JP2010084060A - Apparatus for manufacturing high grade hydrocarbon oil and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus which carries out hydrocracking of fats to produce high grade hydrocarbon oil without receiving a supply of hydrogen from the outside of high-grade hydrocarbon oil manufacturing facilities, and to provide a manufacturing method thereof. <P>SOLUTION: An apparatus 1 for carrying out hydrocracking of fats to produce a high-grade hydrocarbon oil, is equipped with: a hydrogenation reactor 11 which carries out hydrocracking of the fats to produce high-grade hydrocarbon oil and low-grade hydrocarbon containing gas; a partial oxidation furnace 31 which carries out partial oxidation of the low-grade hydrocarbon contained in the low-grade hydrocarbon-containing gas produced in the hydrogenation reactor 11 to generate hydrogen and carbon monoxide; and a shift reaction container 41 which carries out shift reaction on the carbon monoxide generated in the partial oxidation furnace 31 with water vapor supplied from the outside to produce hydrogen and carbon dioxide. The hydrogen generated in the shift reaction container 41 is supplied to the hydrogenation reactor 11. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an apparatus and method for producing a higher hydrocarbon oil by hydrocracking fats and oils.

  Attention has been focused on the effective use of biomass energy as a measure to prevent global warming. Among biomass energy, biomass energy derived from plants does not lead to an increase in carbon dioxide in the atmosphere from the viewpoint of the life cycle of resources because carbon resources converted from carbon dioxide by photosynthesis can be effectively used in the growth process of plants. It has a so-called carbon neutral property.

  Various uses of such biomass energy have been studied in the field of transportation fuel. For example, if a fuel produced from animal and vegetable oils can be used as a diesel fuel, it is expected to play an effective role in reducing carbon dioxide emissions due to a synergistic effect with the high energy efficiency of a diesel engine.

  Patent Document 1 discloses a technique for producing a high-grade hydrocarbon oil by using a fat and oil derived from animal and vegetable oils as a raw material and hydrocracking it as a technique for producing a liquid fuel from biomass. Here, “higher hydrocarbon oil” refers to a hydrocarbon having 5 or more carbon atoms and liquid at room temperature. According to the technique of Patent Document 1, a diesel fuel having high ignitability and excellent stability can be obtained.

In the production process of higher hydrocarbon oil as in Patent Document 1, oil and fat and hydrogen are generally reacted as in the following formulas (1) and (2) under a hydrogenation catalyst. Here, a general component of fats and oils has a fatty acid triglyceride structure in which a fatty acid and glycerin are ester-bonded, and is represented as C ₃ H ₅ (OCO—R) _3, and R— represents a higher alkyl group.

C ₃ H ₅ (OCO-R) ₃ + 12H ₂ → 3R-CH ₃ + C ₃ H ₈ + 6H ₂ O (1)
C ₃ H ₅ (OCO-R) ₃ + aH ₂ → 3R-H + C ₃ H ₈ + bCO ₂ + cCO + dH ₂ O (2)
The reaction of the formula (1) is a hydrocracking reaction, and a higher hydrocarbon oil (R—CH ₃ ) is generated, and propane (C ₃ H ₈ ) and water (H ₂ O) are generated as byproducts. . The reaction of the formula (2) is a decarboxylation reaction that occurs simultaneously with the formula (1). A higher hydrocarbon oil (R—H) is produced, and propane, carbon dioxide (CO ₂ ), carbon monoxide as by-products. (CO) and water are produced. Note that a, b, c, and d in equation (2) are constants.

Further, the generated carbon dioxide reacts with hydrogen (H ₂ ), and a part of the hydrogen is changed into carbon monoxide and water. Moreover, although R- is a higher alkyl group, when it has an unsaturated bond, the part is hydrogenated and a product becomes a higher saturated hydrocarbon.
JP2007-153928

  In the case of obtaining a high-grade hydrocarbon oil that can be used as a diesel fuel by hydrocracking fats and oils as in Patent Document 1 above, supply of hydrogen is indispensable for the production process, and this production process is industrially put to practical use. To do this, it was necessary to locate a manufacturing facility adjacent to facilities that could supply hydrogen, such as refineries and steelworks.

  So far, no technology has been developed for producing high-grade hydrocarbon oils by hydrocracking fats and oils without receiving hydrogen supply from outside the hydrocarbon oil production facility.

  In view of the circumstances as described above, the present invention provides an apparatus for hydrocracking fats and oils to produce higher hydrocarbon oils and a method for producing the same without receiving hydrogen supply from outside a hydrocarbon oil production facility. With the goal.

<First invention>
The high-grade hydrocarbon oil production apparatus according to the present invention produces high-grade hydrocarbon oil by hydrocracking fats and oils.

  In such a higher hydrocarbon oil production apparatus, the present invention provides a hydrogenation reactor that hydrocracks fats and oils to produce a lower hydrocarbon-containing gas and a higher hydrocarbon oil, and a lower carbonization produced in the hydrogenation reactor. A partial oxidation furnace that partially oxidizes lower hydrocarbons contained in a hydrogen-containing gas to produce hydrogen and carbon monoxide, and a carbon monoxide produced in the partial oxidation furnace is subjected to a shift reaction with water vapor received from the outside to generate hydrogen. And a shift reactor for generating carbon dioxide, wherein the hydrogenation reactor is characterized in that hydrogen generated in the shift reactor is supplied. Here, the “lower hydrocarbon” refers to a hydrocarbon having 4 or less carbon atoms and gaseous at normal temperature.

  In the present invention, lower hydrocarbons contained in a lower hydrocarbon-containing gas that is a by-product in the hydrocracking reaction of fats and oils in a hydrogenation reactor are partially oxidized in a partial oxidation furnace to produce hydrogen and carbon monoxide. The carbon monoxide undergoes a shift reaction with water vapor in a shift reactor to generate hydrogen, and the hydrogen is supplied to the hydrogenation reactor. And the hydrogen supplied to the hydrogenation reactor is utilized for hydrocracking of fats and oils in the hydrogenation reactor.

<Second invention>
The high-grade hydrocarbon oil production apparatus according to the present invention also produces high-grade hydrocarbon oil by hydrocracking fats and oils, as in the first invention.

  In such a higher hydrocarbon oil production apparatus, in the present invention, in the present invention, a hydrogenation reactor that hydrocracks fats and oils to produce a lower hydrocarbon-containing gas and a higher hydrocarbon oil, and the lower gas produced in the hydrogenation reactor. A gas-liquid separator that condenses and separates lower hydrocarbons from the hydrocarbon-containing gas; and a decompressor that decompresses the lower hydrocarbon condensate separated by the gas-liquid separator and returns the lower hydrocarbons to a gaseous state; A partial oxidation furnace that partially oxidizes lower hydrocarbons that have been decompressed and returned to a gaseous state by the decompressor to produce hydrogen and carbon monoxide; and lower hydrocarbons from the lower hydrocarbon-containing gas by the gas-liquid separator The hydrogenation reactor comprises: a shift reactor that shifts carbon monoxide contained in the remaining gas from which gas is separated and carbon monoxide generated in the partial oxidation furnace with steam to generate hydrogen and carbon dioxide. It is characterized in that hydrogen generated in the shift reactor are supplied.

  In the present invention, as in the first invention, the lower hydrocarbons contained in the lower hydrocarbon-containing gas that is a by-product in the hydrocracking reaction of fats and oils in the hydrogenation reactor are partially oxidized in the partial oxidation furnace. Hydrogen and carbon monoxide are produced, and the carbon monoxide undergoes a shift reaction with water vapor in the shift reactor to produce hydrogen, which is supplied to the hydrogenation reactor. Furthermore, in the present invention, the lower hydrocarbon is separated from the lower hydrocarbon-containing gas by the gas-liquid separator, and the lower hydrocarbon is supplied to the partial oxidation furnace and partially oxidized. That is, only the lower hydrocarbon is supplied to the partial oxidation furnace, and the remaining gas other than the lower hydrocarbon is not supplied from the gas discharged from the hydrogenation reactor. Therefore, since the remaining gas is not supplied, the scale of the partial oxidation furnace can be reduced, and the equipment can be downsized.

  In the first invention or the second invention, the higher hydrocarbon oil produced in the hydrogenation reactor is dissolved in the higher hydrocarbon oil by performing at least one of heating and decompression treatment. It is preferable that a stripper for separating the lower hydrocarbon gas is further provided so that the lower hydrocarbon gas separated by the stripper is supplied to the partial oxidation furnace. By separating the lower hydrocarbon gas dissolved in the higher hydrocarbon oil with a stripper and partially oxidizing the lower hydrocarbon gas in the partial oxidation furnace, the lower hydrocarbon gas can be used more efficiently.

  Further, in the first invention or the second invention, further comprising a distillation column for distilling the higher hydrocarbon oil extracted from the stripper, the distillation residue discharged from the distillation column is returned to the hydrogenation reactor. Preferably it is. The distillation residue contains unreacted oil and fat, and is returned to the hydrogenation reactor and supplied again to the hydrocracking reaction, whereby the yield of the higher hydrocarbon oil can be increased.

  In the first invention or the second invention, the water vapor remover that condenses and removes the water vapor contained in the gas discharged from the shift reactor, and the carbon dioxide contained in the discharged gas is removed and recovered to the outside. It is preferable to further include a carbon dioxide recovery device. Water vapor and carbon dioxide contained in the gas discharged from the shift reactor can be removed, and a gas with less gas components other than hydrogen can be supplied to the hydrogenation reactor.

  In the first invention or the second invention, the hydrogenation reactor is preferably a slurry bed reactor that supplies a hydrogen-containing gas into a catalyst slurry in which hydrocracking catalyst particles are suspended in oil or fat. The slurry bed reactor has good contact with gas, liquid, and solid, so it can obtain a high reaction rate, and it has temperature controllability that can effectively remove the heat generated by the hydrogenation reaction by the heat exchanger installed inside. Further, even when the catalyst is deteriorated, the catalyst can be replaced by extracting and charging the slurry while continuing the operation.

<Third invention>
The method for producing a higher hydrocarbon oil according to the present invention produces a higher hydrocarbon oil by hydrocracking fats and oils.

  In such a method for producing a higher hydrocarbon oil, in the present invention, the hydrocracking of fats and oils to produce a lower hydrocarbon-containing gas and a higher hydrocarbon oil, and the lower carbonization produced in the hydrogenation reaction step. A partial oxidation process in which lower hydrocarbons contained in a hydrogen-containing gas are partially oxidized to produce hydrogen and carbon monoxide, and a shift in which carbon monoxide produced in the partial oxidation process is subjected to a shift reaction with water vapor to produce hydrogen. And the hydrogenation reaction is performed by reacting the hydrogen produced in the shift reaction step with the fats and oils in the hydrogenation reaction step.

<Fourth Invention>
Similarly to the third invention, the method for producing a higher hydrocarbon oil according to the present invention produces a higher hydrocarbon oil by hydrocracking fats and oils.

  In such a method for producing a higher hydrocarbon oil, in the present invention, the hydrocracking of fats and oils to produce a lower hydrocarbon-containing gas and a higher hydrocarbon oil, and the lower carbonization produced in the hydrogenation reaction step. A gas-liquid separation step for condensing and separating lower hydrocarbons from the hydrogen-containing gas, and a decompression step for depressurizing the lower hydrocarbon condensate separated in the gas-liquid separation step to return the lower hydrocarbons to a gaseous state, A partial oxidation step of partially oxidizing the lower hydrocarbon that has been decompressed and returned to a gaseous state in the decompression step to generate hydrogen and carbon monoxide; and a lower hydrocarbon from the lower hydrocarbon-containing gas in the gas-liquid separation step A shift reaction step in which carbon monoxide contained in the separated residual gas and carbon monoxide generated in the partial oxidation step are subjected to a shift reaction with water vapor to generate hydrogen, and the hydrogenation reaction At step is the hydrogen generated in the shift reaction step characterized by performing a hydrogenolysis is reacted with the fat.

  In the present invention, as described above, hydrogen is produced using lower hydrocarbons, which are by-products in the hydrocracking of fats and oils in the hydrogenation reactor, as raw materials, and the hydrogen is supplied to the hydrogenation reactor. Since it is used for hydrocracking, it is not necessary to receive supply of hydrogen from outside the high-grade hydrocarbon oil production apparatus. Therefore, it is not necessary to install the high-grade hydrocarbon oil production apparatus adjacent to the facility for supplying hydrogen, and the degree of freedom for the installation location of the high-grade hydrocarbon oil production apparatus is increased. Further, by separating the lower hydrocarbons with a gas-liquid separator and supplying only the lower hydrocarbons to the partial oxidation furnace for partial oxidation, the gas discharged from the hydrogenation reactor Since the remaining gas other than the lower hydrocarbon is not supplied to the partial oxidation furnace, the scale of the partial oxidation furnace can be reduced, and the equipment can be downsized. As a result, the efficiency of partial oxidation in the partial oxidation furnace is improved.

<First embodiment>
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the present embodiment, when it is necessary to particularly distinguish the higher hydrocarbon oil, the refined higher hydrocarbon oil is referred to as “refined higher hydrocarbon oil”, and the unrefined higher hydrocarbon oil is referred to as “crude higher hydrocarbon oil”. "

  FIG. 1 is a block diagram showing a configuration of a higher hydrocarbon oil production apparatus according to the present embodiment. The higher hydrocarbon oil production apparatus 1 hydrocracks fats and oils to produce crude higher hydrocarbon oils and lower hydrocarbon gases to be described later, and refines the crude higher hydrocarbon oils to produce purified higher hydrocarbon oils. A hydrocarbon oil production unit 10 that performs the process, and a gas containing lower hydrocarbon gas (hereinafter referred to as “reaction gas”) that is produced by the hydrocarbon oil production unit 10 and extracted from the hydrocarbon oil production unit 10. The reaction gas processing unit 20 that generates a source gas as a raw material for hydrogen generation by liquid separation, and the lower hydrocarbon gas contained in the source gas generated in the reaction gas processing unit 20 is partially oxidized to be oxidized. A partial oxidation treatment unit 30 for producing carbon oxide, and a carbon monoxide produced in the partial oxidation treatment unit 30 is subjected to a shift reaction with water vapor to produce hydrogen and carbon dioxide to produce the hydrogen as the hydrocarbon oil production unit 10. Supply to shift anti And a part 40.

  The hydrocarbon oil production unit 10 includes a hydrogenation reactor 11 that brings oil and fat into contact with a hydrocracking catalyst to hydrocrack the oil to produce crude higher hydrocarbon oil and lower hydrocarbon gas, and the hydrogenation The crude higher hydrocarbon oil is extracted from the reactor 11 together with the catalyst and filtered to separate the catalyst and the crude higher hydrocarbon oil, and the separated crude higher hydrocarbon oil is purified by distillation. And a distillation column 13 for producing a refined higher hydrocarbon oil.

  In this embodiment, the hydrogenation reactor 11 is configured as a slurry bed reactor. The interior of the hydrogenation reactor 11 is filled with a catalyst slurry in which hydrocracking catalyst particles are suspended in oil or fat. A disperser (not shown) is installed at the bottom of the hydrogenation reactor 11, and a hydrogen-containing gas is supplied from the disperser into the hydrogenation reactor 11 as fine bubbles, and the bubbles pass through the catalyst slurry. Ascend while dispersing. A raw material supply port is provided at a position above the disperser on the bottom side surface of the hydrogenation reactor 11, and fats and oils as a raw material are supplied from the raw material supply port.

  In the hydrogenation reactor 11, when the fats and oils come into contact with the hydrocracking catalyst particles in the catalyst slurry, the fats and oils are hydrocracked, and as a result, crude higher hydrocarbon oil is produced. In the hydrocracking reaction of fats and oils, propane is produced as a by-product gas. Moreover, in the hydrogenation reactor 11, the decarboxylation reaction of fats and oils accompanying hydrogenation occurs simultaneously with the above hydrocracking reaction. Propane, carbon monoxide, and carbon dioxide are produced by the decarboxylation reaction, and the carbon dioxide reacts with hydrogen to produce carbon monoxide and water vapor. In the hydrogenation reactor 11, the thermal decomposition reaction of fats and oils also proceeds at the same time, and hydrocarbon gases such as methane and ethane are generated. Hereinafter, in the present invention, propane, which is a by-product gas in each of the hydrocracking reaction of fats and oils and the decarboxylation reaction of fats and oils accompanied by hydrogenation, and hydrocarbon gases such as methane and ethane produced by the thermal cracking reaction of fats and oils Are collectively referred to as “lower hydrocarbon gas” or “lower hydrocarbon”.

  Thus, the reaction gas extracted from the hydrogenation reactor 11 contains lower hydrocarbon gas, carbon monoxide, carbon dioxide, water vapor, and unreacted hydrogen. Further, the reaction gas contains 1 vol% or more of a crude higher hydrocarbon oil as a product in a gaseous state.

  In this embodiment, the oils and fats include animal oils such as lard, beef tallow, and fish oil, as well as vegetable oils such as palm oil and rapeseed oil. Among these, palm oil, lard, beef tallow and the like are preferable because they have a high degree of saturation and can reduce the amount of hydrogen consumption, so that it is less necessary to supply auxiliary raw materials to the partial oxidation furnace described later. It is preferable that the fat is supplied with preheating.

  In this embodiment, a catalyst such as cobalt-molybdenum or nickel-molybdenum is used as the hydrocracking catalyst, but is not limited thereto. The hydrocracking catalyst is preferably fine particles having an average particle size of about 50 to 100 μm so as not to settle in the flowing slurry. Moreover, although it is preferable that the hydrocracking reaction temperature of fats and oils in the hydrogenation reactor 11 is set to 300-400 degreeC and a pressure is about 5-10 MPa, it is not limited to this.

  The filter 12 filters a part of the mixed liquid of the catalyst slurry and the crude higher hydrocarbon oil extracted from the vicinity of the slurry liquid level in the upper part of the hydrogenation reactor 11, and removes the liquid containing the crude higher hydrocarbon oil as the catalyst slurry. Separate from. The liquid containing the crude higher hydrocarbon oil is sent as a crude product to a distillation column 13 for product purification by a pump (not shown), and the catalyst slurry is sent to the hydrogenation reactor 11 by a pump (not shown). Returned. In addition, the height of the liquid level of the mixed liquid in the hydrogenation reactor 11 is controlled so as to be always constant even when the mixed liquid is extracted.

  The crude hydrocarbon oil extracted from the hydrogenation reactor 11 and filtered by the filter 12 is supplied to the distillation column 13 and distilled. As a result, the refined higher hydrocarbon oil is distilled from the top of the distillation column 13 and the distillation residue is discharged from the bottom. The distillation residue contains unreacted fats and oils, is returned from the lower part of the hydrogenation reactor 11 into the hydrogenation reactor 11, and is supplied again to the hydrocracking reaction.

  The reaction gas processing unit 20 cools the reaction gas extracted from the hydrogenation reactor 11 to condense the gaseous crude higher hydrocarbon oil, and condenses the reaction gas cooled by the cooler 21 and the condensation. Separator 22 that separates the crude higher hydrocarbon oil, a cooler 23 that further cools the cooled reaction gas to condense water vapor, and a reaction gas cooled by the cooler 23 and condensed water vapor That is, it has the separator 24 which isolate | separates water.

  The reaction gas withdrawn from the top of the hydrogenation reactor 11 is propane as a by-product gas in hydrocracking reaction and decarbonation reaction, methane by pyrolysis reaction, hydrocarbon gas including ethane, and by decarbonation reaction. Contains carbon monoxide, carbon dioxide, water vapor, and unreacted hydrogen. Further, the reaction gas contains 1 vol% or more of a crude higher hydrocarbon oil as a product in a gaseous state. The reaction gas is cooled by the cooler 21 to a temperature higher than the temperature at which water is condensed and close to the temperature at which water is condensed, for example, about 180 ° C. As a result, the gaseous crude higher hydrocarbon oil contained in the reaction gas is condensed.

  The reaction gas and the condensed crude higher hydrocarbon oil are separated by the separator 22 into the reaction gas and the crude higher hydrocarbon oil. The crude higher hydrocarbon oil is supplied to the distillation tower 13 and distilled together with the crude higher hydrocarbon oil produced in the hydrogenation reactor 11 and extracted from the filter 12. Thus, by recovering the crude higher hydrocarbon oil produced by condensing the gaseous crude feed hydrocarbon oil contained in the reaction gas, the yield of the higher hydrocarbon oil can be increased.

  The reaction gas separated from the crude higher hydrocarbon oil in the separator 22 is cooled by the cooler 23 to a temperature lower than the temperature at which water is condensed and higher than the condensation temperature of the lower hydrocarbon gas, for example, about 50 ° C. The Thus, water vapor is generated by condensing water vapor contained in the reaction gas. The reaction gas and water are separated into the reaction gas and water by the separator 24. Hereinafter, it is referred to as “raw material gas” in the sense of a raw material for supplying a reaction gas from which a crude higher hydrocarbon oil and water have been separated to a partial oxidation treatment section. The raw material gas consists of propane, which is a by-product gas of fat hydrocracking and decarboxylation, carbon monoxide generated by decarboxylation, carbon dioxide, methane, ethane generated by the thermal cracking of fat, and unreacted Contains hydrogen.

  The partial oxidation treatment unit 30 partially oxidizes the lower hydrocarbon gas contained in the raw material gas supplied from the separator 24 to generate hydrogen and carbon monoxide, and the generated hydrogen and carbon monoxide. And a dust removing device 32 that removes soot and dust contained in the contained gas (hereinafter referred to as “partial oxidation gas”).

  The source gas extracted from the separator 24 is supplied to the partial oxidation furnace 31. In the present embodiment, the raw material gas is supplied to the partial oxidation furnace 31 in order to prevent accumulation of inert gas such as nitrogen and argon in the system and to adjust the pressure of the hydrogenation reactor 11. Before, a part of the source gas is extracted as a purge gas.

  The partial oxidation furnace 31 partially oxidizes (partial combustion) the lower hydrocarbon gas in the supplied raw material gas, thereby generating hydrogen and carbon monoxide. In the present embodiment, pure oxygen as an oxidant is supplied from the outside into the partial oxidation furnace 31 to perform partial oxidation. If air is used as the oxidizer, the hydrogen-containing gas, which will be described later, supplied to the hydrogenation reactor 11 will contain nitrogen, resulting in a low hydrogen concentration. However, in this embodiment, pure oxygen is used as the oxidizer. , The hydrogen concentration can be suppressed from decreasing.

  In the present embodiment, as the partial oxidation furnace 31, a partial oxidation furnace that reacts at a high temperature, that is, POX is used. The pressure inside the partial oxidation furnace 31 is suitably about 2 to 5 MPa, but is not limited thereto. In the present embodiment, when the raw material gas is supplied to the partial oxidation furnace 31, the raw material gas is mixed with water vapor, so that the generation of soot in the partial oxidation and the furnace inner wall temperature become abnormally high. It is suppressed.

  In the present embodiment, auxiliary fuel is supplied to the partial oxidation furnace 31 from the outside. When the degree of unsaturation of fats and oils used as raw materials in the hydrocracking reaction of fats and oils is high, or when the thermal cracking reaction of fats and oils in the hydrogenation reactor 11 is not remarkable, hydrogen and carbon monoxide generated in the partial oxidation furnace 31 are described later. The amount of hydrogen produced by reacting with water vapor in this shift reactor may be insufficient for the amount supplied to the hydrogenation reactor 11. Therefore, as in this embodiment, by supplying the auxiliary raw material to the partial oxidation furnace 31, the amount of hydrogen generated in the partial oxidation furnace 31 and thus the amount of hydrogen supplied to the hydrogenation reactor 11 can be increased. it can.

  As the auxiliary material, natural gas, hydrocarbon gas such as propane gas, oxygen-containing organic compound such as methanol and dimethyl ether, and the like can be used. Among these, natural gas is optimal as an auxiliary raw material because it is inexpensive and hardly generates soot.

  Partial oxidation gas generated by partial oxidation of lower hydrocarbons in the partial oxidation furnace 31 is rapidly cooled to about 300 ° C., and soot and dust are removed by the dust removing device 32. The dust removing device 32 may be provided as necessary and is not essential.

  The shift reaction unit 40 shifts the carbon monoxide generated in the partial oxidation furnace 31 with water vapor received from the outside to generate a gas containing hydrogen and carbon dioxide (hereinafter referred to as “hydrogen-containing gas”). By cooling the reactor 41 and the hydrogen-containing gas extracted from the shift reactor 41, water vapor is generated by condensing water vapor contained in the hydrogen-containing gas, and the water is separated from the hydrogen-containing gas and removed. Separator 42, a compressor 43 that pressurizes the hydrogen-containing gas from which the water has been removed, and a carbon dioxide collector 44 that collects carbon dioxide from the pressurized hydrogen-containing gas.

  The partially oxidized gas from which soot and dust have been removed by the dust removing device 32 is supplied to a shift reactor 41 filled with a shift catalyst. The shift reactor 41 is supplied with water vapor from the outside. In the shift reactor 41, carbon monoxide in the partial oxidation gas undergoes a shift reaction with water vapor to generate a hydrogen-containing gas containing hydrogen and carbon dioxide. Examples of the shift catalyst include copper / zinc-based and iron / chromium-based catalysts. The raw material gas supplied to the partial oxidation furnace 31 contains carbon monoxide generated by the decarboxylation reaction of fats and oils in the hydrogenation reactor 11, and this carbon monoxide is also used for the shift reaction.

  Since the shift reaction is exothermic, the shift reaction is preferably performed as a multistage reaction while cooling the gas whose temperature has increased. Thus, the carbon monoxide concentration in the hydrogen-containing gas that is the product gas can be reduced to 1 vol% or less by making the shift reaction a multistage reaction.

  The hydrogen-containing gas extracted from the shift reactor 41 is cooled, whereby water vapor contained in the hydrogen-containing gas is condensed to produce water. The water is separated and removed from the hydrogen-containing gas by the separator 42. Then, the hydrogen-containing gas from which the water has been removed is pressurized to a pressure required for the oil hydrocracking reaction by the compressor 43. The pressure is usually 5 to 10 MPa, but is not limited thereto. The hydrogen-containing gas whose pressure has been increased by the compressor 43 is supplied to the carbon dioxide collector 44, where carbon dioxide is removed. In the carbon dioxide collector 44, cold methanol or an amine-based absorbent is used as the carbon dioxide absorbent, but the carbon dioxide absorbent is not limited to this. The absorption liquid that has absorbed carbon dioxide is sent to a regeneration tower (not shown), and after carbon dioxide is removed in the regeneration tower, it is used again as an absorption liquid.

  The hydrogen-containing gas mainly containing hydrogen extracted from the carbon dioxide collector 44 is supplied to the hydrogenation reactor 11 and used for the hydrocracking reaction with fats and oils.

  In the present embodiment, hydrogen is produced from lower hydrocarbons, which are by-products in the hydrocracking of fats and oils in the hydrogenation reactor 11, and the hydrogen is supplied to the hydrogenation reactor to hydrocrack the fats and oils. Therefore, it is not necessary to receive hydrogen supply from the outside of the higher hydrocarbon oil production apparatus 1. Accordingly, since it is not necessary to install the high-grade hydrocarbon oil production apparatus 1 adjacent to a facility for supplying hydrogen, the degree of freedom for the installation location of the high-grade hydrocarbon oil production apparatus 1 is increased.

  In this embodiment, POX is used as the partial oxidation furnace 31, but instead of this, a spouted bed furnace, a circulating fluidized bed furnace, a fluidized bed furnace, or the like for gasifying coal or biomass is used. Also good. In this case, coal, lignite, biomass, waste plastic, municipal waste, etc. can be supplied as auxiliary raw materials. Biomass is a raw material that does not disperse greenhouse gases, and contributes to the reduction of carbon dioxide emissions in the entire device. As biomass, various things such as wood chips and palm empty fruit bunch can be used.

  In this embodiment, POX is used as the partial oxidation furnace 31, but instead, a reforming catalyst layer is provided at the bottom of the partial oxidation furnace 31 and the raw material is disposed above the reforming catalyst layer. You may use the autothermal reformer (ATR) which passes the crude partial oxidation gas produced | generated from gas through this reforming catalyst layer, and arrives at an equilibrium composition. By installing the reforming catalyst layer, the raw material gas can be completely converted into hydrogen and carbon monoxide at a lower temperature without leaving the hydrocarbon gas. Examples of the reforming catalyst include a nickel-based catalyst.

  Further, instead of the autothermal reformer, a steam reformer that generates hydrogen and carbon monoxide by mixing the raw material gas with steam and passing it through an externally heated catalyst layer to perform steam reforming may be used. . Examples of the steam reformer catalyst include nickel-based catalysts.

<Second embodiment>
In the present embodiment, a reaction gas extracted from the cooler 23, that is, a gas containing lower hydrocarbon, hydrogen, carbon monoxide, carbon dioxide, and water vapor, is converted into lower hydrocarbon, water vapor, and other gas (hereinafter, “ The lower gas is supplied to the partial oxidation furnace, and the remaining gas is supplied to the shift reactor, which is a mixed gas of the lower hydrocarbon and the remaining gas. This is different from the first embodiment in which the raw material gas is supplied to the partial oxidation furnace as it is. In the present embodiment, lower hydrocarbons dissolved in the crude higher hydrocarbon oil produced in the hydrogenation reactor are separated, and the lower hydrocarbons are supplied to the partial oxidation furnace. This is different from the first embodiment in which the crude higher hydrocarbon oil generated in the hydrogenation reactor is supplied to the distillation column as it is in that the crude higher hydrocarbon oil from which hydrogen has been separated is supplied to the distillation column. Since the basic configuration of the higher hydrocarbon oil production apparatus according to the present embodiment is the same as that of the first embodiment, the same reference numerals are assigned and description thereof is omitted, and different points will be mainly described.

  FIG. 2 is a block diagram showing the higher hydrocarbon oil production apparatus according to this embodiment. In this embodiment, the hydrocarbon oil production | generation part 10 is a lower hydrocarbon dissolved in the crude higher hydrocarbon oil isolate | separated by each of this filter 12 and the separator 22 between the filter 12 and the separator 22 and the distillation tower 13. A stripper 14 for separating the two. Further, the reaction gas processing unit 20 does not have the separator 24, and the separator 25 that separates the reaction gas extracted from the cooler 23 into lower hydrocarbon condensate and water and the remaining gas, the lower carbonization. It has a pressure reducing valve 26 for depressurizing the hydrogen condensate and water, and a separator 27 for separating the water and the lower hydrocarbon vaporized by depressurization.

  In the present embodiment, the reaction gas produced in the hydrogenation reactor 11 is first separated from the crude higher hydrocarbon oil cooled in the cooler 21 and condensed in the separator 22 as in the first embodiment. . In this embodiment, in the cooler 23, the reaction gas from which the crude higher hydrocarbon oil is separated is cooled to a temperature at which the lower hydrocarbon is condensed, for example, about 3 to 10 ° C. As a result, the lower hydrocarbon and water vapor are condensed to produce a lower hydrocarbon condensate and water.

  And it is isolate | separated into the condensate of lower hydrocarbons, water, and remainder gas in the separator 25 provided in the downstream of the cooler 23. FIG. The separated remaining gas is supplied to the shift reactor 41. In the shift reactor 41, as in the first embodiment, carbon monoxide in the partial oxidation gas extracted from the partial oxidation furnace undergoes a shift reaction with water vapor to generate hydrogen and carbon dioxide, and in the remaining gas. Hydrogen monoxide is produced by the shift reaction of carbon monoxide with water vapor.

  On the other hand, the lower hydrocarbon condensate and water separated by the separator 25 are depressurized by the pressure reducing valve 26 and supplied to the separator 27. In the separator 27, water and the lower hydrocarbon vaporized by depressurization Are separated. The main components of the lower hydrocarbon are methane, ethane, and propane. The lower hydrocarbon is supplied to the partial oxidation furnace 31 and is partially oxidized in the partial oxidation furnace 31. In the present embodiment, water and lower hydrocarbons are separated by the separator, but instead of this, the separator may be separated by a stripper capable of heating the condensate instead of the separator.

  Further, in this embodiment, the crude higher hydrocarbon oil separated by filtration with the filter 12 and the crude higher hydrocarbon oil separated by the separator 22 are supplied to the stripper 14. In these crude higher hydrocarbon oils, a considerable amount of lower hydrocarbons are dissolved. In this embodiment, the crude higher hydrocarbon oil is heated by the stripper 14 before being supplied to the distillation column 13. Thus, the dissolved lower hydrocarbon is volatilized and separated from the crude higher hydrocarbon. The separated lower hydrocarbon joins with the lower hydrocarbon separated by the separator 27 and is supplied to the partial oxidation furnace 31 where it is partially oxidized. Thus, the lower hydrocarbon gas dissolved in the crude higher hydrocarbon oil is separated by the stripper 14, and the lower hydrocarbon is partially oxidized in the partial oxidation furnace 31, whereby the lower hydrocarbon gas can be used more efficiently.

  In the present embodiment, the lower higher hydrocarbon oil is separated by heating the crude higher hydrocarbon oil with the stripper 14, but instead, the lower higher hydrocarbon oil is depressurized to vaporize the lower hydrocarbon. The crude hydrocarbon oil may be separated and the crude hydrocarbon oil may be heated under reduced pressure to separate the lower hydrocarbon.

  The crude higher hydrocarbon oil discharged from the stripper 14 is supplied to the distillation column 13 and distilled in the distillation column 13. The refined higher hydrocarbon oil produced by distillation is extracted from the top of the distillation column 13, and the distillation residue is discharged from the bottom of the distillation column 13. The distillation residue contains unreacted fats and oils, is returned from the lower part of the hydrogenation reactor 11 into the hydrogenation reactor 11 and is supplied again to the hydrocracking reaction.

  In the present embodiment, the separator 25 separates the lower hydrocarbon condensate into water and the remaining gas, and the separated remaining gas is supplied to the shift reactor 41 without being supplied to the partial oxidation furnace 31. Therefore, the unreacted hydrogen in the reaction gas extracted from the hydrogenation reactor 11 can be supplied to the hydrogenation reactor 11 and used for the hydrocracking reaction without partial oxidation. In the present embodiment, since the lower hydrocarbon is separated and supplied to the partial oxidation furnace 31 in the separator 27, only the lower hydrocarbon is supplied to the partial oxidation furnace 31, and the remaining gas is not supplied. . Therefore, since the remaining gas is not supplied, the scale of the partial oxidation furnace 31 can be reduced, the equipment can be downsized, and the efficiency of partial oxidation in the partial oxidation furnace 31 is improved.

  In the present embodiment, the remaining gas is supplied to the shift reactor 41. However, if it is allowed to accumulate carbon monoxide in the system of the higher hydrocarbon oil production apparatus 1, Instead, the remaining gas may be supplied downstream of the shift reactor 41 and upstream of the carbon dioxide recovery unit 44. In this way, by supplying the gas to the downstream side of the shift reactor 41, the capacity of the shift reactor 41 is reduced by the amount that the remaining gas is not supplied to the shift reactor 41. Can do. Alternatively, by supplying the remaining gas directly to the carbon dioxide recovery unit 44, the gas is not supplied to the compressor 43, so that not only the shift reactor 41 but also the capacity of the compressor 43 is supplied. Can also be reduced.

  The configuration for separating and recovering the lower hydrocarbon gas dissolved in the higher hydrocarbon oil and supplying it to the partial oxidation furnace described in the present embodiment may be provided as necessary and is not essential. Moreover, it cannot be overemphasized that this structure can be provided in the high grade hydrocarbon oil manufacturing apparatus which concerns on 1st embodiment.

It is a block diagram which shows the structure of the higher hydrocarbon oil manufacturing apparatus which concerns on 1st embodiment. It is a block diagram which shows the structure of the higher hydrocarbon oil manufacturing apparatus which concerns on 2nd embodiment.

Explanation of symbols

1 High-grade hydrocarbon oil production equipment 11 Hydrogenation reactor 25 Separator (gas-liquid separator)
26 Pressure reducing valve (pressure reducing device)
31 Partial oxidation furnace 41 Shift reactor 42 Separator (steam remover)
44 carbon dioxide collector

Claims (8)

  In the equipment for hydrocracking fats and oils to produce higher hydrocarbon oils, hydrocracking fats and oils to produce lower hydrocarbon-containing gas and higher hydrocarbon oils, and the above hydrogenation reactor A partial oxidation furnace for partially oxidizing lower hydrocarbons contained in the produced lower hydrocarbon-containing gas to produce hydrogen and carbon monoxide, and carbon monoxide contained in the gas produced in the partial oxidation furnace from outside A shift reactor that generates hydrogen and carbon dioxide by a shift reaction with the received steam, wherein the hydrogenation reactor is supplied with hydrogen generated in the shift reactor. High-grade hydrocarbon oil production equipment.   In the equipment for hydrocracking fats and oils to produce higher hydrocarbon oils, hydrocracking fats and oils to produce lower hydrocarbon-containing gas and higher hydrocarbon oils, and the above hydrogenation reactor A gas-liquid separator that condenses and separates the lower hydrocarbon from the lower hydrocarbon-containing gas, and a lower hydrocarbon condensate separated by the gas-liquid separator is depressurized to convert the lower hydrocarbon to a gaseous state A decompressor to be returned, a partial oxidation furnace that partially oxidizes lower hydrocarbons decompressed and returned to a gaseous state by the decompressor to generate hydrogen and carbon monoxide, and the lower hydrocarbon-containing gas by the gas-liquid separator A shift reactor in which carbon monoxide contained in the remaining gas from which lower hydrocarbons have been separated from carbon and carbon monoxide contained in the gas produced in the partial oxidation furnace are subjected to a shift reaction with steam to produce hydrogen and carbon dioxide When Provided, the hydrogenation reactor, higher hydrocarbon oil producing apparatus characterized by hydrogen generated in the shift reactor are supplied.   A stripper for separating the lower hydrocarbon gas dissolved in the higher hydrocarbon oil from the higher hydrocarbon oil by performing at least one of heating and decompression on the higher hydrocarbon oil produced in the hydrogenation reactor The high-grade hydrocarbon oil production apparatus according to claim 1 or 2, further comprising: a lower hydrocarbon gas separated by the stripper is supplied to a partial oxidation furnace.   The distillation residue discharged | emitted from the said distillation column is further equipped with the distillation column which distills the higher hydrocarbon oil extracted from a stripper, The hydrogenation reactor is returned, The hydrogenation reactor is characterized by the above-mentioned. High-grade hydrocarbon oil production equipment.   A water vapor remover that condenses and removes water vapor contained in the gas discharged from the shift reactor; and a carbon dioxide recovery device that removes carbon dioxide contained in the discharged gas and recovers the carbon dioxide outside. The higher hydrocarbon oil production apparatus according to any one of claims 1 to 4.   The hydrogenation reactor is a slurry bed reactor for supplying a hydrogen-containing gas into a catalyst slurry in which hydrocracking catalyst particles are suspended in an oil or fat. The high-grade hydrocarbon oil production apparatus described in 1.   In a method for producing a higher hydrocarbon oil by hydrocracking fats and oils, a hydrogenation reaction step for hydrocracking fats and oils to produce a lower hydrocarbon-containing gas and a higher hydrocarbon oil, and the above hydrogenation reaction step A partial oxidation step in which lower hydrocarbons contained in the lower hydrocarbon-containing gas are partially oxidized to produce hydrogen and carbon monoxide, and carbon monoxide contained in the gas produced in the partial oxidation step is shifted with water vapor. A high-grade carbonization characterized by comprising a shift reaction step for producing hydrogen by reacting, and in the hydrogenation reaction step, hydrogen produced in the shift reaction step is reacted with the fats and oils to perform hydrocracking Hydrogen oil production method.   In a method for producing a higher hydrocarbon oil by hydrocracking fats and oils, a hydrogenation reaction step for hydrocracking fats and oils to produce a lower hydrocarbon-containing gas and a higher hydrocarbon oil, and the above hydrogenation reaction step A gas-liquid separation step for condensing and separating lower hydrocarbons from the lower hydrocarbon-containing gas, and reducing the lower hydrocarbon condensate separated in the gas-liquid separation step to return the lower hydrocarbons to a gaseous state A decompression step, a partial oxidation step in which the lower hydrocarbon decompressed and returned to the gaseous state in the decompression step is partially oxidized to produce hydrogen and carbon monoxide, and the lower hydrocarbon-containing gas in the gas-liquid separation step. A shift reaction step in which carbon monoxide contained in the remaining gas from which lower hydrocarbons have been separated and carbon monoxide contained in the gas produced in the partial oxidation step are subjected to a shift reaction with water vapor to produce hydrogen. Comprising at the hydrogenation reaction step, a higher hydrocarbon oil manufacturing method of the hydrogen generated in the shift reaction step and performing hydrocracking is reacted with the fat.

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