Method and apparatus for producing hydrocarbons

Abstract

The present disclosure provides a method for producing hydrocarbons, comprising steps of: (S1) heat-treating organic waste in a pyrolysis reactor to generate a first mixed gas; (S2) methane reforming the first mixed gas in a reforming reactor to generate a second mixed gas; (S3) separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; (S4) injecting the first stream and carbon into a reverse Boudouard reactor and converting same into carbon monoxide through a reverse Boudouard reaction; (S5) generating a third mixed gas by mixing the second stream and the carbon monoxide converted in step (S4); (S6) producing synthesis gas from the third mixed gas through a water gas shift reaction; and (S7) producing hydrocarbons from the synthesis gas through a catalytic reaction, wherein the reforming reactor in step (S2) includes a fluidized bed reforming reactor and a fixed bed reforming reactor connected in parallel, and the first mixed gas is switched and supplied to the fluidized bed reforming reactor or the fixed bed reforming reactor.

Description

Hydrocarbon production method and device

[0001] The present disclosure relates to a method and a production device for producing hydrocarbons from organic waste, and more particularly, to a method and a production device for producing hydrocarbons that can improve the production yield of hydrocarbons from organic waste and minimize the generation of carbon dioxide.

[0002] Organic waste can seriously damage the environment through decomposition and other processes during landfill disposal. Therefore, disposal must be categorized by type and processed accordingly. However, simple disposal of organic waste requires securing treatment facilities and extensive manpower, and is often wasteful rather than productive. Therefore, methods and technologies for recycling organic waste are being developed. A prime example is the gasification process, which uses organic waste to produce synthesis gas, converting it into high-value-added products, and ultimately converting it into energy.

[0003] The gasification process generally refers to a series of processes for converting carbonaceous raw materials such as coal, organic waste, and biomass into synthesis gas containing hydrogen and carbon monoxide by reacting them under the supply of steam, oxygen, carbon dioxide, or a mixture thereof. Here, "synthesis gas" typically refers to a mixed gas produced by a gasification reaction and containing hydrogen and carbon monoxide, and may additionally contain carbon dioxide and / or methane.

[0004] Gasification process technology has expanded into producing various compound raw materials and fuels. For example, synthesis gas can be used as a feedstock for the Fischer-Tropsch synthesis reaction to produce high value-added products such as light crude oil, heavy crude oil, diesel oil, wax, jet fuel, and lubricating oil. Furthermore, the hydrogen contained in synthesis gas, the main product of the gasification process, can be used in hydrogen power generation, ammonia production, and oil refining processes. Furthermore, it is known that methanol produced from synthesis gas can be used to produce high value-added chemicals such as acetic acid, olefins, dimethyl ether, aldehydes, fuels, and additives. However, synthesis gas produced from organic waste has a very low production yield, making it difficult to effectively produce high value-added compounds from synthesis gas.

[0005] Recently, catalytic gasification processes have been implemented to produce synthesis gas. However, the gasification process has been plagued by catalyst deactivation due to coke and other contaminants, leading to process failures during continuous operation. Furthermore, to ensure economic viability, the relatively expensive catalyst must be recovered. However, recovering the catalyst, which is discharged in a coagulated state with coke and other contaminants, requires multiple subsequent processes (e.g., air burning), significantly reducing process efficiency.

[0006] Furthermore, the conventional gasification process for organic waste has a significantly low yield of less than 30%, producing synthesis gas that can be converted into high-value-added products. This significantly reduces productivity, limiting its utilization and commercialization. Furthermore, while reducing CO2 emissions is desirable from an environmental perspective, the gasification reaction products of organic waste contain CO2 in addition to H2 and CO. This poses a serious problem, as they generate more carbon dioxide emissions than landfill or pyrolysis processes, potentially contributing to further environmental pollution.

[0007] Accordingly, there is a need for a hydrocarbon production method and production device that can efficiently convert high value-added hydrocarbons by improving the production yield of synthesis gas that can be converted into high value-added products during the gasification process of organic waste, while minimizing the generation of carbon dioxide.

[0008] According to one aspect of the present disclosure, a method and apparatus for producing hydrocarbons from organic waste can be provided, in which the yield of producing hydrocarbons is significantly improved.

[0009] According to one aspect of the present disclosure, a method and apparatus for producing hydrocarbons with significantly improved process efficiency can be provided.

[0010] According to one aspect of the present disclosure, a method and apparatus for producing hydrocarbons capable of minimizing the generation of carbon dioxide can be provided.

[0011] A method for producing hydrocarbons according to the present disclosure comprises: (S1) a step of heat-treating organic waste in a pyrolysis reactor to produce a first mixed gas; (S2) a step of reforming the first mixed gas by methane reforming in a reforming reactor to produce a second mixed gas; (S3) a step of separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; (S4) a step of converting the first stream and carbon into carbon monoxide through a reverse Boudouard reaction by introducing the first stream and carbon into a reverse Boudouard reactor; (S5) a step of mixing the second stream with the carbon monoxide converted in step (S4) to produce a third mixed gas; (S6) a step of producing a synthesis gas from the third mixed gas through a water gas shift reaction; And (S7) a step of producing hydrocarbons from the synthesis gas through a catalytic reaction; wherein the reforming reactor of the step (S2) includes a fluidized bed reforming reactor and a fixed bed reforming reactor connected in parallel, and the first mixed gas is switched and supplied to the fluidized bed reforming reactor or the fixed bed reforming reactor.

[0012] In one example, the first mixed gas may be switched to a fluidized bed reforming reactor and supplied as feed when the C / O element ratio is above a threshold value, and may be switched to a fixed bed reforming reactor and supplied as feed when the C / O element ratio is below the threshold value.

[0013] In one example, the threshold value may be 0.5 to 0.9.

[0014] In one example, the reverse budding reactor may include a fluidized bed reverse budding reactor and a fixed bed reverse budding reactor connected in parallel, and the first stream may be supplied by switching.

[0015] In one example, the fluidized bed reverse carbide reactor of step (S4) may be supplied with the coke catalyst of the fluidized bed reforming reactor as a carbon source, and the fixed bed reverse carbide reactor may be supplied with additional carbon as a separate carbon source.

[0016] In one example, the first mixed gas may further include one or more selected from landfill gas, shale gas, refinery exhaust gas, and biogas.

[0017] In one example, in the step (S6), the synthesis gas contains hydrogen and carbon monoxide, and the ratio of hydrogen and carbon monoxide can be 1.8:1 to 2.2:1.

[0018] In one example, the catalytic reaction of step (S7) may be a Fischer-Tropsch reaction.

[0019] In one example, the catalytic reaction of step (S7) may be a methanol and olefin conversion reaction.

[0020] In one example, the hydrocarbon produced by the above step (S7) may be synthetic petroleum.

[0021] In one example, the hydrocarbon produced by the step (S7) may be a light olefin.

[0022] In one example, the methane reforming may be performed at a temperature of 700°C to 1000°C.

[0023] In one example, the reverse reaction may be performed at a temperature of 600°C to 1000°C and a pressure of 50 KPa to 300 KPa.

[0024] In one example, in the step (S1), the organic waste may be one or more selected from waste plastic, solid waste, biomass, waste oil, waste tires, and volume-based waste bags.

[0025] In one example, prior to the step (S2), a step of purifying the first mixed gas of the step (S1) may be further included.

[0026] A hydrocarbon production device according to the present disclosure comprises: a pyrolysis reactor for generating a first mixed gas by heat-treating organic waste; a reforming reactor for generating a second mixed gas by reforming the first mixed gas into methane; a carbon dioxide separation unit for separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; a reverse Buda reactor for converting the first stream into carbon monoxide through a reverse Buda reaction; a gas mixing unit for generating a third mixed gas by mixing the second stream with carbon monoxide converted in the reverse Buda reactor; and a synthesis gas production unit for converting the third mixed gas into synthesis gas through a water gas shift reaction. And a hydrocarbon conversion unit that converts the synthesis gas into hydrocarbon under a catalyst; wherein the reforming reactor includes a fluidized bed reforming reactor and a fixed bed reforming reactor connected in parallel, and the first mixed gas discharged from the pyrolysis reactor is switched by a switching valve and supplied to the fluidized bed reforming reactor or the fixed bed reforming reactor.

[0027] In one example, a purification unit may be further included between the pyrolysis reactor and the reforming reactor.

[0028] In one example, the reverse osmosis reactor comprises a fluidized bed reverse osmosis reactor and a fixed bed reverse osmosis reactor arranged in parallel, and the first stream can be switched and selectively supplied to the fluidized bed reverse osmosis reactor or the fixed bed reverse osmosis reactor.

[0029] In one example, the hydrocarbon production device further includes a cyclone connected between the fluidized bed reforming reactor and the carbon dioxide separation unit; a catalyst supply line connecting the cyclone and the fluidized bed reverse Buda reactor; and a catalyst recirculation line connecting the fluidized bed reverse Buda reactor and the fluidized bed reforming reactor, wherein the cyclone separates a second mixed gas and a catalyst discharged from the fluidized bed reforming reactor, supplies the second mixed gas to a carbon dioxide separation unit, and supplies the catalyst to the fluidized bed reverse Buda reactor.

[0030] According to one embodiment of the present disclosure, the yield of hydrocarbon production from organic waste can be significantly improved.

[0031] According to one embodiment of the present disclosure, the production efficiency of hydrocarbons can be significantly improved by converting the feed into hydrocarbons using an appropriate process and device according to the C / O element ratio of the feed.

[0032] According to one embodiment of the present disclosure, the generation of carbon dioxide can be minimized during the hydrocarbon production process.

[0033] Figure 1 is a schematic diagram showing a hydrocarbon production device according to the present disclosure.

[0034] FIG. 2 is a schematic diagram showing a hydrocarbon production device including a fixed bed and a fluidized bed reverse osmosis reactor as an example of an embodiment of the present disclosure.

[0035] FIG. 3 is a schematic diagram showing a hydrocarbon production device including a catalyst circulation process as an embodiment of the present disclosure.

[0036] FIG. 4 is a schematic diagram showing a hydrocarbon production device including two carbon dioxide separation units as an example of an implementation according to the present disclosure.

[0037] As used herein, the singular forms of terms may be construed to include the plural forms as well, unless otherwise specified.

[0038] The numerical ranges used herein include the lower and upper limits, all values ​​within those limits, all values ​​delimited by these limits, and all possible combinations of the upper and lower limits of numerical ranges defined in different ways. Unless otherwise specified herein, values ​​outside the numerical ranges that may arise due to experimental error or rounding of values ​​are also included in the defined numerical ranges.

[0039] The term "includes" as used herein is an open-ended description having the equivalent meaning of expressions such as "comprises," "contains," "has," and "characterizes," and does not exclude additional elements, materials, or processes not listed.

[0040] The unit of % used in this specification without special mention means weight% unless otherwise defined. The unit of ppm used in this specification without special definition means mass ppm.

[0041] Conventionally, a gasification process using a catalyst has been implemented as a process for producing synthesis gas. However, there has been a problem that the catalyst is deactivated due to the generation of coke and the like during the gasification process, and process troubles occur due to the deactivated catalyst during continuous operation. In addition, to ensure economic feasibility, the relatively expensive catalyst needs to be recovered. However, in order to recover the catalyst discharged in a coagulated state such as coke, multiple subsequent processes (such as air burning) must be performed, which significantly reduces the process efficiency and causes environmental pollution due to the emission of a large amount of carbon dioxide during the process. Furthermore, the conventional gasification process for organic waste has a significantly low synthesis gas production yield of less than 30%, which reduces productivity and limits the conversion of the gas into high value-added products. Therefore, the inventors of the present disclosure have devised a manufacturing method and device that can efficiently produce hydrocarbons from organic waste while minimizing the generation of carbon dioxide.

[0042] The present disclosure comprises the steps of (S1) heat-treating organic waste in a pyrolysis reactor to produce a first mixed gas; (S2) reforming the first mixed gas in a reforming reactor to produce a second mixed gas; (S3) separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; (S4) introducing the first stream and carbon into a reverse Boudouard reactor to convert them into carbon monoxide through a reverse Boudouard reaction; (S5) mixing the second stream with the carbon monoxide converted in step (S4) to produce a third mixed gas; and (S6) producing a synthesis gas from the third mixed gas through a water gas shift reaction; (S7) producing a hydrocarbon from the synthesis gas through a catalytic reaction. The present invention provides a method for producing a hydrocarbon, wherein the reforming reactor of the step (S2) includes a fluidized bed reforming reactor and a fixed bed reforming reactor connected in parallel, and the first mixed gas is switched and supplied to the fluidized bed reforming reactor or the fixed bed reforming reactor.

[0043] The method for producing hydrocarbons according to the present disclosure can efficiently convert organic waste plastics into synthesis gas compared to conventional gasification processes, thereby maximizing the yield of high-value-added hydrocarbons converted from the synthesis gas. Furthermore, the carbon dioxide generated during the synthesis gas production process can be converted into a raw material for the synthesis gas, thereby minimizing carbon dioxide emissions during the hydrocarbon production process and preventing environmental pollution.

[0044] The above step (S1) is a step of generating a first mixed gas by heat-treating organic waste, in which a gasification reaction of the organic waste can occur.

[0045] In one example, in step (S1), the organic waste may be one or more selected from the group consisting of waste plastic, solid waste, biomass, waste oil, waste tires, and volume-based waste bags.

[0046] Specifically, in the step (S1), one or more gasification reactions selected from the following reaction formulas 1 to 4 may be involved.

[0047] [Reaction Formula 1]

[0048] C x H y + H2O →H2+ CO (water gasification reaction)

[0049] [Reaction Formula 2]

[0050] C x H y + CO2→CO (carbon dioxide gasification reaction)

[0051] [Reaction Formula 3]

[0052] CO + 3H2→CH4+ H2O (methanation reaction)

[0053] [Reaction Formula 4]

[0054] C x H y + O2→ CO2 (oxidation reaction)

[0055] In one example, the first mixed gas may include methane, hydrogen, carbon monoxide, and carbon dioxide. In addition, it may include various impurities such as water vapor, nitrogen oxides, sulfur oxides, and hydrogen chloride.

[0056] In one example, step (S1) may be performed under a first catalyst condition or a non-catalytic condition to increase the methane content in the composition of the first mixed gas. Since increasing the methane content in the composition of the first mixed gas may be advantageous in terms of methane reforming reaction efficiency or synthesis gas production yield, an acid site catalyst or a molybdenum series shaped catalyst may be used as a bed material of the gasifier to increase the methane content in step (S1). If a catalyst is not used, the gasifier may be operated under low-temperature and high-pressure conditions to increase the methane content. The yield improvement effect due to methane reforming can be expected to have the same effect not only on the methane content but also on the C2 to C4 hydrocarbon gas content, and the C2 to C4 gas content can also be increased by using an acid site catalyst or by performing low-temperature and high-pressure gasification operation.

[0057] In one example, the first catalyst may be an acid site catalyst or a molybdenum-based molded catalyst. The acid site catalyst may be a catalyst having a solid acid site derived from alumina or a structure. The alumina may be alumina alone, silica-alumina, alumina dispersed in a carbon structure, etc., and the structure acid site material may be zeolite, SAPO, AlPO, MOF, or a structural modification thereof. The molybdenum-based catalyst refers to a catalyst in which molybdenum is supported on a support, and nickel, cobalt, etc. may be added as needed, and tungsten may be used instead of molybdenum. The support may be any material that has durability capable of supporting an active metal, and may include, for example, a material including one or more selected from the group consisting of silica, alumina, silica-alumina, carbon, and zirconia.

[0058] As another example of increasing the methane content in the first mixed gas, the first mixed gas may further include one or more selected from landfill gas, shale gas, refinery exhaust gas, and biogas. Since the above-described landfill gas, shale gas, refinery exhaust gas, and biogas contain methane and carbon dioxide in an amount of 40% by volume or more, specifically, 50% by volume or more, since the first mixed gas further includes the above-described gases, there is an effect of further improving the production yield of synthesis gas through subsequent processes such as methane reforming reaction and reverse Budar reaction.

[0059] In one example, the step (S1) may further include a step of purifying the first mixed gas.

[0060] The first mixed gas generated by heat treating organic waste may contain one or more impurities selected from the group consisting of tar, sulfur, nitrogen, and chlorine. Specifically, the first mixed gas may contain water-soluble impurities such as H2S, HCl, HOCl, and NH3, and insoluble impurities such as tar. These impurities contained in the first mixed gas may induce catalyst deactivation, thereby reducing the efficiency of a subsequent process. Therefore, by removing the impurities from the first mixed gas and purifying it, the efficiency of the overall process can be improved.

[0061] The method for purifying the first mixed gas may be one or a combination of two or more selected from the group consisting of using a high-pressure dust collecting filter, water washing, alkaline solution washing, and passing through a ceramic filter, but is not limited thereto. When water washing or alkaline solution washing is used, water-soluble impurities such as H2S, HCl, HOCl, and NH3 contained in the first mixed gas can be removed, and when the first mixed gas is passed through a ceramic filter or dust collecting filter, non-water-soluble impurities such as tar and dust can be removed.

[0062] Step (S2) is a step of reforming methane contained in the first mixed gas to produce a second mixed gas. In step (S2), a reforming reaction according to the following reaction formula 5 may occur.

[0063] [Reaction Formula 5]

[0064] CH4+ CO2→2CO + 2H2 (carbon dioxide reforming reaction)

[0065] The reforming reaction of the above step (S2) can be performed at a temperature of 600°C to 1400°C and a pressure of 30 KPa to 2000 KPa.

[0066] The above step (S2) may be operated without a catalyst, but may be operated using a catalyst to increase the reaction conversion rate at a low temperature of about 600°C to 700°C. The catalyst of the above step (S2) may be a composite catalyst in which a hydrogenation metal is supported on a support. The hydrogenation metal may include at least one selected from the group consisting of nickel, vanadium, iron, platinum, palladium, and ruthenium. The hydrogenation metal may be a commonly known metal such as nickel, vanadium, or iron, and in cases where the impurity content in raw materials such as organic waste is low during the heat treatment process, a precious metal such as platinum, palladium, or ruthenium may be used.

[0067] In one example, the support may be a solid acid material such as an oxide or a zeolite. Specifically, the support may be at least one selected from the group consisting of ZSM-5, ZSM-11, USY zeolite, Ferrierite, Mordenite, MCM-22, SUZ-4 or L-type zeolite, silica, alumina, silica-alumina, carbon, zirconia and titania.

[0068] In one example, the reforming reactor of the step (S2) includes a fluidized bed reforming reactor and a fixed bed reforming reactor connected in parallel, and the first mixed gas can be switched and supplied to the fluidized bed reforming reactor or the fixed bed reforming reactor.

[0069] That is, the first mixed gas generated in step (S1) can be supplied to a fluidized bed reforming reactor or a fixed bed reforming reactor in step (S2) to perform the above-described methane reforming reaction. Specifically, if the C / O element ratio of the first mixed gas generated in step (S1) is greater than or equal to a threshold value, it is switched to a fluidized bed reforming reactor and supplied as a feed, and if the C / O element ratio is less than the threshold value, it is switched to a fixed bed reforming reactor and supplied as a feed to perform the above-described methane reforming reaction to produce a second mixed gas (200).

[0070] In one example, the threshold value may be 0.5 to 0.9, 0.6 to 0.85, or 0.7 to 0.8, and when the C / O ratio is above the threshold value, the process may be switched to a fluidized bed process and operated, and when it is below the threshold value, the process may be switched to a fixed bed reactor and operated.

[0071] In step (S2), a methane reforming reaction is performed in a fluidized bed reforming reactor or a fixed bed reforming reactor, so that the methane reforming efficiency of the first mixed gas can be maximized. Specifically, if the C / O element ratio of the first mixed gas is lower than the threshold value, the amount of coke produced by side reactions when the reforming reaction is performed may be small. Therefore, if the C / O element ratio in the first mixed gas is lower than the threshold value, it is advantageous to perform the reforming reaction in a fixed bed reforming reactor, which has the highest conversion rate per catalyst weight. On the other hand, if the C / O element ratio in the first mixed gas is higher than the threshold value, the methane reforming efficiency may decrease over time because the amount of coke produced by side reactions when the reforming reaction is performed is large. Therefore, if the C / O element ratio in the first mixed gas is higher than the threshold value, performing the methane reforming reaction in a fluidized bed reforming reactor can increase the methane reforming efficiency compared to performing it in a fixed bed reforming reactor. In this way, since the present disclosure allows methane reforming to be performed in a fluidized bed reforming reactor or a fixed bed reforming reactor, the methane reforming reaction is performed in a favorable process depending on the ratio of C / O elements contained in the first mixed gas, thereby having the effect of maximizing the efficiency of the methane reforming reaction.

[0072] (S3) Step is a step of separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide.

[0073] In one example, the method for separating the second mixed gas into the first stream and the second stream is not limited to any known method, but the present disclosure allows separation using a carbon dioxide separation unit, and the carbon dioxide separation unit may be an Amine Scrubber. Typically, an Amine Scrubber separates components such as carbon dioxide and hydrogen sulfide from gas vapor by combining and removing carbon dioxide through an amine-based material, and can recover a gas containing hydrogen, carbon monoxide, or an inert gas. Therefore, the first mixed gas can be separated into the first stream and the second stream by using an Amine Scrubber.

[0074] As another example, the carbon dioxide separation unit may be a CCS unit (Carbon capture and storage unit). When a CCS unit is used to separate carbon dioxide, the CCS unit can adsorb and separate carbon dioxide using an adsorbent including one or more selected from calcium oxide, calcium hydroxide, dolomite, limestone, and trona, so the second mixed gas can be separated into a first stream and a second stream using the CCS unit (Carbon capture and storage unit).

[0075] The first stream may contain carbon dioxide in a lower limit of 40% by volume or more, 50% by volume or more, or 60% by volume or more, and an upper limit of 99% by volume or less, 90% by volume or less, 80% by volume or less, or 70% by volume or less. Specifically, the first stream may contain carbon dioxide in an amount of 40 to 99% by volume, and more specifically, 50 to 80% by volume. In a carbon dioxide separation unit, when capturing carbon dioxide and separating it, in order to separate carbon dioxide with high purity, the regeneration tower where the carbon dioxide is separated from the adsorbent must be designed with a high stage, so more energy is consumed. Therefore, since the first stream has carbon dioxide in the above-described range, the carbon dioxide separation process can be performed under slightly milder conditions.

[0076] Step (S4) is a step for converting the first stream separated in step (S3) into carbon monoxide through a reverse Buta reaction. By additionally converting the carbon dioxide contained in the first stream into carbon monoxide through the reverse Buta reaction, environmental pollution can be prevented by reducing carbon dioxide emissions, while also maximizing the yield of synthesis gas. The reverse Buta reaction may involve the following reaction scheme 6.

[0077] [Reaction Formula 6]

[0078] C+CO2→ 2CO

[0079] In one example, the reverse budding reactor may be a fluidized bed reverse budding reactor and a fixed bed reverse budding reactor connected in parallel so that the first stream can be switched and supplied. Specifically, when a fluidized bed reforming reactor is used in step (S2), the first stream can be switched and supplied to the fluidized bed reverse budding reactor in step (S4), and when a fixed bed reforming reactor is used in step (S2), the first stream can be switched and supplied to the fixed bed reverse budding reactor in step (S4).

[0080] First, the first mixed gas having a C / O element ratio greater than a critical point is switched to a fluidized bed reforming reactor during a methane reforming reaction in step (S2) and converted into a second mixed gas, and the second mixed gas is separated from the catalyst and then separated into a first stream containing carbon dioxide and a second stream containing carbon monoxide and hydrogen through step (S3). Thereafter, when step (S4) is performed, the first mixed gas is switched to a fluidized bed inverse reactor, and the first stream is supplied to the fluidized bed inverse reactor and converted into carbon monoxide.

[0081] Similarly, the first mixed gas having a C / O element ratio below the critical point may be switched to a fixed-bed reforming reactor when step (S2) is performed and converted into a second mixed gas through a methane reforming reaction, and the second mixed gas may be separated into a first stream (210) containing carbon dioxide and a second stream (211) containing carbon monoxide and hydrogen through step (S3). Thereafter, the first stream may be switched to a fixed-bed reverse Buda reactor when step (S4) is performed and converted into carbon monoxide through a reverse Buda reaction.

[0082] When methane reforming is performed using a fluidized bed reforming reactor in step (S2), the coke catalyst produced in the fluidized bed reforming reactor can be supplied in step (S4) and used as a carbon source for the inverse Buda reactor, so it may be advantageous to use the fluidized bed inverse Buda reactor in step (S4). That is, when the coke catalyst of the fluidized bed reforming reactor is used as a carbon source, there is no need to additionally supply separate carbon to the fluidized bed inverse Buda reactor in step (S4), enabling economical process operation. Therefore, when a fluidized bed reforming reactor is used in step (S2), it may be advantageous in terms of process efficiency to use the fluidized bed inverse Buda reactor in step (S4).

[0083] In addition, when using a fixed bed reforming reactor in step (S2), it may be advantageous in terms of improving the production amount of synthesis gas to improve the reactivity of the reverse Buta reaction by using a fixed bed reverse Buta reactor with excellent reaction efficiency in step (S4).

[0084] As the present disclosure includes a fluidized bed and a fixed bed reverse sintering reactor as described above, there is an effect that the reverse sintering reaction can be performed by selecting a reactor that can maximize process efficiency by considering the previous process.

[0085] The above-described reverse reaction can be performed using an external carbon source. Specifically, the carbon source may be char derived from the organic waste, and more specifically, char derived from the pyrolysis of waste plastic or char derived from biomass. Alternatively, high-purity graphite may be included to prevent the introduction of impurity gases by the external carbon source.

[0086] Step (S5) is a step of generating a third mixed gas by mixing the second stream separated from the carbon dioxide separation unit and the carbon monoxide converted by the reverse reaction in step (S4).

[0087] The third mixed gas may contain hydrogen and carbon monoxide.

[0088] Step (S6) is a process for generating synthesis gas by controlling the ratio of carbon monoxide and hydrogen in the third mixed gas through a water-gas shift reaction. The third mixed gas can be converted through the water-gas shift reaction to satisfy an appropriate hydrogen:carbon monoxide ratio for the subsequent catalytic reaction process. The water-gas shift reaction may involve the following chemical formula 7.

[0089] [Chemical Formula 7]

[0090] CO + H2O → H2 + CO2

[0091] The water-gas shift reaction can be carried out in the presence of a catalyst containing Fe and Cr. The water-gas shift reaction can be carried out at a temperature of 100°C to 400°C, specifically 100°C to 300°C, and at a pressure of 20 bar to 80 bar, specifically 25 bar to 70 bar.

[0092] The synthesis gas produced by the above-described water-gas shift reaction may have a hydrogen:carbon monoxide ratio of 1.5 to 3:1, specifically 1.9 to 2.1:1. As the hydrogen:carbon monoxide ratio in the synthesis gas satisfies the above-described range, the subsequent catalytic reaction process can be performed smoothly.

[0093] Step (S7) is a step for converting the synthesis gas generated in step (S6) into a hydrocarbon fraction, which can be converted into an appropriate hydrocarbon fraction by a catalytic reaction.

[0094] The above catalytic reaction is not limited to any reaction that can convert synthesis gas into hydrocarbon fractions, but may be a Fischer-Tropsch reaction or a methanol and olefin conversion reaction.

[0095] In one example, when the catalytic reaction of step (S7) is a Fischer-Tropsch reaction, a reaction involving the following chemical formula 8 can be performed using the synthesis gas produced in step (S6) as a raw material.

[0096] [Chemical Formula 8]

[0097] nCO + 2nH2→C n H 2n + nH2O

[0098] The above Fischer-Tropsch reaction can be carried out under a catalyst including cobalt, nickel or iron, and can include alumina, silica, titania, etc. as a support, and can include a noble metal such as Pt, Ru, Re, etc. as a cocatalyst.

[0099] The Fischer-Tropsch reaction can be carried out at a temperature of 100°C to 500°C, specifically 200°C to 350°C, at a pressure of 10 atm to 50 atm, and at a pressure of 10 atm to 30 atm.

[0100] In one example, when the catalytic reaction of step (S7) is a methanol and olefin conversion reaction, step (S7) may include a reaction of converting synthesis gas into methanol; and a reaction of converting methanol into olefin.

[0101] The reaction for converting synthesis gas into methanol may be a reaction involving the following chemical formula 9.

[0102] [Chemical Formula 9]

[0103] CO + 2H2→ CH3OH

[0104] In one example, the reaction of converting synthesis gas into methanol can be performed under a Cu-based catalyst. Specifically, the Cu-based catalyst can be an Fe-based methanol synthesis catalyst, and the carrier of the Fe-based catalyst can use at least one selected from the group consisting of SiO2, ZrO2, Ga2O3Al2O3, MgO, and TiO2. Specifically, the Cu-based methanol synthesis catalyst can be Cu / Zn / Al2O3.

[0105] The reaction of converting the above synthesis gas into methanol can be performed at a temperature of 200°C to 600°C, specifically at 200°C to 500°C, and at a pressure of 0.1 MPa to 10 MPa, specifically at 0.1 MPa to 5 MPa.

[0106] The reaction of converting methanol into olefin can be carried out under a zeolite catalyst or an AlPO4-based molecular sieve catalyst. Specifically, the zeolite catalyst can be ZSM-5, and the AlPO4-based catalyst can be a silicoaluminaphosphate (SAPO) molecular sieve catalyst, and specifically, it can be at least one selected from SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-44, and SAPO-46.

[0107] The reaction of converting methanol into olefin can be carried out at a temperature of 200°C to 600°C, specifically 300°C to 500°C, and a pressure of 1 bar to 10 bar, specifically 1 bar to 5 bar.

[0108] The present disclosure comprises: a pyrolysis reactor (10) for heat-treating organic waste (100) to produce a first mixed gas (110); a reforming reactor (20) for reforming the first mixed gas (110) into methane to produce a second mixed gas (200); a carbon dioxide separation unit (30) for separating the second mixed gas (200) into a first stream (210) containing carbon dioxide and a second stream (211) containing hydrogen and carbon monoxide; a reverse Buda reactor (40) for converting the first stream (210) into carbon monoxide through a reverse Buda reaction; a gas mixing unit (50) for mixing the second stream (211) and carbon monoxide converted in the reverse Buda reactor (40) to produce a third mixed gas (220); A hydrocarbon production device (1) is provided, which includes a synthesis gas production unit (60) that converts the third mixed gas (220) into a synthesis gas (230) through a water gas shift reaction; and a hydrocarbon conversion unit (70) that converts the synthesis gas (230) into a hydrocarbon under a catalyst; wherein the reforming reactor (20) includes a fluidized bed reforming reactor (21) and a fixed bed reforming reactor (22) connected in parallel, and a first mixed gas (110) discharged from the pyrolysis reactor (10) is switched by a switching valve and supplied to the fluidized bed reforming reactor (21) or the fixed bed reforming reactor (22).

[0109] The hydrocarbon production device (1) according to the present disclosure can select a subsequent process reactor between a fluidized bed reactor and a fixed bed reactor depending on the oxygen content contained in the gas produced by gasification of waste, thereby efficiently converting the gas produced by gasification of waste into hydrocarbons. In addition, by capturing carbon dioxide emitted as exhaust gas and using it as a raw material for producing hydrocarbons, the amount of carbon dioxide emitted can be significantly reduced, thereby preventing environmental pollution.

[0110] In one example, referring to FIG. 1, organic waste (100) is introduced into a pyrolysis reactor (10) and heat-treated to generate a first mixed gas (110). The first mixed gas (110) is supplied to a reforming reactor (20), and when the C / O element ratio in the first mixed gas (110) is above a threshold value, the first mixed gas (110) is introduced into a fluidized bed reforming reactor (21) by a switching valve, and when the ratio is below the threshold value, the first mixed gas (110) is introduced into a fixed bed reforming reactor (22) by a switching valve, and the first mixed gas (110) is converted into a second mixed gas (200) through a methane reforming reaction.

[0111] The above switching valve can be controlled to connect the pyrolysis reactor (10) and the fixed bed reforming reactor (22) so that the first mixed gas (110) flows into the fixed bed reforming reactor (22) when the C / O element ratio is lower than the threshold value. In addition, when the first mixed gas (110) flows into the pyrolysis reactor (10) and the fluidized bed reforming reactor (21), the first mixed gas (110) flows into the fluidized bed reforming reactor (21).

[0112] The present disclosure has the effect of maximizing the efficiency of the methane reforming reaction by allowing the reforming reactor (20) to include a fluidized bed reforming reactor (21) and a fixed bed reforming reactor (22) and performing the reforming reaction in an appropriate reactor according to the C / O element ratio of the first mixed gas (110) by means of a switching valve.

[0113] According to an example, the hydrocarbon production device (1) may further include a purification unit (80) between the pyrolysis reactor (10) and the reforming reactor (20). Referring to FIG. 2, the first mixed gas (110) is introduced into the purification unit (80) to remove impurities, and then the first mixed gas (120) from which impurities have been removed is supplied to the reforming reactor (20) to perform a methane reforming reaction.

[0114] The above purification unit (80) includes a sprayer that sprays liquid, receives a first mixed gas (110) from a pyrolysis reactor (10), and contacts the first mixed gas (110) with a weakly basic solution containing water or sodium carbonate to remove water-soluble impurities such as H2S, HCl, HOCl, and NH3, or removes dust using a high-pressure dust collecting filter, and removes insoluble impurities such as tar by including a ceramic filter, etc.

[0115] The second mixed gas (200) generated by the methane reforming reaction in the reforming reactor (20) can be supplied to a carbon dioxide separation unit (30) and separated into a first stream (210) containing carbon dioxide and a second stream (211) containing hydrogen and carbon monoxide. At this time, the second stream (211) is supplied to a gas mixing unit (50), and the first stream (210) is supplied to a reverse Buda reactor (40) and converted into carbon monoxide through a reverse Buda reaction.

[0116] In one example, referring to FIG. 3, the reverse Buda reactor (40) is configured such that a fluidized bed reverse Buda reactor (41) and a fixed bed reverse Buda reactor (42) are connected in parallel, and the fluidized bed reverse Buda reactor (41) and the fixed bed reverse Buda reactor (42) can be switched to selectively supply the first stream (210). Like the reforming reactor (20), the reverse Buda reactor (40) can also perform the reverse Buda reaction by selectively supplying the first stream (210) to the fluidized bed reverse Buda reactor (41) or the fixed bed reverse Buda reactor (42) through a switching valve.

[0117] According to an example, when the reforming reaction is performed in a fluidized bed reforming reactor (21), the first stream (210) may be supplied to a fluidized bed reverse Buda reactor (41) to perform the reverse Buda reaction. Meanwhile, when the reforming reaction is performed in a fixed bed reforming reactor (22), the first stream (210) may be subjected to the reverse Buda reaction in the fixed bed reverse Buda reactor (42). Like the reforming reactor, the reverse Buda reactor may be connected to a carbon dioxide separation unit (30) and a fluidized bed reverse Buda reactor (41) through a switching valve to supply the first stream (210) to the fluidized bed reverse Buda reactor (41) to perform the reverse Buda reaction when the reforming reaction is performed in the fluidized bed reforming reactor (21). In addition, when the reforming reaction is performed in a fixed bed reforming reactor (22), the carbon dioxide separation unit (30) and the fixed bed reverse Buda reactor (42) are connected to supply the first stream (210) to the fixed bed reverse Buda reactor (42), thereby performing the reverse Buda reaction.

[0118] In one example, the hydrocarbon production device (1) further includes a cyclone (90) connected between the fluidized bed reforming reactor (21) and the carbon dioxide separation unit (30); a catalyst supply line connecting the cyclone (90) and the fluidized bed reverse Buda reactor (41); and a catalyst recirculation line connecting the fluidized bed reverse Buda reactor (41) and the fluidized bed reforming reactor (21). The cyclone (90) separates a second mixed gas (200) discharged from the fluidized bed reforming reactor (21) and a catalyst, supplies the second mixed gas (200) to the carbon dioxide separation unit (30), and supplies the catalyst to the fluidized bed reverse Buda reactor (41).

[0119] Referring to FIG. 3, the hydrocarbon production device (1) according to the present disclosure may further include a cyclone (90) between the fluidized bed reforming reactor (21) and the carbon dioxide separation unit (30), and the cyclone (90) receives a second mixed gas (200) from the fluidized bed reforming reactor (21), separates the coke catalyst, and then supplies the second mixed gas (200) to the separation unit (30), and the coke catalyst may be supplied to the fluidized bed reverse catalytic converter (41) along a catalyst supply line connected to the cyclone (90) and the fluidized bed reverse catalytic converter (21). In the fluidized bed reverse catalytic converter (41), the coke catalyst supplied from the cyclone (90) may be regenerated, and the regenerated catalyst may be supplied to the fluidized bed reforming reactor (21) through a recirculation line connected to the fluidized bed reforming reactor (21). In this way, by including a cyclone (90), there is no need to separately supply coke required for the reverse reaction from the outside, so economical process operation is possible, and the catalyst for the methane reforming reaction can be continuously re-supplied, so there is an advantage in efficient process operation.

[0120] In one example, the fixed bed reverse osmosis reactor (42) is connected between the carbon dioxide separation unit (30) and the gas mixing unit (50), and the fixed bed reverse osmosis reactor (42) may further include a first fixed bed reverse osmosis reactor, a second fixed bed reverse osmosis reactor connected in parallel, and a control unit for switching the first fixed bed reverse osmosis reactor and the second fixed bed reverse osmosis reactor.

[0121] The above control unit can control the first mode to be performed by blocking the connection of the carbon dioxide separation unit, the first fixed bed reverse carbide reactor, and the gas mixing unit, so that the first fixed bed reverse carbide reactor is regenerated and the reverse carbide reaction is performed by the second fixed bed reverse carbide reactor.

[0122] In addition, the control unit can control the second mode to be performed in which the second fixed bed reverse carbide reactor is regenerated by blocking the connection between the carbon dioxide separation unit, the second fixed bed reverse carbide reactor, and the gas mixing unit, and the reverse carbide reaction is performed by the first fixed bed reverse carbide reactor.

[0123] Referring to FIG. 4, the carbon dioxide separation unit (30) of the hydrocarbon production device (1) according to the present disclosure may include a first carbon dioxide separation unit (31) connected between a fluidized bed reforming reactor (21) and a fluidized bed inverse reactor (41), and a second carbon dioxide separation unit (32) connected between a fixed bed reforming reactor (22) and a fixed bed inverse reactor (42) and aligned in parallel with the first carbon dioxide separation unit (31).

[0124] When the carbon dioxide separation unit (30) includes a first carbon dioxide separation unit (31) and a second carbon dioxide separation unit (32), the first mixed gas (110) may be supplied to the gas mixing unit (50) through the fluidized bed reforming reactor (21) - the first carbon dioxide separation unit (31) - the fluidized bed inverse reactor (41), or may be supplied to the gas mixing unit (50) through the fixed bed reforming reactor (22) - the second carbon dioxide separation unit (32) - the fixed bed inverse reactor (42). When the hydrocarbon production device includes two reforming reactors, two carbon dioxide separation units, and two reverse carburetor reactors as described above, two processes can be operated simultaneously depending on the C / O element ratio threshold value in the first mixed gas (110), so that there is an effect that continuous process operation is possible even if the value of the C / O element ratio of the first mixed gas changes.

[0125] In the gas mixing unit (50), the second stream (211) separated in the carbon dioxide separation unit (30) and the carbon monoxide converted in the reverse reactor (40) are mixed to produce a third mixed gas (220).

[0126] The generated third mixed gas (220) is converted into synthesis gas (230) by controlling the hydrogen:carbon monoxide ratio in the third mixed gas (220) through a water-gas shift reaction in a synthesis gas generation unit (60).

[0127] Synthesis gas (230) is introduced into a hydrocarbon conversion unit (70) and converted into hydrocarbons through a Fischer-Tropsch reaction or a methanol and olefin conversion reaction, and can be recovered as a high value-added oil fraction.

[0128] In one example, when the hydrocarbon conversion unit (70) performs a methanol and olefin conversion reaction, the hydrocarbon conversion unit (70) may include a methanol conversion unit that receives synthesis gas (230) and converts it into methanol, and an olefin conversion unit that receives methanol from the methanol conversion unit and converts it into olefin.

[0129] In one example, the hydrocarbon production device may further include a separation step that separates the produced hydrocarbons into fractions by boiling point through distillation by being connected to a hydrocarbon conversion unit (70).

[0130] Hereinafter, embodiments of the present invention will be further described with reference to specific experimental examples. The examples and comparative examples included in the experimental examples are merely illustrative of the present invention and do not limit the scope of the appended claims. It will be apparent to those skilled in the art that various modifications and variations of the examples are possible within the scope and technical spirit of the present invention, and it is also natural that such modifications and variations fall within the scope of the appended claims.

[0131] (Example 1)

[0132] After 1000 g of municipal solid waste was fed into a pyrolysis reactor, steam was introduced and heat-treated at a temperature of 1200°C and a pressure of 250 kPa under an alumina bead to recover a first mixed gas having a C / O ratio of 0.69.

[0133] The above mixed gas was cooled and introduced into a purification unit (wet scrubber), where it was treated at 70°C and 100 kPa to remove impurities, and the purified mixed gas was recovered. As a result of treating the mixed gas through the wet scrubber, impurity gases such as NH3, HCl, H2S, and COS were not analyzed in the mixed gas.

[0134] The purified first mixed gas is fed to a fixed bed reforming reactor containing 100 g of Ni / Al2O3 catalyst at 2 L / g cat · A second mixed gas was produced through dry reforming of methane by supplying it at a space velocity of h. Specifically, a fixed-bed reforming reactor filled with a catalyst was reduced for 2 hours by supplying H2 at a flow rate of 3.03 Nl / min at 900°C, and then the first mixed gas was supplied to the fixed-bed reforming reactor at a flow rate of 3.33 Nl / min to perform the dry reforming reaction as a continuous process.

[0135] The Ni / Al2O3 catalyst was manufactured by impregnating alumina particles having a diameter of 1 mm into an aqueous solution of nickel nitrate hexahydrate dissolved in distilled water, drying the solution at 150°C for 2 hours, and then continuously calcining the solution at 500°C for 2 hours. The above process was set as a unit process, and the unit process was repeated multiple times until the nickel content in the catalyst became 20 wt%. The nickel content in the catalyst was measured by XRF (X-Ray Fluorescence Spectrometry) analysis, and the XRF analysis was measured using Thermo's ARL QUANT'X.

[0136] The recovered second mixed gas was fed into the Amine Scrubber after removing water. The carbon dioxide contained in the second mixed gas was captured in the Amine Scrubber, and the second mixed gas from which carbon dioxide was removed was separated into a second stream. Specifically, the second mixed gas was fed into the first Amine Scrubber, and CO2 was captured using an aqueous solution (Amine Solution) containing 12 wt% NH3 dissolved therein at 50 to 60°C, 10 to 20 bar, and a processing capacity of 0.5 Nl / hr, and the uncaptured gas was recovered as the second stream. The amine solution (Amine Solution) of the first Amine Scrubber was fed into the second Amine Scrubber, and separated into an amine solution (Amine Solution) and CO2 at 100°C, and the CO2 was recovered as the first stream.

[0137] The recovered first stream was continuously supplied to a fixed-bed reverse Buta reactor filled with a Ni / Al2O3 catalyst and 5 kg of high-purity graphite to convert carbon dioxide into carbon monoxide through the reverse Buta reaction. The reverse Buta reaction was performed under N2 gas at 750°C, a CO2 flow rate of 2.33 Nl / min, and a space velocity of 2.0 L / g. cat ·It was performed under the condition of h.

[0138] The carbon monoxide converted from the first stream and the second stream separated from the amine scrubber were introduced into a gas mixing unit and mixed at 200°C to produce a third mixed gas. The third mixed gas was introduced into a synthesis gas generation unit and produced a synthesis gas with a molar ratio of H2:CO=2:1 through a water gas shift reaction. The water gas shift reaction was performed under a Cu / Zn / Al2O3 catalyst at 165°C, 35 bar, and a space velocity of 1.4 L / g. cat · It was performed under the reaction conditions of h.

[0139] Synthesis gas is fed to the hydrocarbon conversion unit and is converted into hydrogen at a space velocity of 5000 L / kg under a Co / ZnO (Cobalt Zinc oxide) catalyst. cat·h, the injection rate was set so that the volume ratio of carbon monoxide: hydrogen: argon was 63.2: 31.3: 5.5, and the Fischer-Tropsch reaction was performed at a reaction temperature of 300°C and a pressure of 10 bar for 60 hours to recover hydrocarbon oil.

[0140] (Example 2)

[0141] After recovering the first mixed gas having a C / O ratio of 0.87, hydrocarbons were produced in the same manner as in Example 1, except that the reactor was switched to perform dry reforming and reverse Budah reaction in a fluidized bed reactor.

[0142] Specifically, a Ni / Al2O3 fluidized bed catalyst was prepared according to the following procedure. A mixture solution of 10 parts by weight of pseudo-boehmite alumina and 95 parts by weight of nickel nitrate hexahydrate with 100 parts by weight of water was stirred, and 1 part by weight of formic acid was added. The mixture was reacted for 3 hours to cause gelation to prepare a precursor gel. 30 parts by weight of clay and 1.5 parts by weight of MgO oxide were added and mixed using a homogenizer. The resulting solid mixture was mixed with the precursor gel, and then 10 parts by weight of colloidal silica (Ludox AS40, Aldrich) was added, and 5 parts by weight of water was further added and stirred vigorously to prepare a composite catalyst sol. The composite catalyst sol was spray-dried to prepare a fluidized bed catalyst.

[0143] 100g of the above Ni / Al2O3 catalyst is charged into a fluidized bed reforming reactor, H2 is supplied at a flow rate of 3.03 Nl / min at 900°C, and reduced for 2 hours, and then the purified first mixed gas is introduced at a total flow rate of 3.33 Nl / min and 2.0 L / g cat ·The operation was carried out at a processing capacity of h, and the second mixed gas was recovered.

[0144] After separating the catalyst from the second mixed gas of the fluidized bed reforming reactor using a cyclone, CO2 was separated using an amine scrubber, and the second stream from which the catalyst and carbon dioxide were separated was recovered. Specifically, the second mixed gas was introduced into the first amine scrubber, where CO2 was captured in an aqueous solution (amine solution) containing MEA (Monoethanolamine) at 50°C, and the uncaptured gas was recovered as the second stream. The amine solution of the first amine scrubber was introduced into the second amine scrubber, where it was separated into the amine solution and CO2 at 100°C, and the CO2 was recovered as the first stream.

[0145] The recovered first stream was fed into a fluidized bed reverse Buda reactor and converted into carbon monoxide through reverse Buda reaction. The reverse Buda reaction was performed in a fluidized bed reactor filled with a Ni / Al2O3 catalyst, and the space velocity was 2 L / g. cat ·The first stream was supplied to h, and at this time, the catalyst used in the dry reforming process, on which activated carbon and coke were deposited, was introduced as a carbon source. The catalyst, activated by removing the coke through the reverse Buta reaction, was reintroduced into the first fluidized bed reactor through the recirculation line. The insufficient coke was supplemented by additionally introducing high-purity graphite. Unconverted CO2 after the reverse Buta reaction was separately recovered through an amine scrubber.

[0146] (Example 3)

[0147] Hydrocarbons were produced in the same manner as in Example 2, except that a first mixed gas having a C / O ratio of 1.19 was used.

[0148] (Comparative Example 1)

[0149] Hydrocarbons were produced in the same manner as in Example 1, except that a first mixed gas having a C / O ratio of 0.87 was used.

[0150] (Comparative Example 2)

[0151] Hydrocarbons were produced in the same manner as in Example 1, except that a first mixed gas having a C / O ratio of 1.19 was used.

[0152] The compositions of the first mixed gas recovered in Examples 1 to 3 and Comparative Examples 1 and 2 according to the C / O ratio are summarized in Table 1.

[0153] First mixed gas Example 1 Example 2 and comparative example 1 Example 3 and comparative example 2 C / O mole ratio 0.69 0.87 1.19 H 2 4.8 3 5.5 3 3.26 CO 2 .4 2 2.88 1.63 CO 2 1.67 2.6 16.06 CH 4 6.2 4 4.14.2

[0154] (Experimental Example 1) Evaluation of modification reaction

[0155] The catalytic reaction activity, stability, and coke production amount generated during the methane reforming reaction were evaluated when producing hydrocarbons using the methods of Examples 1 to 3 and Comparative Examples 1 and 2. The coke production amount was measured by recovering the inactivated catalyst after the methane reforming reaction was completed, measuring the weight, oxidizing it at 550°C in an air atmosphere to remove coke, and measuring the weight to determine the difference in weight before and after coke removal, thereby quantifying the amount of coke deposited on the catalyst.

[0156] In Example 1, no catalyst deactivation occurred and no coke was formed on the catalyst even after 20 days of methane reforming operation. Therefore, it can be seen that the first mixed gas having a C / O ratio of 0.69 maintains excellent reforming performance for a long period of time in a fixed-bed reactor.

[0157] On the other hand, in Comparative Example 1, where a methane reforming reaction was performed in a fixed-bed reactor using a first mixed gas having a C / O ratio of 0.87, the reactor was not switched even though the C / O ratio was above the threshold value, resulting in catalyst inactivation after 5 days of operation, and the methane conversion rate dropping to less than 30%. Specifically, since 9 wt% of coke was included relative to the total weight of the catalyst, coke was deposited on the catalyst, resulting in very low methane reforming performance.

[0158] Comparative Example 2: In addition, a methane reforming reaction was performed in a fixed-bed reactor without switching the reactor, even though the C / O ratio of the first mixed gas was 1.19, which was higher than the critical value. As a result, the catalytic activity rapidly decreased to 66% within 2 hours, and 22 wt% of coke was deposited relative to the total catalyst weight, resulting in catalyst deactivation.

[0159] However, as in Examples 2 and 3, when the first mixed gas having a C / O ratio of 0.87 and 1.19 was recovered, and then the reactor was switched to perform dry reforming and reverse Booda reaction in a fluidized bed reactor, the catalyst inactivated by the carbon component deposited by the dry reforming reaction was regenerated by introducing it into the reverse Booda reactor. Since the regenerated catalyst was reintroduced into the fluidized bed reforming reactor and used, high catalytic efficiency was maintained. That is, since catalyst regeneration is possible through a circulation process in a fluidized bed reactor, it was found that even if the catalyst was deactivated by the reforming reaction, it had high reaction activity and reaction stability.

[0160] Accordingly, by connecting a fixed bed reactor and a fluidized bed reactor in parallel, the reforming reaction and the reverse Buta reaction can be performed by selecting an appropriate reactor according to the C / O element ratio of the first mixed gas, thereby significantly improving the process efficiency. When the C / O ratio of the first mixed gas is below a critical value, the reforming reaction and the reverse Buta reaction can be performed using a fixed bed reactor having the advantages of low operating cost, mass productivity, and easy management, and when the C / O ratio of the first mixed gas is above a critical value, the reaction stability can be improved by switching to a fluidized bed reactor capable of a catalyst circulation process.

[0161] The above description is merely an example of applying the principles of the present disclosure, and other configurations may be included without departing from the scope of the present invention.

[0162] [Explanation of symbols]

[0163] 1: Hydrocarbon production device 10: Pyrolysis reactor

[0164] 20: Reforming reactor 21: Fluidized bed reforming reactor

[0165] 22: Fixed bed reforming reactor 30: Carbon dioxide separation unit

[0166] 31: First carbon dioxide separation unit 32: Second carbon dioxide separation unit

[0167] 40: Reverse-bed reactor 41: Fluidized-bed reverse-bed reactor

[0168] 42: Fixed bed reverse osmosis reactor 50: Gas mixing unit

[0169] 60: Syngas generation unit 70: Hydrocarbon conversion unit

[0170] 80: Refining Unit 90: Cyclone

[0171] 100: Organic waste 110: First mixed gas

[0172] 120: First mixed gas with impurities removed 200: Second mixed gas

[0173] 210: First Stream 211: Second Stream

[0174] 220: Third mixed gas 230 Synthetic gas

Claims

1. (S1) A step of generating a first mixed gas by heat-treating organic waste in a pyrolysis reactor; (S2) A step of generating a second mixed gas by subjecting the first mixed gas to methane reforming in a reforming reactor; (S3) A step of separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; (S4) A step of introducing the first stream and carbon into a reverse Boudouard reactor and converting them into carbon monoxide through a reverse Boudouard reaction; (S5) a step of generating a third mixed gas by mixing the second stream and the carbon monoxide converted in step (S4); (S6) a step of generating synthesis gas through a water-gas conversion reaction from the third mixed gas; and (S7) a step of producing hydrocarbons through a catalytic reaction from the above synthesis gas; A method for producing a hydrocarbon, wherein the reforming reactor of the step (S2) includes a fluidized bed reforming reactor and a fixed bed reforming reactor connected in parallel, and the first mixed gas is switched and supplied to the fluidized bed reforming reactor or the fixed bed reforming reactor.

2. In paragraph 1, A method for producing hydrocarbons, wherein the first mixed gas is switched to a fluidized bed reforming reactor and supplied as feed when the C / O element ratio is above a threshold value, and is switched to a fixed bed reforming reactor and supplied as feed when the C / O element ratio is below the threshold value.

3. In paragraph 2, A method for producing a hydrocarbon, wherein the above threshold value is 0.5 to 0.

9.

4. In paragraph 1, The above reverse budding reactor is a method for producing hydrocarbons, in which a fluidized bed reverse budding reactor and a fixed bed reverse budding reactor are connected in parallel, and the first stream is supplied by switching.

5. In paragraph 4, A method for producing hydrocarbons, wherein the fluidized bed reforming reactor of the step (S4) is supplied with the coke catalyst of the fluidized bed reforming reactor as a carbon source, and the fixed bed reforming reactor is supplied with additional carbon as a separate carbon source.

6. In paragraph 1, A method for producing hydrocarbons, wherein the first mixed gas further comprises at least one selected from landfill gas, shale gas, refinery exhaust gas, and biogas.

7. In paragraph 1, A method for producing hydrocarbons, wherein in the step (S6), the synthesis gas contains hydrogen and carbon monoxide, and the ratio of hydrogen and carbon monoxide satisfies 1.8:1 to 2.2:

1.

8. In paragraph 1, The catalytic reaction of the above step (S7) is a Fischer-Tropsch reaction, a method for producing hydrocarbons 9. In paragraph 1, A method for producing hydrocarbons, wherein the catalytic reaction of the above step (S7) is a methanol and olefin conversion reaction.

10. In paragraph 8, A method for producing hydrocarbons, wherein the hydrocarbon produced by the above step (S7) is a synthetic petroleum.

11. In paragraph 9, A method for producing a hydrocarbon, wherein the hydrocarbon produced by the above step (S7) is a light olefin.

12. In paragraph 1, A method for producing hydrocarbons, wherein the above methane reforming is performed at a temperature of 700°C to 1000°C.

13. In paragraph 1, A method for producing a hydrocarbon, wherein the above reverse reaction is performed at a temperature of 600°C to 1000°C and a pressure of 50 KPa to 300 KPa.

14. In paragraph 1, A method for producing hydrocarbons, wherein in the step (S1), the organic waste is one or more selected from waste plastic, solid waste, biomass, waste oil, waste tires, and volume-based waste bags.

15. In paragraph 1, A method for producing hydrocarbons, further comprising a step of purifying the first mixed gas of step (S1) prior to step (S2).

16. A pyrolysis reactor that heat-treats organic waste to produce a first mixed gas; A reforming reactor that reforms the first mixed gas into methane to produce a second mixed gas; A carbon dioxide separation unit that separates the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; A reverse oxidizer reactor that converts the first stream into carbon monoxide through a reverse oxidizer reaction; A gas mixing unit that produces a third mixed gas by mixing the carbon monoxide converted in the second stream and the reverse oxidizer reactor; A synthesis gas generating unit that converts the third mixed gas into synthesis gas through a water-gas shift reaction; and A hydrocarbon conversion unit for converting the above-mentioned synthesis gas into hydrocarbon under a catalyst; A hydrocarbon production device, wherein the reforming reactor comprises a fluidized bed reforming reactor and a fixed bed reforming reactor connected in parallel, and the first mixed gas discharged from the pyrolysis reactor is switched by a switching valve and supplied to the fluidized bed reforming reactor or the fixed bed reforming reactor.

17. In paragraph 16, A hydrocarbon production device further comprising a purification unit between the thermal decomposition reactor and the reforming reactor.

18. In paragraph 16, A hydrocarbon production device wherein the above-mentioned reverse budding reactor comprises a fluidized bed reverse budding reactor and a fixed bed reverse budding reactor arranged in parallel, and the first stream is switched and selectively supplied to the fluidized bed reverse budding reactor or the fixed bed reverse budding reactor.

19. In Article 18, The above hydrocarbon production device, A cyclone connected between the fluidized bed reforming reactor and the carbon dioxide separation unit; A catalyst supply line connecting the above cyclone and the fluidized bed reverse osmosis reactor; and It further includes a catalyst recirculation line connecting the fluidized bed reverse reactor and the fluidized bed reforming reactor. A hydrocarbon production device in which the above cyclone separates the second mixed gas and catalyst discharged from the fluidized bed reforming reactor, supplies the second mixed gas to a carbon dioxide separation unit, and supplies the catalyst to a fluidized bed reverse osmosis reactor.

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