Method and system for producing synthetic oil

Abstract

To provide a method and a system for producing a synthetic oil.SOLUTION: According to the present disclosure, there is provided a method for producing a synthetic oil, comprising the steps of: providing a feed comprising a carbonaceous material; introducing the feed into a synthesis gas production reaction in the presence of a catalyst to produce a synthesis gas; introducing the synthesis gas into a Fischer-Tropsch (FT) reaction to produce a synthetic oil and an FT tail gas; regenerating a catalyst used in the step of producing the synthesis gas in a catalyst regenerator; and feeding the FT tail gas into the catalyst regenerator.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a method and system for producing synthetic oil using FT tail gas. [Background technology]

[0002] The dictionary definition of "biomass" is a compound word of "bio," meaning biological origin, and "mass," meaning material, and refers to a substance of biological origin. "Biogenetic" means that it originates from the photosynthetic products of plants, which are primary producers. Photosynthetic products, in which solar energy is organically fixed, are transferred and transmitted to secondary and tertiary consumers and decomposers via the food chain. All products generated in this process can be called biomass. Generally, all biological organisms that make up an ecosystem can be included in the biomass category. Excrement (e.g., feces, urine) generated during the life cycle of biological organisms and the corpses of animals and plants that are generated when biological organisms die can also be included in biomass, as they are basically derived from living organisms.

[0003] "Municipal Solid Waste (MSW)" refers to solid waste generated in cities or residential areas, including organic and inorganic materials such as food waste, paper, wood, waste plastic, waste vinyl, and scrap iron. MSW has relatively uniform properties and is generated in relatively constant amounts, making it advantageous for utilization.

[0004] Technologies for converting biomass and municipal solid waste into other forms of energy include direct combustion and gasification. Direct combustion is the process of burning waste to obtain heat energy. Incineration can produce greenhouse gases such as carbon dioxide and fine dust. Gasification is a process that produces synthesis gas, which contains carbon monoxide and hydrogen.

[0005] Syngas can be used in the Fischer-Tropsch reaction to produce synthetic oils. In the Fischer-Tropsch reaction, tail gas is produced as a by-product. The tail gas can be burned to provide heat for the process or used as fuel for gas turbines. Recently, research has been conducted to find ways to use tail gas more efficiently. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Korean Patent Registration No. 10-1860529 Summary of the Invention [Problem to be solved by the invention]

[0007] According to one aspect of the present disclosure, a method and system for producing synthetic oil economically and environmentally friendly while suppressing greenhouse gas emissions by regenerating a reforming catalyst using Fischer-Tropsch tail gas as a regenerant can be provided. [Means for solving the problem]

[0008] A method for producing synthetic oil according to the present disclosure may include the steps of providing a feed containing carbonaceous materials, introducing the feed into a synthesis gas production reaction in the presence of a catalyst to produce synthesis gas, introducing the synthesis gas into a Fischer-Tropsch (FT) reaction to produce synthetic oil and FT tail gas, regenerating the catalyst used in the synthesis gas production step in a catalyst regenerator, and supplying the FT tail gas to the catalyst regenerator.

[0009] In one embodiment, the synthesis gas production reaction may include a gasification reaction.

[0010] In one embodiment, the synthesis gas production reaction may include a partial oxidation reaction, a catalytic reforming reaction, a water gas shift reaction, hydrogen input, or a combination thereof.

[0011] In one embodiment, producing the synthesis gas may include physically or chemically scrubbing the products of the synthesis gas production reaction.

[0012] In one embodiment, the method may further include a step of controlling the temperature of the FT tail gas to 400°C to 1000°C before the step of supplying the FT tail gas to the catalyst regenerator.

[0013] In one embodiment, controlling the temperature of the FT tail gas may include partially combusting the FT tail gas, heating the FT tail gas, or a combination thereof.

[0014] In one embodiment, the method may further include controlling the reaction temperature of the catalyst regenerator to 400°C to 1000°C.

[0015] In one embodiment, the step of controlling the reaction temperature of the catalyst regenerator can be performed by heating the catalyst regenerator with an electric heater or an induction magnetic heater.

[0016] In one embodiment, controlling the reaction temperature of the catalyst regenerator may include supplying oxygen to the catalyst regenerator to partially combust the FT tail gas.

[0017] In one embodiment, the catalyst may be a catalyst selected from the group consisting of nickel-based, iron-based, cobalt-based, ruthenium-based, platinum-based, and rhodium-based catalysts.

[0018] In one embodiment, the step of producing synthesis gas is carried out in two or more reactors connected in parallel, and while some of the reactors are in a regeneration mode to regenerate the catalyst, the remaining reactors are in an operation mode to produce synthesis gas, and the catalyst of the reactor in the regeneration mode can be regenerated in a catalyst regenerator.

[0019] In one embodiment, the step of producing synthesis gas is carried out in a circulating fluidized bed reactor, which includes both a reaction section and a catalyst regenerator in communication with the reaction section. The catalyst deactivated in the reaction section is transferred to the catalyst regenerator, and the catalyst regenerated in the catalyst regenerator is transferred to the reaction section, thereby allowing the catalyst to be regenerated in situ while circulating in the circulating fluidized bed reactor.

[0020] In one embodiment, in the step of regenerating the catalyst, the catalyst regenerator produces a catalyst regenerator tail gas, which can be introduced into a synthesis gas production reaction together with a feed.

[0021] A system for producing synthetic oil according to the present disclosure includes a synthesis gas production section to which a feed containing a carbonaceous material is supplied and which produces synthesis gas through a synthesis gas production reaction in the presence of a catalyst; a Fischer-Tropsch (FT) reaction section to which the synthesis gas is introduced and which produces synthetic oil and FT tail gas through a Fischer-Tropsch reaction; and a catalyst regeneration section to regenerate a catalyst used in the synthesis gas production section, and the FT tail gas can be supplied to the catalyst regeneration section.

[0022] In one embodiment, the catalyst regeneration section includes a catalyst regenerator, and the catalyst and FT tail gas can be fed to the catalyst regenerator.

[0023] In one embodiment, the catalyst regeneration section further includes a preheater, a precombustor, or a combination thereof, and the FT tail gas can be supplied to the catalyst regenerator via the preheater, the precombustor, or a combination thereof. [Effects of the Invention]

[0024] According to one embodiment of the present disclosure, methods and systems for producing synthetic oils can be improved economically and environmentally. [Brief explanation of the drawings]

[0025] [Figure 1] 1 is a flow chart of a process for producing synthetic oil according to one embodiment. [Figure 2] 1 is a flowchart of a process for preheating FT tail gas according to one embodiment. [Figure 3] 1 is a flowchart of a process for providing heat of reaction to a catalyst regenerator according to one embodiment. [Figure 4] 1 is a flowchart of a process for providing heat of reaction to a catalyst regenerator according to one embodiment. [Figure 5] 1 is a flowchart of a process for providing heat of reaction to a catalyst regenerator according to one embodiment. [Figure 6] 1 is a graph illustrating the performance of a catalyst for converting methane as a function of reaction time according to one embodiment. [Figure 7] 4 is a graph illustrating the performance of a regenerated catalyst according to one embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0026] The present disclosure will now be described in detail with reference to the accompanying drawings, which are provided for illustrative purposes only and are not intended to limit the present disclosure to the specific embodiments illustrated.

[0027] feed 1 is a flow chart of a process for producing a synthetic oil according to one embodiment. The method for producing a synthetic oil of the present disclosure can include providing a feed 100 comprising a carbonaceous material. The feed 100 comprising a carbonaceous material can be coal, biomass, municipal solid waste, or a mixture thereof. In the present disclosure, municipal solid waste can also be abbreviated as waste.

[0028] In one embodiment, the feed 100 undergoes a sorting step using a classifier 200 to separate the MSW by properties such as origin, size, type, and moisture content. The sorting process begins with a size separation step, in which the MSW is sieved to separate larger items from smaller particles. This initial separation removes bulky items such as plastics, metals, and glass, resulting in a more homogeneous feedstock. Next, a magnetic separation step can be used to extract ferrous metals from the waste stream, improving the quality of the remaining material. Non-magnetic metals are then removed using eddy current separation, which targets non-ferrous metals such as aluminum, further reducing contaminants. After metal removal, the waste is air-classified to separate lighter materials, such as paper and plastics, from denser materials, such as glass and metals, based on differences in density. This classification ensures a consistent, optimized feed for the gasification process. Next, an optical sorting step uses visible and infrared light to distinguish and separate different types of plastics and other materials based on their optical properties. This step can further refine the feedstock composition. Finally, the classified material is subjected to a shredding and grinding process to produce a uniform particle size suitable for feeding into the gasification reactor. This method increases the efficiency of gasification by providing a cleaner, more consistent feedstock while maximizing the potential for energy recovery from municipal solid waste. For example, the classification step can remove metal components contained in the feed 100.

[0029] The method of producing synthetic oil of the present disclosure can include introducing the feed 100 into a synthesis gas production reaction in the presence of a catalyst to produce synthesis gas.

[0030] Gasification Reaction In one embodiment, the synthesis gas production reaction may include a gasification reaction, in which a solid or liquid carbonaceous feedstock 201 containing carbon as a primary component, such as coal, biomass, or waste, is reacted with a gasifying agent 301, such as steam, carbon dioxide, or oxygen, in a gasifier 300 to convert it into synthesis gas 302, which is primarily composed of carbon monoxide and hydrogen.

[0031] The syngas 302 is composed primarily of hydrogen and carbon monoxide, but may include additional components such as carbon dioxide and methane. The syngas stream 302 leaving the gasifier 300 may also include impurities such as tar, solid ash, and slag.

[0032] 1, a gasifying agent 301 containing HO, carbon dioxide, or oxygen and carbon-containing material 201 (e.g., biomass, municipal solid waste, etc.) are introduced into a gasifier 300. The carbon-containing material 201 introduced into the gasifier 300 reacts with the gasifying agent 301, such as HO, carbon dioxide, or oxygen, in the presence of a catalyst or the like to generate products including H, CO, CO, CH, HO, etc. At this time, the following main reactions may occur in the gasifier 300:

[0033] C+H2O←→CO+H2(1) C+CO2←→2CO (2) C+O2←→CO2(3) CO+3H2←→CH4+H2O (4) CH4 + H2O ←→ CO + 3H2 (5) CH4 + CO2 ←→ 2CO + 2H2 (6) CH4+2O2←→CO2+2H2O (7) The catalyst that can be used in the gasification reaction may be a general catalyst that can be used in the gasification reaction of the carbon-containing material 201. Preferably, a catalyst containing an alkali metal or alkaline earth metal or a transition metal catalyst can be used. Usable alkali metal components include Li, Na, K, Rb, Cs, Fr, etc. Usable alkaline earth metal components include Mg, Ca, etc. Transition metal catalysts include, but are not limited to, catalysts containing Fe, Ni, Co, Cu, Zn, etc. It will be obvious to those skilled in the art that other metal components that meet the objectives of the present disclosure can also be used.

[0034] In one embodiment, for maximum conversion of carbonaceous materials, the syngas 302 produced in the primary gasifier 300 may be further passed through a secondary gasifier (not shown).

[0035] In one embodiment, the synthesis gas 302 discharged from the gasifier 300 may pass through at least one of a cyclone 400, a gas filter (not shown), a gas absorber (not shown), and a gas adsorber (not shown).

[0036] The syngas stream 302 discharged from the gasifier 300 can be passed through a cyclone 400 to remove undesirable solid materials 401, such as solid ash and slag. A cyclone is a device that uses centrifugal force to separate solid particles from a mixture containing solid particles. The particles to be separated are those dispersed in the gasifier, and the particles can be catalyst, unreacted feed, solid ash, and slag. The cyclone can be any conventional cyclone known in the art.

[0037] A gas filter (not shown) can also be installed downstream of the cyclone 400. The gas filter can filter out very small dust particles and other particles contained in the gas. Typically, a cyclone can process particles having a size up to about 10 μm, and a gas filter can process particles having a size up to about 1 μm.

[0038] A gas absorber (not shown) or gas adsorber (not shown) may be located upstream or downstream of the cyclone 400. The gas absorber and gas adsorber may remove H2S, HCl, and NH3 contained in the syngas stream 302, 403. The gas absorber and gas adsorber may also remove metal atoms that vaporize or sublimate in the gas absorber and gas adsorber. The gas absorber and gas adsorber may also remove other organic and inorganic impurities.

[0039] In one embodiment, producing synthesis gas may include a partial oxidation reaction, a catalytic reforming reaction, a water gas shift reaction, hydrogen input, or a combination thereof.

[0040] In one embodiment, the syngas 403 discharged from the cyclone 400 may be introduced into the catalytic reformer 500. Additionally, the syngas 403 discharged from the cyclone 400 may be introduced into the catalytic reformer 500 via a partial oxidation reactor (not shown).

[0041] Partial Oxidation (POx) In one embodiment, the synthesis gas production reaction may include a partial oxidation reaction. Referring to Figure 1, the synthesis gas stream 302 discharged from the gasifier 300 may include methane. The methane may be converted to carbon monoxide and hydrogen in a partial oxidation reactor (not shown) via a partial oxidation reaction represented by the following reaction equation (8):

[0042] CH4+1 / 2O2←→CO+2H2ΔH o 298 =-36kJ / mol (8) Catalytic Reforming According to the present disclosure, the synthesis gas production reaction must include a catalytic reforming reaction. Thus, in one embodiment, the synthesis gas production reaction can be sequentially carried out in a gasifier and a catalytic reformer. Also, in one embodiment, the synthesis gas production reaction can be sequentially carried out in a gasifier, a partial oxidation reactor, and a catalytic reformer.

[0043] As described above, the syngas stream 302 discharged from the gasifier 300 may contain methane and hydrocarbons having a carbon number of 2 or greater. The methane and hydrocarbons having a carbon number of 2 or greater may be converted to carbon monoxide and hydrogen in a catalytic reformer (which may also be referred to as a catalytic reforming reactor) 500. The syngas stream 302 discharged from the gasifier 300 may have solids removed in a cyclone 400, and the solids-removed syngas stream 403 may then be introduced into the catalytic reformer 500 either after passing through a partial oxidation reactor (not shown) or without passing through a partial oxidation reactor (not shown).

[0044] In one embodiment, the catalytic reforming reaction may be a steam methane reforming (SMR) reaction represented by the following reaction formula (9).

[0045] CH4+H2O←→CO+3H2ΔH o 298 =206kJ / mol (9) Furthermore, the catalytic reforming reaction may be a steam reforming reaction that converts hydrocarbons having a carbon number of 2 or more (C2+) into carbon monoxide and hydrogen, as represented by the following reaction formula (10).

[0046] C x H y +zH2O←→pCO+qH2(10) Here, x, z, p, and q are integers of 2 or more.

[0047] In one embodiment, the catalyst used in the steam reforming reaction, including the steam methane reforming reaction, may be a transition metal (Ni, Fe, Co, etc.)-based catalyst or a noble metal (Ru, Pt, Rh, etc.)-based catalyst. Preferably, the catalyst used in the steam methane reforming reaction may include Ni, Fe, Co, etc., and their bimetallic materials supported on Al2O3 (Ni-Al2O3, NiFe-Al2O3, NiMgK-Al2O3, Rh-Al2O3). The catalyst may also include alkaline earth metals such as Mg, Ce, and lanthanides.

[0048] In one embodiment, the catalytic reforming reaction may be a dry reforming reaction represented by the following reaction equations (11) and (12).

[0049] CH4+CO2←→2CO+2H2ΔH o 298 =247.44kJ / mol (11) C x H y +zCO2←→pCO+qH2(12) Here, x, z, p, and q are integers of 2 or more.

[0050] In one embodiment, the catalyst used in the dry reforming reaction can be a transition metal (Ni, Fe, Co, etc.) based catalyst or a noble metal (Ru, Pt, Rh, etc.) based catalyst.

[0051] In one embodiment, the catalytic reformer 500 may be a fluidized bed reactor. The catalyst can efficiently activate the reforming reaction between hydrocarbons such as methane and steam or between hydrocarbons such as methane and carbon dioxide while flowing in the fluidized bed reactor. This significantly increases the conversion rate of hydrocarbons such as methane to carbon monoxide and hydrogen, which may ultimately result in the generation of large amounts of carbon monoxide and hydrogen.

[0052] In one embodiment, the catalytic reformer 500 may be a fixed-bed reactor. The reactants, including hydrocarbons such as methane, may pass through the catalyst bed while undergoing the aforementioned steam reforming or dry reforming reactions.

[0053] In one embodiment, the catalytic reformer 500 may be a circulating fluidized bed reactor. The circulating fluidized bed reactor may include both a reaction section and a catalyst regenerator connected to the reaction section. The catalyst deactivated in the reaction section is transferred to the catalyst regenerator, and the catalyst regenerated in the catalyst regenerator is transferred to the reaction section, allowing the catalyst to be regenerated in situ while circulating in the circulating fluidized bed reactor.

[0054] The reformed synthesis gas 502, thus composed primarily of hydrogen and carbon monoxide, exits the catalytic reformer 500 and can be used as a feedstock or reactant in downstream water-gas shift or Fischer-Tropsch (FT) reactions.

[0055] Water-gas shift reaction In one embodiment, the synthesis gas production reaction may include a water gas shift reaction to maintain the H2 / CO ratio of the feed entering the FT reactor 800 at 2. Alternatively, separate hydrogen 701 may be input into the water gas shift reactor 700 to maintain the H2 / CO ratio at 2. The water gas shift reaction may be represented by the following reaction equation (13):

[0056] CO+H2O←→CO2+H2ΔH=-41.1kJ / mol (13) In one embodiment, the catalyst used in the water gas shift reaction can be a platinum-based catalyst, an iron-based catalyst, or a copper-based catalyst.

[0057] Scrub step (Scrubing) In one embodiment, producing a synthesis gas can include scrubbing the synthesis gas production reaction product. A scrubber solution can be injected into the synthesis gas production reaction product to remove solid impurities such as catalyst particles, liquid impurities such as tar, and gas impurities such as H2S from the synthesis gas production reaction product. The scrubber 600 can be located upstream or downstream of the partial oxidation reactor (not shown), the catalytic reforming reactor 500, or the water gas shift reactor 700.

[0058] The scrubber solution can be selected depending on the type of impurities in the syngas production reaction product. The scrubber solution can include, but is not limited to, water, oil, or NaOCl solution. The scrubbed syngas stream 601 can be discharged from the scrubber in gaseous form, since solid and liquid impurities are removed in the scrubber solution.

[0059] In one embodiment, the scrubber may be, but is not limited to, a water scrubber, a venturi scrubber, or an oil scrubber that removes catalyst particles, tar, H2S, etc. contained in the synthesis gas production reaction product.

[0060] Swing Mode In one embodiment, the step of producing synthesis gas can be performed in a so-called swing mode, i.e., the step of producing synthesis gas is performed in two or more reactors connected in parallel, and while some reactors are in a regeneration mode to regenerate the catalyst, the remaining reactors are in an operation mode to produce synthesis gas, and the catalyst of the reactor in the regeneration mode can be regenerated in a catalyst regenerator.

[0061] For example, the catalytic reforming reactor 500 must be shut down to replace the catalytic reforming layer or regenerate the catalyst. However, shutting down the catalytic reforming reactor 500 means shutting down the entire synthesis gas production process. Therefore, shutting down the catalytic reforming reactor 500 is a major factor in reducing the utilization rate of the entire synthesis gas production process.

[0062] In one embodiment, the catalytic reforming step can be performed in a swing mode in two or more catalytic reforming reactors 500. That is, when one catalytic reforming reactor 500 is in an operating mode, the remaining catalytic reforming reactors 500 can be in a regeneration mode. Thus, the catalytic reforming step can be performed continuously.

[0063] Fischer-Tropsch reaction step In one embodiment, a method for producing synthetic oil may include introducing the synthesis gas into a Fischer-Tropsch (FT) reaction to produce synthetic oil and FT tail gas.

[0064] In one embodiment, synthesis gas produced in the water gas shift reaction can be introduced into the Fischer-Tropsch reaction.

[0065] The Fischer-Tropsch reaction can be expressed as follows:

[0066] (2n+1)H2+nCO→C n H 2n+2 +nH2O (14) In one embodiment, the FT reaction can be carried out at a temperature of about 200 to about 350° C. in the presence of an Fe, Co, or Ru catalyst.

[0067] The alkane produced by the FT reaction is in a liquid phase and corresponds to the main product, synthetic oil 801. The alkane contained in the synthetic oil 801 usually has 10 to 20 carbon atoms.

[0068] Unreacted components of the syngas that do not participate in the FT reaction and light hydrocarbons produced from the FT reaction, such as hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4), can be discharged as FT tail gas 802.

[0069] <Catalyst regeneration> The method for producing synthetic oil according to the present disclosure may include a step of regenerating a catalyst used in the step of producing synthesis gas, for example, a catalyst used in a catalytic reforming reaction step, in a catalyst regenerator 1000.

[0070] In one embodiment, the FT tail gas 802, which comprises H2, CO, CO2, and CH4, can be fed to a catalyst regenerator 1000 to regenerate the catalyst used in producing synthesis gas.

[0071] In one embodiment, the catalyst used in the step of producing synthesis gas may be the catalyst used in the catalytic reforming reactor 500 .

[0072] The carbon adsorbed on the catalyst reacts with carbon dioxide or water contained in the FT tail gas as shown in the following reaction formula and is removed, thereby regenerating the catalyst.

[0073] C+CO2→2CO ΔH O =172.4kJ / mol (15) C+H2O→CO+H2ΔH O =131.3 kJ / mol (16) In addition, the sulfur compounds adsorbed on the catalyst (M) are removed by reacting with hydrogen contained in the FT tail gas as shown in the following reaction formula, thereby regenerating the catalyst (M).

[0074] When sulfur is chemisorbed onto catalyst M, the catalyst can be regenerated by the following mechanism:

[0075] When FT tail gas contains only H2: MS(chemisorbed)+H2→M+H2S (17) When FT tail gas contains both steam and H2: M-S+H2O→M-O+H2S (18) M-O+H2→M+H2O (19) When sulfur compounds are attached to the catalyst, the catalyst can be regenerated by the following mechanism.

[0076] When FT tail gas contains only H2: MSx + H2 → M + H2S (20), where x is an integer equal to or greater than 1.

[0077] When FT tail gas contains both steam and H2: MSx+H2O→MOx+H2S (21) MOx + H2 → M + H2O (22) In one embodiment, exhaust gases 502, such as CO and H2, generated during the process of removing carbon and sulfur adsorbed on the catalyst of the catalytic reformer 500 to regenerate the catalyst can be used as feedstock for a downstream Fischer-Tropsch process.

[0078] The carbon dioxide and steam contained in the FT tail gas may cause environmental pollution problems such as the greenhouse effect if they are discharged into the atmosphere.

[0079] Meanwhile, CO2 in the synthesis gas may be removed in an amine absorber (not shown) in the upstream of the FT reactor 800, so that the amount of CO2 contained in the FT tail gas may be trace. Water produced in the FT reaction passes through a three-phase separator (not shown) in the downstream of the FT reactor 800 and is separated into tail gas / water / oil, so that the amount of steam contained in the FT tail gas may be trace.

[0080] In the present disclosure, when producing synthetic oil, FT tail gas containing carbon dioxide, steam, and hydrogen is used to regenerate the reforming catalyst. Thus, the method and system for producing synthetic oil of the present disclosure uses the FT tail gas generated during the process as a catalyst regenerant without using a separate regeneration gas. Therefore, the method and system for producing synthetic oil of the present disclosure are economical because they reduce the amount of regenerant and utility usage, and furthermore, they are environmentally friendly because they reduce greenhouse gas issues.

[0081] The catalytic reformer may include a heater to increase the temperature of the synthesis gas passing through the catalytic reforming layer and to raise the temperature of the catalytic reforming layer. The heater may be provided in contact with the catalytic reforming layer. The heater may increase the temperature of the synthesis gas lost during transport or may heat the synthesis gas to a temperature required for catalyst regeneration to facilitate the reforming reaction. The temperature of the catalytic reforming layer may be maintained at 400°C to 1,000°C, for example, 450°C to 950°C, 500°C to 900°C, 550°C to 850°C, 600°C to 800°C, or 650°C to 750°C, or any range or subrange therebetween, using the thermal energy of the heater.

[0082] High-temperature heaters can be continuously operated to maintain the temperature of the catalytic reforming layer at 400°C to 1,000°C. However, because a considerable amount of electrical energy is required to heat the high-temperature heaters, the heaters can act as a factor that reduces the energy efficiency of the entire gasification system. Therefore, the tail gas discharged at a high temperature after catalyst regeneration can be reintroduced into the synthesis gas production facility and used as an energy source. In this case, impurities contained in the tail gas can be removed from the upstream and / or downstream of the synthesis gas production facility.

[0083] In one embodiment, prior to the step of supplying the FT tail gas to the catalyst regenerator, a step or preheater 900 may further be included in which the temperature of the FT tail gas is controlled to a temperature of 400°C to 1,000°C, for example, 450°C to 950°C, 500°C to 900°C, 550°C to 850°C, 600°C to 800°C, 650°C to 750°C, or any range or subrange therebetween.

[0084] If the temperature of the tail gas is lower than 400°C, the catalyst regeneration reaction is insignificant, and if the temperature of the tail gas is higher than 1000°C, the catalyst may lack thermal stability.

[0085] In the present disclosure, since the FT tail gas is used as a heat transfer medium without a separate heat transfer medium, a significant economic effect can be obtained.

[0086] Figure 2 is a process flow diagram for preheating FT tail gas according to one embodiment. Referring to Figure 2, the step of preheating FT tail gas may involve preheating FT tail gas 802 to a temperature of 400°C to 1,000°C, for example, 450°C to 950°C, 500°C to 900°C, 550°C to 850°C, 600°C to 800°C, 650°C to 750°C, or any of the ranges and subranges therebetween, using a heater or preheater 900, such as, but not limited to, a gas firing heater, an electric heater, or an induction magnetic heater.

[0087] The reforming catalyst is regenerated in the catalyst regenerator 1000 using the preheated FT tail gas 901, and can be reused as a catalyst for the reforming reaction by supplying it back to the catalytic reformer 500. This configuration solves the problem of catalyst deactivation and eliminates the need to continuously add new catalyst for the reforming reaction as in the prior art, thereby achieving significant cost reductions.

[0088] Meanwhile, the step of regenerating the reforming catalyst can be performed in a swing mode together with the catalytic reforming step, so that the catalytic reforming step can be performed continuously without interruption.

[0089] Referring again to FIG. 2, the catalyst regenerator tail gas 1001 discharged after regenerating the reforming catalyst in the catalyst regenerator 1000 is introduced into the catalytic reforming reactor 500 and used as a feedstock for the catalytic reforming step. This increases the yield of hydrogen and carbon monoxide produced in the catalytic reforming step. The tail gas 1001 discharged from the catalyst regenerator may have a temperature ranging from 400°C to 1000°C, for example, 450°C to 950°C, 500°C to 900°C, 550°C to 850°C, 600°C to 800°C, or 650°C to 750°C, or any of the entire ranges and subranges therebetween. Therefore, the catalyst regenerator tail gas 1001 discharged from the catalyst regenerator can provide the necessary reaction heat for the catalytic reforming reactor 500. Furthermore, if necessary, oxygen 501 is supplied to the catalyst regenerator tail gas 1001 discharged from the catalyst regenerator 1000 to oxidize the catalyst regenerator tail gas 1001 under oxygen conditions, thereby providing the reaction heat required for the catalytic reforming reactor 500. At this time, some impurities in the tail gas can also be oxidized and recycled to the synthesis gas production facility.

[0090] Figure 3 is a process flow diagram for supplying reaction heat to a catalyst regenerator 1000 according to one embodiment. Referring to Figure 3, recycled FT tail gas 802 can be introduced into the catalyst regenerator 1000 without a preheating step or preheater 900. In the catalyst regenerator 1000, the recycled FT tail gas 802 can be heated by a heater 1010, such as (but not limited to) an electric heater or an induction magnetic heater, to a temperature of 400°C to 1000°C, for example, 450°C to 950°C, 500°C to 900°C, 550°C to 850°C, 600°C to 800°C, 650°C to 750°C, or any range or subrange therebetween, and can participate in a catalyst regeneration reaction.

[0091] Referring again to FIG. 3, the catalyst regenerator tail gas 1001 discharged after regenerating the reforming catalyst in the catalyst regenerator 1000 can be introduced into the catalytic reforming reactor 500, or can be introduced into the catalytic reforming reactor 500 after removing impurities, or can be oxidized in an oxygen environment to supply heat to a downstream process. The catalyst regenerator tail gas 1001 introduced into the catalytic reforming reactor 500 can be used as a feedstock and fuel in the catalytic reforming step. This can increase the production yield of hydrogen and carbon monoxide in the catalytic reforming step. In addition, the catalyst regenerator tail gas 1001 discharged from the catalyst regenerator can have a temperature of 400°C to 1000°C, for example, 450°C to 950°C, 500°C to 900°C, 550°C to 850°C, 600°C to 800°C, or 650°C to 750°C, or any range or subrange therebetween. Furthermore, when the catalyst regenerator tail gas 1001 is oxidized by the introduction of additional oxygen 501, it may have a temperature of 2,000°C to 3,000°C, e.g., 2,100°C to 2,900°C, 2,200°C to 2,800°C, 2,300°C to 2,700°C, 2,400°C to 2,600°C, or any range or subrange therebetween. The oxidized catalyst regenerator tail gas 1001 is then mixed with the main syngas feed 403 and may have a temperature of 700°C to 1,000°C, e.g., 750°C to 950°C, 800°C to 900°C, 850°C to 900°C, or any range or subrange therebetween. Therefore, the catalyst regenerator tail gas 1001 discharged from the catalyst regenerator 1000 can provide the necessary reaction heat for the catalytic reforming reactor 500.

[0092] FIG. 4 is a process flow diagram for supplying reaction heat to a catalyst regenerator 1000 according to one embodiment. Referring to FIG. 4, recycled FT tail gas 802 can be combined with oxygen 1102 at a less than equivalence ratio and combusted in a combustor 1100. The FT tail gas 802 can be heated by partial combustion to a temperature of 400°C to 1,000°C, for example, 450°C to 950°C, 500°C to 900°C, 550°C to 850°C, 600°C to 800°C, 650°C to 750°C, or any range or subrange therebetween. The heated tail gas 1101 can be introduced into the catalyst regenerator 1000 to participate in the catalyst regeneration reaction.

[0093] Referring again to FIG. 4, the catalyst regenerator tail gas 1001 discharged after regenerating the reforming catalyst in the catalyst regenerator 1000 can be introduced into the catalytic reforming reactor 500, or can be introduced into the catalytic reforming reactor 500 after removing impurities, or can be oxidized in an oxygen 501 environment to supply heat to a downstream process. The catalyst regenerator tail gas 1001 introduced into the catalytic reforming reactor 500 can be used as a feedstock and fuel in the catalytic reforming step. This can increase the production yield of hydrogen and carbon monoxide in the catalytic reforming step. In addition, the catalyst regenerator tail gas 1001 discharged from the catalyst regenerator can have a temperature of 400°C to 1000°C, for example, 450°C to 950°C, 500°C to 900°C, 550°C to 850°C, 600°C to 800°C, or 650°C to 750°C, or any range or subrange therebetween. Furthermore, when additional oxygen 501 is introduced and oxidized, the catalyst regenerator tail gas 1001 may have a temperature of 2,000°C to 3,000°C, for example, 2,100°C to 2,900°C, 2,200°C to 2,800°C, 2,300°C to 2,700°C, 2,400°C to 2,600°C, 2,500°C to 2,550°C, or any range or subrange therebetween. After being mixed with the main syngas feed 403, the oxidation catalyst regenerator tail gas 1001 may have a temperature of 700°C to 1,000°C, for example, 750°C to 950°C, 800°C to 900°C, 850°C to 900°C, or any range or subrange therebetween. Thus, the catalyst regenerator tail gas 1001 discharged from the catalyst regenerator 1000 can provide the necessary reaction heat for the catalytic reforming reactor 500.

[0094] FIG. 5 is a process flow diagram for supplying reaction heat to a catalyst regenerator 1000 according to one embodiment. Referring to FIG. 5, recycled FT tail gas 802 can be combined with oxygen 1002 at a less-than-equivalence ratio and combusted in the catalyst regenerator 1000. The FT tail gas 802 can be heated by partial combustion to a temperature of 400°C to 1,000°C, e.g., 450°C to 950°C, 500°C to 900°C, 550°C to 850°C, 600°C to 800°C, 650°C to 750°C, or any range or subrange therebetween. The heated tail gas 1001 can participate in a catalyst regeneration reaction in the catalyst regenerator 1000. In other words, the FT tail gas 802 can serve as a feedstock, a fuel, or both in the catalyst regenerator 1000.

[0095] Referring again to FIG. 5, the catalyst regenerator tail gas 1001 discharged after regenerating the reforming catalyst in the catalyst regenerator 1000 can be introduced into the catalytic reforming reactor 500, or can be introduced into the catalytic reforming reactor 500 after removing impurities, or can be oxidized in an oxygen environment to supply heat to a downstream process. The catalyst regenerator tail gas 1001 introduced into the catalytic reforming reactor 500 can be used as a feedstock and fuel in the catalytic reforming step. This can increase the production yield of hydrogen and carbon monoxide in the catalytic reforming step. In addition, the catalyst regenerator tail gas 1001 discharged from the catalyst regenerator can have a temperature of 400°C to 1000°C, for example, 450°C to 950°C, 500°C to 900°C, 550°C to 850°C, 600°C to 800°C, or 650°C to 750°C, or any range or subrange therebetween. Furthermore, when the catalyst regenerator tail gas 1001 is oxidized by the introduction of additional oxygen 501, it can have a temperature of 2,000°C to 3,000°C, e.g., 2,100°C to 2,900°C, 2,200°C to 2,800°C, 2,300°C to 2,700°C, 2,400°C to 2,600°C, 2,500°C to 2,550°C, or any range or subrange therebetween. The oxidized catalyst regenerator tail gas 1001 is then mixed with the main syngas feed 403 and can have a temperature of 700°C to 1,000°C, e.g., 750°C to 950°C, 800°C to 900°C, 850°C to 900°C, or any range or subrange therebetween. Therefore, the tail gas discharged from the catalyst regenerator can provide the reaction heat required for the catalytic reforming reactor.

[0096] The disclosed system for producing synthetic oil may include a synthesis gas production section that is supplied with a feed containing carbonaceous materials and produces synthesis gas through a synthesis gas production reaction in the presence of a catalyst.

[0097] In one embodiment, the synthesis gas production section can include a sorter. The feed can be introduced into the sorter, which can separate the feed by component. For example, the sorter can separate and remove metal materials from the feed.

[0098] In one embodiment, the synthesis gas production section may include a gasifier 300, a cyclone 400, a partial oxidation reactor (not shown), a catalytic reforming reactor 500, a water gas shift reactor 700, a scrubber 600, or a combination thereof.

[0099] In one embodiment, a gas filter (not shown) and a gas impurity removal device (not shown) may be installed downstream of the cyclone 400 .

[0100] The feed 201 discharged from the sorter 200 is introduced into the gasifier 300, where it can produce synthesis gas through the gasification reaction described above. The synthesis gas 302 discharged from the gasifier can be introduced into a cyclone 400, where it can remove undesirable solid materials 401, such as solid ash and slag.

[0101] In one embodiment, the syngas 302 discharged from the gasifier 300 or the syngas 403 discharged from the cyclone 400 may be introduced into a partial oxidation reactor (not shown) or a catalytic reforming reactor 500. Hydrocarbons such as methane contained in the syngas may be converted into carbon monoxide and hydrogen by the partial oxidation reaction described above in the partial oxidation reactor. Hydrocarbons such as methane contained in the syngas may be converted into carbon monoxide and hydrogen by the steam methane reforming reaction or dry reforming reaction described above in the catalytic reforming reactor 500.

[0102] In one embodiment, the synthesis gas discharged from the partial oxidation reactor or catalytic reforming reactor 500 may be introduced into a water gas shift reactor 700. Carbon monoxide in the synthesis gas may be converted to carbon monoxide and hydrogen by the water gas shift reaction described above in the water gas shift reactor 700. In one embodiment, a hydrogen input line 701 may be installed in the water gas shift reactor 700.

[0103] In one embodiment, a scrubber 600 may be installed upstream or downstream of the partial oxidation reactor (not shown), the catalytic reforming reactor 500, or the water gas shift reactor 700. The scrubber 600 may remove impurities using water, oil, or a scrubber solution such as an NaOCl solution, depending on the type of impurities in the product of the synthesis gas production reaction.

[0104] The reactors in the synthesis gas production section may be operated in swing mode as previously described.

[0105] The synthesis gas produced in the synthesis gas production section is introduced into the Fischer-Tropsch reaction section, where the aforementioned Fischer-Tropsch (FT) reaction can produce synthesis oil 801 and FT tail gas 802. The FT tail gas is supplied to the catalyst regeneration section, where it can be used to regenerate the catalyst used in the synthesis gas production section.

[0106] In one embodiment, the catalyst regeneration section includes a catalyst regenerator 1000 , and the catalyst and FT tail gas used in the synthesis gas production section can be fed to the catalyst regenerator 1000 .

[0107] In one embodiment, the catalyst regeneration section may further include a preheater 900, a precombustor 1100, or a combination thereof. The FT tail gas may be heated in the preheater 900 to 400°C to 1,000°C, for example, 450°C to 950°C, 500°C to 900°C, 550°C to 850°C, 600°C to 800°C, 650°C to 750°C, or any range or subrange therebetween, before being supplied to the catalyst regenerator 1000. The preheater 900 may include, but is not limited to, a gas-fired heater, an electric heater, or an induction magnetic heater.

[0108] In one embodiment, the FT tail gas 802 can be introduced into a pre-combustor 1100. Oxygen 1102 or air 1102 can be introduced into the pre-combustor 1100 for combustion. After combustion in the pre-combustor 1100, the FT tail gas 802 can be heated to 400°C to 1,000°C, for example, 450°C to 950°C, 500°C to 900°C, 550°C to 850°C, 600°C to 800°C, 650°C to 750°C, or any range or subrange therebetween. The heated FT tail gas 1101 can be supplied to a catalyst regenerator 1000.

[0109] In one embodiment, oxygen 1002 is supplied to the catalyst regenerator 1000 and the FT tail gas 802 may be combusted in the catalyst regenerator 1000 .

[0110] In one embodiment, the catalyst regenerator 1000 can include a heater 1010, such as, but not limited to, an electric heater or an induction magnetic heater.

[0111] The present invention will be further described below with reference to specific experimental examples. The examples and comparative examples included in the experimental examples are merely illustrative of the present invention and do not limit the scope of the appended claims. It is obvious to those skilled in the art that various changes and modifications to the examples are possible within the scope and technical idea of ​​the present invention, and it is obvious that such changes and modifications also fall within the scope of the appended claims.

[0112] Example 1 A laboratory-scale method for producing synthetic oil, including the process flow shown in Figure 1, was conducted. A feed stream containing food waste as biomass was gasified in a gasifier to produce syngas. The gasification reaction was carried out at a temperature of 760°C and a pressure of 3.2 bara. The produced syngas was then introduced into a cyclone to remove ash and dust. The temperature and pressure inside the cyclone were 750°C and 3.0 bara, respectively. The syngas discharged from the cyclone was steam reformed in a catalytic reformer containing a nickel-based catalyst until the nickel-based catalyst was deactivated. The steam reforming reaction was carried out at a temperature of 700-800°C and a pressure of 2-3 bara. The deactivation point was reached when CH4 was no longer converted to CO or H2 by the catalytic reaction. The syngas discharged from the catalytic reformer was introduced into a scrubber containing water as the scrubber solution to remove solid and liquid impurities. The temperature and pressure inside the scrubber were 43°C and 2.5 bara, respectively. The synthesis gas discharged from the scrubber was introduced into a Fischer-Tropsch reactor to produce synthesis oil and tail gas. The temperature and pressure in the Fischer-Tropsch reactor were 200°C and 23 bara, respectively. The deactivated nickel-based catalyst was regenerated in a catalyst regenerator using the produced FT tail gas as a regenerant to prepare a regenerated catalyst.

[0113] The components and concentrations of the FT tail gas were measured by gas chromatography.

[0114] [Table 1]

[0115] Alternatively, composition information of FT tail gas can be obtained from an existing FT reactor, and a simulated gas with the same or similar composition can be used to regenerate the deactivated nickel-based catalyst and prepare a regenerated catalyst.

[0116] Comparative Example 1 A fresh nickel-based catalyst that had not been exposed to impurities was prepared.

[0117] Comparative Example 2 A nickel-based spent catalyst exposed to impurities was regenerated with a general regeneration gas (including H2O and H2) to prepare a regenerated catalyst.

[0118] Comparative Example 3 A spent catalyst that had been exposed to impurities and had not been regenerated was prepared.

[0119] Experimental example: Confirmation of activity recovery of catalyst regenerated with FT tail gas Figure 6 shows the catalyst's ability to convert methane from FT tail gas over time (time on stream, TOS) in the catalyst. In other words, it measures the catalyst's ability to convert methane in the FT tail gas. The FT tail gas contained 10% by volume of CH4, 30% by volume of CO2, 30% by volume of H2, 15% by volume of CO, and 15% by volume of N2. This reaction involves the reaction of CO2 and CH4 to produce H2 and CO. In Figure 6, the y-axis shows the CH4 conversion (%) in the presence of each catalyst.

[0120] 6, in the case of the regenerated catalyst (◯) of Example 1, in which the deactivated catalyst is regenerated by reacting with FT tail gas, performance is low at the beginning of the reaction time, but as the reaction time passes, the catalyst performance recovers to the level of the new catalyst (□) of Comparative Example 1. In addition, the regenerated catalyst of Example 1 (◯) was found to have performance equivalent to that of the catalyst of Comparative Example 2 (△), which was regenerated with ordinary regeneration gas.

[0121] This is a result of the continuous improvement in CH4 conversion in the FT tail gas as the H2 in the FT tail gas regenerates the activity of the catalyst.

[0122] Generally, in the case of spent catalysts, it is impossible to convert CH4 in FT tail gas without a separate regeneration process, but it has been confirmed that it is possible to convert CH4 in FT tail gas by regenerating the catalyst with FT tail gas.

[0123] The methane conversion performance of the catalysts of Example 1 and Comparative Examples 1 to 3 is shown in Figure 7. In Figure 7, the y-axis represents the CH4 conversion rate (%) in the presence of each catalyst.

[0124] 7, the catalyst regenerated according to Example 1 converted methane with performance comparable to that of a fresh catalyst (Comparative Example 1) and a catalyst regenerated with a separate conventional regeneration gas (Comparative Example 2). In other words, the catalyst of Example 1 had similar performance to the catalysts of Comparative Examples 1 and 2, and superior performance to the spent catalyst of Comparative Example 3.

[0125] The foregoing is merely illustrative of the application of the principles of the present disclosure, and other arrangements may be included without departing from the scope of the present invention. [Explanation of symbols]

[0126] 100 Feeds 200 classifier 201 Carbonaceous raw materials 300 Gasifier 301 Gasifying Agent 302 Syngas 400 Cyclone 401 Solid substances 403 Syngas 500 Catalytic reformer 501 Oxygen 502 Syngas 600 Scrubber 601 Scrubbed Syngas Stream 700 Water Gas Shift Reactor 701 Hydrogen 800 Fischer-Tropsch Reactor 801 Synthetic oil 802 Fischer-Tropsch tail gas 803 Preheated Fischer-Tropsch tail gas 900 Preheater 901 Preheated FT tail gas 1000 catalyst regenerator 1001 Catalyst regenerator tail gas 1002 Oxygen 1010 Heater 1100 Combustor 1101 Heated tail gas 1102 Oxygen

Claims

1. 1. A method for producing a synthetic oil, comprising: providing a feed comprising a carbonaceous material; introducing the feed into a synthesis gas production reaction in the presence of a catalyst to produce synthesis gas; introducing the synthesis gas into a Fischer-Tropsch (FT) reaction to produce synthesis oil and FT tail gas; regenerating the catalyst used in the step of producing synthesis gas in a catalyst regenerator; and feeding the FT tail gas to a catalyst regenerator.

2. The method for producing synthetic oil according to claim 1 , wherein the synthesis gas production reaction comprises a gasification reaction.

3. 10. The method for producing synthetic oil according to claim 1, wherein the synthesis gas production reaction comprises a partial oxidation reaction, a catalytic reforming reaction, a water gas shift reaction, hydrogen input, or a combination thereof.

4. 10. The method of claim 1, wherein the step of producing synthesis gas comprises physically or chemically scrubbing the products of the synthesis gas production reaction.

5. 10. The method for producing synthetic oil according to claim 1, further comprising the step of controlling the temperature of the FT tail gas to 400°C to 1000°C before the step of supplying the FT tail gas to a catalyst regenerator.

6. 6. The method of producing synthetic oil according to claim 5, wherein controlling the temperature of the FT tail gas comprises partially combusting the FT tail gas, heating the FT tail gas, or a combination thereof.

7. 10. The method for producing synthetic oil according to claim 1, further comprising the step of controlling the reaction temperature of the catalyst regenerator to 400°C to 1000°C.

8. 8. The method for producing synthetic oil according to claim 7, wherein the step of controlling the reaction temperature of the catalyst regenerator is performed by heating the catalyst regenerator with an electric heater or an induction magnetic heater.

9. 8. The method for producing synthetic oil according to claim 7, wherein the step of controlling the reaction temperature of the catalyst regenerator includes the step of supplying oxygen to the catalyst regenerator to partially combust the FT tail gas.

10. 2. The method for producing synthetic oil according to claim 1, wherein the catalyst is selected from the group consisting of nickel-based, iron-based, cobalt-based, ruthenium-based, platinum-based, and rhodium-based catalysts.

11. 2. The method for producing synthetic oil according to claim 1, wherein the step of producing synthesis gas is carried out in two or more reactors connected in parallel, and while some of the reactors are in a regeneration mode to regenerate a catalyst, the remaining reactors are in an operation mode to produce synthesis gas, and the catalyst of the reactor in the regeneration mode is regenerated in a catalyst regenerator.

12. 2. The method for producing synthetic oil according to claim 1, wherein the step of producing synthesis gas is carried out in a circulating fluidized bed reactor, the circulating fluidized bed reactor including both a reaction section and a catalyst regenerator connected to the reaction section, the catalyst deactivated in the reaction section being transferred to the catalyst regenerator, and the catalyst regenerated in the catalyst regenerator being transferred to the reaction section, thereby allowing the catalyst to be regenerated in situ while circulating in the circulating fluidized bed reactor.

13. In the step of regenerating the catalyst, the catalyst regenerator produces a catalyst regenerator tail gas; 10. The method for producing synthetic oil according to claim 1, wherein the catalyst regenerator tail gas is introduced into a synthesis gas production reaction together with a feed.

14. 1. A system for producing synthetic oil, comprising: a synthesis gas production section to which a feed containing carbonaceous material is supplied and which produces synthesis gas by a synthesis gas production reaction in the presence of a catalyst; a Fischer-Tropsch reaction section into which the synthesis gas is introduced and which produces synthesis oil and FT tail gas by a Fischer-Tropsch (FT) reaction; a catalyst regeneration section for regenerating catalyst used in the synthesis gas production section; The FT tail gas is supplied to a catalyst regeneration section.

15. the catalyst regeneration section includes a catalyst regenerator; 15. The system for producing synthetic oil according to claim 14, wherein the catalyst and FT tail gas are supplied to a catalyst regenerator.

16. the catalyst regeneration section further comprises a preheater, a precombustor, or a combination thereof; 16. The system for producing synthetic oil according to claim 15, wherein the FT tail gas is supplied to a catalyst regenerator via the preheater, precombustor, or a combination thereof.

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