Method and apparatus for preparing hydrocarbons

Abstract

The present disclosure provides a method for preparing hydrocarbons, comprising the steps of: (S1) heat treating organic waste so as to generate a first mixed gas; (S2) dry reforming the first mixed gas in a first fluidized bed reactor so as to generate a second mixed gas; (S3) separating the second mixed gas into a first stream that comprises carbon dioxide and a second stream that comprises hydrogen and carbon monoxide; (S4) introducing the first stream, which was separated out in step (S3), to a second fluidized bed reactor and converting same into carbon monoxide through a reverse Boudouard reaction; (S5) mixing the second stream and the carbon monoxide, which was converted in step (S4), so as to prepare a third mixed gas; (S6) generating syngas from the third mixed gas through a water-gas shift reaction; and (S7) preparing hydrocarbons from the syngas through a catalytic reaction.

Description

Hydrocarbon production method and device

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

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

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

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

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

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

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

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

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

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

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

[0012] In one example, the first mixed gas may further include one or more selected from the group consisting of landfill gas, shale gas, refinery exhaust gas, and biogas.

[0013] In one example, the first stream may contain at least 50% by volume of carbon dioxide.

[0014] In one example, the pyrolysis gas may have a C / O ratio of 0.1 or more.

[0015] In one example, the step (S2) may be performed under a composite catalyst in which an active metal is supported on a support.

[0016] In one example, the active metal may include one or more selected from the group consisting of nickel, vanadium, iron, platinum, palladium, and ruthenium.

[0017] In one example, the support may include one or more selected from the group consisting of silica, alumina, silica-alumina, carbon, zirconia, titania, zeolite, SAPO and ALPO.

[0018] In one example, the step (S2) may be performed at a temperature of 700 to 1000°C.

[0019] In one example, the step (S4) may be performed at a temperature of 600 to 1000°C and a pressure of 50 to 300 KPa.

[0020] In one example, the synthesis gas contains hydrogen and carbon monoxide, and the ratio of hydrogen and carbon monoxide can be 1.8:1 to 2.2:1.

[0021] In one example, in the step (S1), the organic waste may be one or more selected from the group consisting of waste plastic, solid waste, biomass, waste oil, waste tires, and volume-based waste bags.

[0022] In one example, prior to the step (S2), a step of purifying the first mixed gas of the step (S1) may be further included.

[0023] A hydrocarbon production device according to the present disclosure comprises: a pyrolysis reactor that heat-treats organic waste to produce a first mixed gas; a first fluidized bed reactor that catalytically dry-reforms the first mixed gas to produce a second mixed gas; a carbon dioxide separation unit that separates the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; a second fluidized bed reactor that converts the first stream into carbon monoxide through a reverse Boudouard reaction; and a gas mixing unit that mixes the second stream with carbon monoxide converted from the second fluidized bed reactor to produce a third mixed gas; a synthesis gas production unit that converts the third mixed gas into synthesis gas through a water gas shift reaction; and a hydrocarbon conversion unit that converts the synthesis gas into hydrocarbon through a catalytic reaction.

[0024] In one example, the hydrocarbon production device further includes a cyclone connected between the first fluidized bed reactor and the carbon dioxide separation unit; a catalyst supply line connecting the cyclone and the second fluidized bed reactor; and a catalyst recirculation line connecting the second fluidized bed reactor and the first fluidized bed reactor, wherein the cyclone separates a second mixed gas discharged from the fluidized bed reforming reactor and a catalyst, supplies the second mixed gas to the carbon dioxide separation unit, and supplies the catalyst to the second fluidized bed reactor.

[0025] In one example, a purification unit may be further included between the heat treatment reactor and the first fluidized bed reactor.

[0026] According to one embodiment of the present disclosure, the yield of hydrocarbon production from organic waste can be significantly improved.

[0027] According to one embodiment of the present disclosure, the production efficiency of hydrocarbons can be significantly improved by converting the feed into hydrocarbons using a process and device suitable for the C / O element ratio of the feed.

[0028] According to one embodiment of the present disclosure, the generation of carbon dioxide can be minimized during the hydrocarbon production process.

[0029] Figure 1 is a schematic diagram showing a hydrocarbon production device according to an example of the present disclosure.

[0030] Figure 2 is a schematic diagram showing a hydrocarbon production device including a refining process according to an example.

[0031] Figure 3 is a schematic diagram showing a hydrocarbon production device including a catalyst circulation process according to an example.

[0032] As used herein, the singular forms of terms may be construed to include the plural forms as well, unless otherwise specified.

[0033] The numerical ranges used herein include the lower and upper limits, all values ​​within those limits, all values ​​delimited by these limits, and all possible combinations of the upper and lower limits of numerical ranges defined in different ways. Unless otherwise specified herein, values ​​outside the numerical ranges that may arise due to experimental error or rounding of values ​​are also included in the defined numerical ranges.

[0034] The term "includes" as used herein is an open-ended description having the equivalent meaning of expressions such as "comprises," "contains," "has," and "characterizes," and does not exclude additional elements, materials, or processes not listed.

[0035] The unit of % used in this specification without special mention means weight % unless otherwise defined.

[0036] Conventionally, a gasification process using a catalyst has been implemented as a process for producing synthesis gas. However, there has been a problem that the catalyst is deactivated due to the generation of coke and the like during the gasification process, and process troubles occur due to the deactivated catalyst during continuous operation. In addition, to ensure economic feasibility, the relatively expensive catalyst needs to be recovered. However, in order to recover the catalyst discharged in a coagulated state such as coke, multiple subsequent processes (such as air burning) must be performed, which significantly reduces the process efficiency and causes environmental pollution due to the emission of a large amount of carbon dioxide during the process. Furthermore, the conventional gasification process for organic waste has a significantly low synthesis gas production yield of less than 30%, which reduces productivity and limits the conversion of the gas into high value-added products. Therefore, the inventors of the present disclosure have devised a manufacturing method and device that can efficiently produce hydrocarbons from organic waste while minimizing the generation of carbon dioxide.

[0037] The present disclosure provides a method for producing hydrocarbons, comprising: (S1) a step of heat-treating organic waste to produce a first mixed gas; (S2) a step of dry-reforming the first mixed gas in a first fluidized bed reactor to produce a second mixed gas; (S3) a step of separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; (S4) a step of introducing the first stream separated in step (S3) into a second fluidized bed reactor and converting the first stream into carbon monoxide through a reverse Boudouard reaction; (S5) a step of mixing the second stream with the carbon monoxide converted in step (S4) to produce a third mixed gas; (S6) a step of producing a synthesis gas from the third mixed gas through a water gas shift reaction; and (S7) a step of producing a hydrocarbon from the synthesis gas through a catalytic reaction.

[0038] The method for producing hydrocarbons according to the present disclosure can efficiently convert organic waste plastics into synthesis gas compared to conventional gasification processes, thereby maximizing the yield of high-value-added hydrocarbons converted from the synthesis gas. Furthermore, the carbon dioxide generated during the synthesis gas production process can be converted into a raw material for the synthesis gas, thereby minimizing carbon dioxide emissions during the hydrocarbon production process and preventing environmental pollution.

[0039] The above step (S1) is a step of generating a first mixed gas by heat-treating organic waste, in which a gasification reaction of the organic waste can occur.

[0040] In one example, in step (S1), the organic waste may be one or more selected from the group consisting of waste plastic, solid waste, biomass, waste oil, waste tires, and volume-based waste bags.

[0041] Specifically, in the step (S1), one or more gasification reactions selected from the following reaction formulas 1 to 4 may be involved.

[0042] [Reaction Formula 1]

[0043] C x H y + H2O →H2+ CO (water gasification reaction)

[0044] [Reaction Formula 2]

[0045] C x H y + CO2→CO (carbon dioxide gasification reaction)

[0046] [Reaction Formula 3]

[0047] CO + 3H2→CH4+ H2O (methanation reaction)

[0048] [Reaction Formula 4]

[0049] C x H y + O2→ CO2 (oxidation reaction)

[0050] In one example, the first mixed gas may include methane, hydrogen, carbon monoxide, and carbon dioxide, and may also include various impurities such as nitrogen oxides, sulfur oxides, and hydrogen chloride.

[0051] In one example, step (S1) may be performed under a first catalyst condition or a non-catalytic condition to increase the methane content in the composition of the first mixed gas. Since increasing the methane content in the composition of the first mixed gas may be advantageous in terms of methane reforming reaction efficiency or synthesis gas production yield, an acid site catalyst or a molybdenum series shaped catalyst may be used as a bed material of the gasifier to increase the methane content in step (S1). If a catalyst is not used, the gasifier may be operated under low-temperature and high-pressure conditions to increase the methane content. The yield improvement effect due to methane reforming can be expected to have the same effect not only on the methane content but also on the C2 to C4 hydrocarbon gas content, and the C2 to C4 gas content can also be increased by using an acid site catalyst or by performing low-temperature and high-pressure gasification operation.

[0052] In one example, the first catalyst may be an acid site catalyst or a molybdenum-based molded catalyst. The acid site catalyst may be a catalyst having a solid acid site derived from alumina or a structure. The alumina may be alumina alone, silica-alumina, alumina dispersed in a carbon structure, etc., and the structure acid site material may be zeolite, SAPO, AlPO, MOF, or a structural modification thereof. The molybdenum-based catalyst refers to a catalyst in which molybdenum is supported on a support, and nickel, cobalt, etc. may be added as needed, and tungsten may be used instead of molybdenum. The support may be any material that has durability capable of supporting an active metal, and may include, for example, a material including one or more selected from the group consisting of silica, alumina, silica-alumina, carbon, and zirconia.

[0053] As another example of increasing the methane content in the first mixed gas, the first mixed gas may further include one or more selected from the group consisting of landfill gas, shale gas, refinery exhaust gas, and biogas. Since the above-described landfill gas, shale gas, refinery exhaust gas, and biogas contain methane and carbon dioxide in an amount of 40% by volume or more, specifically, 50% by volume or more, since the first mixed gas further includes the above-described gases, there is an effect of further improving the production yield of synthesis gas through subsequent processes such as methane reforming reaction and reverse Budar reaction.

[0054] In one example, the C / O element ratio of the first mixed gas may be, as an upper limit, 0.8 or less, 0.75 or less, and 0.7 or less, and as a lower limit, 0.1 or more, 0.15 or more, and 0.2 or more. Specifically, it may be 0.1 to 0.8, and more specifically, 0.2 to 0.7.

[0055] The method for producing hydrocarbons according to the present disclosure enables a smooth methane reforming reaction even when the first mixed gas contains a relatively high C / O element ratio within the above-described range. Specifically, since the catalyst used in the methane reforming reaction forms a cyclic process as described below, the reaction can be continuously performed regardless of catalyst deactivation due to coke that may be generated by dry reforming of methane.

[0056] In one example, the step (S1) may further include a step of purifying the first mixed gas.

[0057] The first mixed gas generated by heat treating organic waste may contain one or more impurities selected from the group consisting of tar, sulfur, nitrogen, and chlorine. Specifically, the first mixed gas may contain water-soluble impurities such as H2S, HCl, HOCl, and NH3, and insoluble impurities such as tar. These impurities contained in the first mixed gas may induce catalyst deactivation, thereby reducing the efficiency of a subsequent process. Therefore, by removing the impurities from the first mixed gas and purifying it, the efficiency of the overall process can be improved.

[0058] The method for purifying the first mixed gas may be one or a combination of two or more selected from the group consisting of using a high-pressure dust collecting filter, water washing, alkaline solution washing, and passing through a ceramic filter, but is not limited thereto. When water washing or alkaline solution washing is used, water-soluble impurities such as H2S, HCl, HOCl, and NH3 contained in the first mixed gas can be removed, and when the first mixed gas is passed through a ceramic filter or dust collecting filter, non-water-soluble impurities such as tar and dust can be removed.

[0059] Step (S2) is a step of producing a second mixed gas by dry reforming methane contained in the first mixed gas in a first fluidized bed reactor. In step (S2), a reforming reaction according to the following reaction formula 5 may occur.

[0060] [Reaction Formula 5]

[0061] CH4+ CO2→2CO + 2H2 (carbon dioxide reforming reaction)

[0062] The reforming reaction of the above step (S2) can be performed at a temperature of 600°C to 1400°C and a pressure of 30 KPa to 2000 KPa.

[0063] The above step (S2) may be operated without a catalyst, but may be operated using a catalyst to increase the reaction conversion rate at a low temperature of about 600°C to 700°C. The catalyst of the above step (S2) may be a composite catalyst in which an active metal is supported on a support. The active metal may include at least one selected from the group consisting of nickel, vanadium, iron, platinum, palladium, and ruthenium. Typically, the active metal may be nickel, vanadium, or iron, and in cases where the raw material, such as organic waste, has a low impurity content during the heat treatment process, a noble metal such as platinum, palladium, or ruthenium may be used.

[0064] In one example, the support may be a solid acid material such as an oxide or a zeolite, and specifically, may be at least one selected from the group consisting of ZSM-5, ZSM-11, USY zeolite, Ferrierite, Mordenite, MCM-22, SUZ-4, L-type zeolite, silica, alumina, silica-alumina, carbon, zirconia, and titania.

[0065] By performing a dry reforming reaction as a methane reforming reaction in step (S2), the methane reforming efficiency can be improved, thereby increasing the hydrocarbon yield. Specifically, the dry reforming process can more smoothly perform the catalytic reaction of synthesis gas, a subsequent process, because the ratio of the products, hydrogen and carbon monoxide, is close to 1:1.

[0066] In addition, since step (S2) is performed in a fluidized bed reactor, the catalyst used in the methane reforming reaction can be regenerated and then supplied to a subsequent reverse catalytic reaction process, thereby forming a cyclic process. Since the methane reforming reaction in step (S2) is performed dry, coke may accumulate on the catalyst, which may deactivate the catalytic reaction. However, since step (S2) is performed in a fluidized bed reactor, a cyclic process of regenerating and resupplying the catalyst can be performed, so that a continuous reforming reaction is possible even when methane is dry reformed.

[0067] (S3) Step is a step of separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide.

[0068] In one example, the method for separating the second mixed gas into the first stream and the second stream is not limited to any known method, but the present disclosure allows separation using a carbon dioxide separation unit, and the carbon dioxide separation unit may be an Amine Scrubber. Typically, an Amine Scrubber separates components such as carbon dioxide and hydrogen sulfide from gas vapor by combining and removing carbon dioxide through an amine-based material, and can recover a gas containing hydrogen, carbon monoxide, or an inert gas. Therefore, the first mixed gas can be separated into the first stream and the second stream by using an Amine Scrubber.

[0069] As another example, the carbon dioxide separation unit may be a CCS unit (Carbon capture and storage unit). When a CCS unit is used to separate carbon dioxide, the CCS unit can adsorb and separate carbon dioxide using an adsorbent including one or more selected from calcium oxide, calcium hydroxide, dolomite, limestone, and trona, so the second mixed gas can be separated into first and second streams using the CCS unit (Carbon capture and storage unit).

[0070] The first stream may contain carbon dioxide in a lower limit of 40% by volume or more, 50% by volume or more, or 60% by volume or more, and an upper limit of 99% by volume or less, 90% by volume or less, 80% by volume or less, or 70% by volume or less. Specifically, the first stream may contain carbon dioxide in a range of 40 to 99% by volume, and more specifically, 50 to 80% by volume. In a carbon dioxide separation unit, when capturing carbon dioxide and separating it, in order to separate carbon dioxide with high purity, the regeneration tower where the carbon dioxide is separated from the adsorbent must be designed with a high stage, which consumes more energy. Therefore, since the first stream contains carbon dioxide in the above-described range, the carbon dioxide separation process can be performed under slightly milder conditions.

[0071] Step (S4) is a step for converting the first stream separated in step (S3) into carbon monoxide through a reverse Buta reaction in a second fluidized bed reactor. By additionally converting the carbon dioxide contained in the first stream into carbon monoxide through the reverse Buta reaction, it is possible to prevent environmental pollution by reducing carbon dioxide emissions, while also maximizing the yield of synthesis gas. The reverse Buta reaction may involve the following reaction scheme 6.

[0072] [Reaction Formula 6]

[0073] C+CO2→ 2CO

[0074] The above step (S4) can be performed at a temperature of 600°C to 1000°C and a pressure of 50 KPa to 300 KPa.

[0075] In one example, the carbon source for the reverse reaction in step (S4) may be the catalyst on which coke is deposited supplied in step (S2), and may be supplied from outside with a carbon source such as activated carbon, if necessary.

[0076] Specifically, the catalyst on which coke used in the methane dry reforming reaction in step (S2) is deposited can be used in the reverse Buta reaction in step (S4). The coke deposited on the catalyst can be used as a carbon source for the reverse Buta reaction, thereby regenerating the catalyst. The regenerated catalyst can be used again in the methane dry reforming reaction in step (S2). By utilizing this catalyst circulation process, the methane dry reforming reaction can be performed continuously, while eliminating the need for an externally supplied carbon source for the reverse Buta reaction, thereby enabling an economical process.

[0077] That is, the present disclosure can maximize the yield of synthesis gas through methane reforming reaction and reverse Buta reaction, and at the same time, continuous and economical process operation according to catalyst regeneration can be implemented as the first fluidized bed reactor and the second fluidized bed reactor in which the methanation reforming reaction and reverse Buta reaction are performed form a circulation process.

[0078] In one example, the external carbon source may be char derived from the organic waste, more specifically char derived from the pyrolysis of waste plastic or char derived from biomass. Alternatively, the external carbon source may include high-purity graphite to prevent the possibility of introducing impurity gases.

[0079] Step (S5) is a step of generating a third mixed gas by mixing the second stream separated from the carbon dioxide separation unit and the carbon monoxide converted by the reverse reaction in step (S4).

[0080] The third mixed gas may contain hydrogen and carbon monoxide.

[0081] Step (S6) is a process for generating synthesis gas by controlling the ratio of carbon monoxide and hydrogen in the third mixed gas through a water-gas shift reaction. The third mixed gas can be converted through the water-gas shift reaction to satisfy an appropriate hydrogen:carbon monoxide ratio for the subsequent catalytic reaction process. The water-gas shift reaction may involve the following chemical formula 7.

[0082] [Chemical Formula 7]

[0083] CO + H2O → H2 + CO2

[0084] The water-gas shift reaction can be carried out in the presence of a catalyst containing Fe and Cr. The water-gas shift reaction can be carried out at a temperature of 100°C to 400°C, specifically 100°C to 300°C, and a pressure of 20 bar to 80 bar, specifically 25 bar to 70 bar.

[0085] The synthesis gas produced by the above-described water-gas shift reaction may have a hydrogen:carbon monoxide ratio of 1.5 to 3:1, specifically 1.9 to 2.1:1. As the hydrogen:carbon monoxide ratio in the synthesis gas satisfies the above-described range, the subsequent catalytic reaction process can be performed smoothly.

[0086] Step (S7) is a step for converting the synthesis gas generated in step (S6) into a hydrocarbon fraction, which can be converted into an appropriate hydrocarbon fraction by a catalytic reaction.

[0087] The above catalytic reaction is not limited to any reaction that can convert synthesis gas into hydrocarbon fractions, but may be a Fischer-Tropsch reaction or a methanol and olefin conversion reaction.

[0088] In one example, when the catalytic reaction of step (S7) is a Fischer-Tropsch reaction, a reaction involving the following chemical formula 8 can be performed using the synthesis gas produced in step (S6) as a raw material.

[0089] [Chemical Formula 8]

[0090] nCO + 2nH2→C n H 2n + nH2O

[0091] The above Fischer-Tropsch reaction can be carried out under a catalyst including cobalt, nickel or iron, and can include alumina, silica, titania, etc. as a support, and can include a noble metal such as Pt, Ru, Re, etc. as a cocatalyst.

[0092] The Fischer-Tropsch reaction can be carried out at a temperature of 100°C to 500°C, specifically 200°C to 350°C, at a pressure of 10 atm to 50 atm, and at a pressure of 10 atm to 30 atm.

[0093] In one example, when the catalytic reaction of step (S7) is a methanol and olefin conversion reaction, step (S7) may include a reaction of converting synthesis gas into methanol; and a reaction of converting methanol into olefin.

[0094] The reaction for converting synthesis gas into methanol may be a reaction involving the following chemical formula 9.

[0095] [Chemical Formula 9]

[0096] CO + 2H2→ CH3OH

[0097] In one example, the reaction of converting synthesis gas into methanol can be performed under a Cu-based catalyst. Specifically, the Cu-based catalyst can be a Cu-based methanol-based synthesis catalyst, and the support of the Cu-based catalyst can use at least one selected from the group consisting of SiO2, ZrO2, Ga2O3Al2O3, MgO, and TiO2. Specifically, the Cu-based methanol-based synthesis catalyst can be Cu / Zn / Al2O3.

[0098] The reaction of converting the above synthesis gas into methanol can be performed at a temperature of 400°C to 600°C, specifically 430°C to 530°C, and a pressure of 0.1 MPa to 10 MPa, specifically 0.1 MPa to 5 MPa.

[0099] The reaction of converting methanol into olefin can be carried out under a zeolite catalyst or an AlPO4-based molecular sieve catalyst. Specifically, the zeolite catalyst can be ZSM-5, and the AlPO4-based catalyst can be a silicoaluminaphosphate (SAPO) molecular sieve catalyst, and specifically, it can be at least one selected from SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-44, and SAPO-46.

[0100] The reaction of converting methanol into olefin can be carried out at a temperature of 200°C to 600°C, specifically 300°C to 500°C, and a pressure of 1 bar to 10 bar, specifically 1 bar to 5 bar.

[0101] The present disclosure comprises a pyrolysis reactor (10) for generating a first mixed gas (110) by heat-treating organic waste (100); a first fluidized bed reactor (20) for generating a second mixed gas (200) by dry reforming the first mixed gas (110) under a catalyst; a carbon dioxide separation unit (30) for separating the second mixed gas (200) into a first stream (210) containing carbon dioxide and a second stream (211) containing hydrogen and carbon monoxide; a second fluidized bed reactor (40) for converting the first stream (210) into carbon monoxide through a reverse Boudouard reaction; and a gas mixing unit (50) for producing a third mixed gas (220) by mixing the second stream (211) and carbon monoxide converted from the second fluidized bed reactor (40). A hydrocarbon production device is provided, comprising a synthesis gas production unit (60) that converts the third mixed gas (220) into synthesis gas (230) through a water gas shift reaction; and a hydrocarbon conversion unit (70) that converts the synthesis gas (230) into hydrocarbon through a catalytic reaction.

[0102] The hydrocarbon production device (1) according to the present disclosure can efficiently and economically produce synthesis gas and hydrocarbons by using a fluidized bed reactor when performing a reforming reaction and a reverse Budah reaction of methane, and can significantly reduce the amount of carbon dioxide emissions.

[0103] Referring to Fig. 1, organic waste (100) is introduced into a pyrolysis reactor (10) and, after heat treatment, generates a first mixed gas (110). The first mixed gas (110) is introduced into a first fluidized bed reactor (20) and converted into a second mixed gas (220) through a dry reforming reaction.

[0104] In one example, the hydrocarbon device may further include a purification unit (80) connected between the pyrolysis reactor (10) and the first fluidized bed reactor (20). Specifically, referring to FIG. 2, the first mixed gas (110) is introduced into the purification unit (80) to remove impurities, and the first mixed gas (120) from which impurities have been removed is introduced into the first fluidized bed reactor (20) to perform a methane reforming reaction.

[0105] The above purification unit (80) includes a sprayer that sprays liquid, receives a first mixed gas (110) from a pyrolysis reactor (10), and contacts the first mixed gas (110) with a weakly basic solution containing water or sodium carbonate to remove water-soluble impurities such as H2S, HCl, HOCl, and NH3, or removes dust using a high-pressure dust collecting filter, and removes insoluble impurities such as tar by including a ceramic filter, etc.

[0106] The second mixed gas (200) is introduced into a carbon dioxide separation unit (30) and separated into a first stream (210) containing carbon dioxide and a second stream (211) containing hydrogen and carbon monoxide. The second stream (211) is directly supplied to a gas mixing unit (50), and the first stream (210) is supplied to a second fluidized bed reactor (40) and converted into carbon monoxide through a reverse Budah reaction.

[0107] In one example, referring to FIG. 3, the system further includes a cyclone (90) connected between the first fluidized bed reactor (20) and the carbon dioxide separation unit (30); a catalyst supply line connecting the cyclone (90) and the second fluidized bed reactor (40); and a catalyst recirculation line connecting the second fluidized bed reactor (40) and the first fluidized bed reactor (20). The cyclone (90) separates the second mixed gas (200) discharged from the first fluidized bed reactor (20) and the catalyst, supplies the second mixed gas (200) to the carbon dioxide separation unit (30), and supplies the catalyst to the second fluidized bed reactor (40).

[0108] Since the first fluidized bed reactor (20) and the second fluidized bed reactor (40) form a circulating process, continuous process operation is possible due to catalyst regeneration. In addition, the catalyst on which the coke used in the first fluidized bed reactor (20) has been deposited can be utilized without the need for a separate external carbon source to perform the reverse-Buda reaction in the second fluidized bed reactor (40), enabling more economical process operation.

[0109] The gas mixing unit (50) mixes the second stream (211) with carbon monoxide converted in the second fluidized bed reactor (40) to produce a third mixed gas (220). The third mixed gas (220) is supplied to the water gas conversion unit (60) and converted into a synthesis gas (230) by adjusting the hydrogen:carbon monoxide ratio in the third mixed gas (220) through a water gas conversion reaction.

[0110] Synthesis gas (230) is introduced into a hydrocarbon conversion unit (70) and converted into hydrocarbons through a Fischer-Tropsch reaction or a methanol and olefin conversion reaction, and can be recovered as a high value-added oil fraction.

[0111] In one example, when the hydrocarbon conversion unit (70) performs a methanol and olefin conversion reaction, the hydrocarbon conversion unit (70) may include a methanol conversion unit that receives synthesis gas (230) and converts it into methanol, and an olefin conversion unit that receives methanol from the methanol conversion unit and converts it into olefin.

[0112] In one example, the hydrocarbon production device may further include a separation step that separates the produced hydrocarbons into fractions by boiling point through distillation by being connected to a hydrocarbon conversion unit (70).

[0113] Below, specific embodiments of the present disclosure are further described.

[0114] (Example 1)

[0115] 1000g of municipal solid waste was fed into a pyrolysis reactor, and steam was introduced and heat-treated under an alumina bead at a temperature of 1200℃ and a pressure of 250 kPa to recover a first mixed gas having a C / O element ratio of 0.7. The composition of the recovered first mixed gas is shown in Table 1 below, and the composition of trace impurity gases in the first mixed gas is shown in Table 2.

[0116] Feedmol%wt%H2323CO1618CO24072CH4117Total100100

[0117] Impurity GasppmHCl2231H2S1217COS231NH33701

[0118] The first mixed gas was lowered in temperature and introduced into a purification unit (wet scrubber) to be treated at 70°C and 100KPa to remove impurities, and the purified first mixed gas was recovered. As a result of treating the first mixed gas containing impurities with the composition of Table 2 through the wet scrubber, impurity gases such as NH3, HCl, H2S, and COS were not analyzed, confirming that the impurities were effectively removed.

[0119] The first mixed gas from which the above impurities have been removed is fed to a first fluidized bed reactor equipped with a Ni / Al2O3 catalyst at a rate of 2 L / g cat ·The second mixed gas was produced through dry reforming of methane by supplying it at a space velocity of h.

[0120] A Ni / Al2O3 fluidized bed catalyst was prepared according to the following procedure. A mixture solution of 10 parts by weight of pseudo-boehmite alumina and 95 parts by weight of nickel nitrate hexahydrate with 100 parts by weight of water was mixed, and 1 part by weight of formic acid was added while stirring, and the mixture was reacted for 3 hours to cause gelation to prepare a precursor gel. 30 parts by weight of clay and 1.5 parts by weight of MgO oxide were added, and the mixture was mixed using a homogenizer. The solid mixture prepared was mixed with the precursor gel, and then 10 parts by weight of colloidal silica (Ludox AS40, Aldrich) was added, and 5 parts by weight of water was further added, followed by vigorous stirring to prepare a composite catalyst sol. The composite catalyst sol was spray-dried to prepare a fluidized bed catalyst.

[0121] 100g of the above Ni / Al2O3 catalyst is charged into the first fluidized bed reactor, H2 is supplied at a flow rate of 3.03 Nl / min at 900°C, and reduced for 2 hours, and then the purified first mixed gas is introduced at a total flow rate of 3.33 Nl / min and 2.0 L / g cat ·The operation was carried out at a processing capacity of h, and the second mixed gas was recovered.

[0122] After separating the catalyst from the second mixed gas of the first fluidized bed reactor using a cyclone, CO2 was separated using an amine scrubber, and the second stream from which the catalyst and carbon dioxide were separated was recovered. Specifically, the second mixed gas was introduced into the first amine scrubber, where CO2 was captured in an aqueous solution (amine solution) containing MEA (Monoethanolamine) at 50°C, and the uncaptured gas was recovered as the second stream. The amine solution of the first amine scrubber was introduced into the second amine scrubber, where it was separated into the amine solution and CO2 at 100°C, and the CO2 was recovered as the first stream. The recovered first stream was fed into the second fluidized bed reactor and converted into carbon monoxide through the reverse Buta reaction. The reverse Buta reaction was performed in a fluidized bed reactor filled with a Ni / Al2O3 catalyst on which activated carbon and coke were deposited, which was used in the above dry reforming process, and the space velocity was 2 L / g. cat ·The first stream was supplied with h. At this time, the activated catalyst, in which coke was removed through the reverse Buta reaction, was reintroduced into the first fluidized bed reactor through the recycle line. The insufficient carbon source was supplemented by additionally adding high-purity graphite. Unconverted CO2 after the reverse Buta reaction was separately recovered through an amine scrubber.

[0123] Carbon monoxide converted from the first stream and the second stream are introduced into a gas mixing unit and mixed at 200°C to produce a third mixed gas.

[0124] The third mixed gas was introduced into the synthesis gas generation unit and produced synthesis gas with a molar ratio of H2:CO=2:1 through a water gas shift reaction.

[0125] Synthesis gas is fed to the hydrocarbon conversion unit and is converted into hydrogen at a space velocity of 5000 L / kg under a Co / ZnO (Cobalt Zinc oxide) catalyst. cat·The injection rate was set so that the volume ratio of h and carbon monoxide: hydrogen: argon was 63.2:31.3:5.5, and the Fischer-Tropsch reaction was performed at a reaction temperature of 300°C and a pressure of 10 bar for 60 hours to recover hydrocarbon fraction.

[0126] (Comparative Example 1)

[0127] Hydrocarbons were produced and recovered in the same manner as in Example 1, except that the reverse reaction process was not performed in Example 1.

[0128] (Comparative Example 2)

[0129] Example 1 was performed in the same manner as in Example 1, except that the water-gas shift reaction was not performed.

[0130] (Experimental Example 1) Gas composition analysis

[0131] When producing hydrocarbons by the methods of Example 1, Comparative Example 1, and Comparative Example 2, the compositions of the gases included in the first mixed gas, the second mixed gas, the third mixed gas, and the synthesis gas were analyzed and shown in Table 3 below, and the compositions of the major components included in the hydrocarbons produced therefrom were analyzed and shown in Table 4. The gas composition analysis was performed through gas chromatography (GC), and the total amount of gas was confirmed through a gas meter. Specifically, the selectivity for each gas was calculated by quantifying through GC, and the composition for each gas was analyzed through the total amount of gas confirmed through the gas meter.

[0132] Composition Example 1 Comparative Example 1 Comparative Example 2 First mixed gas (mol) H2 6.9 16.9 16.9 1 CO3 46 3.46 3.46 CH4 2.39 2.39 2.39 CO2 8.9 28.9 28.9 2 H2O 000 Second mixed gas (mol) H2 9.4 29.4 29.4 2 CO9.5 8 9.5 8 9.5 8 CH4 0.13 0.13 0.13 CO2 4.4 24.4 24.4 24.4 2 H2O 1.9 3 1.9 3 1.9 3 Second mixed gas Rim (mol) H2 9.34-9.34 CO9.48-9.48 CH4 0.1-0.1 CO2 0.01-0.01 Third mixed gas (mol) H2 9.31-9.31 CO18.03-18.03 CH4 0.1-0.1 CO2 0.09-0.09 Synthetic gas (mol) H2 18.11 11.38-CO8.8 15.71-CH4 0.01 0.01-CO2 0.07 0.15-

[0133] Example 1 Comparative Example 1 Comparative Example 2 Gas (g) 101.66 5.85 4.8 Liquid, Wax (g) 76.84 8.63 9.7 H2O (g) 99.26 0.84 7.8

[0134] As shown in Tables 3 and 4 above, when producing hydrocarbons by the method of Example 1, the carbon dioxide contained in the second mixed gas was recovered and converted into carbon monoxide through the reverse Buda reaction process, thereby not only increasing the production of synthesis gas and hydrocarbons produced therefrom, but also obtaining high-quality synthesis gas. In particular, by adopting a fluidized bed reactor as the reactor for methane reforming and the reverse Buda process, there is an advantage in that a catalyst that has been deactivated by the deposition of carbon components during the methane reforming reaction can be used as a catalyst for the reverse Buda process, and a cyclic process in which the catalyst regenerated through the reverse Buda process is re-introduced into the methane reforming reaction is possible.

[0135] In addition, the synthesis gas of Example 1, which was manufactured sequentially through dry reforming reaction, reverse Buddha reaction, and water gas shift process, was measured to have high H2 and CO contents compared to CH4 and CO2 contents. In addition, as the synthesis gas manufacturing yield was improved, the liquid yield of the hydrocarbon manufactured using the synthesis gas was high at 76.8 g. Therefore, through the hydrocarbon manufacturing method of the present disclosure, high value-added synthesis gas and hydrocarbon can be manufactured from a mixed gas obtained by pyrolyzing organic waste at a high yield, and at the same time, greenhouse gas emissions are reduced, so there is an excellent effect of preventing environmental pollution.

[0136] On the other hand, in the case of Comparative Example 1, since the carbon dioxide contained in the second mixed gas was not recovered through the reverse Buta reaction, the amount of synthesis gas obtained was also small compared to Example 1, and since the synthesis gas contained a large amount of carbon dioxide, the hydrocarbon oil yield was also very low at 48.6 g. In Comparative Example 2, the water gas conversion process of the third mixed gas was not performed, so the hydrogen: carbon monoxide molar ratio of the synthesis gas could not be controlled, and as a result, the hydrocarbon conversion reaction through the Fischer-Tropsch reaction was not smooth, so the hydrocarbon oil yield was measured to be low at 39.7 g.

[0137] Therefore, when producing hydrocarbons by the method according to the present disclosure, the process efficiency is improved, so that synthesis gas and hydrocarbons can be produced at a high yield. Specifically, since the dry reforming and reverse Buta reaction processes of methane are performed using a fluidized bed reactor, the catalyst that has undergone the methane reforming reaction can be regenerated by being fed into the subsequent reverse Buta reaction process. Therefore, even if the catalyst is deactivated by coke in the dry reforming process, a circulation process for regenerating and resupplying the catalyst can be performed, so that there is an advantage of being able to perform a continuous reaction despite being dry reforming. In particular, the reverse Buta reaction has the advantage of being able to reduce carbon dioxide emissions while simultaneously producing a large amount of carbon monoxide from carbon dioxide, since it separates carbon dioxide contained in a mixed gas and converts the carbon dioxide into carbon monoxide. In addition, since a synthesis gas is produced with a controlled ratio of hydrogen and carbon monoxide contained in the mixed gas through a water gas shift process after the reverse Buddha reaction process, the catalytic reaction of the subsequent process is efficiently performed, and thus the yield of synthesis gas and hydrocarbon production can be significantly improved.

[0138] Although the present disclosure has been described with specific details and limited examples, these are provided only to help a more general understanding of the present disclosure, and the present disclosure is not limited to the above examples, and those skilled in the art to which the present disclosure pertains can make various modifications and variations based on these descriptions.

[0139] Therefore, the spirit of the present disclosure should not be limited to the described embodiments, and all things that are equivalent or equivalent to the following claims as well as the claims are considered to fall within the scope of the spirit of the present disclosure.

[0140] [Explanation of symbols]

[0141] 1: Hydrocarbon production device 10: Pyrolysis reactor

[0142] 20: First fluidized bed reactor 30: Carbon dioxide separation unit

[0143] 40: Second fluidized bed reactor 50: Gas mixing unit

[0144] 60: Syngas generation unit 70: Hydrocarbon conversion unit

[0145] 80: Refining Unit 90: Cyclone

[0146] 100: Organic waste 110: First mixed gas

[0147] 120: First mixed gas with impurities removed 200: Second mixed gas

[0148] 210: First Stream 211: Second Stream

[0149] 220: Third mixed gas 230 Synthetic gas

Claims

1. (S1) A step of generating a first mixed gas by heat treating organic waste; (S2) A step of dry reforming the first mixed gas in a first fluidized bed reactor to produce a second mixed gas; (S3) a step of separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; (S4) A step of introducing the first stream separated in the step (S3) into a second fluidized bed reactor and converting it into carbon monoxide through a reverse Boudouard reaction; (S5) a step of producing a third mixed gas by mixing the second stream and the carbon monoxide converted in step (S4); (S6) a step of generating synthesis gas through a water gas conversion reaction from the third mixed gas; and (S7) A method for producing hydrocarbons, comprising: a step of producing hydrocarbons through a catalytic reaction from the above-mentioned synthesis gas.

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

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

4. In paragraph 1, A method for producing hydrocarbons, wherein the above pyrolysis gas has a C / O ratio of 0.1 or higher.

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

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

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

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

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

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

1.

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

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

13. A pyrolysis reactor that heat-treats organic waste to produce a first mixed gas; A first fluidized bed reactor that generates a second mixed gas by dry reforming the first mixed gas under a catalyst; A carbon dioxide separation unit that separates the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; A second fluidized bed reactor that converts the first stream into carbon monoxide through a reverse Boudouard reaction; and A gas mixing unit that produces a third mixed gas by mixing the second stream and carbon monoxide converted from the second fluidized bed reactor; A synthesis gas generating unit that converts the third mixed gas into synthesis gas through a water gas shift reaction; and A hydrocarbon production device, comprising a hydrocarbon conversion unit that converts the above-mentioned synthesis gas into hydrocarbon through a catalytic reaction.

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

15. In paragraph 13, A synthesis gas production device further comprising a purification unit between the above heat treatment reactor and the first fluidized bed reactor.

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