JP5793288B2 - Bio-petroleum fuel production method and catalyst and production system used therefor - Google Patents

Description

  BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a production method for producing bio petroleum fuel from fats and oils, and a catalyst and production system used therefor. The present invention relates to a catalyst and a manufacturing system.

  In recent years, diesel engines have been reviewed from the expectation for carbon dioxide emission reduction, and diesel engines using bio-based fuels are being actively studied from the viewpoint of effective use of resources. Such bio-based fuels for diesel engines are called “biodiesel fuels”, and vegetable oils such as rapeseed oil, sunflower oil, soybean oil, and corn oil, and waste cooking oils thereof are used as crude oil, which is used as alcohol. It is provided as a fatty acid alkyl ester obtained by esterification with glycerol to separate and remove glycerin. When producing biodiesel fuel by fatty acid methyl esterification, methanol with a raw oil / fat ratio of 20% or more and an appropriate molar ratio or more, and a strong alkali agent (in the case of a basic catalyst production method) or a strong acid (in the case of an acid catalyst method) Therefore, an ion exchange resin having a transesterification function or the like is used, a large amount of methanol is required as an auxiliary material, and many of the catalysts are mixed materials that are difficult to reuse. And the fatty acid characteristics of the fats and oils that are the main raw materials remain even after the transesterification, and the residual fat and oil properties cause engine troubles during cold, and the differences in the raw oils and fats are pour point, cloud point, and clogging point. In the fuel quality standard values such as the above, it is difficult to select and manage the fuel for the fuel quality standard value as it appears as a difference in quality as it is.

  On the other hand, the biodiesel fuel is an oxygen-containing fuel that contains oxygen in its chemical structure, and since it contains almost no sulfur, it emits less harmful exhaust gases such as black smoke and is derived from plants, so it is a Kyoto Protocol. According to the regulations shown in, carbon dioxide emissions are zero counts. For this reason, it is attracting attention as an alternative to light oil with a low environmental impact. In Europe and the United States, standards and legal systems have already been established, and in 2005, over 5 million tons of soybean and rapeseed oil are produced and used annually.

  As for biodiesel fuel that has been in the spotlight in this way, a manufacturing method thereof is proposed in Patent Document 1 (Japanese Patent Laid-Open No. 2008-239938). In this Patent Document 1, a process of using oils and fats having an acid value of 20 or less as a raw material, heating the raw material oil under reduced pressure to distill off moisture, odorous substances and free fatty acids, and contacting the raw material oil with a hydrophilic adsorbent A step of adsorbing and removing remaining free fatty acids and acidic substances, a step of transesterification in the presence of a potassium-based alkali catalyst, and a step of purifying a light liquid component of a reaction product by the transesterification reaction in a non-aqueous method. A method for producing biodiesel fuel containing

  Moreover, in patent document 2 (Unexamined-Japanese-Patent No. 2009-138185), in the manufacturing method of the biofuel which makes lower monohydric alcohol react with waste white clay currently disperse | distributed in the organic solvent in presence of an enzyme, and makes it ester. It has been proposed to carry out the reaction in the presence of zeolite, sodium carbonate or alumina.

  Patent Document 3 (Japanese Patent Application Laid-Open No. 2009-235313) discloses contact of fats and oils that synthesize fuel suitable for high-quality diesel engines at low cost and without by-products from deteriorated waste cooking oils and fats and oils containing impurities. Regarding the decomposition method, a granular solid acid catalyst is heated to a temperature range of 350 ° C. 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 catalytic cracking method for synthesizing a hydrocarbon mixture suitable as a fuel for a diesel engine or the like mainly composed of olefins having 10 to 25 carbon atoms and paraffin has been proposed.

JP 2008-239938 A JP 2009-138185 A JP 2009-235313 A

  The biodiesel fuel by fatty acid methyl esterification in the previous example is a production method in which the fatty acid characteristics of the raw oil and fat remain, so even when it is completely methyl esterified, the phenomenon of thickening and clouding occurs at cold temperatures. Appears and causes troubles in vehicles used. In addition, the use of a large amount of expensive methanol derived from fossil raw materials increases the production cost. In addition to producing glycerin and spent catalyst as a by-product, there are problems of secondary waste such as producing residues. is there. Furthermore, impurities (for example, dienes, hydroxyl groups, etc.) in the raw material oil remain in the product, and the produced oil becomes unstable to air, which has been a major obstacle to the spread of biodiesel fuel. .

  Accordingly, the present invention first solves the problems derived from the production of biodiesel fuel by such fatty acid alkyl esterification, and a method for producing bio-petroleum fuel that can be carried out with simple equipment and at low cost, and to be used for it. It is an object to provide a catalyst and a manufacturing system.

  In addition, fatty acid alkyl esterification requires a large amount of methanol derived from fossil fuels, but in the present invention, components derived from such fossil fuels are not used, and bio-petroleum fuel is easily produced from raw oils and fats. The second problem is to improve the fluidity and clogging, which are obstructive factors in the use of fuel by eliminating the characteristics of the raw oil and fat.

  In Patent Document 3, a granular solid acid catalyst is heated to a temperature range of 350 ° C. to 450 ° C. in a reaction vessel, and liquid oil is brought into contact with the solid acid catalyst so that an oxygen-containing component is obtained from the oil. Although a method for catalytic cracking of biodiesel fuels mainly composed of olefins having 10 to 25 carbon atoms and paraffin has been proposed, there is still room for improvement with respect to the stability of the produced biodiesel fuel.

  Therefore, a third object of the present invention is to provide a bio-petroleum fuel production method having higher stability than ever, a catalyst used in the method, and a production system.

  In order to solve at least one of the above problems, the present invention provides a method for producing bio petroleum fuel by a pyrolysis method.

  That is, a bio-petroleum fuel production method for producing bio-petroleum fuel by pyrolyzing fats and oils, wherein the fats and oils are converted into a solid catalyst mainly composed of zeolite in a temperature range of 350 ° C. to 380 ° C., preferably 350 ° C. to 370 ° C. This is a bio-petroleum fuel production method comprising a pyrolysis step for contacting and a cooling step for obtaining bio-petroleum fuel by cooling a gas component generated in this temperature range.

  By lowering the higher fatty acid hydrocarbon chain by thermal decomposition and bringing it closer to the molecular chain of petroleum fuel, it is possible to eliminate fatty acid characteristics that are an impediment to fuel use. In addition, mere thermal decomposition requires heating to raise the temperature to a high temperature range, and measures against organic polymers and corrosive transpiration gases due to carbonyls generated synergistically during thermal decomposition at high temperatures are also required. Therefore, in order to reduce this, that is, in order to obtain a liquefied fuel (bio petroleum fuel) efficiently and with a high yield, a solid catalyst that bears the decomposition power is also used.

  In such a method for producing bio-petroleum fuel, biomass fuel is obtained by thermally decomposing vegetable oils such as palm oil, rapeseed oil, corn oil, soybean oil, animal oils such as lard, and oils and fats such as these waste edible oils, which are raw materials (treatment targets). Unlike the production method of biodiesel fuel by fatty acid methyl esterification, it is not necessary to use a large amount of methanol, and glycerin and its use. Problems such as generation of spent catalyst as a by-product can also be solved.

  The catalyst used in the present invention comprises a base portion made of clay formed in a granular shape, gravel shape, plate shape or cylindrical shape, and a zeolite portion as a surface covering material covering the surface, and is formed on the surface of the base portion. Zeolite is deposited on the surface and calcined. By using such a solid catalyst, the solid catalyst can be used repeatedly, and it can be used repeatedly by placing it in a container for thermal decomposition, and maintenance is also easy. Become. In particular, when the solid catalyst is appropriately modularized into blocks, such as a block, and placed in a container, the ease of taking out can be further improved.

  The zeolite-based solid catalyst is preferably formed by applying zeolite on the surface of a clay formed in a granular shape, gravel shape, plate shape, or cylinder shape and calcining it.

  Zeolite may be synthesized as well as naturally derived. As such zeolite, it is desirable to use natural zeolite itself, but it may be an appropriately crushed and pulverized zeolite. This is because if natural zeolite is used, a porous structure having a large pore size (pore size) and a rich surface can be obtained without destroying the crystal structure. In this way, the zeolite having a large surface area and pore size can improve fluid contact and prevent clogging, and can be used stably over a long period of time. In addition, it is possible to add inorganic oxides such as silica and alumina or active metals such as nickel and molybdenum to the zeolite as necessary.

Clay is a clay used in the manufacture of pottery, and is composed of particles with a particle size of 5μm or less, mainly composed of layered silicate minerals, consisting of calcite, dolomite, feldspar, zeolites, etc. Can be used. In particular, among clay, it is desirable to use porcelain excluding porcelain stones that have not been weathered. Clays particularly desirable for use are clays containing silicon or alumina, and by using these clays, the produced bio petroleum fuel becomes green and the degree of oxidation can be reduced.

  Further, since the zeolite is coated on the surface of the clay and calcined, the properties of the solid catalyst itself as an acidic catalyst are weakened, and as a result, the oxidation stability of the bio-petroleum fuel produced can be enhanced. When firing the clay coated with zeolite, the temperature is desirably set to about 1200 ° C.

  The solid catalyst thus produced becomes a solid catalyst comprising a base portion made of clay formed in a granular, gravel-like, plate-like or cylindrical shape, and a zeolite portion covering the surface thereof, which is also the present invention. And at least one of the above-described problems can be solved.

  The base portion can be formed in various shapes, and is formed into a granular shape with a particle size of about 1 to 3 mm, a gravel shape with a particle size of about 2 to 75 mm, and various columnar bodies such as a triangular column, a quadrangular column, and a cylinder. It can be formed into a shape, a pyramid shape such as a triangular pyramid or a cone, or a flat plate shape, and can also be formed into a shape with an enlarged surface area such as a hollow cylindrical shape or an annular shape. When the surface area is increased by forming holes and protrusions in the base part, the amount of zeolite adhering to this will also increase, further increasing the contact area with the raw oil during pyrolysis This is desirable in terms of production efficiency and the nature of the produced bio petroleum fuel.

  In the method for producing bio-petroleum fuel according to the present invention, it is desirable to use the residue in the pyrolysis step as the fuel in the pyrolysis step.

  When fats and oils are pyrolyzed using a solid catalyst, the raw oils and fats are broken down into bio petroleum fuel, bio heavy oil, acrolein, and water. The molecular chain length of the fatty acid in the oil and fat is lowered and becomes different from that of each fatty acid methyl ester produced by fatty acid methyl esterification by approaching the hydrocarbon oil. By using the generated bio heavy oil as an energy source for thermal decomposition of fats and oils, that is, fuel such as a burner, the raw material is only fats and oils, no external fuel is required, and the generated waste is substantially It is possible to construct a bio-petroleum fuel production method and system that can complete a production cycle that does not occur in

  When fats and oils are thermally decomposed using a solid catalyst by the production method provided by the present invention, the raw oils and fats are decomposed into bio-petroleum fuel, bio-heavy oil, acrolein, and water. And since this pyrolysis does not require the methanol used in the conventional fatty acid methyl esterification, the raw material cost can be greatly reduced, and since it is not necessary to use an alkali component, There is no adverse effect. Furthermore, the use of a strong alkali is a factor that promotes saponification of fatty acids, but in the present invention, such a problem does not occur because the strong alkali is not used.

  Furthermore, in the thermal decomposition method of fats and oils according to the present invention, palm oil, lard, beef tallow with a large amount of cloudy fatty acids, and oils and fats with high iodine value / unsaturated content are equally reduced (decomposed), so there is no waste. It is possible to produce a bio-petroleum fuel with a stable property that is not easily clouded with low clay at low cost.

In addition, the fats and oils used as raw materials have various types and degrees of deterioration, and water and impurities may be mixed in. In the fatty acid methyl esterification, there is a problem that these inhibit the reaction. . In addition, when raw material fats and oils are obtained on the market, fatty acids such as fats and oils with a long fatty acid hydrocarbon chain length such as animal fats and palm oils and fats containing a large amount of unsaturated components, and fats and oils containing food additives, etc. Only raw oils and fats suitable for methyl esterification could not be strictly selected and sorted.

  In this respect, according to the thermal decomposition method of raw material fats and oils according to the present invention, the fatty acid hydrocarbon chain is decomposed and converted into a hydrocarbon oil having a low boiling point, so that there is no azeotropic property between the main component and impurities, and It is possible to achieve a bio-petroleum fuel production system that can be refined under pressure and can be operated at low cost. Furthermore, the thermal decomposition method according to the present invention is applicable to fats and oils in general, has low impediments to decomposition of impurities, and does not require complicated process management, and can reduce raw oil and fat sorting and collection costs and pretreatment costs. it can.

  Furthermore, in the method for producing bio-petroleum fuel according to the present invention, since the above-described solid catalyst is used, the thermal decomposition temperature is suppressed to a comparatively low temperature range (350 to 380 ° C., preferably 350 to 370 ° C.). This eliminates the need for heating energy for raising the temperature to a high temperature range, and also suppresses the corrosive transpiration gas generated synergistically at the time of thermal decomposition at a high temperature, thereby allowing the bio petroleum fuel to be distilled. In addition, it is possible to reduce the production of organic compounds due to carbonyl, such as carboxylic acid which is an impurity of bio petroleum fuel.

Schematic showing a bio-petroleum fuel production apparatus in the present embodiment It is sectional drawing which shows a solid catalyst, (A) shows the solid catalyst formed in gravel shape, (B) has shown the solid catalyst formed in the single-hole cylindrical shape.

  FIG. 1 is a schematic diagram showing a bio-petroleum fuel BF production apparatus according to the present embodiment. The bio-petroleum fuel BF production apparatus according to the embodiment is a container that performs thermal decomposition by bringing a solid catalyst 80 into contact with oil to be treated. The cracking distillation unit 10, the burner unit 20 that superheats the cracking distillation unit 10, the fraction storage unit 30 that stores the bio-petroleum fuel BF decomposed in the cracking distillation unit 10, and the cracking distillation unit 10 An oil feed tank 40 for supplying the raw oil and fat BM and a recovery tank 50 for recovering the heavy oil component BO remaining in the fractional distillation section by thermal decomposition.

  The supply of the raw material fats and oils BM from the oil feed tank 40 to the cracking distillation unit 10 may be a continuous type or a batch type, and the supply timing and supply amount thereof are the first valve 61 provided in a transport pipe provided therebetween. Is done by. If a certain amount of raw material fat BM is continuously supplied to the cracking distillation unit 10, the valve 61 is opened to such an extent that the predetermined material can be supplied, while the raw material fat BM is batch-resolved. In the case of supplying to 10, the valve 61 is closed during the thermal decomposition treatment, and the first valve 61 is opened so as to supply the raw material fat BM to the decomposition distillation unit 10 at the stage when the thermal decomposition is completed. You can also.

  Further, the heavy oil component BO remaining in the cracking distillation unit 10 due to the thermal decomposition is put into the recovery tank 50 by opening and closing the second valve 62 provided in the transport pipe provided between the cracking distillation unit 10 and the recovery tank 50. Collected. The recovery timing of the heavy oil component BO can be recovered every time the thermal decomposition process is completed, or can be recovered after several thermal decompositions. And the heavy oil component BO collect | recovered by the collection tank 50 can be used as a fuel of the burner part 20 which supplies the heat | fever for thermal decomposition.

  In the present embodiment, the cracking distillation section 10 is filled with a solid catalyst 80 having a particle size adjusted to around 10 mm. As the solid catalyst 80, a ceramic clay containing silicon and alumina is shaped into a gravel shape, coated with natural zeolite, and calcined at 1200 ° C. is used. Due to the firing, the zeolite is attached to the surface of the clay and the zeolite comes into contact with the fats and oils. Although it is not considered that natural zeolite can be used as the solid catalyst 80 as it is, in this case, it is necessary to separate the heavy oil component BO remaining in the cracking distillation section 10 from the zeolite. As shown in the embodiment, the solid catalyst 80 is preferably formed in a gravel shape. In addition, the solid catalyst 80 can also be formed in a single-hole cylindrical shape. In this case, the contact area between the zeolite and the fats and oils can be increased by increasing the surface area.

  2 is a cross-sectional view showing the solid catalyst 80 formed as described above. FIG. 2A is a solid catalyst 80 formed in a gravel shape, and FIG. 2B is a single-hole cylindrical shape. A solid catalyst 80 is shown. In any of these solid catalysts 80, zeolite 82 is attached to the surface of the base material portion 81 made of porcelain clay.

  In the bio petroleum fuel BF production apparatus configured as described above, the oil in the cracking distillation unit 10 is heated from 350 ° C. to about 370 ° C. by heating the cracking distillation unit 10 by the burner unit 20. As a result, the oil and fat in the cracking distillation unit 10 is combined with the contact with the solid catalyst 80, and the hydrocarbon chain is cut into a molecular chain equivalent to the hydrocarbon oil, which is discharged as a gas from the outlet. Is done. Gaseous hydrocarbon components discharged from the outlet are cooled and aggregated by a condenser (not shown) installed in a transfer pipe leading to the fraction storage section 30 and fractionated as bio petroleum fuel BF. It is stored in the storage unit 30. It was confirmed that the bio-petroleum fuel BF recovered in the fraction storage 30 by this treatment contains a component close to gasoline in addition to the biodiesel fuel component. It is also effective to supply an inert gas such as helium into the fraction storage 30 during the pyrolysis process to prevent ignition of gas components.

  On the other hand, the heavy oil component BO remaining in the fraction storage unit 30 at the end of the thermal decomposition process is stored in the recovery tank 50 that recovers the heavy oil component BO, and can be used as fuel for the burner unit 20. Further, it is desirable that acrolein and hydrocarbon gas generated by the thermal decomposition of fats and oils are recovered so as not to evaporate to the outside, and are returned to the burner unit 20 for combustion.

  According to the present invention, the ease of manufacturing bio-petroleum fuel can be improved and the manufacturing cost can be greatly reduced, which can greatly contribute to the spread of bio-petroleum fuel. Furthermore, not only the effective use of resources but also the spread of plant-derived bio-petroleum fuel makes it possible to minimize the environmental load, such as zero emissions of carbon dioxide.

DESCRIPTION OF SYMBOLS 10 Cracking distillation part 20 Burner part 30 Fractionation storage part 40 Oil supply tank 50 Recovery tank 61 1st valve 62 2nd valve 80 Solid catalyst 81 Base material part 82 Zeolite BF Bio petroleum fuel BM Raw material fat BO Heavy oil component

Claims (2)

A bio-petroleum fuel production method for producing bio-petroleum fuel by pyrolyzing fats and oils,
A pyrolysis step in which fats and oils mainly contact with a solid catalyst formed in a granular, gravel-like, plate-like or cylindrical shape in a temperature range of 350 ° C. to 380 ° C .;
A cooling step of obtaining bio-petroleum fuel by cooling the gas component generated in this temperature range,
In the pyrolysis step, the solid catalyst and the fat to be treated are filled in the cracking distillation section as a container for contacting the solid catalyst and the fat to be treated for thermal decomposition, and the cracking distillation section is heated, whereby the cracking distillation is performed. close to the molecular chain of the petroleum fuel is lower the higher fatty hydrocarbon chain by pyrolyzed by heating the fat portion to about 370 ° C. from 350 ° C., the oil in the destructive distillation unit, biodiesel fuel component , Decomposed into components close to gasoline, bio heavy oil, acrolein, water,
The solid catalyst is obtained by applying natural zeolite to the surface of clay formed in granular, gravel, plate or cylinder and calcining, and is placed in the cracking distillation section and repeatedly in multiple pyrolysis steps. A method for producing bio-petroleum fuel, characterized by being used.
  The method for producing bio-petroleum fuel according to claim 1, wherein the residue in the pyrolysis step is used as a fuel in the pyrolysis step.