Methods and apparatus for preparing hydrocarbons

Abstract

This invention provides a method for preparing hydrocarbons, the method comprising the following steps: S1) pyrolyzing mixed waste to generate a first mixed gas; S2) reforming the first mixed gas (after removing impurities) in a first fluidized bed reactor with steam to prepare 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 and the carbon monoxide converted in step S4) to generate a third mixed gas, and preparing syngas from the third mixed gas via a water-gas shift reaction; and S6) generating hydrocarbons from the syngas via a catalytic reaction.

Description

Technical Field

[0001] This invention relates to a method and apparatus for preparing hydrocarbons from organic waste, specifically, to a method and apparatus for preparing hydrocarbons by using a catalyst with high activity and durability to improve hydrocarbon conversion yield during a reforming reaction of a mixed gas containing impurities. Background Technology

[0002] Organic waste can severely damage the environment during landfilling due to decomposition, requiring collection based on its specific characteristics and proper disposal through prescribed processes. However, simple disposal of organic waste necessitates the establishment of treatment facilities and consumes significant manpower, resulting in greater waste compared to production processes. Therefore, methods and technologies for recycling organic waste have been developed in recent years. A representative technology is the gasification process, which utilizes organic waste to produce syngas and convert it into high-value-added products for energy conversion.

[0003] Gasification typically refers to a series of processes that convert carbonaceous feedstocks 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.

[0004] 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.

[0005] In recent years, catalyst-based gasification processes have been used to produce 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, relatively expensive catalysts need to be recovered. However, recovering catalysts emitted in aggregated states like coke requires multiple subsequent processes (such as air burning), resulting in a significant reduction in process efficiency. Moreover, the mixed gas obtained from the pyrolysis of organic waste contains not only hydrogen, carbon monoxide, and carbon dioxide, but also water-soluble impurities such as H2S, HCl, HOCl, and NH3, as well as insoluble impurities like tar. This can lead to catalyst deactivation in subsequent syngas production processes, reducing the efficiency of these processes. Purification due to these issues may further decrease the overall process efficiency.

[0006] 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.

[0007] Therefore, there is still a need to develop a method and apparatus for preparing hydrocarbons that can selectively and efficiently remove the various impurities contained in the pyrolysis mixture of organic waste, improve the yield of syngas, and thus efficiently convert it into high-value-added hydrocarbons while minimizing the generation of carbon dioxide. Summary of the Invention

[0008] (a) Technical problems to be solved According to one aspect of the present invention, a method for preparing hydrocarbons by reforming a mixed gas containing impurities such as Cl, S, and N recovered during the gasification process of waste can be provided.

[0009] According to one aspect of the present invention, a method and apparatus for preparing hydrocarbons can be provided, comprising a catalyst that exhibits enhanced reactivity and durability even in a mixed gas containing impurities.

[0010] According to one aspect of the present invention, a method and apparatus for preparing hydrocarbons can be provided, which can reform mixed gases in an environmentally friendly and stable manner, even for mixed gases containing impurities.

[0011] According to one aspect of the present invention, a method and apparatus for preparing hydrocarbons with high added value can be provided for preparing syngas from organic waste, thereby preventing climate change by suppressing pollution and greenhouse gas emissions, and for recycling such hydrocarbons.

[0012] (II) Technical Solution The method for preparing hydrocarbons according to the present invention includes the following steps: S1) pyrolyzing mixed waste to generate a first mixed gas; S2) reforming the first mixed gas (after removing impurities) in a first fluidized bed reactor with steam to prepare 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 through a reverse boudouard reaction; S5) mixing the second stream and the carbon monoxide converted in step S4) to generate a third mixed gas, and preparing syngas from the third mixed gas through a water-gas shift reaction; and S6) generating hydrocarbons from the syngas through a catalytic reaction.

[0013] In one example, steps S2) and S4) may be carried out with a catalyst containing: a first metal comprising a Group VIIIA element, a Group VIA element, or a combination thereof; and a second metal comprising an alkaline earth metal oxide or an alkaline earth metal oxide structure.

[0014] In one instance, the first mixed gas may further include one or more selected from landfill gas, shale gas, refinery waste gas, and biogas.

[0015] In one example, the second fluidized bed reactor in step S4) may receive the coking catalyst from the first fluidized bed reactor in step S2) as a carbon source.

[0016] In one instance, the first feed stream may contain more than 50% by volume carbon dioxide.

[0017] In one example, the C / O element ratio of the pyrolysis gas can be 0.1 or higher.

[0018] In one instance, step S2) can be performed at a temperature of 700°C to 1000°C.

[0019] In one instance, step S4) can be performed at a temperature of 600°C to 1000°C and a pressure of 50 kPa to 300 kPa.

[0020] In one example, the synthesis gas in step S5) may contain hydrogen and carbon monoxide, and the ratio of hydrogen to carbon monoxide may be between 1.8:1 and 2.2:1.

[0021] In one example, the organic waste in step S1) can be selected from one or more of waste plastics, solid waste, biomass, waste oil, waste tires and metered garbage bags.

[0022] This invention includes a hydrocarbon preparation apparatus.

[0023] The hydrocarbon preparation apparatus according to the present invention comprises: a pyrolysis reactor that thermally treats organic waste to generate a first mixed gas; a first fluidized bed reactor that performs a steam reforming reaction on the first mixed gas to generate 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 via a reverse Boudouar reaction; a gas mixing unit that mixes the second 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.

[0024] In one example, the first fluidized bed reactor and the second fluidized bed reactor may contain a catalyst comprising: a first metal comprising elements of Group VIII, Group VIA, or combinations thereof from the periodic table; and a second metal comprising an alkaline earth metal oxide or an alkaline earth metal oxide structure.

[0025] In one example, the hydrocarbon preparation apparatus 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, can supply the second mixed gas to the carbon dioxide separation unit, and can supply the catalyst to the second fluidized bed reactor.

[0026] (III) Beneficial Effects According to one embodiment of the present invention, by introducing a catalyst with excellent reactivity and durability, hydrocarbons can be produced with high efficiency even with mixed gases containing impurities without the occurrence of rapid catalyst deactivation.

[0027] According to one embodiment of the present invention, mixed gases containing impurities such as Cl, N, and S can be reformed in an environmentally friendly and stable manner.

[0028] According to one embodiment of the present invention, hydrocarbons can be converted using appropriate processes and equipment based on the C / O element ratio of the feed, thereby significantly improving the hydrocarbon preparation efficiency. Attached Figure Description

[0029] Figure 1 A schematic diagram illustrating a hydrocarbon preparation apparatus according to an example of the present invention.

[0030] Figure 2 This is a schematic diagram illustrating a hydrocarbon preparation apparatus including a refining process according to one example.

[0031] Figure 3 This is a schematic diagram illustrating a hydrocarbon production apparatus including a catalyst recycling process according to one example. Detailed Implementation

[0032] The present invention will now be described in detail with reference to the accompanying drawings. However, this is merely exemplary, and the present invention is not limited to the specific embodiments described herein.

[0033] Unless otherwise specified, the singular form of the terms used in this specification may be interpreted to also include the plural form.

[0034] 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.

[0035] 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.

[0036] Unless otherwise defined, the units of % used in this specification refer to weight unless otherwise specified.

[0037] As used in this specification and claims, the terms “Group VIIIA element” and “Group VIA element” refer to the elements in their respective groups according to the old version of the periodic table of the International Union of Pure and Applied Chemistry (IUPAC).

[0038] This invention includes a method for preparing hydrocarbons, the method comprising the following steps: S1) pyrolyzing mixed waste to generate a first mixed gas; S2) reforming the first mixed gas with steam in a first fluidized bed reactor to prepare 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 and the carbon monoxide converted in step S4) to generate a third mixed gas, and preparing syngas from the third mixed gas via a water-gas shift reaction; and S6) generating hydrocarbons from the syngas via a catalytic reaction.

[0039] Steps S2) and S4) of the present invention are carried out in a fluidized bed reactor. More specifically, the fluidized bed reactor uses a catalyst comprising: a first metal comprising elements of Group VIIIA, Group VIA, or combinations thereof from the periodic table; and a second metal oxide comprising an alkaline earth metal oxide or a structure thereof, thereby increasing the efficiency of the synthesized gas produced by catalytic reaction while further removing impurities.

[0040] Therefore, compared with existing gasification processes, the hydrocarbon preparation method according to the present invention can effectively remove impurities and prevent catalyst contamination or activity reduction in the catalytic process. Thus, it can efficiently convert organic waste into syngas and maximize the yield of high-value-added hydrocarbons converted from syngas. Furthermore, it minimizes carbon dioxide generation during hydrocarbon preparation, thereby preventing environmental pollution.

[0041] In this invention, the purpose of step S1) is to thermally treat the organic waste to generate the first mixed gas, thereby causing the organic waste to undergo a gasification reaction.

[0042] 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.

[0043] Specifically, step S1) is a gasification process for organic waste, which may be accompanied by one or more gasification reactions selected from the following reaction formulas 1 to 4.

[0044] [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 example, 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, hydrogen chloride, etc., and may also contain water-soluble impurities such as H2S, HCl, HOCl and NH3.

[0045] In one example, to increase the content of dry gas in the composition of the first mixed gas, step S1 can be carried out under catalytic or catalyst-free conditions. Here, the dry gas is a general term for hydrocarbon gases with four or fewer carbon atoms. By increasing the content of dry gas in the composition of the first mixed gas, the efficiency of the methane reforming reaction can be improved, and the syngas production yield can be increased. Therefore, acid-site catalysts or molybdenum-based molding catalysts can be used as the bed material of the pyrolysis reactor. When no catalyst is used in the pyrolysis step, the gasification pyrolysis reactor can be operated under low temperature and high pressure conditions to increase the methane content. Regarding the yield improvement effect brought about by methane reforming, the same effect can be expected not only for the methane content but also for the C2 to C4 hydrocarbon gas content. Therefore, the C2 to C4 hydrocarbon gas content can also be increased by using acid-site catalysts or by low-temperature, high-pressure gasification operation.

[0046] In one example, the catalyst in the pyrolysis reaction can be an acid-site catalyst or a molybdenum-based shaped catalyst. In another example, the acid-site catalyst can be alumina or other inorganic structures with solid acid sites. The alumina can be alumina alone, silica-alumina, or alumina dispersed in a carbon structure. The structure can be zeolite, SAPO, AlPO, metal-organic frameworks (MOFs), or their structural variations. The molybdenum-based catalyst refers to a catalyst with molybdenum supported on a support; nickel, cobalt, etc., can be added as needed, and tungsten can be used instead of molybdenum. The support only needs to be durable for the molybdenum or tungsten; for example, it can contain one or more substances selected from silica, alumina, silica-alumina, carbon, and zirconium oxide.

[0047] As another example of increasing 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 more than 40% by volume of methane and carbon dioxide, specifically, more than 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 methane reforming and reverse Boudouar reactions.

[0048] In one example, the C / O ratio of the first mixed gas can be greater than 0.01, greater than 0.05, or greater than 0.1, with an upper limit of less than 0.9, less than 0.8, or less than 0.7, specifically between 0.01 and 0.9, between 0.05 and 0.8, and more specifically between 0.1 and 0.7.

[0049] When the C / O ratio of the first mixed gas meets the above range, the oxygen content in the first mixed gas is higher than the carbon content when carrying out the following methane reforming reaction, which significantly reduces the amount of coke generated by side reactions and prevents catalyst deactivation, thereby enabling efficient methane reforming reaction.

[0050] Following step S1), impurity gases containing Cl, N, S, etc., in the mixed gas can be selectively removed using a scrubber or adsorbent. As an example, impurities can be selectively removed by one or more combinations selected from water washing, alkaline solution washing, scrubbers, high-pressure dust filters, and ceramic filters, but this is not limited to these methods. For instance, in the above-described methods, when the first mixed gas is passed through a ceramic filter or dust filter, non-water-soluble impurities such as tar and dust can be removed.

[0051] Step S2) of the present invention is a step of performing a steam reforming reaction on 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.

[0052] [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, preferably 600°C to 700°C, and a pressure of 30 kPa to 2000 kPa.

[0053] To improve the reaction conversion rate, step S2) may include a catalyst. The catalyst in step S2) uses a catalyst comprising: a first metal, which includes elements of Group VIIIA or Group VIA of the periodic table, or a combination thereof; and a second metal oxide, which includes an alkaline earth metal oxide or a structure thereof. By carrying out a fluidized bed catalytic reaction, the efficiency of the steam reforming reaction can be improved while further removing impurities.

[0054] The first metal may comprise a Group VIIIA element, a Group VIA element, or a combination thereof, and, for example, may comprise one or more elements selected from nickel (Ni), iron (Fe), molybdenum (Mo), and tungsten (W).

[0055] The second metal oxide may comprise an alkaline earth metal oxide or an alkaline earth metal oxide structure. The second metal oxide may comprise one or more alkaline earth metal oxides selected from beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba), and exemplary, may comprise magnesium oxide (MgO). Furthermore, the alkaline earth metal oxide structure is a structure combining an alkaline earth metal and a metal oxide, and may, for example, comprise magnesium aluminate (MgAl₂O₄) with a spinel structure or hydrotalcite (Mg₆Al₂CO₃(OH)₃) with a spinel structure. 16 One or more of the following: ·4H2O). In this invention, by including the second metal oxide, sulfur, nitrogen and chlorine compounds can be selectively further removed, thus increasing the syngas generation efficiency in the steam reforming process of step S2) and the reverse Boudouar process of step S4).

[0056] Furthermore, the catalyst of the present invention, comprising the first metal and the second metal oxide, exhibits excellent durability and minimal catalyst loss, thus maintaining high catalytic activity for an extended period, even with repeated catalyst coking and regeneration. Extended catalyst replacement cycles can improve process efficiency and economics.

[0057] Specifically, by using a catalyst containing the two metals mentioned above to carry out steam reforming in a fluidized bed reactor, not only can the reforming reactivity be improved, but it can also remove impurities such as chlorine, and there are fewer side reactions such as dehydrogenation and hydrogenation, which can maximize the yield of the synthesized gas.

[0058] In one example, the catalyst is prepared by mixing a ceramic support and a first metal in a solvent to prepare a mixed solution. An organic acid is then added to the mixed solution to prepare a precursor gel. The precursor gel is then mixed with a solid mixture containing a binder and a second metal oxide. An inorganic binder is further added to the mixture to prepare a composite catalyst sol, followed by spray drying to obtain a catalyst with an average particle size of 50 μm to 250 μm. The catalyst prepared by this method not only exhibits excellent activity, but also shows that the first and second metals are uniformly dispersed and firmly bonded within the catalyst, thus improving durability and providing an excellent catalyst lifetime.

[0059] Step S3) is the step of separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide in the carbon dioxide separation unit.

[0060] 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, which can be an amine scrubber. Typically, amine scrubbers use amine substances to bind and remove carbon dioxide, separating components such as carbon dioxide and hydrogen sulfide from gas vapors, and recovering 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.

[0061] 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.

[0062] 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.

[0063] 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 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.

[0064] [Reaction Formula 6] C + CO2 2CO The reaction can be carried out at temperatures ranging from 600°C to 1000°C and pressures ranging from 50 kPa to 300 kPa.

[0065] Furthermore, the reverse Boudouar reaction uses a catalyst that has been used in the steam reforming reaction and has been deposited with coke, thus eliminating the need for a separate external carbon source and allowing for economical process operation. The catalyst, regenerated by removing the deposited coke in the reverse Boudouar reaction step, is then reintroduced into the steam reforming reaction for further catalytic reaction, thus providing the advantage of a recyclable process.

[0066] That is, the yield of syngas can be maximized through methane reforming and reverse Boudouar reaction. The first and second fluidized bed reactors, which carry out methane reforming and reverse Boudouar reaction simultaneously, form a circulating process, thus enabling continuous and economical process operation based on catalyst regeneration.

[0067] Non-limitingly, the reverse Boudouar reaction can be carried out by further obtaining a carbon supply source from an external source. Specifically, the carbon supply source can be char derived from the organic waste, more specifically char derived from the pyrolysis of waste plastics or char derived from biomass. Alternatively, to avoid the possibility of introducing impurity gases through an external carbon supply source, high-purity graphite can be included.

[0068] Step S4) involves carrying out the catalytic reaction described in this invention, which can further remove residual sulfur compounds, nitrogen compounds, and chlorine compounds, thereby increasing the yield of syngas.

[0069] The catalyst in step S4) comprises: a first metal, which comprises elements of Group VIIIA or Group VIA of the periodic table, or combinations thereof; and a second metal oxide, which comprises an alkaline earth metal oxide or a structure thereof. The first metal may be selected from nickel, iron, molybdenum, and tungsten, and the second metal oxide may be selected from MgO, MgAl₂O₄ (spinel), and Mg₆Al₂CO₃(OH). 16 One or more of the following: ·4H2O (hydrotalcite).

[0070] As described above, in the steam reforming process and the reverse Boudouard process, by using catalysts containing the first and second metal oxides, sulfur, nitrogen, and chlorine compounds can be selectively further removed, thus improving the syngas generation efficiency in the steam reforming step and the reverse Boudouard process. For example, the reaction for removing sulfur compounds using a catalyst containing the second metal oxide can be represented by the following reaction formula 7.

[0071] [Reaction Formula 7] S+CO2 SO2 + SO3 + CO SO2 + 1 / 2CO2 SO3 + CO MgO+SO3 MgSO4 In one example, as shown in reaction formula 7, the catalyst containing MgSO4 generated from the reaction of the second metal oxide with the sulfur compound in step S4) is recycled to the first fluidized bed reactor in step S2), so that sulfur can be separated from MgSO4 to remove impurities and the catalyst can be regenerated during the steam reforming reaction. The reaction can be represented by the following reaction formula 8.

[0072] [Reaction Equation 8] MgSO4 + 4H2 MgS + 4H2O MgSO4 + 4H2 MgO + H₂S + 3H₂O MgO + H2O MgO + H2S As a non-limiting example, to prevent the inevitable irreversible deactivation of the catalyst during steps S2) and S4), which would lead to a decrease in catalytic activity, a certain amount of catalyst can be replaced with new catalyst. Removing partially deactivated catalyst from the reactor during steam reforming and the reverse Boudouar reaction process and introducing new catalyst can improve catalytic activity. The catalyst of this invention has very high durability and very low deactivation, thus offering advantages such as long catalyst replacement cycles and small amounts of new catalyst added.

[0073] Step S5) is a step in which syngas is prepared by mixing the second feed stream separated by the carbon dioxide separation unit and the carbon monoxide obtained in step S4) to form a third mixed gas in the syngas generation unit, and then using a water-gas shift reaction. The third mixed gas may contain hydrogen and carbon monoxide.

[0074] The above steps involve converting the third mixed gas through a water-gas shift (WGS) reaction to achieve a hydrogen:carbon monoxide ratio suitable for a subsequent catalytic reaction. The water-gas shift reaction can be represented by the following reaction equation 9.

[0075] [Reaction Formula 9] 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.

[0076] 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.

[0077] Step S6) is the step of converting the syngas generated in step S5) into hydrocarbon fractions, which can be converted into appropriate hydrocarbon fractions through catalytic reaction.

[0078] 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.

[0079] In one instance, when the catalytic reaction in step S6) 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 10.

[0080] [Reaction Formula 10] 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.

[0081] 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.

[0082] In one instance, when the catalytic reaction in step S6) is a methanol-olefin conversion reaction, step S6) may include: a reaction to convert syngas into methanol; and a reaction to convert methanol into olefins.

[0083] The reaction that converts syngas into methanol can be represented by the following reaction formula 11.

[0084] [Reaction Formula 11] 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.

[0085] The reaction of converting the synthesis gas into methanol can be carried out at 150°C to 600°C, specifically at 200°C to 350°C, and at 0.1 MPa to 10 MPa, specifically at 2 MPa to 15 MPa.

[0086] 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.

[0087] 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.

[0088] The hydrocarbon preparation apparatus of the present invention will now be described.

[0089] This invention provides a hydrocarbon preparation apparatus, comprising: a pyrolysis reactor for heat treatment of organic waste to generate a first mixed gas; a first fluidized bed reactor for steam reforming the first mixed gas to generate a second mixed gas; a carbon dioxide separation unit for separating the second mixed gas into a first feed stream containing carbon dioxide and a second feed stream containing hydrogen and carbon monoxide; a second fluidized bed reactor for converting the first feed stream into carbon monoxide via a reverse Boudouar reaction; a gas mixing unit for mixing 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 for converting the third mixed gas into syngas via a water-gas shift reaction; and a hydrocarbon conversion unit for converting the syngas into hydrocarbons via a catalytic reaction.

[0090] According to the hydrocarbon preparation apparatus 1 of the present invention, steam reforming and reverse Boudouar reaction are carried out in a first fluidized bed reactor 20 and a second fluidized bed reactor 40 containing catalysts of a first metal and a second metal oxide. The first mixed gas 110 can be efficiently converted into syngas 230 and hydrocarbons. The apparatus can be installed and operated economically with low installation and operating costs.

[0091] like Figure 1As shown, organic waste 100 is introduced into pyrolysis reactor 10 and, after heat treatment, generates a first mixed gas 110. The first mixed gas 110 can flow into a first fluidized bed reactor 20, where, through steam reforming, methane is converted into carbon monoxide and hydrogen, thereby producing a second mixed gas 200.

[0092] like Figure 2 As shown, before introducing the mixed gas into the first fluidized bed reactor 20, a purification unit 80 for removing impurities contained in the mixed gas may be further included. The purification unit 80 may contain an adsorbent or a scrubber. By selectively removing trace impurity gases such as S, N, and Cl from the mixed gas through the purification unit 80, catalyst deactivation during steam reforming and reverse Boudouar process operation can be reduced, reaction stability improved, and economic efficiency enhanced.

[0093] The second mixed gas 200 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 211 is directly supplied to the gas mixing unit 50, and the first feed stream 210 is supplied to the second fluidized bed reactor 40, thereby being converted into carbon monoxide through the reverse Boudouar reaction.

[0094] Reference Figure 3 The hydrocarbon preparation apparatus further includes: a cyclone separator 90 connected between a first fluidized bed reactor 20 and a carbon dioxide separation unit 30; a catalyst supply line connected between the cyclone separator 90 and a second fluidized bed reactor 40; and a catalyst recirculation line connected between the second fluidized bed reactor 40 and the first fluidized bed reactor 20. The cyclone separator 90 can separate the second mixed gas 200 discharged from the first fluidized bed reactor 20 from the catalyst, supply the second mixed gas 200 to the carbon dioxide separation unit 30, and supply the catalyst to the second fluidized bed reactor 40.

[0095] In one example, the cyclone separator 90 receives a second mixed gas 200 from the first fluidized bed reactor 20 to separate the coking catalyst, and then supplies the second mixed gas 200 to the separation unit 30. The coking catalyst can be supplied to the second fluidized bed reactor 40 via a catalyst supply line connecting the cyclone separator 90 and the second fluidized bed reactor 40. The second fluidized bed reactor 40 can regenerate the coking catalyst received from the cyclone separator 90, and then supply the regenerated catalyst to the first fluidized bed reactor 20 via a recirculation line connected to the fluidized bed reforming reactor 21. Thus, by further including the cyclone separator 90, the coke required for the reverse Boudouar reaction does not need to be supplied separately from an external source, the process can be operated economically, and the catalyst for the methane reforming reaction can be continuously replenished, thus having the advantage of efficient process operation.

[0096] The second fluidized bed reactor 40 can further receive char, specifically char derived from organic waste, which can react with carbon dioxide to convert into carbon monoxide. Non-limitingly, the char can be char derived from the pyrolysis of waste plastics or char derived from biomass.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] In one example, the hydrocarbon preparation apparatus 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.

[0101] 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 do not limit the scope of the claims. It is obvious to those skilled in the art that various changes and modifications can be made to the embodiments within the scope of the present invention and the technical concept, and it is natural that such changes and modifications fall within the scope of the claims.

[0102] (Preparation Example 1) Preparation of Fluidized Bed Catalyst (Ni / Mg / Zeolite / Al2O3) Based on 100 parts by weight of water, 10 parts by weight of pseudo-boehmite and 95 parts by weight of nickel nitrate hexahydrate were mixed to prepare a mixed solution. While stirring the mixed solution, 1 part by weight of formic acid was added and the reaction proceeded for 3 hours to gelation, preparing a precursor gel. Then, a solid mixture obtained by homogenizing 20 parts by weight of clay, 10 parts by weight of USY zeolite, and 1.5 parts by weight of MgO using a homogenizer was mixed with the precursor gel. Next, 10 parts by weight of colloidal silica (Ludox AS40, Aldrich) was added, followed by 5 parts by weight of water, and the mixture was vigorously stirred to prepare a composite catalyst sol. The composite catalyst sol was spray-dried to prepare a fluidized bed catalyst with a particle size of 50 μm to 250 μm. The recovered catalyst was dried in an oven at 120°C and calcined at 550°C for 3 hours to prepare a fluidized bed catalyst.

[0103] (Preparation Example 2) Preparation of Ni / 3 wt% Mg / zeolite / Al2O3 catalyst The catalyst was prepared by the same method as in Preparation Example 1, except that the solid mixture contained 3 parts by weight of MgO.

[0104] (Preparation Example 3) Preparation of Ni / hydrotalcite / zeolite / Al2O3 catalyst The catalyst was prepared using the same method as in Preparation Example 1, except that the solid mixture contained hydrotalcite (Mg6Al2CO3(OH)2). 16 ·4H2O) replaces MgO.

[0105] (Preparation Example 4) Preparation of Ni / MgSiO3 / zeolite / Al2O3 catalyst The catalyst was prepared by the same method as in Preparation Example 1, except that the solid mixture was prepared by replacing MgO with spinel-structured MgSiO3.

[0106] (Preparation Example 5) Preparation of Ni / Ca / zeolite / Al2O3 catalyst The catalyst was prepared using the same method as in Preparation Example 1, except that CaO was used instead of MgO in the solid mixture.

[0107] (Preparation Example 6) Preparation of Ni / K / zeolite / Al2O3 catalyst The catalyst was prepared using the same method as in Preparation Example 1, except that K2O was used instead of MgO in the solid mixture.

[0108] (Preparation Example 7) Preparation of Ni / Al2O3 Catalyst The catalyst was prepared by the same method as in Preparation Example 1, except that the solid mixture contained 30 parts by weight of clay but not MgO and USY zeolite.

[0109] (Preparation Example 8) Preparation of Ni / zeolite / Al2O3 catalyst The catalyst was prepared by the same method as in Preparation Example 1, except that the solid mixture contained 1 part by weight of USY zeolite but not MgO.

[0110] (Experimental Example 1) Catalyst Characteristic Analysis The properties of the catalysts prepared by the methods of Preparation Example 1, Preparation Example 7, and Preparation Example 8 were analyzed and are shown in Table 1 below. Specifically, the wear index was measured using a wear resistance measuring device (3-hole attrition tester) according to the standard ASTM D 5757-95. The nickel content in the catalyst was calculated using X-ray fluorescence spectrometry (XRF) analysis, which was performed using a Thermo Fisher Scientific ARL QUANT' X. BET specific surface area, total pore volume, and pore size were measured using a Micromeritics Tristar 3000 instrument via nitrogen physical adsorption-desorption. Particle size distribution, such as particle size and the content of fine powder contained in the catalyst, was measured using a Malvern Mastersizer 3000. Here, "fine powder" refers to catalyst particles with a particle size of less than 50 μm.

[0111] [Table 1] As shown in Table 1, the catalyst of Preparation Example 1, which contains nickel and MgO, has a wear index as low as 3.1 wt%, while the catalysts of Preparation Examples 7 and 8, which do not contain MgO, have wear indices of 3.5 wt% and 5.3 wt%, respectively. Furthermore, the fine powder content in the catalysts of Preparation Examples 1, 7, and 8 was measured to be 3.5 wt%, 4 wt%, and 5 wt%, respectively. It can be confirmed that the catalyst of Preparation Example 1, with the lowest fine powder content and the lowest wear index, exhibits excellent strength. In addition, the specific surface area of ​​the catalyst of Preparation Example 1 is 124 m². 2 With a pore volume of 0.23 cubic centimeters / g, an average pore size of 48 Å, and an average catalyst particle size of 127 μm, it was confirmed that it has a structure that can fully disperse and load nickel and MgO in a ceramic support, thereby improving the catalyst activity.

[0112] (Example 1) 1000g of municipal solid waste is added to a pyrolysis reactor, and then, in the presence of alumina beads, steam is introduced and heat-treated at a temperature of 1200℃ and a pressure of 250KPa to recover the first mixed gas with a C / O ratio of 0.67.

[0113] The first mixed gas is cooled down, and impurities such as Cl, S, and N contained in the mixed gas are removed by a scrubber to recover the purified first mixed gas.

[0114] The first mixed gas, after removing impurities, is supplied at a space rate of 2 L / g-catalyst / hour to a first fluidized bed reactor containing the catalyst prepared in Preparation Example 1, while water vapor is supplied simultaneously, and the second mixed gas is prepared by water vapor reforming at 700°C.

[0115] The second mixed gas flows into an amine scrubber, where carbon dioxide is captured and separated into a second feed stream with removed carbon dioxide. Specifically, the second mixed gas flows into the first amine scrubber, where CO2 is captured by an aqueous solution (amine solution) containing monoethanolamine (MEA) dissolved in it 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 and is separated into an amine solution and CO2 at 100°C. The CO2 is recovered as the first feed stream.

[0116] The recovered first feed stream flows into a second fluidized bed reactor containing the catalyst of Preparation Example 1 and is converted to carbon monoxide via a reverse Boudouar reaction. The reverse Boudouar reaction is carried out in the second fluidized bed reactor filled with the catalyst of Preparation Example 2, which had been used in the steam reforming reaction and deposited with coke. The first feed stream is continuously supplied at a space rate of 2 L / g-catalyst / hour to convert it to carbon monoxide. The catalyst, activated by removing coke through the reverse Boudouar reaction, is then reintroduced into the first fluidized bed reactor.

[0117] The catalyst separated from the cyclone separator is supplied to the second fluidized bed reactor via a catalyst supply line, where it is used as a carbon source and simultaneously processed during the reverse Boudouar reaction for regeneration. Furthermore, the regenerated catalyst is supplied back to the first fluidized bed reactor via a recirculation line connected to the first fluidized bed reactor, and unconverted CO2 after the reaction is recovered separately via the amine scrubber.

[0118] The carbon monoxide converted from the first feed stream flows into the gas mixing unit and mixes with the second feed stream, and the mixing is carried out at 200°C to generate a third mixed gas.

[0119] The third mixed gas flows into the syngas generation unit and produces syngas with a molar ratio of H2:CO of 1:2 through a water-gas shift reaction.

[0120] Syngas was supplied to the hydrocarbon conversion unit, and the injection rate was set at a space velocity of 5000 L / kg·catalyst / hour under the cobalt / zinc oxide (Co / ZnO) catalyst, so that the volume ratio of carbon monoxide:hydrogen:argon was 63.2:31.3:5.5. 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.

[0121] (Example 2) The process was carried out in the same manner as in Example 1, except that the catalyst of Preparation Example 2 was used instead of the catalyst of Preparation Example 1 as the catalyst for the steam reforming process and the reverse Boudouar reaction process.

[0122] (Example 3) The process was carried out in the same manner as in Example 1, except that the catalyst of Preparation Example 3 was used instead of the catalyst of Preparation Example 1 as the catalyst for the steam reforming process and the reverse Boudouar reaction process.

[0123] (Example 4) The process was carried out in the same manner as in Example 1, except that the catalyst of Preparation Example 4 was used instead of the catalyst of Preparation Example 1 as the catalyst for the steam reforming process and the reverse Boudouar reaction process.

[0124] (Example 5) The process was carried out in the same manner as in Example 1, except that the catalyst of Preparation Example 5 was used instead of the catalyst of Preparation Example 1 as the catalyst for the steam reforming process and the reverse Boudouar reaction process.

[0125] (Example 6) The process was carried out in the same manner as in Example 1, except that the catalyst of Preparation Example 6 was used instead of the catalyst of Preparation Example 1 as the catalyst for the steam reforming process and the reverse Boudouar reaction process.

[0126] (Comparative Example 1) The process was carried out in the same manner as in Example 1, except that the catalyst of Preparation Example 7 was used instead of the catalyst of Preparation Example 1 as the catalyst for the steam reforming process and the reverse Boudouar reaction process.

[0127] (Comparative Example 2) The process was carried out in the same manner as in Example 1, except that the catalyst of Preparation Example 8 was used instead of the catalyst of Preparation Example 1 as the catalyst for the steam reforming process and the reverse Boudouar reaction process.

[0128] (Experimental Example 2) Evaluation of Catalyst Durability When preparing hydrocarbons using the methods of Examples 1 to 6, Comparative Examples 1 and 2, the process of preparing syngas from the first mixed gas is defined as one cycle. After 20 cycles, the catalyst is removed from the reactor, the particle size distribution of the catalyst is analyzed, and the content of fine powder in the catalyst is compared. At this time, the fine powder refers to catalyst particles with a particle size of 50 μm or less.

[0129] A reactor was filled with 2 kg of catalyst, and water was introduced at 3 mL / min at 750 °C. A first mixed gas obtained from waste pyrolysis was supplied to carry out a methane steam reforming reaction. The first mixed gas contained 99.5% CH4. More specifically, the types and contents of impurities contained in the first mixed gas are shown in Table 2 below.

[0130] [Table 2] The particle size distribution of the catalyst remaining in the reactor after 20 reaction cycles was analyzed, and the content of fine powder in the catalyst was measured and shown in Table 3 below. The particle size distribution was measured using a Malvern Mastersizer 3000.

[0131] [Table 3] As shown in Table 3, compared to Comparative Examples 1 and 2 which used catalysts from Preparation Examples 7 and 8 that did not contain a second metal oxide, the catalysts from Examples 1 to 6, which used catalysts from Preparation Examples 1 to 7 containing both a first metal and a second metal oxide, had a lower rate of conversion to fine powder. The increased fine powder content meant that, during 20 cycles, repeated catalyst coking and regeneration processes resulted in catalyst cracking and breakage. In contrast, the catalysts from Preparation Examples 1 to 6, containing both metals, remained intact even after repeated catalyst coking and regeneration processes, allowing for long-term continuous cyclic processing. Therefore, the catalysts of the present invention exhibit excellent durability, and with increased catalyst life, the catalyst replacement cycle is extended, thereby improving process efficiency.

[0132] (Experimental Example 3) Evaluation of Catalyst Performance Similar to Experimental Example 2, the catalysts from Preparation Examples 1 to 8 were run for 1 cycle, 5 cycles, and 20 cycles respectively using the methods of Examples 1 to 6, Comparative Examples 1 and 2, and then 200 g of catalyst was recovered from each. After removing fine powder from the recovered catalyst, a reforming reaction was carried out on methane gas containing impurities in a separate reactor.

[0133] The methane reforming reaction was carried out as follows: 100g of catalyst was packed into a fluidized bed reactor, and catalyst reduction was performed at 900°C for 2 hours under H2 gas flow rate of 3.03 Nl / min. Then, the methane reforming reaction was carried out under the conditions of total gas flow rate of 3.33 Nl / min, throughput of 2.0 L / g-catalyst / hour, and CH4 / H2O = 3. The methane conversion rate of the catalyst is shown in Table 4 below. "Fresh catalyst" in Table 4 refers to a new catalyst that has not undergone catalytic reaction.

[0134] [Table 4] As can be seen from Table 4, in Comparative Examples 1 and 2, which used catalysts from Preparation Examples 7 and 8 that did not contain alkaline earth metals or their structures, although the initial catalyst activity was very high, the methane conversion rates after 5 cycles were 22.3% and 15.5%, respectively, which were significantly lower than the initial methane conversion rates. With repeated catalytic processes, the catalysts rapidly deactivated. Furthermore, the methane conversion rates of Comparative Examples 1 and 2 decreased to 3.0% and 4.1%, respectively, after 20 cycles, confirming that most of the catalyst particles had been deactivated.

[0135] On the other hand, in Examples 1 to 6, which used catalysts containing nickel and alkaline earth metals, high catalyst activity was still observed even after repeated coking and regeneration of the catalyst. In particular, in Examples 1 and 2, which contained MgO, methane conversion rates remained as high as 65.3% and 53.1% respectively after 5 cycles, and 23.5% and 17.2% respectively after 20 cycles, indicating delayed catalyst deactivation. In Examples 3 and 4, which used catalysts containing MgSiO3 with a hydrotalcite or spinel structure as an alkaline earth metal structure, methane conversion rates were measured at 35.9% and 29.2% respectively after 5 cycles, and good methane conversion rates of 9.5% and 8.8% respectively after 20 cycles. In Example 5, which used CaO as an alkaline earth metal oxide, methane conversion rates were measured at 27.1% and 5.9% after 5 and 20 cycles, respectively.

[0136] In addition, in Example 6, which used the catalyst from Preparation Example 6 containing K2O as an alkali metal oxide, the methane conversion rate decreased to 14.0% after 5 cycles and to 3.1% after 20 cycles, confirming that catalyst deactivation could not be suppressed.

[0137] The above examples and comparative examples confirm that when preparing hydrocarbons from pyrolysis gas using the method according to the present invention, the recovery of carbon dioxide from the mixed gas and its conversion to carbon monoxide via the reverse Boudouar reaction process not only improves the yield of syngas and hydrocarbons, but also significantly increases the H2 and CO production of the final syngas, while reducing CO2 production. This has beneficial effects on syngas production yield and prevention of environmental pollution. In particular, by using a fluidized bed reactor as the reactor for the methane reforming and reverse Boudouar processes, and by using a catalyst with excellent durability—composite first metal and second metal oxide containing alkaline earth metals—as the catalyst for the methane reforming and reverse Boudouar reactions, catalyst deactivation caused by coke generated in the methane reforming reaction can be prevented. Even if the catalyst is deactivated by coke, it can be regenerated in the reverse Boudouar reaction process. Therefore, the catalyst replacement cycle is extended, thereby improving process efficiency, and thus achieving excellent syngas conversion rate and hydrocarbon production efficiency. Furthermore, by continuously removing impurities from the mixed gas through a catalyst, steam reforming and reverse Boudouar reaction can be carried out, which has the advantage of obtaining high-purity syngas.

[0138] The above description is merely an example of applying the principles of this invention, and other configurations may be included without departing from the scope of this invention.

[0139] [Explanation of reference numerals in the attached figures] 1 hydrocarbon preparation unit; 10 pyrolysis reactors 20 Fluidized bed reactor No. 1; 30 Carbon dioxide separation unit 40 Second fluidized bed reactor; 50 Gas mixing unit 60 Syngas generation unit; 70 Hydrocarbon conversion unit 80 Refining Units; 90 Cyclone Separators 100 Organic waste; 110 First mixed gas 120 First mixed gas after impurity removal; 200 Second mixed gas 210 First material flow; 211 Second material flow 220 Third gas mixture; 230 Synthesis gas

Claims

1. A method for preparing a hydrocarbon, wherein, The preparation method includes the following steps: S1) Pyrolyze the mixed waste to generate the first mixed gas; S2) The first mixed gas, after impurities have been removed, is subjected to steam reforming in the first fluidized bed reactor to prepare 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 and the carbon monoxide converted in step S4) are mixed to generate a third mixed gas, and the third mixed gas is used to prepare syngas through a water-gas shift reaction; and S6) Hydrocarbons are generated from the syngas via a catalytic reaction.

2. The method for preparing hydrocarbons according to claim 1, wherein, Steps S2) and S4) are carried out in the presence of a catalyst containing the following: A first metal, said first metal comprising Group VIIIA elements, Group VIA elements, or combinations thereof; and The second metal comprises an alkaline earth metal oxide or an alkaline earth metal oxide structure.

3. 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.

4. The method for preparing hydrocarbons according to claim 1, wherein, The second fluidized bed reactor in step S4) receives the coking catalyst from the first fluidized bed reactor in step S2) as a carbon source.

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

6. The method for preparing hydrocarbons according to claim 1, wherein, The C / O element ratio of the pyrolysis gas is 0.1 or higher.

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

8. The method for preparing hydrocarbons according to claim 1, wherein, Step S4) is performed 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, In step S5), the synthesis gas contains hydrogen and carbon monoxide, and the ratio of hydrogen to carbon monoxide satisfies 1.8:1 to 2.2:

1.

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

11. A hydrocarbon preparation apparatus, wherein, The hydrocarbon preparation apparatus includes: A pyrolysis reactor that thermally treats organic waste to generate a first mixed gas; A first fluidized bed reactor is used to perform steam reforming on the first mixed gas 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 through a catalytic reaction.

12. The hydrocarbon preparation apparatus according to claim 11, wherein, The first and second fluidized bed reactors contain catalysts containing the following: A first metal, said first metal comprising elements of Group VIIIA, Group VIA, or combinations thereof from the periodic table; and The second metal comprises an alkaline earth metal oxide or an alkaline earth metal oxide structure.

13. The hydrocarbon preparation apparatus according to claim 11, wherein, The hydrocarbon preparation apparatus 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 fluidized bed reforming reactor, supplies the second mixed gas to the carbon dioxide separation unit, and supplies the catalyst to the second fluidized bed reactor.

Images