Supplying method and supplying device to catalyst

Abstract

To provide a supplying method and a supplying device to a catalyst that are capable of suppressing deterioration in the catalyst capable of synthesizing a hydrocarbon from a synthetic gas containing a carbon oxide gas.SOLUTION: The supplying method is for supplying a synthetic gas containing a hydrogen gas and a carbon oxide gas to a catalyst capable of producing hydrocarbons from the synthetic gas. The method includes: supplying the synthetic gas to the catalyst as a gas containing a poisoning substance that is poisonous to the catalyst; adjusting, by a control unit having hardware, a concentration of the poisoning substance contained in the synthetic gas supplied to the catalyst by controlling an amount of the poisoning substance contained in the synthetic gas supplied to the catalyst; and increasing, by the control unit, the poisoning substance based on the concentration of the poisoning substance contained in the synthetic gas measured by a concentration sensor in adjusting the concentration.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to a method and apparatus for supplying to a catalyst, and is particularly suitable for application to a catalyst for producing liquid fuel by reacting a mixed gas of carbon oxides and hydrogen. [Background technology]

[0002] In recent years, there has been active research and development into improving the selectivity of the target product by controlling the complex reaction pathways using the Fischer-Tropsch (FT) synthesis technology, which synthesizes liquid hydrocarbons from carbon monoxide (CO) and hydrogen (H2).

[0003] Patent Document 1 discloses a hydrocarbon production method comprising: a first reaction step in which a gas containing carbon monoxide and hydrogen is supplied to a first reactor housing an FT catalyst that produces hydrocarbons by a reaction according to the FT process to produce hydrocarbons; a second reaction step in which a gas is supplied to a second reactor housing an FT catalyst that produces hydrocarbons by a reaction according to the FT process to produce hydrocarbons; a first regeneration step in which the supply of gas to the first reactor is stopped to regenerate the performance of the FT catalyst housed in the first reactor; and a second regeneration step in which the supply of gas to the second reactor is stopped to regenerate the performance of the FT catalyst housed in the second reactor, the first regeneration step and the second regeneration step being carried out for mutually different periods. Patent Document 2 discloses a catalyst regeneration method in which the temperature of the catalyst is increased to remove wax, and then the temperature is lowered and oxidizing gas or reducing gas is passed through to regenerate the catalyst.

[0004] Non-Patent Document 1 discloses a regeneration method after poisoning of an FT catalyst that produces hydrocarbons through a reaction using the FT process reduces the CO conversion rate, i.e., the catalytic activity, resulting in poisoning and deterioration. Non-Patent Document 1 discloses a regeneration method in which the heptane solvent is washed at a temperature of 100°C to remove excess wax, and an oxidation treatment is performed by heating in a heating furnace such as a fluidized bed using a mixed gas of air and nitrogen (N2), gradually increasing the oxygen concentration to 3 to 21%, and reduction is performed with hydrogen in the fluidized bed unit. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2022-102703 [Patent Document 2] Special Publication No. 2022-535946 [Non-patent literature]

[0006] [Non-Patent Document 1] “Fundamental understanding of deactivation and regeneration of cobalt Fischer-Tropsch synthesis catalysts”, AM Saiba et al., Catalysis Today 154 (2010) 271-282 Summary of the Invention [Problem to be solved by the invention]

[0007] As described above, catalysts capable of synthesizing hydrocarbons from synthesis gas containing carbon oxides lose their activity over time due to coating or coking of the catalyst surface with hydrocarbons. Therefore, a regeneration process was required in which the synthesis reaction was stopped after a certain period of time and combustion or reaction caused by oxygen- or hydrogen-containing gases was eliminated. However, the regeneration process takes a long time, from several days to a week, including shutting down and starting up the equipment. Because hydrocarbon synthesis cannot be performed during the regeneration process, production volume decreases and costs increase due to the production of oxygen gas and hydrogen gas required for the process. Therefore, a technology to suppress the decline in catalyst activity, i.e., catalyst degradation, was needed.

[0008] The present invention has been made in view of the above, and an object of the present invention is to provide a catalyst supply method and supply device that can suppress deterioration of a catalyst capable of synthesizing hydrocarbons from a synthesis gas containing carbon oxide gas. [Means for solving the problem]

[0009] (1) In order to solve the above-mentioned problems and achieve the object, one aspect of the present invention provides a catalyst supply method for supplying a synthesis gas containing hydrogen gas and carbon oxide gas to a catalyst capable of producing hydrocarbons from the synthesis gas, in which the synthesis gas is supplied to the catalyst as a gas containing a poisoning substance that is poisonous to the catalyst.

[0010] (2) In the catalyst supply method according to one aspect of the present invention, in the invention (1) above, the concentration of the poisoning substance in the synthesis gas is set to be greater than 0 volppm and equal to or less than 1.0 volppm.

[0011] (3) In the catalyst supply method according to one aspect of the present invention, in the invention (1) above, the concentration of the poisoning substance in the synthesis gas is set to 0.01 volppm or more and 0.2 volppm or less.

[0012] (4) In the catalyst supply method according to one aspect of the present invention, in the invention (1) above, the concentration of the poisoning substance in the synthesis gas is set to 0.02 volppm or more and less than 0.1 volppm.

[0013] (5) In a method for supplying a poisoning substance to a catalyst according to one aspect of the present invention, in any one of the above-mentioned (1) to (4), the poisoning substance is a temporary poisoning substance that has temporary poisoning that can regenerate the catalyst.

[0014] (6) In one embodiment of the present invention, in the method for supplying a catalyst according to the invention (5) above, the temporary poisoning substance is at least one compound selected from the group consisting of ammonia (NH3), hydrogen cyanide (HCN), phosphine (PH3), sodium chloride (NaCl), and potassium chloride (KCl).

[0015] (7) A method for supplying a poisoning substance to a catalyst according to one aspect of the present invention is any one of the above-mentioned (1) to (4), wherein the poisoning substance is a permanent poisoning substance that permanently poisons the catalyst and makes it impossible to regenerate the catalyst.

[0016] (8) According to one aspect of the present invention, in the method for supplying to a catalyst according to the above-mentioned (7), the permanent poisoning substance is a compound containing at least one of a compound containing sulfur (S) and hydrogen chloride (HCl).

[0017] (9) In one aspect of the present invention, in the method for supplying a catalyst according to the above (7) or (8), the permanent poisoning substance is at least one compound selected from the group consisting of hydrogen sulfide (HS), carbonyl sulfide (COS), hydrogen chloride (HCl), and arsine (AsH).

[0018] (10) A method for supplying a catalyst according to one aspect of the present invention is any one of the above-mentioned (1) to (8), wherein the catalyst comprises a metal-based catalyst containing a metal compound active in a Fischer-Tropsch synthesis reaction and producing hydrocarbons from a synthesis gas, and a support catalyst containing a metal oxide supporting the metal-based catalyst.

[0019] (11) A method for supplying a catalyst according to one embodiment of the present invention is any one of the above-mentioned (1) to (10), wherein the catalyst comprises a metal-based catalyst that contains a metal and a metal compound active in a Fischer-Tropsch synthesis reaction and produces hydrocarbons from a synthesis gas, and a support catalyst that contains a zeolite that supports the metal-based catalyst, and the metal and the metal compound contain cobalt and at least one metal selected from the group consisting of manganese and ruthenium.

[0020] (12) In one aspect of the present invention, in any one of the above-mentioned (1) to (11) inventions, a supply method to a catalyst includes controlling the amount of the poisoning substance introduced into the synthesis gas to be supplied to the catalyst by a control unit having hardware, thereby adjusting the concentration of the poisoning substance contained in the synthesis gas to be supplied to the catalyst.

[0021] (13) In one aspect of the present invention, in the method of supplying the synthesis gas to the catalyst according to the invention (12) above, the control unit branches off at least a portion of the synthesis gas from the line that supplies the synthesis gas to the catalyst, removes the poisoning substances upstream of the catalyst, and then supplies the synthesis gas together with the remainder of the synthesis gas to the catalyst before supplying the synthesis gas to the catalyst.

[0022] (14) In one aspect of the present invention, in the method for supplying to a catalyst according to the above (12) or (13), the poisoning substance is recovered on the exhaust side of the catalyst, and at least a portion of the recovered poisoning substance is mixed into the synthesis gas to be supplied to the catalyst.

[0023] (15) A supply device according to one aspect of the present invention includes a synthesis gas supply unit configured to be capable of supplying a synthesis gas containing hydrogen gas, carbon oxide gas, and a poisoning substance that is poisonous to a catalyst, and a gas purification unit configured to be capable of adjusting the concentration of the poisoning substance contained in the synthesis gas supplied from the synthesis gas supply unit, and is configured to be capable of supplying the synthesis gas to a synthesis reactor containing the catalyst and configured to be capable of synthesizing hydrocarbons from the hydrogen gas and carbon oxide gas contained in the synthesis gas.

[0024] (16) In the supply device according to one aspect of the present invention, in the invention (15) above, the gas purification unit adjusts the concentration of the poisoning substance in the synthesis gas to greater than 0 volppm and 1.0 volppm or less.

[0025] (17) In one aspect of the supply device of the present invention, in the invention of (15) or (16) above, the gas purification unit includes at least one poisoning substance separation unit configured to be able to separate the poisoning substance from the synthesis gas, and a control unit having hardware capable of controlling the flow rate of the synthesis gas supplied to the poisoning substance separation unit, and upstream of the poisoning substance separation unit, the synthesis gas is caused to flow through at least one of a first path that supplies the synthesis gas to the synthesis reactor without passing through the poisoning substance separation unit, and a second path that supplies the synthesis gas to the synthesis reactor after being supplied to the poisoning substance separation unit, and the control unit controls the flow rate of the synthesis gas flowing through the first path and the flow rate of the synthesis gas flowing through the second path, thereby adjusting the concentration of the poisoning substance.

[0026] (18) In one aspect of the supply device of the present invention, in any one of the above (15) to (17), the poisoning substance separation section is provided in multiple stages in series along the flow direction of the synthesis gas, and the concentration of the poisoning substance can be adjusted by selecting the number of stages of the poisoning substance separation section that supplies the synthesis gas.

[0027] (19) A supply device according to one aspect of the present invention includes a synthesis gas supply unit configured to be able to supply a synthesis gas containing hydrogen gas and carbon oxide gas, and a poisoning substance addition unit capable of adding a poisoning substance that is poisonous to a catalyst to the synthesis gas supplied from the synthesis gas supply unit, and is configured to be able to supply the synthesis gas to a synthesis reactor containing the catalyst and configured to be able to synthesize hydrocarbons from the hydrogen gas and the carbon oxide gas contained in the synthesis gas.

[0028] (20) In a supply device according to one aspect of the present invention, in the invention (19) above, the poisoning substance addition unit adds the poisoning substance to the synthesis gas so that the concentration of the poisoning substance in the synthesis gas is greater than 0 volppm and less than or equal to 1.0 volppm.

[0029] (21) A supply device according to one aspect of the present invention is the above-mentioned (19) or (20) invention, which includes a plurality of poisoning substance separation sections configured to be able to recover and release the poisoning substances, and is configured such that some of the poisoning substance separation sections can recover the poisoning substances downstream of the synthesis reactor along the flow direction of the synthesis gas, and the remaining poisoning substance separation sections can introduce the poisoning substances into the synthesis gas upstream of the synthesis reactor.

[0030] (22) In the supply device according to one aspect of the present invention, in the invention (21) above, the part of the poisoning substance separation units and the remaining poisoning substance separation units are configured to be exchangeable.

[0031] (23) A supply device according to one aspect of the present invention is any one of the above-mentioned (15) to (22) inventions, wherein the catalyst comprises a metal-based catalyst that contains a metal and a metal compound active in a Fischer-Tropsch synthesis reaction and produces hydrocarbons from a synthesis gas, and a support catalyst that includes a zeolite that supports the metal-based catalyst, and the metal and the metal compound contain cobalt and at least one metal selected from the group consisting of manganese and ruthenium. [Effects of the Invention]

[0032] According to the catalyst supply method and supply device of the present invention, it is possible to suppress deterioration of a catalyst capable of synthesizing hydrocarbons from a synthesis gas containing carbon oxides. [Brief explanation of the drawings]

[0033] [Figure 1]FIG. 1 is a graph showing an example of the CO conversion rate over time for catalysts used in synthesis reactions according to one embodiment of the present invention and the prior art. [Figure 2] FIG. 2 is a graph showing the pore size distribution of various samples of FT synthesis catalyst according to one embodiment of the present invention. [Figure 3] FIG. 3 is a graph showing the poisoning substance concentration dependency of the reaction rate decline rate in the FT synthesis catalyst according to one embodiment of the present invention. [Figure 4] FIG. 4 is a schematic diagram showing a method for supplying synthesis gas to a catalyst according to a first embodiment of the present invention. [Figure 5] FIG. 5 is a schematic diagram showing a specific example of a synthesis gas supply unit containing a poisoning substance according to a first example of an embodiment of the present invention. [Figure 6] FIG. 6 is a block diagram showing a gas purification apparatus according to a first embodiment of the present invention. [Figure 7] FIG. 7 is a schematic diagram showing a method for supplying synthesis gas to a catalyst according to a second embodiment of the present invention. [Figure 8] FIG. 8 is a schematic diagram showing a first example of a synthesis gas supply unit according to a second embodiment of the present invention. [Figure 9] FIG. 9 is a block diagram showing a gas purification apparatus according to a second embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0034] Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments described below. First, as an embodiment of the present invention, experiments and intensive studies conducted by the inventors to solve the above-mentioned problems will be described.

[0035] First, the inventors used a Fischer-Tropsch (FT) synthesis catalyst as a catalyst capable of synthesizing hydrocarbons from synthesis gas containing hydrogen gas and carbon dioxide gas. The FT synthesis catalyst is a catalyst composed of a metal-based catalyst containing metals and metal compounds active in the Fischer-Tropsch (FT) synthesis reaction, which produces hydrocarbons from synthesis gas, and a support catalyst containing zeolite supporting the metal-based catalyst. For example, an FT synthesis catalyst can be a catalyst in which a metal catalyst is supported in the pores of a Y-type zeolite support catalyst that has been subjected to cation exchange treatment. In addition to zeolites, various metal oxides such as alumina (Al2O3) and silica (SiO2) can also be used as support catalysts.

[0036] The FT synthesis catalyst is a catalyst capable of producing hydrocarbons from synthesis gas, which includes, for example, a metal-based catalyst that contains a metal and a metal compound active in the FT synthesis reaction and produces hydrocarbons from synthesis gas, and a support catalyst that includes zeolite that supports the metal-based catalyst.

[0037] Here, the metal and metal compound active in the FT synthesis reaction preferably contain cobalt (Co) and at least one metal, preferably two metals, selected from the group consisting of manganese (Mn) and ruthenium (Ru). Here, the amount of Mn supported is preferably 1% by weight or more and 3% by weight or less, the amount of Ru supported is preferably 0.5% by weight or more and 2% by weight or less, and the amount of Co supported is preferably 10% by weight or more and 30% by weight or less.

[0038] Furthermore, the zeolite supporting the metal catalyst preferably contains zeolite having pores that decompose the carbon chains of the produced hydrocarbons, and the pores are preferably mesopores with an opening diameter of 2 nm to 50 nm.The silicon to aluminum ratio (Si / Al ratio) in this zeolite is preferably 2.5 to 3.5.

[0039] The production of such catalysts involves two steps: a pore formation step in which mesopores are formed in the support catalyst, and a catalyst support step in which metals and metal compounds are supported on the support catalyst. Liquid fuels consisting of hydrocarbons are then produced from the synthesis gas by the Fischer-Tropsch synthesis reaction.

[0040] Here, as a first example of the catalyst supporting step, a method including a step of supporting a supported catalyst with at least one of a Co-containing metal and metal compound, a Mn-containing metal and metal compound, and a Ru-containing metal and metal compound, preferably both. In this case, the catalyst supporting step preferably includes a melt-impregnation step of melt-impregnating the supported catalyst with a Co-containing metal compound, and at least one of a Mn-containing metal compound and a Ru-containing metal compound, preferably both. Here, the melt-impregnation step is a step of supporting a Co-containing metal compound on the supported catalyst by melt-impregnation, and then supporting at least one of a Mn-containing metal compound and a Ru-containing metal compound by melt-impregnation. Alternatively, the melt-impregnation step is a step of substantially simultaneously supporting a Co-containing metal compound and at least one of a Mn-containing metal compound and a Ru-containing metal compound on the supported catalyst by melt-impregnation.

[0041] As a second example of the catalyst supporting step, a method can be employed that includes an impregnation step in which a metal compound containing Co is supported on a supported catalyst by an impregnation method, and then the supported catalyst on which Co is supported is immersed in at least one of a solution containing Mn and a solution containing Ru, or a solution containing both, to impregnate the supported catalyst and the supported catalyst supported on the supported catalyst.

[0042] Furthermore, as a third example of the catalyst supporting step, a method can be adopted which includes an impregnation step in which a metal compound containing Co is supported on a supported catalyst by an impregnation method, and the supported catalyst and / or the supported catalyst supported on the supported catalyst are impregnated by immersing the supported catalyst in at least one of a solution containing Mn and a solution containing Ru, or in both solutions.

[0043] Furthermore, as a fourth example of the catalyst supporting step, a method can be employed that includes a melt-impregnation step of melt-impregnating a supported catalyst with a metal compound containing Co, and an impregnation step of immersing the supported catalyst on which the metal compound containing Co has been supported in the melt-impregnation step in at least one of a solution containing Mn and a solution containing Ru, or both of these solutions, to impregnate the supported catalyst and / or the supported catalyst supported on the supported catalyst.

[0044] It is preferable to use a supported catalyst in which a cation is pre-assigned or in which a cation is assigned by a cation exchange process using an ion exchange method carried out before the catalyst supporting process. The cation is preferably, but not limited to, at least one cation selected from the group consisting of lanthanum, potassium, lithium, sodium, and cerium.

[0045] In the hydrocarbon production reaction using the FT method, carbon (C) is produced from carbon oxides such as carbon monoxide (CO) and carbon dioxide (CO2) on the surface of the FT synthesis catalyst, and hydrocarbons are synthesized through a synthesis reaction with hydrogen. Over time, this synthesis reaction causes carbon to deposit on the catalyst surface (carbon deposition), a phenomenon known as coking, and high-melting-point hydrocarbons (waxes) to adhere, deteriorating the catalyst and reducing its activity.

[0046] The present inventors conducted various experiments and studies to delay this decline in activity. First, the present inventors came up with a method of first adsorbing a substance that is highly adsorbent to the catalyst surface and that is poisonous to the catalyst (hereinafter referred to as a poison or catalyst poisoning substance). This allows the poisoning substance to be first adsorbed to the catalyst surface at the portion that will be the starting point for the occurrence of coking (carbon deposition) or the coating of high-melting-point hydrocarbons, thereby suppressing the occurrence and growth of coking. That is, the present inventors came up with the idea that in a synthesis reaction in which hydrocarbons are synthesized from carbon oxides and hydrogen using a catalyst, it is preferable to add a small amount of a poisoning substance to the synthesis gas supplied to the catalyst, or to supply a synthesis gas that already contains a poisoning substance to the catalyst.

[0047] The inventors conducted verification experiments based on the above considerations. Specifically, the inventors measured the change in CO conversion (%) over time when a synthesis gas containing hydrogen sulfide (H2S) as a poisoning substance at a concentration of 0.1 vol ppm was introduced into an FT synthesis reactor containing an FT synthesis catalyst. Note that the components of the synthesis gas other than the impurity components are H2 and CO, and in this embodiment, the ratio of H2 to CO (H2 / CO) is preferably 2 or more (H2 / CO≧2). Here, the concentration ratio was set to H2:CO=2:1.

[0048] That is, a synthesis experiment (hereinafter referred to as a poisoning synthesis test) was conducted by the FT method using a synthesis gas containing a poisoning substance. Furthermore, the inventors subsequently measured the change in CO conversion rate (%) over time when a synthesis gas containing ammonia (NH3) at a concentration of 0.1 vol ppm as a poisoning substance was introduced into the FT synthesis reactor. Thereafter, when the CO conversion rate dropped to about 98%, a reduction treatment using hydrogen (H2) was carried out as in the conventional method. Furthermore, for comparison, the inventors also conducted a synthesis experiment (synthesis test) by the conventional FT method using a synthesis gas that did not contain a poisoning substance, and measured the change in CO conversion rate (%) over time.

[0049] Figure 1 is a graph showing the results of measuring the CO conversion rate over time in a poisoning synthesis test when a poisoning substance was added to the synthesis gas and when no poisoning substance was added. Table 1 below shows the rate of decline in CO conversion (hereinafter referred to as CO conversion rate decline rate (% / h)) for the poisoning substance and concentration contained in the synthesis gas and for the synthesis gas without the poisoning substance, derived from the results shown in Figure 1. Table 2 also shows the conditions for the catalyst temperature and the average temperature of the reaction tube including the catalyst in the synthesis reaction in the experiment, and the CO conversion rate when the catalyst was regenerated.

[0050] [Table 1]

[0051] [Table 2]

[0052] From Figure 1 and Table 1, it can be seen that when synthesis gas containing no poisoning substances according to conventional technology is introduced into an FT synthesis reactor containing an FT synthesis catalyst, the CO conversion decline rate is 0.0287 (% / h). Furthermore, when synthesis gas containing 0.1 vol ppm of hydrogen sulfide (HS) is introduced into the FT synthesis reactor, the CO conversion decline rate is 0.0048 (% / h), which is approximately one-fifth of the conventional rate (0.0048 / 0.0287≒). Similarly, when synthesis gas containing 0.1 vol ppm of ammonia (NH3) is introduced into the FT synthesis reactor, the CO conversion decline rate is 0.0082 (% / h), which is approximately one-third of the conventional rate (0.0082 / 0.0287≒). In other words, when the synthesis gas contains poisonous substances such as H2S and NH3, the rate of decline in CO conversion (% / h) can be reduced to about 1 / 5 to 1 / 3, and degradation is delayed.

[0053] Furthermore, Table 2 shows that the catalyst temperature and CO conversion rate at the start of the poisoning test are equal to the catalyst temperature and CO conversion rate when the synthesis test is carried out again after hydrogen reduction to regenerate the catalyst after the poisoning test. In other words, Table 2 shows that the catalyst can be fully regenerated.

[0054] Furthermore, the inventors also investigated the causes of deterioration. Specifically, the total carbon concentration and hydrocarbon analytical concentration were measured in a 100-hour synthesis test using synthesis gas containing no poisoning substances and in a 100-hour poisoning synthesis test using synthesis gas containing 1 vol ppm of poisoning substances. The total carbon concentration was also measured for the catalyst in its as-prepared state before the synthesis test. Here, the total carbon concentration was measured by the combustion-infrared absorption method, and the hydrocarbon analytical concentration was measured by temperature-programmed desorption-mass spectrometry (TPD-MS). The results are shown in Table 3.

[0055] [Table 3]

[0056] As shown in Table 3, in the synthesis test using synthesis gas containing no sulfur (S), the poisoning substance, the total carbon concentration was 6.56%, with a catalyst ratio of 32.8%. In contrast, in the poisoning synthesis test using synthesis gas containing the poisoning substance S, the total carbon concentration was 0.42%, with a catalyst ratio of 2.1%, confirming a reduction of approximately 1 / 15 (0.42 / 6.56 ≒) . Furthermore, based on the results of measurements of hydrocarbon concentrations using temperature-programmed desorption-mass spectrometry (TPD-MS), it is believed that the wax adhering to the synthesis gas is heated by the constant-rate heating, and the gases desorbed through pyrolysis are detected as tetradecene and undecene. Furthermore, based on the gas concentration ratio, it can be estimated that the wax adhering rate is reduced to less than 1 / 3 (1.1 / 3.6 ≒) 1 / 3 when the synthesis gas contains poisoning substances compared to when the synthesis gas does not contain poisoning substances.

[0057] According to the inventors' investigations, the wax adhering to the catalyst is presumably an aliphatic hydrocarbon compound such as paraffin. The low amount of tetradecene and undecene relative to the total carbon number is presumably due to the presence of high-boiling compounds that do not thermally decompose during constant-rate heating. Thus, catalyst analysis after synthesis testing revealed that the cause of catalyst deterioration was wax, and it was confirmed that the amount of wax and other adhering substances was reduced in the case of synthesis gas containing poisonous substances. Furthermore, when a Co-supported micropore zeolite catalyst is used as the FT synthesis catalyst, coking and wax deposits are likely to occur within the highly active pores. Therefore, the above findings are believed to be even more effective when a Co-supported micropore zeolite catalyst is used as the FT synthesis catalyst.

[0058] Furthermore, the inventors measured the pore size distribution and specific surface area of ​​the zeolite support of the FT synthesis catalyst. The samples used were FT synthesis catalysts in the as-prepared state (catalyst preparation), the state after synthesis tests (1) and (2), and the state after hydrogen reduction treatment after the test (post-test hydrogen reduction). Figure 2 is a graph showing the pore size distribution of a sample made of the above-mentioned FT synthesis catalyst. Table 4 shows the results of the specific surface area calculation based on the N adsorption isotherm results for the sample made of the above-mentioned FT synthesis catalyst.

[0059] The conditions for synthesis test (1) are, for example, a 1.5x ratio of CO to H2 in the synthesis gas, a pressure of 2 MPa, a constant catalyst temperature of 250°C (at the upstream end of the gas), and a continuous test for 260 hours in the absence of poisoning substances.The conditions for synthesis test (2) are, for example, a 2x ratio of CO to H2 in the synthesis gas, a pressure of 2 MPa, a constant catalyst temperature of 260°C (at the upstream end of the gas), and a continuous test for 260 hours in the absence of poisoning substances.

[0060] [Table 4]

[0061] From Table 4, it can be seen that the nitrogen (N2) adsorption isotherm results show that the specific surface area of ​​the FT synthesis catalyst after synthesis tests (1) and (2) is significantly reduced. That is, the specific surface area of ​​the FT synthesis catalyst before the synthesis test was 562 m 2 / g, whereas after synthesis test (1) it was 24m 2 / g, which is about 1 / 23 of the original amount. After synthesis test (2), the 2 / g, which is approximately 1 / 7 of the original value. Furthermore, Fig. 2 also shows that the pore distribution analysis reveals that the specific surface area of ​​pores with diameters of approximately 1 nm to 5 nm significantly decreased after synthesis tests (1) and (2). Based on these results, the inventors' investigations suggest that this is due to the pores in the zeolite support of the FT synthesis catalyst being blocked by waxes.

[0062] Next, based on the above investigations, the inventors conducted experiments and studies on the dependence of the reaction rate decline rate (% / h) on the concentration of poisoning substances. That is, the inventors varied the concentration of poisoning substances contained in the synthesis gas and measured the reaction rate decline rate (% / h). Here, the poisoning substances used were poisoning substances that have temporary poisoning (temporary poisoning) and can be regenerated by hydrogen reduction treatment even after being adsorbed on the FT synthesis catalyst (hereinafter referred to as temporary poisoning substances), and substances that have permanent poisoning and poison the FT synthesis catalyst in an irregenerative state (hereinafter referred to as permanent poisoning substances).

[0063] The temporary poisoning substance is a substance that is a reversible catalytic poison, such as condensation or deposition due to physical adsorption by intermolecular forces on the FT synthesis catalyst. Specific examples of such substances include ammonia (NH3), hydrogen cyanide (HCN), phosphine (PH3), sodium chloride (NaCl), and potassium chloride (KCl).

[0064] Permanent poisons are substances consisting of catalytic poisons that irreversibly adsorb, for example, by chemical adsorption, to the FT synthesis catalyst, and include compounds containing at least one of sulfur (S) and hydrogen chloride (HCl), and specific examples include hydrogen sulfide (HS), carbonyl sulfide (COS), hydrogen chloride (HCl), and arsine (AsH).

[0065] Figure 3 is a graph showing the dependence of the reaction rate decline rate on the poisoning substance concentration in the FT synthesis catalyst according to this embodiment. In the graph shown in Figure 3, ammonia (NH3) is used as an example of a temporary poisoning substance, and hydrogen sulfide (HS) is used as an example of a permanent poisoning substance. In addition, in the graph shown in Figure 3, a concentration of 0 volppm represents a conventional case in which the synthesis gas supplied to the FT synthesis catalyst does not contain any poisoning substances, and the reaction rate decline rate when no poisoning substances are contained is shown by a dashed dotted line.

[0066] 3 shows that when a permanent poisoning substance is contained in the synthesis gas (thick solid line in FIG. 3), the reaction rate decline rate is equal to or less than the reaction rate decline rate when the poisoning substance is not contained (dashed line in FIG. 3) when the concentration of the poisoning substance is greater than 0 volppm and less than 1 volppm. Similarly, FIG. 3 shows that when a temporary poisoning substance is contained in the synthesis gas (dotted line in FIG. 3), the reaction rate decline rate is equal to or less than the reaction rate decline rate when the poisoning substance is not contained (dashed line in FIG. 3) when the concentration of the poisoning substance is greater than 0 volppm and less than or equal to 0.2 volppm. Furthermore, FIG. 3 shows that the reaction rate decline rate is minimum when the concentration is 0.1 volppm, regardless of whether the poisoning substance is a temporary poisoning substance or a permanent poisoning substance. That is, from Figure 3, it can be seen that, regardless of whether the poisoning substance is a temporary poisoning substance or a permanent poisoning substance, by keeping the concentration of the poisoning substance in the synthesis gas below 0.1 vol ppm, the reaction rate decline rate is equal to or lower than the reaction rate decline rate when the poisoning substance is not present. It can also be seen that by keeping the concentration at 0.02 vol ppm or higher, the reaction rate decline rate can be maintained at 0.01% / h or less. This is particularly noticeable when the poisoning substance is a permanent poisoning substance. From the above considerations, it can be seen that by supplying synthesis gas containing poisoning substances to the FT synthesis catalyst, the reaction rate decline rate can be reduced, and the time until the FT synthesis catalyst becomes unusable or requires regeneration can be extended.

[0067] From the above, it can be seen that the concentration of poisoning substances in the synthesis gas is preferably greater than 0 volppm and less than 1 volppm, more preferably greater than 0 volppm and less than 0.2 volppm, and even more preferably 0.02 volppm or more and less than 0.1 volppm. When the concentration of poisoning substances in the synthesis gas is set to around 0.1 volppm, it is preferable to set it to, for example, 0.05 volppm or more and 0.15 volppm or less. Furthermore, when the synthesis gas contains multiple types of poisoning substances, taking into account the phenomenon of poisoning substances being adsorbed onto the FT synthesis catalyst, it is preferable that the concentration of the poisoning substances be the total concentration of the multiple types of poisoning substances. Furthermore, when the concentration of poisoning substances is greater than 0 volppm, it may be 0.001 volppm or more, 0.01 volppm or more, or the like.

[0068] (First Example) Next, embodiments based on the above study by the present inventors will be described. Fig. 4 is a schematic diagram for explaining a synthesis gas supply method according to a first embodiment. Fig. 5 is a schematic diagram showing a specific example of a synthesis gas supply unit 11 containing poisonous substances according to the first embodiment. Fig. 6 is a block diagram showing details of a gas purification device 12 according to the first embodiment.

[0069] As shown in Fig. 4, synthesis gas contains a main component and impurities. Examples of the main components of synthesis gas include hydrogen (H2) and hydrocarbons such as carbon monoxide (CO) and carbon dioxide (CO2). Various impurities may be included, and in the first embodiment, a case is considered in which temporary poisoning substances and permanent poisoning substances are included as poisoning substances.

[0070] That is, in the first embodiment, synthesis gas containing poisoning substances is supplied from a synthesis gas supply unit 11 to a gas purification device 12. The synthesis gas supply unit 11 is configured to be able to generate or store synthesis gas and supply it to the outside. The gas purification device 12, which serves as a gas purification unit, is configured to be able to adjust the concentrations of various gases contained in the synthesis gas. The gas purification device 12, to which synthesis gas containing poisoning substances has been supplied, executes a gas purification process to adjust the concentrations of the poisoning substances contained in the synthesis gas to greater than 0 volppm and less than or equal to 1 volppm, preferably 0.01 volppm or more and 0.1 volppm or less. In this case, it is preferable to adjust the concentrations of the poisoning substances based on the concentration of the entire poisoning substances. In other words, it is preferable to adjust the concentrations of each of multiple types of poisoning substances so that the total concentration of the multiple types of poisoning substances is 0 volppm or more and 1 volppm or less.

[0071] Thereafter, the synthesis gas in which the concentration of poisoning substances has been adjusted by the gas purification device 12 is supplied to an FT synthesis reactor 20 containing a synthesis catalyst, and hydrocarbons are produced by the FT method. In the first embodiment, the synthesis gas supply unit 11 and the gas purification device 12 constitute a synthesis gas supply device 1 as a supply device.

[0072] As shown in Fig. 5, the poison-containing synthesis gas supply unit 11 according to the first embodiment can employ a method in which waste materials such as biomass and garbage are thermally decomposed in a gasification furnace or the like to produce H2 gas and CO2 gas. Since CO2 is also produced, it is also possible to install a buffer tank or the like to separate CO2 and deal with gas fluctuations. In Fig. 5, the dotted line portion may or may not be installed in the synthesis gas supply unit 11.

[0073] As shown in FIG. 6, the gas purification device 12 according to the first embodiment includes a control unit 121, a crude gas purification unit 122, concentration meters 123 and 124, poisonous substance separation units 125 and 126, branch valves 127 and 128, and a pump 129.

[0074] Specifically, the control unit 121 includes a processor such as a CPU (Central Processing Unit), a DSP (Digital Signal Processor), or an FPGA (Field-Programmable Gate Array), and a main storage unit such as a RAM (Random Access Memory) or a ROM (Read Only Memory) (none of which are shown). Furthermore, the control unit 121 may include a storage unit (not shown) configured with a storage medium selected from an EPROM (Erasable Programmable ROM), a hard disk drive (HDD), a solid state drive (SSD), and removable media. The removable media may be, for example, a Universal Serial Bus (USB) memory or a disc storage medium such as a CD (Compact Disc), a DVD (Digital Versatile Disc), or a Blu-ray (registered trademark) Disc (BD). The memory provided in the control unit 121 can store an operating system (OS), various programs, various tables, various databases, etc., and the stored programs are loaded into the working area of ​​the main memory and executed, and through the execution of the programs based on the information on the concentration of poisonous substances supplied from the concentration meters 123 and 124, each component such as branch valves 127 and 128 and pump 129 can be controlled to realize functions that meet a specified purpose.

[0075] The crude gas purification unit 122 is configured to be capable of removing at least a portion of the temporary poisoning substance NH3 and the permanent poisoning substance H2S contained in the synthesis gas. The crude gas purification unit 122 is configured, for example, as a wet crude gas purification device, and specifically is configured to be able to remove NH3 contained in the synthesis gas and desulfurize H2S by, for example, acid or alkali cleaning using a scrubber or desulfurization.

[0076] The concentration meters 123 and 124 are configured with concentration sensors 123a and 124a that measure concentrations, respectively. The concentration sensor 123a is configured to be able to measure the concentration of poisoning substances (poisoning substance concentration) in the synthesis gas on the discharge side of the crude gas purification unit 122. The concentration sensor 124a is configured to be able to measure the poisoning substance concentration in the synthesis gas supplied to the FT synthesis reactor 20. The poisoning substance separation units 125 and 126 are each configured with an adsorption tower or the like configured to be able to adsorb poisoning substances using, for example, activated carbon or the like.

[0077] According to the findings of the present inventors, the concentration of poisoning substances in the synthesis gas in the synthesis gas supply unit 11 varies over time, as shown in the example graph in FIG. 6. Therefore, the present inventors have conceived a method of measuring (monitoring) and controlling the concentration of the synthesis gas supplied to the gas purification device 12. According to the studies of the present inventors, it is preferable to measure the concentration of poisoning substances in the synthesis gas after at least rough purification and the concentration of poisoning substances immediately before being supplied to the FT synthesis reactor. Furthermore, the present inventors have conceived of controlling the concentration of poisoning substances supplied to the FT synthesis reactor 20 to be approximately a predetermined value by using multiple branch valves to branch the synthesis gas into at least two ways depending on the concentration of poisoning substances and adjusting the branch flow rates and branch flow rate ratios.

[0078] In the first embodiment, the synthesis gas initially has an impurity concentration of about 10 to 1000 vol ppm. The synthesis gas is supplied from the synthesis gas supply unit 11 to the crude gas purification unit 122, with the impurity concentration and poisoning substance concentration fluctuating over time. The crude gas purification unit 122 adjusts the poisoning substance concentration in the synthesis gas to between 0.1 vol ppm and 100 vol ppm. The poisoning substance concentration of the synthesis gas discharged from the crude gas purification unit 122 is measured by a concentration sensor 123a. The measurement value measured by the concentration sensor 123a is output to the control unit 121 by a concentration meter 123.

[0079] The synthesis gas from which the poisoning substances have been removed and the poisoning substance concentration has been adjusted is flowed by a pump 129 and branched by a branch valve 127. The branch valve 127 is controlled by a control unit 121. The control unit 121 controls the branch valve 127 and the pump 129 to adjust the branch flow rate of the synthesis gas and performs adjustment so that one of the branched synthesis gases is supplied to the FT synthesis reactor 20 as a first path without passing through the poisoning substance separation unit 125. The other branched synthesis gas is supplied to the poisoning substance separation unit 125 as a second path. In the poisoning substance separation unit 125, the poisoning substances contained in the synthesis gas that has flowed in are separated and removed using, for example, activated carbon.

[0080] That is, when the control unit 121 determines that the concentration of the poisoning substance obtained from the concentration meter 123 is equal to or lower than a predetermined value, the synthesis gas discharged from the crude gas purification unit 122 is passed through as is and supplied to the FT synthesis reactor 20.

[0081] Furthermore, when the control unit 121 determines that the poisoning substance concentration acquired from the concentration meter 123 is higher than a predetermined value, it derives a necessary branch flow rate for the synthesis gas and controls the branch valve 127 to adjust the synthesis gas to be supplied to the poisoning substance separation unit 126 at the derived branch flow rate. In the poisoning substance separation unit 126, poisoning substances contained in the flowed-in synthesis gas are separated and removed using, for example, activated carbon. The route passing through the poisoning substance separation unit 126 is also included in the second route.

[0082] Furthermore, a branch valve 128 is provided between the poisoning substance separation units 125 and 126, in other words, below the poisoning substance separation unit 125 and above the poisoning substance separation unit 126. The synthesis gas discharged from the poisoning substance separation unit 125 is branched by the branch valve 128. The branch valve 128 is controlled by the control unit 121. The control unit 121 adjusts the branch flow rate and branch flow rate ratio of the synthesis gas by controlling the branch valve 128. One of the synthesis gases branched by the branch valve 128 is supplied to the FT synthesis reactor 20. The other branched synthesis gas is further supplied to the poisoning substance separation unit 126.

[0083] The poisoning substance concentration of the synthesis gas supplied to the FT synthesis reactor 20 is measured by the concentration sensor 124a. The control unit 121 receives the poisoning substance concentration of the synthesis gas supplied to the FT synthesis reactor 20 from the concentration meter 124. Here, the control unit 121 determines that the poisoning substance concentration is low when the poisoning substance concentration acquired from the concentration meter 124 is equal to or lower than a predetermined value, for example, equal to or lower than 0.1 vol ppm. In this case, the control unit 121 performs control to increase the branch flow rate of the synthesis gas discharged from the poisoning substance separation unit 125 to be supplied to the FT synthesis reactor 20 without being supplied to the poisoning substance separation unit 126. Furthermore, when the control unit 121 determines that the poisoning substance concentration acquired from the concentration meter 124 is low, the control unit 121 performs control to increase the branch flow rate of the synthesis gas discharged from the crude gas purification unit 122 to be supplied to the FT synthesis reactor 20 without passing through the poisoning substance separation unit 125.

[0084] On the other hand, when the poisoning substance concentration acquired from the concentration meter 124 is higher than a predetermined value, for example, higher than 100 vol ppm, the control unit 121 determines that the poisoning substance concentration input from the concentration meter 124 is high. In this case, the control unit 121 performs control to increase the branch flow rate of the synthesis gas discharged from the poisoning substance separation unit 125 to be supplied to the poisoning substance separation unit 126. Furthermore, when the control unit 121 determines that the poisoning substance concentration is high, the control unit 121 performs control to increase the branch flow rate of the synthesis gas discharged from the raw gas purification unit 122 to be supplied to the poisoning substance separation unit 125.

[0085] As described above, the control unit 121 controls the branch valves 127, 128 so that the concentration of poisoning substances in the synthesis gas supplied to the FT synthesis reactor 20 becomes equal to or less than a predetermined value, for example, equal to or less than 100 volppm, based on the measurement values ​​of the concentration of poisoning substances in the synthesis gas input from the concentration meters 123, 124. That is, the gas purification device 12 is configured to be able to control the concentration of poisoning substances in the synthesis gas supplied to the FT synthesis reactor 20 by providing multiple poisoning substance removal lines that remove poisoning substances from the synthesis gas whose concentration has been reduced to a predetermined poisoning substance concentration by the crude gas purification unit 122.

[0086] In the example of the gas purification apparatus 12 described above, the poisoning substance separation units 125, 126 are configured to have two stages, but three or more stages may be used. In this case, by arranging the poisoning substance separation units in multiple stages in series along the flow direction of the synthesis gas and appropriately providing branch valves on the inlet side, it becomes possible to selectively control the number of stages of the poisoning substance separation units that supply the synthesis gas. This makes it possible to adjust the poisoning substance concentration of the synthesis gas supplied to the FT synthesis reactor 20. Furthermore, the branch valves 127, 128 can be appropriately provided according to the number of stages in which the poisoning substance separation units 125, 126 are provided and the number of branched lines. The configuration of the gas purification apparatus 12 according to the first embodiment makes it possible to control the poisoning substance concentration in the synthesis gas supplied to the FT synthesis reactor 20, thereby suppressing deterioration of a catalyst that can synthesize hydrocarbons from a synthesis gas containing carbon oxides.

[0087] (Second Example) FIG. 7 is a schematic diagram for explaining a synthesis gas supply method according to the second embodiment, and FIG. 8 is a schematic diagram showing a first specific example of the synthesis gas supply unit 11 according to the second embodiment.

[0088] As shown in Figure 7, the synthesis gas contains a main component and impurities, and the concentration of the poisoning substances, which are impurities, is extremely small, on the order of 0 vol ppb to 1 vol ppb. That is, in the second embodiment, we consider a case where the synthesis gas contains almost no temporary poisoning substances or permanent poisoning substances as poisoning substances. The main components of the synthesis gas are the same as those in the first embodiment.

[0089] In the second embodiment, synthesis gas containing almost no poisoning substances is supplied from a synthesis gas supply unit 11 to the FT synthesis reactor 20. The synthesis gas supply unit 11 is configured in the same manner as in the first embodiment. A poisoning substance addition device 13 serving as a poisoning substance addition unit is configured to be able to add a poisoning substance to the reaction gas from the reaction gas supply path from the synthesis gas supply unit 11 to the FT synthesis reactor 20 and to be able to adjust the concentration of the poisoning substance contained in the synthesis gas. The poisoning substance addition device 13 adds a poisoning substance to the synthesis gas supply path, thereby causing the poisoning substance to be contained in the synthesis gas supplied to the FT synthesis reactor 20. The poisoning substance addition device 13 adds the poisoning substance to the synthesis gas so that the concentration of the poisoning substance is greater than 0 volppm and less than or equal to 1 volppm, preferably greater than or equal to 0.01 volppm and less than or equal to 0.1 volppm. In the second embodiment, it is preferable to select one type of poisoning substance as the poisoning substance to ignite the synthesis gas, but multiple types of poisoning substances may be added. When adding multiple types of poisoning substances, it is preferable to adjust the amount of each poisoning substance added based on the total concentration of the poisoning substances. In other words, it is preferable to adjust the amount of each poisoning substance added so that the total concentration of each poisoning substance is greater than 0 volppm and less than 1 volppm.

[0090] The synthesis gas to which the poisoning substance has been added is supplied to an FT synthesis reactor 20 containing a synthesis catalyst, and hydrocarbons are produced by the FT method. In the second embodiment, the synthesis gas supply unit 11 and the poisoning substance addition device 13 constitute a synthesis gas supply device 2 as a supply device.

[0091] Furthermore, as a specific example of the poison-containing synthesis gas supply unit 11 according to the second embodiment, it is possible to employ a method in which CO2 in exhaust gas from a power plant or the atmosphere is separated and collected, converted into CO gas by a reverse shift reaction or electrical reduction, and then mixed with H2 produced by water electrolysis or the like before supplying the CO2, as shown in Fig. 8. In Fig. 8, the dotted line portion may or may not be installed in the synthesis gas supply unit 11.

[0092] Next, a description will be given of a synthesis gas supply device that can realize the synthesis gas supply method according to the second embodiment. Fig. 9 is a block diagram showing a second example of the synthesis gas supply device according to the second embodiment.

[0093] 9, the synthesis gas supply apparatus 2A according to the second embodiment includes a control unit 141, a poisoning substance storage tank 142, a pressure concentration meter 143, a concentration meter 144, poisoning substance separation units 145 and 146, on-off valves 147 and 148, and a gas-liquid separator 149. The control unit 141, the concentration meter 144, and the poisoning substance separation units 145 and 146 are configured similarly to the control unit 121, the concentration meter 124, the poisoning substance separation units 125 and 126, and the branch valves 127 and 128 in the first embodiment described above. The poisoning substance separation units 145 and 146 are both detachable and replaceable with each other, and are configured to discharge the poisoning substances by heating or reducing the pressure. That is, for example, when the amount of poisoning substances adsorbed or stored in the poisoning substance separation unit 146 exceeds a predetermined value, the poisoning substance separation unit 146 is appropriately replaced with the poisoning substance separation unit 145. In this case, the poisoning substance separation unit 145 is in a state where the poisoning substances have been discharged and the amount of poisoning substances adsorbed or stored has been reduced, i.e., in a regenerated state, so that after replacement it will be able to adsorb or store poisoning substances.

[0094] The poisoning substance storage tank 142 is configured to be able to store a poisoning substance such as ammonia (NH3). The pressure concentration meter 143 is configured to have a pressure concentration sensor 143a that can measure pressure and concentration. The pressure concentration sensor 143a is configured to be able to measure the pressure and poisoning substance concentration of the synthesis gas in line 140b, which is a pipe that merges with line 140a that communicates between the synthesis gas supply unit 11 and the FT synthesis reactor 20 from the release side of the poisoning substance separation unit 145 that functions as a poisoning substance release unit. The pressure concentration meter 143 outputs the measured gas pressure and poisoning substance concentration to the control unit 141. The concentration meter 144 is configured to have a concentration sensor 144a that can measure concentration. The concentration sensor 144a is configured to be able to measure the poisoning substance concentration in the synthesis gas flowing in line 140a that is supplied to the FT synthesis reactor 20. The concentration meter 144 outputs the measured concentration of the poisoning substance in the synthesis gas to the control unit 141.

[0095] The control unit 141 can realize functions that meet predetermined purposes by controlling each component such as the on-off valves 147 and 148 based on information on the pressure in the pipe and the concentration of poisoning substances supplied from the pressure concentration meter 143 and the concentration meter 144 through the execution of a program. Specifically, the on-off valves 147 and 148 are controlled by the control unit 141 to open and close and adjust the flow rate of gas, etc. The on-off valve 147 controlled by the control unit 141 can adjust the flow rate of poisoning substances that flow from the poisoning substance storage tank 142 into the line 140a. The on-off valve 148 controlled by the control unit 141 can adjust the flow rate of poisoning substances that are released from the poisoning substance separation unit 145 and flow into the line 140a.

[0096] The gas-liquid separator 149 is provided downstream of the FT synthesis reactor 20 along the flow direction of the synthesis gas. The gas-liquid separator 149 is configured to be able to separate the gas after the FT synthesis into gas and liquid. The liquid component separated in the gas-liquid separator 149 is recovered as synthetic fuel. The gas separated in the gas-liquid separator 149 is supplied to a poisoning substance separation section 146. In the poisoning substance separation section 146, poisoning substances contained in the gas are separated and removed, for example, by activated carbon. The hydrocarbon gas (CH gas) after the poisoning substances have been separated is used, for example, for combustion heating in a synthesis gas furnace, as a raw material, or for power generation.

[0097] In the second embodiment, the synthesis gas supplied from the synthesis gas supply unit 11 contains no or very little poisonous substances. Therefore, a process is carried out in which the synthesis gas supply device 2A adds only the necessary amount of poisonous substances so that the concentration of the poisonous substances in the synthesis gas supplied to the FT synthesis reactor 20 becomes approximately a predetermined value, for example, approximately 0.1 vol ppm.

[0098] That is, first, in the upstream stage of the FT synthesis reactor 20 in the synthesis gas supply device 2A, a concentration meter 144 measures the concentration of poisoning substances in the synthesis gas flowing through the line 140a. As a result, the concentration of poisoning substances mixed into the synthesis gas containing almost no poisoning substances from the poisoning substance storage tank 142 and the poisoning substance separation unit 145 is measured. The concentration measurement value by the concentration meter 144 is output to the control unit 141. Based on the acquired measurement value of the poisoning substance concentration, the control unit 141 controls the on-off valves 147 and 148 so that the poisoning substance concentration of a poisoning substance such as NH3 becomes a predetermined value, thereby controlling the flow rate of the gas containing poisoning substances (poisoning substance-containing gas) flowing into the line 140a from the poisoning substance storage tank 142 and the poisoning substance separation unit 145.

[0099] The product gas generated in the FT synthesis reactor 20 is supplied to a gas-liquid separator 149, where the liquid component is separated and recovered as synthetic fuel. The product gas separated by the gas-liquid separator 149 is supplied to a poisoning substance separation section 146. The product gas contains poisoning substances that were not adsorbed by the catalyst provided in the FT synthesis reactor 20. The poisoning substances contained in the product gas are adsorbed onto, for example, activated carbon and separated and recovered in the poisoning substance separation section 146, and the hydrocarbon gas is recovered.

[0100] By the separation and recovery process of the poisoning substances, the poisoning substances are adsorbed to or stored in activated carbon in the poisoning substance separation section 146. When the adsorption amount of, for example, an adsorption tower constituting the poisoning substance separation section 146 becomes saturated, it is possible to replace it with a poisoning substance separation section 145 that adsorbs or stores a small amount of poisoning substances, or to replace it with a poisoning substance separation section made up of another adsorption tower or the like. For the poisoning substance separation sections 145, 146 that adsorb or store a large amount of poisoning substances, regeneration processes such as heating and decompression are performed to generate gas containing the poisoning substances, and this can be introduced into the line 140a upstream of the FT synthesis reactor 20, thereby allowing the poisoning substances to be reused and reducing costs.

[0101] It is also possible to combine the first and second embodiments described above. That is, it is also possible to use the gas purification device 12 according to the first embodiment to configure a synthesis gas supply unit that supplies synthesis gas to the FT synthesis reactor 20, and to provide the synthesis gas supply device of the second embodiment in a subsequent stage. For example, if the synthesis gas contains a large amount of permanently poisoning substances such as H2S and no or little temporary poisoning substances such as NH3, it is possible to remove H2S in the previous stage and add NH3 in the subsequent stage. This allows the catalyst to be regenerated within the FT synthesis reactor 20, significantly extending the catalyst replacement interval.

[0102] According to the embodiment described above, carbon dioxide (CO x ) from synthesis gas containing hydrocarbons (CH xIn a catalyst capable of synthesizing FT synthesis, the rate of decline in the reaction rate of the FT synthesis catalyst can be reduced, and deterioration of the FT reaction catalyst can be suppressed.

[0103] Further advantages and modifications will readily occur to those skilled in the art. The invention in its broader aspects is not limited to the specific details and representative embodiments shown and described above. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents. [Industrial Applicability]

[0104] The catalyst supply method and supply device according to the present invention are suitable for use in a catalyst for producing liquid fuel by reacting a mixed gas of carbon oxides and hydrogen. [Explanation of symbols]

[0105] 1,2,2A mixed gas supply device 11. Synthetic gas supply section 12 Gas purification equipment 13 Poisonous substance addition device 20 FT Synthesis Reactor 121,141 Control unit 122 Raw Gas Purification Section 123,124,144 Concentration meter 123a, 124a, 144a Concentration sensor 125,126,145,146 Poisonous Substance Separation Department 127,128 Branch valve 129 Pump 140a, 140b lines 142 Poisonous substance storage tank 143 Pressure concentration meter 143a Pressure concentration sensor 147,148 Opening and closing valve 149 Gas-liquid separator

Claims

1. 1. A method for supplying a synthesis gas containing hydrogen gas and carbon oxide gas to a catalyst capable of producing hydrocarbons from the synthesis gas, the method comprising: supplying the synthesis gas to the catalyst as a gas containing a poisoning substance that is poisonous to the catalyst; a control unit having hardware controls the amount of the poisoning substance contained in the synthesis gas supplied to the catalyst, thereby adjusting the concentration of the poisoning substance contained in the synthesis gas supplied to the catalyst; In adjusting the concentration, the control unit increases the poisoning substance based on the concentration of the poisoning substance contained in the synthesis gas measured by a concentration sensor. Method of feeding to catalyst.

2. In adjusting the concentration, the control unit reduces the poisoning substance based on the concentration of the poisoning substance contained in the synthesis gas measured by a concentration sensor.

2. A method for supplying a catalyst according to claim 1.

3. The poisoning substance is a temporary poisoning substance that has a temporary poisoning that can regenerate the catalyst. A method for supplying a catalyst according to claim 1 or 2.

4. The temporary poisoning substance is ammonia (NH 3 ), hydrogen cyanide (HCN), phosphine (PH 3 ), sodium chloride (NaCl), and potassium chloride (KCl). The method for supplying the catalyst according to claim 3.

5. The poisoning substance is a permanent poisoning substance that causes irreversible poisoning of the catalyst. A method for supplying a catalyst according to claim 1 or 2.

6. The permanent poisoning substance is a compound containing at least one of sulfur (S) and hydrogen chloride (HCl). The method for supplying the catalyst according to claim 5.

7. The permanent poison is hydrogen sulfide (H 2 S), carbonyl sulfide (COS), hydrogen chloride (HCl), and arsine (AsH 3 and at least one compound selected from the group consisting of The method for supplying the catalyst according to claim 5.

8. 1. A method for supplying a synthesis gas containing hydrogen gas and carbon oxide gas to a catalyst capable of producing hydrocarbons from the synthesis gas, the method comprising: supplying the synthesis gas to the catalyst as a gas containing a poisoning substance that is poisonous to the catalyst; a control unit having hardware controls the amount of the poisoning substance contained in the synthesis gas supplied to the catalyst, thereby adjusting the concentration of the poisoning substance contained in the synthesis gas supplied to the catalyst; the control unit reduces the poisoning substance based on the concentration of the poisoning substance contained in the synthesis gas measured by a concentration sensor in adjusting the concentration; The control unit Before the synthesis gas is supplied to the catalyst, at least a portion of the synthesis gas is branched off from the line that supplies the catalyst, and the poisoning substances are removed in a stage upstream of the catalyst, and then the branched off portion is supplied to the catalyst together with the remainder of the synthesis gas. Method of feeding to catalyst.

9. The poisoning substances are recovered on the exhaust side of the catalyst, and at least a part of the recovered poisoning substances is mixed into the synthesis gas supplied to the catalyst.

2. A method for supplying a catalyst according to claim 1.

10. a synthesis gas supply unit configured to be able to supply synthesis gas containing hydrogen gas, carbon oxide gas, and a poisoning substance that is poisonous to the catalyst; a concentration sensor that measures the concentration of the poisoning substance contained in the synthesis gas; a gas purification unit configured to be able to adjust the concentration of the poisoning substance contained in the synthesis gas supplied from the synthesis gas supply unit based on the concentration measured by the concentration sensor, a synthesis reactor configured to be capable of supplying the synthesis gas to the catalyst-containing synthesis reactor configured to be capable of synthesizing hydrocarbons from the hydrogen gas and the carbon oxide gas contained in the synthesis gas; Feeding device.

11. the gas purification unit includes at least one poisoning substance separation unit configured to be able to separate the poisoning substance from the synthesis gas, and a control unit having hardware capable of controlling a flow rate of the synthesis gas supplied to the poisoning substance separation unit, In a stage preceding the poisoning substance separation unit, the synthesis gas is flowed through at least one of a first path for supplying the synthesis gas to the synthesis reactor without passing through the poisoning substance separation unit and a second path for supplying the synthesis gas to the poisoning substance separation unit and then to the synthesis reactor; The control unit controls the flow rate of the synthesis gas flowing through the first path and the flow rate of the synthesis gas flowing through the second path, thereby adjusting the concentration of the poisoning substance.

11. The feeding device of claim 10.

12. the poisoning substance separation unit is provided in a plurality of stages in series along the flow direction of the synthesis gas, The concentration of the poisoning substance can be adjusted by selecting the number of stages of the poisoning substance separation section that supplies the synthesis gas.

12. The feeding device of claim 11.

13. a synthesis gas supply unit configured to be able to supply synthesis gas containing hydrogen gas and carbon oxide gas; a poisoning substance adding unit capable of adding a poisoning substance that is poisonous to the catalyst to the synthesis gas supplied from the synthesis gas supply unit; a concentration sensor for measuring the concentration of the poisoning substance contained in the synthesis gas; a synthesis reactor configured to be able to supply the synthesis gas to the catalyst-containing synthesis reactor configured to be able to synthesize hydrocarbons from the hydrogen gas and the carbon oxide gas contained in the synthesis gas; The poisoning substance adding unit adds the poisoning substance based on the concentration measured by the concentration sensor. Feeding device.

14. a plurality of poisoning substance separation units configured to be able to collect and release the poisoning substances; The poisoning substance separation unit is configured to be able to recover the poisoning substance by some of the plurality of poisoning substance separation units on the downstream side of the synthesis reactor along the flow direction of the synthesis gas, and the poisoning substance separation unit is configured to be able to introduce the poisoning substance into the synthesis gas by the remaining poisoning substance separation units on the upstream side of the synthesis reactor.

14. The delivery device of claim 13.

15. The part of the poisoning substance separation unit and the remaining part of the poisoning substance separation unit are configured to be exchangeable.

15. The delivery device of claim 14.

16. The catalyst comprises a metal-based catalyst that contains a metal and a metal compound active in a Fischer-Tropsch synthesis reaction and produces hydrocarbons from a synthesis gas, and a support catalyst that contains a zeolite that supports the metal-based catalyst, and the metal and the metal compound contain at least one metal selected from the group consisting of cobalt, manganese, and ruthenium.

14. A supply device according to claim 10 or 13.

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