Hydrocarbon preparation methods and systems

Abstract

This invention provides a method for preparing hydrocarbons, the method comprising the following steps: (S1) heat-treating organic waste in the presence of a heat transfer medium to generate a first mixed gas; (S2) reforming the first mixed gas with steam in a first fluidized bed 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) feeding the first stream separated in step (S3) into a second fluidized bed reactor and converting it into carbon monoxide via a reverse Boudouar reaction; (S5) mixing the second stream with the carbon monoxide converted in step (S4) to prepare a third mixed gas; (S6) generating syngas from the third mixed gas via a water-gas shift reaction; and (S7) generating hydrocarbons from the syngas via a catalytic reaction, wherein the heat transfer medium contains 1 to 40% by mass of iron (Fe) and 5 to 50% by mass of alkaline earth metal oxides.

Description

Technical Field

[0001] This invention relates to a method and system for preparing hydrocarbons from organic waste, and more specifically, to a method and system for preparing hydrocarbons that can improve the yield of hydrocarbons prepared from organic waste and minimize carbon dioxide production. Background Technology

[0002] Steelmaking slag is a collective term for the large amount of by-products and waste generated in the ironmaking industry. It accounts for about 50% of the total steel production and contains a large amount of recyclable resources such as iron, carbon, and limestone.

[0003] Steelmaking slag is divided into blast furnace slag and steelmaking slag. Blast furnace slag contains almost no iron (Fe), while steelmaking slag, including converter slag and electric arc furnace slag, contains 10% to 30% by mass of iron (Fe) and 20% to 50% by mass of CaO, from which impurities such as sulfur (S) and chloride (Cl) can be removed. Steelmaking slag has a low iron content and a bulk density of 1600 kg / m³. 3 level.

[0004] In commercial gasification reactors, the heat transfer medium primarily uses oxides such as alumina. Hollow alumina is also used to separate high-density impurities such as iron products and glass mixed in with the raw materials through density differences. The bulk density of hollow alumina is 900-1300 kg / m³. 3 The alumina content is lower than that of typical solid impurities, causing them to settle and making it easy to remove within the operating system. However, hollow alumina does not act as a catalyst under operating conditions and cannot alter the reactant composition through additional reactions such as decomposition (cracking). Furthermore, due to its hollow structure, it suffers significant losses from breakage caused by external impacts, and is also expensive, thus requiring regeneration.

[0005] Therefore, there is a need for a method and system for preparing hydrocarbons that can improve the production yield of syngas that can be converted into high-value-added products in the gasification process of organic waste, effectively convert it into high-value-added hydrocarbons, minimize carbon dioxide production, reduce heat transfer medium loss during gasification reaction, and lower process operating costs.

[0006] Furthermore, organic waste can severely damage the environment due to decomposition during landfilling. Therefore, it needs to be collected according to its different properties and disposed of through prescribed treatment processes. However, simple disposal of organic waste requires ensuring treatment facilities and consuming a large amount of manpower, and is more wasteful than production. Therefore, methods and technologies for recycling organic waste have been developed in recent years. A representative technology is the gasification process technology that utilizes organic waste to produce syngas and convert it into high-value-added products for energy conversion.

[0007] Gasification processes typically refer to a series of processes that convert carbonaceous raw materials such as coal, organic waste, and biomass into syngas containing hydrogen and carbon monoxide by reacting them with a supply of steam, oxygen, carbon dioxide, or a mixture thereof. In this case, "syngas" usually refers to a mixed gas generated through a gasification reaction that contains hydrogen and carbon monoxide, and may further contain carbon dioxide and / or methane.

[0008] Gasification technology has expanded to produce feedstocks and fuels for various compounds. For example, syngas can be used as a feedstock in the Fischer-Tropsch synthesis reaction to produce high-value-added products such as light oils, heavy oils, diesel fuel, waxes, aviation fuels, and lubricating oil bases. Furthermore, hydrogen from syngas, a major byproduct of gasification processes, is known to be used in hydrogen power generation, ammonia production, and oil refining processes. Methanol produced from syngas can also be used to obtain high-value-added chemical substances such as acetic acid, olefins, dimethyl ethers, aldehydes, fuels, and additives. However, the yield of syngas derived from organic waste is extremely low, making it difficult to efficiently produce high-value-added compounds from syngas.

[0009] In recent years, catalyst-based gasification processes have been developed for the production of syngas. However, the generation of coke and other contaminants during gasification leads to catalyst deactivation, causing process failures during continuous operation. Furthermore, to ensure economic viability, it is necessary to recover the relatively expensive catalyst. However, recovering catalysts emitted in a state of coke buildup requires multiple subsequent processes (such as air burning), resulting in a significant reduction in process efficiency.

[0010] Furthermore, conventional organic waste gasification processes suffer from significantly low yields of syngas, which can be converted into high-value-added products (below 30%), thus reducing productivity and limiting their application and commercialization. Moreover, while suppressing CO2 emissions is preferable from an environmental perspective, the gasification products of organic waste contain CO2 in addition to H2 and CO. This results in higher carbon dioxide emissions compared to landfill or pyrolysis treatments, potentially leading to further environmental pollution.

[0011] Therefore, there is a need for a method and system for preparing hydrocarbons that can improve the yield of syngas that can be converted into high-value-added products during the gasification process of organic waste, thereby efficiently converting it into high-value-added hydrocarbons while minimizing the generation of carbon dioxide. Summary of the Invention

[0012] (a) Technical problems to be solved According to one aspect of the present invention, a method and system for preparing hydrocarbons from organic waste can be provided, which significantly improves the yield of hydrocarbons.

[0013] Furthermore, according to one aspect of the present invention, a method and system for preparing hydrocarbons with significantly improved process efficiency can be provided.

[0014] According to another aspect of the present invention, a method and system for preparing hydrocarbons that can minimize the generation of carbon dioxide can be provided.

[0015] According to one aspect of the present invention, the yield of syngas preparation during the gasification reaction can be improved.

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

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

[0018] According to one aspect of the invention, catalytic reactions such as decomposition (cracking) and dehydrogenation can be carried out during the gasification reaction.

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

[0020] (II) Technical Solution This invention provides a method for preparing hydrocarbons, the method comprising the following steps: (S1) heat-treating organic waste in the presence of a heat transfer medium to generate a first mixed gas; (S2) reforming the first mixed gas with steam in a first fluidized bed 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) feeding the first stream separated in step (S3) into a second fluidized bed reactor and converting it into carbon monoxide via a reverse Boudouar reaction; (S5) mixing the second stream with the carbon monoxide converted in step (S4) to prepare a third mixed gas; (S6) generating syngas from the third mixed gas via a water-gas shift reaction; and (S7) generating hydrocarbons from the syngas via a catalytic reaction, wherein the heat transfer medium contains 1-40% by mass of iron (Fe) and 5-50% by mass of alkaline earth metal oxides.

[0021] In one embodiment of the invention, the first mixed gas may further include one or more selected from landfill gas, shale gas, refinery waste gas and biogas.

[0022] In one embodiment of the invention, the first feed stream may contain more than 50% by volume of carbon dioxide.

[0023] In one embodiment of the invention, step (S2) can be carried out on a composite catalyst with an active metal supported on a support.

[0024] In one embodiment of the invention, the active metal may include one or more selected from nickel, vanadium, iron, platinum, palladium and ruthenium.

[0025] In one embodiment of the invention, the carrier may include one or more selected from silica, alumina, silica-alumina, carbon, zirconium oxide, titanium dioxide, zeolite, SAPO, and ALPO.

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

[0027] In one embodiment of the invention, step (S4) can be performed at a temperature of 600°C to 1000°C and a pressure of 50 kPa to 300 kPa.

[0028] In one embodiment of the invention, the synthesis gas may comprise hydrogen and carbon monoxide, wherein the ratio of hydrogen to carbon monoxide may be between 1.8:1 and 2.2:1.

[0029] In one embodiment of the present invention, the organic waste in step (S1) may be one or more selected from waste plastics, solid waste, biomass, waste oil, waste tires and metered garbage bags.

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

[0031] This invention provides a hydrocarbon preparation system, comprising: a pyrolysis reactor, wherein the pyrolysis reactor heat-treats organic waste in the presence of a heat transfer medium to generate a first mixed gas; a first fluidized bed reactor, wherein the first fluidized bed reactor performs a steam reforming reaction on the first mixed gas in the presence of a catalyst to generate a second mixed gas; a carbon dioxide separation unit, wherein the carbon dioxide separation unit separates the second mixed gas into a first feed stream containing carbon dioxide and a second feed stream containing hydrogen and carbon monoxide; and a second fluidized bed reactor, wherein the second fluidized bed reactor is... The process includes: a first feed stream converted to carbon monoxide via a reverse Boudouar reaction; a gas mixing unit that mixes the second feed stream with the carbon monoxide converted in the second fluidized bed reactor to prepare a third mixed gas; a syngas generation unit that converts the third mixed gas into syngas via a water-gas shift reaction; and a hydrocarbon conversion unit that converts the syngas into hydrocarbons via a catalytic reaction, wherein the heat transfer medium contains 1-40% by mass of iron (Fe) and 5-50% by mass of alkaline earth metal oxides.

[0032] In one embodiment of the invention, the hydrocarbon preparation system may further include: a cyclone separator connected between the first fluidized bed reactor and the carbon dioxide separation unit; a catalyst supply line connected between the cyclone separator and the second fluidized bed reactor; and a catalyst recirculation line connected between the second fluidized bed reactor and the first fluidized bed reactor, wherein the cyclone separator can separate a second mixed gas discharged from the first fluidized bed reactor and the catalyst, supply the second mixed gas to the carbon dioxide separation unit, and supply the catalyst to the second fluidized bed reactor.

[0033] In one embodiment of the invention, the hydrocarbon preparation system may further include a refining unit between the pyrolysis reactor and the first fluidized bed reactor.

[0034] (III) Beneficial Effects According to one embodiment of the present invention, the method and system for preparing hydrocarbons can significantly improve the yield of hydrocarbons prepared from organic waste by utilizing a gasification process with a heat transfer medium containing 1% to 40% by mass of iron (Fe) and 5% to 50% by mass of alkaline earth metal oxides.

[0035] According to one embodiment of the present invention, the method and system for preparing hydrocarbons can be converted into hydrocarbons using appropriate processes and equipment based on the C / O element ratio of the feed, thereby significantly improving the hydrocarbon preparation efficiency.

[0036] The method and system for preparing hydrocarbons according to one embodiment of the present invention can minimize the generation of carbon dioxide during the preparation of hydrocarbons.

[0037] According to one embodiment of the present invention, the yield of syngas preparation during the gasification reaction can be improved.

[0038] The method and system for preparing hydrocarbons according to another embodiment of the present invention can reduce the loss of heat transfer medium during the gasification reaction.

[0039] The method and system for preparing hydrocarbons according to one embodiment of the present invention can remove impurities such as Cl, S, and N during the gasification reaction.

[0040] According to one embodiment of the present invention, the method and system for preparing hydrocarbons can perform catalytic reactions such as decomposition (cracking) and dehydrogenation during the gasification reaction.

[0041] The method and system for preparing hydrocarbons according to one embodiment of the present invention can reduce the operating cost of gasification processes.

[0042] The method and system for preparing hydrocarbons according to one embodiment of the present invention can produce hydrocarbons from organic waste in an environmentally friendly manner. Attached Figure Description

[0043] Figure 1 A schematic diagram illustrating a hydrocarbon preparation system according to one embodiment of the present invention.

[0044] Figure 2 This is a schematic diagram illustrating a hydrocarbon preparation system including a refining process according to one embodiment of the present invention.

[0045] Figure 3 This is a schematic diagram illustrating a hydrocarbon preparation system including a catalyst recycling process according to one embodiment of the present invention. Detailed Implementation

[0046] Unless otherwise specified, the singular form of the terms used in this specification may be interpreted to also include the plural form.

[0047] The numerical ranges used in this specification include lower and upper limits, as well as all values ​​within that range, all values ​​defined therein, and all possible combinations of upper and lower limits of numerical ranges defined in different forms. Unless otherwise specifically defined in this specification, values ​​outside the defined numerical range that may arise due to experimental error or rounding are also included within the defined numerical ranges.

[0048] The terms “comprising” or “including” used in this specification are open-ended expressions that have the same meaning as expressions such as “possessing,” “containing,” “having,” “characterized in,” etc., and do not exclude elements, materials, or processes not further listed.

[0049] Unless otherwise defined, the units of % used in this specification refer to weight unless otherwise specified.

[0050] Conventional syngas production processes utilize catalyst-based gasification. However, catalyst deactivation due to the generation of coke and other contaminants leads to process failures during continuous operation. Furthermore, to ensure economic viability, relatively expensive catalysts need to be recovered. However, recovering catalysts emitted in aggregated states like coke requires multiple subsequent processes (such as air combustion), significantly reducing process efficiency and resulting in substantial carbon dioxide emissions and environmental pollution. Moreover, conventional organic waste gasification processes achieve syngas yields significantly lower than 30%, reducing productivity and limiting the conversion into high-value-added products. Therefore, the inventors of this invention have designed a method and system for efficiently producing hydrocarbons from organic waste while minimizing carbon dioxide emissions.

[0051] This invention provides a method for preparing hydrocarbons, the method comprising the following steps: (S1) heat-treating organic waste in the presence of a heat transfer medium to generate a first mixed gas; (S2) reforming the first mixed gas with steam in a first fluidized bed 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) feeding the first stream separated in step (S3) into a second fluidized bed reactor and converting it into carbon monoxide via a reverse Boudouar reaction; (S5) mixing the second stream with the carbon monoxide converted in step (S4) to prepare a third mixed gas; (S6) generating syngas from the third mixed gas via a water-gas shift reaction; and (S7) generating hydrocarbons from the syngas via a catalytic reaction, wherein the heat transfer medium contains 1-40% by mass of iron (Fe) and 5-50% by mass of alkaline earth metal oxides.

[0052] Compared to existing gasification processes, the hydrocarbon preparation method according to the present invention can efficiently convert organic waste plastics into syngas, thereby maximizing the yield of high-value-added hydrocarbons converted from syngas. Furthermore, the carbon dioxide generated during syngas preparation can be converted into syngas feedstock, minimizing carbon dioxide production during hydrocarbon preparation and thus preventing environmental pollution.

[0053] The step (S1) is to heat-treat the organic waste in the presence of a heat transfer medium to generate a first mixed gas, in which the gasification reaction of the organic waste may occur.

[0054] In one instance, the organic waste in step (S1) can be selected from one or more of waste plastics, solid waste, biomass, waste oil, waste tires, or metered garbage bags.

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

[0056] [Reaction Formula 1] C x H y +H2O H2 + CO (water-coal gasification reaction) [Reaction 2] C x H y +CO2 CO (carbon dioxide vaporization reaction) [Reaction 3] CO + 3H2 CH4 + H2O (Methanation reaction) [Reaction 4] C x H y +O2 CO2 (oxidation reaction) In one embodiment of the present invention, the first mixed gas may contain methane, hydrogen, carbon monoxide and carbon dioxide, and may also contain various impurities such as nitrogen oxides, sulfur oxides, and hydrogen chloride.

[0057] In one embodiment of the invention, step (S1) can be performed in the presence of a heat transfer medium. The heat transfer medium can also function as a catalyst in step (S1).

[0058] In one embodiment of the present invention, the heat transfer medium may contain iron (Fe) in amounts of 1% or more, 5% or more, 10% or more, 15% or more, 17% or more, 20% or more, 25% or more, less than 40% or less, less than 35% or less, less than 30% or less, less than 25% or less, less than 21% or less, or less than 20% or less, or within the range of the above values. Specifically, it may contain 1-40% by mass, 10-30% by mass, 15-25% by mass, or 17-21% by mass. Since the heat transfer medium contains iron (Fe) in the above-mentioned amounts, it can act as a catalyst during the gasification reaction, enabling catalytic reactions such as decomposition (cracking) and dehydrogenation, thereby improving the yield of syngas.

[0059] In one embodiment of the present invention, the heat transfer medium may contain 5% or more, 10% or more, 20% or more, 25% or more, 26% or more, 30% or more, 40% or more, less than 60% or less, less than 50% or less, less than 44% or less, less than 40% or less, less than 30% or less, or within the range of the above values ​​of alkaline earth metal oxides. Specifically, it may contain 5-50% by mass, 10-50% by mass, 20-50% by mass, 25-45% by mass, or 26-44% by mass of alkaline earth metal oxides. Since the heat transfer medium contains the above-mentioned amounts of alkaline earth metal oxides, impurities such as Cl, S, and N can be removed during the gasification reaction.

[0060] The alkaline earth metal may include at least one selected from calcium (Ca), beryllium (Be), magnesium (Mg), strontium (Sr), barium (Ba), and radium (Ra).

[0061] In one embodiment of the present invention, the heat transfer medium may contain magnesium oxide in amounts of 1% or more, 2% or more, 3% or more, 4% or more, 5% or more, 6% or more, less than 50% or less, less than 40% or less, less than 30% or less, less than 20% or less, less than 15% or less, less than 10% or less, less than 8% or less, less than 7% or less, less than 6% or less, or within the range of the above values. Specifically, it may contain 1-50% or 1-30% or 1-10% or 4-8% magnesium oxide. Since the heat transfer medium contains magnesium oxide in the above-mentioned amounts, impurities such as Cl, S, and N can be removed during the gasification reaction.

[0062] In one embodiment of the present invention, the bulk density of the heat transfer medium can be 650-2000 kg / m³. 3 1000-2000kg / m 3 1300-1800 kg / m 3 Or 1500-1700 kg / m 3 The heat transfer medium falls within the aforementioned range, therefore its density is lower than that of ordinary solid impurities, causing it to settle downwards and making it easily removed within the operating system.

[0063] In one embodiment of the invention, the particle size of the heat transfer medium can be 50-500 μm. Using a heat transfer medium with a particle size within the above range allows for smooth particle flow during the gasification reaction.

[0064] In one embodiment of the invention, the heat transfer medium may be steelmaking slag. Generally, steelmaking slag is a collective term for the large quantities of byproducts and waste generated in the ironmaking industry. Steelmaking slag is divided into blast furnace slag and steelmaking slag. In one embodiment of the invention, steelmaking slag comprising converter slag and electric furnace slag can be used as the heat transfer medium. In this specification, "steelmaking slag" can refer to the slag produced in a converter or electric furnace during the manufacture of iron and steel / ferroalloys from scrap steel or pig iron. Using steelmaking slag as the heat transfer medium is less expensive than using conventionally used hollow alumina, thus reducing process operating costs. Furthermore, compared to alumina, steelmaking slag has superior wear resistance, thus reducing heat transfer medium loss during the gasification reaction.

[0065] To increase the methane content in the first mixed gas, the first mixed gas may further contain one or more selected from landfill gas, shale gas, refinery waste gas, and biogas. The aforementioned landfill gas, shale gas, refinery waste gas, and biogas contain at least 40% by volume of methane and carbon dioxide, specifically, at least 50% by volume of methane and carbon dioxide. Therefore, by further containing the aforementioned gases, the first mixed gas has the effect of further improving the syngas production yield through subsequent processes such as steam reforming and the reverse Boudouar reaction.

[0066] In one embodiment of the present invention, the upper limit of the C / O element ratio of the first mixed gas can be less than 15 or less than 4, and the lower limit can be more than 0.1, more than 0.15, or more than 0.3, specifically from 0.1 to 15, and more specifically from 0.3 to 4.

[0067] According to the method for preparing hydrocarbons of the present invention, even if the first mixed gas contains a relatively high C / O element ratio as described above, a steam reforming reaction can be carried out smoothly. Specifically, by forming a recycling process with the catalyst used in the steam reforming reaction, the reaction can be carried out continuously without being affected by catalyst deactivation caused by coke that may be generated during steam reforming.

[0068] In one instance, after step (S1), a further step of purifying the first mixed gas may be included.

[0069] The first mixed gas generated from the thermal treatment of organic waste may contain one or more impurities selected from tar, sulfur, nitrogen, and chlorine. Specifically, the first mixed gas may contain water-soluble impurities such as H2S, HCl, HOCl, and NH3, as well as non-water-soluble impurities such as tar. These impurities in the first mixed gas can cause catalyst deactivation, potentially reducing the efficiency of subsequent processes. Therefore, removing impurities from the first mixed gas and refining it can improve the overall process efficiency.

[0070] The method for purifying the first mixed gas can be selected from one or more combinations of high-pressure dust collection filters, water washing, alkaline solution washing, and passing through ceramic filters, but is not limited to these. When using water washing or alkaline solution washing, water-soluble impurities such as H2S, HCl, HOCl, and NH3 contained in the first mixed gas can be removed. When the first mixed gas is passed through ceramic filters or dust collection filters, non-water-soluble impurities such as tar and dust can be removed.

[0071] In one embodiment of the invention, step (S2) is a step of steam reforming the methane contained in the first mixed gas in the first fluidized bed reactor to prepare the second mixed gas. Step (S2) may be accompanied by a reforming reaction according to the following reaction formula 5.

[0072] [Reaction 5] CH4+H2O CO + 3H₂ (steam reforming reaction) The reforming reaction in step (S2) can be carried out at a temperature of 600°C to 1400°C and a pressure of 30 kPa to 2000 kPa.

[0073] Step (S2) can be performed without a catalyst, but can be performed using a catalyst to improve the reaction conversion rate at low temperatures of 600°C to 700°C. The catalyst for step (S2) can be a composite catalyst with an active metal supported on a carrier. The active metal can contain one or more selected from nickel, vanadium, iron, platinum, palladium, and ruthenium. Nickel, vanadium, or iron are typically used as the active metal; however, when the impurity content in the raw materials, such as organic waste, is low during the heat treatment process, precious metals such as platinum, palladium, or ruthenium can be used.

[0074] In one embodiment of the present invention, the support may be a solid acid substance such as an oxide or zeolite. Specifically, the support may be one or more selected from ZSM-5, ZSM-11, USY zeolite, Ferrite, Mordenite, MCM-22, SUZ-4, L-type zeolite, silica, alumina, silica-alumina, carbon, zirconium oxide, and titanium dioxide.

[0075] The steam reforming reaction can be carried out in a first fluidized bed reactor. Alternatively, the steam reforming reaction can also be carried out in a first fixed bed reactor. In this case, the reverse Boudouar reaction described below can be carried out in a second fixed bed reactor.

[0076] As step (S2) is carried out in the first fluidized bed reactor, a cyclic process can be formed in which the catalyst is regenerated in the subsequent process, namely the reverse Boudouar reaction process, and then resupplyed. While steam reforming may occur in step (S2), potentially leading to catalytic deactivation, the fact that step (S2) is carried out in the first fluidized bed reactor allows for catalyst regeneration and resupply in a cyclic process, thus enabling continuous reforming even with steam reforming.

[0077] Step (S3) is to separate the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide.

[0078] In one example, the method for separating the second mixed gas into the first and second streams is not limited as long as it is a known method. However, in this invention, a carbon dioxide separation unit can be used for separation, and the carbon dioxide separation unit can be an amine scrubber. Typically, amine scrubbers use amine substances to bind and remove carbon dioxide, and can separate components such as carbon dioxide and hydrogen sulfide from gas vapors. They can also recover gases containing hydrogen, carbon monoxide, or inert gases. Therefore, using an amine scrubber can separate the first mixed gas into the first and second streams.

[0079] As another example, the carbon dioxide separation unit can be a carbon capture and storage unit (CCS). When a CCS unit is used in the separation of carbon dioxide, the CCS unit can adsorb and separate carbon dioxide by utilizing one or more adsorbents selected from calcium oxide, calcium hydroxide, dolomite, limestone or natural alkali. Therefore, the CCS unit can be used to separate the second mixed gas into the first stream and the second stream.

[0080] The lower limit of the carbon dioxide content in the first feed stream can be 40% by volume or more, 50% by volume or more, or 60% by volume or more, and the upper limit of the carbon dioxide content in the first feed stream can be less than 99% by volume, less than 90% by volume, less than 80% by volume, or less than 70% by volume. Specifically, the first feed stream can contain 40% by volume to 99% by volume of carbon dioxide, and more specifically, it can contain 50% by volume to 80% by volume of carbon dioxide. In the carbon dioxide separation unit, when carbon dioxide is captured and then separated, in order to separate carbon dioxide with high purity, the regeneration tower in which carbon dioxide separation occurs in the adsorbent needs to be designed with a high number of trays, thus consuming more energy. Therefore, by having the first feed stream contain carbon dioxide within the above-mentioned range, the carbon dioxide separation process can be carried out under milder conditions.

[0081] Step (S4) involves converting the first feed stream separated in step (S3) into carbon monoxide via a reverse Boudouar reaction in the second fluidized bed reactor. By further converting the carbon dioxide contained in the first feed stream into carbon monoxide via the reverse Boudouar reaction, environmental pollution can be prevented by reducing carbon dioxide emissions, while simultaneously maximizing the yield of syngas. The reverse Boudouar reaction can be represented by the following reaction formula 6.

[0082] [Reaction Formula 6] C + CO2 2CO The step (S4) can be carried out at a temperature of 600°C to 1000°C and a pressure of 50 kPa to 300 kPa.

[0083] In one example, the carbon supply source for the reverse Boudouar reaction in step (S4) can be the catalyst with deposited coke supplied in step (S2), and activated carbon or the like can be received from the outside as needed.

[0084] Reference Figure 3 The second syngas discharged from the first fluidized bed reactor 20 is separated from the catalyst by a cyclone separator 90 and supplied to the second fluidized bed reactor 40, where the reverse Boudouar reaction takes place, via a catalyst supply line. In the second fluidized bed reactor 40, the catalyst is regenerated by reacting as a carbon source for the reverse Boudouar reaction, and the regenerated catalyst is supplied back to the first fluidized bed reactor 20 via a recirculation line. This catalyst recycling process allows for continuous methane reforming without requiring an external carbon source for the reverse Boudouar reaction, thus enabling an economical process.

[0085] That is, the present invention can maximize the yield of syngas through methane reforming and reverse Boudouar reaction. The first fluidized bed reactor and the second fluidized bed reactor, which carry out methane reforming and reverse Boudouar reaction at the same time, form a cycle process, thus achieving continuous and economical process operation through catalyst regeneration.

[0086] Step (S5) is to mix the second feed stream separated in the carbon dioxide separation unit with the carbon monoxide converted by the reverse Boudouar reaction in step (S4) to prepare the third mixed gas.

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

[0088] Step (S6) is a process of adjusting the ratio of carbon monoxide to hydrogen in the third mixed gas through a water-gas shift reaction to generate syngas. The third mixed gas can be converted through a water-gas shift reaction to achieve a hydrogen:carbon monoxide ratio suitable for the catalytic reaction in subsequent processes. The water-gas shift reaction can be represented by the following reaction formula 7.

[0089] [Reaction Formula 7] CO + H₂O H2+CO2 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 temperatures ranging from 100°C to 400°C, specifically from 100°C to 300°C, and at bar levels ranging from 20 bar to 80 bar, specifically from 25 bar to 70 bar.

[0090] The hydrogen to carbon monoxide ratio in the syngas generated by the water-gas shift reaction can be from 1.5 to 3:1, specifically from 1.9 to 2.1:1. When the hydrogen to carbon monoxide ratio in the syngas meets the above range, the catalytic reaction for subsequent processes can proceed smoothly.

[0091] Step (S7) is the step of converting the syngas generated in step (S6) into hydrocarbon fractions, which can be converted into appropriate hydrocarbon fractions through catalytic reaction.

[0092] The catalytic reaction is not limited as long as it can convert syngas into hydrocarbon fractions, but it can specifically be a Fischer-Tropsch synthesis reaction or a methanol-olefin conversion reaction.

[0093] In one instance, when the catalytic reaction in step (S7) is a Fischer-Tropsch synthesis reaction, the syngas generated in step (S6) can be used as a raw material to carry out a reaction accompanied by the following reaction formula 8.

[0094] [Reaction Equation 8] nCO + 2nH2 C n H 2n +nH2O The Fischer-Tropsch synthesis reaction can be carried out in the presence of a catalyst containing cobalt, nickel or iron. The support may include alumina, silica, titanium dioxide, etc., and the co-catalyst may include noble metals such as Pt, Ru, Re.

[0095] The Fischer-Tropsch synthesis reaction can be carried out at temperatures ranging from 100°C to 500°C, specifically from 200°C to 350°C, and at pressures ranging from 10 atm to 50 atm, specifically from 10 atm to 30 atm.

[0096] In one instance, when the catalytic reaction in step (S7) is a methanol-olefin conversion reaction, step (S7) may include: a reaction to convert syngas into methanol; and a reaction to convert methanol into olefins.

[0097] The reaction that converts syngas into methanol can be represented by the following reaction equation 9.

[0098] [Reaction Formula 9] CO + 2H₂ CH3OH In one example, the reaction of converting syngas into methanol can be carried out under a Cu-based catalyst. Specifically, the Cu-based catalyst can be a Cu-based methanol synthesis catalyst, and the support for the Cu-based catalyst can be one or more selected from SiO2, ZrO2, Ga2O3, Al2O3, MgO, and TiO2. Specifically, the Cu-based methanol synthesis catalyst can be Cu / Zn / Al2O3.

[0099] The reaction of converting the synthesis gas into methanol can be carried out at 400°C to 600°C, specifically at 430°C to 530°C, and at 0.1 MPa to 10 MPa, specifically at 0.1 MPa to 5 MPa.

[0100] The reaction of methanol to olefins can be carried out under zeolite-based catalysts or AlPO4-based molecular sieve catalysts. Specifically, the molecular sieve-based catalyst can be ZSM-5, and the AlPO4-based catalyst can be a silica-aluminaphosphate (SAPO) molecular sieve catalyst, specifically selected from one or more of 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.

[0101] The reaction that converts methanol to olefins can be carried out at temperatures ranging from 200°C to 600°C, specifically from 300°C to 500°C, and at pressures ranging from 1 bar to 10 bar, specifically from 1 bar to 5 bar.

[0102] Furthermore, this invention provides a hydrocarbon preparation system. The description of the hydrocarbon preparation method also applies to the hydrocarbon preparation system, to the extent necessary.

[0103] This invention provides a hydrocarbon preparation system, comprising: a pyrolysis reactor, wherein the pyrolysis reactor heat-treats organic waste in the presence of a heat transfer medium to generate a first mixed gas; a first fluidized bed reactor, wherein the first fluidized bed reactor performs a steam reforming reaction on the first mixed gas in the presence of a catalyst to generate a second mixed gas; a carbon dioxide separation unit, wherein the carbon dioxide separation unit separates the second mixed gas into a first feed stream containing carbon dioxide and a second feed stream containing hydrogen and carbon monoxide; and a second fluidized bed reactor, wherein the second fluidized bed reactor is... The process includes: a first feed stream converted to carbon monoxide via a reverse Boudouar reaction; a gas mixing unit that mixes the second feed stream with the carbon monoxide converted in the second fluidized bed reactor to prepare a third mixed gas; a syngas generation unit that converts the third mixed gas into syngas via a water-gas shift reaction; and a hydrocarbon conversion unit that converts the syngas into hydrocarbons via a catalytic reaction, wherein the heat transfer medium contains 1-40% by mass of iron (Fe) and 5-50% by mass of alkaline earth metal oxides.

[0104] According to the hydrocarbon preparation system 1 of the present invention, when heat treatment, steam reforming reaction and reverse Boudouar reaction are carried out in the presence of a heat transfer medium, syngas 230 and hydrocarbons can be produced efficiently and economically by using a fluidized bed reactor, and carbon dioxide emissions can be significantly reduced.

[0105] Reference Figure 1 Organic waste 100 is introduced into a pyrolysis reactor 10 containing a heat transfer medium, and after heat treatment, a first mixed gas 110 is generated. The first mixed gas 110 flows into a first fluidized bed reactor 20 and is converted into a second mixed gas 220 through a dry reforming reaction.

[0106] In one example, the hydrocarbon preparation system may further include a refining unit 80 connected between the pyrolysis reactor 10 and the first fluidized bed reactor 20. Specifically, see... Figure 2 The first mixed gas 110 flows into the refining unit 80 to remove impurities, and the first mixed gas 120 after removing impurities is introduced into the first fluidized bed reactor 20, so that the methane reforming reaction can be carried out.

[0107] The refining unit 80 includes an injector for spraying liquid, receives a first mixed gas 110 from the pyrolysis reactor 10, and contacts the first mixed gas 110 with water or a weakly alkaline solution containing sodium carbonate to remove water-soluble impurities such as H2S, HCl, HOCl and NH3. Alternatively, a high-pressure dust collector can be used to remove dust, and non-water-soluble impurities such as tar can be removed by means of a ceramic filter.

[0108] The second mixed gas flows into the carbon dioxide separation unit 30 and is separated into a first feed stream 210 containing carbon dioxide and a second feed stream 211 containing hydrogen and carbon monoxide. The second feed stream is directly supplied to the gas mixing unit 50, and the first feed stream is supplied to the second fluidized bed reactor 40, thereby being converted into carbon monoxide through the reverse Boudouar reaction.

[0109] In one example, the hydrocarbon preparation system may further include: a cyclone separator connected between the first fluidized bed reactor and the carbon dioxide separation unit; a catalyst supply line connected between the cyclone separator and the second fluidized bed reactor; and a catalyst recirculation line connected between the second fluidized bed reactor and the first fluidized bed reactor, wherein the cyclone separator can separate a second mixed gas discharged from the fluidized bed reformer and the catalyst, supply the second mixed gas to the carbon dioxide separation unit, and supply the catalyst to the second fluidized bed reactor.

[0110] In the hydrocarbon preparation system of the present invention, the first and second fluidized bed reactors form a circulating process, thus enabling continuous process operation through catalyst regeneration. Furthermore, instead of separately supplying a carbon source for the reverse Boudouar reaction to the second fluidized bed reactor, a coke-deposited catalyst supplied from the first fluidized bed reactor can be utilized, thus achieving more economical process operation.

[0111] The gas mixing unit 50 mixes the second feed stream 211 with the carbon monoxide converted in the second fluidized bed reactor 40 to prepare a third mixed gas 220. The third mixed gas 220 is supplied to the water-gas conversion unit 60, and the hydrogen:carbon monoxide ratio in the third mixed gas is adjusted by the water-gas shift reaction, thereby converting it into syngas 230.

[0112] Syngas 230 can be introduced into hydrocarbon conversion unit 70 and converted into hydrocarbons through Fischer-Tropsch synthesis or methanol and olefin conversion, and recovered as high-value-added fractions.

[0113] 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 and an olefin conversion unit, wherein the methanol conversion unit receives syngas 230 and converts it into methanol, and the olefin conversion unit receives methanol from the methanol conversion unit and converts it into olefins.

[0114] In one example, the hydrocarbon preparation system may further include a separation unit connected to the hydrocarbon conversion unit 70, which separates the generated hydrocarbons into different fractions according to their boiling points by distillation.

[0115] The embodiments of the present invention will be further described below with reference to specific experimental examples. The embodiments and comparative examples included in the experimental examples are only for illustrating the present invention and are not intended to limit the claims. Various changes and modifications to the embodiments within the scope and technical concept of the present invention will be obvious to those skilled in the art, and these variations and modifications should naturally fall within the scope of the claims.

[0116] (Example 1) 1000g of municipal solid waste was added to a pyrolysis reactor, and then subjected to a specific gravity of 2.63 and a bulk density of 1620kg / m³. 3 In the presence of steelmaking slag, at a temperature of 800℃, a pressure of 4 bar, a running time of 120 minutes, and a concentration of 3 L / g... 催化剂 Steam was introduced and heat-treated under conditions of 1 hour, and a first mixed gas with a C / O ratio of 0.7 was recovered. The composition of the steelmaking slag is shown in Table 1.

[0117] [Table 1] The first mixed gas was cooled and added to a purification unit (wet scrubber) for treatment at 70°C and 100 kPa to remove impurities, thereby recovering the purified first mixed gas. The results of treating the first mixed gas by the wet scrubber showed that no impurity gases such as NH3, HCl, H2S, and COS were detected, confirming that impurities were effectively removed.

[0118] At 2L / g 催化剂 At a space velocity of 1 hour, the first mixed gas, after impurity removal, is supplied to a first fluidized bed reactor equipped with a Ni / Al2O3 catalyst, and a second mixed gas is prepared by steam reforming.

[0119] The Ni / Al2O3 fluidized bed catalyst was prepared according to the following steps. Based on 100 parts by weight of water, 10 parts by weight of pseudo-boehmite alumina and 95 parts by weight of nickel nitrate hexahydrate were mixed to obtain a mixed solution. While stirring the mixed solution, 1 part by weight of formic acid was added, and the reaction was carried out for 3 hours to gel, thus preparing a precursor gel. 30 parts by weight of clay and 1.5 parts by weight of MgO oxide were added, and the resulting solid mixture was mixed with the precursor gel using a homogenizer. Then, 10 parts by weight of colloidal silica (Ludox AS40, Aldrich) was added, followed by 5 parts by weight of water. The mixture was stirred vigorously to prepare a composite catalyst sol. The composite catalyst sol was spray-dried to prepare the fluidized bed catalyst.

[0120] 100 g of the Ni / Al₂O₃ catalyst was packed into the first fluidized bed reactor, and H₂ was supplied at 900 °C at a flow rate of 3.03 Nl / min for 2 hours for reduction. Then, purified first mixed gas was introduced at a total flow rate of 3.33 Nl / min, and the concentration was increased to 2.0 L / g. 催化剂 • The steam reforming reaction is carried out under the operating conditions of hourly processing capacity and CH4 / H2O=3, and the second mixed gas is recovered.

[0121] The catalyst is separated from the second mixed gas in the first fluidized bed reactor using a cyclone separator, and then CO2 is separated using an amine scrubber. The second feed stream, which contains both catalyst and CO2, is then recovered. Specifically, the second mixed gas flows into the first amine scrubber, where CO2 is captured by a 12% by weight amine solution containing monoethanolamine (MEA) dissolved at 50°C. The uncaptured gas is recovered as the second feed stream. The amine solution from the first amine scrubber flows into the second amine scrubber, where it is separated into an amine solution and CO2 at 100°C. The CO2 is recovered as the first feed stream.

[0122] The recovered first feed stream flows into the second fluidized bed reactor, where it is converted into carbon monoxide via a reverse Boudouar reaction. The reverse Boudouar reaction is carried out as follows: the first feed stream is supplied to the second fluidized bed reactor simultaneously with a continuous supply of high-purity graphite, using spent Ni / Al₂O₃ catalyst from the first fluidized bed reactor, at 750°C and a throughput of 2.0 L / g. 催化剂The reaction was carried out under 24-hour operating conditions. The catalyst, activated by removing coke through the reverse Boudouar reaction, was reintroduced into the first fluidized bed reactor via a recirculation line. Unconverted CO2 after the reverse Boudouar reaction was recovered separately via an amine scrubber.

[0123] The carbon monoxide converted from the first feed stream and the second feed stream flow into the gas mixing unit and are mixed at 200°C to generate the third mixed gas.

[0124] The third mixed gas flows into the syngas generation unit, and is processed at 165°C, 35 bar, and a throughput of 1.4 L / g under a Cu / Zn / Al2O3 catalyst. 催化剂 Syngas with a molar ratio of H2:CO of 2:1 was prepared by water-gas shift reaction under operating conditions for 2 hours.

[0125] Syngas is passed through the amine scrubber to remove carbon dioxide and then supplied to the hydrocarbon conversion unit at a rate of 5000 L / kg under a cobalt / zinc oxide (Co / ZnO) based catalyst. 催化剂 • The space velocity was set to an injection rate such that the volume ratio of carbon monoxide:hydrogen:argon was 63.2:31.3:5.5, and the Fischer-Tropsch synthesis reaction was carried out for 60 hours at a reaction temperature of 300°C and a pressure of 10 bar, and the hydrocarbon fraction was recovered.

[0126] (Comparative Example 1) Hydrocarbons were prepared and recovered using the same method as in Example 1, except that alumina beads were used as the heat transfer medium instead of steelmaking slag.

[0127] (Experimental Example 1) Analysis of Gas Composition The compositions of the gases contained in the first, second, and third mixed gases and the synthesis gas, obtained by removing impurities during the preparation of hydrocarbons using the methods of Example 1 and Comparative Example 1, are analyzed and shown in Table 2 below. The compositions of the major components contained in the hydrocarbons thus prepared are analyzed and shown in Table 3. Gas composition analysis was performed by gas chromatography (GC), and the total amount of gas was confirmed by a gas meter. Specifically, quantification was performed by GC to calculate the selectivity of different gases, and the composition of each gas was analyzed by the total amount of gas confirmed by the gas meter.

[0128] [Table 2] [Table 3] As shown in Tables 2 and 3 above, when preparing hydrocarbons by gasification reaction in the presence of steelmaking slag using the method of Example 1, not only can the yield of syngas and the yield of hydrocarbons prepared from the syngas be increased, but also high-quality syngas can be obtained.

[0129] Specifically, the syngas from Example 1, prepared sequentially through steam reforming, reverse Boudouar reaction, and water-gas shift process, showed high H2 and CO contents, at 116.9 mol% and 58.5 mol%, respectively. Furthermore, with the increase in syngas production yield, the yield of hydrocarbon fraction (liquid) produced using the syngas reached as high as 449 g. Therefore, the hydrocarbon production method of the present invention can produce high-value-added syngas and hydrocarbons in high yield from a mixed gas obtained by the pyrolysis of organic waste, while simultaneously reducing greenhouse gas emissions, thus exhibiting excellent environmental pollution prevention effects.

[0130] On the other hand, in the case of Comparative Example 1, the gasification reaction was carried out in the presence of alumina instead of steelmaking slag, so the amount of syngas obtained was less than that in Example 1, and the amount of hydrocarbon fraction obtained was as low as 382g.

[0131] That is, when hydrocarbons are prepared by gasification reaction in the presence of steelmaking slag as per the method according to the invention, the process efficiency is improved, and it can be confirmed that syngas and hydrocarbons can be prepared in high yield.

[0132] (Experimental Example 2) Analysis of Attrition Index According to ASTM D5757, the cold attrition index was analyzed for the steelmaking slag of Example 1 and the alumina beads of Comparative Example 1. Only particles of 45–150 μm were separated for attrition index analysis before the experiment, and the results were calculated using the following formula. The results are shown in Table 4 below.

[0133] Wear index = [[Increase in fine particles (<20μm) before and after the experiment] / Initial sample amount] × 100 (%) [Table 4] The analysis results show that the wear index of the alumina beads was 5.7, while the wear index of the steelmaking slag was 2.1. This confirms that the steelmaking slag has better wear resistance than alumina and can reduce losses during operation when used as a heat transfer medium for gasification reaction.

[0134] As described above, the present invention has been illustrated with specific content and limited embodiments, but this is only provided to help to understand the present invention more fully. The present invention is not limited to the above embodiments, and those skilled in the art can make various modifications and variations based on these descriptions.

[0135] Therefore, the concept of this invention should not be limited to the illustrated embodiments, and all contents of the claims of this invention and those equivalent to or having equivalent variations thereof are within the scope of the concept of this invention.

[0136] 1 Hydrocarbon Preparation System 10. Pyrolysis reactor 20. Fluidized Bed Reactor No. 1 30 Carbon Dioxide Separation Units 40. Fluidized Bed Reactor No. 2 50 Gas Mixing Unit 60 Syngas Generation Unit 70 Hydrocarbon Conversion Unit 80 Refined Units 90 Cyclone Separator 100 Organic waste 110 First Mixed Gas 120 First mixed gas for removing impurities 200 Second Mixed Gas 210 First Material Flow 211 Second Material Flow 220 Third Mixed Gas 230 Syngas

Claims

1. A method for preparing a hydrocarbon, wherein, The preparation method includes the following steps: (S1) The organic waste is heat-treated in the presence of a heat transfer medium to generate a first mixed gas; (S2) The first mixed gas is reformed with steam in the first fluidized bed reactor to generate the second mixed gas; (S3) Separate the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; (S4) The first material stream separated in step (S3) is fed into the second fluidized bed reactor and converted into carbon monoxide through the reverse Boudouar reaction; (S5) The second feed stream is mixed with the carbon monoxide converted in step (S4) to prepare the third mixed gas; (S6) Syngas is generated from the third mixed gas via a water-gas shift reaction; and (S7) Hydrocarbons are generated from the syngas via a catalytic reaction. The heat transfer medium contains 1-40% by mass of iron (Fe) and 5-50% by mass of alkaline earth metal oxides.

2. The method for preparing hydrocarbons according to claim 1, wherein, The first mixed gas further includes one or more selected from landfill gas, shale gas, refinery waste gas, and biogas.

3. The method for preparing hydrocarbons according to claim 1, wherein, The first feed stream contains more than 50% by volume carbon dioxide.

4. The method for preparing hydrocarbons according to claim 1, wherein, The step (S2) is carried out in the presence of a composite catalyst with an active metal supported on a support.

5. The method for preparing hydrocarbons according to claim 4, wherein, The active metal includes one or more selected from nickel, vanadium, iron, platinum, palladium and ruthenium.

6. The method for preparing hydrocarbons according to claim 5, wherein, The carrier includes one or more selected from silicon dioxide, alumina, silicon dioxide-alumina, carbon, zirconium oxide, titanium dioxide, zeolite, SAPO, and ALPO.

7. The method for preparing hydrocarbons according to claim 1, wherein, The step (S2) is performed at a temperature of 700°C to 1000°C.

8. The method for preparing hydrocarbons according to claim 1, wherein, The step (S4) is carried out at a temperature of 600°C to 1000°C and a pressure of 50 kPa to 300 kPa.

9. The method for preparing hydrocarbons according to claim 1, wherein, The synthesis gas comprises hydrogen and carbon monoxide, wherein the ratio of hydrogen to carbon monoxide is between 1.8:1 and 2.2:

1.

10. The method for preparing hydrocarbons according to claim 1, wherein, In step (S1), the organic waste is selected from one or more of the following: waste plastics, solid waste, biomass, waste oil, waste tires, and metered garbage bags.

11. The method for preparing hydrocarbons according to claim 1, wherein, Prior to step (S2), the process further includes a step of purifying the first mixed gas from step (S1).

12. A hydrocarbon preparation system, wherein, The hydrocarbon preparation system includes: A pyrolysis reactor, wherein organic waste is thermally treated in the presence of a heat transfer medium to generate a first mixed gas; A first fluidized bed reactor, wherein the first mixed gas is reformed with steam in the presence of a catalyst to generate a second mixed gas; A carbon dioxide separation unit separates the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide. The second fluidized bed reactor converts the first feed stream into carbon monoxide via a reverse Boudouar reaction; A gas mixing unit that mixes the second feed stream with carbon monoxide converted in the second fluidized bed reactor to prepare a third mixed gas; Syngas generation unit, wherein the syngas generation unit converts the third mixed gas into syngas through a water-gas shift reaction; and A hydrocarbon conversion unit that converts the syngas into hydrocarbons via a catalytic reaction. The heat transfer medium contains 1-40% by mass of iron (Fe) and 5-50% by mass of alkaline earth metal oxides.

13. The hydrocarbon preparation system according to claim 12, wherein, The hydrocarbon preparation system further includes: A cyclone separator is connected between the first fluidized bed reactor and the carbon dioxide separation unit; A catalyst supply line connecting the cyclone separator and the second fluidized bed reactor; and A catalyst recirculation line, which connects the second fluidized bed reactor and the first fluidized bed reactor, The cyclone separator separates the second mixed gas and the 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.

14. The hydrocarbon preparation system according to claim 12, wherein, A refining unit is further included between the pyrolysis reactor and the first fluidized bed reactor.

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