JPWO2010134219A1 - Biodiesel fuel oil production method and apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a fuel oil having a low viscosity, a low pour point and a high cetane number by pyrolyzing palm fruit bunches and the like. [MEANS FOR SOLVING PROBLEMS] Palm fruit bunch, palm fruit, palm powder, palm oil, coconut fruit, coconut oil, jatropha fruit, vegetable waste edible oil, animal waste edible oil and these septics Alternatively, when a plurality of raw materials are heated to a temperature of 360 ° C. or more and 510 ° C. or less and a temperature within a range of 440 ° C. to 470 ° C. is set as a set temperature, a temperature within a range of 360 ° C. or more and less than the above set temperature Then, an alkaline compound is added to the raw material after dehydration to perform low-temperature pyrolysis, and when the set temperature is reached, a decomposition catalyst selected from porous inorganic oxides is added, and the temperature is in the range from the set temperature to 510 ° C. High-temperature pyrolysis is performed at the internal temperature, and a low-viscosity, high-fluidity, and high-cetane fuel oil is obtained from the resulting pyrolysis medium oil. As the cracking catalyst, silicon oxide-aluminum oxide, natural clay or zeolite can be used.

Description

  The present invention relates to a method and apparatus for producing biodiesel fuel oil, and in particular, palm fruit bunch, palm fruit, palm powder, palm oil, coconut fruit, coconut oil, jatropha fruit, vegetable waste edible oil, animal waste food. The present invention relates to a method and an apparatus for producing a fuel oil having a low viscosity, a low pour point and a high cetane number by thermally decomposing oil and these septics.

  Recently, biomass energy that can be substituted for fossil fuels has been actively researched, and biodiesel fuel (hereinafter referred to as BDF) is attracting attention as an alternative to light oil. Although soybean is mainly used as a raw material for BDF, since soybean is used for human staple food and livestock feed, the use of soybean for BDF may cause food difficulties.

  Conventionally, when producing BDF, a method of producing a fat or oil of animals or plants by adding methanol, an alkaline compound or the like and causing a transesterification reaction at a temperature within a range of 60 ° C. to 260 ° C. (Patent Document 1, Patent Document 2), a method for obtaining BDF by transesterifying oils such as palm oil, soybean oil, and waste food oil has been proposed.

  However, when palm is used as a raw material, for example, a fruit is obtained by steaming a palm fruit bun (Fresh Fruit Bunch, hereinafter referred to as “FFB”), and the palm fruit is squeezed and washed to obtain crude palm oil ( CPO) is not only expensive, but also a large amount of wastewater generated when obtaining fruit from FFB becomes a problem.

  Furthermore, when CPO is used as a raw material, the resulting BDF is about 25% by weight with respect to the palm fruit in the previous stage of CPO, and even if palm fruit is relatively inexpensive, the resulting cost increases. For practical use, the yield must be improved.

  In addition, when BDF is produced by transesterification, the viscosity of BDF increases, fluidity is poor, and clogging is likely to occur, so that it is not suitable for use in cold regions.

  In contrast, a method of obtaining liquid oil by pyrolysis by adding sodium carbonate or potassium hydroxide to vegetable oil (Non-patent Document 1), adding sodium carbonate to sunflower oil and heating at 400 ° C. or 420 ° C. A method for producing pyrolyzed oil by decomposition (Non-patent Document 2), a method for producing a fuel oil having properties similar to diesel fuel by pyrolyzing palm oil (Non-Patent Document 3), and an oil palm from which oil and fat raw materials are removed There are known methods (non-patent literature 4 and non-patent literature 5) for obtaining pyrolyzed oil using an alkali catalyst with respect to the fruit skin from which bunches and fats are extracted.

  In the method for producing BDF by the pyrolysis method in the presence of the above-mentioned alkaline compound, the viscosity of the obtained fuel oil is lower than that of the transesterification method, and BDF having good fluidity and less clogging can be produced. .

JP 2005-29715 A JP 2008-81730 A

Fuel Processing Technology, 1998, No.57, p81-92 J. Anal. Appl. Pyrolysis, 2004, No. 71, p.987-996 Energy Sources, Part A, June 1, 2008, Vol.30, No.9, p.1060-1064 Proceedings of the Spring Meeting of Japan Society of Resources and Materials (II) Materials, 2006, p.1-12 Energy Sources, 2000, Vol.22, No.7, p.631-639

  In the BDF production method by pyrolysis described in Non-Patent Documents 1 to 5 above, the viscosity of BDF is lower than that of the transesterification method, but the viscosity is still high when used in a cold district, and the pour point (on cooling) In fact, the minimum temperature at which clogging occurs was high and it was actually difficult to use.

  In view of such problems, the present invention provides a method for producing biodiesel fuel oil and a device for producing the same, which can produce a low viscosity and low pour point fuel oil suitable for use in cold regions with a high yield. The issue is to provide.

  Therefore, the method for producing biodiesel fuel oil according to the present invention includes palm fruit bunch, palm fruit, palm powder, palm oil, coconut fruit, coconut oil, jatropha fruit, vegetable waste edible oil, and animal waste edible oil. And a method of producing fuel oil from one or more raw materials selected from the group of these septics, wherein the one or more raw materials are heated to a temperature of 360 ° C. or more and 510 ° C. or less, and 440 ° C. When a temperature within a range of ˜470 ° C. is set as a set temperature, an alkaline compound is added to the raw material after dehydration at a temperature within a range of 360 ° C. or higher and lower than the set temperature, and low-temperature heat is present in the presence of the alkaline compound. When the decomposition temperature is reached and the set temperature is reached, a decomposition catalyst selected from porous inorganic oxides is added, and high temperature heat is present in the presence of the decomposition catalyst at a temperature within the range of the set temperature to 510 ° C. Solution was performed and the resulting low pour point from the pyrolysis of fuel oil at low viscosity, and is characterized in that to obtain a high cetane number fuel oil.

  One of the features of the present invention is palm fruit bunch, palm fruit, palm powder, palm oil, coconut fruit, coconut oil, jatropha fruit, vegetable waste edible oil, animal waste edible oil and groups of these septics After adding an alkaline compound to one or more raw materials selected from the above and performing low temperature pyrolysis at a temperature lower than the set temperature within the range of 440 ° C. to 470 ° C., the decomposition catalyst is added above the set temperature and high temperature heat is applied. It is in the point which made it decompose.

  A low-viscosity and high-fluidity fuel oil with less wax fraction (heavy oil component) can be obtained from palm fruit bunches, etc. by low-temperature pyrolysis below the set temperature in the presence of alkaline compounds, and the wax fraction remains The highly viscous undecomposed oil (in addition to the alkaline compound when the alkaline compound remains) is pyrolyzed at a high temperature above the set temperature in the presence of a cracking catalyst, so that a fuel oil with a low wax fraction is obtained. be able to.

  As a result, the viscosity and pour point of the fuel oil were significantly lowered, and the cetane number was increased, making it possible to use biodiesel fuel oil in cold regions. BDF was analyzed by gas chromatograph-mass spectrometry (GC-MS), and as a result, C9 to C18 were obtained. This was similar to light oil (C13 to C17) obtained from petroleum, and a high cetane number was confirmed.

  In the present invention, the raw material of the fuel oil is palm fruit bunch, palm fruit, palm powder, palm oil, coconut fruit, coconut extract, jatropha fruit, vegetable waste edible oil, animal waste edible oil and these septics. Although it is used, it is particularly suitable for producing fuel oil using palm fruit bunch and its rot as a main raw material.

  Examples of vegetable waste edible oils include used waste oils of vegetable oils such as soybean oil, rapeseed oil, sunflower oil, cottonseed oil, sesame oil, peanut oil, coconut oil, and animal waste edible oils include beef fat, pork Examples include used waste oils of animal fats such as fat, horse fat, fish oil and whale oil.

  In the present invention, since low-temperature pyrolysis below the set temperature in the presence of an alkaline compound and high-temperature pyrolysis above the set temperature in the presence of a decomposition catalyst, raw materials that are difficult to pyrolyze, specifically palm fruit bunch, palm fruit, Palm powder, palm oil, coconut fruit, coconut oil, jatropha fruit, vegetable waste edible oil, and animal waste edible oil can be used as raw materials.

  In addition, since waste edible oil that has been disposed of in the past can be used as a raw material for fuel oil, it is extremely useful from the viewpoint of resource saving and environmental viewpoint.

  Furthermore, since it is thermally decomposed in the presence of an alkaline compound, palm fruit bunch, palm fruit, coconut fruit and jatropha fruit that have not been processed into oil can be used as a raw material for fuel oil, and further processed into oil Therefore, the manufacturing efficiency is high and the cost can be reduced. The production method of the present invention is technically different from the conventional production method of biodiesel fuel oil in that a raw material not processed with oil can be directly used.

  Usually, it is extract | collected from the palm tree in the state of a fruit bunch (FFB), and it can be set as a palm fruit by processing this FFB by a steaming method etc. Furthermore, palm oil can be extracted and washed to obtain palm oil (CPO). In the present invention, palm fruit bunch, palm fruit, coconut fruit and jatropha fruit are roughly crushed and used as a raw material for thermal decomposition.

  Since the amount of condensed water when processing FFB into fruit is large and the BOD value is high, it is difficult to treat with a normal wastewater treatment method, resulting in environmental problems and costly disposal. The pre-treatment process for processing the fruit into palm oil or palm oil is no longer necessary, and the cost can be greatly reduced.

  Furthermore, when the roughly crushed FFB is used as a raw material for pyrolysis, a portion that has conventionally been discarded when it is processed into fruit or oil is thermally decomposed to obtain useful cracked gas, carbon residue, and fuel oil. Therefore, the yield of biodiesel fuel oil can be improved.

  In order to reduce the wax fraction, it is preferable to use calcium hydroxide, calcium oxide, sodium carbonate, sodium hydroxide, or potassium hydroxide that can be dissolved in glycerin as the alkaline compound.

  The porous inorganic oxide of the cracking catalyst is a catalyst capable of cracking undecomposed oil containing a large amount of heavy oil (WAX) at high temperature, specifically one or more of inexpensive silicon oxide-aluminum oxide, natural clay, zeolite Can be used.

  The pyrolysis medium oil has a high acid value (mgKOH / g) as it is. Accordingly, in the present invention, the fuel oil is solvent-extracted from the pyrolysis medium oil. When impurities are removed by a solvent, an appropriate acid value can be obtained, and odor can also be reduced. The solvent extraction may be performed twice or more. By performing the treatment a plurality of times, the acid value can be further improved.

  Examples of the solvent include alcohols such as methanol and ethanol, ketones such as acetone, and ethers such as dimethyl ether. Alcohols are preferable from the viewpoint of high extraction effect and availability.

  As the extraction method, for example, the pyrolysis intermediate oil and the solvent are sufficiently mixed and allowed to stand, and the fuel oil can be extracted by separating the solvent layer containing impurities. The solvent containing impurities should be reused by separating the impurities by evaporating only the solvent.

Further, instead of solvent extraction, the pyrolysis medium oil may be purified by hydrogen gas addition low pressure reaction. That is, after the thermal decomposition in the fuel oil is preheated to a temperature in the range of 260 ° C~427 ° C, feeding the reactor with hydrogen gas, in the reaction tower ^{3.5kg / cm 2 · g~56kg / cm} 2 · When the reaction is carried out at a pressure of g in the presence of a reproducible metal oxide catalyst, the hue and oxidation stability are improved, impurities are reduced, and the odor can be improved. Hydrogen is separated from the obtained fuel oil, and hydrogen gas is reused.

  As a heat source for heat dehydration and pyrolysis, dewatered steam from the pyrolysis tank is retained in a combustion furnace at a temperature of 600 ° C. or higher (preferably 800 ° C. or lower) for 2 to 3 seconds to heat and deodorize, and superheated steam Is used as a heat source for dehydration and pyrolysis of the raw material. Thereby, waste heat can be utilized effectively.

  When the amount of processing is large and the amount of heat is insufficient with the heat transfer area of the pyrolysis tank jacket and the heat transfer area of the heat removal steam alone, pyrolysis light oil or a thermally stable fluid (for example, toluene) is used in a circulating furnace. It is preferable to heat or heat the palm oil or wax fraction to about 450 ° C. and blow it into the pyrolysis tank. It is also useful to blow 600 ° C superheated steam directly into the pyrolysis tank. The amount at that time is max 0.16 ton / kl-feed.

  That is, as a heat source for the dehydration and pyrolysis of the raw material, in addition to the deodorized water vapor that has been deodorized by heating, it is possible to further heat and use pyrolysis light oil or toluene. Further, as a heat source for dehydration and pyrolysis of the raw material, palm oil or wax fraction can be heated and used in addition to the deodorized water vapor dehydrated by heating.

  Pyrolysis gas and pyrolysis light oil are used as the fuel for heating the pyrolysis light oil, toluene, palm oil, and wax fraction, but if there is a shortage, the pyrolysis residue can be used as the solid fuel.

  The alkaline compound is added in an amount of 5 to 15% by weight based on the raw material, and the cracking catalyst is added in an amount of 3 to 10% by weight based on the undecomposed oil. As a result, a fuel oil with a small wax fraction can be obtained, resulting in an increase in the yield of BDF.

For example, the following conditions can be adopted as the thermal decomposition temperature (liquid phase lower temperature) and the reaction time.
The temperature is maintained at 1.360 ° C. to 390 ° C. for 3 to 5 hours, an alkaline compound is added, and the first stage low temperature pyrolysis is performed in the liquid phase. In this case, the temperature may be kept constant within the range, or the temperature may be raised within the range.
2. Hold at 390 ° C. to 450 ° C. for 3 to 4 hours, and perform the second stage low temperature pyrolysis in the liquid phase. In this case, the temperature may be kept constant within the range, or the temperature may be raised within the range.
3. Hold at 450 ° C. to 510 ° C. for 2 to 3 hours, add cracking catalyst, and perform third stage high temperature pyrolysis in liquid phase. In this case, the temperature may be kept constant within the range, or the temperature may be raised within the range.

The pyrolysis tank has a structure in which a jacket is provided on the tank wall and a plurality of heating plates are provided inside, and the maximum distance between the heating plates is 1 m. In addition, a raw material charging / cleaning port is provided at the top of the pyrolysis tank. The coking substance produced on the inner wall of the pyrolysis tank is cleaned by blowing in saturated steam (5 kg / cm ² or more) or high-pressure water from the raw material input / cleaning port. At this time, the alkaline compound and the decomposition catalyst can be removed from the residue with condensed water, but the thermal decomposition residue to which the alkaline compound and the decomposition catalyst are attached may be taken out.

  Among the pyrolysis oil, a fraction of 150 ° C. to 350 ° C. is separated from cracked oil gas, light oil (boiling point: 150 ° C.), and wax fraction in a distillation column before being exposed to air. The pyrolyzed medium oil is extracted with a solvent such as methanol after cooling, but the conditions are normal pressure, 30 ° C to 59 ° C, and methanol is 1 to 1 in volume relative to the pyrolyzed medium oil to be treated. Contact twice as much. Methanol can be reused about 95% by weight. Moreover, it can replace with solvent extraction and can reduce impurities by the hydrogen gas addition low-pressure reaction.

  The undecomposed oil discharged out of the system is preferably heated to evaporate the oil to form a carbon residue. This carbon residue can be used as an in-house fuel, an activated carbon raw material, or a high-value-added carbon material.

  Of the obtained pyrolysis oil, medium oil having a boiling point of 150 ° C. or higher can be used as biodiesel fuel (BDF). The medium oil obtained by the production method according to the present invention has a cetane number of 60, a clogging point (pour point) of -17.5 ° C., a sulfur content of 2 ppm, automobile diesel fuel, boiler fuel, and power generation. It is extremely useful as a machine fuel and effective in preventing air pollution.

  In addition, although the method of thermally decomposing in presence of an alkaline compound is proposed, in this technique, there are many heavy oil components (wax fraction) of fuel oil, and if it removes a heavy oil component and uses it as fuel oil, The yield is as low as about 25% by weight with respect to the raw material. If the yield is to be increased, the amount of heavy oil component increases and the viscosity of the fuel oil increases, which is problematic for use in cold regions. is there.

  In contrast, in the present invention, the wax fraction (heavy oil component) is further thermally decomposed at a high temperature in the presence of a cracking catalyst, so that the viscosity of the fuel oil is low, the pour point can be lowered, and the yield It was confirmed that the yield of about 28 to 29% by weight can be ensured with respect to the raw material, as compared with the method of thermally decomposing in the presence of the alkaline compound.

  Pyrolysis oils of vegetable oils and animal fats are high in acid value, so they are likely to be altered (discoloration, odor, precipitate). However, by adopting solvent extraction with methanol or hydrogen gas addition low-pressure reaction, the oil quality Is stable and can be stored for a long time.

  Moreover, since the pyrolysis residue at the time of using palm FFB and fruit as a raw material is coconut husk charcoal, it becomes a raw material of granular activated carbon with high added value. In particular, the pyrolysis residue can be burned and used as a heat source for pyrolysis tanks and dryers, but the pyrolysis residue contains a decomposition catalyst and an alkaline compound, so it is useful for the remaining ash. It contains an alkaline component and is ideal for fertilizers.

  The biodiesel fuel oil production apparatus according to the present invention includes palm fruit bunch, palm fruit, palm powder, palm oil, coconut fruit, coconut oil, jatropha fruit, vegetable waste edible oil, animal waste edible oil And a fuel oil production apparatus for thermally decomposing one or more raw materials selected from the group of these septic products in the presence of an alkaline compound and a cracking catalyst, comprising a high-temperature combustion gas containing pyrolyzed light oil or superheated steam The heat source is charged with the one or more raw materials, the one or more raw materials are heated to a temperature of 360 ° C. or higher and 510 ° C. or lower, and a temperature within a range of 440 ° C. to 470 ° C. is set as a set temperature. The raw material after dehydration is pyrolyzed at a low temperature in the presence of an alkaline compound at a temperature in the range of 360 ° C. or higher and lower than the preset temperature, and porous at a temperature in the range of the preset temperature to 510 ° C. or lower. A pyrolysis tank that thermally decomposes at high temperature in the presence of a cracking catalyst selected from inorganic oxides, a condenser that condenses the pyrolysis oil from the pyrolysis oil gas of the pyrolysis tank, and the condensed pyrolysis oil is distilled. And a distillation column for separating light oil and medium oil, and a purifier for purifying fuel oil from the separated pyrolysis medium oil.

  Here, the heat dehydration of the raw material may be performed in a pyrolysis tank, but a dehydrator is provided in the previous stage of the pyrolysis tank, and after heat dehydration of one or a plurality of raw materials, the dehydrated raw material is converted into a pyrolysis tank You may make it send to.

  Since the thermal decomposition tank has a large liquid level fluctuation in the tank when it is continuously operated, it is usually operated in a batch mode. However, when the raw material can be continuously charged and the pyrolysis residue can be discharged continuously, it is continuously operated. Is also possible.

  Since the pyrolysis residue can be used as a fuel, it can be incinerated in a fluidized bed incinerator and the hot sand in the incinerator can be sent to a dryer, preheater, or pyrolysis tank and used as a heat source.

  In addition, the dewatered steam from one or more raw materials is heated to 600 ° C. or higher (preferably 800 ° C. or lower) to be heated and deodorized, and the high-temperature combustion gas containing this superheated steam is removed from It is good to further provide a heating furnace (hot blast furnace) to be supplied.

  A plurality of heating plates are provided in the pyrolysis tank at predetermined intervals, a jacket is provided on the outer wall of the pyrolysis tank, and a high-temperature combustion gas containing dewatered steam is circulated through the heating plate and the jacket. Can be.

It is a conceptual diagram which shows preferable embodiment of the manufacturing apparatus of the biodiesel fuel oil based on this invention in the case of performing spin-drying | dehydration and thermal decomposition in one thermal decomposition tank. It is a block diagram which shows an example of the structure of the thermal decomposition tank in the said embodiment. It is a figure which shows the chart of the result of having measured the physical property of the fuel oil obtained by the Example using the gas chromatograph-hydrogen flame ionization type | mold detector. It is a figure which shows another chart. It is a conceptual diagram which shows 2nd Embodiment in the case of performing dehydration and thermal decomposition by another process. It is a figure which shows the example of the operation schedule of the thermal decomposition tank in the said embodiment. It is a figure which shows 3rd Embodiment. It is a figure which shows 4th Embodiment. It is a figure which shows 5th Embodiment. It is a figure which shows 6th Embodiment.

  Hereinafter, the present invention will be described in detail based on specific examples shown in the drawings. 1 and 2 show a preferred embodiment of a biodiesel fuel oil production apparatus according to the present invention. In the figure, 1 is a crusher for roughly crushing the raw material, 2 is a hopper for storing the roughly crushed raw material, 3 is a thermal decomposition tank for dehydrating and pyrolyzing the raw material, 5 is a residue receiving tank for receiving residues, 6 is A hot blast furnace (heating furnace) that heats and deodorizes the raw water vapor and supplies it to the pyrolysis tanks 3 and 4 as a heat source, 7 is a cyclone, 8 is a condenser that condenses the pyrolysis oil gas, and 9 is a condensed pyrolysis oil. 10 is a distillation column for distilling pyrolysis oil, 11 is a light oil condenser for condensing light oil, 12 is a light oil tank for receiving light oil, 13 is a BDF cooler for cooling fuel oil, 14 Is a separation tank for separating methanol and fuel oil, 15 and 16 are methanol evaporators for evaporating methanol, 17 is a methanol condenser for condensing methanol, 18 is a methanol receiving tank, 19 is a chimney, and 21 is a heating plate.

  For example, a structure as shown in FIG. The tank wall 30 is provided with a jacket 31, and the tank is provided with a plurality of heating plates 32. The distance between the heating plates 32 and the distance between the heating plate 32 and the tank wall 30 are set to 1 m or less. ing. The tank lid 33 is provided with a raw material charging / cleaning port 34 between the heating plates 32 and between the heating plate 32 and the tank wall 31, a residue discharge port 35 is formed at the bottom of the tank, and high temperature combustion gas Is introduced into the jacket 31 and the heating plate 32 of the pyrolysis tanks 3 and 4, and heated pyrolysis heavy oil (WAX) is directly blown into the pyrolysis tanks 3 and 4.

  When producing fuel oil, a palm fruit bunch and its spoilage are prepared as main raw materials. As necessary, one or more of palm fruit, palm powder, palm oil, coconut fruit, coconut oil, jatropha fruit, vegetable waste edible oil, animal waste edible oil, and these septics are prepared as auxiliary ingredients. can do. These raw materials are roughly crushed by the crusher 1 and stored in the hopper 2.

  A high-temperature combustion gas containing a large amount of superheated steam is generated in the hot stove 6 and supplied to the jacket 31 and the heating plate 32 of the pyrolysis tanks 3 and 4 to raise the temperature of the pyrolysis tanks 3 and 4, while the steam whose temperature has decreased Released from the chimney 19 to the atmosphere. The pyrolysis tanks 3 and 4 operate alternately according to the operation schedule. The roughly crushed raw material is put into the pyrolysis tanks 3 and 4. The moisture contained in the raw material was evaporated, and the steam was separated without being condensed in the cyclone 7, sent to the hot stove 6, and kept in the hot stove 6, for example, at 700 ° C. or more for 2 to 3 seconds and deodorized by heating. Thereafter, the high-temperature combustion gas containing a large amount of superheated steam is supplied to the jacket 31 and the heating plate 32 of the thermal decomposition tanks 3 and 4, and the thermal decomposition tanks 3 and 4 are heated.

  When the dehydrated raw material reaches a temperature in the range of 360 ° C. to 390 ° C. in the pyrolysis tanks 3 and 4, an alkaline compound such as calcium hydroxide, oxidized from the raw material charging and cleaning port 34 of the pyrolysis tanks 3 and 4. Calcium, sodium carbonate, sodium hydroxide, or potassium hydroxide is added. The input amount is 5 to 15% by weight with respect to the raw material. After the raw materials in the pyrolysis tanks 3 and 4 are subjected to the first stage low temperature pyrolysis at a temperature within the range of 360 ° C to 390 ° C for 3 to 5 hours, 390 ° C to 450 ° The temperature is raised to a temperature within the range of C, and the low-temperature pyrolysis of the second stage is performed over 3 to 4 hours. The temperature control of the pyrolysis tanks 3 and 4 can be performed by controlling the flow rate of high-temperature combustion gas or pyrolysis heavy oil.

  The crudely crushed and dehydrated raw material is pyrolyzed at low temperature in two stages in the presence of an alkaline compound, and the pyrolysis oil gas having a small wax fraction is sent to the condenser 8 and the pyrolysis medium having a boiling point of 150 ° C. or higher. The oil is condensed, and among the pyrolysis oil gas, light oil having a boiling point of 150 ° C. or less is condensed by the condenser 11, stored in the pyrolysis light oil tank 12, and used as fuel for the hot stove 6.

  The condensed oil of the pyrolysis oil gas is sent to the distillation tower 10, the light oil component of the distilled oil component is returned to the condenser 11, and the medium oil of the distilled oil component is cooled by the cooler 13 and then methanol and After mixing, impurities in the pyrolysis medium oil are extracted and separated into methanol in the separation tank 14 under the conditions of normal pressure and 30 ° C to 59 ° C. Methanol is used in an amount of 1 to 2 times the volume of pyrolysis medium oil to be extracted.

  The pyrolysis intermediate oil and methanol are sent from the separation tank 14 to the evaporators 15 and 16, the methanol containing impurities is evaporated and separated from the pyrolysis intermediate oil, the methanol is condensed by the condenser 17, and the receiving tank 18. It is stored at. Methanol is reused about 95% by weight. From the evaporators 15 and 16, the pyrolysis intermediate oil from which methanol has been separated is obtained as a high-quality fuel oil BDF with a small wax fraction. The heavy oil containing the wax content at the bottom of the distillation column 10 is heated and returned to the thermal decomposition tanks 3 and 4 and used as a heat source and again thermally decomposed.

  Highly viscous undecomposed oil such as wax fraction that has not been pyrolyzed remains in the bottom of the pyrolysis tanks 3 and 4. Therefore, when the undecomposed oil in the thermal cracking tanks 3 and 4 reaches 450 ° C, the cracking catalyst is added, and in the presence of the cracking catalyst at a temperature within the range of 450 ° C to 510 ° C over 2 to 3 hours. High-temperature pyrolysis is performed. As the decomposition catalyst, a porous inorganic oxide such as silicon oxide-aluminum oxide, natural clay or zeolite is employed. The addition amount of the cracking catalyst is 3 to 10% by weight based on the undecomposed oil.

  Then, in the presence of the alkaline compound, the undecomposed oil is further pyrolyzed at a high temperature in the presence of the decomposition catalyst in addition to the alkaline compound, and the wax fraction from the pyrolysis oil gas is the same as in the case of less than 450 ° C. Pyrolytic intermediate oil with a small amount of water is condensed, impurities are extracted and separated with methanol, and a high-quality fuel oil with a low viscosity, a low pour point and a high cetane number is produced.

When the thermal decomposition is completed, the thermal decomposition residue is discharged from the discharge port 35. Saturated steam (or high-pressure water) of 5 kg / cm ² or more is blown into the thermal decomposition tanks 3 and 4 from the raw material charging and cleaning port 34 to clean the Coking substance generated on the inner walls of the thermal decomposition tanks 3 and 4. Alkaline compounds and decomposition catalysts adhering to the pyrolysis residue can be removed by washing with saturated steam (or high-pressure water), but the pyrolysis residues adhering to the alkaline compound and decomposition catalyst should be used as fuel for the hot stove 6. Since the combustion ash contains a large amount of alkali components, it can be used for fertilizers. Finally, the residue is discharged from the discharge port 35 to the receiving tank 5.

  After the thermal decomposition in one of the thermal decomposition tanks 3 and 4 is finished, the raw material is thermally decomposed in the other thermal decomposition tanks 4 and 3. The pyrolysis tanks 3 and 4 are charged in accordance with the operation schedule → dehydration → three-stage pyrolysis → firing / stiffening → cooling in the tank → residue discharging → cleaning in the tank.

  The physical properties of the fuel oil obtained by the above examples were measured. The measurement was performed using a gas chromatograph-hydrogen flame ionization detector. The measurement was performed under the conditions shown in Table 1. The analysis result charts are shown in FIGS. As a result of the analysis, the obtained fuel oil could be identified as N-paraffinic hydrocarbon from C10 to C15 as the main components.

  FIG. 5 shows a second embodiment. In the figure, 101 is a crusher, 102 is a hopper, 103 is a rotary kiln type dehydrator, 104 is a cyclone, 105 is a hot air furnace (heating furnace), 106 is a dry matter / catalyst mixing tank, 107 is a feed catalyst, 108A, B, C are pyrolysis tanks, 109A, B, C are residue receiving tanks, 110 is a pyrolysis oil receiving tank, 111 is a pyrolysis oil condenser, 112 light oil condenser, 113 light oil receiving tank, 114 is a distillation tower, 115 is A solvent extraction unit, 116 is a circulating oil heating furnace, 117 is a chimney, and 120 is a rotary kiln type preheater.

  A hot combustion gas of 600 ° C. or more, for example, 800 ° C. containing a large amount of superheated steam is generated in the hot air furnace 105, and supplied to the jacket and heating plate of the thermal decomposition tank 108 to raise the temperature. The steam whose temperature has decreased is discharged from the chimney 117 to the atmosphere. If the amount of heat is insufficient, the distillation bottom oil (wax fraction) is heated to 500 ° C. in the circulating oil heating furnace 116 and blown into the pyrolysis tanks 108A and 108B.

  On the other hand, the roughly crushed raw material is put into the dehydrator 103 from the hopper 102. A high-temperature combustion gas containing superheated steam is supplied from the hot air furnace 105 to the jacket of the dehydrator 103 and heated, and the contained moisture evaporates from the charged raw material, and the steam is separated without being condensed in the cyclone 104. And then sent to the hot stove 105 and kept in the hot stove 105 at 700 ° C. or more for 2 to 3 seconds to be deodorized by heating, and then supplied to the jacket and heating plate of the pyrolysis tank 108 and the dehydrator 103, It is a heat source for dehydration and pyrolysis. The hot stove 105 uses pyrolysis residue and pyrolysis light oil cracked gas as fuel.

  The dehydrated raw material is mixed with an alkali catalyst (alkaline compound) 107 such as calcium hydroxide, calcium oxide, sodium carbonate, sodium hydroxide, or potassium hydroxide in a mixing tank 106. The input amount is 5 to 15% by weight with respect to the raw material. After the raw material is mixed with the alkali catalyst, it is preheated to about 300 ° C. by the preheater 120, and is put into the pyrolysis tanks 108A, 108B, 108C, and reaches a temperature in the range of 360 ° C. to 390 ° C. In the presence of an alkali catalyst, the first-stage low-temperature pyrolysis is performed over 3 to 5 hours, and then the second-stage low-temperature pyrolysis is performed at 450 ° C. over 3 to 4 hours. The catalyst is charged and allowed to reach 510 ° C. over 2 to 3 hours, and the third stage high temperature thermal decomposition is performed.

  Then, pyrolysis oil gas is produced | generated from 360-390 degreeC, and pyrolysis oil begins to distill from 390 degreeC or more. The pyrolysis oil gas is sent to the condenser 111 to condense the pyrolysis oil having a boiling point of 150 ° C. or higher, and among the pyrolysis oil gas, the light oil having a boiling point of 150 ° C. or less is condensed in the condenser 112 to be light. It is stored in the oil receiving tank 113 and the cracked gas and water are separated.

  Pyrolysis oil having a boiling point of 150 ° C or higher is sent to the distillation tower 114, light oil components of the distillate oil are returned to the condenser 112, and medium oil of the distillate oil is mixed with methanol (solvent) after cooling. And sent to the solvent extraction tank 115 to become BDF.

  When the amount of heat is insufficient or when making a large plant, the bottom oil (wax fraction) of the distillation column 114 is heated to approximately 500 ° C. in the circulating oil heating furnace 116 to serve as a heat source for the pyrolysis tanks 108A, 108B, and 108C. At the same time of use, it is subjected to re-pyrolysis. It is also possible to use heat-stable toluene, raise the temperature to 550 ° C. in the circulating heating furnace 116, and blow directly into the pyrolysis tanks 108A, 108B, and 108C in a 100% gas state. In addition, it is also useful to directly blow superheated steam at 550 ° C. into the pyrolysis tanks 108A, 108B, and 108C in terms of suppressing cocking and making the residue properties uniform.

  The pyrolysis intermediate oil and methanol are sent to the solvent extraction tank 115, where the methanol containing impurities is evaporated and separated from the pyrolysis intermediate oil, and obtained as a low-viscosity and good-quality fuel oil BDF with little wax fraction. It is done. Methanol can be condensed and reused.

Residues are discharged from the pyrolysis tanks 108A, 108B, 108C to the residue receiving tanks 109A, 109B, 109C. When the thermal decomposition is completed, steam (or high-pressure water) of 5 kg / cm ² or more is blown into the thermal decomposition tanks 108A, 108B, 108C, and the Coking substance generated on the inner walls of the thermal decomposition tanks 108A, 108B, 108C is cleaned. At this time, the alkaline compound and decomposition catalyst adhering to the thermal decomposition residue can also be removed.

  FIG. 6 shows an example of a batch type operation schedule of the pyrolysis tanks 108A, 108B, and 108C of this example. In the pyrolysis tank 108A, a raw material charging / heating step I, a heating / pyrolysis step II, and a cooling / residue removal / cleaning step III are performed, for example, every 8 hours. The pyrolysis tank 108B is synchronized with the process I, process II, and process III of the pyrolysis tank 108A, and the process II, process III, process I, and the pyrolysis tank 108C are performed as process III, process I, and process II.

  FIG. 7 shows a third embodiment, in which the same or corresponding parts as FIG. 5 are shown. In this example, a rotary kiln-type preheater 120 is provided at the next stage of the dehydrator 103 so that the dehydrated raw material is heated up to 300 ° C. and supplied to the thermal decomposition tank 108A or 108B.

  The roughly crushed raw material is put into the dehydrator 103 from the hopper 102. Moisture content is evaporated from the charged raw material, and the vapor is separated by the cyclone 104 and sent to the hot air oven 105, where it is retained in the hot air oven 105 at 600 ° C. or higher, for example, 800 ° C. for 2 to 3 seconds for heating deodorization. After that, it is supplied to the jacket of the dehydrator 103 and the preheater 120 and the jacket and heating plate of the thermal decomposition tank 108 to serve as a heat source for the dehydration and thermal decomposition of the raw material.

  The dehydrated raw material is mixed with the alkaline compound 107 in the mixing tank 106, then preheated to 300 ° C. by the preheater 120, and inserted into the pyrolysis tanks 108 A and 108 B, and in the range of 360 ° C. to 390 ° C. When the temperature is reached, the first stage low temperature pyrolysis is carried out over 3 to 5 hours, and then the second stage low temperature pyrolysis is carried out at 450 ° C. over 3 to 4 hours. And is allowed to reach 510 ° C. over 2 to 3 hours, and the third stage high temperature pyrolysis is performed.

  The pyrolysis oil gas is generated from 360 to 390 ° C, and the pyrolysis oil starts to distill from 390 ° C or higher. The pyrolysis oil gas is sent to the condenser 111 to condense pyrolysis oil having a boiling point of 150 ° C. or higher, and among the pyrolysis gas, light oil having a boiling point of 150 ° C. or less is condensed by the condenser 112, It is stored in the receiving tank 113 and the decomposition gas and moisture are separated.

  Pyrolysis oil having a boiling point of 150 ° C or higher is sent to the distillation tower 114, light oil components of the distillate oil are returned to the condenser 112, and medium oil of the distillate oil is mixed with methanol (solvent) after cooling. And sent to the solvent extraction tank 115 to become BDF.

  When the amount of heat is insufficient or when making a large plant, distillation tower bottom oil (wax fraction) is heated to approximately 500 ° C. in the circulating oil heating furnace 116 and used as a heat source for the pyrolysis tanks 108A and 108B. It is also possible to use heat-stable toluene, raise the temperature to 550 ° C. in the circulating heating furnace 116, and blow directly into the pyrolysis tanks 108A and 108B in a 100% gas state. In addition, it is also useful to directly blow superheated steam at 550 ° C. into the thermal decomposition tanks 108A and 108B in terms of suppressing cocking and making the residue properties uniform.

  The pyrolysis intermediate oil and methanol are sent to the solvent extraction tank 115, where the methanol containing impurities is evaporated and separated from the pyrolysis intermediate oil, and obtained as a low-viscosity and good-quality fuel oil BDF with little wax fraction. It is done. Methanol can be condensed and reused.

The residue is discharged from the pyrolysis tanks 108A and 108B to the residue receiving tanks 109A and 109B. When the thermal decomposition is completed, steam (or high-pressure water) of 5 kg / cm ² or more is blown into the thermal decomposition tanks 108A and 108B, and the Coking substance generated on the inner walls of the thermal decomposition tanks 108A and 108B is cleaned. At this time, the alkaline compound and decomposition catalyst adhering to the thermal decomposition residue can be removed.

  As described above, in this example, dehydration and preheating are continuously performed, thermal decomposition is performed in a batch manner, and distillation and solvent extraction are continuously performed. In place of the residue receiving tanks 109A and 109B of the pyrolysis tanks 108A and 108B, if a residue discharge screw is provided to continuously discharge, the thermal decomposition can be performed continuously.

  FIG. 8 shows a fourth embodiment, in which the same reference numerals as those in FIG. 7 denote the same or corresponding parts. In this example, one pyrolysis tank 108 is used, and pyrolysis heavy oil (WAX) heated to 450 ° C. is directly blown into the pyrolysis tank 108 to provide a heat source. The pyrolysis tank 108 is continuously operated, and the pyrolysis residue is continuously discharged by the residue discharge screw 121. Since other operations are the same as those in the third embodiment, a description thereof will be omitted.

  As described above, in this example, dehydration / preheating, thermal decomposition, distillation / solvent extraction are performed continuously.

  FIG. 9 shows a fifth embodiment, in which the same reference numerals as those in FIGS. 7 and 8 denote the same or corresponding parts. In this example, an incinerator 130 having a fluidized bed structure is provided after the thermal decomposition tank 108 having a tank structure, and low-temperature thermal decomposition to 450 ° C. is performed in two stages in the presence of an alkaline compound in the thermal decomposition tank 108. Thereafter, high-temperature pyrolysis is performed in the presence of a cracking catalyst at a temperature of 450 ° C. or more and 510 ° C., and the pyrolysis residue is sent to the incinerator 130 having a fluidized bed structure by the residue discharge screw 122 and about 800 ° C. Incinerated at.

  The hot sand of 500 ° C to 600 ° C extracted from the fluidized bed incinerator 130 is supplied to the preheater 120 and the pyrolysis tank 108 and used as a heat source for the preheater 120 and the pyrolysis tank 108 and incinerated. Hot hot air generated in the furnace 130 is sent to the jacket of the dryer 103 and the preheater 120 to heat the dryer 103 and the preheater 120.

  The raw material dried by the dryer 103 is rotated with hot sand by the preheater 120 and heated to 320 ° C., and then charged into the pyrolysis tank 108 together with the alkaline compound and hot sand, and 360 ° C. while being stirred by the stirrer. First-stage low-temperature pyrolysis at a temperature in the range of ˜390 ° C. and second-stage low-temperature pyrolysis at a temperature in the range of 390 ° C. to 450 ° C. are performed.

  When the low temperature pyrolysis is completed, that is, when the raw material reaches 450 ° C., the cracking catalyst is put into the pyrolysis tank 108, and the undecomposed oil containing the wax fraction is 450 ° C. to 510 ° C. in the presence of the cracking catalyst. , It is pyrolyzed at high temperature over 3-6 hours.

  After high-temperature pyrolysis, undecomposed oil (thermal decomposition residue) containing a wax fraction is sent to an incinerator 130 having a fluidized bed structure by a residue discharge screw 122 and incinerated at about 800 ° C. The hot sand in the fluidized bed extracted from the incinerator 130 is heated to 500 ° C. to 600 ° C., and is put into the preheater 120 and the thermal decomposition tank 108 to be used as a heat source.

  Air is fed into the incinerator 130 having a fluidized bed structure, whereby the fluidized bed is agitated and a flame is formed in the furnace to raise the temperature to about 800 ° C.

FIG. 10 shows a sixth embodiment. This example shows a system for performing a hydrogenation low-pressure reaction in place of solvent extraction of pyrolysis medium oil. In the figure, pyrolytic intermediate oil is sent to a preheater 134 together with hydrogen gas, preheated to a temperature within a range of 260 ° C. to 427 ° C., sent to a reaction tower 131, and a recyclable metal oxide catalyst. For example, the reaction is performed under a pressure of 50 kg / cm ² · g, and impurities are reduced to obtain a fuel oil. The fuel oil is cooled by the cooler 132, the hydrogen gas is separated by the separator 133, and the hydrogen gas is reused.

3, 4, 108, 108A, 108B, 108B Pyrolysis tank 103 Dehydrator 5, 105, 116 Heating furnace 8,111 Condenser 10,114 Distillation tower 14,115 Separation tank 120 Preheater 130 Incinerator 131 Reactor

Claims (20)

One or more ingredients selected from the group of palm fruit bunch, palm fruit, palm powder, palm oil, coconut fruit, coconut oil, jatropha fruit, vegetable waste edible oil, animal waste edible oil, and these septics A method for producing biodiesel fuel from
Heating the one or more raw materials to a temperature of 360 ° C. or higher and 510 ° C. or lower;
Presence of the alkaline compound by adding an alkaline compound to the raw material after dehydration at a temperature in the range of 360 ° C. or higher and lower than the preset temperature when the temperature within the range of 440 ° C. to 470 ° C. is set as the set temperature. Let low temperature pyrolysis underneath,
When the set temperature is reached, a cracking catalyst selected from porous inorganic oxides is added, and high-temperature pyrolysis is performed in the presence of the cracking catalyst at a temperature in the range of the set temperature to 510 ° C,
A method for producing a biodiesel fuel oil, characterized in that a low viscosity, low pour point, high cetane number fuel oil is obtained from the obtained pyrolytic intermediate oil.   At a temperature in the range of 360 ° C. or higher and lower than 390 ° C., an alkaline compound is added to the one or more raw materials after dehydration to perform first-stage low-temperature pyrolysis, and the set temperature is 390 ° C. or higher. The method for producing biodiesel fuel oil according to claim 1, wherein the second-stage low-temperature pyrolysis is performed at a temperature within a range of less than.   The method for producing biodiesel fuel oil according to claim 1, wherein the alkaline compound is a compound selected from calcium hydroxide, calcium oxide, sodium carbonate, sodium hydroxide, and potassium hydroxide.   The method for producing biodiesel fuel according to claim 1, wherein the cracking catalyst is a porous inorganic oxide selected from silicon oxide-aluminum oxide, natural clay, or zeolite.   The method for producing biodiesel fuel oil according to claim 1, wherein 5-15% by weight of the alkaline compound is added to the raw material and 3-10% by weight of the cracking catalyst is added to the undecomposed oil.   The method for producing biodiesel fuel oil according to claim 1, wherein the heat dehydration and pyrolysis of the raw material are performed in a pyrolysis tank (3,4).   The biodepositor according to claim 1, wherein a dehydrator (103) is provided in a pre-thermal decomposition step, and the raw material after the dehydration (103) is heated and dehydrated, and then the dehydrated raw material is pyrolyzed. A method for producing diesel fuel oil.   The dewatered steam from the palm fruit bunch or its septic is retained in a combustion furnace at 600 ° C. or higher for 2 to 3 seconds to heat and deodorize, and the high-temperature combustion gas containing this dewatered steam is used as a heat source for dehydration and thermal decomposition of raw materials. The method for producing a biodiesel fuel oil according to claim 1, wherein the biodiesel fuel oil is used as a fuel.   Whether the wax fraction, light oil, or heat-stable toluene of the pyrolysis oil is heated to 500 ° C and blown directly into the pyrolysis tank when the amount of heat generated by the high-temperature combustion gas containing degassed steam is insufficient The method for producing biodiesel fuel oil according to claim 8, wherein the heat amount of heat dehydration and pyrolysis is compensated by directly blowing superheated steam at 550 ° C into the pyrolysis tank.   A plurality of thermal decomposition tanks (3,4, 108A, 108B, 108C) are provided, and thermal decomposition in the plurality of thermal decomposition tanks (3,4, 108A, 108B, 108C) is performed based on the operation schedule, and each thermal decomposition The method for producing biodiesel fuel according to claim 1, wherein the thermal decomposition in the tank (3,4, 108A, 108B, 108C) is carried out in a batch manner.   The pyrolysis residue of the pyrolysis tank (108) is put into a fluidized bed incinerator (130) for incineration, and the hot sand in the incinerator (130) is dried by a dryer (103), preheater (120) and pyrolysis The method for producing biodiesel fuel oil according to claim 1, wherein the heat source is supplied to at least one of the tanks (108).   The method for producing a biodiesel fuel oil according to claim 1, wherein the fuel oil is solvent-extracted from the obtained pyrolytic medium oil.   The method for producing a biodiesel fuel oil according to claim 1, wherein the obtained pyrolytic intermediate oil is reacted with hydrogen gas under a predetermined low pressure to obtain a fuel oil.   The method for producing a biodiesel fuel oil according to claim 1, wherein the thermal decomposition residue contains a decomposition catalyst and / or an alkaline compound. One or more ingredients selected from the group of palm fruit bunch, palm fruit, palm powder, palm oil, coconut fruit, coconut oil, jatropha fruit, vegetable waste edible oil, animal waste edible oil, and these septics Is a fuel oil production apparatus for thermally decomposing oil in the presence of an alkaline compound and a cracking catalyst,
When the one or more raw materials are charged, the one or more raw materials are heated to a temperature of 360 ° C. or higher and 510 ° C. or lower, and a temperature in the range of 440 ° C. to 470 ° C. is set as a set temperature 360 The raw material after dehydration is pyrolyzed at a low temperature in the presence of an alkaline compound at a temperature in the range of ° C or higher and lower than the set temperature, and from the porous inorganic oxide at a temperature in the range of the set temperature to 510 ° C or lower. A pyrolysis tank (3,4,108,108A, 108B, 108C) that undergoes high-temperature pyrolysis in the presence of a selected cracking catalyst;
A condenser (8, 111) for condensing pyrolysis oil from the pyrolysis gas of the pyrolysis tank (3,4, 108, 108A, 108B, 108C);
A distillation column (10,114) for distilling the condensed pyrolysis oil and separating light oil and medium oil;
A refiner (14,115,131) for refining fuel oil from the separated pyrolysis medium oil;
An apparatus for producing biodiesel fuel oil, comprising:   A dehydrator (103) provided in a preceding stage of the thermal decomposition tank (108, 108A, 108B), which heat-dehydrates the one or more raw materials and then supplies the dehydrated raw materials to the thermal decomposition tank (108, 108A, 108B). The apparatus for producing biodiesel fuel oil according to claim 15, further comprising:   The dewatered steam from the one or more raw materials is heated to a temperature of 600 ° C. or higher and deodorized by heating, and the high-temperature combustion gas containing the dewatered steam is converted into the pyrolysis tank (3,4, 108A, 108B, 108C) and / or The apparatus for producing biodiesel fuel oil according to claim 15, further comprising a heating furnace (6, 105, 116) for supplying to the dehydrator (103).   18. The biodiesel fuel oil production apparatus according to claim 17, wherein the heat source of the heating furnace (105) is a pyrolysis residue and / or a pyrolysis light oil.   A fluidized bed incinerator (130) for incinerating the pyrolysis residue discharged from the pyrolysis tank (108) is further provided, and the hot sand from the incinerator (130) is dried by a dryer (103), a preheater (120 And the pyrolysis tank (108) as a heat source.   A plurality of heating plates (32) are provided at predetermined intervals in the pyrolysis tank (3,4), and a jacket (31) is provided on the outer wall of the pyrolysis tank (3,4). 18. The biodiesel fuel oil production apparatus according to claim 17, wherein the heating plate (32) and the jacket (31) are provided with a high-temperature combustion gas containing the dewatered steam.

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