal oxides, alkali metal salts such as KF / Al ₂ O ₃ and LiCO ₃ / SiO _2, and the like can be used. And a mixture or support (for example, a support in which a solid base is supported on silica, coke or the like) or the like may be used. Minerals such as dolomite which is a mixture of MgO and CaO when heated can also be preferably used.

The ammonia temperature-escaping temperature is in the range of 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. Na poisoned FCC catalyst at 30 to 200 ° C, magnesium oxide-supported silicon oxide at 0 to 60 ° C, and magnesium oxide-supported activated carbon at 0 to 70 ° C. The ammonia temperature elevation temperature higher than 400 ° C is a very strong acid catalyst, and the product is easily broken down by cutting off the carbon-carbon bond of the alkyl group in the oil and attacking the carbon-carbon double bond to generate a large amount of aromatic. . For this reason, the yield of the produced oil is lowered, the activity of the catalyst is lowered by the increased coke, the decarbonation capacity is lowered, the production of the carboxylic acid is increased, and the quality of the produced oil is lowered. If the ammonia temperature rise temperature is higher than 400 ° C, it is inadequate for practical use as a diesel fuel because it has a low cetane number and high acidity due to a large amount of aromatics in the produced oil. In the case of using a catalyst such as activated carbon or activated coke in the catalyst having an ammonia temperature rise temperature of 100 DEG C or lower, a mixture of oil and mineral oil can be used as a raw material. Catalysts such as activated carbon and activated coke do not convert mineral oil to low molecular weight. Examples of the mineral oil include an atmospheric residue obtained by distilling crude oil, a reduced pressure diesel oil obtained by further distilling the atmospheric residue at reduced pressure, a reduced pressure residue, a hydrotreated oil thereof, or a mixture thereof. Hydrocarbons produced by decarbonation of the oil may also be used. These mineral oils function as an extracting agent of the residual oil remaining in the residues, thereby further increasing the efficiency.

When the heating temperature of the deasphalting decarboxylation catalyst is lower than 350 ° C, the progress of the decarbonation decomposition reaction is slowed, and the polymerization of the oil is solidified and the productivity of the hydrocarbon is lowered. In addition, when the temperature is higher than 475 DEG C, the amount of production of light gas or coke having 4 or less carbon atoms is increased, and the amount of products containing olefins and paraffins having 8 to 24 carbon atoms as a main component tends to be lowered.

As a reaction device for producing the biodiesel fuel, for example, a device having a reaction vessel containing a decalinized carbonic acid decomposition catalyst and a heating device for heating a decarbonate decomposition catalyst in the reaction vessel is used. The reaction vessel may be a fixed bed system, a fluidized bed system, a rotary kiln system, a stirring system, or the like. Among them, the stirring method is preferable. Decomposition products such as oils and the like (aromatic compounds and the like) are polymerized and adhered to the surface of the sustained decarboxylation catalyst when the reaction conditions and the like deteriorate during operation, and a plurality of fat decarboxylation catalysts are bonded by the polymerizate, It is impossible to operate it. However, it is possible to prevent mechanical agglomeration by mechanical agitation.

In the decarboxylic acid decomposition step, when the catalyst is heated to a reaction temperature by heating the deasphalted carbonic acid decomposition catalyst, the milking raw material and the oil are introduced into the reaction vessel by spraying, spraying, dropping, The treatment can be performed continuously, and the treatment can be performed in a batch manner. The oil is decomposed in contact with the heated sustained decarboxylating catalyst and has a vapor pressure as a combustible gas. A combustible gas generated by continuously or intermittently introducing an inert gas such as nitrogen gas or helium gas or a flow gas such as water vapor can be discharged out of the system. The discharged combustible gas is cooled to become biodiesel fuel oil. By using water vapor as the flow gas, the water-soluble component is dissolved in water vapor to obtain a cleaning effect of the combustible gas. When a catalyst such as CaO is used, the catalyst activity can be prevented from lowering as described later.

The deactivated retained decarboxylation catalyst can also be regenerated after extraction from the reaction vessel or from the reaction vessel if necessary.

When an example of the reaction of the fat contacted with the decalinized carbonate decomposition catalyst is shown, MgO (catalyst) decomposes the fat by binding with the CO ₂ of the fat to become magnesium carbonate. Since magnesium carbonate decomposes at 350 to 450 ° C and decarboxylic acid occurs, MgO after decarbonation contributes to the decomposition of the oil repeatedly.

In addition, CaO (catalyst) decomposes the fat by binding with CO ₂ of the oil in the presence of water, and becomes calcium hydrogen carbonate. Calcium hydrogencarbonate is decomposed at around 300 ° C to cause decarbonation, so CaO after decarbonation contributes to the decomposition of the oil repeatedly.

The pressure in the reaction vessel is preferably maintained at atmospheric pressure or at a constant pressure. Since a combustible gas such as diesel oil or kerosene is produced by decomposition of decarbonic acid such as oil or the like, there is a possibility that air is introduced into the reaction vessel if it is a negative pressure, and is ignited and exploded by the generated combustible gas.

The liquid-space velocity representing the amount (volume) per hour of the maintenance decarbonation cracking catalyst (volume) in the decarbonation cracking step is preferably 0.05 / h to 2.0 / h, more preferably 0.3 / h to 1.0 / h Lt; / RTI > When the liquid space velocity is less than 0.05 / h, the treatment efficiency is low, and the produced oil is hard gasified by secondary decomposition and the yield of light oil and light oil is lowered, which is not preferable. On the other hand, if it exceeds 2.0 / h, the contact time of the catalyst with the oil and the like is shortened, and the rate of degradation of the oil storage is lowered, which is not preferable.

The invention according to claim 2 of the present invention resides in a method for producing a biodiesel fuel as set forth in claim 1, wherein either or both of the above-mentioned fat decarbonation decomposition catalyst and the fat are in contact with each other, As shown in Fig.

With this configuration, in addition to the effect obtained in claim 1, the following actions are obtained.

(1) One or both of the heated decarbonate decomposition catalyst and the heated oil become a heating medium, the temperature of the portion contacting with the oil at the surface of the oil decarboxylating catalyst is increased, and the action of the oil decomposition catalyst The cleavage of the ester-bonded portion of glycerin proceeds smoothly.

Here, it is preferable to heat both the decarbonate decomposing catalyst and the fuel oil at the start of operation so that the temperature in the reaction vessel is uniformly maintained and the reaction proceeds smoothly. After the reaction is stabilized, the energy consumption can be lowered by heating one side.

According to a third aspect of the present invention, there is provided a method of producing a biodiesel fuel as set forth in the first or second aspect, wherein the milking material is used instead of the above-mentioned holding.

With this configuration, in addition to the function obtained in the first or second aspect, the following actions are obtained.

(1) Milking material is maintained at 350 ° C to 475 ° C. When contact with the decalcification cracking catalyst occurs, celluloses such as shells in the milking raw material are carbonized, and the oil retaining ingredient of the milking raw material is eluted and contacted with the oil retaining decarboxylating catalyst, The ester bond portion is cleaved, and de-CO ₂ or de-CO shown in (Chemical Formula 1) occurs, and a decomposition gas (hydrocarbon) which becomes a biodiesel fuel can be obtained.

(2) The milking raw material generates water vapor when it is decomposed by heating, so it is preferable to use a decalboxylating decomposition catalyst which functions well in the presence of water such as CaO.

Examples of the milking material include seeds of oil palm, seeds, cocoa seeds, seeds, fruit of olives, seeds such as perilla or arachis, yatropha curcus (yatropha), and cornus wisoniana Fruits and seeds of plants before milking such as seeds can be used. In addition, it is known that some kinds of algae accumulate the fat in the cells, and the algae can be dehydrated and concentrated. The milking raw material is preferably used after being dried. This is to remove the moisture and increase the heating efficiency. In order to increase the decomposition efficiency by the deasphalted decarbonic acid decomposition catalyst, the milking raw material is preferably pulverized or crushed to increase its surface area. A milking raw material after milking by pressing or the like can also be used. It is known that they still have a large amount of oil remaining after milking.

Further, the cellulose such as the shell of the milking raw material is carbonized and remains in the reaction vessel. Therefore, the remaining carbide may be extracted from the reaction vessel as needed.

Milk or a mixture of a milking raw material and a mineral oil may be used as a milking raw material after thermally milking with a mineral oil such as hexane. It is known that they still have a large amount of oil remaining after milking.

In addition, alkaline scum, fish residue, livestock residue (internal product), etc. discharged from the purification process of the oil are also retained and can be used as a raw material because of a large amount of lipid.

Further, the above-described firing decarbonation decomposition catalyst can be regenerated by heating to 500 ° C to 600 ° C and exposing it to an atmosphere containing oxygen. The coke adhering to the surface of the retained decarboxylation catalyst is lost by recycling the retained decarboxylative decomposition catalyst whose activity has deteriorated due to the attachment of coke or the like while heating it, so that resource saving is excellent.

The reaction vessel can be used as it is for the regeneration of the decarbonate decomposition catalyst. The temperature of the heating for regeneration is preferably 500 ° C to 600 ° C. When the temperature is less than 500 ° C, it takes a long time to regenerate it, which is not practical. If the temperature is higher than 600 ° C, the structure of the ceramics may change, which may lead to denaturation of the catalyst for decomposing the decarbonated hydrocarbon, resulting in a decrease in activity, which is not preferable.

There is a problem that the organic acid contained in the feedstock or the milking raw material becomes a catalyst poison and thereby deteriorates the activity of the catalyst. However, since the organic acid is easily decomposed into hydrocarbons and carbon dioxide gas by the decarbonate decomposition catalyst, Problems are hard to occur. For this reason, there is no need to use a large amount of catalyst in anticipation of the amount of deactivation, and the running cost is not increased or the productivity is not lowered by the auxiliary operation such as the treatment or re-activation of the used catalyst.

The invention according to claim 4 of the present invention resides in a method for producing a biodiesel fuel according to claim 3, wherein the method for producing a biodiesel fuel comprises heating the remaining carbide originating from the milking raw material after production of the biodiesel fuel in the reaction vessel Activated carbon, so that the activated carbon is contained.

With this configuration, in addition to the effect obtained in claim 3, the following actions are obtained.

(1) By heating in an oxygen atmosphere, the coke accumulated on the surface of the sustained decarboxylation catalyst in the reaction vessel is burned to regenerate the decarbonated decarbonation catalyst.

(2) Cellulose such as a shell of a milking raw material is carbonized and remains in the reaction vessel. Therefore, it is necessary to appropriately extract and dispose of the cellulose. However, since it is converted into activated carbon, it can be effectively used as a catalyst.

(3) It is possible to procure a dehydrocarbon decomposition catalyst easily even in an area where industrialization or transportation network is not undergoing maintenance.

Here, the reaction vessel can be used as it is for activating the carbide derived from the milking raw material. The temperature of the heating for regeneration is preferably 500 ° C to 600 ° C. When it is less than 500 ° C, regeneration of the catalyst and activation of the carbon take time, which is not practical. If the temperature is higher than 600 ° C, the structure of the ceramics may be changed and the dehydrogenative decarboxylation catalyst may be denatured, resulting in a decrease in activity, which is not preferable.

The invention according to claim 5 of the present invention is the method for producing a biodiesel fuel according to any one of claims 1 to 4, wherein the method for producing a biodiesel fuel comprises the steps of: Formed zeolite, and a mixture of these composites.

With this configuration, the following actions are obtained in addition to the actions obtained in claims 1 to 4.

(1) When a mixture of activated charcoal, activated coke, alumina, silica, magnesium oxide, alkaline-modified fly ash-modified zeolite, and their complexes does not substantially change the mineral oil to low molecular weight, It can act as an extracting agent for the milking raw material and the remaining oil in the residue, thereby further increasing the efficiency.

The method for producing a biodiesel fuel according to claim 6 of the present invention is the method for producing a biodiesel fuel according to any one of claims 1 to 5, wherein the molar ratio of the biodiesel fuel is 1/10 to 10/1 (H ₂ O / maintenance) of water vapor coexists.

With this configuration, in addition to the effects obtained in claims 1 to 5, the following actions are obtained.

(1) The hydrolysis of the ester bond is promoted by steam, so that the decomposition efficiency of the fat is improved.

Here, in the decarbonation decomposition reaction of the fat in the present invention, since water is necessarily generated at the side reaction, the reaction proceeds without adding water vapor separately. Therefore, the promoting effect is not clear when the amount of water vapor is less than 1/10 of the molar ratio.

If the water content in the raw material exceeds 10/1 by mole ratio, moisture is increased in the produced oil, which leads to deterioration of the quality of the oil. Therefore, it is necessary to remove (dry) the water from the raw material stage or the produced oil channel. This is the case where milking raw material or fish residue is used. In the case of soybean of Example 6 described later, as shown in Table 3, this is because there are many water components. However, if a step of removing the water component from the generation flow path is added to the rear end, there is no particular problem.

The apparatus for producing a biodiesel fuel according to claim 7 of the present invention is an apparatus for producing a biodiesel fuel for use in the method for producing a biodiesel fuel according to any one of claims 1 to 6, A heating unit for heating the oil or fat or oil for storage, a feed unit for feeding the milking raw material or oil into the first reaction vessel, and a feed unit for feeding the produced gas mixture to the first reaction vessel, And a first gas lead-out portion leading out from the reaction vessel.

With this configuration, the following actions are obtained.

(1) Since the raw material for milking and the fat are heated by the heated decalinized carbonic acid decomposition catalyst and the decarboxylic acid decomposition reaction proceeds, it is possible to produce a fuel with less occurrence of coke and the like, good thermal efficiency and good yield.

(2) The raw material holding or milking raw material is heated and supplied, and continuous operation is possible, and the structure of the reaction container becomes simple and easy to manage.

Here, the first reaction vessel may be provided with a stirring device. In particular, in the case of using the milking raw material, it is preferable to provide a stirring device so that the catalyst in the reaction vessel and the milking raw material can sufficiently contact with each other.

When the catalyst is heated to a reaction temperature in the decarbonation decomposition step, the raw milk or the oil is put into a reaction vessel by spraying, spraying, dropping, or scattering, and brought into contact with the decalboxylating decomposition catalyst. Feeding of the holding and milking raw materials can be carried out continuously or batchwise. The oil is decomposed in contact with the heated sustained decarboxylating catalyst to have a vapor pressure as a combustible gas. A combustible gas generated by continuously or intermittently introducing an inert gas such as nitrogen gas or helium gas or a flow gas such as water vapor can be discharged out of the system. The discharged combustible gas is cooled to become biodiesel fuel oil.

The amount of the dehydrogenative decarbonation catalyst is preferably 5% by volume or more, more preferably 20% by volume or more. If the amount of the dehydrogenative decarbonation catalyst is less than 5% by volume, the ratio of the oil that can be brought into contact with the catalyst decreases and the proportion of the oil to be pyrolyzed by heating increases, so that the generation of the light gas increases, I can not. In the case of feeding the milking raw material, when it exceeds 60% by volume, when the raw material such as a milking raw material is added, it is not possible to contact with the catalyst and the amount of the heated raw material is increased and the frequency of the residue is increased.

In the case of feeding the milking raw material, the amount of the decarbonating decomposition catalyst is preferably 50% by volume or less.

When the milking raw material and the fat are decomposed by heating, when they reach the reaction temperature, the milking raw material and the fat are put into the reaction vessel by spraying, spraying, dropping, scattering, etc., and brought into contact with the fat decarboxylating catalyst. Since the catalyst is heated by heated holding or the like, continuous treatment can be performed. When batchwise treatment is carried out, it is preferable to heat the milking raw material and the fat to a high temperature in consideration of the amount of heat required for heating the catalyst, or preheat the catalyst.

The invention according to claim 8 of the present invention is the apparatus for producing a biodiesel fuel as set forth in claim 7, further comprising: a second reaction vessel connected to the first gas lead-out unit and filled with the holding decarbonation decomposition catalyst; And a second gas lead-out section for leading out a decarbonated cracked gas mixture in the second decontamination catalyst of the second reaction vessel Lt; / RTI >

With this configuration, in addition to the effect obtained in claim 7, the following actions are obtained.

(1) a second reaction vessel for introducing a gas mixture produced from the first reaction vessel is filled in the holding decarboxylation catalyst, and the organic acid in the gas produced from the first reaction vessel is maintained in the second reaction vessel Decomposed by decarboxylic acid decomposition catalyst so that 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 material feedstock passes through the upper portion of the first reactor and is not brought into contact with the catalyst but is led out together with the gas generated in the first reactor, The organic acid in the product is reduced and high quality is maintained.

(3) If the function of the catalyst is deteriorated by operating the apparatus for a long time, the reaction becomes incomplete in the first reaction vessel, and the organic acid, which can not react all the time, is mixed into the produced gas mixture. By suppressing the deterioration of the quality, the apparatus can be operated for a longer time and the operation efficiency is improved.

Here, the firing decarbonation decomposition catalyst used in the first reaction vessel and the second reaction vessel need not always be the same. Further, since the gas mixture derived 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 maintained decarboxylation catalyst in the second reaction vessel. However, when the temperature of the holding decarboxylative decomposition catalyst in the second reaction vessel during operation is lower than 350 占 폚, a heating apparatus for heating the catalyst for decomposing carbon decarboxylation in the second reaction vessel is required. As the second reaction vessel, a packed bed reactor such as a single tube or a radial flow type is used.

The method for producing a biodiesel fuel according to claim 9 of the present invention is a method for producing a biodiesel fuel according to any one of claims 1 to 6 or a method for producing a biodiesel fuel using the method for producing a biodiesel fuel according to claim 7 or 8, And a solid acid catalyst in which the acid point is poisoned by at least one of an alkali metal and an alkaline earth metal.

With this configuration, the following actions are obtained.

(1) As the acid sites are weakened, the cleavage of the double bond moiety in the oil is inhibited, and decarboxylic acid decomposition occurs efficiently. The production of fatty acids is also inhibited. Therefore, the production yield of the fuel is increased.

(2) generation of coke is suppressed, maintenance of the apparatus is reduced, and catalyst deterioration is slowed.

Here, 50% or more is employed as poisoning of the acid point, and more preferably 90% or more is employed. If the poison of the acid point is less than 50%, the production of coke and light gas increases, which is undesirable.

When the acid point is poisoned, the ammonia temperature drop-off temperature is lowered. The ammonia temperature-rise temperature is preferably lower than 400 占 폚, more preferably lower than 200 占 폚, further preferably lower than 100 占 폚. When the temperature is higher than 400 ° C, the resulting product tends to be low-molecular-weight, and a large amount of aromatic is produced, which results in the formation of coke, which tends to lower the catalytic activity. When the temperature is less than 100 ° C, the carbon-carbon bond is hardly cleaved, and therefore, it can be used also for raw materials in which mineral oil and the like are mixed.

The invention according to Claim 10 of the present invention is the storage deterioration carbonic acid decomposition catalyst according to Claim 9, wherein the solid acid catalyst comprises an FCC catalyst.

With this configuration, in addition to the effect obtained in claim 9, the following actions are obtained.

(1) Since it is possible to use FCC catalyst widely used in the flow catalytic cracking of petroleum, it is easy to obtain a catalyst.

Here, the FCC catalyst is a solid acid catalyst based on a granular synthetic zeolite granulated in a particle size of 40 to 80 占 퐉 which is used in a fluid catalytic cracking process of petroleum. Various methods can be used for poisoning by the alkali metal of the FCC catalyst. For example, a method of immersing the alkali metal salt aqueous solution by immersing the FCC catalyst in the aqueous solution may be used.

FCC spent catalysts that are treated as industrial wastes may also be used as FCC catalysts. The FCC waste catalyst is one that is discharged from the flow contact cracking process of petroleum. In the flow catalytic cracking process of petroleum, coke accumulates on the surface of the catalyst, and the catalytic activity gradually decreases. Therefore, the process of regenerating the catalyst by heating and burning the coke has a process of adding a new catalyst and a process of extracting an old catalyst in order to keep the catalytic activity constant, although it has a fluid catalytic cracking process of petroleum. This extracted old catalyst is an FCC waste catalyst, and most of it is being treated as industrial waste. FCC waste catalysts still have sufficient catalytic activity and are available at very low cost. In the case where coke is accumulated on the surface of the FCC spent catalyst and the catalyst function is degraded, the catalyst can be regenerated by burning the coke on the catalyst surface by heating the catalyst in an oxygen atmosphere.

An eleventh aspect of the present invention resides in a method for producing a biodiesel fuel according to any one of the first to sixth aspects or a method for producing a biodiesel fuel according to the seventh or eighth aspect of the present invention, Any one or more of activated carbon, activated coke, alumina, silica, alumina-modified zeolite modified with alkali, clay mineral, and a mixture thereof coated with a weakly alkaline compound composed of at least one of hydroxide, As shown in Fig.

With this configuration, the following actions are obtained.

(1) activated carbon, activated coke, alumina, silica, alkaline-modified fly ash-modified zeolite, clay minerals, and their complexes coated with a weakly alkaline compound consisting of at least one of hydroxide, oxide and carbonate of magnesium Since the mixture does not substantially make the mineral oil small, the extraction efficiency of the oil can be improved and the yield of the decomposition oil can be increased by using a mixture of the oil and the milking raw material and the mineral oil as the raw material.

(Effects of the Invention)

As described above, according to the method for producing a 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, alcohol as a subsidiary material is not required, and the running cost can be greatly reduced. Further, impurities such as dienes and hydroxyl groups in the raw material holding are hard to remain in the product, Production of biodiesel fuel which is excellent in storage stability which is stable to air and which is hard to generate blackness and odor and which is excellent in fluidity around -20 캜, Method can be provided.

(2) Unlike the conventional FAME method, since glycerin is not produced as a by-product, there is no need for establishing a treatment technique of glycerin or a treatment process, and a step of adsorbing and removing impurities such as peroxide using an adsorbent is also unnecessary, In addition, it is possible to provide a method for producing a biodiesel fuel which is less liable to cause catalyst deactivation due to precipitation of the coke on the surface of the catalyst, and to prevent the catalyst from being agglomerated by the catalyst, and stable operation can be achieved with a high yield.

(3) Although free fatty acid is present in the raw material, impurities such as carboxylic acid (free fatty acid) are less likely to be produced as a result of cleavage of the ester bond portion of glycerin such as fat and de-CO ₂ , and even if free fatty acid (Free fatty acid), it is difficult to reduce the activity of the catalyst and it is not necessary to use a large amount of the catalyst in anticipation of the decrease in the activity of the catalyst. Therefore, It is possible to provide a production method of a biodiesel fuel which is excellent in production efficiency and productivity because the running cost and the productivity are not increased by the auxiliary operation such as the treatment or the reactivation.

(4) a pretreatment for removing free fatty acid from the raw material oil is not required, and the reaction can be carried out under atmospheric pressure, so that the production process and the reaction apparatus of the biodiesel fuel can be simplified, and the productivity can be improved. It is possible to provide a method of manufacturing a biodiesel fuel which can be manufactured at a low cost and which can form a dispersion type energy supply system that supplies necessary energy at a necessary place.

(5) It is possible to provide a method for producing a biodiesel fuel in which thermal degradation is suppressed, the yield is improved, the concentration of fatty acid in the product is lowered, and the product can be safely used as a fuel.

(6) Since the catalyst stably maintains its activity, it is possible to provide a method for producing a biodiesel fuel which can be used repeatedly and is of low cost and of good quality.

According to the invention described in claim 2, in addition to the effect of claim 1,

(1) One of the heated decalinized decarboxylation catalyst or the heated oil becomes a heating medium, and the temperature of the portion contacting with the oil at the surface of the oil separation and decarboxylation catalyst is increased. By the action of the oil decomposition catalyst, And the reaction for cleavage of the ester bond portion of the biodiesel fuel can proceed smoothly. Therefore, it is possible to provide a method for producing biodiesel fuel which can lower the energy consumption for heating.

(2) A method for producing a biodiesel fuel in which the temperature in the reaction vessel is uniformly maintained by heating both the deasphalating decarbonation catalyst and the oil at the start of operation, and the reaction proceeds smoothly.

According to the invention described in claim 3, in addition to the effect of claim 1 or 2,

(1) The milking material is maintained at 350 ° C to 475 ° C. When contact with the dehydrocarbonating catalyst occurs, the cellulose such as the shell in the milking raw material is carbonized, and the holding component of the milking raw material is eluted and contacted with the holding decarboxylating catalyst, The ester bond portion is cleaved and the decomposition gas (hydrocarbon) in which de-CO ₂ or de-CO shown in (Chemical Formula 1) occurs to be a biodiesel fuel can be obtained. Thus, only organic matter containing a large amount of oil- It is possible to provide a method for producing a biodiesel fuel which can be used as a raw material.

(2) Since the milking raw material generates steam when it is heated and decomposed, it is preferable when using a decalinized decarboxylating catalyst that functions well in the presence of water such as CaO. Therefore, production of biodiesel fuel having higher efficiency using milking raw materials Method can be provided.

According to the invention described in claim 4, in addition to the effect of claim 3,

(1) It is possible to provide a method for producing a biodiesel fuel in which the catalyst is repeatedly used because the coke accumulated on the surface of the sustained decarbonic acid catalyst in the reaction vessel is burnt by heating in an oxygen atmosphere to regenerate the sustained decarboxylation catalyst .

(2) Cellulose such as a shell of a milking raw material is carbonized and remains in the reaction vessel. Therefore, it is necessary to appropriately extract and dispose of it. However, since it is converted into activated carbon, it can be effectively used as a catalyst, It is possible to provide a method for producing a biodiesel fuel.

(3) Since a decarbonate decomposing catalyst capable of continuous operation can be procured even in an area where industrialization is not proceeding, it is possible to provide a method of manufacturing biodiesel fuel which is easy to introduce regardless of the region.

According to the invention as set forth in claim 5, in addition to the effects of claims 1 to 4,

(1) When a mixture of activated charcoal, activated coke, alumina, silica, magnesium oxide, alkaline-modified fly ash-modified zeolite, and their complexes does not substantially change the mineral oil to low molecular weight, It is possible to provide a method for producing a biodiesel fuel which acts as an extracting agent for the oil and has high efficiency.

According to the invention as set forth in claim 6, in addition to the effects of claims 1 to 5,

(1) A method for producing a biodiesel fuel in which the decomposition efficiency of the fat is improved because steam is promoted by hydrolysis of the ester bond.

According to the invention of claim 7,

(1) A method of manufacturing a biodiesel fuel having a low yield of coke, a good thermal efficiency, and a high yield because the raw milk or fat is contacted with the decarbonated decomposition catalyst at 350 ° C to 475 ° C at the same time, Can be provided.

(2) An apparatus for producing biodiesel fuel which is easy to carry out continuous operation, has good thermal efficiency, and is easy to manage can be provided by heating and inputting the raw material holding or milking raw material.

According to the eighth aspect of the present invention, in addition to the effect of claim 7,

(1) a second reaction vessel for introducing a gas mixture generated from the first reaction is filled in the interior of the holding decarboxylative decomposition catalyst, and the organic acid in the gas generated from the first reaction vessel is charged into the holding vessel of the second reaction vessel It is possible to provide an apparatus for producing a biodiesel fuel which is decomposed decarboxylated by a carbonic acid decomposition catalyst, so that the acid in the product is further reduced and the quality of the produced oil is good.

(2) the organic acid generated in the first reaction vessel or the organic acid contained in the raw material feedstock passes through the upper portion of the first reactor and is not brought into contact with the catalyst but is led out together with the gas generated in the first reactor, It is possible to provide an apparatus for producing a biodiesel fuel in which organic acid in the product is reduced due to decarbonation and high quality of the produced oil is maintained.

(3) If the function of the catalyst is deteriorated by operating the apparatus for a long time, the reaction becomes incomplete in the first reaction vessel, the organic acid in the resulting gas mixture increases, and the quality of the produced oil decreases. The deterioration of the quality is suppressed, so that the apparatus can be operated for a longer time, and an apparatus for producing biodiesel fuel having high operation efficiency can be provided.

According to the invention of claim 9,

(1) As the acid sites are weakened, the cleavage of the double bond moiety in the oil is inhibited, and decarboxylic acid decomposition occurs efficiently. The production of organic acids is also inhibited. Therefore, it is possible to provide a stable decarbonated cracking catalyst having a high production yield of fuel.

(2) It is possible to provide a stable decarbonated decomposition catalyst in which the generation of coke is suppressed, the maintenance of the apparatus is reduced, and the deterioration of the catalyst is slow.

According to the invention defined in claim 10, in addition to the effect of claim 9,

(1) Since the widely used FCC catalyst can be used by simple operation, it is easy to carry out. In addition, the FCC catalyst can be easily regenerated even when the catalyst function is degraded, so that a large-scale regenerator is not required. Also, since the treatment method is established even if the treatment is carried out without regeneration, it is possible to provide a decarbonate decomposing catalyst which can operate the facility safely.

(2) Since the spent catalyst of the FCC treated as waste can also be used, it is possible to provide a decarbonated decomposition catalyst having a very low running cost.

According to the invention set forth in claim 11,

(1) activated carbon, activated coke, alumina, silica, alkaline-modified sparingly-shaped zeolite, clay minerals, and composite thereof coated with a weakly alkaline compound consisting of at least one of hydroxide, oxide and carbonate of magnesium Since the mixture does not substantially make the mineral oil less denatured, the use of a mixture of the oil or the milk-derived raw material and the mineral oil as the raw material improves the extraction efficiency of the oil and can provide a decarbonate decomposition catalyst having a high yield of the oil.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a configuration diagram of a reaction apparatus of Embodiment 1. FIG.
2 is a configuration diagram of the reaction apparatus of the second embodiment.
3 is a configuration diagram of the reaction apparatus of the third embodiment.
4 is a view showing the carbon number distribution of the decomposition oil obtained in Example 2. Fig.
5 is a graph showing the carbon number distribution of the decomposition oil obtained in Example 7. Fig.
6 is a graph showing the carbon number distribution of the decomposition oil obtained in Example 8. Fig.
7 is a graph showing the carbon number distribution of the decomposition oil obtained in Example 9. Fig.
8 is a graph showing the carbon number distribution of the decomposition oil obtained in Example 10. Fig.

Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to these examples.

(Embodiment 1)

First, the reaction apparatuses used in Examples 1 to 7 and Examples 9 to 14 will be described.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a configuration diagram of a reaction apparatus of Embodiment 1. FIG.

In the drawings, reference numeral 1 denotes a reaction apparatus of Embodiment 1 used in the embodiment of the present invention, 2 denotes a reaction vessel, 3 denotes silica in a separated form contained in the reaction vessel 2, activated carbon, solid base, and poisoned FCC catalyst 4 is a heater for heating the catalyst 3 contained in the reaction vessel 2 to 350 to 475 DEG C and 5 is a feedstock to the reaction vessel 2 by spraying, dropping, A flow gas introducing portion 6 for introducing a flow gas such as an inert gas such as nitrogen gas or water vapor into the reaction vessel 2, 7 an agitator for stirring the catalyst 3, 8 a reaction vessel 2, (9) is connected to the first outlet pipe (8) so that the boiling point of the product is from 0 ° C to the decomposition product of the temperature of the reaction vessel (Hereinafter referred to as " decomposed oil "), 11 is a cooling pipe provided in the discharge pipe 10 for cooling the discharge pipe 10 to 0 DEG C to liquefy the cracked oil in the product and 12 is a cooling pipe (Hereinafter referred to as "light oil") having the boiling point of -80 to 0 ° C, the other end of which is connected to the cooling trap device 12 Gas discharge pipe.

(Embodiment 2)

Next, the reaction apparatus of Embodiment 2 used in Embodiment 8 will be described.

2 is a configuration diagram of the reaction apparatus of the second embodiment.

In the figure, reference numeral 21 denotes the reaction apparatus of the second embodiment. 1 are denoted by the same reference numerals, and description thereof is omitted. Reference numeral 22 denotes a heating unit for heating raw material or milking raw material. Reference numeral 23 denotes an auxiliary heating unit for heating the catalyst 3 when the temperature of the catalyst 3 is low at the start of operation.

(Embodiment 3)

Next, the reaction apparatus of Embodiment 3 used in Example 15 will be described.

3 is a configuration diagram of the reaction apparatus of the third embodiment.

In the figure, reference numeral 31 denotes a reaction device of the third embodiment. 1 are denoted by the same reference numerals, and a description thereof will be omitted. 32 is the first reaction vessel of Embodiment 3 and corresponds to the reaction vessel 2 of Fig. Reference numeral 33 denotes a discrete decarbonation catalyst A such as silica on a granular phase contained in the first reaction vessel 32 and 8 denotes a catalyst for separating the product formed in the first reaction vessel 32 into a flow gas, Reference numeral 34 denotes a second reaction vessel, reference numeral 35 denotes a catalyst for separating and decomposing carbonaceous materials such as silica, activated carbon, solid bases and the like contained in the second reaction vessel 34. Reference numeral 38 denotes a second reaction And is a second outlet pipe for deriving the decarbonated gas in the vessel (34).

Example 1

A catalyst for silica (manufactured by Fujisiri Chemical Co., Ltd., trade name: Carriact Q-15, particle size 1.18 to 2.36 mm) was used as the catalyst 3 50 mL of the catalyst was placed in a 150 mL reaction vessel 2 and heated to 420 DEG C while stirring with an agitator 7 (50 rpm). The heating temperature of the catalyst 3 was measured by bringing a not shown thermocouple put in the reaction vessel 2 into contact with the catalyst 3.

The palm oil (oil) was dropped into the reaction vessel 2 under an atmospheric pressure from the raw material input portion 5, confirming that the catalyst 3 had risen to 420 캜 of the reaction temperature. The feed amount of the oil was 0.25 mL / min, and the flow gas (nitrogen gas) from the flow gas inlet 6 was introduced at 50 mL / min.

The total amount of the oil was 75 g to obtain a product. The components of the cracked oil stored in the cracked oil reservoir 9 and the gas substances (carbon monoxide, carbon dioxide, and light hydrocarbon gas) discharged from the gas discharge pipe 13 were analyzed. Analysis of the decomposition oil was performed using GC-MS. The analysis of carbon monoxide and carbon dioxide in the gaseous substance was performed using GC-TCD, and the analysis of the light hydrocarbon gas was performed using GC-FID. Further, the catalyst after the experiment was analyzed by TG-DTA.

Example 2

The same procedure as in Example 1 was carried out except that a catalyst in which MgO was supported on silica for catalyst used in Example 1 was used and the reaction temperature was set to 410 ° C.

In the case of the catalyst in which MgO was supported on silica, an aqueous solution of magnesium nitrate (Mg (NO ₃ ) ₂ .6H ₂ O) in an amount corresponding to 10 mass% as metal magnesium was added to the silica for catalyst used in Example 1 under Incipient Wetness Impregnation with silica by impregnation, drying at 120 캜 after impregnation, and then calcining at 500 캜 for 3 hours in air.

Example 3

The same procedure as in Example 1 was carried out except that an activated coke (manufactured by Mitsui Chemicals, Inc., particle size after crushing: 1.18 to 2.36 mm) was used as the deasphalting carbon dioxide decomposition catalyst and the reaction temperature was set to 400 캜.

Example 4

The same procedure as in Example 1 was carried out except that a catalyst in which MgO was carried on the activated coke used in Example 3 was used and the reaction temperature was set to 400 캜.

The catalyst in which MgO was loaded on the activated coke was prepared by adding an aqueous solution of magnesium nitrate (Mg (NO ₃ ) ₂ .6H ₂ O) in an amount corresponding to 10 mass% as metal magnesium to the activated coke used in Example 3, Impregnated with the activated coke, dried at 120 캜 after impregnation, and then calcined at 350 캜 for 3 hours in a nitrogen atmosphere.

Comparative Example 1

The same procedure as in Example 1 was carried out except that an FCC waste catalyst was used as the catalyst and the reaction temperature was set to 420 캜.

In addition, the FCC waste catalyst is a regenerated solid acid catalyst based on synthetic zeolite particles granulated in a particle size of 40-80 μm used in a fluid catalytic cracking (FCC) process of petroleum.

The results of the analysis of the products in the above Examples and Comparative Examples will be described.

Table 1 shows the amounts of products and the yields of the decomposition oils in Examples 1 to 4 and Comparative Example 1. [

From Table 1, it was found that the decomposed oil yields of Examples 1 to 4 were all 50% or more, and that of Comparative Example 1 was 46%. The residues of Examples 1 to 4 were lower than those of Comparative Example 1. So we will examine this residue.

From the results of the TG-DTA analysis of the catalyst after the experiment, it was found that about 9% of coke remained in the catalysts of Examples 1 to 4, but about 30% of the coke remained in the catalyst of Comparative Example 1 (FCC spent catalyst) . From the analysis results of the decomposition oil by GC-MS, it was found that about 50% of paraffins, about 20% of olefins and about 20% of aromatic compounds were present in the cracked oil of Comparative Example 1, About 50 to 60% of paraffins and about 30 to 40% of olefins are present, but almost no aromatics are present. From these results, it was presumed that the residue was mainly coke, and coke was a polymer of aromatic compounds derived from olefin produced by the acid sites of the catalyst (FCC waste catalyst). In Examples 1 to 4, since neutral silica or a solid base was used as a catalyst, it was presumed that aromatic compounds were scarcely produced, and thus the production of coke was small and the amount of residue was reduced.

In Comparative Example 1, a small amount of alcohol and fatty acid were detected as oxygenated substances in the cracked oil, but these were not detected in Examples 1 to 4, and ketones were mainly produced. It was found that the decomposed oil of Comparative Example 1 was odorless and darkened enough to be visually recognized when it was left for about one week, but the decomposed oil of Examples 1 to 4 was not blackened or odorless, and the storage stability was excellent. This cause was presumed to be the influence of impurities such as carboxylic acid (fatty acid) contained in the decomposed oil of Comparative Example 1.

4 is a graph showing the carbon number distribution as a result of the decomposition oil obtained in Example 2. Fig. The fatty acid composition of the oil (palm oil) used in the experiment was 0.2% lauric acid (C12), 1.1% myristic acid (C14), 44.0% palmitic acid (C16), 4.5% stearic acid (C18) : 1) 39.2%, linoleic acid (C18: 2) 10.1% and linolenic acid (C18: 3) 0.4%. From FIG. 4, it can be seen that the paraffin or olefin of the carbon number corresponding to the fatty acid contained in the fat is mainly produced in Example 2. Other embodiments were of the same tendency.

The pour point of the obtained cracked oil was measured according to JIS K2269 (pour point of crude oil and petroleum product and cloud point test method of petroleum product) as -12.5 ° C. Since the pour point of common diesel sold on the market is -7 ° C, it was found that a cracked oil having a low pour point can be produced at about the level of ordinary diesel oil.

Table 2 shows the amounts of carbon monoxide and carbon dioxide in the gaseous substances produced in Examples 1 to 4 and Comparative Example 1. [

It was found that the amounts of carbon dioxide were increased in the order of Comparative Example 1, Example 1, and Examples 2 to 4. The catalysts of Comparative Example 1 are selected from a solid acid, the catalyst of Example 1 is silica (neutral), and the catalysts of Examples 2 to 4 are solid bases. As in Examples 1 to 4, It was confirmed that CO ₂ could be recovered.

From the results of Table 2 and Fig. 4, the decomposition mechanism of the fat is presumed as follows. The oil contacted with the heated sustained decarboxylating catalyst is released from glycerin and fatty acids are produced. In the produced fatty acid, a portion of the carboxyl group is removed as CO ₂ , and the remaining carbon chain is recovered as the decomposition oil. The glycerin group is recovered as a light hydrocarbon gas such as propane.

According to the above examples, the amount of coke produced is small and impurities such as carboxylic acid (free fatty acid) are not easily produced as a by-product. Therefore, it is stable to air and the like, It became clear that excellent biodiesel fuel can be obtained.

In addition, the same result was obtained when activated carbon was used in place of the activated coke as a catalyst in Example 3.

Example 5

(75 g of a mixture of soybean oil and vegetable oil) actually used for one week in a university restaurant was dropped into a reaction vessel under atmospheric pressure using a catalyst in which MgO was supported on silica for catalyst and 0.25 mL / min) and He gas (50 mL / min) was used as the flow gas.

Example 6

Experiments were carried out to produce a cracked oil from a milking raw material by using commercial soybean (dried soybean, Hokkaido) as a milking raw material. The soybeans were crushed to a size of about half to facilitate degradation. The same procedure as in Example 2 was carried out except that a catalyst (the same catalyst as that used in Example 2) in which silica for catalyst was used, the reaction temperature was set to 410 ° C and a small amount of a crushed soybean product (500 g) The procedure of Example 1 was otherwise made.

Example 7

Experiments were carried out to produce a cracked oil from a milking raw material by using rice bran discharged from a rice mill as a raw material holding material. Except that the reaction temperature was set to 410 ° C and a small amount of rice bran (500 g) was added into the reaction vessel under atmospheric pressure by using a microfeeder, except that a catalyst in which MgO was supported on the silica for catalyst was used (the same catalyst as in Example 2) The same as Example 1.

Example 8

Experiments were carried out to produce a cracked oil using the reaction apparatus of Embodiment 2 with yatrofas as a raw material retention which has a large amount of unsaturated fatty acids as raw material retention and low recovery rate of decomposition oil in the conventional method.

As the dehydrogenative decarbonation catalyst 3, a 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. And the raw material holding was heated up to 450 占 폚 in the heating part 22. The heating temperature of the raw material holding was measured by bringing a not shown thermocouple put in the heating portion 22 into contact with the raw material holding.

Confirmation that the raw material retention has risen to 450 ° C. of the reaction temperature and yatropha oil (oil) is dropped from the raw material charging section 5 into the reaction vessel 2 under atmospheric pressure and then introduced. The injection amount of the oil was 1.0 mL / min, and the introduction amount of the flow gas (nitrogen gas) from the flow gas introduction part 6 was 50 mL / min.

The total amount of the oil was 75 g to obtain a product.

Example 9

Experiments were carried out to produce a cracked oil using the animal fat as a raw material. The same procedure as in Example 4 was conducted except that the fat (500 g) of the pig discharged from the meat processing factory as the raw material holding was heated to 80 캜 and used as a liquid phase.

Example 10

The same procedure as in Example 4 was carried out except that the fat (500 g) of the cow discharged from the meat processing factory as the raw material holding was heated to 80 캜 and used as a liquid phase.

Table 3 shows the yields of the product and the yield of the decomposition oil in Examples 5, 6 and 8.

In Example 6, the oil component, the water component, the precipitate and the suspended matter were mixed in the cracked oil. It is considered that the milking raw material abundantly contains components other than the oil. Therefore, the rate of the cracked oil in Example 6 was excluded from the influence of sediment and the like, so that it was converted from the ratio of the oil component to the amount of the input, unlike Examples 1 to 5. In Example 6, analysis of gaseous substances was not performed. This is because the influence of ingredients other than oil is high.

In the case where the feedstock contains a large amount of water such as the case of using the milking feedstock, the water component is increased in the cracked oil produced as in Example 6, and therefore, a step of removing water from the raw material or from the cracked channel is required for use as fuel .

As shown in Table 3, it was confirmed that the decomposed oil was obtained from the waste cooking oil at a yield of 60% or more. This is almost the same result as in Examples 1 to 4 in which palm oil was used as a raw material. It is considered that the degree of oxidation of the waste cooking oil is remarkably higher than that of the palm oil, but it has become clear that the present embodiment can obtain the decomposed oil at a high yield.

Further, as shown in Example 6, it was confirmed that a milk component was obtained from the milking raw material (soybean) at a yield of 5.7%. Since the content of soybean oil in domestic soybean is said to be about 10 wt%, the yield of oil component is 5.7 wt%, which is a considerable high yield.

Fig. 5 shows the carbon number distribution of the decomposition oil obtained from rice bran in Example 7. Fig. Production of hydrocarbons with a wide carbon number ranging from C5 to C34 was observed. Particularly, it contained a lot of light and light oil of carbon number C10 to C20. In addition, the cracked oil contained about 2% of C6-C13 aromatic hydrocarbons. The rice bran had a large amount of lipase and a large amount of free fatty acid, but the oxidation degree was 0.35 mgKOH / g and the oxidation stability was 24 hours or more.

Table 3 shows the results obtained from the yttrophasia in Example 8. Yatropha oil is low in pyrolysis method because it has a high ratio of unsaturated fatty acid with 14.9% of palmitic acid (C16), 6.9% of stearic acid (C18), 41.8% of oleic acid (C18: 1) and 34.8% of renolenic acid The yield of the recovered oil was 63.1%. The carbon number distribution of the hydrocarbon in the cracked oil obtained in Fig. 6 is shown. It is shown that the carbon number is distributed over a wide range, but double bonds are conserved.

In addition, yatropha oil has a high content of phosphoric acid and remains in the fuel oil when it is converted into fuel by the conventional method, and it has become a problem to damage the engine and the like. In the IPC, the concentration of phosphoric acid in yalatrophasic oil was determined to be about 10 mg / L in the case of crude oil and 0.9 mg / liter in decomposed oil. It was shown that the phosphoric acid in the raw material holding was not transferred to the decomposition channel and the decomposed oil having a low phosphoric acid content was obtained.

The carbon number distribution of hydrocarbons in the cracked oil obtained from lard in Example 9 is shown in Fig. 7, and the carbon number distribution of hydrocarbons in the cracked oil obtained from the tongue in Example 10 is shown in Fig. Hydrocarbons having a wide carbon number from C5 to C34 from the lard and C5 to C31 from the tallow were produced. The contents of light oil and light oil in the cracked oil were all about 65%.

It has become apparent from the above examples that oil components can be easily collected from waste cooking oil, milking raw materials and animal fats. The method of producing the biodiesel fuel according to the present invention does not require an alcohol (sub ingredient) and is highly useful because glycerin is not produced as a by-product.

Example 11

The same procedure as in Comparative Example 1 was carried out except that the catalyst used in Comparative Example 1, in which the spent catalyst was poisoned with NaCl, was used.

In addition, a catalyst in which the FCC spent catalyst was poisoned with NaCl was prepared by adding 1.0 L of 50 g / L NaCl aqueous solution to 50 g of the FCC spent catalyst at 50 캜 5 캜 for 1 hour. The acid point of the catalyst obtained by this method was about 90% poisoned. When the acid sites of the catalysts obtained by this method were evaluated by the ammonia oxidation escape method, about 90% of the acid sites were poisoned.

Example 12a

The same procedure as in Comparative Example 1 was carried out except that silica serving as a solid acid catalyst was used as a catalyst.

Example 12b

The same procedure as in Comparative Example 1 was carried out except that the catalyst used in Example 12a was used in which the silica was poisoned with an aqueous magnesium nitrate solution.

A catalyst in which silica was impregnated with an aqueous solution of magnesium nitrate was prepared by adding 1.0 L of an aqueous solution of 50 g / L of Mg (NO ₃ ) ₂ to 50 g of silica and treating the mixture at 50 ° C ± 5 ° C for 1 hour. When the acid sites of the catalysts obtained by this method were evaluated by the ammonia oxidation escape method, about 90% of the acid sites were poisoned.

Example 13

The same procedure as in Comparative Example 1 was carried out except that the catalyst used in Comparative Example 1 was an FCC spent catalyst poisoned with Mg and further loaded with magnesium oxide.

In addition, in the case of the catalyst in which the FCC spent catalyst was poisoned with Mg and magnesium oxide was loaded, 1.0 L of 50 g / L of Mg (NO ₃ ) ₂ aqueous solution was added to 50 g of the FCC spent catalyst and the mixture was treated at 50 ° C ± 5 ° C for 1 hour I wrote. The term "supported" as used herein refers to a state in which magnesium oxide is included in the catalyst, which is more than poisoning of the acid.

Table 4 shows the results when poisoning the acid sites. The upper part of the table shows the yields of the products and the yield of the decomposition oils in Comparative Examples 1, 11, 12a, 12b, and 13.

Alkali poisoning of the solid acid catalyst increased the production of CO ₂ and improved the yield of the cracking oil. Further, by supporting magnesium oxide, the production of CO ₂ is increased and the yield of the decomposition oil is improved. The yield was improved and the amount of residue was reduced. The details of the residue are shown in Table 4 below. It is considered that the amount of the coke to be poured in comparison with Comparative Examples 1 and 2 was remarkably decreased and the yield of the decomposition oil was improved because the cleavage of the double bond portion in the oil was reduced by alkaline poisoning of the solid acid catalyst.

Example 14

The procedure of Example 2 was repeated except that the reaction temperature was set to 350 캜.

Example 15

The procedure of Example 2 was repeated except that the reaction temperature was changed to 475 ° C.

Comparative Example 2

The procedure of Example 2 was repeated except that the reaction temperature was set to 300 캜.

Comparative Example 3

The procedure of Example 2 was repeated except that the reaction temperature was 550 캜.

Table 5 is a table showing the influence on the rate of the cracked oil at each temperature and shows the amount of product and the yield of the cracked oil in Comparative Example 2, Example 14, Example 2, Example 15 and Comparative Example 3 .

From this, it was shown that the temperature range of the reaction was preferably 350 ° C to 475 ° C. 300 ° C (Comparative Example 2), the reaction is slow and not practical. Further, since the polymerization solidification of the oil occurred, it was considered that the residual amount increased and the productivity of the hydrocarbon decreased. In Comparative Example 3, the yield of the decomposition oil was low and the amount of residue was large, so that pyrolysis occurred and the amount of gas or coke was increased.

Comparative Example 4

When the reaction is repeated a lot, the activity of the catalyst is gradually lowered. The same procedure as in Example 2 was carried out except that the 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 maintained at 500 ° C ± 20 ° C for 6 hours while flowing a mixed gas of 50% air and 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 wing was rotated at 10 times / minute and stirred slowly. The same procedure as in Example 2 was followed except that the regenerated catalyst was used.

Example 17

And the holding temperature at the time of regeneration was 550 占 폚 占 쏙옙 20 占 폚.

Example 18

And the holding temperature at the time of regeneration was 600 占 폚 占 20 占 폚.

Comparative Example 5

And the heating and holding temperature of the catalyst at the time of regeneration was changed to 450 ° C ± 20 ° C.

Comparative Example 6

And the heating and holding temperature of the catalyst at the time of regeneration was set to 650 ° C ± 20 ° C.

Table 6 shows the results of Example 2, Comparative Examples 4 to 6, and Examples 16 to 18 showing the influence of the regeneration and regeneration temperature of the catalyst. From this, it was shown that the catalyst can be regenerated by keeping the temperature at 500 to 600 占 폚 in an atmosphere containing oxygen. At 450 ° C (Comparative Example 4), the regeneration was slow, the carbon remained, and the activity was low. In addition, it has been shown that activity is lowered at 650 DEG C, which is not preferable. It is believed that the regenerated product (Example 16-18) exhibited a higher recovery rate of the recovered oil than the new catalyst (Example 2) contributed by the weakening of the acid point by use.

Example 19

And the liquid space velocity was 0.05 / h.

Example 20

And the liquid space velocity was 2.0 / h.

Comparative Example 7

And the liquid space velocity was 0.02 / h.

Comparative Example 8

And the liquid space velocity was 4.0 / h.

Table 7 shows the effect of the liquid space velocity on the decomposition oil yield and shows the amount of product and the yield of decomposition oil in Comparative Example 7, Example 19, Example 20 and Comparative Example 8. [

From this, it was shown that the range of the liquid space velocity is preferably 0.05 / h to 2.0 / h. In the case of 0.02 / h (Comparative Example 7), the processing rate is low, the treatment efficiency is low, and the yield is lowered due to secondary decomposition of the resulting oil component, which is not preferable. In the case of 4.0 / h (Comparative Example 8), the yield of the decomposition oil is low and the amount of the residue is large, so that the contact time with the catalyst and the oil or the like is shortened and the degradation rate of the maintenance degradation is considered to be decreased.

Example 21

The same procedure as in Comparative Example 4 was carried out except that the reactor of Embodiment 3 was used. In the first reaction vessel 32 of the reaction apparatus C, silica in which magnesium oxide was supported as the retained decarbonic acid catalyst A (33) was used. In the second reaction vessel 34, an FCC spent catalyst poisoned with Na was used as the sustained decarboxylation catalyst B (35).

In addition, the silica carrying magnesium oxide was prepared in the same manner as in Example 2.

The FCC spent 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 addition, the oxidation and iodine values in Table 8, and the measurement of the oxidation stability were in accordance with the BDF specification of the Ministry of Resources and Energy. The acid in the product was reduced by installing a second reaction furnace.

(Industrial availability)

Disclosure of the Invention It is an object of the present invention to provide a process for producing glycerin, which does not require an alcohol (subsidiary raw material) from a fat or milking raw material and does not produce glycerin as a by-product and also prevents impurities such as dienes and hydroxyl groups from being retained in the product, It is possible to provide a method for producing a biodiesel fuel which is stable against air and is hardly blackened or odorous and is excellent in storage stability because impurities such as carboxylic acid (free fatty acid) are not easily produced as a by-product. Further, the pretreatment for removing the free fatty acid from the raw material oil is not required, and the reaction can be performed at atmospheric pressure, so that the manufacturing process can be simplified and the reaction device can be simplified, It is possible to provide an apparatus for producing biodiesel fuel capable of constructing a supply system. In addition, since there is no problem that the activity of the catalyst is lowered by the by-produced free fatty acid, there is no increase in the running cost or a decrease in the productivity due to the additional operation such as treatment or re-activation of the used catalyst, It is possible to provide a decarbonated decomposition catalyst for use in a production method of a biodiesel fuel having excellent productivity.

1: Reactor 2 of Embodiment 1: Reaction vessel
3: Deasphalting decomposition catalyst 4: Heater
5: Raw material input portion 6: Flow gas introduction portion
7: Stirring apparatus 8: First deriving tube
9: decomposition oil storage section 10: discharge pipe
11: Cooling tube 12: Cooling trap device
13: gas discharge pipe 21: reaction device of Embodiment 2
22: raw material holding heating unit 23: auxiliary heating unit
31: Reactor 32 of Embodiment 3: First reaction vessel
33: Deuterated decarbonation catalyst A 34: Second reaction vessel
35: Deasphalting carbonic acid decomposition catalyst B 38: Second derivation pipe

Claims (14)

Wherein the oil or fat is contacted with a fatty acid decarboxylating catalyst comprising a solid acid catalyst in which the acid point is poisoned by at least one of an alkali metal and an alkaline earth metal in a reaction vessel at 350 DEG C to 475 DEG C, method of producing a biodiesel fuel which comprises mainly produce hydrocarbons of C ₈ ~C ₂₄ in the decarboxylation reaction represented by (screen 1) decomposition by the acid catalyst.
However,

The method according to claim 1,
Wherein the solid acid catalyst comprises an FCC catalyst. At least one of a mixture of activated carbon, activated coke, alumina, silica, alkaline-modified non-acid-modified zeolite, clay minerals, and their complexes in the reaction vessel at 350 ° C to 475 ° C is a hydroxide, in maintaining decarboxylation decomposition catalyst and the holding or decarboxylation reaction milking material is to be contacted, and represented by (screen 2) by the holding decarboxylation decomposition catalyst comprising coated by at least one of the carbonate C ₈ ~ _Wherein the hydrocarbons are mainly formed of hydrocarbons of C < RTI ID = 0.0 > _{24. &} Lt; / RTI >
[Figure 2]

4. The method according to any one of claims 1 to 3,
Wherein the oil or fat is contacted with the deasphalting decomposition catalyst and heated to 350 ° C to 475 ° C prior to decarboxylation. 4. The method according to any one of claims 1 to 3,
Wherein a water vapor having a molar ratio of 1/10 to 10/1 (H ₂ O / sustained) coexists in the decarbonation decomposition reaction. An apparatus for producing a biodiesel fuel for use in a method for producing a biodiesel fuel according to any one of claims 1 to 3,
A first reaction vessel having the deasphalting decarboxylase decomposition catalyst therein; a heating unit for heating the fat decarbonation decomposition catalyst or the oil or fat or milk-growing raw material; a feed unit for feeding the milking raw material or oil into the first reaction vessel; And a first gas lead-out portion for leading the generated gas mixture from the first reaction vessel. The method according to claim 6,
A second reaction vessel connected to the first gas lead-out unit and filled with the holding decarbonation decomposition catalyst, a gas introduction unit for introducing the product gas mixture of the first reaction vessel into the inside of the second reaction vessel, 2. A biodiesel fuel producing apparatus according to claim 1, further comprising a second gas leading-out portion for leading a decarbonated gas mixture to said holding decarboxylation cracking catalyst in said reaction vessel. delete delete delete delete delete delete delete

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