Method and apparatus for producing hydrocarbons

Abstract

Disclosed is a method for producing hydrocarbons, the method comprising the steps of: S1) thermally decomposing a mixed waste to produce a first mixed gas; S2) steam-reforming the first mixed gas, removed of impurities, in a first fluidized bed reactor to produce a second mixed gas; S3) separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; S4) introducing the first stream, separated in step S3), into a second fluidized bed reactor and converting the first stream into carbon monoxide through a reverse Boudouard reaction; S5) mixing the second stream and the carbon monoxide, converted in step S4), to produce a third mixed gas, and producing a synthesis gas (Syngas) through a water-gas conversion reaction using the third mixed gas; and S6) producing hydrocarbons 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 hydrocarbon conversion yield by using a catalyst having high activity and durability during a reforming reaction of a mixed gas containing impurities.

[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, a gasification process using a catalyst has been implemented as a process for producing synthesis gas. However, there is a problem that the catalyst is deactivated due to the generation of coke and other substances during the gasification process, and process trouble occurs due to the deactivated catalyst during continuous operation. In addition, to ensure economic feasibility, it is necessary to recover the relatively expensive catalyst, but in order to recover the catalyst discharged in an agglomerated state such as coke, multiple subsequent processes (such as air burning) must be performed, which significantly reduces the process efficiency. In addition, the mixed gas obtained by pyrolyzing organic waste contains, in addition to hydrogen, carbon monoxide, and carbon dioxide, water-soluble impurities such as H2S, HCl, HOCl, and NH3, as well as insoluble impurities such as tar. This induces the deactivation of the catalyst used in the subsequent synthesis gas production process, reducing the efficiency of the subsequent process. If this problem is purified, it can reduce the efficiency of the entire process.

[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 and limits its utilization or commercialization. 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 still a need for the development of a hydrocarbon production method and production device that can selectively and effectively remove the various impurities contained in the pyrolysis mixed gas of organic waste, thereby improving the production yield of synthesis gas and efficiently converting it into high value-added hydrocarbons while minimizing the generation of carbon dioxide.

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

[0009] According to one aspect of the present disclosure, a method and apparatus for producing hydrocarbons including a catalyst having improved reaction activity and durability even in a mixed gas containing impurities can be provided.

[0010] According to one aspect of the present disclosure, a method and apparatus for producing hydrocarbons capable of reforming a mixed gas containing impurities in an environmentally friendly and stable manner can be provided.

[0011] According to one aspect of the present disclosure, a method and apparatus for producing hydrocarbons can be provided, which can be used for recycling eco-friendly chemical raw materials to prevent climate change by producing high value-added synthesis gas from organic waste and thereby suppressing pollution and greenhouse gas emissions.

[0012] A method for producing hydrocarbons according to the present disclosure comprises the steps of S1) pyrolyzing mixed waste to produce a first mixed gas; S2) steam reforming the first mixed gas from which impurities have been removed in a first fluidized bed reactor to produce a second mixed gas; S3) separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; S4) introducing the first stream separated in step S3) into a second fluidized bed reactor and converting it into carbon monoxide through a reverse Boudouard reaction; S5) mixing the second stream with the carbon monoxide converted in step S4) to produce a third mixed gas, and producing a synthesis gas (Syngas) from the third mixed gas through a water gas shift reaction; and S6) producing a hydrocarbon from the synthesis gas through a catalytic reaction.

[0013] In one example, steps S2) and S4) may be performed under a catalyst containing a first metal including a group VIIIA element, a group VIA element, or a combination thereof; and a second metal including an alkaline earth metal oxide or an alkaline earth metal oxide structure.

[0014] 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.

[0015] In one example, the second fluidized bed reactor of step S4) may be supplied with the coke catalyst of the first fluidized bed reactor of step S2) as a carbon source.

[0016] In one example, the first stream may contain at least 50% by volume of carbon dioxide.

[0017] In one example, the pyrolysis gas may have a C / O element ratio of 0.1 or more.

[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 S5) 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] The present disclosure includes a hydrocarbon production device.

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

[0024] In one example, the first fluidized bed reactor and the second fluidized bed reactor may include a catalyst comprising a first metal including a group VIIIA element, a group VIA element, or a combination thereof of the periodic table; and a second metal including an alkaline earth metal oxide or an alkaline earth metal oxide structure.

[0025] In one example, the hydrocarbon production device further includes a cyclone connected between the first fluidized bed reactor and the carbon dioxide separation unit; a catalyst supply line connecting the cyclone and the second fluidized bed reactor; and a catalyst recirculation line connecting the second fluidized bed reactor and the first fluidized bed reactor, wherein the cyclone separates a second mixed gas discharged from the fluidized bed reforming reactor and a catalyst, supplies the second mixed gas to the carbon dioxide separation unit, and supplies the catalyst to the second fluidized bed reactor.

[0026] According to one embodiment of the present disclosure, by introducing a catalyst having excellent reaction activity and durability, hydrocarbons can be produced with high efficiency without rapid deactivation of the catalyst even for a mixed gas containing impurities.

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

[0028] According to one embodiment of the present disclosure, the production efficiency of hydrocarbons can be significantly improved by converting the feed into hydrocarbons using a process and device suitable for the C / O element ratio of the feed.

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

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

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

[0032] Hereinafter, the present disclosure will be described in detail with reference to the attached drawings. However, these are merely exemplary and the present disclosure is not limited to the specific embodiments described as examples.

[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 terms “group VIIIA element” and “group VIA element” as used in this specification and the appended claims mean elements corresponding to their respective groups in the periodic table according to the former IUPAC (International Union of Pure and Applied Chemistry).

[0038] The present disclosure includes a method for producing hydrocarbons, comprising the steps of: S1) generating a first mixed gas by pyrolyzing mixed waste; S2) steam reforming the first mixed gas in a first fluidized bed reactor to produce a second mixed gas; S3) separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; S4) introducing the first stream separated in step S3) into a second fluidized bed reactor and converting it into carbon monoxide through a reverse Boudouard reaction; S5) mixing the second stream with the carbon monoxide converted in step S4) to produce a third mixed gas, and producing a synthesis gas (Syngas) from the third mixed gas through a water gas shift reaction; and S6) generating a hydrocarbon from the synthesis gas through a catalytic reaction.

[0039] The steps S2) and S4) of the present disclosure are performed in a fluidized bed reactor, and more specifically, the fluidized bed reactor can perform a reaction using a catalyst including a first metal including a group VIIIA element, a group VIA element, or a combination thereof of the periodic table and a second metal oxide including an alkaline earth metal oxide or a structure thereof, thereby additionally removing impurities and simultaneously increasing the efficiency of a synthesis gas produced through the catalytic reaction.

[0040] Therefore, the method for producing hydrocarbons according to the present disclosure can efficiently remove impurities and prevent contamination or deterioration of catalyst activity during the catalytic process, thereby enabling the conversion of organic waste into synthesis gas with high efficiency compared to conventional gasification processes and maximizing the yield of high-value-added hydrocarbons converted from the synthesis gas. Furthermore, the method can prevent environmental pollution by minimizing the generation of carbon dioxide during the hydrocarbon production process.

[0041] In the present disclosure, the step S1) is a step of generating a first mixed gas by heat-treating organic waste, thereby causing a gasification reaction of the organic waste.

[0042] 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.

[0043] Specifically, the above step S1) is a gasification process of organic waste, and may involve one or more gasification reactions selected from the following reaction formulas 1 to 4.

[0044] [Reaction Formula 1]

[0045] C x H y + H2O →H2+ CO (water gasification reaction)

[0046] [Reaction Formula 2]

[0047] C x H y + CO2→CO (carbon dioxide gasification reaction)

[0048] [Reaction Formula 3]

[0049] CO + 3H2→CH4+ H2O (methanation reaction)

[0050] [Reaction Formula 4]

[0051] C x H y + O2→ CO2 (oxidation reaction)

[0052] 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, hydrogen chloride, and water-soluble impurities such as H2S, HCl, HOCl, and NH3.

[0053] In one example, step S1) may be performed under catalytic or non-catalytic conditions to increase the dry gas content in the composition of the first mixed gas. At this time, the dry gas generally refers to hydrocarbon gas having 4 or fewer carbon atoms. Increasing the dry gas content in the composition of the first mixed gas can increase the efficiency of the methane reforming reaction and can be advantageous in terms of the yield of synthesis gas production, so an acid site catalyst or a molybdenum-based molded catalyst can be used as a bed material of a pyrolysis reactor. If a catalyst is not used in the pyrolysis step, the methane content can be increased by operating the gasification pyrolysis reactor under low temperature and high pressure conditions. Since 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, 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.

[0054] In one example, the catalyst in the thermal decomposition reaction may be an acid site catalyst or a molybdenum-based molded catalyst. In one example, the acid site catalyst may be alumina or another inorganic structure having a solid acid site. The alumina may be alumina alone, silica-alumina, alumina dispersed in a carbon structure, etc. The structure 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 against the molybdenum or tungsten, and may include, for example, a material including one or more selected from the group consisting of silica, alumina, silica-alumina, carbon, and zirconia.

[0055] 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.

[0056] In one example, the C / O element ratio of the first mixed gas may be 0.01 or more, 0.05 or more, or 0.1 or more, and the upper limit may be 0.9 or less, 0.8 or less, or 0.7 or less, specifically 0.01 to 0.9, 0.05 to 0.8, and more specifically 0.1 to 0.7.

[0057] 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.

[0058] After the above step S1), impurity gases containing impurities such as Cl, N, and S in the mixed gas can be selectively removed using a scrubber or an adsorbent. For example, impurities can be selectively removed through one or a combination of two or more selected from the group consisting of water washing, alkaline solution washing, scrubber, high-pressure dust collecting filter, and ceramic filter passage, but the present invention is not limited thereto. For example, if the first mixed gas is passed through a ceramic filter or dust collecting filter among the above means, insoluble impurities such as tar and dust can be removed.

[0059] Step S2) of the present disclosure is a step of producing a second mixed gas by subjecting methane contained in the first mixed gas to a steam reforming reaction in a first fluidized bed reactor. In step S2), a reforming reaction according to the following reaction formula 5 may be performed.

[0060] [Reaction Formula 5]

[0061] CH4+ H2O →CO + 3H2 (steam reforming reaction)

[0062] The reforming reaction of the above step S2) can be performed at a temperature of 600°C to 1400°C, preferably 600°C to 700°C, and a pressure of 30 KPa to 2000 KPa.

[0063] The above step S2) may include a catalyst to increase the reaction conversion rate. The catalyst of the above step S2) may include a first metal including a group VIIIA element, a group VIA element, or a combination thereof of the periodic table, and a second metal oxide including an alkaline earth metal oxide or a structure thereof, thereby performing a fluidized bed catalytic reaction to additionally remove impurities and increase the efficiency of the steam reforming reaction.

[0064] The first metal may include a group ⅧA element, a group ⅥA element, or a combination thereof, and may include at least one selected from the group including, for example, nickel (Ni), iron (Fe), molybdenum (Mo), and tungsten (W).

[0065] The second metal oxide may include an alkaline earth metal oxide or an alkaline earth metal oxide structure. The second metal oxide may include one or more alkaline earth metal oxides selected from the group consisting of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba), and may include magnesium oxide (MgO) as an example. In addition, the alkaline earth metal oxide structure is a structure in which an alkaline earth metal is combined with a metal oxide, and for example, magnesium aluminate (MgAl2O4) having a spinel structure, hydrotalcite (Mg6Al2CO3(OH)) 16 ·4H2O) and the like. By including the second metal oxide in the present disclosure, sulfur, nitrogen and chlorine compounds can be selectively added and removed, thereby increasing the production efficiency of synthesis gas in the steam reforming process of step S2) and the reverse Boudouard process of step S4).

[0066] Furthermore, the catalyst of the present disclosure, comprising the first metal and second metal oxides, exhibits excellent durability and minimal catalyst loss, even after repeated catalyst coking and catalyst regeneration, thereby maintaining high catalytic activity for a long period of time. As the catalyst replacement cycle is extended, process efficiency and economic feasibility can be improved.

[0067] Specifically, by performing a steam reforming reaction in a fluidized bed reactor using a catalyst containing the above two types of metals, not only is the reforming reactivity improved, but impurities such as chlorine are removed, and side reactions including dehydrogenation and hydrogenation are reduced, so that the yield of the produced synthesis gas can be maximized.

[0068] In one example, the method for preparing the catalyst may include preparing a mixed solution by mixing a ceramic support and a first metal in a solvent, then adding an organic acid to the mixed solution to prepare a precursor gel, and then mixing the precursor gel with a solid mixture containing a binder and a second metal oxide. An inorganic binder may be further added to the mixture to prepare a composite catalyst sol, which may then be spray-dried to obtain a catalyst having an average particle size of 50 μm to 250 μm. The catalyst prepared by the above-described method not only has excellent catalytic activity, but also has improved durability and can provide an excellent catalyst lifespan because the first metal and the second metal are uniformly dispersed and strongly bonded within the catalyst.

[0069] Step S3) is a step of separating the second mixed gas in a carbon dioxide separation unit into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide.

[0070] 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.

[0071] As another example, the carbon dioxide separation unit may be a CCS unit (Carbon capture and storage unit). When a CCS unit is used to separate carbon dioxide, the CCS unit can adsorb and separate carbon dioxide using an adsorbent including one or more selected from calcium oxide, calcium hydroxide, dolomite, limestone, and trona, so the second mixed gas can be separated into first and second streams using the CCS unit (Carbon capture and storage unit).

[0072] 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.

[0073] Step S4) is a step of converting the first stream separated in step S3) into carbon monoxide through a reverse Boudouard reaction in a second fluidized bed reactor. By additionally converting the carbon dioxide contained in the first stream into carbon monoxide through the reverse Boudouard 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 Boudouard reaction may involve the following reaction scheme 6.

[0074] [Reaction Formula 6]

[0075] C+CO2→ 2CO

[0076] The above reaction can be carried out at a temperature of 600°C to 1000°C and a pressure of 50 KPa to 300 KPa.

[0077] Furthermore, since the reverse-Buddha reaction utilizes a catalyst with coke deposited thereon, eliminating the need for a separate external carbon source, the process can be operated economically. The catalyst, regenerated by removing the coke deposited on the catalyst during the reverse-Buddha reaction, can be reintroduced into the steam reforming reaction to perform the catalytic reaction, thereby providing the advantage of a cyclic process.

[0078] That is, while the yield of synthesis gas can be maximized through the methane reforming reaction and the reverse Buta reaction, continuous and economical process operation can be simultaneously implemented through catalyst regeneration as the first fluidized bed reactor and the second fluidized bed reactor, in which the methanation reforming reaction and the reverse Buta reaction are performed, form a circulating process.

[0079] In addition to being limiting, the above-described reverse-Buda reaction may be performed by additionally supplying a carbon source from an external 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 possibility of impurity gases being introduced by the external carbon source.

[0080] The above S4) step can further remove remaining sulfur compounds, nitrogen compounds, and chlorine compounds by performing the catalytic reaction of the present disclosure, thereby increasing the yield of synthesis gas (Syngas).

[0081] The catalyst of the above step S4) includes a first metal including a group ⅧA element, a group ⅥA element, or a combination thereof of the periodic table, and a second metal oxide including an alkaline earth metal oxide or a structure thereof. The first metal may include one selected from the group including nickel, iron, molybdenum, and tungsten, and the second metal oxide may include MgO, MgAl2O4(Spinel), Mg6Al2CO3(OH). 16 ·It may include one or more selected from the group including 4H2O (Hydrotalcite).

[0082] As described above, by using a catalyst comprising the first metal and the second metal oxide in the steam reforming process and the reverse Boudouard process, sulfur, nitrogen, and chlorine compounds can be selectively added and removed, thereby increasing the production efficiency of synthesis gas in the steam reforming step and the reverse Boudouard process. For example, the reaction for removing sulfur compounds by a catalyst comprising the second metal oxide can be represented by the following reaction formula 7.

[0083] [Reaction Formula 7]

[0084] S +CO2→ SO2+SO3+CO

[0085] SO2+1 / 2CO2→ SO3+CO

[0086] MgO +SO3→ MgSO4

[0087] For example, as in the above reaction formula 9, the catalyst including MgSO4 generated by the reaction of the second metal oxide with the sulfur compound in step S4) is recovered in the first fluidized bed reactor in step S2), thereby separating sulfur from MgSO4 during the steam reforming reaction, removing impurities, and regenerating the catalyst. The above reaction can be represented by the following reaction formula 8.

[0088] [Reaction Formula 8]

[0089] MgSO4+ 4H2→ MgS + 4H2O

[0090] MgSO4+4H2→ MgO + H2S + 3H2O

[0091] MgO +H2O → MgO + H2S

[0092] As a non-limiting example, in order to prevent the decline in catalytic activity due to irreversible deactivation of the catalyst that inevitably occurs during the process of performing steps S2) and S4), a certain amount of the catalyst may be replaced with a new catalyst. In the steam reforming and reverse catalytic reaction processes, the partially deactivated catalyst may be removed from the reactor and a new catalyst may be introduced to improve the catalytic activity. The catalyst of the present disclosure has the advantages of very high durability, a very low degree of catalyst deactivation, a long catalyst replacement cycle, and a small amount of new catalyst to be replaced and introduced.

[0093] Step S5) is a step of producing synthesis gas through a water gas shift reaction in a synthesis gas production unit using a third mixed gas obtained by mixing the second stream separated in the carbon dioxide separation unit and the carbon monoxide obtained in step S4). The third mixed gas may include hydrogen and carbon monoxide.

[0094] In the above step, the third mixed gas can be converted to a hydrogen:carbon monoxide ratio suitable for the subsequent catalytic reaction through the water gas shift (WGS) reaction. The water gas shift reaction may be accompanied by the following reaction formula 9.

[0095] [Reaction Formula 9]

[0096] CO + H2O → H2 + CO2

[0097] The water-gas shift reaction can be carried out in the presence of a catalyst containing Fe and Cr. The water-gas shift reaction can be carried out at a temperature of 100°C to 400°C, specifically 100°C to 300°C, and a pressure of 20 bar to 80 bar, specifically 25 bar to 70 bar.

[0098] 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.

[0099] Step S6) is a step for converting the synthesis gas generated in step S5) into a hydrocarbon fraction, which can be converted into an appropriate hydrocarbon fraction by a catalytic reaction.

[0100] 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.

[0101] In one example, when the catalytic reaction of step S6) is a Fischer-Tropsch reaction, a reaction involving reaction formula 10 can be performed using the synthesis gas produced in step S6) as a raw material.

[0102] [Reaction Formula 10]

[0103] nCO + 2nH2→CnH2n + nH2O

[0104] 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.

[0105] 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.

[0106] In one example, in one example, when the catalytic reaction of step S6) is a methanol and olefin conversion reaction, step S6) may include a reaction of converting synthesis gas into methanol; and a reaction of converting methanol into olefin.

[0107] The reaction for converting synthesis gas into methanol may be a reaction involving the following reaction scheme 11.

[0108] [Reaction Formula 11]

[0109] CO + 2H2→ CH3OH

[0110] 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.

[0111] The reaction of converting the above synthesis gas into methanol can be performed at 150°C to 600°C, specifically 200°C to 350°C, and 0.1 MPa to 10 MPa, specifically 2 MPa to 15 MPa.

[0112] 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.

[0113] 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.

[0114] Hereinafter, the hydrocarbon production device of the present disclosure will be described.

[0115] The present disclosure includes a hydrocarbon production device, comprising: a pyrolysis reactor that heat-treats organic waste to produce a first mixed gas; a first fluidized bed reactor that steam reforms the first mixed gas to produce a second mixed gas; a carbon dioxide separation unit that separates the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; a second fluidized bed reactor that converts the first stream into carbon monoxide through a reverse Boudouard reaction; a gas mixing unit that mixes the second stream with carbon monoxide converted from the second fluidized bed reactor to produce a third mixed gas; a synthesis gas production unit that converts the third mixed gas into synthesis gas through a water gas shift reaction; and a hydrocarbon conversion unit that converts the synthesis gas into hydrocarbon through a catalytic reaction.

[0116] The hydrocarbon production device (1) according to the present disclosure performs a steam reforming reaction and a reverse Budar reaction through a first fluidized bed reactor (20) and a second fluidized bed reactor (40) including a catalyst including a first metal and a second metal oxide, thereby converting a first mixed gas (110) into a synthesis gas (230) and hydrocarbons with high efficiency, and the device can be installed and operated economically with low installation and operating costs.

[0117] As illustrated in Fig. 1, organic waste (100) is introduced into a pyrolysis reactor (10) and, after heat treatment, produces a first mixed gas (110). The first mixed gas (110) is introduced into a first fluidized bed reactor (20) and, through a steam reforming reaction, methane is converted into carbon monoxide and hydrogen to produce a second mixed gas (200).

[0118] As illustrated in Fig. 2, before introducing the mixed gas into the first fluidized bed reactor (20), a purification unit (80) for removing impurities contained in the mixed gas may be further included. The purification unit (80) may include an adsorbent or a scrubber. By selectively removing trace impurity gases such as S, N, and Cl in the mixed gas through the purification unit (80), the deactivation of the catalyst during steam reforming and reverse catalytic reduction process operation can be reduced, thereby increasing reaction stability and improving economic efficiency.

[0119] The second mixed gas (200) is introduced into a carbon dioxide separation unit (30) and separated into a first stream (210) containing carbon dioxide and a second stream (211) containing hydrogen and carbon monoxide. The second stream (211) is directly supplied to a gas mixing unit (50), and the first stream (210) is supplied to a second fluidized bed reactor (40) and converted into carbon monoxide through a reverse Buta reaction.

[0120] Referring to FIG. 3, the reactor further includes a cyclone (90) connected between the first fluidized bed reactor (20) and the carbon dioxide separation unit (30); a catalyst supply line connecting the cyclone (90) and the second fluidized bed reactor (40); and a catalyst recirculation line connecting the second fluidized bed reactor (40) and the first fluidized bed reactor (20). The cyclone (90) separates a second mixed gas (200) discharged from the first fluidized bed reactor (20) and a catalyst, supplies the second mixed gas (200) to the carbon dioxide separation unit (30), and supplies the catalyst to the second fluidized bed reactor (4).

[0121] In one example, the cyclone (90) receives the second mixed gas (200) from the first fluidized bed reactor (20), separates the coke catalyst, and then supplies the second mixed gas (200) to the separation unit (30). The coke catalyst can be supplied to the second fluidized bed reactor (40) along a catalyst supply line connected to the cyclone (90) and the second fluidized bed reactor (40). In the second fluidized bed reactor (40), the coke catalyst supplied from the cyclone (90) can be regenerated, and the regenerated catalyst can be supplied to the first fluidized bed reactor (20) through a recirculation line connected to the fluidized bed reforming reactor (21). In this way, by including a cyclone (90), there is no need to separately supply coke required for the reverse reaction from the outside, so economical process operation is possible, and the catalyst for the methane reforming reaction can be continuously re-supplied, so there is an advantage in efficient process operation.

[0122] The second fluidized bed reactor (40) can additionally receive 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.

[0123] The gas mixing unit (50) mixes the second stream (211) with carbon monoxide converted in the second fluidized bed reactor (40) to produce a third mixed gas (220). The third mixed gas (220) is supplied to the water gas conversion unit (60) and converted into synthesis gas (230) by controlling the hydrogen:carbon monoxide ratio in the third mixed gas through a water gas conversion reaction.

[0124] 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.

[0125] 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.

[0126] In one example, the hydrocarbon production device may further include a separation step that separates the produced hydrocarbons into fractions by boiling point through distillation by being connected to a hydrocarbon conversion unit (70).

[0127] Hereinafter, embodiments of the present invention will be further described with reference to specific experimental examples. The embodiments and comparative examples included in the experimental examples are only illustrative of the present invention and do not limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications to the embodiments are possible within the scope and technical idea of ​​the present invention, and it is natural that such changes and modifications fall within the scope of the appended claims.

[0128] (Manufacturing Example 1) Manufacturing of a fluidized bed catalyst (Ni / Mg / Zeolite / Al2O3)

[0129] Based on 100 parts by weight of water, 10 parts by weight of pseudo-boehimite alumina and 95 parts by weight of nickel nitrate hexahydrate were mixed to prepare a mixed solution. 1 part by weight of formic acid was added while stirring the mixed solution, and the mixture was reacted for 3 hours to gelate, thereby preparing a precursor gel. 20 parts by weight of clay, 10 parts by weight of USY Zeolite, and 1.5 parts by weight of MgO were added, and the solid mixture mixed using a homogenizer was mixed with the precursor gel. 10 parts by weight of colloidal silica (Ludox AS40, Aldrich) was added, and 5 parts by weight of water was further added, followed by vigorous stirring to prepare a composite catalyst sol. The composite catalyst sol was spray-dried to prepare a fluidized bed catalyst having a particle size of 50 to 250 μm. The recovered catalyst was dried in an oven at 120°C and calcined at 550°C for 3 hours to prepare a fluidized bed catalyst.

[0130] (Manufacturing Example 2) Manufacturing of Ni / Mg 3wt% / Zeolite / Al2O3 catalyst

[0131] A catalyst was prepared in the same manner as in Preparation Example 1, except that the solid mixture contained 3 parts by weight of MgO.

[0132] (Manufacturing Example 3) Manufacturing of Ni / hydrotalcite / Zeolite / Al2O3 catalyst

[0133] The solid mixture is hydrotalcite (Mg6Al2CO3(OH)) instead of MgO. 16 ·4H2O) was included, the catalyst was prepared in the same manner as in Manufacturing Example 1.

[0134] (Manufacturing Example 4) Manufacturing of Ni / MgSiO3 / Zeolite / Al2O3 catalyst

[0135] A catalyst was prepared in the same manner as in Preparation Example 1, except that the solid mixture contained MgSiO3 with a spinel structure instead of MgO.

[0136] (Manufacturing Example 5) Manufacturing of Ni / Ca / Zeolite / Al2O3 catalyst

[0137] A catalyst was prepared in the same manner as in Preparation Example 1, except that the solid mixture contained CaO instead of MgO.

[0138] (Manufacturing Example 6) Manufacturing of Ni / K / Zeolite / Al2O3 catalyst

[0139] A catalyst was prepared in the same manner as in Preparation Example 1, except that the solid mixture contained K2O instead of MgO.

[0140] (Manufacturing Example 7) Manufacturing of Ni / Al2O3 catalyst

[0141] A catalyst was prepared in the same manner as in Manufacturing Example 1, except that the solid mixture did not contain MgO and USY Zeolite and contained 30 parts by weight of clay.

[0142] (Manufacturing Example 8) Manufacturing of Ni / Zeolite / Al2O3 catalyst

[0143] A catalyst was prepared in the same manner as in Preparation Example 1, except that the solid mixture did not contain MgO and contained 1 part by weight of USY Zeolite.

[0144] (Experimental Example 1) Catalyst Characterization

[0145] The characteristics of the catalysts manufactured by the methods of Manufacturing Examples 1, 7, and 8 are analyzed and shown in Table 1 below. Specifically, the wear index was measured using a wear resistance measuring device (3-hole attrition tester) according to the standard according to ASTM D 5757-95. The nickel content in the catalyst was calculated as a result of XRF (X-Ray Flourescence Spectrometry) analysis, and the XRF analysis was measured using an ARL QUANT'X from Thermo. The BET surface area, total pore volume, and pore size were measured using a Tristar 3000 from Micromeritics by a nitrogen physical adsorption-desorption method. The particle size distribution, such as the particle size and the fine powder content contained in the catalyst, was measured using a Mastersizer 3000 from Malvern. Here, “fine powder” means a catalyst particle having a particle diameter of 50 ㎛ or less.

[0146] Manufacturing Example 1 Manufacturing Example 7 Manufacturing Example 8 Wear Index (wt%) 3.1 3.5 5.3 BET Surface Area (m 2 / g)12479129Total pore volume (cc / g)0.230.20.23Average pore size (Å)483449Average particle size (㎛)127126121Fine powder content in catalyst (wt%)3.545Ni content in catalyst (wt%)29.130.128.5

[0147] As shown in Table 1, the catalyst of Preparation Example 1 including nickel and MgO had a low wear index of 3.1 wt%, whereas the catalysts of Preparation Examples 7 and 8 not including MgO had wear indices of 3.5 wt% and 5.3 wt%, respectively. In addition, the fine powder contents included in the catalysts of Preparation Examples 1, 7, and 8 were measured to be 3.5 wt%, 4 wt%, and 5 wt%, respectively. It can be seen that the catalyst of Preparation Example 1, which had the smallest fine powder content and the lowest wear index, had excellent strength. In addition, the catalyst of Preparation Example 1 had a specific surface area of ​​124 m 2 / g, pore volume of 0.23 cc / g, average pore diameter of 48 Å, and average catalyst diameter of 127 ㎛ were measured, confirming that it has a structure capable of sufficiently dispersing and supporting nickel and MgO within the ceramic support to improve catalytic activity.

[0148] (Example 1)

[0149] After 1000 g of municipal solid waste was fed into a pyrolysis reactor, steam was introduced and heat-treated at a temperature of 1200°C and a pressure of 250 kPa under an alumina bead to recover a first mixed gas having a C / O element ratio of 0.67.

[0150] The temperature of the first mixed gas was lowered, and impurities such as Cl, S, and N contained in the mixed gas were removed through a scrubber, and the purified first mixed gas was recovered.

[0151] The first mixed gas from which the above impurities were removed was supplied to a first fluidized bed reactor containing the catalyst manufactured in Manufacturing Example 1 at a space velocity of 2 L / g-cat. / h, and steam was simultaneously supplied to manufacture a second mixed gas through steam reforming at 700°C.

[0152] The second mixed gas was introduced into the Amine Scrubber, and the carbon dioxide in the second mixed gas was captured in the Amine Scrubber and separated into a second stream from which the carbon dioxide was separated. Specifically, the second mixed gas was introduced into the first Amine Scrubber, and CO2 was captured in an aqueous solution (Amine Solution) containing MEA (Monoethanolamine) at 50°C, and the uncaptured gas was recovered as the second stream. The Amine Solution of the first Amine Scrubber was introduced into the second Amine Scrubber, and separated into the Amine Solution and CO2 at 100°C, and the CO2 was recovered as the first stream.

[0153] The recovered first stream was fed into a second fluidized bed reactor containing the catalyst of Manufacturing Example 1 and converted into carbon monoxide through a reverse Buta reaction. The reverse Buta reaction was performed in a second fluidized bed reactor filled with the catalyst of Manufacturing Example 2, which was used in the steam reforming reaction and had coke deposited on it, and the first stream was continuously supplied at a space velocity of 2 L / g-cat. / h to be converted into carbon monoxide. The catalyst, activated by removing coke through the reverse Buta reaction, was reintroduced into the first fluidized bed reactor.

[0154] The catalyst separated from the cyclone was supplied to the second fluidized bed reactor via a catalyst supply line and utilized as a carbon source, while simultaneously being processed during the reverse Buda reaction to perform a regeneration process. The regenerated catalyst was then resupplied to the first fluidized bed reactor via a recirculation line connected to the first fluidized bed reactor, and the unconverted CO2 after the reaction was separately recovered via the amine scrubber.

[0155] The carbon monoxide converted from the first stream and the second stream were introduced into a gas mixing unit, mixed, and mixed at 200°C to produce a third mixed gas.

[0156] The third mixed gas was introduced into the synthesis gas generation unit and produced synthesis gas with a molar ratio of H2:CO=1:2 through a water gas shift reaction.

[0157] The synthesis gas was supplied to a hydrocarbon conversion unit, and the injection rate was set so that the space velocity was 5000 L / kg·cat / h and the volume ratio of carbon monoxide: hydrogen: argon was 63.2: 31.3: 5.5 under a Co / ZnO (Cobalt Zinc oxide) catalyst, and the Fischer-Tropsch reaction was performed at a reaction temperature of 300°C and a pressure of 10 bar for 60 hours to recover hydrocarbon fraction.

[0158] (Example 2)

[0159] The steam reforming process and the reverse carbothermal reaction process were performed in the same manner as in Example 1, except that the catalyst of Manufacturing Example 2 was used instead of the catalyst of Manufacturing Example 1.

[0160] (Example 3)

[0161] The steam reforming process and the reverse Buddha reaction process were performed in the same manner as in Example 1, except that the catalyst of Manufacturing Example 3 was used instead of the catalyst of Manufacturing Example 1.

[0162] (Example 4)

[0163] The process was performed in the same manner as Example 1, except that the catalyst of Manufacturing Example 4 was used instead of the catalyst of Manufacturing Example 1 as the steam reforming process and reverse carbothermal reaction process catalyst.

[0164] (Example 5)

[0165] The process was performed in the same manner as Example 1, except that the catalyst of Manufacturing Example 5 was used instead of the catalyst of Manufacturing Example 1 as the steam reforming process and reverse carbothermal reaction process catalyst.

[0166] (Example 6)

[0167] The process was performed in the same manner as Example 1, except that the catalyst of Manufacturing Example 6 was used instead of the catalyst of Manufacturing Example 1 as the steam reforming process and reverse carbothermal reaction process catalyst.

[0168] (Comparative Example 1)

[0169] The same procedure as Example 1 was followed, except that the catalyst of Manufacturing Example 7 was used instead of the catalyst of Manufacturing Example 1 in the steam reforming process and the reverse carbothermal reaction process.

[0170] (Comparative Example 2)

[0171] The same procedure as Example 1 was followed, except that the catalyst of Manufacturing Example 8 was used instead of the catalyst of Manufacturing Example 1 in the steam reforming process and the reverse carbothermal reaction process.

[0172] (Experimental Example 2) Catalyst durability evaluation

[0173] When producing hydrocarbons using the methods of Examples 1 to 6 and Comparative Examples 1 and 2, the process of producing synthesis gas from the first mixed gas was defined as 1 cycle, and after performing this for 20 cycles, the catalyst was taken out from the reactor, the particle size distribution of the catalyst was analyzed, and the fine particle content in the catalyst was compared. At this time, the fine particle refers to particles having a particle size of 50 μm or less.

[0174] A methane steam reforming reaction was performed by charging a reactor with 2 kg of catalyst, introducing 3 cc / min of water at 750°C, and supplying a first mixed gas obtained by thermal decomposition of waste. The first mixed gas contained 99.5% CH4, and more specifically, the types and contents of impurities contained in the first mixed gas are shown in Table 2 below.

[0175] Impurity content (ppm)HCl200H2S100COS20NH3350

[0176] After the reaction was carried out for 20 cycles, the particle size distribution of the catalyst remaining in the reactor was analyzed to measure the fine particle content in the catalyst, which is shown in Table 3 below. The particle size distribution was measured using a Mastersizer 3000 from Malvern.

[0177] Catalyst type Fine powder content (wt%) Example 1 Manufacturing example 1 (Ni / Mg 1 wt% / Zeolite / Al2O3) 12.8 wt% Example 2 Manufacturing example 2 (Ni / Mg 3 wt% / Zeolite / Al2O3) 11.2 wt% Example 3 Manufacturing example 3 (Ni / Hydrotalcite / Zeolite / Al2O3) 14.7 wt% Example 4 Manufacturing example 4 (Ni / MgSiO3 / Zeolite / Al2O3) 14.0 wt% Example 5 Manufacturing example 5 (Ni / Ca / Zeolite / Al2O3) 14.1 wt% Example 6 Manufacturing example 6 (Ni / K / Zeolite / Al2O3) 14.9 wt% Comparative example 1 Manufacturing example 7(Ni / Al2O3)17.5 wt%Comparative Example 2 Manufacturing Example 8(Ni / Zeolite / Al2O3)22.7 wt%

[0178] As shown in Table 3 above, in Examples 1 to 6 using the catalysts of Preparation Examples 1 to 7 including the first metal and the second metal oxide, the rate at which the catalyst was converted to fine powder was lower compared to Comparative Examples 1 and 2 including the catalysts of Preparation Examples 7 and 8 not including the second metal oxide. The increase in the fine powder content means that cracks and breakage occurred in the catalyst by repeating the coking and catalyst regeneration for 20 cycles. As in the catalysts of Preparation Examples 1 to 6, which include two types of metals, the catalyst was not damaged and maintained its original state even when the catalyst coking and catalyst regeneration processes were repeated, so that the cyclic process could be performed continuously for a long period of time. Therefore, the catalyst of the present disclosure has excellent durability, so that the catalyst life is improved, the catalyst replacement cycle can be extended, and the process efficiency can be improved.

[0179] (Experimental Example 3) Catalyst Performance Evaluation

[0180] In the same manner as in Experimental Example 2, the catalysts of Manufacturing Examples 1 to 8 were operated for 1 cycle, 5 cycles, and 20 cycles, respectively, using the methods of Examples 1 to 6 and Comparative Examples 1 and 2, and then 200 g of the catalyst was recovered. After removing fine particles from the recovered catalyst, a reforming reaction for methane gas containing impurities was performed in a separate reactor.

[0181] The methane reforming reaction was performed by charging 100 g of each catalyst into a fluidized bed reactor, and performing catalytic reduction at a temperature of 900°C for 2 hours under the conditions of an H2 gas flow rate of 3.03 Nl / min, followed by a methane reforming reaction under the conditions of a total gas flow rate of 3.33 Nl / min, a throughput of 2.0 L / gcat·h, and CH4 / H2O = 3. The methane conversion rate of the catalyst is shown in Table 4 below. In Table 4, “Fresh cat.” means a new catalyst that has not undergone a catalytic reaction.

[0182] Catalyst type Methane conversion rate (%) Fresh cat. 1 cycle 5 cycle 20 cycle Example 1 Manufacturing example 1 (Ni / Mg 1 wt% / Zeolite / Al2O3) 98.3 8 5.2 6 5.3 2 3.5 Example 2 Manufacturing example 2 (Ni / Mg 3 wt% / Zeolite / Al2O3) 97.0 8 3.2 5 3.1 1 7.2 Example 3 Manufacturing example 3 (Ni / Hydrotalcite / Zeolite / Al2O3) 97.5 7 9.9 3 5.9 9.5 Example 4 Manufacturing example 4 (Ni / MgSiO3 / Zeolite / Al2O3) 97.3 7 7.1 2 9.2 8.8 Example 5 Manufacturing example 5(Ni / Ca / Zeolite / Al2O3)97.575.027.15.9Example 6Manufacturing Example 6(Ni / K / Zeolite / Al2O3)93.379.314.03.1Comparative Example 1Manufacturing Example 7(Ni / Al2O3)99.373.922.33.0Comparative Example 2Manufacturing Example 8(Ni / Zeolite / Al2O3)99.078.315.54.1

[0183] Referring to Table 4, in the case of Comparative Examples 1 and 2 using the catalysts of Preparation Examples 7 and 8 that do not include alkaline earth metals or their structures, the initial catalytic activity was very high, but the methane conversion rates after 5 cycles were 22.3% and 15.5%, respectively, which significantly decreased compared to the initial methane conversion rates, confirming that the catalysts were rapidly deactivated as the catalytic process was repeated. Even after 20 cycles, the methane conversion rates for Comparative Examples 1 and 2 decreased to 3.0% and 4.1%, respectively, confirming that most of the catalyst particles were deactivated.

[0184] On the other hand, in the case of Examples 1 to 6 using the catalysts of Preparation Examples 1 to 6 containing nickel and alkaline earth metals, high catalytic activity was exhibited even after repeated catalyst coking and regeneration. In particular, in the case of Examples 1 and 2 containing MgO, the methane conversion was high at 65.3% and 53.1%, respectively, even after 5 cycles, and the methane conversion was 23.5% and 17.2%, respectively, even after 20 cycles, indicating delayed catalyst deactivation. In the case of Examples 3 and 4 using the catalysts of Preparation Examples 3 and 4 containing MgSiO3 having an alkaline earth metal structure such as hydrotalcite or spinel, the methane conversion was measured to be 35.9% and 29.2%, respectively, after 5 cycles, and good methane conversions of 9.5% and 8.8%, respectively, were exhibited even after 20 cycles. The catalyst of Manufacturing Example 5 using CaO as an alkaline earth metal oxide also measured methane conversion rates of 27.1% and 5.9% after 5 and 20 cycles, respectively.

[0185] Meanwhile, in the case of Example 6 including the catalyst of Preparation Example 6 including K2O, which is an alkali metal oxide, the methane conversion rate decreased to 14.0% after 5 cycles, and the methane conversion rate decreased to 3.1% after 20 cycles, confirming that catalyst deactivation was not suppressed.

[0186] Through the above examples and comparative examples, when producing hydrocarbons from pyrolysis gas by the method according to the present disclosure, not only does the yield of synthesis gas and hydrocarbons increase by recovering carbon dioxide in the mixed gas through the reverse Buta reaction process and converting it into carbon monoxide, but also the amounts of H2 and CO produced in the final synthesis gas are significantly increased and the amount of CO2 produced is reduced, which has advantageous effects in terms of the yield of synthesis gas production and prevention of environmental pollution. In particular, by adopting a fluidized bed reactor as the reactor for the methane reforming and reverse Buta process, and using a catalyst having excellent durability by complexing a first metal and a second metal oxide including an alkaline earth metal as the catalyst for the methane reforming and reverse Buta reaction, catalyst deactivation due to coke generated during the methane reforming reaction is prevented, and even if the catalyst is deactivated due to coke, the catalyst can be regenerated in the reverse Buta reaction process. As a result, the catalyst replacement cycle is extended, thereby improving process efficiency, and further, excellent synthesis gas conversion rate and hydrocarbon production efficiency can be achieved. In addition, there is an advantage in that high-purity synthesis gas can be obtained by performing steam reforming and reverse Boudha reaction while continuously removing impurities in the mixed gas through a catalyst.

[0187] The above description is merely an example of applying the principles of the present disclosure, and other configurations may be further included without departing from the scope of the present invention.

[0188] [Explanation of symbols]

[0189] 1 Hydrocarbon production device 10 Pyrolysis reactor

[0190] 20 First fluidized bed reactor 30 Carbon dioxide separation unit

[0191] 40 Second fluidized bed reactor 50 Gas mixing unit

[0192] 60 synthesis gas generation units 70 hydrocarbon conversion units

[0193] 80 refining units 90 cyclones

[0194] 100 Organic waste 110 First mixed gas

[0195] 120 First mixed gas with impurities removed 200 Second mixed gas

[0196] 210 First Stream 211 Second Stream

[0197] 220 Third mixed gas 230 Synthetic gas

Claims

1. S1) A step of generating a first mixed gas by thermally decomposing mixed waste; S2) A step of producing a second mixed gas by steam reforming the first mixed gas from which the impurities have been removed in a first fluidized bed reactor; S3) A step of separating the second mixed gas into a first stream containing carbon dioxide and a second stream containing hydrogen and carbon monoxide; S4) A step of introducing the first stream separated in the step S3) into a second fluidized bed reactor and converting it into carbon monoxide through a reverse Boudouard reaction; S5) a step of mixing the second stream and the carbon monoxide converted in step S4) to produce a third mixed gas, and producing a synthesis gas (Syngas) through a water gas conversion reaction of the third mixed gas; and S6) 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, The above steps S2) and S4) include a first metal including a group VIIIA element, a group VIA element, or a combination thereof; and A method for producing hydrocarbons, carried out under a catalyst containing a second metal; including an alkaline earth metal oxide or an alkaline earth metal oxide structure.

3. 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.

4. In paragraph 1, A method for producing hydrocarbons, wherein the second fluidized bed reactor of step S4) is supplied with the coke catalyst of the first fluidized bed reactor of step S2) as a carbon source.

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

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

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

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

9. In paragraph 1, A method for producing hydrocarbons, wherein in the step S5), the synthesis gas contains hydrogen and carbon monoxide, and the ratio of hydrogen and carbon monoxide satisfies 1.8:1 to 2.2:

1.

10. 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.

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

12. In paragraph 11, A hydrocarbon production device, wherein the first fluidized bed reactor and the second fluidized bed reactor include a catalyst including a first metal including a group VIIIA element, a group VIA element, or a combination thereof in the periodic table; and a second metal including an alkaline earth metal oxide or an alkaline earth metal oxide structure.

13. In paragraph 11, The above hydrocarbon production device, A cyclone connected between the first fluidized bed reactor and the carbon dioxide separation unit; A catalyst supply line connecting the above cyclone and the second fluidized bed reactor; and It further includes a catalyst recirculation line connecting the second fluidized bed reactor and the first fluidized bed reactor, A hydrocarbon production device in which the above cyclone separates the second mixed gas and catalyst discharged from the fluidized bed reforming reactor, supplies the second mixed gas to a carbon dioxide separation unit, and supplies the catalyst to a second fluidized bed reactor.

Images