Method and apparatus for producing hydrocarbon

Abstract

The present disclosure provides a method for producing hydrocarbon, comprising the steps of: (S1) generating a first mixed gas by heat-treating organic waste; (S2) generating a second mixed gas by dry-reforming the first mixed gas in a first fixed-bed reactor; (S3) separating the second mixed gas into a first stream including carbon dioxide and a second stream including hydrogen and carbon monoxide; (S4) introducing the first stream obtained by separation in step (S3) into a second fixed-bed reactor and converting the first stream into carbon monoxide through a reverse Boudouard reaction; (S5) producing a third mixed gas by mixing the second stream and the carbon monoxide obtained by conversion in step (S4); (S6) generating a synthetic gas from the third mixed gas through a water gas conversion reaction; and (S7) producing hydrocarbon from the synthetic gas 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 can be provided in which the production yield of hydrocarbons is significantly improved.

[0009] 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.

[0010] 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 fixed-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 fixed-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.

[0011] 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.

[0012] In one example, the second fixed bed reactor can be supplied with a carbon source from outside.

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

[0014] In one example, the first mixed gas may have a C / O element ratio of 0.8 or less.

[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°C to 1000°C.

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

[0020] In one example, the synthesis gas in the step (S6) includes 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 fixed 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 fixed 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 fixed 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 second fixed bed reactor is connected between the carbon dioxide separation unit and the gas mixing unit, and the second fixed bed reactor may include a second-first fixed bed reactor and a second-second fixed bed reactor connected in parallel.

[0025] In one example, the second fixed bed reactor further includes a control unit that switches the second-first fixed bed reactor and the second-second fixed bed reactor, and the control unit can control the second fixed bed reactor to be operated in a first mode in which the second-first fixed bed reactor is regenerated and a reverse Buda reaction is performed by the second-second fixed bed reactor by blocking the connection of the carbon dioxide separation unit-the second-first fixed bed reactor-gas mixing unit; or in a second mode in which the second-second fixed bed reactor is regenerated and a reverse Buda reaction is performed by the second-first fixed bed reactor by blocking the connection of the carbon dioxide separation unit-the second-second fixed bed reactor-gas mixing unit.

[0026] In one example, a purification unit may be further included between the pyrolysis reactor and the first fixed bed reactor.

[0027] According to one embodiment of the present disclosure, the production yield of hydrocarbons produced from organic waste can be significantly improved.

[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.

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

[0031] Figure 3 is a schematic diagram showing a hydrocarbon production device including a switchable reverse osmosis reactor according to an example.

[0032] Figure 4 is a graph showing the methane conversion rate measured according to the dry reforming reaction time when producing hydrocarbons using a method according to an example.

[0033] As used herein, the singular forms of terms may be construed to include the plural forms as well, unless otherwise specified.

[0034] 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.

[0035] 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.

[0036] The unit of % used in this specification without special mention means weight % unless otherwise defined.

[0037] Conventionally, a catalytic gasification process has been used to produce synthesis gas. However, the gasification process has the problem of catalyst deactivation due to coke and other substances generated, leading to process problems during continuous operation. Furthermore, to ensure economic feasibility, the relatively expensive catalyst must be recovered. However, recovering the catalyst, which is discharged in a coagulated state, requires multiple subsequent processes (e.g., air burning), significantly reducing process efficiency. Furthermore, the conventional gasification process for organic waste has a significantly low synthesis gas production yield of less than 30%, resulting in low productivity and limitations in converting it into high-value-added products. Furthermore, while suppressing CO2 emissions is desirable from an environmental perspective, the gasification reaction products of organic waste contain CO2 in addition to H2 and CO, resulting in higher carbon dioxide emissions than landfill or pyrolysis, posing a serious problem of further environmental pollution. Therefore, the inventors of the present disclosure have devised a manufacturing method and device capable of efficiently producing hydrocarbons from organic waste while minimizing carbon dioxide emissions.

[0038] 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 fixed-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 fixed-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.

[0039] The method for producing hydrocarbons according to the present disclosure can efficiently convert organic waste into synthesis gas compared to conventional gasification processes, thereby maximizing the yield of high-value-added hydrocarbons converted from the synthesis gas. Specifically, when reforming gas derived from organic waste, a fixed-bed reactor with the highest conversion rate per catalyst weight is used to enhance the efficiency of the reforming reaction, thereby improving the production yield of synthesis gas and hydrocarbons. Furthermore, the method can prevent environmental pollution by minimizing carbon dioxide emissions during the hydrocarbon production process.

[0040] 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.

[0041] 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.

[0042] Specifically, in the step (S1), one or more gasification reactions selected from the following reaction formulas 1 to 4 may be involved.

[0043] [Reaction Formula 1]

[0044] C x H y + H2O →H2+ CO (water gasification reaction)

[0045] [Reaction Formula 2]

[0046] C x H y + CO2→CO (carbon dioxide gasification reaction)

[0047] [Reaction Formula 3]

[0048] CO + 3H2→CH4+ H2O (methanation reaction)

[0049] [Reaction Formula 4]

[0050] C x H y + O2→ CO2 (oxidation reaction)

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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, or 0.7 or less, and as a lower limit, 0.1 or more, 0.2 or more, or 0.3 or more. Specifically, it may be 0.1 to 0.8, and more specifically, 0.3 to 0.7.

[0056] When the C / O element ratio of the first mixed gas satisfies the above-described range, when the methane reforming reaction described later is performed, the oxygen content in the first mixed gas is high compared to the carbon content, so that the amount of coke produced by the side reaction is significantly reduced, thereby preventing deactivation of the catalyst, and thus the methane reforming reaction can be performed with high efficiency.

[0057] In one example, the step (S1) may further include a step of purifying the first mixed gas.

[0058] 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.

[0059] 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.

[0060] Step (S2) is a step of producing a second mixed gas by dry reforming methane contained in the first mixed gas in a first fixed bed reactor. In step (S2), a reforming reaction according to the following reaction scheme 5 may occur.

[0061] [Reaction Formula 5]

[0062] CH4+ CO2→2CO + 2H2 (carbon dioxide reforming reaction)

[0063] 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.

[0064] 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.

[0065] 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.

[0066] (S2) Since the methane dry reforming reaction is performed in a fixed-bed reactor, the reforming efficiency of methane can be improved, thereby increasing the yield of hydrocarbons. Specifically, the dry reforming process can more smoothly perform the catalytic reaction of the subsequent process, synthesis gas, because the ratio of the products, hydrogen and carbon monoxide, is close to 1:1. In addition, since the dry reforming of methane is performed in a fixed-bed reactor, even if the methane content in the first mixed gas is small, methane can be effectively converted into hydrogen and carbon monoxide.

[0067] That is, by dry reforming the first mixed gas in the fixed bed reactor at step (S2), not only can the yield of synthesis gas be improved, but also the hydrocarbon conversion reaction of the synthesis gas can be smoothly performed, thereby ensuring the production yield of hydrocarbons.

[0068] (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.

[0069] 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.

[0070] 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 a first stream and a second stream using the CCS unit (Carbon capture and storage unit).

[0071] 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.

[0072] 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 fixed 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 the amount of carbon dioxide emitted, while also maximizing the yield of synthesis gas. The reverse Buta reaction may involve the following reaction scheme 6.

[0073] [Reaction Formula 6]

[0074] C+CO2→ 2CO

[0075] 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.

[0076] The above-described reverse reaction can be performed using an external carbon source. Specifically, the carbon source may be char derived from the organic waste, and more specifically, char derived from the pyrolysis of waste plastic or char derived from biomass. Alternatively, high-purity graphite may be included to prevent the introduction of impurity gases by the external carbon source.

[0077] Since the reverse reaction of the above step (S4) is performed in the second fixed bed reactor, carbon dioxide can be converted into carbon monoxide with high efficiency even if the first stream contains carbon dioxide at a low purity.

[0078] In the present disclosure, dry reforming of methane in the first fixed-bed reactor at step (S2) is performed with high efficiency using carbon dioxide contained in the first mixed gas as a reactant. Therefore, since the content of carbon dioxide in the first stream, which includes the second mixed gas converted from the first mixed gas and carbon dioxide derived from the second mixed gas, is very low, it may be advantageous to perform the reverse Buta reaction in the fixed-bed reactor with the highest conversion rate per catalyst weight in order to efficiently convert it into carbon monoxide.

[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 comprising one or more metals selected from the group consisting of Fe, Cu, Zn, 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 at 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 400°C to 600°C, specifically 430°C to 530°C, and 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 fixed 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 (320) containing carbon dioxide and a second stream (211) containing hydrogen and carbon monoxide; a second fixed 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) with carbon monoxide converted from the second fixed bed reactor (40). A hydrocarbon production device (1) 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 (23) into hydrocarbon through a catalytic reaction.

[0102] The hydrocarbon production device (1) according to the present disclosure can convert a first mixed gas (110) into synthesis gas (230) and hydrocarbons with high efficiency using a fixed bed reactor, while significantly reducing carbon dioxide emissions, thereby preventing environmental pollution. In addition, it has the effect of providing an economical process by using a fixed bed reactor, which is easier to manage and requires lower equipment and operating costs compared to a fluidized bed reactor.

[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 fixed bed reactor (20) and converted into a second mixed gas (220) through a dry methane 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 fixed 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 fixed 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 fixed bed reactor (40) and converted into carbon monoxide through a reverse Buta reaction.

[0107] In one example, the second fixed bed reactor (40) is connected between the carbon dioxide separation unit (30) and the synthesis gas generation unit (60), and referring to FIG. 3, the second fixed bed reactor (40) may include a 2-1 fixed bed reactor (41) and a 2-2 fixed bed reactor (42) connected in parallel. Since the second fixed bed reactor (40) includes the 2-1 fixed bed reactor (41) and the 2-2 fixed bed reactor (42), the reactors can be switched and used depending on the activity of the catalyst of the fixed bed reactor, thereby improving the overall process efficiency and enabling continuous process operation.

[0108] In another example, the second fixed bed reactor (40) may further include a control unit (not shown) that switches the second-first fixed bed reactor (41) and the second-second fixed bed reactor (42).

[0109] The above control unit (not shown) can control to perform a first mode in which the connection between the carbon dioxide separation unit (30) - the second-first fixed bed reactor (41) - the synthesis gas generation unit (60) is blocked, the second-first fixed bed reactor (41) is regenerated, and the reverse reaction is performed by the second-second fixed bed reactor (42).

[0110] In addition, the control unit (not shown) can control the second mode to be performed by blocking the connection of the carbon dioxide separation unit (30) - the 2-2 fixed bed reactor (42) - the synthesis gas generation unit (60), so that the 2-2 fixed bed reactor (42) is regenerated and the reverse reaction is performed by the 2-1 fixed bed reactor (41).

[0111] The second fixed bed reactor (40) can be supplied with char, specifically char derived from organic waste, and the supplied char can react with carbon dioxide to be converted into carbon monoxide. Without limitation, the char can be char derived from pyrolysis of waste plastic or char derived from biomass.

[0112] The gas mixing unit (50) mixes the second stream (211) with carbon monoxide converted in the second fixed bed reactor (40) to produce a third mixed gas (220). The third mixed gas (220) is supplied to the synthesis gas production unit (60) and converted into synthesis gas (230) by controlling the hydrogen:carbon monoxide ratio in the third mixed gas (220) through a water gas shift reaction.

[0113] 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.

[0114] 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.

[0115] In one example, the hydrocarbon production device (1) may further include a separation step of separating the produced hydrocarbon into fractions by boiling point through distillation by being connected to a hydrocarbon conversion unit (70).

[0116] Below, specific embodiments of the present disclosure are further described.

[0117] (Example 1)

[0118] 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 0.69. The composition of the recovered first mixed gas is shown in Table 1 below.

[0119] Feedmol%wt%H2323CO1618CO24072CH4117Total100100

[0120] The first mixed gas was lowered in temperature and introduced into a purification unit including a wet scrubber, where it was treated at 70°C and 100KPa to remove impurities, and the purified first mixed gas was recovered. The compositions of the first mixed gas and the impurity gases contained in the purified first mixed gas are shown in Table 2 below. As shown in Table 2, when the mixed gas was purified through a wet scrubber, impurity gases such as NH3, HCl, H2S, and COS were not detected, confirming that the impurities contained in the first mixed gas were effectively removed.

[0121] Impurity Gas 1st Mixed Gas (ppm) Purified 1st Mixed Gas (ppm) HCl2231N / DH2S1217N / DCOS231N / DNH33701N / D

[0122] The purified first mixed gas is fed to the first fixed bed reactor containing 100 g of Ni / Al2O3 catalyst at 2 L / g cat · A second mixed gas was produced through dry reforming of methane by supplying it at a space velocity of h. Specifically, the first fixed-bed reactor filled with a catalyst was reduced for 2 hours by supplying H2 at a flow rate of 3.03 Nl / min at 900°C, and then the first mixed gas was supplied to the first fixed-bed reactor at a flow rate of 3.33 Nl / min to perform the dry reforming reaction as a continuous process.

[0123] The Ni / Al2O3 catalyst was manufactured by impregnating alumina particles having a diameter of 1 mm into an aqueous solution of nickel nitrate hexahydrate dissolved in distilled water, drying the solution at 150°C for 2 hours, and then continuously calcining the solution at 500°C for 2 hours. The above process was set as a unit process, and the unit process was repeated multiple times until the nickel content in the catalyst became 20 wt%. The nickel content in the catalyst was measured by XRF (X-Ray Flourescence Spectrometry) analysis, and the XRF analysis was measured using Thermo's ARL QUANT'X.

[0124] The recovered second mixed gas was fed into the Amine Scrubber after removing water. The carbon dioxide contained in the second mixed gas was captured in the Amine Scrubber, and the second mixed gas from which carbon dioxide was removed was separated into a second stream. Specifically, the second mixed gas was fed into the first Amine Scrubber, and CO2 was captured using an aqueous solution (Amine Solution) containing 12 wt% NH3 dissolved therein at 50 to 60°C, 10 to 20 bar, and a processing capacity of 0.5 Nl / hr, and the uncaptured gas was recovered as the second stream. The amine solution (Amine Solution) of the first Amine Scrubber was fed into the second Amine Scrubber, and separated into an amine solution (Amine Solution) and CO2 at 100°C, and the CO2 was recovered as the first stream.

[0125] The recovered first stream was continuously supplied to the second fixed-bed reactor filled with a Ni / Al2O3 catalyst and 5 kg of high-purity graphite to convert carbon dioxide into carbon monoxide through the reverse Buta reaction. The reverse Buta reaction was performed under N2 gas at 750°C, a CO2 flow rate of 2.33 Nl / min, and a space velocity of 2.0 L / g. cat ·It was performed under the condition of h.

[0126] The carbon monoxide converted from the first stream and the second stream separated from the amine scrubber were introduced into a gas mixing unit and mixed at 200°C to produce a third mixed gas. The third mixed gas was introduced into a synthesis gas generation unit and produced a synthesis gas with a molar ratio of H2:CO=2:1 through a water gas shift reaction. The water gas shift reaction was performed under a Cu / Zn / Al2O3 catalyst at 165°C, 35 bar, and a space velocity of 1.4 L / g. cat · It was performed under reaction conditions of h.

[0127] 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 ·h, the injection rate was set so that the volume ratio of 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 oil.

[0128] (Comparative Example 1)

[0129] Example 1 was performed in the same manner as Example 1, except that the reverse reaction process was not performed and the hydrocarbon was produced using a second mixed gas.

[0130] (Comparative Example 2)

[0131] The same method as Example 1 was performed, except that the water-gas shift reaction was not performed in Example 1 and the hydrocarbon was produced using a third mixed gas.

[0132] (Experimental Example 1) Dry reforming performance evaluation

[0133] When producing hydrocarbons by the method of Example 1, the methane conversion rate according to the operating time of the dry reforming process is shown in Table 3 and Fig. 4 below. The methane conversion rate was calculated by analyzing the CH4 content in the second mixed gas discharged at each hour and then using Equation 1 below. The gas composition analysis method was performed using 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 it through GC, and the composition of each gas was analyzed through the total amount of gas confirmed through the gas meter.

[0134] [Formula 1]

[0135]

[0136] Driving time (min) CH4 conversion rate (%) 1097.143098.875097.587097.309097.4111097.45

[0137] As shown in Table 3 and Figure 4, the methane conversion rate did not decrease even after performing the dry reforming process for 120 minutes, maintaining a methane conversion rate of over 97%. By maintaining excellent catalytic activity even over long reaction times, it can be seen that catalyst deactivation due to coke was significantly reduced even when using a fixed-bed reactor. Therefore, when producing hydrocarbons using the method according to the present disclosure, dry reforming could be performed continuously in a fixed-bed reactor for an extended period of time.

[0138] (Experimental Example 2) Gas composition analysis

[0139] 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 4 below, and the compositions of the major components included in the hydrocarbons produced therefrom were analyzed and shown in Table 5. The gas composition analysis was performed through gas chromatography (GC) in the same manner as in Experimental Example 1, and the total amount of gas was confirmed through a gas meter. Specifically, the selectivity for each gas was calculated by quantifying it through GC, and the composition for each gas was analyzed through the total amount of gas confirmed through the gas meter.

[0140] 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 10.15 10.15 10.15 CO9 19 9.19 9.19 CH4 0.05 0.05 0.05 CO2 4.9 24.9 24.9 2 H2O 1.35 1.35 1.35 Second stream ( mol)H210.01-10.01CO9.11-9.11CH40.03-0.03CO20.01-0.01Third mixed gas(mol)H210.01-10.01CO18.73-18.73CH40.03-0.03CO20.11-0.11Synthetic gas(mol)H219.0412.67-CO9.556.33-CH40.020.01-CO20.090.11-

[0141] Example 1 Comparative Example 1 Comparative Example 2 Gas (g) 113.17 3.78 1.1 Liquid, Wax (g) 77.35 8.16 2.8 H2O (g) 109.0 75.89 1.6

[0142] As shown in Tables 4 and 5, 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 Buddha reaction process, thereby not only increasing the production of hydrocarbons produced, but also obtaining high-quality synthesis gas and hydrocarbons.

[0143] More specifically, referring to Table 4, the synthesis gas of Example 1, which was manufactured sequentially through dry reforming, reverse Budar reaction, and water gas shift processes, was measured to have higher 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 77.3 g. Therefore, the hydrocarbon manufacturing method of the present disclosure can manufacture high value-added synthesis gas and hydrocarbon from a mixed gas obtained by pyrolyzing organic waste at a high yield, and at the same time, it has an excellent environmental pollution prevention effect because it reduces greenhouse gas emissions.

[0144] On the other hand, in the case of Comparative Example 1, the carbon dioxide contained in the second mixed gas was recovered through a reverse Buddha reaction and was not converted into carbon monoxide, but rather synthesis gas and hydrocarbons were produced from the second mixed gas. Accordingly, the contents of H2 and CO contained in the synthesis gas produced were reduced compared to Example 1, and since the synthesis gas contained a large amount of carbon dioxide, the yield of the hydrocarbon fraction (Liquid) produced was 58.1 g, which was very low compared to Example 1.

[0145] Comparative Example 2 did not perform the water gas conversion process, so the molar ratio of hydrogen and carbon monoxide contained in the third mixed gas could not be controlled, and as a result, hydrocarbon conversion through a catalytic reaction was not smooth, so the yield of the manufactured hydrocarbon fraction (Liquid) was measured to be low at 62.8 g.

[0146] Therefore, when producing hydrocarbons by the method according to the present disclosure, the dry reforming reaction and the reverse Buta reaction are performed in a fixed bed reactor, and the mixed gas obtained through the reverse Buta reaction is converted into water gas, thereby improving the process efficiency and producing synthesis gas and hydrocarbons with a high yield. Specifically, by performing the dry reforming process in a fixed bed reactor, the reforming efficiency of methane is improved, and by maintaining a high methane conversion rate even when the dry reforming reaction is performed for a long time, a continuous process can be performed. At the same time, by performing the reverse Buta reaction in the fixed bed reactor, carbon dioxide in the mixed gas can be converted into carbon monoxide with high efficiency. In particular, the reverse Buta reaction has the advantage of being able to reduce carbon dioxide emissions while producing a large amount of carbon monoxide because it separates carbon dioxide contained in the mixed gas and converts the carbon dioxide into carbon monoxide. In addition, since the water-gas conversion process produces synthesis gas with a controlled ratio of hydrogen and carbon monoxide contained in the mixed gas, the catalytic reaction of the subsequent hydrocarbon production process can be efficiently performed, significantly improving the yield of synthesis gas and hydrocarbon production.

[0147] 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.

[0148] 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.

[0149] [Explanation of symbols]

[0150] 1: Hydrocarbon production device 10: Pyrolysis reactor

[0151] 20: First fixed bed reactor 30: Carbon dioxide separation unit

[0152] 40: Second fixed bed reactor 41: Second-first fixed bed reactor

[0153] 42: 2-2 fixed bed reactor 50: gas mixing unit

[0154] 60: Syngas generation unit 70: Hydrocarbon conversion unit

[0155] 80: Refining Unit 100: Organic Waste

[0156] 110: First mixed gas 120: First mixed gas with impurities removed

[0157] 200: Second mixed gas 210: First stream

[0158] 211: Second stream 220: Third mixed gas

[0159] 230 Syngas

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 fixed 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 fixed 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 second fixed bed reactor receives a carbon source from outside.

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

5. In paragraph 1, A method for producing hydrocarbons, wherein the first mixed gas has a C / O element ratio of 0.8 or less.

6. 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.

7. In paragraph 6, 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.

8. 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.

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

10. 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 50KPa to 300KPa.

11. In paragraph 1, A method for producing hydrocarbons, wherein in the step (S6), the synthesis gas contains hydrogen and carbon monoxide, and the ratio of hydrogen and carbon monoxide satisfies 1.8:1 to 2.2:

1.

12. 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.

13. 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).

14. A pyrolysis reactor that heat-treats organic waste to produce a first mixed gas; A first fixed 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 fixed bed reactor that converts the first stream into carbon monoxide through a reverse Boudouard reaction; A gas mixing unit that produces a third mixed gas by mixing the second stream and carbon monoxide converted from the second fixed 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.

15. In paragraph 14, A hydrocarbon production device, wherein the second fixed bed reactor is connected between the carbon dioxide separation unit and the gas mixing unit, and the second fixed bed reactor includes a second-first fixed bed reactor and a second-second fixed bed reactor connected in parallel.

16. In paragraph 15, The above second fixed bed reactor further includes a control unit for switching the 2-1 fixed bed reactor and the 2-2 fixed bed reactor, The above control unit blocks the connection of the carbon dioxide separation unit-the 2-1 fixed bed reactor-the gas mixing unit, so that the 2-1 fixed bed reactor is regenerated and the reverse reaction is performed by the 2-2 fixed bed reactor; or A hydrocarbon production device that controls the second mode in which the connection of the carbon dioxide separation unit, the second-second fixed bed reactor, and the gas mixing unit is blocked so that the second-second fixed bed reactor is regenerated and a reverse reaction is performed by the second-first fixed bed reactor.

17. In paragraph 14, A synthesis gas production device further comprising a purification unit between the above pyrolysis reactor and the first fixed bed reactor.

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