JP2009179785A - Apparatus for manufacturing fuel oil, method for manufacturing fuel oil, and fuel oil obtained thereby - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide such an apparatus for manufacturing a fuel oil as is slight in a load to the environment and is excellent in the operation efficiency and also is capable of manufacturing in high yield a fuel oil usable even in a cold district. <P>SOLUTION: The fuel-oil manufacturing apparatus which manufactures a fuel oil from at least one oil-stuff plant selected from the group consisting of fruits of an oil palm, fruits of jatropha, sesame seeds, soy bean seeds and rape seeds, comprises a pulverization means for pulverizing an oil-stuff plant, a first heating means for heating a vegetable oil obtained from the oil-stuff plant pulverized by the pulverization means to thereby remove the water content, a second heating means for heating and vaporizing the vegetable oil, the water of which is removed by the first heating means, a catalyst vessel for modifying a gas which is vaporized by the second heating means, with making contact with an aluminosilicate-based catalyst, and a cooling means for cooling and liquefying the gas modified in the catalyst vessel. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a fuel oil production apparatus, a fuel oil production method, and a fuel oil obtained thereby.

In recent years, the global warming phenomenon has become a serious problem on a global scale. As one of the solutions, biomass energy such as biodiesel fuel (BDF) that can be used as a substitute for fossil fuel has been actively researched. It is being put into practical use.
BDF is a fatty acid ester that is subjected to a transesterification reaction by adding methanol, a catalyst, etc. to fats and oils of animals and plants, and has attracted attention as an alternative fuel for light oil. As a raw material for BDF, soybean is mainly used, but soybean is used as a staple food in many countries and also as a livestock feed. For this reason, the use of soybeans for BDF has caused problems such as the possibility of causing food difficulties in various countries around the world, and the rise in prices of everyday items other than soybeans.

As a BDF raw material other than soybean, palm oil obtained from oil palm fruit has been studied. Oil palm fruit, which is a raw material of palm oil, is grown and planted in large quantities in Southeast Asia and the like, and can be harvested three times or more a year, and the price is lower than other raw material plants. Furthermore, it has been used only for limited applications such as cosmetics and soaps.
The present inventors tried to use oil palm as a BDF raw material, using crude palm oil (CPO) obtained by squeezing and washing oil palm fruit as a raw material, heating the CPO to remove moisture, and then pyrolyzing There has already been proposed a method for producing fuel oil by heating and gasifying in a tank and bringing this gas into contact with an aluminosilicate catalyst in a catalytic cracking tank. In this method, vegetable oils such as corn oil, soybean oil, rapeseed oil and the like can be used as a material to be treated in addition to CPO.

By the way, the characteristics of BDF are somewhat affected by the raw materials. When palm oil is used as a raw material, it tends to harden at a low temperature, so that there is a problem that it is difficult to use in cold regions. In order to enable use in a cold region, it is desirable for BDF to have a pour point of −15 ° C. or lower, but this has been difficult to achieve.
Oil palm fruit is very perishable and usually needs to be processed into CPO within 24 hours after harvest. Therefore, it becomes necessary to quickly process the CPO around the raw material collection site, and the place and time for manufacturing are limited, which is a factor of reducing workability.
Moreover, since the fruit of the oil palm which has been rotted is discarded, it has been a cause of waste and high cost.
Furthermore, when CPO was used as a raw material, the BDF obtained was about 20% when the mass of the oil palm fruit in the previous stage of CPO was 100%. In this yield, even if the fruit of oil palm is relatively inexpensive, the cost increases as a result, and it is necessary to improve the yield for commercialization.
Furthermore, when CPO is used as a raw material, impurities such as glycerin are generated in the production process of BDF, so it is necessary to remove glycerin by performing chemical treatment such as methyl esterification. Furthermore, the separated waste liquid such as glycerin can cause environmental destruction.

Therefore, an object of the present invention is to provide a fuel oil production apparatus that can produce a high yield of fuel oil that has a low environmental load, is excellent in workability, and can be used even in cold regions.
Another object of the present invention is to provide a method for producing fuel oil that can produce a high yield of fuel oil that has a low environmental burden, is excellent in workability, and can be used even in cold regions.
Another object of the present invention is to provide a fuel oil that has a low environmental load and can be used even in cold regions.

As a result of intensive studies, the present inventor has produced a fuel oil that produces fuel oil from at least one oil plant selected from the group consisting of oil palm fruit, jatropha fruit, sesame seed, soybean seed and rapeseed. An apparatus comprising: a pulverizing means for pulverizing the oil plant; a first heating means for removing moisture by heating the vegetable oil obtained from the oil plant pulverized by the pulverizing means; A second heating means for heating and vaporizing the vegetable oil from which moisture has been removed by the heating means; a catalyst tank for reforming the gas vaporized by the second heating means by contacting with the aluminosilicate catalyst; and According to the fuel oil production apparatus having a cooling means for cooling and liquefying the gas reformed in the catalyst tank, the fuel oil has a low yield on the environment, excellent workability, and can be used even in cold regions. Found that can be produced.
The present inventor has also provided a fuel oil production method for producing fuel oil from at least one oil plant selected from the group consisting of oil palm fruit, jatropha fruit, sesame seed, soybean seed and rapeseed. A pulverizing step of pulverizing the oil plant, a first heating step of heating the vegetable oil obtained from the oil plant pulverized in the pulverizing step to remove moisture, and the first heating step. A second heating step for heating and vaporizing the vegetable oil from which moisture has been removed; a reforming step for reforming the gas vaporized in the second heating step by contacting with the aluminosilicate catalyst; and the reforming According to the fuel oil manufacturing method having the cooling step of cooling and liquefying the gas reformed in the process to obtain the fuel oil, the fuel oil has a low environmental load, is excellent in workability, and can be used even in cold regions. Found that can be produced in yields.
Furthermore, the present inventor has found that the fuel oil obtained by the above production method has a small environmental load and can be used even in cold regions.
The present inventor has completed the present invention based on these findings.

That is, the present invention provides the following (1) to (21).
(1) A fuel oil production apparatus for producing fuel oil from at least one oil plant selected from the group consisting of oil palm fruit, jatropha fruit, sesame seed, soybean seed and rapeseed,
Pulverizing means for pulverizing the oil plant;
First heating means for removing moisture by heating the vegetable oil obtained from the oil plant pulverized by the pulverizing means;
Second heating means for heating and vaporizing the vegetable oil from which moisture has been removed by the first heating means;
A catalyst tank for reforming the gas vaporized by the second heating means by contacting with the aluminosilicate catalyst;
A fuel oil production apparatus comprising cooling means for cooling and liquefying the gas reformed in the catalyst tank.
(2) The fuel oil production apparatus according to (1), wherein the pulverizing means pulverizes the oil plant to an average particle size of 1 cm or less.
(3) The fuel oil production apparatus according to (1 or 2) above, wherein the oil plant is oil palm fruit.
(4) The fuel oil production apparatus according to any one of (1) to (3), wherein the fuel oil is a light oil alternative fuel.
(5) The fuel oil production apparatus according to any one of (1) to (4), wherein the pour point of the fuel oil is −15 ° C. or lower.
(6) The fuel oil production apparatus according to any one of (1) to (5), wherein the second heating unit heats the vegetable oil to 250 to 385 ° C. to vaporize the vegetable oil.
(7) The above (1) to (1), wherein the catalyst tank is a catalyst tank for reforming the gas vaporized by the second heating means by bringing the gas into contact with a zinc catalyst or a nickel catalyst and an aluminosilicate catalyst. 6) The fuel oil production apparatus according to any one of 6).
(8) The fuel oil production apparatus according to any one of (1) to (7), further comprising a filtering means for filtering the vegetable oil obtained from the oil plant pulverized by the pulverizing means.
(9) The fuel oil according to (8), wherein the filtration means is a compression type filter having a compression means for compressing the pulverized oil plant and the vegetable oil obtained from the pulverized oil plant. Manufacturing equipment.
(10) The fuel oil production apparatus according to any one of (1) to (9), further including a residue carry-out means for discharging a solid residue generated when the vegetable oil is heated in the second heating means.

(11) A fuel oil production method for producing fuel oil from at least one oil plant selected from the group consisting of oil palm fruit, jatropha fruit, sesame seed, soybean seed and rapeseed,
Crushing step of crushing the oil plant;
A first heating step of removing moisture by heating the vegetable oil obtained from the oil plant pulverized in the pulverization step;
A second heating step of heating and vaporizing the vegetable oil from which moisture has been removed by the first heating step;
A reforming step of reforming the gas vaporized by the second heating step by bringing it into contact with an aluminosilicate catalyst;
And a cooling step of cooling the gas reformed in the reforming step to obtain a fuel oil.
(12) The method for producing fuel oil according to (11), wherein in the pulverization step, the oil plant is pulverized to an average particle size of 1 cm or less.
(13) The method for producing fuel oil according to (11) or (12) above, wherein the oil plant is oil palm fruit.
(14) The fuel oil production method according to any one of (11) to (13), wherein the fuel oil is a light oil alternative fuel.
(15) The fuel oil production method according to any one of (11) to (14), wherein the pour point of the fuel oil is −15 ° C. or lower.
(16) The above (11) to (15), wherein the reforming step is performed by bringing the gas vaporized in the second heating step into contact with a zinc-based catalyst or a nickel-based catalyst and an aluminosilicate-based catalyst. A fuel oil production method according to any one of the above.
(17) The fuel oil production according to any one of (11) to (16), further including a filtration step of filtering the vegetable oil obtained from the oil plant pulverized in the pulverization step after the pulverization step. Method.
(18) Any of the above (11) to (17), further including a residue carrying-out step of discharging solid residue generated when the vegetable oil is heated in the second heating step after the second heating step. The fuel oil manufacturing method as described in any one of.
(19) The fuel oil according to any one of (11) to (18), wherein the fuel oil is produced from the oil plant using the fuel oil production apparatus according to any one of (1) to (10) above. Production method.

(20) A fuel oil obtained by the fuel oil production method according to any one of (11) to (19) above.
(21) The fuel oil according to the above (20), which is a light oil alternative fuel.

According to the fuel oil production apparatus of the present invention, it is possible to produce a high-yield fuel oil that has a low environmental load, is excellent in workability, and can be used even in cold regions.
Moreover, according to the fuel oil production method of the present invention, a fuel oil that has a low environmental load, is excellent in workability, and can be used even in cold regions can be produced in high yield.
Further, the fuel oil of the present invention has a small environmental load and can be used even in cold regions.

  First, a fuel oil production apparatus of the present invention (hereinafter referred to as “the apparatus of the present invention”) will be described in detail based on a preferred embodiment shown in the accompanying drawings. However, the apparatus of this invention is not limited to embodiment shown below.

FIG. 1 is a diagram schematically showing an entire example of a fuel oil production apparatus of the present invention.
As shown in FIG. 1, the fuel oil production apparatus (hereinafter referred to as “the apparatus of the present invention”) 1 of the present invention is selected from the group consisting of oil palm fruit, jatropha fruit, sesame seed, soybean seed and rapeseed. A pulverizer 2 for pulverizing at least one oil plant, a filter 4 for filtering vegetable oil obtained from the oil plant pulverized by the pulverizer 2, and heating the vegetable oil filtered by the filter 4 A melting tank 12 for removing moisture, a heating furnace body 22 for heating and vaporizing the vegetable oil from which moisture has been removed by the melting tank 12, and a gas vaporized by the heating furnace body 22 as a zinc-based catalyst or a nickel-based catalyst. And a catalyst tank 32 for reforming by contacting with an aluminosilicate catalyst, and a heat exchanger 34 for cooling and liquefying the gas reformed in the catalyst tank 32.

  As oil plants used as a raw material for fuel oil in the present invention, oil palm fruit, jatropha fruit, sesame seed, soybean seed and rapeseed can be used. Oil palm fruit is preferred because of its low price and excellent yield. Jatropha fruit can also be cultivated in rough land where oil palm fruit does not grow, and Jatropha fruit can be suitably used because it is non-edible and does not cause a problem of food shortage.

The pulverizer 2 is not particularly limited as long as it is a means capable of pulverizing oil plants to obtain vegetable oil. Examples of the pulverizer 2 include a centrifugal pulverizer that can pulverize oil plants using centrifugal force (for example, a supermass colloider manufactured by Masuko Sangyo Co., Ltd.). Among these, a centrifugal grinder is preferable from the viewpoint of easily specifying the particle size.
As the centrifugal pulverizer, known centrifugal pulverizers can be used without particular limitation, and examples thereof include a rotary pulverizer described in JP-A-9-313967.

As the pulverizer 2, one having the ability to pulverize oil plants to an average particle size of 1 cm or less is preferable from the viewpoint of increasing the yield of vegetable oil. The yield at this time is about 40% by mass, for example, when oil palm fruit is used as a raw material, and the mass of oil palm fruit is 100%. When the yield is in this range, a profit is obtained in the business of the fuel oil obtained by the present invention. Therefore, it is a great practical advantage to make the yield in this range.
The pulverizer 2 has a performance capable of pulverizing to 10 to 200 μm, more preferably from the viewpoint of higher yield.

By the way, the oil palm fruit rots very rapidly, so in the method for producing fuel oil using CPO as a raw material, it is necessary to use palm oil processed within about 24 hours after harvesting as a raw material.
On the other hand, when the apparatus of the present invention is used, a spoiled oil palm fruit itself can be used as a raw material. Moreover, since the period which can be utilized as a raw material can be extended by freezing the fruit of oil palm, it is excellent in workability | operativity. It is preferable to use frozen oil palm fruit after it has been thawed from the point of being able to suppress the mixing of moisture.

  As the pulverizer 2, a commercially available product can be used. For example, Supermass colloider (centrifugal type) manufactured by Masuko Sangyo Co., Ltd., Selenmeister (stone mill type) manufactured by Masuko Sangyo Co., Ltd., or the like can be used.

The filter 4 is connected to the pulverizer 2 via a pipe line. Further, the filter 4 may be configured integrally with the pulverizer 2.
The filter 4 is not particularly limited as long as it can filter the vegetable oil obtained from the oil plant pulverized by the pulverizer 2. Examples of the filter 4 include a compression filter provided with a compression means for compressing a pulverized oil plant and a vegetable oil obtained from the pulverized oil plant. This is preferable from the viewpoint of increasing the yield of vegetable oil.
As the compression filter, a known compression filter can be used without particular limitation, and for example, a general filter press type compression filter can be used.

  As the filter 4, a commercially available product can be used, for example, a filter press machine manufactured by Nippon Reactor Co., Ltd. can be used.

The device 1 of the present invention preferably has a tank 16 connected to the filter 4 via a pipeline. The tank 16 is connected to the dissolution tank 12 through a pipe line P ₁ . Vegetable oils filtered by the filtration device 4 is stored temporarily in the tank 16 is supplied to the dissolving tank 12 from the tank 16 via line P _1. Tank outlet valve 16a is provided in the conduit P _1.

  A burner 14 is disposed in the lower part of the dissolution tank 12. By burning the kerosene supplied from a kerosene tank (not shown) in the burner 14, the vegetable oil is heated in the dissolution tank 12 to remove moisture. be able to.

A first hot air tank 18 is preferably disposed adjacent to the burner 14. Smoke caused by the combustion of the dissolution tank 12 is sent to the first temperature Kazeso 18 via line P _2, heat of the flue gas is recycled during the combustion of the burner 14. The dissolution tank 12 is connected to a smoke exhaust fan 12b via a dissolution tank smoke outlet valve 12a, and excess smoke is discharged.

The apparatus 1 of the present invention preferably has a tank 20 connected to the dissolution tank 12 via a pipe line P ₃ . The vegetable oil from which moisture has been removed in the dissolution tank 12 is sent to the tank 20 through the pipe line P ₃ and temporarily stored. Dissolving tank outlet valve 12c is provided in the conduit P _3. The tank 20 is provided with an inlet valve 20a, an outlet valve 20b, an inlet valve 20c, and a check valve 20d.

The preheated vegetable oil is supplied to the heating furnace body 22 from the tank 20 via the pipe line P ₄ . The tank 20 is provided with an inlet valve 20a and an outlet valve 20b.
The heating furnace body 22 includes a stirrer 22a and a fan 22b for discharging the smoke generated by the combustion.
Inside the heating furnace main body 22, a pyrolysis tank 24 for vaporizing vegetable oil at a high temperature is disposed. A burner 26 is disposed at the lower part of the heating furnace body 22. By burning the kerosene supplied from a kerosene tank (not shown) in the burner 26, the vegetable oil in the thermal decomposition tank 24 can be heated to 250-385 degreeC and can be vaporized.

  When vegetable oil is heated in the heating furnace body 22, a solid residue such as charcoal is generated. It is preferable that a screw conveyor 28 for discharging the residue is disposed at the lower portion of the heating furnace body 22. The discharged residue is a solid content and can be easily discharged by the screw conveyor 28. Since this residue can be reused for fertilizers and the like, there is an advantage that the load on the environment is small.

A second hot air tank 30 is preferably disposed adjacent to the burner 26. Smoke generated by the combustion in the pyrolysis tank 24 is sent to the second hot air tank 30 through the pipe P ₅ , and the heat of the smoke is reused when the burner 26 is burned.

The gas vaporized in the heating furnace body 22 is sent to the catalyst tank 32 through the pipe P _6, and passes through the zinc-based catalyst having a desulfurizing effect or the nickel-based catalyst having a desulfurizing effect filled in the catalyst tank 32. It is reformed in contact with an aluminosilicate catalyst.

The catalyst tank 32 is filled with a zinc-based catalyst or a nickel-based catalyst and an aluminosilicate-based catalyst, and can be reformed by contacting the gas vaporized in the heating furnace body 22 with the catalyst. The catalyst tank 32 may be filled only with an aluminosilicate catalyst, but when the zinc catalyst or nickel catalyst and the aluminosilicate catalyst are filled, the sulfur content contained in the vegetable oil can be removed. There is an advantage that a fuel oil closer to light oil can be obtained. Furthermore, since the zinc-based catalyst is generally cheaper than the nickel-based catalyst and has an excellent desulfurization effect, the catalyst tank 32 is more preferably filled with a zinc-based catalyst and an aluminosilicate-based catalyst.
The order of contacting the vaporized gas is preferably the order of zinc-based catalyst, nickel-based catalyst, and aluminosilicate-based catalyst. Before contacting the vaporized gas with the aluminosilicate catalyst, the sulfur content in the gas is reduced by bringing it into contact with the zinc catalyst or nickel catalyst, so that the aluminosilicate catalyst is less likely to deteriorate and the aluminosilicate catalyst. There is an advantage that the effect can be sustained for a long time. Moreover, the catalyst tank 32 has the smoke exhaust fan 32b for discharging | emitting smoke.

The zinc-based catalyst is not particularly limited as long as it has a desulfurization effect, and a known zinc-based catalyst can be used. For example, zinc oxide, copper, calcium, silica, chromium, alumina, calcium oxide (CaO), include those containing at least one such as calcium aluminate _{(CaO / Al 2 O 3)} . More specifically, a catalyst containing zinc oxide and alumina and a catalyst containing zinc oxide and calcium aluminate are preferred from the viewpoint of excellent desulfurization effect.
The content of zinc oxide in the zinc-based catalyst is preferably 10 to 95% by mass, more preferably 50 to 90% by mass, and 80 to 90% by mass from the viewpoint of excellent desulfurization effect. Is more preferable.

As the zinc-based catalyst, a catalyst obtained by calcining a catalyst precursor formed by coprecipitation using a zinc-containing component with alumina as a core is preferable from the viewpoint of excellent desulfurization effect.
Examples of the alumina include γ-alumina, β-alumina, pseudoboehmite and the like. These may be used alone or in combination of two or more.
The alumina is preferably in powder form.
The particle diameter of the alumina is preferably 1000 μm or less, more preferably 500 μm or less, and even more preferably 200 μm or less. When the particle size of the alumina is within this range, the alumina can be uniformly dispersed in the system, and a precipitate is easily formed on the alumina. Although there is no restriction | limiting in particular about the minimum of the particle size of an alumina, Usually, it is preferable that it is 1 nm or more, and it is more preferable that it is 10 nm or more.

The coprecipitation method for forming a component containing zinc with alumina as a core is specifically suspended in an aqueous zinc compound solution and mixed with a base, or suspended in an aqueous base solution. A catalyst precursor is formed by mixing an aqueous solution of the zinc compound with the suspension to cause precipitation of the zinc compound on the alumina.
As the zinc compound, zinc chloride, nitrate, sulfate, organic acid salt, hydroxide and the like can be used. Specific examples include zinc chloride, zinc nitrate, zinc sulfate, zinc acetate, and zinc hydroxide.
As the base, an aqueous solution of ammonia, sodium carbonate, sodium hydrogen carbonate, potassium carbonate or the like can be used.

A precipitate of zinc compound is produced on alumina using alumina as a nucleus, and the produced precipitate product (catalyst precursor) is filtered and washed with ion-exchanged water or the like. Insufficient cleaning leaves chlorine, nitric acid traces, sulfuric acid traces, acetic acid traces, sodium, potassium, etc. on the catalyst, which adversely affects catalyst performance. If ion-exchanged water cannot be used for sufficient washing, an aqueous solution of a base such as ammonia, sodium carbonate, sodium hydrogen carbonate, or potassium carbonate may be used as the washing liquid. In this case, it is preferable to first wash the precipitated product with an aqueous base solution, and then wash with ion-exchanged water.
After washing the precipitated product, the precipitated product is pulverized and then dried. After drying, baking is subsequently performed. If washing after precipitation is insufficient, washing may be performed again after firing. Also in this case, ion-exchanged water or an aqueous solution of the above-mentioned base can be used.

  The drying method is not particularly limited, and examples thereof include natural drying in air and degassing drying under reduced pressure. Usually, drying is performed at 100 to 150 ° C. for 5 to 15 hours in an air atmosphere. Moreover, it does not specifically limit as said baking method, Usually, it bakes at 200-600 degreeC in an air atmosphere, Preferably it is 250-450 degreeC for 0.1 to 10 hours, Preferably it is 1 to 5 hours.

The zinc-based catalyst obtained by calcining the catalyst precursor contains zinc oxide and alumina as constituent components.
The content of alumina in the catalyst is preferably 0.1 to 40% by mass, more preferably 0.5 to 35% by mass, and 1 to 30% by mass from the viewpoint of excellent desulfurization effect. Is more preferable.

  When the zinc-based catalyst prepared by the above method is used, it can be used for the reaction as it is, but a reduction treatment with hydrogen or the like may be performed as a pretreatment. As the conditions, the temperature is preferably 150 to 500 ° C, more preferably 250 to 400 ° C, and the time is preferably 0.1 to 15 hours, more preferably 2 to 10 hours.

The shape of the zinc-based catalyst is not particularly limited, and the catalyst obtained as a powder may be used as it is, or may be formed by tableting into a molded product. Moreover, it is good also as a catalyst which adjusted the particle size in the suitable range after grind | pulverizing the molded article. Furthermore, an extruded catalyst can be used. In molding, an appropriate binder may be added.
The binder is not particularly limited, and carbon black, alumina, silica, titania, zirconia, or a composite oxide thereof can be used.
As for the addition amount of a binder, it is preferable that an upper limit is 50 mass% or less, and it is more preferable that it is 30 mass% or less. The lower limit is not particularly limited as long as it can function as a binder, and is preferably 1% by mass or more, and more preferably 5% by mass or more.

The nickel-based catalyst is not particularly limited as long as it has a desulfurization effect, and a known nickel-based catalyst can be used. For example, what contains nickel and at least 1 sort (s), such as copper, zinc oxide, ruthenium, an alumina, is mentioned.
The content of nickel in the nickel-based catalyst is preferably 40% by mass or more, more preferably 50 to 70% by mass, from the viewpoint of excellent desulfurization effect.

  As the aluminosilicate catalyst, zeolite containing silica and alumina as constituent components is preferable. In particular, β-type zeolite and ZSM-type zeolite are more preferable because they can reduce the odor and foam of the fuel oil from which the ZSM-type zeolite is obtained, and ZSM-type zeolite is more preferable because it can obtain a fuel oil having a composition closer to light oil. .

  As the ZSM type zeolite, for example, a ZSM-5 catalyst described in Japanese Patent No. 3560610 and Japanese Patent Publication No. 11-507321 can be used. In addition to ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, and the like can be used, but ZSM-5 is preferred because of its excellent shape selectivity.

An example of the manufacturing method of ZSM-5 is shown below.
A solution containing 1.89 parts H ₂ O and 1.53 parts 50% NaOH solution was added to 7.63 parts H ₂ O and 1 part Al ₂ (SO ₄ ) ₃ .xH ₂ O (17. 2% Al ₂ O ₃ ). To this mixture is added 3.38 parts Ultrasil (VN3SP) precipitated silica and 0.09 parts ZSM-5 seed, followed by an additional 0.39 parts n-propylamine and the mixture is stirred until homogeneous. The mixture is crystallized in a reactor stirred at 160 ° C. for 26 hours. The crystals can be filtered, washed with water and dried at 120 ° C. to obtain ZSM-5.
Ultrasil is a precipitated spray-dried silica manufactured by DeGussa Corporation containing about 90% by weight SiO ₂ .

  As the β-type zeolite, for example, β-type zeolite described in JP-A-6-287015 can be used.

An example of a synthesis method of β-type zeolite is shown below.
First, a sodium silicate aqueous solution (SiO ₂ 130 g / L, Na ₂ O 41.8 g / L, Al ₂ O ₃ 0.05 g / L) and sulfuric acid were added to an agitated overflow type reaction tank (actual volume 4.8 L). An aqueous aluminum solution (Al ₂ O ₃ 21.3 g / L, SO ₄ 240 g / L) was simultaneously supplied at a flow rate of 18.2 L / h and 4.5 L / h, respectively, and the pH of the reaction tank during the reaction was 6-8. The amount of sodium silicate aqueous solution supplied is finely adjusted so that the reaction temperature is kept at 40 ° C., and the reaction is carried out with stirring to obtain a slurry product. The slurry-like product overflowed from the reaction tank is dehydrated with Nutsche and then washed with water to obtain granular amorphous aluminosilicate A.
Next, 187 g of a granular amorphous aluminosilicate A wet cake (moisture content of 70 wt%), 1.5 g of solid sodium hydroxide, 3.5 g of solid potassium hydroxide, and 480 g of a 20 mass% tetraethylammonium hydroxide aqueous solution were added. Stir for 30 minutes in a 0 L beaker. This mixture is put into a 1 L autoclave, stirred at a peripheral speed of 0.8 m / sec, and crystallized at 135 ° C. for 120 hours. The reaction product is subjected to solid-liquid separation, washed with warm water at 70 ° C., and then dried at 110 ° C. overnight to obtain β-type zeolite.

Further, as described in U.S. Pat. No. 3,308,069, β-type zeolite uses sodium aluminate, 30% silica sol, and tetraethylammonium hydroxide as a template at 75 to 200 ° C. and 2 to 48. A product obtained by hydrothermal synthesis, washing with distilled water, treatment with ammonium chloride, washing with distilled water and baking again can be used. In particular, the SiO ₂ / Al ₂ O ₃ ratio is 10 to 200, the Na ₂ O / tetraethylammonium hydroxide ratio is 0.0 to 0.1, the tetraethylammonium hydroxide / SiO ₂ ratio is 0.1 to 1.0, Those having an H ₂ O / tetraethylammonium hydroxide ratio in the range of 20 to 75 are preferred.

  In addition to aluminum, metals such as gallium and iron can be introduced into the framework structure of β-type zeolite. The β-type zeolite is subjected to ion exchange of the organic cation introduced in the above production process by a conventionally known method. After the ion exchange, the organic cation is washed until chlorine is not detected, and thereafter 300 to 650 ° C., preferably 400 to 600. It is preferably calcined at a temperature of 0.5 to 10 hours and used as an acidic zeolite. The β-type zeolite used in the present invention may be formed by molding various matrix materials at an arbitrary ratio, such as alumina, silica, titania, zirconia, silica-alumina, silica-titania, silica-zirconia, etc. Can be used.

  The aluminosilicate-based catalyst described above is preferably partially hydrogenated (acid type), and can be used with a platinum group metal or the like added as necessary.

In the apparatus of the present invention, it is possible to adjust the characteristics of the fuel oil obtained by selecting the catalyst to be used. In other words, there are aluminosilicate-based catalysts that are mainly active (acid type main) and that have low activity (less acid type or acid point ratio) and high selectivity (shape selectivity). Depending on the selection and combination of the catalysts, it is possible to adjust the amount of gasoline in the product to be increased or the amount of kerosene oil to be increased. This means that the product can be adjusted according to the demand trend of the fuel oil and the user's demand, which is a great practical advantage.
In particular, there are two or more catalyst layers in the catalyst tank, and in order from the bottom, a zinc-based catalyst, a cracking activated aluminosilicate-based catalyst, and a shape-selective aluminosilicate-based catalyst are arranged, and the gas is zinc-based catalyst and decomposed. By contacting the activated aluminosilicate catalyst and the shape-selective aluminosilicate catalyst in this order, a product having properties such as the carbon number, distillation distribution, specific gravity and the like of the product very close to that of light oil can be obtained.

The cracking activation type aluminosilicate-based catalyst has a large number of acid active sites (preferably 50% or more is the acid type), and examples include cracking activation type β-type zeolite.
The shape selective aluminosilicate-based catalyst has few decomposition active points, and in particular, ZSM-5 containing a platinum group metal is preferably used.

The heat exchanger 34 is connected to the catalyst tank 32 via a pipe line P ₇ , and cools and liquefies the gas reformed in the catalyst tank 32. As the heat exchanger 34, a known heat exchanger such as a water-cooled type can be used without particular limitation.

The apparatus 1 of the present invention has an oil recovery machine 36 for recovering oil liquefied by the heat exchanger 34. The oil recovery machine 36 has an oil recovery port valve 36a and a recovered drain water outlet valve 36b.
The apparatus 1 of the present invention preferably includes an off-gas combustion furnace 38 for burning off-gas generated by combustion in the heating furnace body 22. The off gas combustion furnace 38 includes an off gas combustion furnace burner 38a and a smoke exhaust fan 38b.

  Next, a preferred example of the fuel oil production method of the present invention (hereinafter referred to as “the production method of the present invention”) will be described. However, the manufacturing method of this invention is not limited to embodiment shown below.

First, an oil plant is put into the pulverizer 2 of the apparatus of the present invention described above and pulverized. At this time, it is preferable that the average particle diameter of the oil plant is 1 cm or less, more preferably 10 to 200 μm from the viewpoint of increasing the yield of vegetable oil.
As the oil plant, oil palm fruit, jatropha fruit, sesame seed, soybean seed and rapeseed can be used. Oil palm fruit is preferred because of its low price and excellent yield. Jatropha fruit can also be cultivated in rough land where oil palm fruit does not grow, and Jatropha fruit can be suitably used because it is non-edible and does not cause a problem of food shortage.

  The vegetable oil extracted from the pulverized oil plant is filtered by the filter 4. At this time, it is preferable to use a compression filter. By filtering oil plants and vegetable oils pulverized using a compression filter while applying pressure, the yield of vegetable oil is increased.

The filtered vegetable oil is temporarily stored in the tank 16. The tank outlet valve 16 a is opened and the vegetable oil is supplied to the dissolution tank 12.
Gas and moisture are removed by heating the vegetable oil supplied to the dissolution tank 12 with the burner 14. The smoke generated by the combustion in the melting tank 12 is sent to the first hot air tank 18 through the pipe P ₂ , and the heat of the smoke is reused when the burner 14 is burned.
In the dissolution tank 12, vegetable oil gas and moisture are removed is fed to the tank 20 through line P _3, it is temporarily stored.

Then, by opening the inlet valve 20c provided in the pipe P ₄ extending from the tank 20 to the furnace body 22, and supplies a vegetable oil pre-treated in a heating furnace body 22. At that time, since the check valve 20d is provided in the conduit P _4, never vegetable oil backflow.
The vegetable oil supplied to the heating furnace body 22 is heated by the burner 26 and vaporized. The heating temperature at this time is preferably 250 to 385 ° C. from the viewpoint of excellent conversion to light oil alternative fuel. In the heating furnace body 22, it is preferable to stir the vegetable oil by the stirrer 22a so that the vegetable oil is efficiently heated.
The smoke generated by the combustion in the heating furnace body 22 is sent to the second hot air tank 30 through the pipe line P ₅ , and the heat of the smoke is reused when the burner 26 is burned.

The gas vaporized in the heating furnace main body is supplied to the catalyst tank 32 via a pipe line P ₆ extending from the heating furnace main body 22 to the catalyst tank 32. The catalyst installed in the catalyst tank 32 is provided with innumerable pores in length and breadth, and a chemical reaction occurs when the gas passes through the pores, thereby reforming.

The reformed gas is supplied to the heat exchanger 34 through a pipe line P ₇ extending from the catalyst tank 32 to the heat exchanger 34, and is liquefied by being cooled in the heat exchanger 34. The liquefied gas is sent to the oil recovery machine 36.

Off-gas generated by combustion in the heating furnace main body 22 is sent to the off-gas combustion furnace 38 through a pipe line P ₈ extending from the heating furnace main body 22 to the off-gas combustion furnace 38, and is subjected to combustion processing.
Further, off-gas is also sent from the oil recovery machine 36 through the line P ₉ to the off-gas combustion furnace 36 for combustion treatment.

  Further, when vegetable oil is heated in the heating furnace body 22, a solid residue such as charcoal is generated. This residue is preferably discharged by a screw conveyor 28 installed at the bottom of the heating furnace body 22. The discharged residue is a solid content and can be easily discharged by the screw conveyor 28. Since this residue can be reused for fertilizers and the like, there is an advantage that the load on the environment is small.

According to the apparatus of the present invention and the production method of the present invention described above, fuel oil can be obtained in high yield from oil plants. For example, the yield of the method using CPO as a raw material when the amount of oil palm fruit is 100% by mass was about 20% by mass, whereas the apparatus of the present invention using oil palm fruit as a raw material and the production of the present invention According to the method, the yield of fuel oil can be 40% or more. The reason why fuel oil can be obtained in such a high yield is that, when conventional CPO is used as a raw material, a step of removing impurities by centrifugation after filtration is necessary, but in the present invention, impurities are not removed. This is because it can be gasified in a heating furnace.
Moreover, since the apparatus of this invention and the manufacturing method of this invention can use the fruit of a spoiled oil palm as a raw material, it is excellent in workability | operativity. The reason why spoiled oil palm fruit can be used as a raw material is that it oxidizes and increases the amount of free fatty acid when it rots, but in the present invention, it is gasified without changing the type of fatty acid and converted to a light oil alternative fuel It is because it can do.
Moreover, according to the apparatus of this invention and the manufacturing method of this invention, since impurities, such as glycerol, do not generate | occur | produce in a manufacture process, it is not necessary to perform chemical treatments, such as methyl esterification, and removes glycerol, and it is excellent in workability | operativity.
Moreover, since the apparatus of this invention and the manufacturing method of this invention use the said oil plant as a raw material, the residue produced when manufacturing fuel oil turns into solid content like charcoal, and can discharge | emit easily. Since this residue can be reused for fertilizers and the like, there is an advantage that the load on the environment is small.

In addition, the fuel oil of the present invention produced as described above can be used as a light oil substitute fuel because it shows properties similar to those of light oil.
Further, the fuel oil of the present invention has a pour point of −15 ° C. or lower, and therefore can be used even in cold regions. The pour point of the fuel oil of the present invention is preferably −20 ° C. or less from the viewpoint of excellent applicability to cold regions and ensuring engine performance at low temperatures.
In this specification, the pour point is a value measured according to JIS K2269-1987.

  Moreover, since the fuel oil of the present invention uses oil plants as a raw material, it can suppress the emission of carbon dioxide and has a low environmental load. Further, the fuel oil of the present invention has an advantage that there are few odors and bubbles.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

Example 1
Using the fuel oil production apparatus of the present invention as shown in FIG. 1, fuel oil was produced from oil palm fruit according to the following procedure.
First, 150 kg of oil palm fruits were put into a centrifugal grinder and ground to an average particle size of about 100 μm. The crushed oil palm fruit and palm oil obtained therefrom were filtered with a compression filter to recover 67 kg of palm oil.
Next, the palm oil obtained by filtration is put in a dissolution tank, and the temperature is raised from room temperature to 80 ° C. At that stage, the temperature is maintained until most of the water in the palm oil has been evaporated, and further 5 ° C. The temperature was raised gradually to 150 ° C., and it was confirmed that no water vapor was observed. Next, palm oil from which moisture was removed was placed in a thermal decomposition tank, and the temperature was raised to 350 ° C. while stirring with a stirrer, and the temperature was maintained. Meanwhile, gasification of palm oil progressed. Moreover, since the solid residue like charcoal produced when palm oil was heated, this was discharged | emitted with the screw conveyor.
The gas emitted from the upper part of the pyrolysis tank is a cylindrical body with an internal volume of 10 L, and in order from the lower layer, a zinc-based catalyst, a cracking activation type β-type zeolite (Zeolist, the same applies hereinafter), ZSM-5 type zeolite (Zeolist) The same was applied to the catalytic cracking tank filled with Zinc catalyst, β-type zeolite, and ZSM-5 type zeolite in this order for reforming. Next, the reformed gas was cooled through a heat exchanger and liquefied to recover 60 kg of product oil. The yield of the product oil was 40% by mass with respect to 100% by mass of the oil palm fruit. The resulting product oil had less odor and foam.
Incidentally, the zinc-based catalyst, zinc oxide (ZnO) 80-90 wt% and calcium aluminate (CaO / Al ₂ O ₃₎ containing 10 to 20 wt%.

  About the product oil of Example 1 obtained above, pour point measurement, gas chromatographic analysis, and distillation property test were performed by the following methods.

(Measure pour point)
The pour point of the product oil obtained above was measured according to JIS K2269-1987. The pour point of the product oil obtained in Example 2 was −20 ° C. or lower.

(Gas chromatograph analysis)
Gas chromatographic analysis was performed on the product oil obtained in Example 1 obtained above.
The obtained chart is shown in FIG.

(Distillation property test)
The resulting product oil was distilled, the distillation temperature was measured every 10 ml of distillate, and the distillation properties were evaluated. The results are shown in Table 1 below.

Properties of the product oil obtained in Example 1 other than the above (the measurement method is shown in parentheses) are shown below.
- 15 Density at ℃ (JIS K2249) 0.8210g / cm 3
・ Kinematic viscosity at 40 ° C. (JIS K2283) 2.0 mm ² / s
・ Clogging point (JIS K2288) -16 ℃
・ Cetane index (JIS K2280) 55.0
・ Acid value (JIS K2501) 0.13 mgKOH / g
・ Moisture (JIS K2275) 0.01% by mass

(Reference Example 1)
Gas chromatographic analysis of light oil was performed as a comparative sample.
The obtained chart is shown in FIG.
In addition, light oil was distilled and the distillation temperature was measured every 10 ml of distillate to evaluate the distillation properties. The results are shown in Table 2.

From the results shown in FIG. 2, Table 1 and Table 2, it was found that the product oil of Example 1 had properties close to light oil.
(Example 2)
Using the fuel oil production apparatus of the present invention as shown in FIG. 1, fuel oil was produced from oil palm fruit according to the following procedure.
First, 150 kg of oil palm fruits were put into a centrifugal grinder and ground to an average particle size of about 100 μm. The crushed oil palm fruit and palm oil obtained therefrom were filtered with a compression filter to recover 67 kg of palm oil.
The obtained palm oil is put into a 100 L dissolution tank, heated from room temperature to 80 ° C., maintained at that stage until most of the water in the palm oil has been evaporated, and further heated up by 5 ° C. The temperature was raised to 150 ° C., and it was confirmed that no water vapor was observed. Next, palm oil from which moisture was removed was placed in a thermal decomposition tank, and the temperature was raised to 350 ° C. while stirring with a stirrer, and the temperature was maintained. Meanwhile, gasification of palm oil progressed. Moreover, since the solid residue like charcoal produced when palm oil was heated, this was discharged | emitted with the screw conveyor.
The gas emitted from the upper part of the pyrolysis tank was led to a contact catalyst tank filled with ZSM-5 type zeolite as a catalyst in a cylindrical body having an internal volume of 10 L, and reformed by contacting with the catalyst. Next, the reformed gas was cooled through a heat exchanger and liquefied to recover 60 kg of product oil. The yield of the product oil was 40% by mass with respect to 100% by mass of the oil palm fruit. The resulting product oil had less odor and foam.
Moreover, the product oil of Example 2 was a property close to light oil.

  About the product oil obtained above, the pour point of the product oil obtained above was measured according to JIS K2269-1987. The pour point of the product oil obtained in Example 1 was −20 ° C. or lower.

(Example 3)
As the catalytic cracking tank, using the catalytic cracking tank filled with the zinc-based catalyst used in Example 1 and the cracking activation type β-type zeolite in order from the lower layer, the gas is brought into contact with the zinc-based catalyst and the β-type zeolite in this order. A fuel oil was produced in the same manner as in Example 1 except that the fuel oil was reformed. The yield of the product oil was 40% by mass with respect to 100% by mass of the oil palm fruit.
Compared with Example 2, the amount of gasoline produced increased the amount of gasoline, and the amount of diesel oil decreased. This is presumably because the reaction progressed too much because β-zeolite with strong catalytic action was used.
Moreover, as a result of measuring the pour point of the obtained product oil by the same method as described above, the pour point was −20 ° C. or lower. The resulting product oil had less odor and foam.

(Comparative Example 1)
A fuel oil was produced in the same manner as in Example 2 except that palm oil (CPO) was used as a raw material using a device obtained by removing the grinder 2 and the filter 4 from the apparatus as shown in FIG.
The yield of the product oil was 23% by mass with respect to 100% by mass of the oil palm fruit.

FIG. 1 is a diagram schematically showing an entire example of a fuel oil production apparatus of the present invention. FIG. 2A is a chart showing the results of gas chromatographic analysis of the product oil obtained in Example 1, and FIG. 2B is a chart showing the results of gas chromatographic analysis of light oil.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Fuel oil manufacturing apparatus 2 Crusher 4 Filter 12 Melting tank 12a Melting tank exhaust outlet valve 12b Smoke exhaust fan 12c Melting tank outlet valve 14 Burner 16 Tank 16a Tank outlet valve 18 First hot air tank 20 Tank 20c Input valve 20d Check valve 22 Reheating furnace body 22a Stirrer 22b Smoke exhaust fan 24 Pyrolysis tank 26 Burner 28 Screw conveyor 30 Second hot air tank 32 Catalyst tank 32a Catalyst 32b Smoke fan 34 Heat exchanger 36 Oil recovery machine 36a Oil recovery port valve 36b Recovery drain water outlet valve 38 Off-gas combustion furnace 38a Off-gas combustion furnace burner 38b Smoke exhaust fan

Claims (21)

A fuel oil production apparatus for producing fuel oil from at least one oil plant selected from the group consisting of oil palm fruit, jatropha fruit, sesame seed, soybean seed and rapeseed,
Pulverizing means for pulverizing the oil plant;
First heating means for removing moisture by heating the vegetable oil obtained from the oil plant pulverized by the pulverizing means;
Second heating means for heating and vaporizing the vegetable oil from which moisture has been removed by the first heating means;
A catalyst tank for reforming the gas vaporized by the second heating means by contacting with the aluminosilicate catalyst;
A fuel oil production apparatus comprising cooling means for cooling and liquefying the gas reformed in the catalyst tank.   The fuel oil production apparatus according to claim 1, wherein the pulverizing means pulverizes the oil plant to an average particle diameter of 1 cm or less.   The fuel oil production apparatus according to claim 1 or 2, wherein the oil plant is oil palm fruit.   The fuel oil production apparatus according to any one of claims 1 to 3, wherein the fuel oil is a light oil alternative fuel.   The fuel oil production apparatus according to any one of claims 1 to 4, wherein a pour point of the fuel oil is -15 ° C or lower.   The fuel oil manufacturing apparatus according to any one of claims 1 to 5, wherein the second heating means heats the vegetable oil to 250 to 385 ° C to vaporize the vegetable oil.   7. The catalyst tank according to claim 1, wherein the catalyst tank is a catalyst tank that reforms the gas vaporized by the second heating means by bringing the gas into contact with a zinc-based catalyst or a nickel-based catalyst and an aluminosilicate-based catalyst. The fuel oil manufacturing apparatus as described.   Furthermore, the fuel oil manufacturing apparatus in any one of Claims 1-7 provided with the filtration means which filters the vegetable oil obtained from the oil plant ground by the said grinding | pulverization means.   The fuel oil production apparatus according to claim 8, wherein the filtering means is a compression type filter having a compressing means for compressing the pulverized oil plant and the vegetable oil obtained from the pulverized oil plant.   Furthermore, the fuel oil manufacturing apparatus in any one of Claims 1-9 which have a residue carrying-out means to discharge | emit the solid residue produced when vegetable oil is heated in said 2nd heating means. A fuel oil production method for producing fuel oil from at least one oil plant selected from the group consisting of oil palm fruit, jatropha fruit, sesame seed, soybean seed and rapeseed,
Crushing step of crushing the oil plant;
A first heating step of removing moisture by heating the vegetable oil obtained from the oil plant pulverized in the pulverization step;
A second heating step of heating and vaporizing the vegetable oil from which moisture has been removed by the first heating step;
A reforming step of reforming the gas vaporized by the second heating step by bringing it into contact with an aluminosilicate catalyst;
And a cooling step of cooling the gas reformed in the reforming step to obtain a fuel oil.   The method for producing fuel oil according to claim 11, wherein in the pulverization step, the oil plant is pulverized to an average particle size of 1 cm or less.   The method for producing fuel oil according to claim 11 or 12, wherein the oil plant is an oil palm fruit.   The fuel oil manufacturing method according to claim 11, wherein the fuel oil is a light oil substitute fuel.   The fuel oil production method according to any one of claims 11 to 14, wherein a pour point of the fuel oil is -15 ° C or lower.   16. The reforming step according to any one of claims 11 to 15, wherein the reforming step is performed by bringing the gas vaporized in the second heating step into contact with a zinc-based catalyst or a nickel-based catalyst and an aluminosilicate-based catalyst. Fuel oil production method.   The fuel oil production method according to any one of claims 11 to 16, further comprising a filtration step of filtering the vegetable oil obtained from the oil plant pulverized in the pulverization step after the pulverization step.   The fuel oil production according to any one of claims 11 to 17, further comprising, after the second heating step, a residue carrying-out step for discharging a solid residue generated when the vegetable oil is heated in the second heating step. Method.   The fuel oil manufacturing method in any one of Claims 11-18 which manufactures fuel oil from the said oil plant using the fuel oil manufacturing apparatus in any one of Claims 1-10.   The fuel oil obtained by the fuel oil manufacturing method in any one of Claims 11-19.   The fuel oil according to claim 20, which is a light oil substitute fuel.

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