Method and system for producing hydrocarbons

Abstract

The present disclosure provides a method for producing hydrocarbons, comprising the steps of: (S1) heat treating organic waste in the presence of a heat transfer medium so as to generate a first mixed gas; (S2) steam reforming the first mixed gas in a first fluidized bed reactor so as to generate a second mixed gas; (S3) separating the second mixed gas into a first stream including carbon dioxide and a second stream including hydrogen and carbon monoxide; (S4) introducing, into a second fluidized bed reactor, the first stream separated out in step (S3), and converting same into carbon monoxide through reverse Boudouard reaction; (S5) mixing the second stream and the carbon monoxide obtained through conversion in step (S4), so as to produce a third mixed gas; (S6) generating syngas from the third mixed gas through a water-gas shift reaction; and (S7) generating hydrocarbons from the syngas through a catalytic reaction, wherein the heat transfer medium comprises 1-40 mass% of iron (Fe) and comprises 5-50 mass% of an alkaline earth metal oxide.

Description

Hydrocarbon production method and system

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

[0002] Steel slag is a collective term for the massive byproducts and waste generated in the steel industry. It accounts for approximately 50% of the total steel production, and contains a significant amount of recyclable resources such as iron, carbon, and limestone.

[0003] Steel slag is divided into blast furnace slag and steelmaking slag. Blast furnace slag has almost no iron content, while steelmaking slag, which includes converter slag and electric furnace slag, contains iron (Fe) at 10 to 30 mass% and also contains CaO, which can remove impurities such as sulfur and chloride, at 20 to 50 mass%. Steelmaking slag has a low iron content, so its bulk density is 1600 kg / m. 3 It's a level.

[0004] The heat transfer medium in the gasification reactor used in commercial gasification reactions mainly uses oxides such as alumina, but hollow alumina is also used to separate high-density impurities such as iron and glass mixed with the raw material through the difference in density. Hollow alumina has an apparent density of 900 to 1300 kg / m3, which is lower than the density of general solid impurities, and has the advantage of easy removal within the operating system because the solid impurities settle to the bottom. However, hollow alumina does not act as a catalyst under operating conditions, so there is no change in the reactant composition through additional reactions such as separate cracking. In addition, because the inside is hollow, it is prone to large losses due to breakage from external impact, and it is expensive, so regeneration is essential.

[0005] Accordingly, there is a need for a hydrocarbon manufacturing method and manufacturing system that can efficiently convert high value-added hydrocarbons into high value-added products 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, reducing the loss of heat transfer medium during the gasification reaction, and reducing process operation costs.

[0006] Meanwhile, organic waste can seriously damage the environment through decomposition and other processes during landfill. Therefore, disposal requires sorting by type and following a prescribed treatment process. 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 representative example is the gasification process, which produces synthesis gas from organic waste and converts it into high-value-added products for energy conversion.

[0007] 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" generally 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.

[0008] 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.

[0009] Recently, catalytic gasification processes have been implemented to produce synthesis gas. However, the gasification process has been plagued by problems such as catalyst deactivation caused by coke formation, 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 steps (e.g., air burning), significantly reducing process efficiency.

[0010] 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.

[0011] Accordingly, there is a need for a hydrocarbon manufacturing method and manufacturing system 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.

[0012] According to one aspect of the present disclosure, a method and system for producing hydrocarbons from organic waste can be provided, in which the yield of producing hydrocarbons is significantly improved.

[0013] In addition, according to one aspect of the present disclosure, a method and system for producing hydrocarbons with significantly improved process efficiency can be provided.

[0014] According to another aspect of the present disclosure, a method and system for producing hydrocarbons capable of minimizing the generation of carbon dioxide can be provided.

[0015] According to one aspect of the present disclosure, the production yield of synthesis gas during a gasification reaction can be improved.

[0016] According to one aspect of the present disclosure, loss of a heat transfer medium during a gasification reaction can be reduced.

[0017] According to another aspect of the present disclosure, impurities such as Cl, S, and N can be removed during a gasification reaction.

[0018] According to one aspect of the present disclosure, catalytic reactions such as cracking and dehydrogenation may occur during a gasification reaction.

[0019] According to another aspect of the present disclosure, the cost of operating a gasification process can be reduced.

[0020] The present disclosure comprises the steps of: (S1) heat-treating organic waste in the presence of a heat transfer medium to produce a first mixed gas; (S2) steam reforming the first mixed gas in a first fluidized bed 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 separated in step (S3) into a second fluidized bed reactor and converting it 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; (S6) generating a synthesis gas from the third mixed gas through a water gas shift reaction; And (S7) a step of producing hydrocarbons through a catalytic reaction from the synthesis gas; a method for producing hydrocarbons, comprising: the heat transfer medium containing 1 to 40 mass% of iron (Fe) and 5 to 50 mass% of alkaline earth metal oxide.

[0021] In one embodiment according to the present disclosure, the first mixed gas may further include one or more selected from the group consisting of landfill gas, shale gas, refinery exhaust gas, and biogas.

[0022] In one embodiment according to the present disclosure, the first stream may contain carbon dioxide in an amount of at least 50% by volume.

[0023] In one embodiment according to the present disclosure, the step (S2) may be performed under a composite catalyst in which an active metal is supported on a support.

[0024] In one embodiment according to the present disclosure, the active metal may include one or more selected from the group consisting of nickel, vanadium, iron, platinum, palladium, and ruthenium.

[0025] In one embodiment according to the present disclosure, the support may include at least one selected from the group consisting of silica, alumina, silica-alumina, carbon, zirconia, titania, zeolite, SAPO and ALPO.

[0026] In one embodiment according to the present disclosure, the step (S2) may be performed at a temperature of 700 to 1000°C.

[0027] In one embodiment according to the present disclosure, the step (S4) may be performed at a temperature of 600 to 1000°C and a pressure of 50 to 300 KPa.

[0028] In one embodiment according to the present disclosure, the synthesis gas includes hydrogen and carbon monoxide, and the ratio of hydrogen and carbon monoxide can be satisfied in a range of 1.8:1 to 2.2:1.

[0029] In one embodiment according to the present disclosure, in step (S1), the organic waste may be at least one selected from the group consisting of waste plastic, solid waste, biomass, waste oil, waste tires, and volume-based waste bags.

[0030] In one embodiment according to the present disclosure, the hydrocarbon production method may further include a step of purifying the first mixed gas of the step (S1) prior to the step (S2).

[0031] The present disclosure comprises: a pyrolysis reactor that heat-treats organic waste in the presence of a heat transfer medium to produce a first mixed gas; a first fluidized bed reactor that catalytically steam reforms the first mixed gas 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 second fluidized bed reactor that converts the first stream into carbon monoxide through a reverse Boudouard reaction; a gas mixing unit that mixes the second stream with carbon monoxide converted from the second fluidized bed reactor to produce a third mixed gas; and a synthesis gas generation unit that converts 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 through a catalytic reaction; a hydrocarbon production system is provided, wherein the heat transfer medium contains 1 to 40 mass% of iron (Fe) and 5 to 50 mass% of alkaline earth metal oxide.

[0032] In one embodiment according to the present disclosure, the hydrocarbon production system further includes a cyclone connected between the first fluidized bed reactor and the carbon dioxide separation unit; a catalyst supply line connecting the cyclone and the second fluidized bed reactor; and a catalyst recirculation line connecting the second fluidized bed reactor and the first fluidized bed reactor, wherein the cyclone separates a second mixed gas and a catalyst discharged from the first fluidized bed reactor, supplies the second mixed gas to the carbon dioxide separation unit, and supplies the catalyst to the second fluidized bed reactor.

[0033] In one embodiment according to the present disclosure, the hydrocarbon production system may further include a purification unit between the pyrolysis reactor and the first fluidized bed reactor.

[0034] A method and system for producing hydrocarbons according to one embodiment of the present disclosure can significantly improve the yield of producing hydrocarbons from organic waste through a gasification process utilizing a heat transfer medium containing 1 to 40 mass% of iron (Fe) and 5 to 50 mass% of alkaline earth metal oxide.

[0035] The hydrocarbon production method and production system according to one embodiment of the present disclosure can convert feed into hydrocarbon using a process and device suitable for the C / O element ratio of the feed, thereby significantly improving the production efficiency of the hydrocarbon.

[0036] A hydrocarbon production method and production system according to one embodiment of the present disclosure can minimize the generation of carbon dioxide during a hydrocarbon production process.

[0037] According to one embodiment of the present disclosure, the production yield of synthesis gas during a gasification reaction can be improved.

[0038] A hydrocarbon production method and production system according to another embodiment of the present disclosure can reduce the loss of a heat transfer medium during a gasification reaction.

[0039] The hydrocarbon production method and production system according to one embodiment of the present disclosure can remove impurities such as Cl, S, and N during a gasification reaction.

[0040] In a hydrocarbon production method and production system according to one embodiment of the present disclosure, catalytic reactions such as cracking and dehydrogenation can occur during a gasification reaction.

[0041] A hydrocarbon production method and production system according to one embodiment of the present disclosure can reduce the operating cost of a gasification process.

[0042] A hydrocarbon production method and production system according to one embodiment of the present disclosure can produce hydrocarbons from organic waste in an eco-friendly manner.

[0043] FIG. 1 is a schematic diagram showing a hydrocarbon production system according to one embodiment of the present disclosure.

[0044] FIG. 2 is a schematic diagram showing a hydrocarbon production system including a purification process according to one embodiment of the present disclosure.

[0045] FIG. 3 is a schematic diagram showing a hydrocarbon production system including a catalyst circulation process according to one embodiment of the present disclosure.

[0046] As used herein, the singular forms of terms may be construed to include the plural forms as well, unless otherwise specified.

[0047] 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.

[0048] 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.

[0049] The unit of % used in this specification without special mention means weight % unless otherwise defined.

[0050] 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 becomes inactivated due to the formation of coke, etc., and process troubles occur due to the inactivated 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 system that can efficiently produce hydrocarbons from organic waste while minimizing the amount of carbon dioxide produced.

[0051] The present disclosure comprises the steps of: (S1) heat-treating organic waste in the presence of a heat transfer medium to produce a first mixed gas; (S2) steam reforming the first mixed gas in a first fluidized bed 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 separated in step (S3) into a second fluidized bed reactor and converting it 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; (S6) generating a synthesis gas from the third mixed gas through a water gas shift reaction; And (S7) a step of producing hydrocarbons through a catalytic reaction from the synthesis gas; a method for producing hydrocarbons, comprising: the heat transfer medium containing 1 to 40 mass% of iron (Fe) and 5 to 50 mass% of alkaline earth metal oxide.

[0052] 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.

[0053] The above step (S1) is a step of generating a first mixed gas by heat-treating organic waste in the presence of a heat transfer medium, whereby a gasification reaction of the organic waste can occur.

[0054] 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.

[0055] Specifically, in the step (S1), one or more gasification reactions selected from the following reaction formulas 1 to 4 may be involved.

[0056] [Reaction Formula 1]

[0057] C x H y + H2O →H2+ CO (water gasification reaction)

[0058] [Reaction Formula 2]

[0059] C x H y + CO2→CO (carbon dioxide gasification reaction)

[0060] [Reaction Formula 3]

[0061] CO + 3H2→CH4+ H2O (methanation reaction)

[0062] [Reaction Formula 4]

[0063] C x H y + O2→ CO2 (oxidation reaction)

[0064] In one embodiment according to the present disclosure, the first mixed gas may include methane, hydrogen, carbon monoxide, and carbon dioxide, and may also include various impurities such as nitrogen oxides, sulfur oxides, and hydrogen chloride.

[0065] In one embodiment according to the present disclosure, step (S1) may be performed in the presence of a heat transfer medium. The heat transfer medium may also function as a catalyst in step (S1).

[0066] In one embodiment according to the present disclosure, the heat transfer medium may contain iron (Fe) in an amount of 1 mass% or more, 5 mass% or more, 10 mass% or more, 15 mass% or more, 17 mass% or more, 20 mass% or more, 25 mass% or more, 40 mass% or less, 35 mass% or less, 30 mass% or less, 25 mass% or less, 21 mass% or less, 20 mass% or less, or a value between the above values, and specifically, may contain iron (Fe) in an amount of 1 to 40 mass%, 10 to 30 mass%, 15 to 25 mass%, or 17 to 21 mass%. Since the heat transfer medium contains iron (Fe) in the above amount, it acts as a catalyst during a gasification reaction, so that catalytic reactions such as cracking and dehydrogenation can proceed, thereby increasing the production yield of synthesis gas.

[0067] In one embodiment according to the present disclosure, the heat transfer medium can contain an alkaline earth metal oxide in an amount of 5 mass% or more, 10 mass% or more, 20 mass% or more, 25 mass% or more, 26 mass% or more, 30 mass% or more, 40 mass% or more, 60 mass% or less, 50 mass% or less, 44 mass% or less, 40 mass% or less, 30 mass% or less, or a value between the above values, and specifically, can contain 5 to 50 mass%, 10 to 50 mass%, 20 to 50 mass%, 25 to 45 mass%, or 26 to 44 mass%. Since the heat transfer medium contains an alkaline earth metal oxide in the above content, impurities such as Cl, S, and N can be removed during a gasification reaction.

[0068] The alkaline earth metal may include at least one selected from the group consisting of calcium (Ca), beryllium (Be), magnesium (Mg), strontium (Sr), barium (Ba), and radium (Ra).

[0069] In one embodiment according to the present disclosure, the heat transfer medium can contain magnesium oxide in an amount of 1 mass% or more, 2 mass% or more, 3 mass% or more, 4 mass% or more, 5 mass% or more, 6 mass% or more, 50 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, 8 mass% or less, 7 mass% or less, 6 mass% or less, or a value between the above values, and specifically, 1 to 50 mass%, 1 to 30 mass%, 1 to 10 mass%, or 4 to 8 mass%. Since the heat transfer medium contains magnesium oxide in the above content, impurities such as Cl, S, and N can be removed during a gasification reaction.

[0070] In one embodiment according to the present disclosure, the bulk density of the heat transfer medium is 650 to 2000 kg / m 3 , 1000 to 2000 kg / m 3 , 1300 to 1800 kg / m 3 or 1500 to 1700 kg / m 3 It may be within the range. The heat transfer medium has a lower density than general solid impurities within the range as described above, so it sinks downward and can be easily removed within the driving system.

[0071] In one embodiment according to the present disclosure, the particle size of the heat transfer medium may be 50 to 500 μm. By using a heat transfer medium having a particle size in the above range, fluidization of the particles can be easily performed during a gasification reaction.

[0072] In one embodiment according to the present disclosure, the heat transfer medium may be steelmaking slag. Generally, steelmaking slag is a general term for large amounts of byproducts and waste generated in the steel industry. Steelmaking slag is divided into blast furnace slag and steelmaking slag, and steelmaking slag, including converter slag and electric furnace slag, may be used as a heat transfer medium in one embodiment according to the present disclosure. In this specification, “steelmaking slag” may refer to steel slag generated in the process of manufacturing steel or alloy iron using scrap iron or pig iron in a converter or electric furnace. When steelmaking slag is used as a heat transfer medium, the cost of process operation can be reduced because it is cheaper compared to when hollow alumina, which is commonly used, is used as a heat transfer medium. In addition, steelmaking slag has superior wear characteristics compared to alumina, so that the loss of the heat transfer medium during the gasification reaction can be reduced.

[0073] In order to increase the methane content in the first mixed gas, the first mixed gas may further include one or more selected from the group consisting of 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 steam reforming and reverse Budar reaction.

[0074] In one embodiment according to the present disclosure, the C / O element ratio of the first mixed gas may be, as an upper limit, 15 or less and 4 or less, and as a lower limit, 0.1 or more, 0.15 or more, 0.3 or more, specifically, 0.1 to 15, and more specifically, 0.3 to 4.

[0075] The method for producing hydrocarbons according to the present disclosure enables a steam reforming reaction to be smoothly performed even when the first mixed gas contains a relatively high C / O element ratio within the above-described range. Specifically, since the catalyst used in the steam reforming reaction forms a cyclic process described below, the reaction can be continuously performed regardless of catalyst deactivation due to coke that may be generated during steam reforming.

[0076] In one example, the step (S1) may further include a step of purifying the first mixed gas.

[0077] 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.

[0078] 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.

[0079] In one embodiment according to the present disclosure, step (S2) is a step of producing a second mixed gas by steam reforming methane contained in a first mixed gas in a first fluidized bed reactor. In step (S2), a reforming reaction according to the following reaction formula 5 may be performed.

[0080] [Reaction Formula 5]

[0081] CH4+ H2O →CO + 3H2 (steam reforming reaction)

[0082] The reforming reaction of the above step (S2) can be performed at a temperature of 600 to 1400°C and a pressure of 30 to 2000 KPa.

[0083] 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 600 to 700°C. The catalyst of the above step (S2) may be a composite catalyst in which an active metal is supported on a support. The active metal may include at least one selected from the group consisting of nickel, vanadium, iron, platinum, palladium, and ruthenium. Typically, the active metal may be nickel, vanadium, or iron, and in cases where the raw material, such as organic waste, has a low impurity content during the heat treatment process, a precious metal such as platinum, palladium, or ruthenium may be used.

[0084] In one embodiment according to the present disclosure, the support may be a solid acid material such as an oxide or a zeolite, and specifically, may be at least one selected from the group consisting of ZSM-5, ZSM-11, USY zeolite, Ferrierite, Mordenite, MCM-22, SUZ-4, L-type zeolite, silica, alumina, silica-alumina, carbon, zirconia, and titania.

[0085] The above steam reforming reaction may be performed in a first fluidized bed reactor. Furthermore, the above steam reforming reaction may be performed in a first fixed bed reactor. In this case, the reverse reaction, described later, may be performed in a second fixed bed reactor.

[0086] As step (S2) is performed in the first fluidized bed reactor, the catalyst can be regenerated and then supplied to the subsequent reverse catalytic reaction process, forming a circulation process. As the steam reforming reaction is performed in step (S2), coke may accumulate on the catalyst, which may deactivate the catalytic reaction. However, since step (S2) is performed in the first fluidized bed reactor, a circulation process of regenerating and resupplying the catalyst can be performed, continuous reforming reaction is possible even during steam reforming.

[0087] (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.

[0088] 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 a 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.

[0089] 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 that the second mixed gas can be separated into first and second streams using the CCS unit (carbon capture and storage unit).

[0090] 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 a range 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, which consumes more energy. Therefore, since the first stream contains carbon dioxide in the above-described range, the carbon dioxide separation process can be performed under slightly milder conditions.

[0091] Step (S4) is a step for converting the first stream separated in step (S3) into carbon monoxide through a reverse Buta reaction in a second fluidized bed reactor. By additionally converting the carbon dioxide contained in the first stream into carbon monoxide through the reverse Buta reaction, it is possible to prevent environmental pollution by reducing carbon dioxide emissions, while also maximizing the yield of synthesis gas. The reverse Buta reaction may involve the following reaction scheme 6.

[0092] [Reaction Formula 6]

[0093] C+CO2→ 2CO

[0094] The above step (S4) can be performed at a temperature of 600 to 1000°C and a pressure of 50 to 300 KPa.

[0095] In one example, the carbon source for the reverse reaction in step (S4) may be the catalyst on which coke is deposited supplied in step (S2), and may be supplied from outside, such as activated carbon, as needed.

[0096] Referring to FIG. 3, the second synthesis gas discharged from the first fluidized bed reactor (20) is supplied to the second fluidized bed reactor (40) where the reverse Buta reaction is performed through a catalyst supply line after the catalyst is separated by a cyclone (90). In the second fluidized bed reactor (40), the catalyst is regenerated by reacting as a carbon source for the reverse Buta reaction, and the regenerated catalyst is supplied back to the first fluidized bed reactor (20) through a recirculation line. By utilizing this catalyst circulation process, the methane reforming reaction can be performed continuously, and since there is no need to supply a carbon source required for the reverse Buta reaction from the outside, the process can be performed economically.

[0097] That is, the present disclosure can maximize the yield of synthesis gas through methane reforming reaction and reverse Buta reaction, and at the same time, continuous and economical process operation according to catalyst regeneration can be implemented as the first fluidized bed reactor and the second fluidized bed reactor in which the methanation reforming reaction and reverse Buta reaction are performed form a circulation process.

[0098] 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).

[0099] The third mixed gas may include hydrogen and carbon monoxide.

[0100] 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.

[0101] [Chemical Formula 7]

[0102] CO + H2O → H2 + CO2

[0103] 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 to 400°C, specifically 100 to 300°C, and at a pressure of 20 to 80 bar, specifically 25 to 70 bar.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] [Chemical Formula 8]

[0109] nCO + 2nH2→C n H 2n + nH2O

[0110] 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.

[0111] The Fischer-Tropsch reaction can be carried out at a temperature of 100 to 500°C, specifically 200 to 350°C, and a pressure of 10 to 50 atm, and 10 to 30 atm.

[0112] 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.

[0113] The reaction for converting synthesis gas into methanol may be a reaction involving the following chemical formula 9.

[0114] [Chemical Formula 9]

[0115] CO + 2H2→ CH3OH

[0116] 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 a Cu-based methanol-based synthesis catalyst, and the support of the Cu-based catalyst can use at least one selected from the group consisting of SiO2, ZrO2, Ga2O3Al2O3, MgO, and TiO2. Specifically, the Cu-based methanol-based synthesis catalyst can be Cu / Zn / Al2O3.

[0117] The reaction of converting the above synthesis gas into methanol can be performed at 400 to 600°C, specifically 430 to 530°C, and 0.1 to 10 MPa, specifically 0.1 to 5 MPa.

[0118] 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 silicoalumina phosphate (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.

[0119] The reaction of converting methanol into olefin can be carried out at a temperature of 200 to 600°C, specifically 300 to 500°C, and a pressure of 1 to 10 bar, specifically 1 to 5 bar.

[0120] Additionally, the present disclosure provides a hydrocarbon production system. The description of the hydrocarbon production method can be equally applied to the hydrocarbon production system, within the overlapping scope.

[0121] The present disclosure comprises: a pyrolysis reactor that heat-treats organic waste in the presence of a heat transfer medium to produce a first mixed gas; a first fluidized bed reactor that catalytically steam reforms the first mixed gas 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 second fluidized bed reactor that converts the first stream into carbon monoxide through a reverse Boudouard reaction; and a gas mixing unit that mixes the second stream with carbon monoxide converted from the second fluidized bed reactor to produce a third mixed gas; a synthesis gas generation unit that converts 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 through a catalytic reaction; a hydrocarbon production system is provided, wherein the heat transfer medium contains 1 to 40 mass% of iron (Fe) and 5 to 50 mass% of alkaline earth metal oxide.

[0122] The hydrocarbon production system (1) according to the present disclosure can efficiently and economically produce synthesis gas (230) and hydrocarbons by using a fluidized bed reactor when performing heat treatment, steam reforming reaction, and reverse Budar reaction in the presence of a heat transfer medium, and can significantly reduce carbon dioxide emissions.

[0123] Referring to Fig. 1, organic waste (100) is introduced into a pyrolysis reactor (10) in which a heat transfer medium exists, and a first mixed gas (110) is generated after heat treatment. The first mixed gas (110) is introduced into a first fluidized bed reactor (20) and converted into a second mixed gas (220) through a dry reforming reaction.

[0124] In one example, the hydrocarbon production system may further include a purification unit (80) connected between the pyrolysis reactor (10) and the first fluidized bed reactor (20). Specifically, referring to FIG. 2, the first mixed gas (110) is introduced into the purification unit (80) to remove impurities, and the first mixed gas (120) from which impurities have been removed is introduced into the first fluidized bed reactor (20) to perform a methane reforming reaction.

[0125] 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.

[0126] The second mixed gas is introduced into 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. The second stream is directly supplied to a gas mixing unit (50), and the first stream is supplied to a second fluidized bed reactor (40) and converted into carbon monoxide through a reverse Budah reaction.

[0127] In one example, the method further comprises: a cyclone connected between the first fluidized bed reactor and the carbon dioxide separation unit; a catalyst supply line connecting the cyclone and the second fluidized bed reactor; and a catalyst recirculation line connecting the second fluidized bed reactor and the first fluidized bed reactor, wherein the cyclone separates a second mixed gas discharged from the fluidized bed reforming reactor and a catalyst, supplies the second mixed gas to the carbon dioxide separation unit, and supplies the catalyst to the second fluidized bed reactor.

[0128] The hydrocarbon production system of the present disclosure enables continuous process operation based on catalyst regeneration, as the first and second fluidized bed reactors described above form a circulating process. Furthermore, the coke-deposited catalyst supplied from the first fluidized bed reactor can be utilized without the need for a separate carbon source for performing the reverse Buta reaction in the second fluidized bed reactor, enabling more economical process operation.

[0129] The gas mixing unit (50) mixes the second steam (211) and carbon monoxide converted in the second fluidized bed reactor (40) to produce a third mixed gas (220). The third mixed gas (220) is supplied to the water gas conversion unit (60) and converted into a synthesis gas (230) by adjusting the hydrogen:carbon monoxide ratio in the third mixed gas through a water gas conversion reaction.

[0130] 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.

[0131] 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.

[0132] In one example, the hydrocarbon production system may further include a separation step that separates the produced hydrocarbons into fractions by boiling point through distillation connected to the hydrocarbon conversion unit (70).

[0133] Hereinafter, embodiments of the present disclosure 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 disclosure and do not limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications to the examples are possible within the scope and technical idea of ​​the present disclosure, and it is also natural that such changes and modifications fall within the scope of the appended claims.

[0134] (Example 1)

[0135] After putting 1000g of municipal solid waste into the pyrolysis reactor, the specific gravity was 2.63 and the apparent density was 1620 kg / m. 3 In the presence of steelmaking slag, temperature 800℃, pressure 4 bar, operating time 120 minutes and 3L / g cat · Steam was introduced under h conditions and heat treatment was performed to recover the first mixed gas having a C / O element ratio of 0.7. The composition of the steelmaking slag is shown in Table 1.

[0136] Steelmaking slag composition by mass %SiO221.5CaO44.1Al2O33.5Fe17.0MgO7.7MnO3.7TiO22.5

[0137] The first mixed gas was lowered in temperature and introduced into a purification unit (wet scrubber) to be treated at 70°C and 100KPa to remove impurities, and the purified first mixed gas was recovered. As a result of treating the first mixed gas through the wet scrubber, impurity gases such as NH3, HCl, H2S, and COS were not analyzed, confirming that the impurities were effectively removed.

[0138] The first mixed gas from which the above impurities have been removed is fed to a first fluidized bed reactor equipped with a Ni / Al2O3 catalyst at a rate of 2 L / g cat ·The second mixed gas was produced through steam reforming by supplying it at a space velocity of h.

[0139] 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.

[0140] 100g of the above Ni / Al2O3 catalyst is charged into the first fluidized bed 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 steam reforming reaction was carried out under the operating conditions of CH4 / H2O = 3 with an h treatment volume, and the second mixed gas was recovered.

[0141] After separating the catalyst from the second mixed gas of the first fluidized bed 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 a 12 wt% amine solution containing MEA (Monoethanolamine) dissolved therein 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.

[0142] The recovered first stream was fed into the second fluidized bed reactor and converted into carbon monoxide through the reverse Buta reaction. The reverse Buta reaction was performed by supplying the first stream to the second fluidized bed reactor and simultaneously continuously supplying high purity graphite to the first fluidized bed reactor at 750°C and a throughput of 2.0 L / g under the Ni / Al2O3 spent catalyst. cat ·The process was performed under h operating conditions. The activated catalyst, after removing coke through the reverse Buta reaction, was reintroduced into the first fluidized bed reactor through a recycle line. Unconverted CO2 after the reverse Buta reaction was separately recovered through an amine scrubber.

[0143] Carbon monoxide converted from the first stream and the second stream are introduced into a gas mixing unit and mixed at 200°C to produce a third mixed gas.

[0144] The third mixed gas is fed into the synthesis gas generation unit and is produced under the Cu / Zn / Al2O3 catalyst at 165 ℃, 35 bar, throughput 1.4 L / g cat · Synthesis gas with a molar ratio of H2:CO=2:1 was produced through a water-gas shift reaction performed under operating conditions of h.

[0145] The synthesis gas is passed through the above amine scrubber to remove carbon dioxide and then supplied to the hydrocarbon conversion unit, where it is heated to a space velocity of 5000 L / kg under a Co / ZnO (Cobalt Zinc oxide) catalyst. cat ·h and carbon monoxide: hydrogen: argon volumes were set to have a volume ratio of 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 fraction.

[0146] (Comparative Example 1)

[0147] Hydrocarbons were produced and recovered in the same manner as in Example 1, except that alumina beads, instead of steelmaking slag, were used as a heat transfer medium.

[0148] (Experimental Example 1) Gas composition analysis

[0149] When producing hydrocarbons by the methods of Example 1 and Comparative Example 1, the compositions of the gases contained in the first mixed gas, the second mixed gas, the third mixed gas, and the synthesis gas from which impurities were removed were analyzed and shown in Table 2 below, and the compositions of the major components contained in the hydrocarbons produced therefrom were analyzed and shown in Table 3. The gas composition analysis was performed through gas chromatography (GC), and the total amount of gas was confirmed through a gas meter. Specifically, the selectivity for each gas was calculated by quantifying through GC, and the composition for each gas was analyzed through the total amount of gas confirmed through the gas meter.

[0150] Composition Example 1 Comparative Example 1 First mixed gas with impurities removed (mol%) H2 9.5 3 2 CO2 8.4 16 CO2 4 0.5 4 0 CH4 2 1.6 1 Second mixed gas (mol%) H2 6 2.7 5 1.8 CO6 0.8 4 1.8 CO2 29.5 2 5.7 CH4 0.2 ...

[0151] Example 1 Comparative Example 1 Gas (g) 703585 Liquid, Wax (g) 449382 H2O (g) 689579

[0152] As shown in Tables 2 and 3 above, when a gasification reaction was performed in the presence of steelmaking slag using the method of Example 1 to produce hydrocarbons, not only did the production of synthesis gas and hydrocarbons produced therefrom increase, but also high-quality synthesis gas could be obtained.

[0153] Specifically, the synthesis gas of Example 1, which was manufactured sequentially through steam reforming, reverse Budar reaction, and water gas shift processes, was measured to have high H2 and CO contents of 116.9 mol% and 58.5 mol%, respectively. In addition, as the synthesis gas manufacturing yield was improved, the liquid yield of the hydrocarbon manufactured using the synthesis gas was high at 449 g. Therefore, the hydrocarbon manufacturing method of the present disclosure can manufacture high value-added synthesis gas and hydrocarbon from a mixed gas obtained by pyrolyzing organic waste at a high yield, and at the same time, it has an excellent environmental pollution prevention effect because it reduces greenhouse gas emissions.

[0154] On the other hand, in the case of Comparative Example 1, since the gasification reaction was carried out in the presence of alumina rather than steelmaking slag, the amount of synthesis gas obtained was smaller than in Example 1, and the hydrocarbon fraction yield was also low at 382 g.

[0155] That is, when producing hydrocarbons by performing a gasification reaction in the presence of steelmaking slag as in the method according to the present disclosure, it can be confirmed that the process efficiency is improved, so that synthesis gas and hydrocarbons can be produced at a high yield.

[0156] (Experimental Example 2) Attrition index analysis

[0157] Cold attrition index (CAI) analysis was performed on the steelmaking slag of Example 1 and the alumina beads of Comparative Example 1 according to ASTM D5757. Before the experiment, only particles sized 45 to 150 μm were separated, analyzed, and the attrition index was calculated according to the following formula. The results are shown in Table 4.

[0158] Attrition index = [Increase in fine particles (< 20 um) before and after the experiment] / Initial sample amount] x 100 (%)

[0159] Example 1 Comparative Example 1 Wear Index 2.15.7

[0160] The analysis results showed that the wear index of alumina beads was 5.7, while that of steelmaking slag was 2.1, confirming that the wear characteristics of steelmaking slag were superior to those of alumina, and thus, when used as a heat transfer medium for gasification reactions, losses during operation could be reduced.

[0161] Although the present disclosure has been described with specific details and limited examples, these are provided only to help a more general understanding of the present disclosure, and the present disclosure is not limited to the above examples, and those skilled in the art to which the present disclosure pertains can make various modifications and variations based on these descriptions.

[0162] Therefore, the spirit of the present disclosure should not be limited to the described embodiments, and all things that are equivalent or equivalent to the following claims as well as the claims are considered to fall within the scope of the spirit of the present disclosure.

[0163] 1 Hydrocarbon production system

[0164] 10 Pyrolysis Reactor

[0165] 20 First fluidized bed reactor

[0166] 30 carbon dioxide separation units

[0167] 40 Second fluidized bed reactor

[0168] 50 gas mixing units

[0169] 60 synthesis gas generation units

[0170] 70 hydrocarbon conversion units

[0171] 80 refined units

[0172] 90 cyclone

[0173] 100 organic waste

[0174] 110 First mixed gas

[0175] 120 First mixed gas with impurities removed

[0176] 200 Second mixed gas

[0177] 210 First Stream

[0178] 211 Second Stream

[0179] 220 Third mixed gas

[0180] 230 Syngas

Claims

1. (S1) A step of generating a first mixed gas by heat treating organic waste in the presence of a heat transfer medium; (S2) A step of generating a second mixed gas by steam reforming the first mixed gas in a first fluidized bed 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 separated in the above step (S3) into a second fluidized bed reactor and converting it into carbon monoxide through a reverse Boudouard reaction; (S5) A step of producing 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 method for producing hydrocarbons, comprising: a step of producing hydrocarbons through a catalytic reaction from the above synthesis gas; A method for producing hydrocarbons, wherein the heat transfer medium contains 1 to 40 mass% of iron (Fe) and 5 to 50 mass% of alkaline earth metal oxide.

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

3. In paragraph 1, A method for producing hydrocarbons, wherein the first stream contains carbon dioxide in an amount of 50% by volume or more.

4. In paragraph 1, A method for producing hydrocarbons, wherein the above step (S2) is performed under a composite catalyst in which an active metal is supported on a support.

5. In paragraph 4, A method for producing hydrocarbons, wherein the active metal comprises at least one selected from the group consisting of nickel, vanadium, iron, platinum, palladium, and ruthenium.

6. In paragraph 5, A method for producing hydrocarbons, wherein the support comprises at least one selected from the group consisting of silica, alumina, silica-alumina, carbon, zirconia, titania, zeolite, SAPO and ALPO.

7. In paragraph 1, A method for producing hydrocarbons, wherein the above step (S2) is performed at a temperature of 700 to 1000°C.

8. In paragraph 1, A method for producing hydrocarbons, wherein the above step (S4) is performed at a temperature of 600 to 1000°C and a pressure of 50 to 300 KPa.

9. In paragraph 1, A method for producing hydrocarbons, wherein the above synthesis gas contains hydrogen and carbon monoxide, and the ratio of hydrogen and carbon monoxide satisfies 1.8:1 to 2.2:

1.

10. In paragraph 1, A method for producing hydrocarbons, wherein in the step (S1), the organic waste is at least one selected from the group consisting of waste plastic, solid waste, biomass, waste oil, waste tires, and volume-based waste bags.

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

12. A pyrolysis reactor that heat-treats organic waste in the presence of a heat transfer medium to produce a first mixed gas; A first fluidized bed reactor that generates a second mixed gas by subjecting the first mixed gas to a steam reforming reaction under a catalyst; 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 second fluidized bed reactor that converts the first stream into carbon monoxide through a reverse Boudouard reaction; and A gas mixing unit that produces a third mixed gas by mixing the second stream and carbon monoxide converted from the second fluidized bed reactor; A synthesis gas generation unit that converts the third mixed gas into synthesis gas through a water gas shift reaction; and A hydrocarbon production system comprising a hydrocarbon conversion unit that converts the above-mentioned synthesis gas into hydrocarbon through a catalytic reaction; A hydrocarbon production system, wherein the heat transfer medium contains 1 to 40 mass% of iron (Fe) and 5 to 50 mass% of alkaline earth metal oxide.

13. In paragraph 12, The above hydrocarbon production system, A cyclone connected between the first fluidized bed reactor and the carbon dioxide separation unit; A catalyst supply line connecting the above cyclone and the second fluidized bed reactor; and It further includes a catalyst recirculation line connecting the second fluidized bed reactor and the first fluidized bed reactor, A hydrocarbon production system in which the cyclone separates the second mixed gas and catalyst discharged from the first fluidized bed reactor, supplies the second mixed gas to a carbon dioxide separation unit, and supplies the catalyst to the second fluidized bed reactor.

14. In paragraph 12, A hydrocarbon production system further comprising a purification unit between the above pyrolysis reactor and the first fluidized bed reactor.

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