Manufacturing apparatus and method for producing hydrocarbons

Abstract

To provide a manufacturing apparatus and method capable of efficiently producing hydrocarbons with a higher number of carbon atoms. [Solution] A manufacturing apparatus is provided, comprising: a first reaction section that obtains an unsaturated hydrocarbon by introducing a double bond to a raw material hydrocarbon through dehydrogenation of the raw material hydrocarbon; a second reaction section that obtains an aldehyde by isomerization of the unsaturated hydrocarbon supplied from the first reaction section, moving the double bond to the end of its molecular chain, and hydroformylation by the addition of carbon monoxide and hydrogen; and a third reaction section that deoxygenates the aldehyde supplied from the second reaction section by reduction with hydrogen, obtaining a product hydrocarbon with one more carbon atom than the raw material hydrocarbon.

Description

Technical Field

[0001] The present disclosure relates to a manufacturing apparatus and a method for producing a hydrocarbon product.

Background Art

[0002] In recent years, various methods for synthesizing hydrocarbons have been studied. For example, Patent Document 1 discloses a method for synthesizing hydrocarbons from carbon dioxide and water using a photocatalyst.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, in Patent Document 1, insufficient consideration has been given to improving the efficiency of hydrocarbon synthesis.

[0005] In view of the above circumstances, the present disclosure aims to provide a manufacturing apparatus and the like that can efficiently produce hydrocarbons with a larger number of carbon atoms.

Means for Solving the Problems

[0006] According to one aspect of the present invention, there is provided a manufacturing apparatus including: a first reaction unit that introduces a double bond into a raw material hydrocarbon by dehydrogenating the raw material hydrocarbon to obtain an unsaturated hydrocarbon; a second reaction unit that moves the double bond to the end of the molecular chain of the unsaturated hydrocarbon supplied from the first reaction unit by isomerization of the unsaturated hydrocarbon, and obtains an aldehyde by hydroformylation with the addition of carbon monoxide and hydrogen; and a third reaction unit that deoxygenates the aldehyde supplied from the second reaction unit by reduction with hydrogen, and obtains a hydrocarbon product having one more carbon atom than the raw material hydrocarbon.

[0007] 注:原文本中“<所追加の

[0003] ”这部分不太明确准确含义,按照原样保留翻译。According to this embodiment, it is possible to provide a manufacturing apparatus capable of efficiently producing hydrocarbons with a higher number of carbon atoms. [Brief explanation of the drawing]

[0008] [Figure 1] This is a conceptual diagram showing the configuration of an example manufacturing system. [Figure 2] This diagram shows the flow of material in a manufacturing apparatus. [Figure 3] This is a conceptual diagram showing an example of the configuration of a catalyst recovery unit. [Figure 4] These are block diagrams showing the hardware configuration of the information processing device (Figure 4(a)) and the functional configuration of the information processing device (Figure 4(b)). [Figure 5] This is a flowchart outlining the information processing according to this embodiment. [Modes for carrying out the invention]

[0009] Embodiments of the present invention will be described below with reference to the drawings. The various features shown in the embodiments below can be combined with each other.

[0010] [Manufacturing System] First, an embodiment of the manufacturing system will be described. Figure 1 is a conceptual diagram showing the configuration of an example of a manufacturing system. The manufacturing system 100 shown in Figure 1 comprises a manufacturing apparatus 1, an information processing apparatus 10, a supply unit 20, and a discharge unit 30. In this specification, the upstream side with respect to the flow direction of the raw materials and products will also be simply referred to as the "upstream side," and the downstream side will also be simply referred to as the "downstream side."

[0011] <Supply section> The supply unit 20 supplies raw material hydrocarbons to the manufacturing apparatus 1. The supply unit 20 only needs to be able to supply raw material hydrocarbons that will be used as raw materials in the manufacturing apparatus 1. For example, the supply unit 20 could be a container such as a raw material tank, a pipe connected from a raw material hydrocarbon supply source such as an oil refinery, or other equipment.

[0012] The raw material hydrocarbon is not particularly limited, but can be a hydrocarbon with a relatively small number of carbon atoms, such as crude oil, diesel fuel, kerosene, heavy fuel oil A, or mixtures thereof. The number of carbon atoms in the raw material hydrocarbon is preferably between 1 and 50, preferably between 1 and 10, and more preferably between 1 and 5. In this way, a raw material hydrocarbon with a relatively small number of carbon atoms can be effectively increased by the manufacturing apparatus 1 described later. In particular, the raw material hydrocarbon is preferably diesel fuel, kerosene, or heavy fuel oil A that conforms to JIS standards or the Act on Securing the Quality of Gasoline, etc. (hereinafter also referred to as the "Quality Assurance Act"). This makes it possible to expect to produce the desired product hydrocarbon with high quality. Furthermore, the raw material hydrocarbons may be derived from waste. This improves the life cycle assessment (LCA) of the hydrocarbons produced by the manufacturing apparatus 1.

[0013] <Discharge section> The discharge section 30 discharges the hydrocarbon products manufactured by the manufacturing apparatus 1. The discharge section 30 only needs to be capable of storing or discharging the hydrocarbon products manufactured by the manufacturing apparatus 1. For example, the discharge section 30 could be a container such as a storage tank, a pipe connected to a supply destination for the hydrocarbon products such as a factory, or other equipment. The generated hydrocarbon is not particularly limited, but can be a fuel such as gasoline, kerosene, jet fuel, light oil, or diesel fuel. The number of carbon atoms in the generated hydrocarbon is preferably between 3 and 100, more preferably between 5 and 50, and even more preferably between 8 and 30. Generated hydrocarbons having such a number of carbon atoms can be suitably used as fuel. In particular, it is preferable that the generated hydrocarbon is a fuel oil that conforms to JIS standards or the Quality Assurance Act. This makes it easier to use the generated hydrocarbon in existing infrastructure facilities, etc.

[0014] <Manufacturing equipment> (Overall structure) A manufacturing apparatus 1 is connected between the supply unit 20 and the discharge unit 30 as described above. FIG. 2 is a diagram showing the flow of substances in the manufacturing apparatus. As shown in FIG. 2, the manufacturing apparatus 1 manufactures a produced hydrocarbon from the raw material hydrocarbon supplied from the supply unit 20. More specifically, in the manufacturing apparatus 1, the reaction shown by the following reaction formula (1) proceeds. R-CH3+CO+2H2→R-CH2-CH3+H2O (1) Thus, it is possible to manufacture a produced hydrocarbon having one more carbon atom per cycle than the raw material hydrocarbon.

[0015] In this specification, it will be described that all of the raw material hydrocarbon, the produced hydrocarbon, and the aldehyde described later are in a liquid state in the manufacturing apparatus 1. However, the raw material hydrocarbon, the produced hydrocarbon, and the aldehyde may be in a gaseous state, a critical state, a mixed phase, a mist state, etc. at normal temperature and pressure, or may take a state different from the state at normal temperature and pressure by pressurizing or depressurizing in the manufacturing apparatus 1.

[0016] As shown in FIGS. 1 and 2, the manufacturing apparatus 1 mainly includes a first reaction unit 3, a second reaction unit 4, a third reaction unit 5, a supply unit 20 and a discharge unit 30, and a liquid line LL1 that connects each reaction unit 3 to 5 in series. In this way, by connecting the independent reaction units 3 to 5 in series, each reaction condition can be optimized to produce a desired produced hydrocarbon. In addition, cross-deactivation due to the mixing of catalysts can be suppressed, and variations in the quality of the produced hydrocarbon can be reduced. In addition, if necessary, the liquid line LL1 and each line described later may be provided with a liquid or gas transfer pump (not shown). Thereby, the pressure of each part can be appropriately adjusted, and the transfer of liquid or gas can be smoothly performed.

[0017] (First reaction unit) The first reaction unit 3 is configured to introduce a double bond into a raw material hydrocarbon by dehydrogenation of the raw material hydrocarbon to obtain an unsaturated hydrocarbon (olefin). The first reaction section 3 is, for example, a fixed-bed reactor containing a dehydrogenation catalyst and a hydrogen capturer 31 inside.

[0018] The dehydrogenation catalyst is not particularly limited, but examples include metallic elements such as palladium, platinum, rhodium, and nickel. The dehydrogenation catalyst is preferably further equipped with a co-catalyst. Examples of co-catalysts include alkali metals such as potassium and sodium, alkaline earth metals such as calcium, magnesium, and strontium, transition metals such as tin, gallium, manganese, iron, and cobalt, halogens such as chlorine and fluorine, and alloys containing these. Among these, the dehydrogenation catalyst preferably contains platinum, tin, and potassium. This suppresses cracking of the raw material hydrocarbons. Furthermore, it exhibits high dehydrogenation selectivity, making it easier to introduce double bonds as intended. The dehydrogenation catalyst is not limited to being composed of a single catalyst, but may contain multiple catalysts.

[0019] Furthermore, the dehydrogenation catalyst may be supported on a carrier. The carrier can be any material that is not easily modified depending on the raw hydrocarbon material and reaction conditions, and examples include oxides such as aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, and zeolites, carbides such as graphite and graphene, and combinations of several of these. In particular, the carrier preferably contains aluminum oxide. This improves the thermal stability of the carrier, allowing the first reaction unit 3 to be operated stably over a long period of time.

[0020] In summary, the dehydrogenation catalyst preferably contains a platinum-tin-potassium catalyst supported on aluminum oxide. The platinum content in the dehydrogenation catalyst is preferably between 0.1% and 1% by mass, the tin content is preferably between 0.5% and 1.5% by mass, and the potassium content is preferably between 0.1% and 0.4% by mass. A dehydrogenation catalyst containing platinum in these proportions readily facilitates the reaction. Furthermore, the BET specific surface area of ​​the dehydrogenation catalyst is 100 m². 2 / g or more 180m 2It is preferable that the BET specific surface area is approximately 1 / g or less. A dehydrogenation catalyst having this level of BET specific surface area can ensure sufficient contact area with the raw material hydrocarbons and promote the reaction.

[0021] The hydrogen capturer 31 is configured to capture hydrogen that has been desorbed from the raw hydrocarbon. The hydrogen capturer 31 is not particularly limited as long as it can capture hydrogen, but it is preferable that it be configured as a hydrogen selective permeable membrane that selectively permeates hydrogen and does not permeate unsaturated hydrocarbons. In this case, the first reaction section 3 can be configured as a membrane reactor, and the generation of unsaturated hydrocarbons and hydrogen capture can proceed simultaneously. The constituent material of the hydrogen selective permeable membrane is not particularly limited, but examples include metals such as palladium, nickel, niobium, vanadium, silver, and copper, and alloys containing these. The thickness of the hydrogen selective permeable membrane is preferably about 5 μm to 12 μm. With a hydrogen selective permeable membrane having an appropriate thickness, hydrogen can be sufficiently captured (selectively permeated). Also, the hydrogen selective permeable membrane can permeate hydrogen smoothly if its thickness is not too large. Furthermore, the hydrogen selective permeable membrane has a separation coefficient α(H2 / N2) of 10 4 Preferably, the hydrogen flux J(H2) at 400°C and Δp (pressure difference) 1 bar (0.1 MPa) is 0.15 mol / m³. 2 It is preferable that the performance is approximately s or higher. Having such performance allows for sufficient hydrogen capture.

[0022] The hydrogen capturer 31 may consist of other devices such as a physicosmic swing adsorption (PSA) device, a thermal swing adsorption (TSA) device, a PTSA device, or a chemical absorption device, instead of, or in addition to, a hydrogen selective permeable membrane. However, it is preferable that the hydrogen recovery rate of the hydrogen capturer 31 be around 90 mol% or more. By recovering sufficient hydrogen in this way, it can be supplied to other parts and effectively utilized. The hydrogen recovery rate refers to the molar ratio of recovered hydrogen to generated hydrogen.

[0023] The hydrogen capturer 31 is connected to a gas line GL1 that supplies the captured hydrogen to at least one of the gas reforming unit 7 (second reaction unit 4) and the third reaction unit 5, which supply gas to the second reaction unit 4. This configuration allows for the effective utilization of hydrogen within the production apparatus 1 and reduces the environmental burden associated with hydrogen production and transportation. In other words, the production apparatus 1 further includes a gas line GL1 (hydrogen supply line) that connects the hydrogen capturer 31 to at least one of the gas reforming unit 7 (second reaction unit 4) and the third reaction unit 5, and supplies the hydrogen captured by the hydrogen capturer 31.

[0024] In the first reaction section 3, the reaction temperature is preferably between 360°C and 420°C, and the pressure is preferably between atmospheric pressure (1.01325 bar: 0.1013 MPa) and 5 bar (0.5 MPa). By adjusting the reaction temperature and pressure in the first reaction section 3 to these levels, damage to the hydrogen capturer 31 (hydrogen selective permeable membrane) and the like can be suppressed. Furthermore, it is preferable to pass the raw material hydrocarbons through the first reaction section 3 multiple times. This improves the final yield even under the relatively mild reaction conditions described above. The raw material hydrocarbons may be passed through the first reaction section 3 for approximately two to five times. That is, the first reaction section 3 further includes a return line LL31 that returns the mixture of raw material hydrocarbons and unsaturated hydrocarbons back to the first reaction section 3 itself.

[0025] In the first reaction section 3, it is preferable that monoolefins are selectively obtained, and more preferably that the monoolefin selectivity is 60% or higher. This selective generation of monoolefins allows the reactions in the second and third reaction sections 4 and 5, described later, to proceed favorably, thereby obtaining a product hydrocarbon having the desired number of carbon atoms. Note that the monoolefin selectivity refers to the mole fraction of monoolefins in the hydrocarbon product in the first reaction section 3. In other words, the monoolefin selectivity refers to the mole fraction of monoolefins among the converted raw material hydrocarbons. The same definition of "selectivity" can be used hereafter. The unsaturated hydrocarbon (monoolefin) produced in the first reaction section 3 is supplied to the second reaction section 4 via the liquid line LL1.

[0026] (Second reaction section) In the second reaction section 4, the unsaturated hydrocarbon supplied from the first reaction section 3 isomerizes, moving a double bond to the end of its molecular chain. Then, an aldehyde is obtained by hydroformylation through the addition of carbon monoxide and hydrogen. The second reaction section 4 is a reactor that contains an isomerization-hydroformylation catalyst (hereinafter also referred to as the "IHF catalyst") inside.

[0027] The IHF catalyst comprises a bidentate phosphytic ligand with a large bite angle (e.g., 100° or more) and a metal element. The bidentate phosphytic ligand is preferably biphephos. The metal element is preferably rhodium or ruthenium, and more preferably rhodium. Using such an IHF catalyst allows for efficient isomerization and hydroformylation of unsaturated hydrocarbons. The IHF catalyst is not limited to a single catalyst and may contain multiple catalysts.

[0028] Furthermore, the IHF catalyst is preferably a homogeneous catalyst. In other words, it is preferable that the reaction in the second reaction section 4 proceeds using an IHF catalyst dissolved in a solvent. In this case, the IHF catalyst molecules are easily dispersed uniformly in the solvent, making it easier for them to come into contact with unsaturated hydrocarbon molecules at the molecular level. This means that the reaction efficiency of isomerization and hydroformylation in the second reaction section 4 is high, and improvements in reaction rate and yield can be expected. The IHF catalyst is recovered by the catalyst recovery section 6 and returned to the second reaction section 4 via the catalyst return line LL3 (see below).

[0029] The IHF catalyst preferably has a concentration of its metal element in the solvent of approximately 80 mg / kg to 300 mg / kg. Furthermore, the molar ratio of the bidentate phosphytic ligand to the metal element is preferably between 5 and 10. By including the IHF catalyst at such concentrations and proportions, the reaction in the second reaction section 4 can proceed appropriately. This also prevents the unnecessary consumption of the expensive IHF catalyst. Here, hydrophobic liquids such as isoparaffin, decalin, mineral oil, and vegetable oil can be used as solvents.

[0030] The reaction temperature in the second reaction section 4 is preferably between 80°C and 120°C, the pressure is preferably between 10 bar (1 MPa) and 25 bar (2.5 MPa), and the weight hourly space velocity (WHSV) is preferably between 0.2 / h and 1 / h. Furthermore, the molar ratio of hydrogen to supplied carbon monoxide (hereinafter also referred to as the "H2 / CO ratio") is preferably between 1 and 2.2. By satisfying these conditions, isomerization and hydroformylation in the second reaction section 4 can proceed appropriately. Furthermore, the water content in the solvent according to the Karl Fischer method is preferably around 100 mg / kg or less, and the mole fraction of oxygen is preferably around 10 ppm or less. This makes it easier to maintain the performance of the IHF catalyst.

[0031] In such a second reaction section 4, it is preferable that the mole fraction of molecules with one more carbon atom (hereinafter also referred to as the "+1C insertion rate") among the supplied unsaturated hydrocarbons is about 65% or more. Furthermore, it is preferable that aldehydes are selectively obtained, and it is more preferable that the terminal aldehyde selectivity is about 75% or more. In this specification, "terminal aldehyde" refers to an aldehyde having a formyl group at the end of the main chain of the hydrocarbon. By selectively obtaining terminal aldehydes in this way, the reaction in the third reaction section 5 proceeds efficiently, and highly linear product hydrocarbons can be obtained. In addition, it is easier to systematically increase the number of carbon atoms. The aldehyde generated in the second reaction section 4 is supplied to the third reaction section 5 along with the solvent.

[0032] (Third reaction section) In the third reaction section 5, the aldehyde supplied from the second reaction section 4 is deoxygenated by reduction with hydrogen, yielding a product hydrocarbon with one more carbon atom than the raw material hydrocarbon. The third reaction section 5 is a two-stage fixed-bed reactor comprising, for example, a deoxygenation catalyst bed 51 for carrying out deoxygenation and a hydrogenation catalyst bed 52 for finishing to completely saturate the product. The mixed solution containing aldehyde and solvent (permeate and eluate: see below) supplied to the third reaction section 5 passes sequentially through the deoxygenation catalyst bed 51 and the hydrogenation catalyst bed 52. Hydrogen is supplied to the deoxygenation catalyst bed 51 and the hydrogenation catalyst bed 52 from the hydrogen capturer 31 via the gas line GL1, or from a hydrogen supply source (cylinder, piping, etc.) not shown.

[0033] In the deoxygenation catalyst bed 51, the aldehyde is first hydrogenated into an alcohol, and then the carbon-oxygen bond is cleaved to remove water. The deoxygenation catalyst packed into the deoxygenation catalyst bed 51 is not particularly limited, but examples include metal elements such as nickel, molybdenum, platinum, and palladium, and combinations thereof. The deoxygenation catalyst is preferably a nickel-molybdenum-based catalyst that has been treated with sulfurization. This allows the deoxygenation reaction to proceed with high reliability. The deoxygenation catalyst may be supported on a carrier. Preferably, an oxide such as aluminum oxide, titanium oxide, or silicon oxide is used as the carrier. This allows the carrier to enhance the deoxygenation performance of the deoxygenation catalyst.

[0034] The hydrogenation catalyst packed into the hydrogenation catalyst bed 52 is not particularly limited, but examples include metallic elements such as ruthenium, platinum, palladium, and nickel, and combinations thereof. The hydrogenation catalyst is particularly preferably ruthenium. This is expected to more reliably saturate the product (derived hydrocarbons). The hydrogenation catalyst may also be supported on a carrier. For example, a carbon carrier is preferred as the carrier. This facilitates the dispersion of the hydrogenation catalyst, allowing the hydrogenation reaction to proceed smoothly.

[0035] In the third reaction section 5, the reaction temperature is preferably between 230°C and 320°C, and the pressure is preferably between 20 bar (2 MPa) and 50 bar (5 MPa). Under these conditions, deoxygenation and hydrogenation can proceed favorably to obtain the desired hydrocarbon product. In the third reaction section 5, it is preferable that the mole fraction of the generated hydrocarbon relative to the supplied aldehyde is 99% or more. By converting most of the aldehyde in this way, it is possible to suppress unintended reactions when the generated hydrocarbon is returned to the first reaction section 3 via the return line LL2 described later. With the above configuration, such a high yield can be expected.

[0036] Furthermore, in the third reaction section 5, the generated hydrocarbons in the mixed solution that has passed through the hydrogenation catalyst bed 52 may be hydrocracched to adjust the molar ratio of straight-chain hydrocarbon molecules to branched hydrocarbon molecules in the generated hydrocarbons (hereinafter also referred to as the "L / B ratio"). In other words, a second hydrogenation catalyst bed (not shown) may be provided. This allows the cold filter plugging point (CFPP) to be adjusted and the properties of the generated hydrocarbons to be controlled. Also, depending on the desired properties of the generated hydrocarbons, at least a portion of the mixed solution that has passed through the deoxygenation catalyst bed 51 may be bypassed by omitting passage through the hydrogenation catalyst bed 52. In other words, the third reaction section 5 further includes a bypass line LL51 configured so that the mixed solution that has passed through the deoxygenation catalyst bed 51 bypasses the hydrogenation catalyst bed 52 (see Figure 2).

[0037] The hydrocarbon products obtained in the third reaction section 5 are separated in the separation section 9 (described later) and discharged to the discharge section 30 or returned to the first reaction section 3 via the return line LL2. In other words, the manufacturing apparatus 1 further connects the third reaction section 5 and the first reaction section 3 and includes a return line that returns the hydrocarbon products from the third reaction section 5 to the first reaction section 3. The first reaction section 3 then uses the returned hydrocarbon products as raw material hydrocarbons. In this way, by repeating the reactions in the first reaction section 3, the second reaction section 4, and the third reaction section 5, a hydrocarbon product having a desired number of carbon atoms can be obtained.

[0038] (separation part) The manufacturing apparatus 1 further includes a separation unit 9. The separation unit 9 is located downstream of the third reaction unit 5 and separates the generated hydrocarbons by their molecular weight. The generated hydrocarbons with a predetermined number of carbon atoms or more (having the target number of carbon atoms) are discharged to the discharge unit 30, and the generated hydrocarbons with a number of carbon atoms less than the predetermined number (not reaching the target number of carbon atoms) are returned to the first reaction unit 3. At this time, it is preferable that the solvent is also removed from the generated hydrocarbons. The removed solvent is returned to the second reaction unit 4 via the return line LL5. This allows the solvent to be reused, further reducing the environmental burden when manufacturing the generated hydrocarbons.

[0039] Examples of such separation units 9 include distillation apparatuses, apparatuses for removing low-boiling-point substances, and apparatuses for removing high-boiling-point substances. These apparatuses may be used individually or in combination of two or more. Furthermore, the separation unit 9 may also include apparatuses including permeation vaporization membranes, zeolite dehydration membranes, organic membranes, and ion exchange membranes. In this case, the generated hydrocarbons can be supplied to the first reaction unit 3 or discharge unit 30 after removing excess water and other foreign substances.

[0040] (Impurity removal section) The manufacturing apparatus 1 further includes an impurity removal unit 8 upstream of the first reaction unit 3. The impurity removal unit 8 removes impurities such as sulfur or sulfur compounds, chlorine or chlorine compounds, and cyanide compounds. Among these, it is preferable to remove sulfur compounds, particularly hydrogen sulfide, as impurities. By removing hydrogen sulfide, it is possible to effectively prevent an extreme decrease in the reactivity or deactivation of the catalyst and filler downstream of the impurity removal unit 8. The impurity removal section 8 can be configured to include, for example, a reactor filled with a desulfurizing agent such as activated carbon, zinc oxide, or copper-zinc alloy.

[0041] (Gas reforming section) The manufacturing apparatus 1 further includes a gas reforming unit 7 that generates carbon monoxide and hydrogen, which are used in the second reaction unit 4, from carbon dioxide and water. Thus, since carbon dioxide can be used as a raw material for the generated hydrocarbons, the environmental impact when producing the generated hydrocarbons using the manufacturing apparatus 1 can be kept low. In particular, it is preferable that the carbon dioxide is derived from exhaust gas. This further improves the life cycle assessment (LCA) of the generated hydrocarbons. The gas reforming unit 7 includes a reformer for reforming the gas and an electrolytic dial 71.

[0042] As the reformer for the gas reforming unit 7, for example, a solid oxide electrolytic cell (SOEC), a reverse water-gas shift reactor, etc., can be used. In this embodiment, the gas reformer is a solid oxide electrolytic cell (SOEC) 72. This allows for the production of both carbon monoxide and hydrogen, thus enabling miniaturization of the entire production apparatus 1. Furthermore, it is possible to improve the efficiency of hydrogen utilization. Note that carbon monoxide and hydrogen may be produced simultaneously or alternately. In addition, the gas reforming unit 7 is equipped with a reverse water-gas shift reactor (RWGS) 73 as a backup reformer in case of power outage or failure of the SOEC 72. This enables a stable supply of produced hydrocarbons.

[0043] The electrolytic dial 71 of the gas reforming unit 7 is configured to control the molar ratio of hydrogen to carbon monoxide (H2 / CO ratio). The electrolytic dial 71 is a mechanism that allows the H2 / CO ratio to be freely adjusted during operation. This allows the gas reforming unit 7 to monitor and control the reaction in the second reaction unit 4 in real time. This enables adjustments such as the carbon addition (hydroformylation) rate and the suppression of side reactions. For example, the electrolytic dial 71 can change the H2 / CO ratio during operation within a range of approximately 1 to 2.2.

[0044] The gas reforming unit 7 is connected to the second reaction unit 4 via a gas line GL2, for example, to supply carbon monoxide and hydrogen to the second reaction unit 4. The gas reforming unit 7 may also be connected to the third reaction unit 5 via a gas line (not shown), in which case hydrogen can also be supplied to the third reaction unit 5.

[0045] (Catalyst recovery unit) The manufacturing apparatus 1 further includes a catalyst recovery unit 6 located between the second reaction unit 4 and the third reaction unit 5, which recovers the IHF catalyst from the aldehyde. In other words, the manufacturing apparatus 1 includes a catalyst recovery unit 6 located on the outlet side of the second reaction unit 4, which generates the product (aldehyde) using the IHF catalyst dissolved in the solvent, and which recovers the IHF catalyst from the mixture containing the product and the IHF catalyst. As described above, it is preferable to use a homogeneous catalyst such as the IHF catalyst in the second reaction unit 4, but the IHF catalyst tends to flow downstream together with the aldehyde generated in the second reaction unit 4. Therefore, by arranging the catalyst recovery unit 6, the IHF catalyst can be suitably recovered.

[0046] Figure 3 is a conceptual diagram showing the configuration of an example of a catalyst recovery unit. As shown in Figure 3, the catalyst recovery unit 6 comprises a separation membrane 61, a concentration tank 62, and a separation column 63 filled with a chemical adsorbent, through which aldehydes are permeated to capture the IHF catalyst. The manufacturing apparatus 1 also includes a catalyst return line LL3 that returns the IHF catalyst captured (recovered) by the catalyst recovery unit 6 to the second reaction unit 4.

[0047] The separation membrane 61 is equipped with permeable pores and is configured to separate the mixed liquid into a retaining liquid that does not pass through the permeable pores and a permeate that does pass through the permeable pores. The retaining liquid contains a larger amount of IHF catalyst than the permeate. In other words, the permeable pores are configured to capture the IHF catalyst. It is preferable that the separation membrane 61 be provided in two or more stages. In this embodiment, the separation membrane 61 has a two-stage configuration consisting of a first separation membrane 61a and a second separation membrane 61b.

[0048] Preferably, the permeable pores of the first separation membrane 61a, which is the first stage (upstream) separation membrane, are larger than those of the second separation membrane 61b, which is the second stage and subsequent (downstream) separation membranes. This allows for more reliable recovery of the IHF catalyst while reducing pressure loss. Furthermore, the amount of solvent in the holding liquid can be reduced, saving solvent and thus reducing the environmental impact. For example, among two adjacent separation membranes 61a and 61b, the molecular weight cut-off (MWCO) of the upstream first separation membrane 61a can be set to approximately 800 Da to 1500 Da, and the MWCO of the downstream second separation membrane 61b can be set to approximately 500 Da to 800 Da.

[0049] The materials of each separation membrane 61a and 61b may be the same, but it is preferable that they be different. This allows, for example, the upstream first separation membrane 61a to be made of a material with high mechanical strength, and the downstream second separation membrane 61b to be made of a material with low MWCO and high solvent resistance. In other words, different functions can be assigned depending on whether it is upstream or downstream. Examples of materials for the upstream first separation membrane 61a include polyimide. Examples of materials for the downstream second separation membrane 61b include polybenzimidazole. These materials may be further treated to improve mechanical strength, such as by crosslinking or the inclusion of fillers. Of course, the separation membrane 61 may be composed of three or more stages.

[0050] The ratio of the concentration of the IHF catalyst in the mixed solution before it was supplied to the separation membranes 61 to the concentration of the IHF catalyst in the permeate that has passed through all the separation membranes 61 (first and second separation membranes 61a and 61b) is preferably about 1000 or more, and more preferably about 2000 or more (i.e., the catalyst recovery rate is preferably about 99.9% by mass or more, and more preferably about 99.95% by mass or more). In this way, most of the IHF catalyst can be recovered by the separation membranes 61.

[0051] Furthermore, the time variation of the pressure difference (differential pressure) between the upstream and downstream sides of each separation membrane 61 (hereinafter also referred to as "ΔP drift") is preferably about 10% / 24h or less, and more preferably about 5% / 24h or less. By managing it in this way, the IHF catalyst can be recovered stably, and the accumulation of damage to the separation membrane 61 can be prevented.

[0052] Furthermore, the ratio of the mass of solvent in the permeate that has passed through the entire separation membrane 61 to the mass of solvent in the mixed solution supplied to the separation membrane 61 per unit time is preferably about 0.99 or higher, and more preferably about 0.995 or higher. In other words, the so-called solvent loss is preferably about 1% by mass or less, and more preferably about 0.5% by mass or less. This allows for effective utilization of the solvent. In addition, the concentration of the IHF catalyst in the holding solution can be improved, making the processing in the concentration tank 62 more efficient. Any retaining liquid that does not permeate any of the separation membranes 61 is supplied to the concentration tank 62 via the liquid line LL4. On the other hand, the permeate that has permeated all of the separation membranes 61 is supplied downstream of the separation column 63 (upstream of the third reaction section 5) via the liquid line LL1.

[0053] The concentration tank 62 separates the retaining liquid into a catalyst extract containing the IHF catalyst and a separation liquid containing less IHF catalyst than the catalyst extract, using a concentrate that has a high affinity for the IHF catalyst. More specifically, examples of concentrates include polyethylene glycol, propylene carbonate, polar organic solvents such as N,N-dimethylformamide and N-methyl-2-pyrrolidone, and ionic liquids such as imidazolium and phosphonium. Among these, polyethylene glycol or 1-butyl-3-methylimidazolium tetrafluoroborate with a molecular weight of approximately 200 to 400 is preferred. These liquids are easy to handle as concentrates and do not volatilize easily, thus contributing to the long-term operation of the manufacturing apparatus 1. The catalyst extract obtained in the concentration tank 62 is returned to the second reaction unit 4 via the catalyst return line LL3. Meanwhile, the separated liquid is supplied to the separation column 63 via the liquid line LL4.

[0054] The separation column 63 is supplied with the separation liquid separated in the concentration tank 62. Then, by chemically capturing the IHF catalyst from the permeate and separation liquid, the mixture is separated into a catalyst-containing liquid containing the IHF catalyst and a passlime containing less IHF catalyst than the catalyst-containing liquid. The separation column 63 functions as a so-called scavenger. The separation column 63 is packed with a chemical adsorbent, such as a resin, that has a high affinity for the IHF catalyst or its residue. Examples of chemical adsorbents that can be used include thiol resins, amino resins, and combinations thereof. In the separation column 63, the catalyst-containing liquid, including the IHF catalyst or its residue captured by the packing material, is returned to the second reaction section 4 via the catalyst return line LL3. Meanwhile, the liquid that was not captured by the packing material is supplied to the third reaction section 5 via the liquid line LL4 and then the liquid line LL1.

[0055] The IHF catalyst recovery rate in the catalyst recovery unit 6 is preferably 99.9% by mass or higher. Because it has three distinct mechanisms, the catalyst recovery unit 6 can adequately capture the IHF catalyst, which is generally difficult to recover, and return it to the second reaction unit 4. This allows the manufacturing apparatus 1 to be operated economically for extended periods and reduces environmental impact due to metal contamination.

[0056] (Heat transfer mechanism) Referring to Figure 1, the manufacturing apparatus 1 further includes a heat transfer mechanism HL that transfers heat generated in at least one of the second reaction section 4 and the third reaction section 5 to at least one of the first reaction section 3 and the gas reforming section 7. With this configuration, the environmental burden of operating the manufacturing apparatus 1 can be further reduced by effectively utilizing the heat.

[0057] A heat transfer mechanism HL only needs to be able to transfer heat and can be composed of, for example, a heat exchanger, a waste heat boiler, a heat pump, or piping containing a heat transfer medium such as steam. The heat transfer mechanism HL may have different mechanisms depending on the object to which heat is being transferred. In particular, when transferring heat to the SOEC72 of the gas reforming section 7, it is preferable to convert the heat into steam at approximately 8 bar (0.8 MPa) to 12 bar (1.2 MPa) and 185°C to 190°C, and supply it as a raw material for hydrogen. This makes it possible to reduce the power consumed to generate steam in the SOEC72. Furthermore, when transferring heat to the first reaction section 3, the heat generated in the second reaction section 4 or the third reaction section 5 may be transferred to a heat transfer medium in the piping, and the heat transfer medium may be supplied to the jacket (not shown) of the first reaction section 3. In this case, for example, the jackets may be connected to each other between the reaction sections to perform heat exchange. Alternatively, heat may be recovered at the outlet of the second reaction section 4 or the third reaction section 5 by a heat transfer medium arranged around the liquid line LL1.

[0058] In such a heat transfer mechanism HL, it is preferable that the pinch temperature difference is controlled to be within a predetermined range. More specifically, it is preferable that the pinch temperature difference is between 8°C and 12°C. This makes it possible to minimize the heat supply from external power sources, etc., and further reduce the environmental burden on the manufacturing apparatus 1.

[0059] (Purge mechanism) The manufacturing apparatus 1 further includes a purging mechanism for purging liquid lines LL1 and LL2. More specifically, the purging mechanism includes a purging gas pump P and a gas line GL3 connected to the purging gas pump P. The purge gas pump P is configured to supply purge gas to the liquid line LL1 via the gas line GL3, thereby enabling the purging of the liquid line LL1. The purge gas is not particularly limited as long as it is an inert gas, but examples include nitrogen, hydrogen, and argon.

[0060] Gas line GL3 is configured to supply purge gas at least between the first reaction section 3 and the second reaction section 4, between the second reaction section 4 (catalyst recovery section 6) and the third reaction section 5, and between the third reaction section 5 and the first reaction section 3. This prevents the catalyst and other substances from mixing between the reaction sections, allowing the reaction to proceed efficiently in each reaction section. Gas line GL3 may also be configured to supply purge gas to other parts of liquid line LL1, such as between the supply section 20 and the first reaction section 3, and between the third reaction section 5 and the discharge section 30, as well as to other lines of the manufacturing apparatus 1, such as liquid lines LL3 and LL4, and gas lines GL1 and GL2.

[0061] The timing of the purging mechanism is not particularly limited and may be, for example, when the manufacturing apparatus 1 is started up, at predetermined intervals (e.g., 1 week, 10 days, 2 weeks, 30 days, 1 month, 3 months, 1 year), at predetermined yields (e.g., when the amount of generated hydrocarbons discharged to the discharge section 30 is 1 ton, 3 tons, 5 tons, 10 tons, 30 tons, 100 tons), at predetermined batches (e.g., 1 batch, 3 batches, 5 batches, 10 batches, 30 batches, 100 batches) (when the manufacturing apparatus 1 is operated in batch mode), etc.

[0062] As described above, the manufacturing apparatus 1 can produce hydrocarbons having a desired number of carbon atoms. Therefore, compared to conventional methods such as the Fischer-Tropsch process or methanol-based methods, at least a part of the purification process after hydrocarbon production can be omitted or simplified. In other words, the size of the manufacturing apparatus 1 can be kept down. Therefore, for example, the manufacturing device 1 can be configured as a skid-type module. This allows the manufacturing device 1 to be installed in existing facilities or factories. Furthermore, it is possible to realize a circular system at the local level in which recovered carbon dioxide is used to produce fuels and other hydrocarbons. In other words, it is possible to achieve both decarbonization and energy independence. Furthermore, as described above, the manufacturing apparatus 1 has a catalyst recovery unit 6, a heat transfer mechanism HL, etc., which enables the production of hydrocarbons with a low environmental impact. This contributes to energy independence at the regional level.

[0063] Furthermore, the inventors have confirmed multiple instances of increased raw material hydrocarbons (production of generated hydrocarbons) using the manufacturing apparatus 1 according to this embodiment. In other words, it can be expected that the manufacturing apparatus 1 according to this embodiment will enable the industrial production of generated hydrocarbons having a desired number of carbon atoms. Furthermore, the information processing device 10, which will be described next, allows for flexible operation control, enabling the production of various hydrocarbon products under optimal conditions.

[0064] <Information Processing Device> The information processing device 10 is configured to perform various information processing, such as monitoring the status and controlling the operation, for various devices included in the manufacturing system 100 (e.g., manufacturing device 1, supply unit 20, discharge unit 30, etc.). The information processing device 10 may be a device independent of the manufacturing device 1, supply unit 20, and discharge unit 30 (e.g., a management terminal), or it may be implemented in at least one of these units.

[0065] (Hardware configuration) Figure 4 shows a block diagram (Figure 4(a)) illustrating the hardware configuration of the information processing device and a block diagram (Figure 4(b)) illustrating the functional configuration of the information processing device. As shown in Figure 4(a), the information processing device 10 comprises a processor 101, a storage unit 102, a communication unit 103, an input unit 104, and an output unit 105. The processor 101, storage unit 102, communication unit 103, input unit 104, and output unit 105 are electrically connected within the information processing device 10 via a communication bus 106.

[0066] The processor 101 performs processing and control of the overall operation related to the information processing device 10. The processor 101 is, for example, a Central Processing Unit (CPU). The processor 101 realizes various functions related to the information processing device 10 by reading predetermined programs stored in the memory unit 102. That is, information processing by software stored in the memory unit 102 can be concretely realized by the processor 101, which is an example of hardware, and executed as each functional unit of the processor 101. In other words, the processor 101 can execute programs so that each functional unit is performed. These will be described in more detail in the next section. Note that the processor 101 is not limited to being a single unit, and the information processing device 10 may be implemented to have multiple processors 101 for each function. Furthermore, the information processing device 10 may be composed of a combination of these.

[0067] The memory unit 102 stores various types of information as defined above. This can be done, for example, as a storage device such as a solid-state drive (SSD) that stores various programs related to the information processing device 10 executed by the processor 101, or as memory such as random access memory (RAM) that stores temporarily necessary information (arguments, arrays, etc.) related to program calculations. The memory unit 102 stores various programs, variables, etc., related to the information processing device 10 executed by the processor 101.

[0068] The communication unit 103 may be a wired communication means such as USB, IEEE1394, Thunderbolt®, or wired LAN network communication, or it may be a wireless communication means such as mobile communication such as 3G / LTE / 5G, Bluetooth® communication, or wireless LAN network communication. Furthermore, it is preferable that the communication unit 103 be implemented as a collection of these multiple communication means. In other words, the information processing device 10 may communicate various types of information with the outside world via the communication unit 103 and the network. For example, the information processing device 10 may be configured to download control programs from the outside world via the communication unit 103 and the network.

[0069] The input unit 104 receives operation inputs made by the user. The operation inputs are transmitted to the processor 101 via the communication bus 106 as command signals. The processor 101 can perform predetermined controls and calculations based on the transmitted command signals as needed. The processor 101 may be included in the housing of the information processing device 10 or it may be external. For example, if the input unit 104 is implemented as a touch panel, the user can input tap operations, swipe operations, etc. to the input unit 104. Instead of a touch panel, the input unit 104 can be a switch button, mouse, trackpad, QWERTY keyboard, etc. For example, the user can manually input desired conditions (objective function, etc.) regarding the quality of the produced hydrocarbons, or various states related to the manufacturing apparatus 1, via the input unit 104.

[0070] The output unit 105 outputs electrical signals to each part of the manufacturing apparatus 1 to change various conditions. For example, the output unit 105 is configured to output electrical signals to each reaction unit 3-5, catalyst recovery unit 6, gas reforming unit 7, purge mechanism, separation unit 9, heat transfer mechanism HL, etc., so that the flow rate of hydrocarbons, raw material supply amount, reaction temperature, purge frequency, etc. can be adjusted.

[0071] (Functional Configuration) The information processing performed by the software stored in the memory unit 102 is concretely realized by the processor 101, which is an example of hardware, and can be executed as each functional unit included in the processor 101 (at least one processor provided by the information processing device 10).

[0072] As shown in Figure 4(b), the processor 101 (information processing device 10) comprises an acquisition unit 111, an arithmetic unit 112, and an output control unit 113.

[0073] The acquisition unit 111 is configured to receive various data from the storage unit 102, various parts of the manufacturing system 100, or other information processing terminals as an acquisition step. For example, the acquisition unit 111 is configured to acquire information about the state of various parts of the manufacturing system 100, such as information about the state of the generated hydrocarbons discharged to the discharge unit 30.

[0074] The calculation unit 112 is configured to perform various calculations as calculation steps. For example, the calculation unit 112 is configured to calculate the conditions to be adjusted based on information about the state and a reference state.

[0075] The output control unit 113 outputs a signal as an output step to change the conditions of each part of the manufacturing apparatus 1. For example, the output control unit 113 outputs an electrical signal to the object to be adjusted via the output unit 105 based on the conditions to be adjusted calculated by the calculation unit 112.

[0076] (Information processing methods) Referring to Figure 5, the information processing performed by the information processing device 10 will be described. Figure 5 is a flowchart illustrating the overview of the information processing according to this embodiment. In this information processing, the program stored in the storage unit (storage medium) 102 is read by the processor 101, and the following steps are executed. That is, the information processing method comprises each step of the program. The program also causes at least one computer to execute each step of the information processing method.

[0077] In step S001, the acquisition unit 111 acquires information regarding the status of the manufacturing system 100 as an acquisition step. Here, information regarding the state includes the temperature in the first to third reaction sections 3 to 5, the flow rate of the raw material relative to the mass of the catalyst in the first to third reaction sections 3 to 5 (gravimetric space velocity, WHSV), the separation coefficient α and hydrogen flux J of the hydrogen capturer 31, the water content and oxygen concentration in the second reaction section 4, the ratio of hydrogen to carbon monoxide supplied to the second reaction section 4, the ΔP drift of each separation membrane 61 (first separation membrane 61a and second separation membrane 61b) in the catalyst recovery section 6, the flow velocity passing through each separation membrane 61 (hereinafter also referred to as "permeation flux"), the carbon insertion rate in the second reaction section 4, and the L / B ratio, +1C insertion rate, CFPP, cetane number, carbon number distribution, type of functional group, density, viscosity, pour point, and power consumption relative to the number of inserted carbons (hereinafter also referred to as "unit insertion energy").

[0078] Information regarding the state may be obtained based on measurements indicated by sensors (not shown) attached to various parts of the manufacturing system 100, or based on preset values, or based on user input via the input unit 104. In this embodiment, measurements from sensors are used; that is, online analysis is performed. Examples of sensors include soft sensors that integrate multidimensional gas chromatography (GC×GC), flame ionization detectors (FID), Fourier transform infrared (FTIR) sensors, viscosity sensors, density sensors, and pour point sensors.

[0079] Next, in step S002, the calculation unit 112 calculates the conditions to be adjusted based on the acquired state information and reference information as a calculation step. The reference information includes various functions and artificial intelligence (AI) stored in the memory unit 102, and a combination of these may be used.

[0080] Examples of various functions include functions based on classical control, such as PID control and feedback control, and functions based on modern control, such as state feedback control, robust control, and model predictive control. Examples of AI include trained models that have been pre-trained with information about the state and the conditions for obtaining the desired state. In this embodiment, the reference information includes the predictive model, objective function, and constraints of the model predictive control. In other words, in this embodiment, the calculation unit 112 is a model predictive controller (MPC).

[0081] The calculation unit 112 is more preferably a hierarchical MPC, which improves the real-time performance of the information processing method. More specifically, the calculation unit 112 has, for example, a two-stage configuration. In the first stage, which is one of the two stages, information on the state of various reaction conditions is used, such as the temperature in the first to third reaction units 3 to 5, the WHSV in the first to third reaction units 3 to 5, the H2 / CO ratio supplied to the second reaction unit 4, the ΔP drift of each separation membrane 61 in the catalyst recovery unit 6, and the permeation flux of each separation membrane 61. On the other hand, the second level of the two-tiered structure uses information related to the quality of the generated hydrocarbons and the overall energy efficiency of the production system 100, such as the L / B ratio of the generated hydrocarbons, CFPP, cetane number, and unit insertion energy.

[0082] Furthermore, the reference information includes, as variables of the objective function, at least the cetane number, cold fluidity, L / B ratio, +1C insertion rate, and unit insertion energy of the generated hydrocarbon. The calculation unit 112 then calculates information about the conditions to be adjusted in order to adjust the quality of the generated hydrocarbon to within the acceptable quality range defined by the objective function, based on the state information and the reference information.

[0083] In step S003, the output control unit 113, as an output step, adjusts each part of the manufacturing system 100 based on the information regarding the conditions to be adjusted, calculated by the calculation unit 112. For example, the output control unit 113 outputs electrical signals to perform actions such as changing the H2 / CO ratio (set value of the electrolytic dial 71) of the gas reforming unit 7, cleaning each separation membrane 61 of the catalyst recovery unit 6, changing the flow rate ratio returned from the catalyst recovery unit 6 to the second reaction unit 4, and changing the flow rate ratio to omit (bypass) the hydrogenation catalyst in the third reaction unit 5. The electrical signal output in step S003 preferably includes at least one of the following: the H2 / CO ratio supplied to the second reaction unit 4 (set value of the electrolytic dial 71), the membrane permeation load of the product between each step, the circulation ratio in each step, and the reaction conditions in each step, and more preferably includes at least the H2 / CO ratio (set value of the electrolytic dial 71).

[0084] According to the information processing method described above, it is possible to monitor the reaction conditions and the quality of the generated hydrocarbons in real time and adjust various conditions accordingly. When operating the manufacturing system 100, it is preferable that the fluctuations of the various conditions are within a range of ±1-2%. This makes it possible to expect the production of high-quality generated hydrocarbons with minimal variability. In other words, the quality of the generated hydrocarbons can be designed and controlled in real time, and therefore, at least part of the process of purifying the generated hydrocarbons discharged to the discharge section 30 can be omitted or simplified. Furthermore, it is possible to monitor the utilization status of the catalyst and the condition of the separation membrane 61 and perform maintenance, enabling the production system 100 to be operated efficiently over the long term. Furthermore, by changing the reference information (objective function), the properties of the generated hydrocarbons, such as their cetane number, low-temperature fluidity, and L / B ratio, can be altered. This allows for the production of multiple types of generated hydrocarbons.

[0085] It can also be said that the information processing device 10 and the catalyst recovery unit 6 constitute a catalyst recovery system. The catalyst recovery unit 6 of the catalyst recovery system is located on the outlet side of the reactor (second reaction unit 4) that produces products using IHF catalyst dissolved in a solvent, and recovers the IHF catalyst from the mixture of product and catalyst. The catalyst recovery unit 6 comprises a separation membrane 61, a concentration tank 62, a separation column 63, a catalyst return line LL3, and the information processing device 10. The information processing device 10 detects (acquires) at least one of the ΔP drift of each separation membrane 61 (first separation membrane 61a and second separation membrane 61b) and the permeate flux. Based on at least one of the ΔP drift and the permeate flux, the information processing device 10 starts washing the catalyst recovery unit 6 (separation membrane 61). For example, the information processing device 10 starts washing when the ΔP drift becomes 5% / 24h or more. With such a catalyst recovery system, the catalyst recovery rate is 99.9% or more.

[0086] Furthermore, the information processing device 10 and the heat transfer mechanism HL can be said to constitute a thermal coupled system. The thermal coupled system comprises a heat transfer mechanism HL that transfers (exchanges) heat between each reactor (first reaction section 3 to third reaction section 5, gas reforming section 7, etc.) and the information processing device 10. The information processing device 10 detects (acquires) the pinch temperature difference of the heat transferred by the heat transfer mechanism HL and controls it to maintain it within a predetermined range. With a manufacturing system 100 having such a heat exchange network, it can be expected that the unit energy consumption will be reduced by a predetermined percentage or more compared to standard operation.

[0087] <Manufacturing method> Next, a method for producing the generated hydrocarbon according to the embodiment will be described. The production method is carried out using the production system 100 described above. The production method comprises the steps of: obtaining an unsaturated hydrocarbon by introducing a double bond to a liquid raw material hydrocarbon by dehydrogenation of the raw material hydrocarbon (first step); obtaining a liquid aldehyde by isomerization of the unsaturated hydrocarbon to move the double bond to the end of its molecular chain, and hydroformylation by addition of carbon monoxide and hydrogen (second step); and obtaining a liquid generated hydrocarbon with one more carbon atom than the raw material hydrocarbon by deoxygenation through reduction of the aldehyde with hydrogen (third step).

[0088] [1] First, the raw material hydrocarbons are prepared. The raw material hydrocarbons are supplied from the supply unit 20. [2] Next, raw hydrocarbons are supplied to the manufacturing apparatus 1. Impurities such as sulfur components are removed from the raw hydrocarbons supplied to the manufacturing apparatus 1 in the impurity removal unit 8.

[0089] [3] The raw material hydrocarbons from which impurities have been removed are supplied to the first reaction section 3 via the liquid line LL1. When the raw material hydrocarbons come into contact with the dehydrogenation catalyst packed in the first reaction section 3, double bonds are introduced into the raw material hydrocarbons, and unsaturated hydrocarbons are obtained. The reaction conditions in the first reaction section 3 are preferably between 360°C and 420°C, and between atmospheric pressure (1.01325 bar: 0.1013 MPa) and 5 bar (0.5 MPa). The reaction conditions (states) of each section are monitored and adjusted as appropriate by the information processing device 10.

[0090] Hydrogen removed from the raw material hydrocarbon is removed by the hydrogen capturer 31. In other words, the method for producing the generated hydrocarbon further includes a hydrogen capture step for capturing the hydrogen that was removed from the raw material hydrocarbon in the first step. In this embodiment, the hydrogen capture membrane, which serves as the hydrogen capturer 31, has a separation coefficient α(H2 / N2) of 10 4 As described above, the hydrogen flux J (H2) at 400℃ and a pressure difference of Δp (0.1 MPa) of 1 bar (0.1 MPa) is approximately 0.15 mol / m³. 2 It is preferable that it be approximately s or higher.

[0091] The removed hydrogen is supplied to at least one of the gas reforming section 7 (second reaction section 4) and the third reaction section 5 via gas line GL1 or GL2. In other words, the captured hydrogen is supplied to at least one of the second and third steps. Furthermore, the mixture of raw material hydrocarbons and unsaturated hydrocarbons is preferably returned to the first reaction section 3 via the return line LL31 and passed through the first reaction section 3 multiple times (for example, two to five times).

[0092] [4] The unsaturated hydrocarbon is supplied to the second reaction section 4 via the liquid line LL1. In the second reaction section 4, the unsaturated hydrocarbon comes into contact with the IHF catalyst, which is a homogeneous catalyst (catalyst dissolved in the solvent), causing double bonds to be moved to the ends of the molecular chains of the unsaturated hydrocarbon, and carbon monoxide and hydrogen are added to obtain an aldehyde. The reaction conditions in the second reaction section 4 are preferably 80°C to 120°C and 10 bar (1 MPa) to 25 bar (2.5 MPa). Furthermore, the water content in the solvent according to the Karl Fischer method is preferably 100 mg / kg or less, and the mole fraction of oxygen is preferably 10 ppm.

[0093] Hydrogen and carbon monoxide are supplied to the second reaction unit 4 from the gas reforming unit 7 via the gas line GL2. The hydrogen and carbon monoxide are generated from carbon dioxide and water by SOEC72 (or, if SOEC72 is unavailable, RWGS73 as a backup). The ratio and amount of hydrogen and carbon monoxide supplied to the second reaction unit 4 can be adjusted by the electrolytic dial 71. The electrolytic dial 71 is controlled by the information processing device 10.

[0094] [5] The aldehyde is supplied to the catalyst recovery unit 6 via the liquid line LL1. At this time, the aldehyde is in the state of a mixture with a solvent containing the homogeneous catalyst IHF catalyst. In the catalyst recovery unit 6, the mixture is first separated into a permeate and a retaining liquid with a higher IHF catalyst content than the permeate by at least two separation membranes 61. At this time, the ΔP drift of the separation membrane 61 and the permeate flux are monitored by the information processing device 10. Next, the retaining liquid is separated into a separation liquid and a catalyst extract with a higher IHF catalyst content than the separation liquid by a concentration tank 62. The separation liquid is then separated into a passlime and a catalyst-containing liquid with a higher IHF catalyst content than the passlime by a separation column 63. The catalyst extract and the catalyst-containing liquid are then returned to the second reaction unit 4 via the catalyst return line LL3. That is, the manufacturing method further includes a catalyst recovery step of recovering the catalyst from the aldehyde.

[0095] [6] Meanwhile, the permeate and permeate that merge into liquid line LL1 via liquid line LL4 are supplied to the third reaction section 5 via liquid line LL1. The permeate and permeate are in the state of a mixed solution containing aldehyde and solvent. In the third reaction section 5, the mixed solution is first supplied to the deoxygenation catalyst bed 51 to deoxygenate the aldehyde and obtain the product hydrocarbon. Next, at least a portion of the mixed solution that has passed through the deoxygenation catalyst bed 51 is supplied to the hydrogenation catalyst bed 52 to perform a finishing treatment to saturate the product hydrocarbon.

[0096] [7] The mixed solution containing the generated hydrocarbons and the solvent is supplied to the separation unit 9. In the separation unit 9, the generated hydrocarbons in the mixed solution are separated according to the number of carbon atoms, and the solvent is removed. Hydrocarbons with a predetermined number of carbon atoms or more are discharged from the separation unit 9 to the discharge unit 30. On the other hand, generated hydrocarbons with a predetermined number of carbon atoms or less are returned to the first reaction unit 3. In other words, the method for producing generated hydrocarbons involves supplying the generated hydrocarbons obtained in the third step as raw material hydrocarbons to the first step, and repeating the first to third steps until a generated hydrocarbon having the desired number of carbon atoms is obtained. Furthermore, the removed solvent is returned to the second reaction section 4 and reused. As described above, the resulting hydrocarbons can be produced by adding one carbon atom at a time to the raw material hydrocarbons.

[0097] [8] As described above, the state of each part is monitored by the information processing device 10 and controlled according to the information processing method. In other words, the method for producing the hydrocarbon further includes a condition adjustment step of adjusting predetermined conditions based on an objective function. The objective function includes at least one of the cetane number, low-temperature fluidity, straight-chain / branched ratio, and unit energy consumption of the hydrocarbon. The predetermined conditions include at least one of the molar ratio of hydrogen to carbon monoxide supplied in the second step (H2 / CO ratio), the membrane permeation load of the product between each step, the circulation ratio in each step, and the reaction conditions in each step. It is more preferable that the predetermined conditions include at least the H2 / CO ratio to carbon monoxide supplied in the second step (set value of the electrolytic dial 71). Furthermore, monitoring the state of each part (during the condition adjustment process) is preferably performed by online analysis using at least one of multidimensional gas chromatography and infrared spectroscopy. The information processing device 10 then adjusts the quality of the generated hydrocarbons based on these states and the objective function. In this configuration, the information processing device 10 automatically monitors the status and adjusts the conditions. This enables real-time management and control of the quality of the generated hydrocarbons.

[0098] Furthermore, they may be provided in the following embodiments.

[0099] (1) A manufacturing apparatus comprising: a first reaction section that introduces a double bond to a raw material hydrocarbon by dehydrogenation of the raw material hydrocarbon to obtain an unsaturated hydrocarbon; a second reaction section that isomerizes the unsaturated hydrocarbon supplied from the first reaction section to move the double bond to the end of its molecular chain, and obtains an aldehyde by hydroformylation through the addition of carbon monoxide and hydrogen; and a third reaction section that deoxygenates the aldehyde supplied from the second reaction section by reduction with hydrogen to obtain a product hydrocarbon having one more carbon atom than the raw material hydrocarbon.

[0100] (2) A manufacturing apparatus as described in (1) above, further comprising a connection between the third reaction section and the first reaction section, a return line for returning the generated hydrocarbon from the third reaction section to the first reaction section, and the first reaction section using the returned generated hydrocarbon as the raw material hydrocarbon.

[0101] (3) A manufacturing apparatus according to (1) or (2) above, wherein the first reaction unit is equipped with a hydrogen capturer for capturing hydrogen desorbed from the raw material hydrocarbon, and the manufacturing apparatus further comprises a hydrogen supply line that connects the hydrogen capturer to at least one of the second reaction unit and the third reaction unit and supplies the hydrogen captured by the hydrogen capturer.

[0102] (4) A manufacturing apparatus according to any one of (1) to (3) above, further comprising a gas reforming unit that generates carbon monoxide and hydrogen used in the second reaction unit from carbon dioxide and water.

[0103] (5) A manufacturing apparatus as described in (4) above, wherein the gas reforming unit is capable of controlling the molar ratio of hydrogen to carbon monoxide.

[0104] (6) A manufacturing apparatus according to (4) or (5) above, further comprising a heat transfer mechanism for transferring heat generated in at least one of the second reaction section and the third reaction section to at least one of the first reaction section and the gas reforming section.

[0105] (7) A manufacturing apparatus according to any one of (1) to (6) above, wherein the second reaction section is equipped with a homogeneous catalyst, and the manufacturing apparatus further comprises a catalyst recovery section provided between the second reaction section and the third reaction section for recovering the homogeneous catalyst from the aldehyde.

[0106] (8) A manufacturing apparatus as described in (7) above, wherein the catalyst recovery unit comprises a separation membrane and a chemical adsorbent, and captures the homogeneous catalyst by permeating the aldehyde through them.

[0107] (9) A manufacturing apparatus according to any one of (1) to (8) above, further comprising a line connecting the first reaction unit, the second reaction unit, and the third reaction unit in series, and a purging mechanism for purging the line.

[0108] (10) A manufacturing apparatus described in any one of (1) to (9) above, which is configured as a skid-type module.

[0109] (11) A method for producing a hydrocarbon, comprising: a first step of introducing a double bond to a raw material hydrocarbon by dehydrogenation of the raw material hydrocarbon to obtain an unsaturated hydrocarbon; a second step of isomerizing the unsaturated hydrocarbon to move the double bond to the end of its molecular chain, and obtaining an aldehyde by hydroformylation through the addition of carbon monoxide and hydrogen; and a third step of deoxygenating the aldehyde by reduction with hydrogen to obtain a hydrocarbon having one more carbon atom than the raw material hydrocarbon.

[0110] (12) A method for producing hydrocarbons as described in (11) above, wherein the produced hydrocarbon obtained in the third step is supplied to the first step as the raw material hydrocarbon, and the first to third steps are repeated until the produced hydrocarbon having the desired number of carbon atoms is obtained.

[0111] (13) A method for producing a generated hydrocarbon as described in (11) or (12) above, further comprising a hydrogen capture step for capturing hydrogen removed from the raw material hydrocarbon in the first step, wherein the captured hydrogen is supplied to at least one of the second step and the third step.

[0112] (14) A method for producing hydrocarbons according to any one of (11) to (13) above, wherein in the second step, the reaction is carried out by a homogeneous catalyst, and the production method further includes a catalyst recovery step of recovering the homogeneous catalyst from the aldehyde.

[0113] (15) A method for producing hydrocarbons according to any one of (11) to (14) above, further comprising a condition adjustment step for adjusting predetermined conditions based on an objective function, wherein the objective function includes at least one of the cetane number, low-temperature fluidity, straight-chain / branched ratio, and unit energy consumption of the produced hydrocarbon, and the predetermined conditions include at least one of the molar ratio of hydrogen to carbon monoxide supplied in the second step, membrane permeation load of the product between each step, circulation ratio in each step, and reaction conditions in each step.

[0114] (16) A method for producing hydrocarbons according to (15) above, wherein in the condition adjustment step, the quality of the produced hydrocarbons is adjusted based on online analysis using at least one of multidimensional gas chromatography and infrared spectroscopy and the objective function. Of course, this is not always the case.

[0115] Finally, various embodiments of the present invention have been described, but these are presented as examples and are not intended to limit the scope of the invention. These novel embodiments can be implemented in a variety of other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their variations are included in the scope and spirit of the invention, as well as in the claims and their equivalents. [Explanation of Symbols]

[0116] 100: Manufacturing System 1: Manufacturing equipment 10: Information Processing Device 101: Processor 102: Storage section 103: Communications Department 104: Input section 105: Output section 106: Communications bus 111: Acquisition Department 112: Arithmetic section 113: Output Control Unit 20: Supply section 30: Discharge section 3: First reaction section 31: Hydrogen trap 4: Second reaction section 5: Third reaction section 51: Deoxygenation catalyst bed 52: Hydrogenation catalyst bed 6: Catalyst recovery unit 61: Separation membrane 61a: 1st separation membrane 61b:Second separation membrane 62:Concentrator tank 63: Isolation column 7: Gas reforming section 71: Electrolytic dial 72: SOEC 73: RWGS 8: Impurity removal section 9: Separation section GL1: Gas line GL2: Gas line GL3: Gas line HL: Heat transfer mechanism J: Hydrogen flux LL1: Liquid line LL2: Return Line LL3: Catalyst return line LL31: Return Line LL4: Liquid line LL5: Return Line LL51: Bypass Line P: Purge gas pump

Claims

1. A manufacturing apparatus, A first reaction unit in which a double bond is introduced into a raw material hydrocarbon by dehydrogenation of the raw material hydrocarbon to obtain an unsaturated hydrocarbon, A second reaction unit is formed in which the unsaturated hydrocarbon supplied from the first reaction unit is isomerized to move the double bond to the end of its molecular chain, and an aldehyde is obtained by hydroformylation through the addition of carbon monoxide and hydrogen, A third reaction unit, which deoxygenates the aldehyde supplied from the second reaction unit by hydrogen reduction to obtain a product hydrocarbon with one more carbon atom than the raw material hydrocarbon, The third reaction section and the first reaction section are connected, and a return line is provided for returning the generated hydrocarbon from the third reaction section to the first reaction section. The first reaction unit uses the returned product hydrocarbon as the raw material hydrocarbon. Manufacturing equipment.

2. In the manufacturing apparatus described in claim 1, The first reaction unit is equipped with a hydrogen capturer that captures hydrogen released from the raw material hydrocarbon, The manufacturing apparatus further includes a hydrogen supply line that connects the hydrogen capturer to at least one of the second reaction section and the third reaction section, and supplies the hydrogen captured by the hydrogen capturer. Manufacturing equipment.

3. In the manufacturing apparatus described in claim 1, Furthermore, the system includes a gas reforming unit that generates carbon monoxide and hydrogen used in the second reaction unit from carbon dioxide and water. Manufacturing equipment.

4. In the manufacturing apparatus described in claim 3, The gas reforming unit is capable of controlling the molar ratio of hydrogen to carbon monoxide. Manufacturing equipment.

5. In the manufacturing apparatus described in claim 3, Furthermore, the system includes a heat transfer mechanism that transfers heat generated in at least one of the second reaction section and the third reaction section to at least one of the first reaction section and the gas reforming section. Manufacturing equipment.

6. In the manufacturing apparatus described in claim 1, The second reaction section comprises a homogeneous catalyst, The manufacturing apparatus further includes a catalyst recovery unit provided between the second reaction unit and the third reaction unit for recovering the homogeneous catalyst from the aldehyde. Manufacturing equipment.

7. In the manufacturing apparatus described in claim 6, The catalyst recovery unit comprises a separation membrane and a chemical adsorbent, which permeate the aldehyde to capture the homogeneous catalyst. Manufacturing equipment.

8. In the manufacturing apparatus described in claim 1, Furthermore, the system includes a line connecting the first reaction section, the second reaction section, and the third reaction section in series, and a purging mechanism for purging the line. Manufacturing equipment.

9. In the manufacturing apparatus described in claim 1, It is configured as a skid-type module. Manufacturing equipment.

10. A method for producing hydrocarbons, A first step involves introducing a double bond into a raw material hydrocarbon by dehydrogenation of the raw material hydrocarbon to obtain an unsaturated hydrocarbon, The second step involves isomerizing the unsaturated hydrocarbon to move the double bond to the end of its molecular chain, and obtaining an aldehyde by hydroformylation through the addition of carbon monoxide and hydrogen. The process includes a third step of deoxygenating the aldehyde by hydrogen reduction to obtain the generated hydrocarbon, which has one more carbon atom than the raw material hydrocarbon. The generated hydrocarbon obtained in the third step is supplied to the first step as the raw material hydrocarbon, and the first to third steps are repeated until the generated hydrocarbon having the desired number of carbon atoms is obtained. A method for producing hydrocarbons.

11. In the method for producing hydrocarbons according to claim 10, Furthermore, the process includes a hydrogen capture step for capturing the hydrogen removed from the raw material hydrocarbon in the first step, The captured hydrogen is supplied to at least one of the second and third steps. A method for producing hydrocarbons.

12. In the method for producing hydrocarbons according to claim 10, In the second step, the reaction is carried out using a homogeneous catalyst. The above manufacturing method further includes a catalyst recovery step of recovering the homogeneous catalyst from the aldehyde. A method for producing hydrocarbons.

13. In the method for producing hydrocarbons according to claim 10, Furthermore, it includes a condition adjustment step that adjusts predetermined conditions based on the objective function, The objective function includes at least one of the cetane number, low-temperature fluidity, straight-chain / branched ratio, and unit energy consumption of the generated hydrocarbon. The predetermined conditions include at least one of the following: the molar ratio of hydrogen to carbon monoxide supplied in the second step, the membrane permeation load of the product between each step, the circulation ratio in each step, and the reaction conditions in each step. A method for producing hydrocarbons.

14. In the method for producing hydrocarbons according to claim 13, In the condition adjustment step, the quality of the generated hydrocarbon is adjusted based on online analysis using at least one of multidimensional gas chromatography and infrared spectroscopy, and the objective function. A method for producing hydrocarbons.

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