Hydrocarbon production method and apparatus

Abstract

The invention provides a hydrocarbon preparation method. The hydrocarbon preparation method comprises the following steps: (S1) carrying out heat treatment on organic waste in a pyrolysis reactor to generate a first mixed gas; (S2) performing methane reforming treatment on the first mixed gas in a reforming reactor to generate second mixed gas; (S3) separating a first stream comprising carbon dioxide and a second stream comprising hydrogen and carbon monoxide from the second mixed gas; (S4) adding the first stream and carbon to a reverse Boudala reactor and converting to carbon monoxide by a reverse Boudala reaction; (S5) mixing the second stream with the carbon monoxide converted in step (S4) to produce a third mixed gas; (S6) generating synthesis gas from the third mixed gas through a water-gas shift reaction; and (S7) producing hydrocarbons from the synthesis gas by a catalytic reaction, in which the reforming reactor in the step (S2) comprises a fluidized bed reforming reactor and a fixed bed reforming reactor connected in parallel, and the first mixed gas is supplied to the fluidized bed reforming reactor or the fixed bed reforming reactor by switching.

Description

TECHNICAL FIELD

[0001] The present application relates to a method and a preparation apparatus for producing hydrocarbons from organic waste, and more particularly, to a method and a preparation apparatus for producing hydrocarbons, which can improve the yield of hydrocarbons produced from organic waste and minimize the generation of carbon dioxide. BACKGROUND

[0002] Organic waste can seriously damage the environment when it is buried, and needs to be collected according to different properties and disposed of through a prescribed process. However, simple disposal of organic waste requires the installation of a disposal facility and consumes a large amount of manpower, and is more wasteful than production, and thus methods and technologies for recycling organic waste are being developed in recent years. A representative technology can be a gasification process technology that produces synthesis gas from organic waste and converts it into high-value-added products to achieve energy.

[0003] The gasification process generally refers to a series of processes for converting carbonaceous raw materials such as coal, organic waste, biomass, etc. into synthesis gas containing hydrogen and carbon monoxide by reacting them in the presence of steam, oxygen, carbon dioxide, or a mixture thereof, at this time, "synthesis gas" generally refers to a mixed gas containing hydrogen and carbon monoxide generated by a gasification reaction, and can further contain carbon dioxide and / or methane.

[0004] The gasification process technology has expanded to a technology for producing raw materials for various compounds and fuels, for example, synthesis gas can be used as a raw material for a fischer-tropsch synthesis reaction to produce light oil, heavy oil, diesel, wax, aviation oil, lubricating oil base oil, and other high-value-added products. In addition, it is known that hydrogen in synthesis gas, which is a main product of the gasification process, can be used for hydrogen power generation, ammonia production, oil refining processes, etc., and high-value-added chemicals such as acetic acid, olefins, dimethyl ether, aldehydes, fuels, and additives can be obtained from methanol produced from synthesis gas. However, the production yield of synthesis gas produced from organic waste is extremely low, so it is difficult to efficiently produce high-value-added compounds from synthesis gas.

[0005] In recent years, as a process for producing synthesis gas, a gasification process using a catalyst is being conducted, but in the gasification process, the catalyst is deactivated due to the generation of coke and the like, and there is a problem that process failure occurs due to the deactivated catalyst when continuously operated. In addition, in order to secure economic efficiency, it is necessary to recover the relatively high-priced catalyst, but for recovering the catalyst discharged in an aggregated state such as coke, a plurality of subsequent processes (air burning, etc.) need to be performed, and thus there is a problem that the process efficiency is significantly reduced.

[0006] Further, in the case of the gasification process of organic waste performed in the past, since the production yield of synthesis gas which can be converted into a high added value product is remarkably low to 30% or less, productivity is reduced, and thus there are limitations in applying or commercializing the same. Also, in the aspect of environmental protection, it is preferable to suppress the emission of CO2, but the gasification reaction product of organic waste contains CO2 in addition to H2 and CO, and thus the amount of carbon dioxide emission is more than that in the case of landfill or pyrolysis treatment, and thus there is a serious problem in that environmental pollution can be further induced.

[0007] Therefore, there is a need for a hydrocarbon production method and a production apparatus which can improve the production yield of synthesis gas which can be converted into a high added value product when performing a gasification process of organic waste, and can efficiently convert the same into a high added value hydrocarbon while minimizing the generation of carbon dioxide. SUMMARY

[0008] (1) Technical Problem to be Solved According to an aspect of the present application, a hydrocarbon production method and a production apparatus in which the yield of hydrocarbon produced from organic waste is remarkably improved can be provided.

[0009] According to an aspect of the present application, a hydrocarbon production method and a production apparatus in which the process efficiency is remarkably improved can be provided.

[0010] According to an aspect of the present application, a hydrocarbon production method and a production apparatus in which the generation of carbon dioxide can be minimized can be provided.

[0011] (2) Technical Solution The hydrocarbon production method according to the present application includes the steps of (S1) performing thermal treatment on organic waste in a pyrolysis reactor to generate a first mixed gas; (S2) performing a methane reforming process on the first mixed gas in a reforming reactor to generate a second mixed gas; (S3) separating a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide from the second mixed gas; (S4) adding the first stream and carbon to a reverse Boudouard reactor and converting into carbon monoxide by a reverse Boudouard reaction; (S5) mixing the second stream with the carbon monoxide converted in the step (S4) to generate a third mixed gas; (S6) generating synthesis gas from the third mixed gas by a water gas shift reaction; and (S7) generating a hydrocarbon from the synthesis gas by a catalytic reaction, wherein the reforming reactor of the step (S2) includes a fluidized bed reforming reactor and a fixed bed reforming reactor connected in parallel, and the first mixed gas is supplied to the fluidized bed reforming reactor or the fixed bed reforming reactor by switching.

[0012] In one example, when the C / O element ratio of the first mixed gas is greater than or equal to a critical value, it can be switched and supplied as a feed to the fluidized-bed reforming reactor, and when the C / O element ratio of the first mixed gas is less than the critical value, it can be switched and supplied as a feed to the fixed-bed reforming reactor.

[0013] In one example, the critical value can be 0.5 to 0.9.

[0014] In one example, the reverse Boudouard reactor can be connected in parallel with a fluidized-bed reverse Boudouard reactor and a fixed-bed reverse Boudouard reactor, and the first stream can be supplied by switching.

[0015] In one example, the fluidized-bed reverse Boudouard reactor of the step (S4) can be supplied with a coked catalyst of the fluidized-bed reforming reactor as a carbon supply source, and the fixed-bed reverse Boudouard reactor can be supplied with an additional carbon as a separate carbon supply source.

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

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

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

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

[0020] In one example, the hydrocarbon generated through the step (S7) can be synthetic petroleum.

[0021] In one example, the hydrocarbon generated through the step (S7) can be light olefins.

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

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

[0024] In one example, the organic waste of the step (S1) can be any one or two or more selected from waste plastic, solid waste, biomass, waste oil, waste tire, or a metered garbage bag.

[0025] In one example, the first mixed gas of the step (S1) can be further refined before the step (S2).

[0026] The hydrocarbon production apparatus according to the present application includes: a pyrolysis reactor that thermally treats organic waste to produce a first mixed gas; a reforming reactor that performs methane reforming on the first mixed gas to produce a second mixed gas; a carbon dioxide separation unit that separates the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; a reverse Boudouard reactor that converts the first stream into carbon monoxide through a reverse Boudouard reaction; a gas mixing unit that mixes the second stream with the carbon monoxide converted in the reverse Boudouard reactor to produce a third mixed gas; a syngas generation unit that converts the third mixed gas into syngas through a water gas shift reaction; and a hydrocarbon conversion unit that converts the syngas into hydrocarbons under a catalyst, wherein the reforming reactor includes a fluidized bed reforming reactor and a fixed bed reforming reactor connected in parallel, and the first mixed gas discharged from the pyrolysis reactor is switched by a switching valve and supplied to the fluidized bed reforming reactor or the fixed bed reforming reactor.

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

[0028] In one example, the reverse Boudouard reactor can include a fluidized bed reverse Boudouard reactor and a fixed bed reverse Boudouard reactor disposed in parallel, and the first stream can be selectively supplied to the fluidized bed reverse Boudouard reactor or the fixed bed reverse Boudouard reactor by switching.

[0029] In one example, the hydrocarbon production apparatus can further include: a cyclone separator connected between the fluidized bed reforming reactor and the carbon dioxide separation unit; a catalyst supply line connecting the cyclone separator and the fluidized bed reverse Boudouard reactor; and a catalyst recirculation line connecting the fluidized bed reverse Boudouard reactor and the fluidized bed reforming reactor, wherein the cyclone separator can separate the second mixed gas and the catalyst discharged from the fluidized bed reforming reactor, the second mixed gas can be supplied to the carbon dioxide separation unit, and the catalyst can be supplied to the fluidized bed reverse Boudouard reactor.

[0030] (III) ADVANTAGEOUS EFFECTS According to one embodiment of the present application, the yield of hydrocarbons produced from organic waste can be significantly improved.

[0031] According to one embodiment of the present application, the hydrocarbon can be converted using a proper process and apparatus according to the C / O element ratio of the feed, and thus the efficiency of the hydrocarbon production can be significantly improved.

[0032] According to one embodiment of the present application, the production of carbon dioxide can be minimized during the production of the hydrocarbon. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 A schematic diagram showing a hydrocarbon production apparatus according to the present application.

[0034] Figure 2 A schematic diagram showing a hydrocarbon production apparatus including a fixed bed reverse Boudouard reactor and a fluidized bed reverse Boudouard reactor as one embodiment of the present application.

[0035] Figure 3 A schematic diagram showing a hydrocarbon production apparatus including a catalyst circulation process as one embodiment of the present application.

[0036] Figure 4 A schematic diagram showing a hydrocarbon production apparatus including two carbon dioxide separation units as one embodiment according to the present application. DETAILED DESCRIPTION

[0037] The singular form of the terms used in the present specification can be interpreted as including the plural form, unless otherwise specifically stated.

[0038] The numerical ranges used in the present specification include the lower and upper limit values and all values within the range, all values defined therein, and all possible combinations of the upper and lower limits of the numerical ranges defined in different forms from each other. Values other than the numerical ranges due to experimental errors or rounding of values are also included in the defined numerical ranges, unless otherwise specifically defined in the present specification.

[0039] The "comprising" or "including" described in the present specification is an open expression equivalent to "having", "containing", "providing", "characterized by", and the like, and does not exclude elements, materials, or processes not further listed.

[0040] The units used in the present specification, unless otherwise specifically defined, refer to weight %. The ppm unit, which is not specifically defined and used in the present specification, refers to mass ppm.

[0041] In the past, as a process for preparing synthesis gas, a gasification process using a catalyst was performed, but in the gasification process, the catalyst was deactivated due to the generation of coke and the like, and thus there was a problem in that a process failure occurred due to the deactivated catalyst when continuously operated. In addition, in order to secure economic efficiency, it was necessary to recover the catalyst which was relatively expensive, but in order to recover the catalyst discharged in an aggregated state such as coke, a plurality of subsequent processes (air combustion or the like) were required, and thus the process efficiency was significantly reduced, and a large amount of carbon dioxide was emitted in the process, and thus there was a problem in that environmental pollution was caused. In addition, the preparation yield of synthesis gas in the gasification process of organic waste, which was performed in the past, was significantly low to 30% or less, and thus the productivity was reduced, and thus there were limitations in converting it into a high value-added product. Therefore, the inventors of the present invention designed a preparation method and apparatus which can efficiently prepare a hydrocarbon from organic waste while minimizing the amount of carbon dioxide generated.

[0042] The present invention provides a method of preparing a hydrocarbon, the method comprising the steps of: (S1) heat-treating organic waste in a pyrolysis reactor to generate a first mixed gas; (S2) performing a methane reforming process on the first mixed gas in a reforming reactor to generate a second mixed gas; (S3) separating a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide from the second mixed gas; (S4) adding the first stream and carbon to a reverse Boudouard reactor and converting it into carbon monoxide by a reverse Boudouard reaction; (S5) mixing the second stream with the carbon monoxide converted in the step (S4) to generate a third mixed gas; (S6) generating synthesis gas from the third mixed gas by a water-gas shift reaction; and (S7) generating a hydrocarbon from the synthesis gas by a catalytic reaction, wherein the reforming reactor of the step (S2) comprises a fluidized bed reforming reactor and a fixed bed reforming reactor connected in parallel, and the first mixed gas is supplied to the fluidized bed reforming reactor or the fixed bed reforming reactor by switching.

[0043] The method of preparing a hydrocarbon according to the present invention can efficiently convert organic waste plastic into synthesis gas compared to the existing gasification process, and thus can maximize the yield of a high value-added hydrocarbon converted from synthesis gas. In addition, carbon dioxide generated in the synthesis gas preparation process can be converted into a raw material for synthesis gas, and thus the generation of carbon dioxide in the hydrocarbon preparation process can be minimized, and thus environmental pollution can be prevented.

[0044] The step (S1) is a step of heat-treating organic waste to generate a first mixed gas, and a gasification reaction of the organic waste can occur.

[0045] In one example, the organic waste in step (S1) can be one or more selected from waste plastics, solid waste, biomass, waste oil, waste tires, or metered garbage bags.

[0046] Specifically, the gasification reaction in step (S1) can be accompanied by any one or two or more selected from the following reaction formula 1 to reaction formula 4.

[0047] [Reaction formula 1] C x H y + H2O H2 + CO (water gasification reaction) [Reaction formula 2] C x H y + CO2 CO (carbon dioxide gasification reaction) [Reaction formula 3] CO + 3H2 CH4 + H2O (methanation reaction) [Reaction formula 4] C x H y + O2 CO2 (oxidation reaction) In one example, the first mixed gas can include methane, hydrogen, carbon monoxide, and carbon dioxide. In addition to these, various impurities such as water vapor, nitrogen oxides, sulfur oxides, hydrogen chloride, etc. can also be included.

[0048] In one example, in order to increase the content of methane in the composition of the first mixed gas, step (S1) can be performed under a first catalyst condition or a condition without a catalyst. Increasing the content of methane in the composition of the first mixed gas can be advantageous in terms of the efficiency of the methane reforming reaction or the yield of the synthesis gas preparation, and thus in order to increase the content of methane in step (S1), an acid site catalyst or a molybdenum-based shaped catalyst can be used as a bed material of the gasifier. In the case of not using a catalyst, the gasifier operating conditions can be operated under low-temperature high-pressure conditions to increase the content of methane. In terms of the yield improvement effect due to methane reforming, the same effect can be expected not only for the content of methane but also for the content of C2 to C4 hydrocarbon gas, and the content of C2 to C4 hydrocarbon gas can also be increased by using an acid site catalyst or by low-temperature high-pressure gasification operation.

[0049] In one example, the first catalyst can be an acid-site catalyst or a molybdenum-based shaped catalyst. The acid-site catalyst can be alumina or a catalyst with solid acid sites derived from a structure. Alumina can be alumina alone, silica-alumina, or alumina dispersed in a carbon structure, etc., and the acid-site material can be zeolite, SAPO, AlPO, metal-organic framework (MOF), or its structural variations. A molybdenum-based catalyst refers to a catalyst in which molybdenum is supported on a support; nickel, cobalt, etc., can be added as needed, and tungsten can be used instead of molybdenum. The support can be a durable support capable of supporting active metals; for example, it can contain one or more substances selected from silica, alumina, silica-alumina, carbon, and zirconium oxide.

[0050] 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.

[0051] In one instance, after step (S1), a further step of purifying the first mixed gas may be included.

[0052] 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.

[0053] 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.

[0054] Step (S2) is the step of reforming the methane contained in the first gas mixture to prepare the second gas mixture. Step (S2) may be accompanied by a reforming reaction according to the following reaction formula 5.

[0055] [Reaction 5] CH4+CO2 2CO + 2H₂ (Carbon dioxide 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.

[0056] 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 a hydrogenated metal supported on a carrier. The hydrogenated metal can contain one or more selected from nickel, vanadium, iron, platinum, palladium, and ruthenium. Commonly known metals such as nickel, vanadium, and iron can be used for hydrogenation; 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.

[0057] In one example, 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 or L-type zeolite, silica, alumina, silica-alumina, carbon, zirconium oxide and titanium dioxide.

[0058] In one example, the reforming reactor in step (S2) may include a fluidized bed reforming reactor and a fixed bed reforming reactor connected in parallel, and the first mixed gas may be supplied to either the fluidized bed reforming reactor or the fixed bed reforming reactor by switching.

[0059] That is, the first mixed gas generated in step (S1) can be supplied to the fluidized bed reformer or fixed bed reformer in step (S2) for the aforementioned methane reforming reaction. Specifically, when the C / O ratio of the first mixed gas generated in step (S1) is greater than or equal to a critical value, the first mixed gas is switched and supplied as feed to the fluidized bed reformer; when the C / O ratio of the first mixed gas generated in step (S1) is less than the critical value, the first mixed gas is switched and supplied as feed to the fixed bed reformer for the aforementioned methane reforming reaction, thereby generating the second mixed gas 200.

[0060] In one example, the critical value can be 0.5 to 0.9, 0.6 to 0.85, or 0.7 to 0.8. When the C / O ratio is greater than or equal to the critical value, the process is switched to a fluidized bed and operated. When the C / O ratio is less than or equal to the critical value, the process is switched to a fixed bed reactor and operated.

[0061] In step (S2), the reforming reaction of methane is carried out in a fluidized bed reformer or a fixed bed reformer, thereby maximizing the methane reforming efficiency of the first mixed gas. Specifically, when the C / O ratio of the first mixed gas is less than a critical value, the amount of coke generated due to side reactions during the reforming reaction may be less. Therefore, when the C / O ratio in the first mixed gas is less than the critical value, it is advantageous to carry out the reforming reaction in a fixed bed reformer, which has the highest conversion rate per unit weight of catalyst. Conversely, when the C / O ratio of the first mixed gas is greater than the critical value, the amount of coke generated due to side reactions during the reforming reaction is greater, and therefore, the methane reforming efficiency may decrease over time. Therefore, when the C / O ratio in the first mixed gas is greater than the critical value, the methane reforming efficiency can be improved when the methane reforming reaction is carried out in a fluidized bed reformer compared to the case where it is carried out in a fixed bed reformer. Thus, since the present invention can carry out methane reforming in a fluidized bed reformer or a fixed bed reformer, the methane reforming reaction can be carried out in an advantageous process according to the C / O element ratio contained in the first mixed gas, thereby maximizing the efficiency of the methane reforming reaction.

[0062] 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.

[0063] 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 second mixed gas into the first and second streams.

[0064] 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 a second mixed gas into a first stream and a second stream.

[0065] 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 passing carbon dioxide with the above-mentioned range in the first feed stream, the carbon dioxide separation process can be carried out under milder conditions.

[0066] Step (S4) involves converting the first feed stream separated in step (S3) into carbon monoxide via a reverse Boudouar reaction. 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 may be accompanied by the following reaction formula 6.

[0067] [Reaction Formula 6] C + CO2 2CO In one example, the reverse Boudouar reactor can be connected in parallel with a fluidized bed reverse Boudouar reactor and a fixed bed reverse Boudouar reactor, so that the first feed stream can be switched and supplied. Specifically, when a fluidized bed reformer is used in step (S2), the first feed stream can be switched and supplied to the fluidized bed reverse Boudouar reactor in step (S4); when a fixed bed reformer is used in step (S2), the first feed stream can be switched and supplied to the fixed bed reverse Boudouar reactor in step (S4).

[0068] First, a first mixed gas with a C / O ratio greater than or equal to a critical value is converted into a second mixed gas during the methane reforming reaction in step (S2) by switching to a fluidized bed reformer. The second mixed gas is separated from the catalyst and then separated in step (S3) into a first feed stream containing carbon dioxide and a second feed stream containing carbon monoxide and hydrogen. Then, in step (S4), the first feed stream is supplied to a fluidized bed reverse Boudouar reactor, where it can be converted into carbon monoxide.

[0069] Similarly, the first mixed gas, having a C / O ratio less than or equal to a critical value, is converted into a second mixed gas in step (S2) by switching to a fixed-bed reformer and undergoing a methane reforming reaction. The second mixed gas is then separated in step (S3) into a first feed stream 210 containing carbon dioxide and a second feed stream 211 containing carbon monoxide and hydrogen. Subsequently, the first feed stream, in step (S4), can be converted into carbon monoxide by switching to a fixed-bed reverse Boudouar reactor and undergoing a reverse Boudouar reaction.

[0070] When methane reforming is performed using a fluidized bed reformer in step (S2), a coking catalyst is generated in the fluidized bed reformer. This coking catalyst can be supplied to step (S4) and used as a carbon supply source for the reverse Boudouar reactor. Therefore, using a fluidized bed reverse Boudouar reactor in step (S4) is advantageous. That is, when the coking catalyst from the fluidized bed reformer is used as a carbon supply source, there is no need to further supply separate carbon to the fluidized bed reverse Boudouar reactor in step (S4), thus achieving economical process operation. Therefore, when a fluidized bed reformer is used in step (S2), using a fluidized bed reverse Boudouar reactor in step (S4) is advantageous in terms of process efficiency.

[0071] Furthermore, when a fixed-bed reforming reactor is used in step (S2), a fixed-bed reverse Boudouar reactor with excellent reaction efficiency is used in step (S4) to improve the reactivity of the reverse Boudouar reaction, which can help increase the amount of syngas produced.

[0072] As described above, the present invention, by including a fluidized bed reverse Boudouar reactor and a fixed bed reverse Boudouar reactor, has the effect of allowing the selection of a reactor that maximizes process efficiency by taking into account preceding processes, and carrying out the reverse Boudouar reaction.

[0073] The reverse Boudouar reaction can be carried out by 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.

[0074] Step (S5) is to mix the second stream separated in the carbon dioxide separation unit with the carbon monoxide converted by the reverse Boudouar reaction in step (S4) to prepare a third mixed gas.

[0075] The third gas mixture may contain hydrogen and carbon monoxide.

[0076] Step (S6) is a process of adjusting the carbon monoxide to hydrogen ratio in the third gas mixture to generate syngas via a water-gas shift reaction. The third gas mixture can be converted via a water-gas shift reaction to achieve a hydrogen:carbon monoxide ratio suitable for a subsequent catalytic reaction. The water-gas shift reaction can be accompanied by the following reaction formula 7.

[0077] [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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] [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, silicon dioxide, titanium dioxide, etc., and the co-catalyst may include noble metals such as Pt, R, Re.

[0083] 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.

[0084] 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.

[0085] The reaction that converts syngas into methanol can be accompanied by the following reaction formula 9.

[0086] [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.

[0087] The reaction of converting the synthesis gas into methanol can be carried out at 200°C to 600°C, specifically at 200°C to 500°C, and at 0.1 MPa to 10 MPa, specifically at 0.1 MPa to 5 MPa.

[0088] 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.

[0089] 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.

[0090] This invention provides a hydrocarbon preparation apparatus 1, comprising: a pyrolysis reactor 10, which heat-treats organic waste 100 to generate a first mixed gas 110; a reforming reactor 20, which reforms the first mixed gas 110 with methane to generate a second mixed gas 200; a carbon dioxide separation unit 30, which separates the second mixed gas 200 into a first stream 210 containing carbon dioxide and a second stream 211 containing hydrogen and carbon monoxide; a reverse Boudouar reactor 40, which converts the first stream 210 into carbon monoxide through a reverse Boudouar reaction; and a gas mixing unit 5. 0. The gas mixing unit 50 mixes the second feed stream 211 with the carbon monoxide converted in the reverse Boudouar reactor 40 to generate a third mixed gas 220; the syngas generation unit 60 converts the third mixed gas 220 into syngas 230 through a water-gas shift reaction; and the hydrocarbon conversion unit 70 converts the syngas 230 into hydrocarbons in the presence of a catalyst. The reforming reactor 20 includes a fluidized bed reforming reactor 21 and a fixed bed reforming reactor 22 connected in parallel. The first mixed gas 110 discharged from the pyrolysis reactor 10 is switched and supplied to the fluidized bed reforming reactor 21 or the fixed bed reforming reactor 22 through a switching valve.

[0091] According to the hydrocarbon preparation apparatus 1 of the present invention, a fluidized bed reactor or a fixed bed reactor can be selected as the reactor for subsequent processes based on the oxygen content in the gas generated from the gasification of waste, thereby efficiently converting the gas generated from the gasification of waste into hydrocarbons. Furthermore, by capturing carbon dioxide emitted as waste gas and using it as a raw material for hydrocarbon preparation, carbon dioxide emissions can be significantly reduced, thus preventing environmental pollution.

[0092] In one instance, refer to Figure 1Organic waste 100 is introduced into pyrolysis reactor 10 and subjected to heat treatment to generate a first mixed gas 110. The first mixed gas 110 is supplied to reforming reactor 20. Based on the C / O element ratio in the first mixed gas 110, when it is greater than or equal to a critical value, the first mixed gas 110 is introduced into fluidized bed reforming reactor 21 through a switching valve. When the C / O element ratio is less than the critical value, the first mixed gas 110 is introduced into fixed bed reforming reactor 22 through a switching valve. Through methane reforming reaction, the first mixed gas 110 is converted into a second mixed gas 200.

[0093] When a first mixed gas 110 with a C / O ratio less than a critical value is introduced, the switching valve can connect the pyrolysis reactor 10 and the fixed-bed reforming reactor 22, and be adjusted to allow the first mixed gas 110 to flow into the fixed-bed reforming reactor 22. Furthermore, when a first mixed gas 110 with a C / O ratio greater than or equal to the critical value is introduced, the switching valve can connect the pyrolysis reactor 10 and the fluidized-bed reforming reactor 21, and be adjusted to allow the first mixed gas 110 to flow into the fluidized-bed reforming reactor 21.

[0094] The reforming reactor 20 of the present invention includes a fluidized bed reforming reactor 21 and a fixed bed reforming reactor 22. The reforming reaction can be carried out in an appropriate reactor by switching valve according to the C / O element ratio of the first mixed gas 110, thus having the effect of maximizing the efficiency of the methane reforming reaction.

[0095] According to one example, the hydrocarbon preparation apparatus 1 may further include a refining unit 80 between the pyrolysis reactor 10 and the reforming reactor 20. (See also...) Figure 2 The first mixed gas 110 can flow into the purification unit 80 to remove impurities, and then the first mixed gas 120 with impurities removed is supplied to the reforming reactor 20 to carry out the methane reforming reaction.

[0096] The refining unit 80 includes a sprayer for injecting liquid, receiving a first mixed gas 110 from the pyrolysis reactor 10, and contacting 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.

[0097] The second mixed gas 200 generated in the reforming reactor 20 via the methane reforming reaction can be supplied to the carbon dioxide separation unit 30, where it is separated into a first feed stream 210 containing carbon dioxide and a second feed stream 211 containing hydrogen and carbon monoxide. At this point, the second feed stream 211 is supplied to the gas mixing unit 50, and the first feed stream 210 is supplied to the reverse Boudouar reactor 40, where it is converted into carbon monoxide via the reverse Boudouar reaction.

[0098] In one instance, refer to Figure 3 The reverse Boudouar reactor 40 includes a fluidized bed reverse Boudouar reactor 41 and a fixed bed reverse Boudouar reactor 42 connected in parallel. By switching, the first feed stream 210 can be selectively supplied to either the fluidized bed reverse Boudouar reactor 41 or the fixed bed reverse Boudouar reactor 42. Similar to the reforming reactor 20, the reverse Boudouar reactor 40 can also selectively supply the first feed stream 210 to either the fluidized bed reverse Boudouar reactor 41 or the fixed bed reverse Boudouar reactor 42 via a switching valve to carry out the reverse Boudouar reaction.

[0099] According to one example, when the reforming reaction is carried out in a fluidized bed reformer 21, the first feed stream 210 can be supplied to a fluidized bed reverse Boudouar reactor 41 for a reverse Boudouar reaction. Alternatively, when the reforming reaction is carried out in a fixed bed reformer 22, the first feed stream 210 can also be supplied to the fixed bed reverse Boudouar reactor 42 for a reverse Boudouar reaction. Similar to the reformer, for the reverse Boudouar reactor, when the reforming reaction is carried out in the fluidized bed reformer 21, a carbon dioxide separation unit 30 can be connected to the fluidized bed reverse Boudouar reactor 41 via a switching valve, and the first feed stream 210 can be supplied to the fluidized bed reverse Boudouar reactor 41 for a reverse Boudouar reaction. Furthermore, when the reforming reaction is carried out in a fixed bed reformer 22, a carbon dioxide separation unit 30 can be connected to the fixed bed reverse Boudouar reactor 42, and the first feed stream 210 can be supplied to the fixed bed reverse Boudouar reactor 42 for a reverse Boudouar reaction.

[0100] In one example, the hydrocarbon preparation apparatus 1 may further include: a cyclone separator 90 connected between the fluidized bed reforming reactor 21 and the carbon dioxide separation unit 30; a catalyst supply line connected between the cyclone separator 90 and the fluidized bed reverse Boudouar reactor 41; and a catalyst recirculation line connected between the fluidized bed reverse Boudouar reactor 41 and the fluidized bed reforming reactor 21, wherein the cyclone separator 90 can separate a second mixed gas 200 discharged from the fluidized bed reforming reactor 21 and the catalyst, supplying the second mixed gas 200 to the carbon dioxide separation unit 30 and the catalyst to the fluidized bed reverse Boudouar reactor 41.

[0101] Reference Figure 3According to the present invention, the hydrocarbon preparation apparatus 1 may further include a cyclone separator 90 between the fluidized bed reforming reactor 21 and the carbon dioxide separation unit 30. The cyclone separator 90 receives a second mixed gas 200 from the fluidized bed reforming reactor 21, separates the coking catalyst, and then supplies the second mixed gas 200 to the carbon dioxide separation unit 30. The coking catalyst can be supplied to the fluidized bed reverse Boudouar reactor 41 along a catalyst supply line connected to the cyclone separator 90 and the fluidized bed reverse Boudouar reactor 21. The coking catalyst received from the cyclone separator 90 is regenerated in the fluidized bed reverse Boudouar reactor 41, and the regenerated catalyst is supplied back to the fluidized bed reforming reactor 21 through a recirculation line connected to the fluidized bed reforming reactor 21. Thus, when the cyclone separator 90 is further included, there is no need to supply the coke required for the reverse Boudouar reaction separately from an external source, thereby achieving economical process operation, and the catalyst for the methane reforming reaction can be continuously resupplyed, thus having the advantage of efficient process operation.

[0102] In one example, the fixed-bed reverse Boudouar reactor 42 is connected between the carbon dioxide separation unit 30 and the gas mixing unit 50. The fixed-bed reverse Boudouar reactor 42 may further include a first fixed-bed reverse Boudouar reactor, a second fixed-bed reverse Boudouar reactor connected in parallel, and a control unit for switching between the first fixed-bed reverse Boudouar reactor and the second fixed-bed reverse Boudouar reactor.

[0103] The control unit can control the operation to a first mode, which involves disconnecting the carbon dioxide separation unit, the first fixed-bed reverse Boudouar reactor, and the gas mixing unit, regenerating the first fixed-bed reverse Boudouar reactor, and conducting the reverse Boudouar reaction through the second fixed-bed reverse Boudouar reactor.

[0104] Furthermore, the control unit can control the operation to a second mode, which involves disconnecting the carbon dioxide separation unit, the second fixed-bed reverse Boudouar reactor, and the gas mixing unit, regenerating the second fixed-bed reverse Boudouar reactor, and conducting the reverse Boudouar reaction through the first fixed-bed reverse Boudouar reactor.

[0105] Reference Figure 4 The carbon dioxide separation unit 30 of the hydrocarbon preparation apparatus 1 according to the present invention may include: a first carbon dioxide separation unit 31, which is connected between the fluidized bed reformer 21 and the fluidized bed reverse Boudouar reactor 41; and a second carbon dioxide separation unit 32, which is connected between the fixed bed reformer 22 and the fixed bed reverse Boudouar reactor 42 and is arranged in parallel with the first carbon dioxide separation unit 31.

[0106] When the carbon dioxide separation unit 30 includes a first carbon dioxide separation unit 31 and a second carbon dioxide separation unit 32, the first mixed gas 110 can be supplied to the gas mixing unit 50 via a fluidized bed reformer 21-first carbon dioxide separation unit 31-fluidized bed reverse Boudouard reactor 41, or via a fixed bed reformer 22-second carbon dioxide separation unit 32-fixed bed reverse Boudouard reactor 42. When the hydrocarbon preparation apparatus includes two reformers, two carbon dioxide separation units, and two reverse Boudouard reactors as described above, two processes can be operated simultaneously based on the critical C / O ratio in the first mixed gas 110. Therefore, even if the C / O ratio of the first mixed gas changes, the process can be operated continuously.

[0107] The gas mixing unit 50 mixes the second feed stream 211 separated in the carbon dioxide separation unit 30 with the carbon monoxide converted in the reverse Boudouard reactor 40 to generate a third mixed gas 220.

[0108] The generated third mixed gas 220 is converted into syngas 230 in the syngas generation unit 60 by adjusting the ratio of hydrogen to carbon monoxide in the third mixed gas 220 through a water-gas shift reaction.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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 used to illustrate the present invention and are not intended to limit the scope of the claims. Various changes and modifications can be made to the embodiments within the scope of the present invention and the technical concept, which will be obvious to those skilled in the art, and it is only natural that such variations and modifications fall within the scope of the claims.

[0113] (Example 1) 1000g of municipal solid waste was added to a pyrolysis reactor, and then heat-treated with steam at 1200℃ and 250kPa under alumina beads to recover the first mixed gas with a C / O ratio of 0.69.

[0114] The 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 mixed gas. As a result of the wet scrubber treatment, no impurity gases such as NH3, HCl, H2S, and COS were detected in the mixed gas.

[0115] The refined first mixed gas was then used at 2L / g 催化剂(cat) A second mixed gas is prepared by dry reforming methane using a space velocity of h to a fixed-bed reforming reactor containing 100 g of Ni / Al2O3 catalyst. Specifically, reduction is carried out for 2 hours at 900 °C while H2 is supplied to the catalyst-filled fixed-bed reforming reactor at a flow rate of 3.03 Nl / min. Then, a first mixed gas is supplied to the fixed-bed reforming reactor at a flow rate of 3.33 Nl / min, and the dry reforming reaction is carried out in a continuous process.

[0116] The Ni / Al2O3 catalyst was prepared by impregnating 1 mm diameter alumina particles in an aqueous solution of nickel nitrate hexahydrate dissolved in distilled water, followed by drying at 150 °C for 2 hours and then continuous calcination at 500 °C for 2 hours. This process was repeated multiple times as a unit process until the nickel content in the catalyst reached 20% by weight. The nickel content in the catalyst was measured by X-ray fluorescence spectrometry (XRF) analysis using Thermo Fisher Scientific's ARL QUANT' X.

[0117] The recovered second mixed gas, after water removal, flows into an amine scrubber. Carbon dioxide contained in the second mixed gas is captured in the amine scrubber, and the carbon dioxide-free second mixed gas is separated into a second feed stream. Specifically, the second mixed gas flows into a first amine scrubber, where CO2 is captured using an aqueous solution (amine solution) containing 12% by weight of NH3 at a temperature of 50°C to 60°C, 10 bar to 20 bar, and a throughput of 0.5 Nl / hour. 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 amine solution and CO2 at 100°C. The CO2 is recovered as the first feed stream.

[0118] The recovered first feed stream is continuously supplied to a fixed-bed reverse Boudouar reactor packed with Ni / Al₂O₃ catalyst and 5 kg of high-purity graphite, where carbon dioxide is converted to carbon monoxide via the reverse Boudouar reaction. The reverse Boudouar reaction is carried out under N₂ gas at 750 °C, a CO₂ flow rate of 2.33 Nl / min, and a space velocity of 2.0 L / g. 催化剂 It is carried out under the condition of h.

[0119] Carbon monoxide converted from the first feed stream and the second feed stream separated from the amine scrubber flow into the gas mixing unit and are mixed at 200°C to prepare a third mixed gas. The third mixed gas flows into the syngas generation unit, where it is converted into syngas with a molar ratio of H2:CO = 2:1 via a water-gas shift reaction. The water-gas shift reaction is carried out at 165°C, 35 bar, and a space velocity of 1.4 L / g under a Cu / Zn / Al2O3 catalyst. 催化剂 The reaction is carried out under the reaction conditions of h.

[0120] Syngas is supplied to the hydrocarbon conversion unit, and the injection rate is set to achieve a space velocity of 5000 L / kg under the Co / ZnO (Cobalt Zinc Oxide) catalyst. 催化剂 The volume ratio of carbon monoxide:hydrogen:argon was 63.2:31.3:5.5, and the Fischer-Tropsch synthesis reaction was carried out at a reaction temperature of 300°C and a pressure of 10 bar for 60 hours to recover the hydrocarbon fraction.

[0121] (Example 2) Hydrocarbons were prepared using the same method as in Example 1, except that after recovering the first mixed gas with a C / O ratio of 0.87, the reactor was switched and dry reforming and reverse Boudouar reaction were carried out in a fluidized bed reactor.

[0122] Specifically, 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 mixture was reacted for 3 hours to gelatinize and prepare a precursor gel. 30 parts by weight of clay and 1.5 parts by weight of MgO oxide were added and mixed using a homogenizer to prepare a solid mixture. This solid mixture was then mixed with the precursor gel, and 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 then spray-dried to prepare the fluidized bed catalyst.

[0123] 100 g of the Ni / Al2O3 catalyst was packed into a fluidized bed reformer, and reduction was carried out for 2 hours at 900 °C while supplying H2 at a flow rate of 3.03 Nl / min. Then, a purified first mixed gas was introduced at a total flow rate of 3.33 Nl / min, and 2.0 L / g of H2 was supplied. 催化剂 The system operates at a throughput of h to recover the second mixed gas.

[0124] A cyclone separator is used to separate the catalyst from the second mixed gas in the fluidized bed reformer. Then, an amine scrubber is used to separate CO2, and the second feed stream containing both catalyst and CO2 is recovered. Specifically, the second mixed gas flows into a first amine scrubber, where CO2 is captured by an aqueous solution of monoethanolamine (MEA) dissolved in it at 50°C (amine solution). The uncaptured gas is recovered as the second feed stream. The amine solution from the first amine scrubber flows into a second amine scrubber, where it is separated into amine solution and CO2 at 100°C. The CO2 is recovered as the first feed stream.

[0125] The recovered first feed stream flows into a fluidized bed reverse Boudouar reactor, where it is converted into carbon monoxide via the reverse Boudouar reaction. The reverse Boudouar reaction is carried out in a fluidized bed reactor packed with Ni / Al₂O₃ catalyst at a rate of 2 L / g. 催化剂 The first feed stream is supplied at a space velocity of h. At this time, the catalyst used as a carbon source in the dry reforming process, which deposits activated carbon and coke, is added. The catalyst activated by removing coke through the reverse Boudouar reaction is then reintroduced into the fluidized bed reformer via a recirculation line. If coke is insufficient, high-purity graphite is added to supplement it. Unconverted CO2 after the reverse Boudouar reaction is recovered separately via an amine scrubber.

[0126] (Example 3) Hydrocarbons were prepared using the same method as in Example 2, except that a first mixed gas with a C / O element ratio of 1.19 was used.

[0127] (Comparative Example 1) Hydrocarbons were prepared using the same method as in Example 1, except that a first mixed gas with a C / O element ratio of 0.87 was used.

[0128] (Comparative Example 2) Hydrocarbons were prepared using the same method as in Example 1, except that a first mixed gas with a C / O element ratio of 1.19 was used.

[0129] The composition of the first mixed gas recovered in Examples 1 to 3, Comparative Example 1 and Comparative Example 2 according to the C / O element ratio is summarized in Table 1.

[0130] [Table 1] (Experimental Example 1) Evaluation of the reforming reaction The catalytic activity, stability, and coke production during the preparation of hydrocarbons using the methods of Examples 1 to 3, Comparative Example 1, and Comparative Example 2 in the methane reforming reaction were evaluated. The coke production was measured by the following method: after the methane reforming reaction was completed, the deactivated catalyst was recovered and its weight was measured; it was then oxidized in air at 550°C to remove coke, and its weight was measured again. The weight difference before and after coke removal was confirmed, thereby quantitatively measuring the amount of coke deposited on the catalyst.

[0131] In Example 1, even after the methane reforming reaction ran for 20 days, no catalyst deactivation occurred, and no coke was formed on the catalyst. Therefore, it can be seen that the first mixed gas with a C / O ratio of 0.69 can maintain excellent reforming performance for a long time in a fixed-bed reactor.

[0132] On the other hand, in Comparative Example 1, where a first mixed gas with a C / O ratio of 0.87 was used to carry out a methane reforming reaction in a fixed-bed reactor, the reactor was not switched even when the C / O ratio was greater than or equal to the critical value. This resulted in catalyst deactivation after 5 days of operation, with the methane conversion rate dropping to below 30%. Specifically, since the coke content relative to the total weight of the catalyst was 9% by weight, and coke was deposited on the catalyst, the methane reforming performance was very low.

[0133] In Comparative Example 2, even though the C / O ratio of the first mixed gas was 1.19, a value greater than or equal to the critical value, the methane reforming reaction was carried out in a fixed-bed reactor without switching the reactor. As a result, the catalyst activity rapidly decreased to 66% within 2 hours, and 22% by weight of coke was deposited relative to the total catalyst weight, leading to catalyst deactivation.

[0134] However, as in Examples 2 and 3, when recovering the first mixed gas with C / O ratios of 0.87 and 1.19, respectively, and then switching reactors and carrying out dry reforming and reverse Boudouar reaction in a fluidized bed reactor, the catalyst deactivated by carbon deposition during the dry reforming reaction is added to the reverse Boudouar reactor to regenerate the catalyst. The regenerated catalyst is then added back to the fluidized bed reforming reactor and reused, thus maintaining high catalyst efficiency. That is, it can be seen that the catalyst can be regenerated in the fluidized bed reactor through a recycling process, thus maintaining high reactivity and reaction stability even if the catalyst is deactivated by the reforming reaction.

[0135] Therefore, by connecting fixed-bed and fluidized-bed reactors in parallel, and selecting an appropriate reactor based on the C / O ratio of the first mixed gas for reforming and the reverse Boudouar reaction, process efficiency can be significantly improved. When the C / O ratio of the first mixed gas is less than or equal to the critical value, a fixed-bed reactor, which has the advantages of low operating cost, mass production capability, and ease of management, is used for reforming and the reverse Boudouar reaction. When the C / O ratio of the first mixed gas is greater than or equal to the critical value, the process is switched to a fluidized-bed reactor capable of catalyst recycling, thereby improving reaction stability.

[0136] The above description is merely an example of applying the principles of the present invention, and other configurations may be included without departing from the scope of the present invention.

[0137] [Explanation of reference numerals in the attached figures] 1: Hydrocarbon preparation apparatus; 10: Pyrolysis reactor 20: Reforming reactor; 21: Fluidized bed reforming reactor 22: Fixed-bed reforming reactor; 30: Carbon dioxide separation unit 31: First carbon dioxide separation unit; 32: Second carbon dioxide separation unit 40: Reverse Boudouar reactor; 41: Fluidized bed reverse Boudouar reactor 42: Fixed-bed reverse Butuar reactor; 50: Gas mixing unit 60: Syngas generation unit; 70: Hydrocarbon conversion unit 80: Refining unit; 90: Cyclone separator 100: Organic waste; 110: First mixed gas 120: First mixed gas after removing impurities; 200: Second mixed gas 210: First material flow; 211: Second material flow 220: Third mixture gas; 230: Synthesis gas

Claims

1. A method for preparing a hydrocarbon, wherein, The preparation method includes the following steps: (S1) The organic waste is thermally treated in a pyrolysis reactor to generate a first mixed gas; (S2) The first mixed gas is subjected to methane reforming in a reforming reactor to generate a second mixed gas; (S3) Separate a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide from the second mixed gas; (S4) The first feed stream and carbon are added to the reverse Boudouar 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 generate a 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 reforming reactor in step (S2) includes a fluidized bed reforming reactor and a fixed bed reforming reactor connected in parallel, and the first mixed gas is supplied to the fluidized bed reforming reactor or the fixed bed reforming reactor by switching.

2. The method for preparing hydrocarbons according to claim 1, wherein, When the C / O ratio of the first mixed gas is greater than or equal to a critical value, it is switched and supplied as feed to the fluidized bed reformer; when the C / O ratio of the first mixed gas is less than a critical value, it is switched and supplied as feed to the fixed bed reformer.

3. The method for preparing hydrocarbons according to claim 2, wherein, The critical value is between 0.5 and 0.

9.

4. The method for preparing hydrocarbons according to claim 1, wherein, The reverse Boudouar reactor is connected in parallel with a fluidized bed reverse Boudouar reactor and a fixed bed reverse Boudouar reactor, and the first feed stream is supplied by switching.

5. The method for preparing hydrocarbons according to claim 4, wherein, The fluidized bed reverse Boudouar reactor in step (S4) is supplied with carbon from the coking catalyst of the fluidized bed reformer, while the fixed bed reverse Boudouar reactor is supplied with additional carbon from a separate carbon source.

6. 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.

7. The method for preparing hydrocarbons according to claim 1, wherein, The synthesis gas in step (S6) contains hydrogen and carbon monoxide, and the ratio of hydrogen to carbon monoxide satisfies 1.8:1 to 2.2:

1.

8. The method for preparing hydrocarbons according to claim 1, wherein, The catalytic reaction in step (S7) is a Fischer-Tropsch synthesis reaction.

9. The method for preparing hydrocarbons according to claim 1, wherein, The catalytic reaction in step (S7) is a methanol-olefin conversion reaction.

10. The method for preparing hydrocarbons according to claim 8, wherein, The hydrocarbons produced through step (S7) are synthetic petroleum.

11. The method for preparing hydrocarbons according to claim 9, wherein, The hydrocarbons generated through step (S7) are light olefins.

12. The method for preparing hydrocarbons according to claim 1, wherein, The methane reforming is carried out at a temperature of 700°C to 1000°C.

13. The method for preparing hydrocarbons according to claim 1, wherein, The reverse Boudouar reaction is carried out at temperatures ranging from 600°C to 1000°C and pressures ranging from 50 kPa to 300 kPa.

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

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

16. 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 reforming reactor, wherein the first mixed gas is reformed with methane to produce a second mixed gas; A carbon dioxide separation unit that separates the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; A reverse Boudouard reactor, wherein the reverse Boudouard reactor converts the first feed stream into carbon monoxide via a reverse Boudouard reaction; A gas mixing unit that mixes the second feed stream with carbon monoxide converted in the reverse Boudouar reactor to generate 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 in the presence of a catalyst. The reforming reactor includes a fluidized bed reforming reactor and a fixed bed reforming reactor connected in parallel. The first mixed gas discharged from the pyrolysis reactor is switched and supplied to the fluidized bed reforming reactor or the fixed bed reforming reactor through a switching valve.

17. The hydrocarbon preparation apparatus according to claim 16, wherein, A refining unit is further included between the pyrolysis reactor and the reforming reactor.

18. The hydrocarbon preparation apparatus according to claim 16, wherein, The reverse Boudouar reactor includes a fluidized bed reverse Boudouar reactor and a fixed bed reverse Boudouar reactor arranged in parallel, and the first feed stream is selectively supplied to the fluidized bed reverse Boudouar reactor or the fixed bed reverse Boudouar reactor by switching.

19. The hydrocarbon preparation apparatus according to claim 18, wherein, The hydrocarbon preparation apparatus further includes: A cyclone separator is connected between the fluidized bed reformer and the carbon dioxide separation unit; Catalyst supply line, the catalyst supply line connecting the cyclone separator and the fluidized bed reverse Boudouar reactor; and A catalyst recirculation line connects the fluidized bed reverse Boudouar reactor and the fluidized bed reforming 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 fluidized bed reverse Boudouar reactor.

Images