Conversion of organic solid biomass for liquid fuels / chemicals production in the presence of methane gas environment and catalyst structures

Abstract

The present invention provides a method for providing value-added natural abundant organic solid biomass in the presence of a specific gas atmosphere of catalyst structure. The method effectively converts the organic solid feedstock while producing valuable liquid hydrocarbon products, and provides economic and environmental benefits in the oil and gas industry using methane-rich resources.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to the following: U.S. Provisional Patent Application Serial No. 63 / 070,368, filed August 26, 2020, entitled "Organic Solid Wastes Conversion for Liquid Fuels / Chemicals Production in the Presence of Methane Containing Gas Environment and Catalyst Structure"; and U.S. Provisional Patent Application Serial No. 63 / 192,720, filed May 25, 2021, entitled "Organic Solid Wastes Conversion for Liquid Fuels / Chemicals Production in the Presence of Methane Containing Gas Environment and Catalyst Structure", the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] This invention relates to a method for valorization of organic solid biomass, belonging to the field of solid feedstock processing and upgrading technology. Background Technology

[0004] Organic solid waste, including municipal solid waste and agricultural and forestry residues, is gaining increasing attention worldwide as the only sustainable alternative to fossil fuels due to its low cost, availability, and carbon-neutral properties, and its potential use in the production of renewable liquid fuels and chemicals. Nevertheless, it remains largely unused as a raw material in these sectors due to technical and economic considerations.

[0005] Besides gases and biochar, pyrolysis of organic solid waste is another method for producing crude bio-oil. However, bio-oil obtained through direct pyrolysis ages gradually due to its low H / C ratio, and the aging rate is accelerated when exposed to light, oxygen, or heat above 80°C, leading to storage and stability issues. Furthermore, due to its high oxygen content, the resulting bio-crude oil has a low calorific value, making it unsatisfactory as a substitute for traditional liquid fuels in power generation, and it also contains contaminants such as sulfur, nitrogen, chlorine, and trace metals.

[0006] To overcome these problems, various processes have been developed to upgrade bio-oils by removing or chemically modifying unwanted compounds. The most widely used process is hydrodeoxygenation. It can produce a product of better quality, energy density, and non-corrosiveness, and can be further upgraded. However, it must consume large amounts of hydrogen and operate under high pressure conditions (e.g., from about 15 atm to about 35 atm). The involvement of such an expensive, non-naturally available hydrogen source will inevitably lead to a significant increase in the cost of this upgrading process. Moreover, this high-pressure operation will inevitably lead to further increases in capital and operating costs.

[0007] Another method for upgrading bio-oils is catalytic cracking on zeolites, which can produce aromatics at atmospheric pressure without the need for hydrogen. This process is still in its early stages and is limited by the low H / C content of the final product. Therefore, there is a strong need to develop an economically attractive process for upgrading bio-oils using abundant and readily available raw materials.

[0008] Methane, the main component of natural gas, is an undervalued natural resource. Natural gas production has surged in recent decades, primarily due to the so-called shale gas revolution in North America and the corresponding price decline. Utilizing methane or natural gas as a hydrogen donor to upgrade organic solid waste to produce high-value-added liquid products would not only be more environmentally friendly and economical but also significantly increase the added value of natural gas, which would be highly beneficial for the current oil and gas industry. Furthermore, if the associated operational burdens can be further reduced, the entire process would become even more economically attractive and competitive. Summary of the Invention

[0009] According to the embodiments described herein, a value-added method for organic solid biomass feedstocks used in the production of liquid fuels and / or chemicals includes introducing the organic solid biomass feedstock into the reaction zone of a methanol decomposition reaction system in the presence of a methane gas and a methanol decomposition catalyst structure, so as to convert the solid organic feedstock into liquid bio-oil products and syngas products through methanol decomposition, and introducing the syngas products into a liquefaction reaction system in the presence of a second gas (optional) and a liquefaction catalyst structure, so as to convert the syngas products into liquid oil products through liquefaction.

[0010] In other embodiments, the method of forming liquefied fuel oil products includes: providing syngas as input to a mixed-bed reactor comprising a plurality of liquefaction catalyst structures, liquefying the syngas to produce liquefied fuel oil products and gaseous products, and separating the liquefied fuel oil products from the gaseous products.

[0011] In a further embodiment, the method for forming the methanol decomposition catalyst structure includes: dissolving two or more metal salts in water to form a metal precursor solution comprising any two or more metals selected from Mo, Ni, Co, Ag, Ga, Ce, and Zn; loading the metal precursor solution into a porous support structure; drying the porous support structure loaded with the metal precursor at a temperature of about 80°C to about 120°C for at least 2 hours; and calcining the dried support structure loaded with the metal precursor in a gas atmosphere and at a heating rate of about 5°C / min to about 20°C / min in a temperature range of about 300°C to about 700°C to form the methanol decomposition catalyst structure.

[0012] In a further embodiment, the method for forming the liquefied catalyst structure includes: dissolving two metal salts in water to form a mixed metal precursor solution; introducing an alkaline solution as a precipitant into the mixed metal precursor solution dropwise under stirring to form a slurry; aging the slurry at a temperature of about 25°C to about 28°C for at least 12 hours; repeatedly washing and filtering the aged slurry to form a precipitate; subsequently drying the precipitate at about 90°C to about 105°C for about 6 hours to about 12 hours to form a dry support structure; and calcining the dry support structure at 550°C under static air. The process involves: forming a mixed metal oxide support structure for 3 hours; dissolving a single alkali metal salt in water to form a metal precursor solution; loading the metal precursor solution into the mixed metal oxide support structure; drying the mixed metal oxide support structure loaded with the metal precursor at a temperature of about 80°C to about 120°C for at least 2 hours to form a dry catalyst structure loaded with a single alkali metal; and calcining the dry catalyst structure loaded with the single alkali metal in a gas atmosphere at a temperature range of about 300°C to about 700°C and a heating rate of about 5°C / min to about 20°C / min to form a liquefied catalyst structure.

[0013] This article further describes methods, systems, and catalyst structures for achieving organic solid biomass value-added in specific gaseous environments, which can efficiently produce value-added liquid fuels and / or chemicals through simple process operations.

[0014] The above and further features and advantages of the invention will become clear from the following detailed description of specific embodiments thereof. Attached Figure Description

[0015] The accompanying drawings are included to illustrate certain aspects of the invention. These drawings and their description are intended to facilitate understanding and should not be considered as limiting the invention. In the included drawings:

[0016] Figure 1This is a process flow diagram for producing liquid fuels / chemicals from organic solid biomass (biowaste) in a methane-containing gaseous environment.

[0017] Figure 2 This is a schematic diagram of a dual-bed reactor structure used for syngas liquefaction at near atmospheric pressure.

[0018] Figure 3 It is a process flow diagram, including Figure 1 Configuration and additional processing flow for converting upgraded bio-oil into liquid biofuel products. Detailed Implementation

[0019] This invention relates to the formulation of heterogeneous catalyst structures and methods and systems for using such catalysts to upgrade organic solid biomass in a methane or natural gas environment to produce high-value-added liquid fuels and / or chemicals without generating negative environmental impacts.

[0020] Specifically, this paper describes catalyst structures, systems, and methods for using such catalyst structures to add value to organic solid biomass (e.g., biowaste) in a methane-containing environment. Methane has been observed to be effectively activated, which facilitates methanol decomposition and liquefaction processes to maximize the formation of high-value-added liquid fuels and / or chemicals with minimized CO2 formation, thus benefiting environmental protection. The disclosures provided herein promote a shift in the production of renewable liquid fuels and / or chemicals within the oil and gas industry.

[0021] For example, the systems and methods described herein simultaneously convert methane-rich gases and organic solid biomass (e.g., solid biowaste) into valuable liquid chemicals or fuels, minimizing ash formation, for use as filler in the construction industry and as flammable gases for residential applications. In a broader sense, the systems and methods described herein utilize catalyst structures to pyrolyze and upgrade organic solid biomass feedstocks (e.g., municipal solid waste, agricultural and / or residential residues) in a single step using methane-containing gases. The methanol decomposition process combines the pyrolysis and upgrading of bio-oil in one step. After appropriate condensation for collecting the upgraded bio-oil, the simultaneously generated syngas and unconverted methane-containing gases undergo a series of purification steps and a water-gas shift reaction to obtain products with an ideal CO:H2 ratio, followed by a liquefaction step facilitated by another catalyst structure to form liquid hydrocarbon products. This process can be carried out at lower pressures (e.g., below 5 atm) using methane-containing gases (instead of the expensive hydrogen used in the prior art). The catalyst structures provide high-quality performance for initiating methane activation under non-oxidizing conditions in the presence of other higher hydrocarbons or oxygenates. The collected, upgraded bio-oil can be further improved through the additional treatments described herein. The systems and processes described not only enhance the quality of organic solid biomass but also, due to the introduction of inexpensive methane-containing gases, can produce more oil.

[0022] In the detailed description below, while various aspects of this disclosure are disclosed, alternative embodiments of this disclosure and their equivalents may be devised without departing from the spirit or scope of this disclosure. It should be noted that any discussion herein with reference to “an embodiment,” “an embodiment,” “an exemplary embodiment,” etc., indicates that the described embodiment may include specific features, structures, or characteristics, and that such specific features, structures, or characteristics are not necessarily included in every embodiment. Furthermore, references to the foregoing do not necessarily include references to the same embodiment. Finally, whether explicitly described or not, those skilled in the art will readily understand that each specific feature, structure, or characteristic of a given embodiment may be used in combination or in combination with features, structures, or characteristics of any other embodiment discussed herein.

[0023] Various operations can be described sequentially as multiple discrete actions or operations in a manner most conducive to understanding the claimed subject matter. However, the order of description should not be construed as implying that these operations necessarily depend on the order. In particular, these operations may not be performed in the order presented. The described operations may be performed in a different order than the described embodiments. Various additional operations may be performed in additional embodiments and / or the described operations may be omitted.

[0024] For the purposes of this disclosure, the phrase "A and / or B" means (A), (B), or (A and B). For the purposes of this disclosure, the phrase "A, B, and / or C" means (A), (B), (C), (A and B), (A and C), (B and C), or (A, B, and C).

[0025] The terms “comprising,” “including,” “having,” etc., used in the embodiments of this disclosure are synonymous.

[0026] According to exemplary embodiments, this document describes catalyst structures for use in conjunction with organic solid biomass value-added processes utilizing methane-containing resources (e.g., natural gas, biogas, and coalbed methane), and for combining two or more such catalyst structures to obtain high-quality liquid products. Biogas can be produced by converting biomass into a gaseous component containing methane and carbon dioxide. Natural gas also primarily contains methane, but may also contain components such as carbon dioxide and water vapor.

[0027] The use of methane-containing gas instead of hydrogen in organic solid biomass value-added processes avoids the need for economically unfavorable hydrogenation steps at high pressures and temperatures. Catalyst design is crucial for the effectiveness of this method in order to activate methane and selectively form the desired products. In particular, the catalyst structure described herein facilitates methanol decomposition and liquefaction processes at low temperatures (e.g., from about 350°C to about 600°C, preferably from about 400°C to about 500°C, for example, about 400°C) and pressures (e.g., in the range of about 1 atm to about 10 atm, preferably about 5 atm), in the presence of methane-rich gas, and in the presence of the catalyst structure itself.

[0028] Solid biomass used to form hydrocarbon fuel products

[0029] Any suitable solid organic or biomass / bio-waste material can be used as a starting input or feed material for the process described herein, wherein the organic material undergoes methanol decomposition to produce upgraded bio-oil products and further refined / upgraded hydrocarbon fuel products.

[0030] Examples of solid organic or solid biomass materials that can be used as method inputs include, but are not limited to: solid biowaste, such as municipal waste (e.g., municipal solid waste or MSW), including organic materials; lignin-based sources, including agricultural and / or forestry residues, such as corn stalks; lignin-derived feedstocks from wood (e.g., wood pellets, wood mill residues, etc.) and / or any other suitable lignin; algae; sources of industrial waste streams, including organic materials; and any other suitable type of biomass material.

[0031] Catalyst structure for methanol decomposition

[0032] According to the present invention, a catalyst structure for methanol decomposition is provided, comprising one or a combination of one or more metal (e.g., bimetallic) active components loaded on a highly porous support, for the pyrolysis of organic solid biomass in a methane-containing gas environment as described herein (see [link]). Figure 1 It should be noted that the catalyst structure described herein can also be used for desulfurization in other gaseous environments such as H2, He, and N2, although methane or natural gas environments are preferred.

[0033] Methanol decomposition catalyst structures can be synthesized by impregnating or doping suitable support materials with two or more metals. Suitable porous support materials can be alumina (i.e., Al2O3), aluminosilicates (e.g., zeolites), and / or silicon oxide (i.e., SiO2).

[0034] Some non-limiting examples of zeolite materials suitable as support materials for catalyst structures include HZSM-5 type zeolite, L-type zeolite, HX type zeolite, HY type zeolite, and zeolite structures commercially available from Rive Technology (Monmouth Junction, New Jersey). Ammonium-type zeolites can also be used by conversion to hydrogen-type zeolites (e.g., by calcination in static air at a temperature of about 400°C to about 600°C for a period of about 4 to about 6 hours). When using zeolite materials as support materials, the SiO2 to Al2O3 ratio of the zeolite support material can be in the range of about 2.5 to about 280 (i.e., the SiO2 to Al2O3 ratio is in the range of about 2.5:1 to about 280:1).

[0035] Suitable metals that can be loaded onto a porous support material, such as by impregnation or doping, include one or more selected from molybdenum (Mo), nickel (Ni), cobalt (Co), silver (Ag), gallium (Ga), zinc (Zn), and cerium (Ce). Each metal dopant or combination of metal dopants can be provided within the catalyst structure in an amount from about 0.1 wt% to about 20 wt% (i.e., based on the total weight of the catalyst structure). For certain metals, a preferred metal loading is from about 0.1 wt% to about 20 wt%. Specific examples of different metal loadings for catalyst structures are provided herein.

[0036] Porous support materials can be doped with appropriate amounts of one or more metals in the following manner: One or more metal salts can be dissolved in deionized water to form an aqueous solution of suitable concentration. Metal precursor salts that can be used to form the catalyst structure include, but are not limited to, chlorides, nitrates, sulfates, sulfides, and polythiometalates. Then, one or more metal precursors in solution are loaded into the porous support material to obtain the desired amount of metal (e.g., about 0.1 wt% to about 20 wt%) within the catalyst structure. Any suitable loading process can be performed to load the metal into the porous support material. Some non-limiting examples of metal loading processes include: IWI (initial wet impregnation, in which an active metal precursor is first dissolved in an aqueous or organic solution, and then the metal-containing solution is added to a catalyst support containing a pore volume equal to the volume of the added solution, wherein capillary action draws the solution into the pores); WI (wet impregnation, in which a liquid volume greater than that of IWI is added to the support, and then the solvent is removed by evaporation); IE (ion exchange, in which metal cations are exchanged from the solution to the support); and FI (framework incorporation, in which the metal is added to the support material during the synthesis step of the support).

[0037] Depending on the specific loading process, the resulting catalyst structure with loaded metal can be dried at a temperature of about 80°C to about 120°C for a period of about 2 hours to about 24 hours. The dried catalyst structure can then be calcined at a temperature of about 300°C to about 700°C in air, N2, or He at a suitable ramped or gradually increasing heating rate (e.g., about 5°C / min to about 20°C / min), wherein such calcination temperature, time, and heating rate can be modified according to the type of one or more metals doped into the catalyst structure and the reaction conditions associated with the use of the catalyst structure.

[0038] The resulting metal-doped catalyst structure is suitable for organic solid biomass pyrolysis in a methane-containing gas environment as described herein. The catalyst structure can be processed into granular form with specific particle sizes required for certain operations.

[0039] Catalyst structure for liquefaction (gas-to-liquid or GTL)

[0040] The liquefaction catalyst structure exists in the dual-bed device or dual-bed reactor described herein (see [link]). Figure 2 This invention aims to transform the traditional Fischer-Tropsch (FT) reaction pathway into a new one, in which the syngas feed stream passes through two consecutive catalyst beds with completely different formulations, but operates under the same reaction conditions. The catalyst in the first bed is designed to convert syngas into a mixture of light hydrocarbons (C1-C4) and residual C4 hydrocarbons within a temperature range of 350°C to 450°C at near atmospheric pressure.5+ The resulting product stream will then be exposed to a catalyst structure in a second bed, where the liquid product will be reacted under the same reaction conditions based on methane and coexisting higher hydrocarbons (C14-C24-C24). 2+ The synergistic effect between the reactions is maximized. Unreacted gaseous residues can be recycled back to the reactor inlet for further reaction (optional).

[0041] The first liquefaction catalyst structure in the first bed is a slightly modified conventional FT catalyst, consisting of any single alkali metal loaded in a mixed metal oxide structure and two or more mixed metal oxide structures including Co3O4, Fe2O3, NiO, and MnO2. The alkali metal loaded in the mixed metal oxide structure is present in an amount from about 0.1 wt% to about 10 wt%.

[0042] The first liquefaction catalyst structure can be synthesized by impregnation or doping with a suitable support material using a single alkali metal. A suitable mixed metal oxide support material can be prepared by co-precipitation of two or more metal oxides selected from Co3O4, Fe2O3, NiO, and MnO2: nitrate precursors of the selected two metals are dissolved in deionized water to provide a clear aqueous solution. An alkaline solution, such as sodium carbonate, is then introduced dropwise into the aqueous solution as a precipitant while maintaining a pH of 9 to 10 with stirring. The resulting slurry is vigorously stirred for 0.5 to 2 hours. The precipitate is aged at room temperature (e.g., from about 25°C to about 28°C) for at least 12 hours (e.g., about 12–48 hours), then filtered and washed several times with deionized water. The precipitate is dried overnight (e.g., for a period of about 6 to about 12 hours) at about 90°C to about 105°C and calcined at about 350°C to about 550°C for a period of about 2 to about 6 hours. The resulting mixed metal oxide support is then ready for impregnation.

[0043] Suitable metals that can be loaded onto the support material by impregnation or doping include any single alkali metal (e.g., lithium, sodium, potassium, etc.). Each metal dopant or combination of metal dopants may be provided in the catalyst structure in an amount of about 0.1% to about 10% by weight (i.e., based on the total weight of the catalyst structure).

[0044] The support material can be doped with a suitable amount of a metal in the following ways: A metal salt can be dissolved in deionized water to form an aqueous solution of suitable concentration. Metal precursor salts that can be used to form the catalyst structure include, but are not limited to, chlorides, nitrates, sulfates, sulfides, and polythiometallic salts. The metal precursor in solution is then loaded into the support material to obtain the desired amount of metal (e.g., about 0.1% to about 10% by weight) within the catalyst structure. Any suitable loading process can be performed to load the metal into the support material. Some non-limiting examples of metal loading processes include: IWI (initial wet impregnation, in which an active metal precursor is first dissolved in an aqueous or organic solution, and then the metal-containing solution is added to a catalyst support containing pores with a volume equal to the volume of the added solution, wherein capillary action draws the solution into the pores); WI (wet impregnation, in which a liquid volume greater than that of IWI is added to the support, and then the solvent is removed by evaporation); IE (ion exchange, in which metal cations are exchanged from the solution to the support); and FI (framework incorporation, in which the metal is added to the support material during the synthesis step of the support).

[0045] Depending on the specific loading process, the resulting first liquefied catalyst structure with loaded metal can be dried at a temperature of about 80°C to about 120°C for a period of about 2 hours to about 24 hours. The dried catalyst structure can then be calcined at a temperature of about 300°C to about 700°C in air, N2, or He at a suitable inclination or gradually increasing heating rate (e.g., a heating rate of about 5°C / min to about 20°C / min), wherein such calcination temperature, time, and heating rate can be modified according to the type of one or more metals doped into the catalyst structure and the reaction conditions associated with the use of the catalyst structure.

[0046] The resulting metal-doped first catalyst structure is suitable for the conversion of syngas in a methane-containing gas environment in a process as described herein to form C1-C4 light hydrocarbons and residual C. 5+ Products. The first catalyst structure can be processed into granular form with the particle size required for a specific operation.

[0047] According to the present invention, a second catalyst structure in a second bed is provided, comprising one or a combination of one or more metal (e.g., bimetallic) active components loaded on a highly porous support for liquefying light hydrocarbons in a methane-containing gas environment.

[0048] The second liquefaction catalyst structure can be synthesized by impregnating or doping a suitable support material with two or more metals. Suitable porous support materials can be alumina (i.e., Al2O3), aluminosilicates (e.g., zeolites), and / or silica (i.e., SiO2). Some non-limiting examples of suitable zeolite materials as support materials for the catalyst structure include HZSM-5 type zeolite, L-type zeolite, HX type zeolite, HY type zeolite, and zeolite structures commercially available from Rive Technology (Monmouth Junction, New Jersey). Ammonium-type zeolites can also be used by converting them into hydrogen-type zeolites (e.g., by calcining them in static air at a temperature of about 400°C to about 600°C for a period of about 4 to about 6 hours). When using zeolite materials as support materials, the SiO2 to Al2O3 ratio of the zeolite support material can be in the range of about 2.5 to about 280 (i.e., the SiO2 to Al2O3 ratio is in the range of 2.5:1 to 280:1).

[0049] Suitable metals that can be loaded onto a porous support material by impregnation or doping include any one or more (e.g., any two or more) from the group consisting of molybdenum (Mo), nickel (Ni), cobalt (Co), silver (Ag), gallium (Ga), zinc (Zn), and cerium (Ce). Each metal dopant or combination of metal dopant may be provided within the second catalyst structure in an amount from about 0.1 wt% to about 20 wt% (i.e., based on the total weight of the catalyst structure). For certain metals, a preferred metal loading is from about 0.1 wt% to about 20 wt%. Specific examples of different metal loadings for the second liquefaction catalyst structure are provided herein.

[0050] Porous support materials can be doped with appropriate amounts of one or more metals in the following ways: One or more metal salts can be dissolved in deionized water to form an aqueous solution of suitable concentration. Metal precursor salts that can be used to form the catalyst structure include, but are not limited to, chlorides, nitrates, sulfates, sulfides, and polythiometallic acid salts. One or more metal precursors in solution are then loaded into the porous support material to achieve the desired amount of metal (e.g., about 0.1% to about 20% by weight) within the catalyst structure. Any suitable loading process can be performed to load the metal into the porous support material. Some non-limiting examples of metal loading processes include: IWI (initial wet impregnation, in which an active metal precursor is first dissolved in an aqueous or organic solution, and then the metal-containing solution is added to a catalyst support containing a pore volume equal to the volume of the added solution, wherein capillary action draws the solution into the pores); WI (wet impregnation, in which a liquid volume greater than the IWI volume is added to the support, and then the solvent is removed by evaporation); IE (ion exchange, in which metal cations are exchanged from the solution to the support); and FI (framework incorporation, in which the metal is added to the support material during the synthesis step of the support).

[0051] Depending on the specific loading process, the resulting metal-loaded second liquefaction catalyst structure can be dried at a temperature of about 80°C to about 120°C for a period of about 2 hours to about 24 hours. The dried catalyst structure can then be calcined in air, N2, or He at a suitable sloping or gradually increasing heating rate (e.g., from about 5°C / min to about 20°C / min) within a temperature range of about 300°C to about 700°C, wherein such calcination temperature, time, and heating rate can be modified according to the type of one or more metals doped into the second catalyst structure and the reaction conditions associated with the use of the second liquefaction catalyst structure.

[0052] The resulting metal-doped second liquefaction catalyst structure is suitable for liquefying light hydrocarbons in a methane-containing gas environment as described herein. The second liquefaction catalyst structure can be processed into granular form with a specific particle size required for certain operations.

[0053] Systems and methods for organic solid biomass value-added in a methane-containing gas environment using catalyst structures

[0054] Figure 1System 100 is depicted, comprising a methanol decomposition reaction system 102, which includes multiple container units or receptacles, including a methanol decomposition reaction zone 104, a regeneration zone 106, and multiple gas cyclone separator units 110A, 110B, and 110C. Biomass, including a biowaste stream 105 containing biowaste material and a supply 108 of methane (e.g., natural gas), is fed into reaction zone 104 to promote gasification and pyrolysis (methanol decomposition) within the reaction zone in the presence of a methanol decomposition catalyst structure provided therein. The methanol decomposition catalyst structure circulates between reaction zone 104 and regeneration zone 106 via circulation lines 112 (extending from the regeneration zone outlet to the reaction zone inlet) and 114 (extending from the reaction zone outlet to the regeneration zone inlet), wherein combustion of material within the regeneration zone promotes regeneration of the methanol decomposition catalyst structure before it is circulated back to the reaction zone. Furthermore, output material flowing from the regeneration zone to the reaction zone promotes further heat transfer to the reaction zone.

[0055] Reaction zone 104 operates in a methane / natural gas environment at a temperature range of approximately 400°C to approximately 500°C. Gaseous products formed within the reaction zone exit or exit the reaction zone and are separated from solid particles containing catalyst and biochar in the first cyclone unit 110A. Ash particles generated and carried away by the product gas stream in flow path 115 exiting the first cyclone unit 110A can be separated from the product gas stream in the second cyclone unit 110B. This allows for continuous feeding of pretreated biowaste into the reactor system and continuous ash removal. Circulation line 114 provides the output solid material (including the methanol decomposition catalyst structure) from the first cyclone separator unit 110A as input to regeneration zone 106.

[0056] In regeneration zone 106, air is also introduced along with the solids output from cyclone unit 110A to promote combustion within the regeneration zone. This combustion completely oxidizes the char formed by the methanol decomposition catalyst structure carried away from reaction zone 104, generating heat to compensate for the energy requirements of the endothermic gasification / pyrolysis reactions within the reaction zone, thus minimizing the external energy input required for the reaction zone. In cases where coke has already deposited on its surface (during pyrolysis / gasification), the recycled methanol decomposition catalyst structure can also be renewed through this air introduction. In other words, any coke or other carbonaceous material formed above the surface portion of the methanol decomposition catalyst structure can be removed by the oxidation process. This benefits the lifespan / lifespan extension / continuous reuse of the methanol decomposition catalyst structure. The regenerated methanol decomposition catalyst structure (also used as a heater carrier) is transported from regeneration zone 106 and separated from the generated flue gas in third cyclone unit 110C, then circulated back to reaction zone 104 via circulation line 112 to initiate the next cycle of pyrolysis / gasification of the input biowaste.

[0057] The product stream exiting the second cyclone separator unit 110B is supplied to the condenser unit to form an upgraded liquid bio-oil product (also referred to herein as product A) from the gaseous products, including syngas (syngas) and any unreacted natural gas. The liquid bio-oil product / product A is separated from the syngas in separation unit 122 and can then be collected at section 124. The syngas and unreacted / unconverted natural gas exiting separation unit 122 can undergo a series of conventional purification steps (e.g., a series of units for the removal of H2S, NH3, HCl, and heavy metals) in purification unit section 126.

[0058] Next, the treated syngas leaving the purification unit section 126 can be transported together with the supplied steam to the reactor section 130, where the syngas undergoes a water-gas shift reaction to obtain the desired CO to H2 ratio of the gaseous products, wherein unconverted H2O can be removed from the syngas as condensate.

[0059] The treated syngas leaving the purification unit section 126 is fed into a liquefaction reaction system including a catalytic liquefaction or gas-to-liquid (GTL) unit 140, wherein the syngas undergoes a liquefaction process in the presence of multiple liquefaction catalyst structures, wherein the syngas is first converted into a mixture of light hydrocarbons, and then, based on the synergistic effect between methane and higher hydrocarbons, liquid hydrocarbon products are formed in a temperature range of about 350°C to about 450°C.

[0060] refer to Figure 2 The GTL unit 140 includes a dual-bed reactor comprising a first catalyst bed 142 and a second catalyst bed 144. The first catalyst bed 142 comprises a first liquefaction catalyst structure as previously described herein, and the second catalyst bed 144 comprises a second liquefaction catalyst structure as previously described herein. Each of the first and second liquefaction catalyst structures can be provided in particulate form within any suitable particle size range considered suitable for the reaction process. As mentioned above, the GTL unit 140 operates in a temperature range of about 350°C to about 450°C. Furthermore, the GTL unit 140 can operate at atmospheric pressure or near atmospheric pressure (e.g., an operating pressure not exceeding about 5 atm). A syngas feed stream (comprising H2, CO, CO2, and CH4) is delivered through the GTL unit 140, where it encounters the first catalyst bed 142 and then the second catalyst bed 144. As previously stated, the consecutively arranged first and second catalyst beds comprise significantly different catalyst structures but can operate under the same or substantially similar reaction conditions. The first liquefaction catalyst structure in the first catalyst bed 142 facilitates the conversion of syngas into a mixture of light hydrocarbons (e.g., C1-C4 range, with the residue component containing C...). 5+Then, under the same reaction conditions as the first catalyst bed, the product stream passing through the first catalyst bed 142 is exposed to the second catalyst bed 144 within the GTL unit 140, causing at least some of the gaseous components to liquefy in a methane atmosphere to form liquid hydrocarbon products. After leaving the GTL unit 140, unreacted gaseous substances can be separated from the liquid hydrocarbon products and recycled back to the inlet of the GTL unit 140 for further reactions.

[0061] The liquid hydrocarbon products can be further processed in separation or distillation unit 150 to separate and collect the liquid fuel product of interest (also referred to herein as product B) in section 160. Condensate and gaseous hydrocarbon products, including methane / natural gas, can be removed from the products. The methane / natural gas can be recycled from distillation unit 150 back to transport reactor system 102 via recirculation line 170, where it is mixed with the input methane / natural gas to reaction zone 104.

[0062] Figure 1 The systems and related methods facilitate the conversion of organic solid biomass and the selectivity for valuable liquid hydrocarbon products, which can be further fine-tuned in methane-containing environments using catalyst structures as described herein. Different reactor systems and improved operating conditions (e.g., temperature and pressure), as well as improvements to the catalyst structure within the reactor system, can also be implemented to obtain diverse product compositions.

[0063] Methane, as a major component of natural gas, is particularly useful for converting organic solid biomass in the presence of the catalyst structure described herein. Methane is generally considered chemically inert due to its stable structure, and methane activation has always been a challenge in natural gas utilization. However, according to the invention described herein, with the aid of the aforementioned catalyst structure, system, and corresponding method, the utilization of methane in biomass material value-added can be significantly improved.

[0064] Organic solid biomass conversion utilizing the catalyst structures, systems, and methods described herein further minimizes CO2 production. In particular, methane activation and incorporation using catalyst structures described herein can result in the production or generation of less than 5% by weight of the oil product, in some cases less than 3% by weight, or even less than 1% by weight of CO2 (e.g., virtually no CO2 is formed in the process).

[0065] exist Figure 3 In another embodiment shown, Figure 1The system has been modified to include a further hydrocarbon upgrading system that processes the upgraded bio-oil product (Product A) into a refined / further upgraded light oil product. For example, the upgraded light oil product may have properties such as lower viscosity and oxygen content than the bio-oil product. The bio-oil upgrading method can be carried out using the method described in U.S. Patent Application Serial No. 16 / 792,574, the contents of which are incorporated herein by reference in their entirety. Specifically, Product A collected at 124 of System 100 can be provided to the hydrocarbon upgrading system 200 for upgrading the bio-oil into a light oil fuel product (also referred to herein as Product C). A feedstock source 202 comprising Product A, together with a methane source 204 (e.g., natural gas or other hydrocarbon source containing about 95% by weight of methane), is provided as input to System 200 and combined in a mixing unit 206 and heated to a suitable temperature (e.g., from about 350°C to about 450°C, for example about 420°C) in a heater unit 208 before being conveyed to the catalytic reactor 210.

[0066] Catalytic reactor 210 includes a catalyst bed with a fixed catalyst structure. The catalyst structure of reactor 210 comprises a suitable porous support material impregnated or doped with two or more metals (e.g., using methods such as wet impregnation or ion exchange to adsorb metal ions onto the porous surface of the support material). Suitable porous support materials can be alumina materials (e.g., Al₂O₃), aluminosilicate (zeolite) materials, or zirconium oxide materials (e.g., ZrO₂). Some non-limiting examples of suitable zeolite materials used as support materials for the catalyst structure include ZSM-5 type zeolites (e.g., HZSM-5 zeolite, NaZSM-5 zeolite, etc.), A-type zeolites, L-type zeolites, HY-type zeolites, and zeolite structures commercially available from Rive Technology (Monmouth Junction, New Jersey). Ammonium-type zeolites can also be used by conversion to hydrogen-type zeolites (e.g., by calcination in static air at a temperature of about 400°C to about 600°C for a period of about 4 to about 6 hours). When zeolite materials are used as carrier materials, the SiO2 to Al2O3 ratio of the zeolite carrier material can be in the range of about 1 to about 280 (i.e., the SiO2 to Al2O3 ratio is 1:1 to 280:1), for example, in the range of 5-28, or in the range of 23-280. Zeolite materials can also have a SiO2 to Al2O3 ratio of about 350 μm. 2 / g to approximately 950m 2 The BET surface area is within the range of / g. The support material can optionally be modified with phosphorus before being synthesized into a suitable catalyst structure.

[0067] Suitable metals for use as doping porous support materials include any one or more (and preferably any two or more) of gallium (Ga), silver (Ag), zinc (Zn), molybdenum (Mo), cobalt (Co), and cerium (Ce). Each metal dopant or combination of metal dopants can be provided within the catalyst structure (e.g., in the form of a metal or metal oxide) in an amount from about 0.1 to about 20% by weight (i.e., based on the total weight of the catalyst structure). For some metals, such as Ag and Ga, a preferred metal loading is from about 0.2% to about 2% by weight. For other metals, such as Co, a preferred metal loading is from about 0.3% to about 3% by weight. The catalyst support structure is formed by doping or impregnating the porous support structure with one or more metals in the desired weight percentages described herein, which can be achieved in a manner similar to other types of catalyst structures formed from similar porous support structures as described herein. Furthermore, the catalyst support structure for reactor 210 can be converted into pellets or provided in powder or granular form. Additionally, the catalyst structure can be regenerated before or after its use for upgrading the hydrocarbons of feedstock 202 to enhance the performance of the catalyst structure. The regeneration process includes rinsing the catalyst with toluene, drying it in air to remove the toluene (e.g., drying at about 100°C to about 200°C, or about 150°C for at least 1 hour, or about 3 hours or more), and calcining it (heating it in air) at a temperature of at least about 500°C (e.g., about 600°C or more) for a sufficient period of time, such as at least about 3 hours (e.g., about 5 hours or more). The regeneration process can also be repeated any number of times, depending on the specific application.

[0068] In the presence of a catalyst structure within the catalytic reactor 210, bio-oil (product A) is converted into light fuel oil product (product C). The output from reactor 210 is conveyed to separator 220, which separates the light fuel oil (product C) from the gaseous components, including unreacted methane. The gaseous components can be recycled back to the input of mixing unit 206 via line 222, while the light fuel oil (product C) can be collected at 230.

[0069] Therefore, in Figure 3 The process produces three types of upgraded hydrocarbon products: upgraded bio-oil (product A), light hydrocarbon products (product B) formed from the syngas separated from the upgraded bio-oil in the GTL (gas-liquid) process, and light fuel oil (product C) formed by reacting the upgraded bio-oil (product A) with methane.

[0070] Example #1

[0071] Execute and use Figure 3The system's process is to form a bio-oil product (product A) from solid bio-waste (or other biomass) materials and to form a light fuel oil (product C) from the upgraded bio-oil. Products are obtained by continuously generating product A for 60 days by operating a methanol decomposition process (within reaction zone 104 of transfer reaction system 102) and by operating system 200 for continuously generating product C for 30 days.

[0072] The catalyst used for methanol decomposition in reaction zone 104 to form bio-oil (product A) has a structure of 1 wt% Ga-5 wt% Zn-10 wt% Ce / HZSM-5 (80:1), while the catalyst used for converting bio-oil (product A) into light fuel oil product (product C) in reactor 210 has a structure of 1 wt% Ag-1 wt% Ga-2 wt% Co-6 wt% Mo-10 wt% Ce / HZSM-5 (80:1). The solid organic biomass material supplied to reaction zone 104 is wood chips.

[0073] During the methanol decomposition process (forming product A), the conditions in reaction zone 104 are as follows:

[0074] Reaction temperature: 400℃

[0075] Reaction pressure: 10-15 psig (0.68-1.02 atm)

[0076] Biomass feed rate: 70 g / min

[0077] Gas flow rate: 2m 3 / minute

[0078] Catalyst loading: 35kg

[0079] Total mass balance: 96% by weight

[0080] Carbon yield: 30% by weight

[0081] Gas production rate: 10% by weight

[0082] Liquid yield: 56 wt% (water-rich liquid phase yield: 23 wt%; oil-rich liquid phase yield: 33 wt%)

[0083] In the fixed-bed upgrading process (forming product C) under methane conditions, the process conditions are as follows:

[0084] Reaction temperature: 400℃

[0085] Reaction pressure: 50 bar (49.3 atm)

[0086] WHSV (Weight-Time Velocity): 1hr -1

[0087] Liquid yield: 99% by weight

[0088] The characteristics of each bio-oil (product A) and light fuel oil (product C) formed by this process under the stated process conditions are as follows:

[0089] Table 1: Characteristics of Product A (Bio-oil)

[0090]

[0091]

[0092]

[0093] Table 2: Characteristics of Product C (Light Fuel Oil)

[0094]

[0095]

[0096]

[0097] Example #2

[0098] Execute and use Figure 3 The system's process is to form bio-oil product (product A) from solid bio-waste materials and light fuel oil (product C) from upgraded bio-oil. Products are obtained by running a methanol decomposition process (within reaction zone 104 of transfer reaction system 102) to continuously form product A for 30 days and running system 200 to continuously form product C for 30 days.

[0099] The catalyst used for methanol decomposition in reaction zone 104 to form bio-oil (product A) has a structure of 1 wt% Ga-5 wt% Zn-10 wt% Ce / HZSM-5 (80:1), while the catalyst used for converting bio-oil (product A) into light fuel oil product (product C) in reactor 210 has a structure of 1 wt% Ag-1 wt% Ga-2 wt% Co-6 wt% Mo-10 wt% Ce / HZSM-5 (80:1). The solid organic biomass material supplied to reaction zone 104 is rice straw.

[0100] During the methanol decomposition process (forming product A), the conditions in reaction zone 104 are as follows:

[0101] Reaction temperature: 400℃

[0102] Reaction pressure: 10-15 psig (0.68-1.02 atm)

[0103] Biomass feed rate: 70 g / min

[0104] Gas flow rate: 2m3 / minute

[0105] Catalyst loading: 35kg

[0106] Total mass balance: 96% by weight

[0107] Carbon yield: 43% by weight

[0108] Gas production rate: 15% by weight

[0109] Liquid yield: 38 wt% (water-rich liquid phase yield: 21 wt%; oil-rich liquid phase yield: 17 wt%)

[0110] In the fixed-bed upgrading process (forming product C) under methane conditions, the process conditions are as follows:

[0111] Reaction temperature: 400℃

[0112] Reaction pressure: 50 bar (49.3 atm)

[0113] WHSV (Weight-Time Velocity): 1hr -1

[0114] Liquid yield: 97.5% by weight

[0115] Under the stated process conditions, the characteristics of each bio-oil (product A) and light fuel oil (product C) formed by this process are as follows:

[0116] Table 3: Characteristics of Product A (Bio-oil)

[0117]

[0118]

[0119]

[0120] Table 4: Characteristics of Product C (Light Fuel Oil)

[0121]

[0122]

[0123]

[0124] Example #3

[0125] Execute and use Figure 3The system's process is to form bio-oil product (product A) from solid bio-waste materials and light fuel oil (product C) from upgraded bio-oil. Products are obtained by running a methanol decomposition process (within reaction zone 104 of transfer reaction system 102) to continuously form product A for 30 days and running system 200 to continuously form product C for 30 days.

[0126] The catalyst used for methanol decomposition in reaction zone 104 to form bio-oil (product A) has a structure of 1 wt% Ga-5 wt% Zn-10 wt% Ce / HZSM-5 (80:1), while the catalyst used for converting bio-oil (product A) into light fuel oil product (product C) in reactor 210 has a structure of 1 wt% Ag-1 wt% Ga-2 wt% Co-6 wt% Mo-10 wt% Ce / HZSM-5 (80:1). The solid organic biomass material supplied to reaction zone 104 is corn straw.

[0127] In the methanol decomposition process (forming product A), the conditions in reaction zone 104 are as follows:

[0128] Reaction temperature: 400℃

[0129] Reaction pressure: 10-15 psig (0.68-1.02 atm)

[0130] Biomass feed rate: 70 g / min

[0131] Gas flow rate: 2m 3 / minute

[0132] Catalyst loading: 35kg

[0133] Total mass balance: 96.5% by weight

[0134] Coking rate: 23.5% by weight

[0135] Gas production rate: 13.5% by weight

[0136] Liquid yield: 59.5 wt% (water-rich liquid phase yield: 28 wt%; oil-rich liquid phase yield: 31.5 wt%)

[0137] In the methane upgrading process in a fixed bed (forming product C), the process conditions are as follows:

[0138] Reaction temperature: 400℃

[0139] Reaction pressure: 50 bar (49.3 atm)

[0140] WHSV (Weight-Time Velocity): 1hr -1

[0141] Liquid yield: 97% by weight

[0142] The characteristics of each bio-oil (product A) and light fuel oil (product C) formed by this process under the stated process conditions are as follows:

[0143] Table 5: Characteristics of Product A (Bio-oil)

[0144]

[0145]

[0146] Table 6: Characteristics of Product C (Light Fuel Oil)

[0147]

[0148]

[0149] Compared to traditional bio-oil or fuel oil products, each upgraded hydrocarbon product (products A, B, and C) exhibits significantly lower oxygen content, significantly lower water (acetic acid) content, and lower viscosity bio-oil or fuel oil products. For products A and C, upgrading product A to form product C yields upgraded biofuels with even lower viscosity, lower sulfur content, lower oxygen content, lower TAN value, lower water content, and other enhanced properties compared to the unupgraded bio-oil. Product B can be formed from syngas, as it has a viscosity of less than 2 x 10⁻⁶. 3 Light hydrocarbon products (e.g., light oils, such as diesel products) with dynamic viscosity cP (mPa·s).

[0150] The upgrading process of hydrocarbon products results in changes to one or more properties of the hydrocarbon products. These changes (from the first hydrocarbon product to the upgraded second hydrocarbon product) include, but are not limited to: changes in density (decreased), viscosity (decreased), sulfur content (decreased), total acid number (TAN) (reduced), amount of olefins (e.g., weight percentage) (decreased), amount of nitrogen (e.g., weight percentage) (decreased), pour point (decreased), amount of one or more aromatics (e.g., weight percentage) (increased), hydrogen-to-carbon ratio (H / C ratio) (increased), and cetane number (increased).

[0151] Therefore, the methods and systems described herein, including the selection of various catalyst structures in the reactor for the formation of each upgraded hydrocarbon product, facilitate the use of a wide variety of solid organic or biomass / biowaste feedstocks, and further facilitate the generation of enhanced hydrocarbon products for a wide range of applications.

[0152] Although the invention has been described in detail with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made thereto without departing from its spirit and scope. Therefore, the invention is intended to cover modifications and variations thereof, provided they fall within the scope of the appended claims and their equivalents.

Claims

1. A method for value-added organic solid biomass feedstock for the production of liquid fuels and / or chemicals, the method comprising: In the presence of a methane gas and methanol decomposition catalyst structure, organic solid biomass raw materials are introduced into the reaction zone of a methanol decomposition reaction system, thereby converting the solid organic raw materials into liquid bio-oil products and syngas products through methanol decomposition. The methanol decomposition catalyst structure includes a porous support structure, which includes one or more of alumina, aluminosilicate materials and silicon oxide, and multiple metals loaded in the porous support structure, including Ga, Ce and Zn. In the presence of a second gas and a liquefaction catalyst, syngas products are introduced into the liquefaction reaction system, thereby converting the syngas products into liquid oil products through liquefaction. The methanol decomposition catalyst structure is circulated between the reaction zone and the regeneration zone, wherein the carbonaceous material deposited on the methanol decomposition catalyst structure is oxidized and removed from the methanol decomposition catalyst structure in the regeneration zone to form a regenerated methanol decomposition catalyst structure, and the regenerated methanol decomposition catalyst structure is guided from the regeneration zone to the reaction zone; and The gaseous products leaving the liquefaction reaction system are provided as input to the methanol decomposition reaction system.

2. The method according to claim 1, wherein the temperature in the methanol decomposition reaction system is about 400°C to about 500°C, and the pressure in the methanol decomposition reaction system is about 1 atm to about 10 atm.

3. The method according to claim 1, wherein the organic solid biomass raw material comprises one or more of municipal solid waste and agricultural and / or forestry solid waste residues.

4. The method of claim 1, wherein the methane-containing gas further comprises one or more of biogas and natural gas.

5. The method of claim 1, wherein the methane-containing gas further comprises one or more of nitrogen, helium, carbon dioxide, and water.

6. The method according to claim 1, wherein the methanol decomposition reaction system comprises a circulating fluidized bed reactor for catalytic methanol decomposition of organic solid biomass feedstock, and the liquefaction reaction system comprises a fixed bed reactor for catalytic liquefaction of the syngas.

7. The method of claim 1, wherein each metal loaded in the porous support structure is present in an amount of about 0.1% by weight to about 20% by weight, based on the total weight of the methanol decomposition catalyst structure.

8. The method of claim 1, wherein the liquefaction catalyst structure is disposed in a dual-bed reactor within the liquefaction reaction system.

9. The method of claim 8, wherein the liquefaction catalyst structure comprises a first catalyst structure in the first bed of the dual-bed reactor, the first catalyst structure comprising a mixed metal oxide structure comprising two or more of Co3O4, Fe2O3, NiO and MnO2, and a single alkali metal loaded in the mixed metal oxide structure, and the single alkali metal loaded in the mixed metal oxide structure is present in an amount of about 0.1 wt% to about 10 wt% of the first catalyst structure.

10. The method of claim 9, wherein the liquefaction catalyst structure further comprises a second catalyst structure in the second bed of the dual-bed reactor, the second catalyst structure comprising a porous support structure comprising one or more of alumina, aluminosilicate materials and silicon oxide, and two or more metals loaded in the porous support structure, wherein the two or more metals loaded in the porous support structure are selected from Ni, Mo, Co, Ga, Ag, Zn and Ce, and each metal loaded in the porous support structure is present in an amount from about 0.1 wt% to about 20 wt% of the second catalyst structure.

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