Method and apparatus for preparing hydrocarbons

Abstract

The present disclosure relates to a method and apparatus for preparing hydrocarbons from organic waste. The method and apparatus for preparing hydrocarbons, according to the present disclosure, improve reforming efficiency of methane by performing a wet reforming process in a fluidized-bed reactor, and maintain a high methane conversion rate even when performing a wet reforming reaction for a long time, thereby enabling a continuous process. At the same time, a reverse Boudouard reaction is performed in the fluidized-bed reactor so as to enable carbon dioxide in a mixed gas to be converted into carbon monoxide with high efficiency. In particular, through the reverse Boudouard reaction, carbon dioxide contained in the mixed gas is separated and converted into carbon monoxide, thus providing the advantages of reducing carbon dioxide emissions while simultaneously enabling the production a large amount of carbon monoxide. In addition, by producing synthesis gas having a controlled ratio of hydrogen and carbon monoxide contained in the mixed gas, through a water-gas shift process, a catalytic reaction in a hydrocarbon production process, which is a subsequent process, can be performed efficiently, thereby significantly improving the production yields of synthesis gas and hydrocarbons.

Description

Hydrocarbon production method and device

[0001] The present disclosure relates to a method and apparatus for producing hydrocarbons from organic waste.

[0002] Organic waste can seriously damage the environment through decomposition and other processes during landfill. Therefore, disposal requires sorting by type and following a prescribed treatment process. 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 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 raw material 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] The purpose of the present disclosure is to provide a method and apparatus for producing hydrocarbons in which the production yield of hydrocarbons is significantly improved.

[0008] In addition, another object of the present disclosure is to provide a method and apparatus for producing hydrocarbons that can expand the product range obtainable from organic waste.

[0009] In addition, another object of the present disclosure is to provide a method and apparatus for producing hydrocarbons capable of minimizing the generation of carbon dioxide.

[0010] A method for producing hydrocarbons according to the present disclosure includes: (S1) a step of heat-treating organic waste to produce a pyrolysis product; (S2) a step of gas-liquid separating the pyrolysis product into a first mixed gas and a mixed liquid; (S3) a step of wet reforming the first mixed gas in the presence of a reforming catalyst in a first fluidized bed reactor to produce a second mixed gas; (S4) a step of separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; (S5) a step of introducing the reformed spent catalyst and the first stream into a second fluidized bed reactor and producing carbon monoxide through a reverse Boudouard reaction; (S6) a step of producing a synthesis gas through a water gas shift reaction from the second stream and the carbon monoxide produced in step (S5); and (S7) a step of producing a hydrocarbon from the synthesis gas through a catalytic reaction.

[0011] In one embodiment, the heat treatment may have a ratio of pyrolysis catalyst to organic waste (Cat / oil ratio) of 2 to 50.

[0012] A reforming catalyst according to one embodiment may be a composite catalyst in which an active metal is supported on a support.

[0013] According to one embodiment, the active metal may include one or more selected from the group consisting of nickel, vanadium, iron, platinum, palladium, and ruthenium.

[0014] According to one embodiment, the carrier may include one or more selected from the group consisting of silica, alumina, silica-alumina, carbon, zirconia, titania, zeolite, SAPO and ALPO.

[0015] Wet modification according to one embodiment can be performed at a temperature of 500 to 1500°C.

[0016] In one embodiment, the reverse reaction can be performed at a temperature of 500 to 1000°C.

[0017] In one embodiment, the reverse reaction can be performed by further introducing an external carbon source into the second fluidized bed reactor.

[0018] A method for producing hydrocarbons according to one embodiment may further include a step of producing a third mixed gas by mixing the second stream and carbon monoxide produced in step (S5).

[0019] The water-gas shift reaction according to one embodiment can be performed at a temperature of 100 to 500° C. and a pressure of 10 to 50 bar.

[0020] In one embodiment, the carbon dioxide produced in step (S6) may be recycled to the second fluidized bed reactor.

[0021] According to one embodiment, the synthesis gas has a molar ratio of hydrogen and carbon monoxide (m H2 / m CO ) can satisfy 1 to 10.

[0022] A method for producing hydrocarbons according to one embodiment may further include, prior to step (S3), a step of purifying the first mixed gas.

[0023] A hydrocarbon production device according to the present disclosure comprises: a pyrolysis reactor that heat-treats organic waste to produce pyrolysis products; a gas-liquid separation unit that separates the pyrolysis products into a first mixed gas and a mixed liquid; a first fluidized bed reactor that wet-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 reverse-reforms the reformed spent catalyst produced in the first fluidized bed reactor and the first stream to produce carbon monoxide; a synthesis gas production unit that produces synthesis gas through a water gas shift reaction from the second stream and carbon monoxide produced in the second fluidized bed reactor; and a hydrocarbon conversion unit that converts the synthesis gas into hydrocarbon through a catalytic reaction.

[0024] A hydrocarbon production device according to one embodiment may further include a gas mixing unit that produces a third mixed gas by mixing the second stream and carbon monoxide produced from the second fluidized bed reactor.

[0025] According to one embodiment, the first fluidized bed reactor and the second fluidized bed reactor may be connected to a reforming catalyst recirculation line.

[0026] The synthesis gas generation unit and the second fluidized bed reactor according to one embodiment may be connected to a carbon dioxide recirculation line.

[0027] A hydrocarbon production device according to one embodiment may further include a first purification unit for purifying a first mixed gas.

[0028] The synthesis gas production method and production device according to the present disclosure can significantly improve the production yield of hydrocarbons.

[0029] The hydrocarbon production method and production device according to the present disclosure can expand the product range that can be obtained from organic waste.

[0030] The hydrocarbon production method and production device according to the present disclosure can minimize the generation of carbon dioxide during the hydrocarbon production process.

[0031] Figure 1 is a schematic diagram showing a hydrocarbon production device according to the present disclosure.

[0032] Figure 2 is a schematic diagram showing a pyrolysis reactor according to the present disclosure.

[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] The hydrocarbon production method according to the present disclosure performs a wet reforming process in a fluidized bed reactor to improve the reforming efficiency of methane, and maintains a high methane conversion rate even when performing the wet reforming reaction for a long period of time, thereby enabling a continuous process. Simultaneously, a reverse Buta reaction is performed in the fluidized bed reactor to efficiently convert carbon dioxide in a mixed gas into carbon monoxide. In particular, the reverse Buta reaction separates carbon dioxide contained in the mixed gas and converts it to carbon monoxide, thereby having the advantage of reducing carbon dioxide emissions while simultaneously producing a large amount of carbon monoxide. In addition, since a synthesis gas having a controlled ratio of hydrogen and carbon monoxide contained in the mixed gas is produced through a water gas shift process, the catalytic reaction of the subsequent hydrocarbon production process can be efficiently performed, thereby significantly improving the yields of the synthesis gas and hydrocarbon production. As such, the hydrocarbon production method according to the present disclosure organically combines each process, enabling the production of large quantities of high-value-added hydrocarbons from a mixed gas produced by pyrolysis of organic waste, while simultaneously reducing greenhouse gas emissions. Furthermore, compared to the pyrolysis process alone, the obtainable hydrocarbon product line can be expanded. The hydrocarbon production method and production device of the present disclosure will now be described in detail.

[0038] The present disclosure provides a method for producing hydrocarbons, comprising: (S1) a step of heat-treating organic waste to produce a pyrolysis product; (S2) a step of gas-liquid separating the pyrolysis product into a first mixed gas and a mixed liquid; (S3) a step of wet reforming the first mixed gas in the presence of a reforming catalyst in a first fluidized bed reactor to produce a second mixed gas and a reformed spent catalyst; (S4) a step of separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; (S5) a step of introducing the reformed spent catalyst and the first stream into a second fluidized bed reactor and producing carbon monoxide through a reverse Boudouard reaction; (S6) a step of producing a synthesis gas through a water gas shift reaction from the second stream and the carbon monoxide produced in step (S5); and (S7) a step of producing a hydrocarbon from the synthesis gas through a catalytic reaction.

[0039] The above step (S1) is a step of heat-treating organic waste (100) to produce a pyrolysis product (110), and specifically, it is a step of heat-treating organic waste (100) in the presence of a pyrolysis catalyst (290) to produce a pyrolysis product (110) and a coked catalyst. In one example, the pyrolysis product may include at least one gaseous component selected from the group consisting of methane, hydrogen, carbon monoxide, and carbon dioxide, and may include at least one liquid component selected from the group consisting of aromatic hydrocarbons, gasoline, middle distillate, and wax, and may also include various impurities such as nitrogen oxides, sulfur oxides, and hydrogen chloride. The coked catalyst may mean a catalyst in which the pyrolysis catalyst used in the heat treatment in step (S1) is coked and deactivated.

[0040] In one example, in the step (S1), the organic waste (100) 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] In one example, the thermal decomposition catalyst (290) 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, or alumina dispersed in a carbon structure, and the structure acid site material may be zeolite, SAPO, AlPO, MOF, or a structural modification thereof. The molybdenum-based catalyst used in the hydrogenation process 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. If this is satisfied, the composition of the first mixed gas has a high methane content and / or C2 to C4 gas content, which may be advantageous in terms of subsequent wet reforming efficiency and / or water gas shift reaction efficiency.

[0042] As another example of increasing the methane content in the first mixed gas (120), the first mixed gas (120) may further include one or more selected from the group consisting of landfill gas, shale gas, refinery exhaust gas, and biogas. The landfill gas, shale gas, refinery exhaust gas, and biogas described above contain methane and carbon dioxide in an amount of 40% by volume or more, specifically, 50% by volume or more. Therefore, since the first mixed gas (120) further contains the above-described gases, there is an effect of further improving the production yield of synthesis gas through subsequent processes such as wet reforming and reverse Budar reaction.

[0043] In one example, the heat treatment in the step (S1) may be performed at a temperature of 300°C to 800°C, specifically 450°C to 750°C, and more specifically 500°C to 650°C, but is not limited thereto.

[0044] In one example, the heat treatment in the step (S1) may be performed under the condition that the ratio (Cat / oil ratio) of the thermal decomposition catalyst (290) and organic waste (100) is 0.1 to 100. When this is satisfied, the content of methane in the first mixed gas (120) may be further increased.

[0045] In one example, the step (S1) may include a process for regenerating the coke catalyst. Specifically, the coke catalyst may be regenerated by being separated from the thermal decomposition product (110) and then introduced into a regenerator (12) together with air to oxidize and remove the coke. The regenerated coke catalyst may be recycled and reused as a thermal decomposition catalyst.

[0046] In one example, the separation of the coke catalyst is not limited to a method known in the art, but can be performed through a physical separation method using a cyclone.

[0047] In one example, the process for regenerating the coke catalyst may be performed at a temperature of 500°C to 1000°C, specifically 600°C to 900°C, and more specifically 700°C to 800°C. When this is satisfied, there is an advantage of excellent coke removal efficiency.

[0048] In one example, the process for regenerating the coke catalyst may be performed under conditions in which the air injection rate is 500 lps to 2000 lps, specifically 700 lps to 1500 lps, and more specifically 850 lps to 1000 lps. When this is satisfied, there is an advantage of excellent coke removal efficiency.

[0049] The above step (S2) is a step of separating the thermal decomposition product (110) generated in the above step (S1) into a first mixed gas (120) and a mixed liquid (130).

[0050] In one example, the first mixed gas (120) may include methane and carbon dioxide, and may further include hydrogen or carbon monoxide. In one example, the mixed liquid (130) may include, but is not limited to, aromatic hydrocarbons, gasoline, middle distillates, and waxes.

[0051] In one example, the hydrocarbon production method of the present disclosure may further include a step of purifying the first mixed gas (120) after the step (S2).

[0052] The first mixed gas (120) generated by heat-treating the organic waste (100) may contain one or more impurities selected from the group consisting of tar, sulfur, nitrogen, and chlorine. Specifically, the first mixed gas (120) may contain water-soluble impurities such as H2S, HCl, HOCl, and NH3, and insoluble impurities such as tar. The impurities contained in the first mixed gas (120) may induce deactivation of the catalyst used in the present disclosure, thereby reducing the efficiency of the subsequent process. Therefore, by removing the impurities from the first mixed gas and purifying it, the efficiency of the overall process can be improved.

[0053] In one example, the method for purifying the first mixed gas (120) 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 (120) can be removed, and when the first mixed gas (120) is passed through a ceramic filter or a dust collecting filter, insoluble impurities such as tar and dust can be removed.

[0054] The above step (S3) is a step of wet reforming methane contained in the first mixed gas (120) in the presence of a reforming catalyst in a first fluidized bed reactor (40) to produce a second mixed gas (150). Through the wet reforming, methane can be converted into carbon dioxide, thereby improving the yield of synthesis gas. The above step (S3) may be accompanied by a wet reforming reaction according to the following reaction scheme 1.

[0055] [Reaction Formula 1]

[0056] CH4+ H2O →CO + 3H2

[0057] The wet reforming of the above step (S3) can be performed at a temperature of 500 to 1500°C, specifically 650 to 1300°C, more specifically 800 to 1000°C, and can be performed at a pressure of 0.3 to 20 bar, specifically 0.5 to 15 bar, more specifically 1 to 10 bar, but is not limited thereto.

[0058] In one example, the reforming catalyst may be a composite catalyst in which an active metal is supported on a support. The active metal may include one or more 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 impurity content of raw materials such as organic waste is low during the heat treatment process, a precious metal such as platinum, palladium, or ruthenium may be used. When this is satisfied, excellent wet reforming efficiency can be exhibited even under low-temperature conditions of 700°C or less.

[0059] 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.

[0060] Since the above step (S3) is performed in a fluidized bed reactor, contact between the fluid and the catalyst is facilitated, enabling the production of high-yield synthesis gas, thereby improving the yield of hydrocarbons. Furthermore, when methane is reformed using a wet reforming reaction in a fluidized bed reactor, not only is reforming reactivity improved compared to dry reforming, but impurities such as chlorine are also removed.

[0061] The above step (S4) is a step of separating the second mixed gas (150) into a first stream (170) containing carbon dioxide and a second stream (180) containing hydrogen and carbon monoxide.

[0062] In one example, the method of separating the second mixed gas (120) into the first stream (170) and the second stream (180) is not limited to any known method, but the present disclosure allows separation using a carbon dioxide separation unit (50), and for example, the carbon dioxide separation unit (50) 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, by using an amine scrubber, the second mixed gas (120) can be separated into the first stream (170) and the second stream (180).

[0063] As another example, the carbon dioxide separation unit (50) may be a CCS unit (Carbon capture and storage unit). When the 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, or trona, and thus the second mixed gas (120) can be separated into a first stream (170) and a second stream (180) using the CCS unit.

[0064] In one example, the first stream (170) may contain carbon dioxide in an amount of at least 10% by volume, at least 15% by volume, or at least 20% by volume, and an upper limit of at most 90% by volume, at most 60% by volume, or at most 30% by volume. Specifically, the first stream (170) may contain carbon dioxide in an amount of 10 to 90% by volume, specifically 15 to 60% by volume, and more specifically 20 to 30% 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 (170) contains carbon dioxide in the above-described range, the carbon dioxide separation process can be performed under mild conditions.

[0065] The above step (S5) is a step of introducing the reformed waste catalyst and the first stream (170) into the second fluidized bed reactor (60) and generating carbon monoxide (200) through a reverse Boudouard reaction. The reformed waste catalyst may refer to a catalyst that has been deactivated due to carbon accumulation in the reformed catalyst after wet reforming in the above step (S4). The reverse Boudouard reaction may involve the following reaction scheme 2.

[0066] [Reaction Formula 2]

[0067] C+CO2→ 2CO

[0068] In one example, the reformed waste catalyst produced by wet reforming in the first fluidized bed reactor (40) can be separated from the second mixed gas (150) and then supplied to the second fluidized bed reactor (60).

[0069] Through the above step (S5), the carbon contained in the reformed waste catalyst and the carbon dioxide contained in the first stream are converted into carbon monoxide, thereby regenerating the reformed waste catalyst and reducing carbon dioxide emissions, thereby preventing environmental pollution and improving the yield of synthesis gas.

[0070] In one example, the reformed waste catalyst can be regenerated through a reverse reaction, and the regenerated reformed waste catalyst can be supplied back to the first fluidized bed reactor (40) through the reforming catalyst recirculation line (210).

[0071] In one example, the reverse reaction in the step (S5) may be performed at a temperature of 600 to 1500°C, specifically 650 to 1300°C, more specifically 700 to 1100°C, and may be performed at a pressure of 0.5 to 30 bar, specifically 1 to 15 bar, more specifically 1 to 10 bar, but is not limited thereto.

[0072] Meanwhile, in the above step (S5), the reverse reaction can be performed by adding an external carbon source (190) as needed, and in one example, the external carbon source (190) can be graphite, but is not limited thereto.

[0073] The above step (S6) is a step of introducing the second stream (180) and carbon monoxide generated in the above step (S5) into a synthesis gas generation unit (80) and generating synthesis gas (230) through a water gas shift reaction. The water gas shift reaction may involve the following reaction formula 3.

[0074] [Reaction Formula 3]

[0075] CO + H2O → H2 + CO2

[0076] In one example, the water-gas shift reaction in step (S6) may be performed in the presence of a water-gas shift catalyst containing Cu and Zn. The water-gas shift reaction in step (S6) may be performed at a temperature of 100 to 500°C, specifically 125 to 300°C, more specifically 150 to 200°C, and a pressure of 20 to 80 bar, specifically 25 to 60 bar, more specifically 30 to 40 bar.

[0077] In one example, the synthesis gas (230) produced in the step (S6) has a molar ratio of hydrogen and carbon monoxide (m H2 / m CO ) may be 1 to 10, specifically 1.3 to 5, and more specifically 1.8 to 2.5. By satisfying the above range, the subsequent process, the catalytic reaction process, can be performed smoothly.

[0078] In one example, the carbon dioxide generated in the step (S6) may be recycled to the second fluidized bed reactor (60) through the reforming catalyst recirculation line (210) and become a carbon dioxide source for the reverse reaction in the step (S5).

[0079] In one example, the method for producing hydrocarbons according to the present disclosure may further include, before step (S6), a step of producing a third mixed gas (220) by mixing the second stream (180) and the carbon monoxide (200) produced in step (S5). In this case, a single stream including the third mixed gas may be fed into a synthesis gas production unit (80) to cause a water-to-gas conversion reaction.

[0080] In one example, the method for producing hydrocarbons according to the present disclosure may further include a step of purifying the synthesis gas (230). By purifying the synthesis gas (230), carbon dioxide contained in the synthesis gas (230) can be removed. In one example, when the method for producing hydrocarbons according to the present disclosure further includes a step of producing the third mixed gas (220), the third mixed gas (220) can be purified.

[0081] The above step (S7) is a step of producing hydrocarbons (250) through a catalytic reaction from the synthesis gas (230) produced in the above step (S6).

[0082] The above catalytic reaction is not limited to a reaction that can produce hydrocarbons from synthesis gas (230), but may be a methanol to olefins (MTO) conversion reaction or a Fischer-Tropsch synthesis reaction.

[0083] In one example, when the catalytic reaction is a Fischer-Tropsch synthesis reaction, a reaction involving the following reaction formula 4 can be performed using the synthesis gas (230) generated in step (S6) as a raw material.

[0084] [Reaction Formula 4]

[0085] nCO + 2nH2→C n H 2n + nH2O

[0086] In one example, the Fischer-Tropsch synthesis reaction may be performed under a Fischer-Tropsch reaction catalyst including cobalt, nickel or iron, and may include alumina, silica, titania or the like as a support, and may include a noble metal such as Pt, Ru or Re as a cocatalyst.

[0087] In one example, the Fischer-Tropsch synthesis reaction may be performed at a temperature of 100 to 500°C, specifically 200 to 350°C, and at a pressure of 10 to 50 bar, specifically 20 to 40 bar. When the above ranges are satisfied, the yield of the product is excellent.

[0088] In one example, when the catalytic reaction is a methanol-olefin conversion reaction, the methanol-olefin conversion reaction may include a reaction of converting synthesis gas into methanol; and a reaction of converting methanol into olefin.

[0089] The reaction for converting the above synthesis gas (230) into methanol may be a reaction involving the following reaction formula 5.

[0090] [Reaction Formula 5]

[0091] CO + 2H2→ CH3OH

[0092] In one example, the reaction of converting the synthesis gas (230) 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.

[0093] In one example, the reaction of converting the synthesis gas (230) into methanol can be performed at a temperature of 150 to 600°C, specifically 200 to 400°C, and at a pressure of 1 to 150 bar, specifically 50 to 100 bar, but is not limited thereto.

[0094] In one example, the reaction of converting methanol into olefin can be performed under a zeolite-based catalyst or an AlPO4-based molecular sieve catalyst. Specifically, the zeolite-based catalyst can be ZSM-5, and the AlPO4-based catalyst can be a silicoaluminaphosphate (SAPO) molecular sieve catalyst, and specifically, 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.

[0095] In one example, the reaction of converting methanol into olefin can be performed at a temperature of 200 to 600°C, specifically 300 to 500°C, and at a pressure of 1 to 10 bar, specifically 1 to 5 bar, but is not limited thereto.

[0096] In one example, the hydrocarbon production method of the present disclosure may further include a separation step for separating the hydrocarbon (250) produced in step (S7). In one example, the method for separating the hydrocarbon (250) produced in step (S7) is not particularly limited as long as it is a method known in the art, but may be distillation as an example.

[0097] In another aspect, the present disclosure provides a hydrocarbon production device, comprising: a pyrolysis reactor (10) for heat-treating organic waste to produce pyrolysis products; a gas-liquid separation unit (20) for separating the pyrolysis products into a first mixed gas and a mixed liquid; a first fluidized bed reactor (40) for wet reforming the first mixed gas to produce a second mixed gas; a carbon dioxide separation unit (50) for separating 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 (60) for performing a reverse Boudouard reaction on the reformed waste catalyst produced in the first fluidized bed reactor and the first stream to produce carbon monoxide; a synthesis gas production unit (80) for producing synthesis gas through a water gas shift reaction from the second stream and carbon monoxide produced in the second fluidized bed reactor; and a hydrocarbon conversion unit (90) for converting the synthesis gas into hydrocarbons through a catalytic reaction.

[0098] The description of the hydrocarbon production method may be equally applied to the description of the hydrocarbon production device to the extent of overlap.

[0099] The hydrocarbon production device according to the present disclosure can efficiently and economically produce synthesis gas and hydrocarbons by using a fluidized bed reactor when performing wet reforming and reverse Budah reaction, and can significantly reduce carbon dioxide emissions.

[0100] In one example, the pyrolysis reactor (10) may include a cracker (11) and a regenerator (12). The organic waste (100) and the pyrolysis catalyst (290) may be fed into the cracker (11) and heat-treated to produce a pyrolysis product (110), and the coke catalyst separated from the pyrolysis product through the first cyclone may be fed into the regenerator through the first catalyst supply line (260) and regenerated, and then resupplied to the cracker (11) through the pyrolysis catalyst recirculation line (270).

[0101] The above thermal decomposition product (110) may be introduced into a gas-liquid separation unit (20) and subjected to gas-liquid separation into a first mixed gas (120) and a mixed liquid (130). The first mixed gas (120) may be introduced into a first fluidized bed reactor (40) and converted into a second mixed gas (150) through wet reforming.

[0102] In one example, the hydrocarbon production device of the present disclosure may further include a first purification unit (30) connected between the gas-liquid separation unit (20) and the first fluidized bed reactor (40). Specifically, the first mixed gas (120) may be introduced into the first purification unit (30) to remove impurities, and the first mixed gas (140) from which impurities have been removed may be introduced into the first fluidized bed reactor (40) to be wet reformed.

[0103] The first purification unit (30) includes a sprayer that sprays liquid, receives the first mixed gas (120) from the gas-liquid separation unit (20), and contacts the first mixed gas (120) 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.

[0104] The carbon dioxide separation unit (50) can separate the second mixed gas (150) into a first stream (170) containing carbon dioxide and a second stream (180) containing hydrogen and carbon monoxide. The first stream (170) can be supplied to the second fluidized bed reactor (60) and converted into carbon monoxide (200) through a reverse Buder reaction. The second stream (180) can be supplied to a synthesis gas production unit (80), and when the hydrocarbon production device according to the present disclosure further includes a gas mixing unit (70) to be described later, it can be supplied to the gas mixing unit (70).

[0105] In one example, the hydrocarbon production device of the present disclosure may further include a second cyclone connected to the first fluidized bed reactor (40); a second catalyst supply line (160) connecting the second cyclone and the second fluidized bed reactor (60); and a second recirculation line (210) connecting the second fluidized bed reactor (60) and the first fluidized bed reactor (40). The second cyclone separates the reformed waste catalyst from the second mixed gas (150), and the separated reformed waste catalyst is supplied to the second fluidized bed reactor (60) through the second catalyst supply line (160), and the reformed waste catalyst regenerated by the reverse Budar reaction may be resupplied to the first fluidized bed reactor (40) through the reforming catalyst recirculation line (210).

[0106] Since the hydrocarbon production device of the present disclosure forms a circulation process with the first fluidized bed reactor (40) and the second fluidized bed reactor (60) described above, continuous process operation according to catalyst regeneration is possible.

[0107] In one example, the hydrocarbon production device of the present disclosure may further include a gas mixing unit (70) that mixes the second stream (180) and carbon monoxide produced from the second fluidized bed reactor (60) to produce a third mixed gas (220). In this case, the third mixed gas (220) may be supplied to a synthesis gas production unit (80) and converted into synthesis gas (230) through a water gas shift reaction.

[0108] In one example, the synthesis gas generation unit (80) and the second fluidized bed reactor (60) may be connected to the carbon dioxide recirculation line (240), and carbon dioxide generated by the water gas shift reaction may be supplied to the second fluidized bed reactor (60) through the carbon dioxide recirculation line (240) to serve as a carbon dioxide supply source for the reverse Budar reaction.

[0109] In one example, the hydrocarbon production device of the present disclosure may further include a second purification unit for purifying the synthesis gas (230).

[0110] The above synthesis gas (230) is introduced into the hydrocarbon conversion unit (90) and converted into hydrocarbon (250) through a methanol-olefin conversion reaction or a Fischer-Tropsch synthesis reaction, and can be recovered as a high value-added oil fraction.

[0111] In one example, when the hydrocarbon conversion unit (90) performs a methanol-olefin conversion reaction, the hydrocarbon conversion unit (90) may include a methanol conversion unit that receives the synthesis gas 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 of the present disclosure may further include a separation unit connected to the hydrocarbon conversion unit (90) to separate the produced hydrocarbon (250). In one example, the separation unit may be, but is not limited to, a distillation column.

[0113]

[0114] The following examples further illustrate the hydrocarbon production method and apparatus according to the present disclosure. However, the following examples are merely a reference for further illustrating the present disclosure and are not intended to limit the present disclosure, which may be implemented in various forms. Furthermore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. Furthermore, the terminology used in the description of this disclosure is solely for the purpose of effectively describing specific embodiments and is not intended to limit the present disclosure.

[0115] Example

[0116] 1. Catalytic pyrolysis

[0117] 2 kg of waste plastic was dried at 105 ℃ for 12 hours.

[0118] Alumina gel was prepared by introducing pseudoboehmite into water and stirring at room temperature, adding formic acid, and maintaining the mixture for 3 hours. Clay, ZSM-5, and MgO were introduced into a mixer so that the Mg / Al molar ratio was 25, and stirred for 10 minutes. At this time, the amount of MgO introduced was 5 wt% of the total amount of clay and ZSM-5 materials. The mixture of clay, ZSM-5, and MgO was stirred in the mixer, and after making it uniform into small particles through a homogenizer, the alumina gel was added, and stirred again with the mixer. Ludox (AS 40) was introduced during stirring, and the viscosity of the slurry was measured using a viscometer. The slurry was spray-dried and calcined during the process of converting the viscosity from sol to gel. After separating only those particles having a particle size of 30 to 200 ㎛, ion exchange was performed at 60°C for 3 hours with a 5% RE-metal solution, and drying and calcination were performed to produce a thermal decomposition catalyst.

[0119] The waste plastic and steam were introduced into the pyrolysis reactor at injection rates of 850 g / h and 80 g / h, respectively, and heat-treated at a Cat / Oil ratio of 10, 570°C, and 1.1 bar to generate pyrolysis products.

[0120] The coke catalyst was separated from the above pyrolysis product through a cyclone, and the remainder was fed into a gas-liquid separation unit, where the mixed liquid was recovered in a chiller trap at -4°C, and the first mixed gas was captured separately. The recovered mixed liquid was analyzed for components and composition through GC analysis, and the results are shown in Tables 1 and 2, respectively.

[0121] Composition (vol%) Benzene67.5Toluene11.0Xylene17.0Ethyl benzene0.2Styrene1.3Trimethylbenzene0.2Cyclopentane0.7Others2.1

[0122] Composition (wt%): Gasoline 76.1, middle distillate 22.8, wax 1.1

[0123] 2. Purification of impurities

[0124] The first mixed gas was lowered in temperature and introduced into a purification unit including a wet scrubber to remove impurities under conditions of 70°C and 1 bar, and the purified first mixed gas was recovered. The purified first mixed gas was analyzed for components and composition through gas chromatography, and the results are shown in Table 2 below. As shown in Table 2 below, 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.

[0125] Composition (vol%) CH432.8CO223.7CO43.5NH3N / DHCNN / DH2SN / DCOSN / DHClN / DCHCl3N / DCCl4N / DCH3CCl3N / DC2H2Cl2N / DH2SN / D

[0126] 3. Wet modification

[0127] 100 mol of the above purified first mixed gas was added to the first fluidized bed reactor equipped with a Ni / Al2O3 catalyst at 2.0 L / g cat · The second mixed gas was produced through wet reforming by supplying it at a space velocity of h. In detail, the first fluidized bed reactor filled with the 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 fluidized bed reactor at a flow rate of 3.33 Nl / min to obtain a molar ratio of methane and water vapor (m CH4 / m H2O ) was wet reformed for 120 hours under the condition of 3 to produce a second mixed gas.

[0128] 4. Stream separation

[0129] The Ni / Al2O3 spent catalyst was separated from the second mixed gas using the second cyclone and supplied to the second fluidized bed reactor. The second mixed gas from which the Ni / Al2O3 spent catalyst was separated was introduced into the first Amine Scrubber, where CO2 was captured using an aqueous solution (Amine Solution) containing 12 wt% NH3 dissolved at a processing capacity of 0.5 Nl / hr at 50°C and 15 bar, and the uncaptured hydrogen and carbon monoxide were 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 an amine solution and carbon dioxide at 100°C, and the carbon dioxide was recovered as the first stream.

[0130] 5. Reverse Buddha reaction

[0131] 5 kg of high-purity graphite and the recovered first stream were supplied to the second fluidized bed reactor equipped with the above Ni / Al2O3 spent catalyst, and carbon dioxide was converted 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.

[0132] 6. Gas mixing

[0133] The carbon monoxide and the second stream generated by the above reverse reaction were introduced into a gas mixing unit and mixed at 200°C to generate a third mixed gas.

[0134] 7. Syngas production

[0135] The above third mixed gas is introduced into the synthesis gas generation unit and, under the Cu / Zn / Al2O3 catalyst, 165 o C, 35 bar, space velocity 1.4 L / g cat ·The molar ratio of hydrogen and carbon monoxide (m) is determined by performing the water-gas shift reaction under h conditions. H2 / m CO ) produced a synthesis gas satisfying 2.

[0136] 8. Hydrocarbon production

[0137] The above synthesis gas is supplied to the hydrocarbon conversion unit and is produced under the Co(10%) / ZrO2 catalyst at a space velocity of 1.6 L / g. cat ·h, Fischer-Tropsch synthesis reaction was performed at 245 ℃, 35 bar to recover hydrocarbon fraction.

[0138]

[0139] (Experimental example)

[0140] When producing hydrocarbons by the example method, the components and 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.

[0141] Composition (mol) First mixed gas H20CO43.5CH432.8CO223.7 Second mixed gas H298.2CO76.2CH40.1CO223.7 Second stream H210.01CO9.11CH40.03CO20.01 Third mixed gas H298CO609CH40.01CO2579 Synthesis gas H2472CO236CH40.02CO2952

[0142] Composition (g)Gas2857Liquid, Wax1865H2O2828

[0143] As shown in Tables 4 and 5, as the yield of synthesis gas production improved, the liquid yield of the hydrocarbon produced using the synthesis gas was high at 1865 g. Therefore, it was confirmed that the hydrocarbon production method according to the present disclosure can produce high value-added hydrocarbons at a high yield from a mixed gas obtained by pyrolyzing organic waste, and at the same time, it has an excellent effect in preventing environmental pollution by reducing greenhouse gas emissions. In addition, it was confirmed that the hydrocarbon product group, such as fuels such as naphtha, kero, LGO, and SAF, solvents, and lubricating base oils derived from FT-Wax, which can be obtained compared to when only the pyrolysis process is performed, can be expanded.

[0144]

[0145] 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.

[0146] 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.

[0147] [Explanation of symbols]

[0148] 1 Hydrocarbon production device 10 Pyrolysis reactor

[0149] 11 crackers 12 players

[0150] 20 Gas-liquid separation unit 30 First purification unit

[0151] 40 1st fluidized bed reactor 50 Carbon dioxide separation unit

[0152] 60 Second fluidized bed reactor 70 Gas mixing unit 80 Syngas generation unit

[0153] 90 Hydrocarbon Conversion Unit 100 Organic Waste

[0154] 110 Pyrolysis products 120 First mixed gas

[0155] 130 Mixed liquid 140 Purified first mixed gas 150 Second mixed gas 160 Second catalyst supply line 170 First stream

[0156] 180 Second stream 190 External carbon source 200 Carbon monoxide

[0157] 210 Reforming catalyst recirculation line 220 Third mixed gas 230 Synthesis gas

[0158] 240 Carbon dioxide recirculation line 250 Hydrocarbon 260 First catalyst supply line

[0159] 270 Pyrolysis catalyst recirculation line 280 Air 290 Pyrolysis catalyst

Claims

(S1) A step of heat treating organic waste to produce a pyrolysis product; (S2) A step of separating the above pyrolysis product into a first mixed gas and a mixed liquid; (S3) A step of wet reforming the first mixed gas in the presence of a reforming catalyst in a first fluidized bed reactor to produce a second mixed gas; (S4) A step of separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; (S5) A step of introducing the reformed waste catalyst and the first stream into a second fluidized bed reactor and generating carbon monoxide through a reverse Boudouard reaction; (S6) a step of generating synthesis gas through a water gas shift reaction from the second stream and carbon monoxide generated in the step (S5); and (S7) A method for producing hydrocarbons, comprising: a step of producing hydrocarbons through a catalytic reaction from the above synthesis gas. In the first paragraph, A method for producing hydrocarbons, wherein the above heat treatment is performed under conditions where the ratio of the pyrolysis catalyst to organic waste (Cat / oil ratio) is 2 to 50. In the first paragraph, A method for producing hydrocarbons, wherein the above-mentioned reforming catalyst is a composite catalyst in which an active metal is supported on a support. In the third paragraph, 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. In the third paragraph, 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. In the first paragraph, A method for producing hydrocarbons, wherein the above wet reforming is performed at a temperature of 500 to 1500°C. In the first paragraph, A method for producing hydrocarbons, wherein the above reverse reaction is performed at a temperature of 500 to 1000°C. In the first paragraph, A method for producing hydrocarbons, wherein the above reverse reaction is performed by further introducing an external carbon source into the second fluidized bed reactor. In the first paragraph, A method for producing hydrocarbons, further comprising a step of producing a third mixed gas by mixing the second stream and carbon monoxide produced in step (S5). In the first paragraph, A method for producing hydrocarbons, wherein the above-mentioned water gas shift reaction is performed at a temperature of 100 to 500°C and a pressure of 10 to 50 bar. In the first paragraph, A method for producing hydrocarbons, wherein the carbon dioxide produced in the above step (S6) is recycled to the second fluidized bed reactor. In the first paragraph, The above synthesis gas has a molar ratio of hydrogen and carbon monoxide (m H2 / m CO ) is a method for producing hydrocarbons, wherein 1 to 10 are satisfied. In the first paragraph, A method for producing hydrocarbons, further comprising a step of purifying the first mixed gas prior to the step (S3). A pyrolysis reactor that heat-treats organic waste to produce pyrolysis products; A gas-liquid separation unit that separates the above pyrolysis product into a first mixed gas and a mixed liquid; A first fluidized bed reactor that wet 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 produces carbon monoxide by performing a reverse Boudouard reaction on the reformed waste catalyst and the first stream produced in the first fluidized bed reactor; A synthesis gas generation unit that generates synthesis gas through a water gas shift reaction from the second stream and carbon monoxide generated in the second fluidized bed reactor; and A hydrocarbon production device comprising a hydrocarbon conversion unit that converts the above-mentioned synthesis gas into hydrocarbon through a catalytic reaction. In Article 14, A hydrocarbon production device further comprising a gas mixing unit that produces a third mixed gas by mixing the second stream and carbon monoxide produced from the second fluidized bed reactor. In Article 14, A hydrocarbon production device, wherein the first fluidized bed reactor and the second fluidized bed reactor are connected to a reforming catalyst recirculation line. In Article 14, A hydrocarbon production device, wherein the above-mentioned synthesis gas production unit and the second fluidized bed reactor are connected to a carbon dioxide recirculation line. In Article 14, A hydrocarbon production device further comprising a first purification unit for purifying the first mixed gas.

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