Aqueous effluent treatment system

Abstract

An aqueous effluent treatment system (1) includes a supercritical reactor system (2), an aqueous effluent source (3) connected upstream to the supercritical reactor system via a waste feed pump (P1), a fluid extraction system (4) connected downstream to the supercritical reactor system, and a solids extraction system (8) connected downstream to the supercritical reactor system. The supercritical reactor system includes multiple reactors, each having a vessel with a reactor chamber therein, each reactor operable to generate a pressure exceeding 22.1 MPa and a temperature exceeding 374 °C, configured to generate a supercritical zone within the reactor chamber. At least one reactor is a first moving bed reactor, the first moving bed reactor including: a fluid effluent outlet (25) at the top of the first moving bed reactor chamber, a solids feed inlet (36) at the top of the first moving bed reactor chamber for injecting moving bed solids into the reactor chamber, and a solids outlet (30) connected to the solids extraction system for extracting solids from the first moving bed reactor chamber.

Description

Technical Field

[0001] This invention relates to a system for treating various types of aqueous effluents, and more specifically, to a catalytic hydrothermal gasification system and method for treating aqueous effluents. Background Technology

[0002] Catalytic hydrothermal gasification is a well-known technique for treating aqueous effluents. This method utilizes the unique properties of supercritical water (T > 374 °C, p > 22.1 MPa) to efficiently convert organic compounds into syngases such as hydrogen, carbon dioxide, methane, ethane, butane, and / or propane using a catalyst. The nonpolar, low-density supercritical water facilitates the separation of inorganic and organic components. Unlike other oxidation processes (e.g., incineration, wet oxidation), this technique does not require air or oxygen to convert organic molecules, thus avoiding particulate matter and acidic gases (NOx). X The emissions of volatile organic compounds (VOCs) such as HCl, HF, and SO2 are reduced. The resulting high-calorific-value gases can be used on-site to generate heat and / or electricity, or injected into natural gas networks, while CO2 can be easily captured as a liquefaction product with very low energy consumption. The high performance of the catalyst enables high conversion of organic compounds, resulting in clean water effluent.

[0003] It is known that supercritical water separation (SCWS) systems are provided to separate wastewater sludge into its organic and inorganic components. SCWS can also be used to treat other aqueous effluents in aqueous media, such as coffee waste, microalgae, manure, and various other waste products. The organic components can be converted into syngas using, for example, a hydrothermal gasification unit, while the inorganic components can be converted into fertilizer. Some conventional reactor designs suffer from clogging and corrosion due to the precipitation of insoluble inorganic compounds and harsh reactor conditions.

[0004] Some of these drawbacks are overcome in SCWS systems for treating aqueous effluents, as described in WO2020173888A1. However, given the wide variety of inorganic and organic compounds in waste streams, the fluid products output from SCWS systems can contain a variety of undesirable or incompletely treated compounds (such as sulfur-containing compounds) and various organic compounds for end-use, which require further treatment and therefore storage and transport to further treatment facilities. This increases costs and reduces the overall energy efficiency of the treatment process. Summary of the Invention

[0005] The purpose of this invention is to provide an SCWS system for treating aqueous effluents that effectively reduces pollutant output and is globally energy efficient and economical.

[0006] Advantageously, it provides a water-based effluent treatment system that reduces the need for post-treatment of output products.

[0007] Advantageously, an aqueous effluent treatment system is provided that can effectively, efficiently and economically separate inorganic compounds from organic compounds, achieving high-quality separation between the organic and inorganic compounds.

[0008] Advantageously, it provides a water-based effluent treatment system that is robust and economically operated and maintained.

[0009] Aqueous effluents may include wastewater, or various other biological and non-biological wastes and substrates carried in aqueous media.

[0010] The object of the present invention is achieved by providing an aqueous effluent treatment system according to the independent claims.

[0011] Disclosed herein is an aqueous effluent treatment system comprising a supercritical reactor system, an aqueous effluent source connected upstream to the supercritical reactor system via a waste feed pump, a fluid extraction system connected downstream to the supercritical reactor system, and a solids extraction system connected downstream to the supercritical reactor system. The supercritical reactor system comprises one or more reactors, each reactor having a vessel having a reactor chamber, each reactor being operable to generate a pressure exceeding 22.1 MPa and a temperature exceeding 374 °C, configured to generate a supercritical zone within the reactor chamber.

[0012] At least one reactor is a moving bed reactor, which includes: - The fluid effluent outlet at the top of the moving bed reactor chamber. - A solid particle feed inlet at the top of the moving bed reactor chamber for injecting moving bed solid particles into the reactor chamber, and - A solids outlet at the bottom of the moving bed reactor chamber, which is connected to a solids extraction system for extracting solid particles from the moving bed reactor chamber.

[0013] According to a first aspect of the invention, the supercritical reactor system further includes at least a second reactor downstream of the first moving bed reactor, the inlet of the second reactor being connected to the fluid effluent outlet of the first moving bed reactor.

[0014] According to a second aspect of the invention, the solid extraction system includes a loop configured to recycle moving bed solid particles to a moving bed solid particle tank connected to the solid particle feed inlet of each moving bed reactor.

[0015] According to a third aspect of the invention, a solids extraction system includes a collector coupled to a solids outlet via a collector inlet valve, wherein a moving bed solids tank is connected to the collector via a valve and a solids pump, the collector being configured to pump solids from the solids tank into the collector, and wherein a water source is coupled to a high-pressure pump connected to the collector via a collector valve configured to inject water into the collector and inject solids from the collector into a reactor chamber via the solids feed inlet.

[0016] In an advantageous embodiment, the system further includes a second moving bed reactor downstream of the first moving bed reactor, the second moving bed reactor including a solid particle feed inlet at the top of the reactor chamber of the second moving bed reactor for injecting solid particles into the reactor chamber, an input at the lower portion of the reactor chamber connected to the fluid effluent outlet of the first moving bed reactor, and a solid outlet at the bottom of the reactor chamber of the second moving bed connected to a solid extraction system for extracting solid particles from the reactor chamber of the second moving bed reactor.

[0017] In one advantageous embodiment, the supercritical reactor system includes at least one separation reactor configured to generate a supercritical region in the upper portion of the separation reactor chamber and a subcritical region in the lower portion of the separation reactor chamber, the separation reactor comprising: - The input at the lower portion of the separation reactor chamber is connected to an aqueous effluent source. - A liquefied fluid outlet at the upper portion of the separation reactor chamber, which is connected to the fluid effluent inlet of the first moving bed reactor, and - A solids outlet at the bottom of the separation reactor chamber, which is connected to a solids extraction system for extracting solid residues from the subcritical zone of the separation reactor chamber.

[0018] In an advantageous embodiment, the solids outlet of the separation reactor and the solids outlet of the moving bed reactor are connected to the solids extraction system via valves (e.g., three-way valves).

[0019] In one advantageous embodiment, the moving bed solid particles comprise sulfur trapping material configured to remove sulfur substances such as H2S, simple organosulfur compounds, and complex organosulfur compounds.

[0020] In an advantageous embodiment, the sulfur-capturing material is selected from the group consisting of metals or metal oxides, wherein the metal is a transition metal or a lanthanide element, such as Fe, Co, Mo, Ni, Cu, Zn, Mn, Ce, La, Cr, W, optionally wherein the sulfur-removing metal is supported on a catalyst support selected from the group consisting of carbon-based materials (e.g., activated carbon), alumina, zirconium oxide, titanium dioxide, cerium oxide, and magnesium oxide.

[0021] In an advantageous embodiment, the particle size of the moving bed solid particles is less than 1 mm, preferably in the range of about 20 to 500 micrometers.

[0022] In an advantageous embodiment, the moving bed solid particles comprise a catalyst configured to selectively decompose intermediate organic molecules (e.g., alcohols, acetic acid, aldehydes, ketones) into gaseous molecules, such as hydrogen, carbon dioxide, methane, ethane, butane, and / or propane, under supercritical water conditions. The catalyst is selected from the group consisting of metals (e.g., Ni, Ru, Fe, Pt, Pd, Rh, Cu, Co) or bimetals (e.g., Ni-Ru), and is supported on a catalyst carrier such as carbon-based materials (e.g., activated carbon, graphene, carbon nanotubes, carbon nanofibers), alumina, zirconium oxide, titanium dioxide, cerium oxide, magnesium oxide, zeolite, calcium oxide, zinc oxide, or silicates.

[0023] In an advantageous embodiment, the catalyst is doped with a promoter selected from the group consisting of Mo, K, Cu, Sn, Ce, Na, Y, Au, and La.

[0024] In one advantageous embodiment, the supercritical reactor system includes a fixed-bed reactor, comprising: - Input, which is connected to the fluid effluent outlet of the first moving bed reactor or (if there are two moving bed reactors) to the fluid effluent inlet of the second moving bed reactor, and - Fluid product outlet, which is connected to the fluid extraction system.

[0025] In an advantageous embodiment, the fixed-bed reactor includes a catalyst configured to selectively decompose intermediate organic molecules (e.g., alcohols, acetic acids, aldehydes, ketones) into gaseous molecules (e.g., CH4, CO2, H2) under supercritical water conditions.

[0026] In an advantageous embodiment, the fixed-bed reactor catalyst is selected from the group consisting of metals (including Ni, Ru, Fe, Pt, Pd, Rh, Cu, Co) or bimetals (e.g., Ni-Ru), supported on a catalyst support such as carbon-based materials (e.g., activated carbon, graphene, carbon nanotubes, carbon nanofibers), alumina, zirconium oxide, titanium dioxide, cerium oxide, magnesium oxide, zeolite, calcium oxide, zinc oxide, silicate, and optionally the fixed catalyst is a doped promoter selected from the group consisting of Mo, K, Cu, Sn, Ce, Na, Y, Au, La.

[0027] In one advantageous embodiment, the solids extraction system includes a collector coupled to a solids outlet via a collector inlet valve.

[0028] In one embodiment, the solid extraction system further includes a gas feed circuit connected to the collector via a gas supply valve operable to be opened to extract solid residues and particles from the collector to a solid output tank connected to the collector via a collector solid output valve.

[0029] In one advantageous embodiment, the bottom wall of each moving bed reactor chamber has a funnel shape.

[0030] In one advantageous embodiment, the solids extraction system includes a loop configured to recycle moving bed solid particles to a moving bed solids tank connected to a solids feed inlet of each moving bed reactor.

[0031] In one advantageous embodiment, the solid extraction system is configured to inject solid particles from a collector into a moving bed reactor. Attached Figure Description

[0032] Other objects and advantageous features of the invention will be apparent from the claims, the detailed description, and the accompanying drawings, wherein: Figure 1a This is a schematic layout diagram of an aqueous effluent treatment system according to an embodiment of the present invention, wherein this embodiment is designed to treat effluents containing mineral salts. Figure 1b This is according to one embodiment of the present invention. Figure 1a , Figure 3a , Figure 3b A schematic cross-sectional view of the separation reactor of the system; Figure 1c This is a schematic cross-sectional view of a moving bed reactor according to one embodiment of the present invention; Figure 1d This is according to one embodiment of the present invention. Figure 1a , Figure 3c , Figure 3fA schematic cross-sectional view of the fixed-bed reactor system; Figures 2a to 2g This is a schematic layout diagram of the solid extraction system of an aqueous effluent treatment system according to an embodiment of the present invention. Figures 2a to 2g Different steps in a solid extraction process according to an embodiment of the present invention are shown.

[0033] Figures 3a-3b This is a schematic layout diagram of an aqueous effluent treatment system according to an embodiment of the present invention, wherein this embodiment is designed to treat effluents containing mineral salts. Figures 3c-3d This is a schematic layout diagram of an aqueous effluent treatment system according to an embodiment of the present invention, wherein this embodiment is designed to treat effluents containing little or no mineral salts. Figure 3f This is a schematic layout diagram of an aqueous effluent treatment system according to an embodiment of the present invention, wherein this embodiment is designed for injecting solid particles; Figures 4a to 4g This is a schematic layout diagram of the solid particle injection system of an aqueous effluent treatment system according to an embodiment of the present invention. Figures 4a to 4g Different steps in an injection system for solid particles according to an embodiment of the present invention are shown.

[0034] Figure 5a It is a graph showing the changes in catalyst activity and gas composition, expressed as carbon gasification efficiency (GEc), during the catalytic hydrothermal gasification of 10 wt.% glycerol (T = 400 °C, p = 25 MPa).

[0035] Figure 5b It is a graph showing the catalyst activity, expressed as carbon gasification efficiency (GEc), during catalytic hydrothermal gasification (T = 400 °C, p = 25 MPa) containing 47 mg / L dimethyl sulfoxide in 10 wt.% isopropanol in the presence of several sulfur trapping materials (ZnO, CuO / C, Ni / Al2O3) to protect the Ru / C catalyst. Detailed Implementation

[0036] Referring to the accompanying drawings, an aqueous effluent treatment system 1 according to an embodiment of the present invention includes a supercritical reactor system 2, an aqueous effluent source 3 connected upstream to the supercritical reactor system via a waste feed pump P1, a fluid extraction system 4 connected downstream to the supercritical reactor system, and a solids extraction system 8 connected downstream to the supercritical reactor system.

[0037] The supercritical reactor system includes one or more reactors 6, 7, 7b, 9, each reactor having a vessel containing a reactor chamber, each reactor being operable to generate pressures exceeding 22.1 MPa and temperatures exceeding 374 °C, configured to generate a supercritical region within the reactor chamber.

[0038] Supercritical reactor system 2 is configured to extract inorganic products, primarily as solid residues, from the aqueous effluent, and also to extract fluid products from the aqueous effluent, which include organic products treated for gasification. Supercritical reactor system 2 is further configured to convert certain undesirable waste compounds (particularly sulfur-containing compounds) into inert or readily disposable or recyclable compounds.

[0039] In all embodiments, the supercritical reactor system includes a moving bed reactor 7, which can be configured as follows: Figure 3d The supercritical reactor system 2 in the embodiment is the only reactor, or may be as follows: Figure 1a , 3a One of the multiple reactors in the supercritical reactor system 2 in embodiments 3b, 3c, and 3e. Figure 1a , 3a In embodiments 3b and 3b, the moving bed reactor 7 is arranged downstream of the separation reactor 6 of the supercritical reactor system 2. This separation reactor is configured to separate solid residual waste from fluid waste, which is then fed into the moving bed reactor for further treatment, particularly for the conversion of undesirable compounds, especially sulfur-containing compounds, and optionally for the vaporization of organic molecules (e.g., alcohols, acetic acid, aldehydes, ketones) into gaseous molecules including various gases (such as hydrogen, carbon dioxide, methane, ethane, butane, and / or propane). Vaporization can also be performed in... Figure 1a and 3c The gasification is performed in a fixed-bed reactor 9 provided in the embodiment, which is connected downstream to the outlet of a moving-bed reactor. Alternatively, gasification can also be performed in... Figure 3b and 3e The second moving bed reactor provided in the embodiment is used.

[0040] exist Figure 3d In the implementation of the supercritical reactor system 2 (where the moving bed reactor 7 forms the only reactor), the moving bed reactor is configured to perform the following functions: separating solid residual waste from fluid waste of aqueous effluent directly fed into the moving bed reactor, and treating the separated fluid waste with moving bed particles for conversion and gasification of undesirable compounds as described above.

[0041] The moving bed reactor 7 includes - Fluid effluent outlet 25 at the top of the moving bed reactor chamber, - A solid particle feed inlet 36 at the top of the moving bed reactor chamber is used to inject solid particles into the reactor chamber, and - A solid outlet 30 at the bottom of the moving bed reactor chamber is connected to a solid extraction system for removing solid particles from the moving bed reactor chamber after use.

[0042] The second moving bed reactor 7b includes: - Fluid effluent outlet 25 at the top of the second moving bed reactor chamber, - A solid particle feed inlet 36 at the top of the second moving bed reactor chamber is used to inject solid particles into the reactor chamber, and - A solid outlet 30b at the bottom of the second moving bed reactor chamber is connected to a solid extraction system for extracting solid particles from the second moving bed reactor chamber after use.

[0043] The solid particles injected into the moving bed reactor are solid particles with catalytic or reactive properties, configured to catalyze the chemical reactions of fluid compounds and / or react with fluid compounds under aqueous supercritical conditions, for the conversion of the aforementioned undesirable compounds and the gasification of liquid and solid organic compounds.

[0044] Advantageously, supercritical reactor systems with moving bed reactors allow for more efficient treatment of aqueous effluent waste than known systems by integrating solid (inorganic)-fluid (organic) waste separation and further fluid effluent treatment to directly output different waste products and useful gaseous products requiring minimal further treatment.

[0045] Compared with conventional fixed-bed reactors, the moving-bed reactor according to embodiments of the present invention has many advantages: »It reduces the risk of blockages caused by coke or mineral salt deposits; Used sulfur-capturing materials and / or catalysts can be easily removed from the process without interrupting it, thus reducing maintenance frequency and reactor volume, which translates into lower investment and operating costs.

[0046] »Fresh sulfur capture material and / or catalyst can also be injected into the process without interrupting operation; »The overall catalytic performance is enhanced because smaller particle sizes (<1 mm) can be used, reducing internal mass transfer limitations.

[0047] With reference to the accompanying drawings, various embodiments will now be described in more detail.

[0048] The aqueous effluent from source 3 is pressurized by a waste feed pump P1, including, for example, a high-pressure piston pump, to form pressurized aqueous waste effluent. The pressurized aqueous waste effluent passes through a first heat exchanger Hx1, where the temperature is raised to near the supercritical temperature of water.

[0049] exist Figures 1a to 1d and Figures 3a to 3b In this embodiment, the heated effluent enters the separation reactor 6, passes through the inlet 23 near the bottom of the container of the separation reactor 6, and flows upward in the separation reactor chamber 37.

[0050] Solid residues (e.g., mineral salts, other solids) are collected at the bottom of the separation reactor chamber 37 and can be extracted from the separation reactor 6 in a semi-continuous manner through the solid residue outlet 29 to the solid extraction system 8, and then transferred to the solid residue output tank 20. The extracted solid residues can then be dehydrated, with the liquid phase being recycled to the tank of the waste feed source 3, while the solid fraction can be disposed of or used for other downstream processes for conversion (e.g., phosphorus recovery).

[0051] The separated waste fluid (which contains no solid residue) exits the separation reactor 6 at outlet 24 near the top of the separation reactor chamber 37 and is injected into the moving bed reactor 7 via inlet 33 near the bottom of the moving bed reactor chamber 41, flowing upward through reactor chamber 41. Moving bed solid particles from solid particle source 21 are pressurized by a high-pressure pump P3 (e.g., a piston pump) to form a pressurized slurry of moving bed particles injected into the moving bed reactor chamber 41 via solid particle inlet 36. The moving bed solid particles can be used to remove sulfurous substances and / or to partially or completely vaporize organic compounds contained in the fluid effluent received from the separation reactor 6. The solid particles enter the moving bed reactor chamber 41 near the top of the vessel of the moving bed reactor 7 and flow downward countercurrently to the flow of fluid effluent injected through fluid inlet 33. The moving bed solid particles are held in the reactor chamber 41 in the form of a recirculating fixed bed or fluidized bed for a certain processing time. The moving bed solid particles accumulated in the moving bed reactor 7 are then extracted in a semi-continuous manner from the moving bed reactor 7 to the solid extraction unit 8, and then transferred to the tank of the solid particle source 21 for disposal or to another tank. The moving bed solid particles can be reused, regenerated, or disposed of.

[0052] exist Figures 1a to 1d and Figure 3c In this embodiment, the fluid effluent exits the moving bed reactor 7 at outlet 25 near the top of the moving bed reactor chamber 41 and is injected into the fixed bed reactor 9. The fixed bed reactor 9 is filled with a metal-supported catalyst, such as Ru and / or Ni on activated carbon. In variations, for example, Figure 3a ,3b As shown in Figure 3d, if gasification is fully completed in the moving bed reactor 7, the separate fixed bed reactor can be omitted. The catalyst serves to achieve complete gasification of the organic compounds. The output product gas exits the fixed bed reactor 9 and enters the first heat exchanger Hx1, where the temperature is reduced to below 100 °C, ideally at about 50 °C or lower. The cooled output fluid passes through filter 10, which protects the back pressure regulator R2 from any solid particulate waste (e.g., coke) in the fluid effluent. The pressure throughout the system is maintained and controlled by the back pressure regulator R2. The reduced-pressure output fluid product is injected via inlet 28 into the gas / liquid phase separator 11 to separate the product gas from the process water subsequently collected in the process water tank 12. The gas outlet 46 of the gas / liquid phase separator 11 can be connected to a gas tank to collect the gaseous product output of the aqueous effluent treatment system.

[0053] exist Figure 3b and Figure 3e In this embodiment, the fluid effluent exits the moving bed reactor 7 at outlet 25 near the top of the moving bed reactor chamber 41 and is injected into a second moving bed reactor 7b having a similar design to the moving bed reactor 7. Injection is performed via inlet 33 near the bottom of the moving bed reactor chamber 41 and flows upward through reactor chamber 42. Moving bed solid particles from solid particle source 21b are pressurized by a high-pressure pump P3 (e.g., a piston pump) to form a pressurized slurry of moving bed particles injected into the moving bed reactor chamber 41 via solid particle inlet 36. In this reactor, the role of the moving bed solid particles is to completely vaporize them from the separation reactor 6 ( Figure 3b ) or from the first moving bed reactor ( Figure 3e The received fluid effluent contains organic compounds. Solid particles enter the moving bed reactor chamber 41 near the top of the vessel of the second moving bed reactor 7b and flow countercurrently downwards towards the flow of fluid effluent injected through the fluid inlet 33. The moving bed solid particles are held for a certain processing time in the reactor chamber 42 in the form of a recirculating fixed bed or fluidized bed. Then, the moving bed solid particles accumulated in the second moving bed reactor 7b are extracted from the second moving bed reactor 7b in a semi-continuous manner to the solids extraction unit 8, and can then be transferred to the tank or disposal of the solid particles source 21b or transferred to another tank. The moving bed solid particles can be reused, regenerated, or disposed of.

[0054] The water-based effluent treatment system 1 can be used to treat wastewater streams such as sewage sludge, manure, microalgae, industrial / domestic wastewater, hazardous waste, plastic residue, and food industry waste.

[0055] In particular, the aqueous effluent treatment system 1 of the present invention can be advantageously used to treat digestate, microalgae, manure, coffee waste, wine lees, palm oil milling effluent, and hazardous waste such as waste solvents, industrial residues, industrial wastewater, and plastic residues.

[0056] The aqueous effluent treatment system 1 is capable of extracting mineral salts that form solid particles from subcritical and supercritical aqueous phases (p > 22.1 MPa, T > 300 °C) to atmospheric pressure to remove sulfur and fully vaporized organic compounds from the supercritical aqueous phase (p > 22.1 MPa, T > 374 °C) using a novel moving bed reactor, which can optionally be coupled with a fixed bed reactor or a second moving bed reactor.

[0057] Description of Separation Reactor 6 The separation reactor 6 may be similar to the separation reactor described in WO2020173888A1, and is a high-pressure reactor operating in reactor chamber 37 at a pressure exceeding 22.1 MPa and a temperature exceeding 300 °C. It is configured to generate a supercritical region 38 in a first portion of the reactor chamber, to which a liquefied fluid outlet 24 is connected, and to a subcritical region 39 in a second portion of the reactor chamber 37, to which a solid residue outlet 29 is connected. Typically, the supercritical region is formed in the upper portion of the reactor chamber 37, and the subcritical region is formed in the lower portion of the reactor chamber 37. The separation between the supercritical and subcritical regions is defined by a temperature gradient within the reactor chamber. The temperature gradient formed in the separation reactor 6 to create a subcritical region at the bottom of the reactor chamber and a supercritical region at the top of the reactor chamber can be achieved by employing heat exchange elements arranged along the reactor chamber. The temperature gradient within the reactor chamber can be formed by heat exchange units coupled to the reactor chamber at different locations within the chamber. The separation reactor 6 includes a solids outlet 29 connected to the lower end of a chamber within the subcritical zone 39. The aqueous effluent feed inlet 23 is preferably connected to the subcritical zone of the reactor chamber 37. However, the feed inlet 23 can also be directly connected to the supercritical zone, depending on the type of feed. Therefore, the aqueous effluent feed inlet 23 can be connected to either the subcritical or supercritical zone of the reactor chamber 37.

[0058] The solid residue outlet allows for the semi-continuous extraction of solid residues, particularly mineral salts collected during the extraction process, from the reactor chamber. This semi-continuous process corresponds to an extraction cycle in which the solid residue outlet is in liquid communication with the extraction system 8 to allow solid residues to flow out of the separation reactor 6 and into the extraction system 8, interrupted by the cycle (in which the communication between the separation reactor 6 and the solid residue extraction system 8 is closed) to allow residues to accumulate at the bottom of chamber 37 of the separation reactor 6.

[0059] At the bottom 40 of reactor chamber 37, a funnel shape may be provided to facilitate the extraction of solid residue from solid residue outlet 29.

[0060] Due to the low dielectric constant and low density of supercritical water, the supercritical zone acts as a barrier for inorganic compounds in waste feed, while organic compounds are fully dissolved in the supercritical zone and can be extracted through the liquefied fluid outlet 24 at the top of the chamber of the separation reactor 6.

[0061] Unlike the organic-rich liquid effluent, the inorganic compounds in the waste feed precipitate and fall to the bottom of the chamber of the separation reactor 6 by gravity, where they gradually accumulate.

[0062] Description of moving bed reactor Moving bed reactors 7 and 7b are high-pressure reactors operating in reactor chamber 41 at pressures exceeding 22.1 MPa and temperatures exceeding 374 °C. They are configured to generate a supercritical zone 42 in reactor chamber 41, which is connected to a liquid / gas effluent outlet 25, a liquefied fluid inlet 33, a moving bed solid particle inlet 36, and a moving bed solid particle outlet 30.

[0063] Preferably, the moving bed solid particles in the first moving bed reactor 7 are sulfur-capturing materials composed of metals or metal oxides, wherein the metal is a transition metal or a lanthanide element, such as Fe, Co, Mo, Ni, Cu, Zn, Mn, Ce, La, Cr, and W. The metal can also be supported on a catalyst support, such as carbon-based materials (e.g., activated carbon), alumina, zirconium oxide, titanium dioxide, cerium oxide, or magnesium oxide.

[0064] The role of sulfur trapping materials is to remove any sulfur substances (such as H2S), simple and complex organic sulfur compounds, from the liquefied fluid inlet 33 to protect the downstream catalyst in the moving bed reactor 7b or fixed bed reactor 9. For example... Figure 5b As shown, ZnO, CuO / C, and Ni / Al2O3 effectively removed sulfur compounds during treatment with 10 wt% isopropanol containing 47 mg / L dimethyl sulfoxide. Therefore, the catalyst lifetime was significantly improved compared to tests performed using only the inert material (Al2O3). Among the materials tested, Ni / Al2O3 was considered the most effective for protecting the Ru / C catalyst.

[0065] Preferably, the moving bed solid particles in the second moving bed reactor (7b) are catalysts composed of metals (such as Ni, Ru, Fe, Pt, Pd, Rh, Cu, Co) or bimetals (such as Ni-Ru) supported on catalyst supports such as carbon-based materials (e.g., activated carbon, graphene, carbon nanotubes, carbon nanofibers), alumina, zirconium oxide, titanium dioxide, cerium oxide, magnesium oxide, zeolite, calcium oxide, zinc oxide, or silicates. To improve the performance of the catalyst, it may be doped with promoters such as Mo, K, Cu, Sn, Ce, Na, Y, Au, and La. The catalyst's role is to partially or completely vaporize the organic compounds contained in the liquefied fluid inlet 33.

[0066] The moving bed solid particles can be any other material that allows the removal of any type of contaminant to protect the catalyst located downstream of the liquefied fluid inlet 33.

[0067] The moving bed solid particle inlet 36 allows moving bed solid particles, particularly fresh catalyst particles or fresh sulfur absorbent, to be injected into the reactor chamber by gravity. The physical properties of the moving bed solid particles (such as particle size and density) are selected so that they settle at the bottom of the reactor chamber 41 and are not conveyed to the liquid / gas outlet 25. Typical particle sizes are less than 1 mm, preferably between about 20 and 500 micrometers. Particle size can be measured using a particle size analyzer or simply by using a sieve.

[0068] Solid particle tank 21 contains fresh or partially deactivated catalyst, or fresh or partially deactivated sulfur trapping material. The moving bed solid particles form a slurry. Waste catalyst or sulfur trapping material is transferred from extraction unit 8 and collected in solid particle tank 21. The latter can be disposed of or transferred to another process for regeneration, or even reinjected into moving bed reactor 7.

[0069] The moving bed solids outlet 30 allows for the semi-continuous extraction of solids, particularly spent catalyst particles or sulfur capture material, as well as other coke deposits and mineral salts, from the reactor chamber. This semi-continuous extraction corresponds to an extraction cycle in which the moving bed solids outlet 30 is in liquid communication with the extraction system 8 to allow the moving bed solids to flow out of the moving bed reactor 7 and into the extraction system 8, interrupted by a cycle in which the communication between the moving bed reactor 7 and the extraction system 8 is closed to allow the moving bed solids to remain in the chamber 41 of the moving bed reactor 7.

[0070] At the bottom 43 of the reactor chamber 41, a funnel shape may be provided to facilitate the extraction of moving bed solid particles from the moving bed solid particle outlet 30.

[0071] Description of fixed-bed reactor 9 The fixed-bed reactor 9 is a high-pressure reactor operating in reactor chamber 44 at pressures exceeding 22.1 MPa and temperatures exceeding 374 °C. It is configured to generate a supercritical zone 45 within the reactor chamber, with a liquid / gas product outlet 26 and a liquid / gas effluent outlet 25 connected thereto. The catalyst is fixed inside reactor chamber 44 and consists of metals (such as Ni, Ru, Fe, Pt, Pd, Rh, Cu, Co) or bimetals (such as Ni-Ru) supported on catalyst supports such as carbon-based materials (e.g., activated carbon, graphene, carbon nanotubes, carbon nanofibers), alumina, zirconium oxide, titanium dioxide, cerium oxide, magnesium oxide, zeolite, calcium oxide, zinc oxide, and silicates. To improve catalyst performance, the catalyst may be doped with promoters such as Mo, K, Cu, Sn, Ce, Na, Y, Au, and La. The catalyst's role is to completely vaporize the organic compounds output from the moving-bed reactor 7 and injected into the fluid (liquid / gas) inlet 27.

[0072] Extract the description of unit 8 (especially the reference) Figures 2a-2g and Figures 4a-4f ) Solid residue effluent collected from the bottom of the reactor chamber of separation reactor 6 and moving bed solid particle effluent collected from the bottom of the reactor chambers of moving bed reactor 7 and the second moving bed reactor 7b are extracted in a semi-continuous manner by the operation of extraction system 8. This extraction system includes an output circuit 31 coupled to the solid residue outlet 29 of separation reactor 6, an output circuit 32 coupled to the moving bed solid particle outlet 30 of moving bed reactor 7, a high-pressure water feed circuit 34, and a gas feed circuit 35. Figure 3b and Figure 3e In one embodiment, the extraction system also includes an output loop 50 coupled to the second moving bed solid particle outlet 30b of the second moving bed reactor 7b.

[0073] The output loops 31 and 32 of the extraction system include two heat exchanger cooling systems Hx2 and Hx3 (second and third heat exchangers), a collector 17, a solids output tank 20, and a water source tank 15. Cooling system Hx2 (the second heat exchanger) is connected to the solids residue outlet 29 of the separation reactor 6, located upstream of cooling system Hx2, and to the collector 17, located downstream of cooling system Hx2. Cooling system Hx3 (the third heat exchanger) is connected to the moving bed solids particle outlet 30 of the moving bed reactor 7, located upstream of cooling system Hx3, and to the collector 17, located downstream of cooling system Hx3. Figure 3b and Figure 3eIn this embodiment, the output circuit 50 of the extraction system includes a heat exchanger cooling system Hx4 (fourth heat exchanger), a collector 17, a solid output tank 21b, and a water source tank 15. The cooling system Hx4 (fourth heat exchanger) is connected to the second moving bed solid particle outlet 30b of the second moving bed reactor 7b arranged upstream of the cooling system Hx4, and is connected to the collector 17 located downstream of the cooling system Hx4.

[0074] The cooling system is used to cool the extracted solid residues and particulate effluents to a temperature preferably below 100 °C, so that the extraction system can operate at a temperature below the boiling point of water at atmospheric pressure, reducing thermal stress and constraints on the components of the extraction system.

[0075] exist Figure 1a , 3a In embodiments 3c and 3d, the three-way valve V1 is connected downstream to the output circuits 31 and 32 and upstream of the collector 17, allowing solid residue to be extracted from the output circuit 31 or moving bed solid particles to be extracted from the output circuit 32. Figure 3b and 3e In this embodiment, the three-way valve V1 is connected downstream to the output circuits 32 and 50 and upstream to the collector 17, allowing the extraction of moving bed solid particles from the output circuit 32 or from the output circuit 50.

[0076] exist Figure 3b In this embodiment, valve V9 is connected downstream to the output circuit 31 and upstream to the collector 17, allowing solid residue to be extracted from the output circuit 31.

[0077] Collector 17 is connected to water tank 15 via filter 19 and collector liquid output valve V4.

[0078] Collector 17 is connected to solid residue outlet tank 20 and moving bed solid particle tank 21 via outlet valve V13 and three-way valve V6. Figure 3b and 3e In this embodiment, collector 17 is also connected to the second moving bed solid particle tank 21b via output valve V13 and three-way valve V6, and to the solid residue output tank 20 via valve V10 (only for...). Figure 3b Implementation method).

[0079] Collector 17 is also connected to water feed circuit 34 via collector valve V7 and filter 19 and via backflush valve V2.

[0080] Collector 17 is also connected to gas feed circuit 35 via gas supply valve V5 and filter 19.

[0081] Filter 19 is configured to prevent solid residue particles and moving bed solid particles from flowing into water output tank 15. The filter thus protects flow control valve F4 and pressure relief valve R1.

[0082] The water feed circuit 34 includes a water tank 15 coupled to a high-pressure pump P2, which is coupled to a collector valve V7, a backflush valve V2, and an outlet valve V3 connected to the downstream water tank 15.

[0083] Water tank 15 is connected to outlet valve V3 and pressure relief valve R1 for circulating water. Water tank 15 receives water extracted from separation reactor 6 through solid residue outlet 29 and collector 17, or from moving bed reactor 7 through solid residue outlet 30 and collector 17. An external water source can also be connected to refill water tank 15.

[0084] The gas feed circuit 35 includes a compressed gas source 18 connected to the collector 17 via a gas supply valve V5. The gas feed circuit is used to extract solid residues from the collector 17 to the solid output tank 20 during the solid residue extraction process, or to extract solid particles from the collector 17 to the moving bed solid particle tank 21 or tank 21b during the moving bed solid particle extraction process.

[0085] The gas supply valve V5 can be coupled to the flow control valve F5 to regulate the flow rate of compressed gas, or the flow control valve can be integrated into the gas supply valve V5. The gas supply valve can be, for example, a ball valve, and the flow control valve F5 can be, for example, a needle valve. However, those skilled in the art will understand that various valves known per se, which enable fluid communication between the gas source and the collector and regulate the flow rate, can be used within the scope of this invention; such valves and flow control systems are well known in the field of pneumatic systems.

[0086] The gas feed circuit can be based on compressed air or an inert gas, such as nitrogen, for example, compressed air pumped into a compressed air tank; such systems are well known in the field of pneumatic systems. In embodiments of the invention, the compressed gas source is configured to supply gas at a pressure preferably greater than 2 bar, preferably greater than 3 bar, and typically in the range of 2-10 bar.

[0087] Collector input valves V1, V9, V12, collector liquid output valve V4, water feed circuit 34 outlet valve V3, backflush valve V2, collector solid output valves V6, V10, V13, collector valve V7, and backflush valve V2 may each be in the form of ball valves; however, other valve systems known in the art for hydraulic systems may be used without departing from the scope of the invention.

[0088] In one embodiment, the collector liquid output valve V4 may be connected to the flow control valve F4 to regulate the water output flow from the collector 17, wherein the flow control valve F4 may be separate from or integrally formed with the collector liquid output valve V4.

[0089] The pressure relief valve R1 can be coupled downstream of the collector liquid output valve V4 and upstream of the water output tank 15. The pressure relief valve R1 regulates the pressure drop from the separation reactor 6, the moving bed reactor 7, and the second moving bed reactor 7 through the collector 17 to the water output tank 15. The pressure drop controls the flow rate of solid residue effluent from the separation reactor 6 into the collector 17, as well as the flow rate of solid particles effluent from the moving bed reactor 7 and the second moving bed reactor 7b into the collector 17.

[0090] In one advantageous embodiment, collector 17 is in the form of a tubular conduit, for example made of stainless steel, wound in a spiral or coil shape; however, those skilled in the art will understand that collector 17 may include conduits arranged in a serpentine or other shape, or the collector may simply comprise a cylindrical container with chambers to receive solid residues and moving bed solid particles.

[0091] Extraction of solid residues and moving bed solid particles is achieved by performing an extraction cycle in semi-continuous mode. A typical extraction cycle includes the following steps: refer to Figure 2a By starting the high-pressure pump P2 and opening the collector valve V7, water from water source 15 is used by the water feed circuit 34 to pressurize the gas feed circuit 35 and the collector 17. The pressure is then adjusted to be substantially equal to the pressure in the separation reactor 6, the moving bed reactor 7, and the second moving bed reactor 7b.

[0092] refer to Figure 2b To extract solid residue from the separation reactor 6, the separation reactor 6 is connected to the extraction system 8 by opening the collector inlet valve V9. This step is performed only when the pressure in the output circuit 31 is similar to the pressure in the separation reactor 6, which is ensured by pressurizing the output circuit through the aforementioned water feed circuit 34.

[0093] To extract moving bed solid particles from the moving bed reactor 7, the connection between the moving bed reactor 7 and the extraction system 8 is performed by opening the collector inlet valves V12 and V1 to the moving bed reactor 7. This step is performed only when the pressure in the output circuit 32 is similar to that in the moving bed reactor 7, which is ensured by pressurizing the output circuit through the aforementioned water feed circuit 34.

[0094] To extract moving bed solid particles from the second moving bed reactor 7b, the connection between the second moving bed reactor 7b and the extraction system 8 is performed by opening the collector inlet valves V12 and V1 to the moving bed reactor 7b. This step is performed only when the pressure of the output circuit 50 is similar to that of the second moving bed reactor 7b, which is ensured by pressurizing the output circuit through the aforementioned water feed circuit 34.

[0095] refer to Figure 2c By creating a negative pressure gradient (suction), the solid residue effluent is transferred from the separating reactor 6 or the moving bed solid particle effluent from the moving bed reactor 7 or the second moving bed reactor 7b to the collector 17. This is performed by opening the collector liquid outlet valve V4, which is connected to the flow control valve F4 and the pressure reducing valve R1. The pressure reducing valve R1 is calibrated to open at a pressure lower than that in the separating reactor chamber 37 and the moving bed reactor chamber 41 (e.g., approximately 1 MPa to 7 MPa lower), thus creating a negative pressure gradient for drawing the solid residue effluent from the separating reactor chamber 37 and the moving bed solid particle effluent from the moving bed reactor chamber 41. Therefore, the pressure relief valve R1 can be calibrated to open at pressures greater than approximately 15-21 MPa, while the pressure in the reactor chamber is higher than approximately 22 MPa (more specifically, higher than 22.1 MPa under supercritical water conditions), thus creating a negative pressure gradient for drawing solid residual effluent from reactor chamber 37 or moving bed solid particle effluent from moving bed reactor chamber 41. Water collected during suction is recirculated in water tank 15. A flow control valve F4 (e.g., a needle valve) can be located between the collector liquid output valve V4 and the pressure reducing valve R1 to control (reduce) the flow rate. A filter 19 is installed upstream of valves V4 and F4 to protect them from any solid particles that could damage the valves due to mechanical wear. At the end of the suction process, the collector liquid output valve V4 closes.

[0096] In some cases, it may not be necessary to create a negative pressure gradient, and gravity may be sufficient to transport solid residues and moving bed solid particles to collector 17, for example, in the case of large pipe diameters.

[0097] refer to Figure 2dBefore closing the collector inlet valves V1, V12, or V9, backwash the collector with water. This step aims to remove any solid particles deposited during the transfer of solid residues and moving bed solid particles from the collector inlet valves V1, V12, or V9. This is achieved by opening the backwash valve V2 for a short time (e.g., a few seconds) and starting the water feed loop pump P2. The flow rate and pressure of the water pumped by the water feed loop 34 are set to be higher than the pressure in the chambers of the separation reactor 6, the moving bed reactor 7, or the second moving bed reactor 7b, to convey the moving bed solid particles upward toward the separation reactor 6, the moving bed reactor 7, or the second moving bed reactor 7b.

[0098] An important parameter is the terminal velocity of the solid residue and moving bed solid particles, which allows for the transport of solid particles. The latter depends on several parameters, such as the density and particle size of the solid residue and moving bed solid particles. Therefore, in order to transport the solid residue and moving bed solid particles out of the collector inlet valve V12 or V9, the fluid velocity inside the collector inlet valve V12 or V9 should be higher than the terminal velocity of the solid particles.

[0099] At the end of the cleaning step, the collector inlet valve V12 or V9 and the water feed circuit backflushing valve V2 are closed.

[0100] refer to Figure 2e The pressure reduction in collector 17 is achieved by opening outlet valve V3. Outlet valve V3 can be connected to flow control valve F3, which is designed to smooth the pressure reduction by reducing the flow rate. The water obtained during pressure reduction is circulated in water tank 15. At the end of the pressure reduction process, outlet valve V3 closes.

[0101] refer to Figure 2f Solid residues are extracted from collector 17 to solid output tank 20, or moving bed solid particles are extracted from collector 17 to moving bed solid particle tank 21 or second moving bed solid particle tank 21b, by applying pressurized gas, preferably compressed air, from gas feed circuit 35. This step is achieved by opening gas supply valve V5 and collector solid outlet valves V10, V13, and V6. Flow control valve F5 (e.g., needle valve) may be located downstream of gas supply valve V5 to control air flow. When all solid residues or moving bed solid particles have been collected in solid output tank 20, moving bed solid particle tank 21, or second moving bed solid particle tank 21b, air flow is stopped by closing gas supply valve V5.

[0102] refer to Figure 2gThen, the collector 17 can be flushed and refilled with water by starting the water feed loop pump P2. At the end of the flushing, close the collector valve V7 and the collector solids outlet valves V13 and V10. To clean the filter 19 and the collector 17, it is also beneficial to flush the line from the filter 19 to the solids outlet tank 20 or the moving bed solids tank 21 or the second moving bed solids tank 21b with water.

[0103] Advantageously, the extraction system 8 according to an embodiment of the invention is configured such that no high pressure differential is generated across valves V12, V9, V13, and V10 where solid particles flow. This allows the valves to be protected from mechanical wear caused by the solid particle flow. The main pressure differential in output circuits 31, 32, and 50 is generated downstream of filter 19, where no solid particles are present.

[0104] Advantageously, in one embodiment, the collector may include a coil or serpentine structure of tube, the length of which may be adjustable, for example by changing the number of spirals or windings according to the amount of inorganic precipitate to be extracted, thus making the solid extraction system 8 easily expandable as needed.

[0105] Advantageously, pressurized gas is used to flush solid residues out of collector 17, which avoids diluting the solid residue effluent or solid particulate effluent.

[0106] like Figure 3f As shown, in one embodiment, the extraction unit can also be used to inject solid particles from collector 17 into reactor chamber 4. Advantageously, in this embodiment, the solid particles are injected from tank 21 into collector 17 at atmospheric pressure, and then collector 17 is pressurized with water to the pressure of reactor chamber 41. This significantly improves the pumpability of the solid particles, reduces the risk of damaging the pump's check valve, and preserves the solid particles by avoiding wear caused by the check valve when the fluid is pressurized. In this embodiment, a high-pressure pump is not required, and pump 3 can be an inexpensive low-pressure pump (e.g., a screw pump), thus reducing the overall cost of the extraction unit. However, those skilled in the art will understand that various pumps known per se transfer solid particles from tank 21 to collector 17.

[0107] The injection of solid particles is achieved by executing an injection cycle in semi-continuous mode. A typical injection cycle may include those described below and... Figures 4a to 4g The steps are shown in the diagram.

[0108] Reference Figure 4aThe collector 17 is flushed from the water source 15 via the water feed circuit 34 by starting the high-pressure pump P2, opening the collector valve V7 and the collector solids output valve V13, and connecting V6 from the collector 17 to the flush water / solids tank 20. Solids collected in the flush water / solids tank 20 can be reused in the solids tank 21. The flushing aims to remove any remaining solids from the water feed circuit 34 and the collector 17 from the previous injection cycle. At the end of the cleaning step, pump P2 is shut off.

[0109] refer to Figure 4b By connecting V11 from the solid particle tank 21 to pump P3, connecting V6 from the solid particle tank 21 to collector 17, opening outlet valve V3, and starting pump P3, collector 17 is filled with solid particles from solid particle tank 21. When collector 17 is approximately 80% full of solid particles, pump P3 is shut off. The solid particles in solid particle tank 21 are mixed with water, wherein the concentration of solid particles is >10 wt.%. A mechanical stirrer can be used to keep the solid particles in suspension.

[0110] refer to Figure 4c Collector 17 is filled with water from tank 21b by connecting V11 to pump P3 and starting pump P3. When collector 17 is about 20% full, pump P2 is turned off. This step is intended to remove any solid particles still accumulated in the collector's solids outlet circuit to collector 17. At the end of filling, pump P3 is turned off and collector valve V7 is closed.

[0111] refer to Figure 4d The collector solids outlet circuit is flushed via water feed circuit 34 from water source 35 by starting high-pressure pump P2, opening collector valve V2, and connecting V13 from collector 17 to flush water / solids tank 20. This step prevents solids from accumulating in the collector solids outlet circuit and removes any solids from collector solids outlet valves V13 and V6. Solids collected in flush water / solids tank 20 can be reused in solids tank 21. At the end of the flushing step, pump P2 is turned off, and collector valve V2 and collector solids outlet valve V13 are closed.

[0112] refer to Figure 4e Start the high-pressure pump P2 and open the collector valve V7 to pressurize the gas feed circuit 35 and collector 17 with water from water source 35 through water feed circuit 34. Adjust the pressure to be substantially equal to the pressure in moving bed reactor 7 and the second moving bed reactor 7b.

[0113] refer to Figure 4fBy opening collector inlet valve V12, connecting collector inlet valve V14 from collector 17 to reactor chamber 41, and starting high-pressure pump P2, water feed circuit 34 injects solid particles from collector 17 into reactor chamber 41 using water from water source 15. When all remaining solid particles have been transferred in reactor chamber 41, pump P2 is turned off and collector inlet valve V12 is closed.

[0114] An important parameter is the end velocity of the solid particles that allows for their transport. The latter depends on several parameters, such as the density and particle size of the solid residue particles and the moving bed solid particles. Therefore, in order to transport solid particles from collector 17 to the reactor chamber, the flow velocity inside the collector and other pipes should be higher than the end velocity of the solid particles.

[0115] refer to Figure 4g Pressure reduction in collector 17 is achieved by opening outlet valve V3. Outlet valve V3 can be connected to flow control valve F3, which is designed to smooth the pressure reduction by reducing the flow rate. The water obtained during pressure reduction is circulated in water tank 15. At the end of the pressure reduction process, outlet valve V3 closes.

[0116] Example The following is an example illustrating the effect of solid particle (20% Ni / carbon) injection on gasification performance in a moving bed reactor (with solid particles of 40 to 100 µm size fractions) during the catalytic hydrothermal gasification of 10 wt.% glycerol (T = 400 °C, p = 25 MPa). Figure 5a As shown, the injection of moving bed solid particles into the flow at different times significantly improved the carbon gasification efficiency (GEc) and the methane content in the gas. Therefore, the recording of GEC and gas composition during the experiment provides information on when fresh moving bed solid particles should be injected to maintain GEC close to 100%.

[0117] List of reference numerals used Waterborne effluent treatment system 1 Water-based effluents (e.g., sewage sludge, industrial wastewater) source 3 Waste feed pump P1, such as a piston pump Supercritical reactor system 2 Separation reactor 6 Reactor chamber 37 Funnel-shaped bottom 40 Waste feeding inlet 23 Solid residue outlet 29 liquefied fluid outlet 24 Supercritical region 38 Subcritical region 39 Moving bed reactor 7, second moving bed reactor 7b Moving bed solid particle tank 21, second moving bed solid particle tank 21b Reactor chamber 41 Funnel-shaped bottom 43 Liquefied fluid inlet 33 Moving bed solid particle inlet 36 Moving bed solid particle outlet 30, second moving bed solid particle outlet 30b Liquid / Gas Outlet 25 Supercritical region 42 Fixed-bed reactor 9 Reactor chamber 44 Liquid / Gas Inlet 27 Liquid / Gas Outlet 26 Supercritical region 45 Solid extraction system 8 (for extracting solid residues and solid particles) Output circuit 31 for solid residues Cooling system Hx2 Output circuit 32 for solid particles Cooling system Hx3 Output circuit 50 for solid particles Cooling system Hx4 Collector input valve V1 Collector input valve V12 Collector input valve V14 Collector input valve V9 Collector 17 Filter 19 Collector liquid output valve V4 Flow control valve F4 Pressure reducing valve R1 Collector solids outlet valve V13 Collector solids outlet valve V6 Collector solids outlet valve V10 Solid residue output tank 20 Solid Particle Can 21 Water tank 21b Solid Particle Inlet Valve V8 Solid Particle / Water Inlet Valve V11 Pump P3 Water feed circuit 34 Water source 15 Pump P2 Outlet valve V3 Flow control valve F3 Collector valve V7 Backflush valve V2 Gas feed circuit 35 Compressed gas source 18 Gas supply valve V5 Flow control valve F5 Fluid extraction system 4 Output circuit Heat exchanger Hx1 Filter 10 Pressure regulator R2 Gas / liquid separator 11 Liquid outlet Gas outlet 46 Process water tank 12.

Claims

1. An aqueous effluent treatment system (1) comprising a supercritical reactor system (2), an aqueous effluent source (3) connected upstream to the supercritical reactor system via a waste feed pump (P1), a fluid extraction system (4) connected downstream to the supercritical reactor system, and a solids extraction system (8) connected downstream to the supercritical reactor system, said supercritical reactor system comprising a plurality of reactors, each reactor having a vessel having a reactor chamber therein, each reactor being operable to generate a pressure exceeding 22.1 MPa and a temperature exceeding 374 °C, configured to generate a supercritical zone in the reactor chamber, wherein at least one reactor is a first moving bed reactor, the first moving bed reactor comprising: - Fluid effluent outlet (25) at the top of the first moving bed reactor chamber. - A solid particle feed inlet (36) at the top of the first moving bed reactor chamber is used to inject moving bed solid particles into the reactor chamber, and - A solids outlet (30) connected to a solids extraction system for extracting solid particles from the first moving bed reactor chamber. Furthermore, the supercritical reactor system also includes at least a second reactor (7b, 9) downstream of the first moving bed reactor (7), the inlet of which is connected to the fluid effluent outlet of the first moving bed reactor.

2. The system according to claim 1, wherein The second reactor is a second moving bed reactor (7b), which includes: A solid particle feed inlet (36) at the top of the reactor chamber of the second moving bed reactor is used to inject solid particles into the reactor chamber, the inlet being arranged at the lower portion of the reactor chamber connected to the fluid effluent outlet (25) of the first moving bed reactor. and a solid outlet (30b) at the bottom of the reactor chamber of the second moving bed connected to the solid extraction system, for extracting solid particles from the second moving bed reactor chamber. Or one of them The second reactor is a fixed-bed reactor (9) having an inlet (27) connected to the fluid effluent outlet (25) of the first moving-bed reactor and a fluid product outlet (26) connected to the fluid extraction system (4).

3. The system according to claim 1 or 2, wherein the supercritical reactor system comprises at least one separation reactor (6) configured to generate a supercritical region (38) in the upper portion of the separation reactor chamber and a subcritical region (39) in the lower portion of the separation reactor chamber, the separation reactor comprising: - Input (23) at the lower part of the separation reactor chamber connected to the aqueous effluent source (3). - The liquefied fluid outlet (24) at the upper portion of the separation reactor chamber connected to the fluid effluent inlet of the first moving bed reactor, and - A solid outlet (29) connected to the bottom of the separation reactor chamber of the solid extraction system is used to extract solid residues from the subcritical zone of the separation reactor chamber.

4. The system according to the preceding claims, wherein the solids outlet of the separation reactor and the solids outlet of the moving bed reactor are connected to the solids extraction system via, for example, a three-way valve (V1).

5. The system according to any of the preceding claims, wherein the moving bed solid particles comprise sulfur removal materials configured for removing sulfur substances such as H2S, simple organosulfur compounds and complex organosulfur compounds.

6. The system according to the preceding claims, wherein the sulfur removal material is selected from the group consisting of metals or metal oxides, wherein the metal is a transition metal or a lanthanide element, such as Fe, Co, Mo, Ni, Cu, Zn, Mn, Ce, La, Cr, W, optionally wherein the sulfur removal metal is supported on a catalyst support selected from the group consisting of carbon-based materials, alumina, zirconium oxide, titanium dioxide, cerium oxide, and magnesium oxide.

7. The system according to the preceding claims, wherein the particle size of the moving bed solid particles is less than 1 mm, preferably in the range of about 20 to 500 micrometers.

8. The system according to the preceding claims, wherein the moving bed solid particles comprise a catalyst configured to selectively decompose intermediate organic molecules (e.g., alcohols, acetic acid, aldehydes, ketones) into gaseous molecules, such as hydrogen, carbon dioxide, methane, ethane, butane, and / or propane, under supercritical water conditions.

9. The system according to the preceding claims, wherein the catalyst configured to selectively decompose intermediate organic molecules is selected from the group consisting of metals or bimetals supported on a catalyst support, such as Ni, Ru, Fe, Pt, Pd, Rh, Cu, Co, and bimetals such as Ni-Ru, and the catalyst support is selected from the group consisting of carbon-based materials, alumina, zirconium oxide, titanium dioxide, cerium oxide, magnesium oxide, zeolite, calcium oxide, zinc oxide, silicates, or combinations thereof.

10. The system according to the preceding claims, wherein the carbon-based material is selected from the group consisting of activated carbon, graphene, carbon nanotubes, carbon nanofibers, or the like.

11. The system according to the preceding claim, wherein the catalyst is doped with a promoter selected from the group consisting of Mo, K, Cu, Sn, Ce, Na, Y, Au, and La.

12. The system according to any preceding claim in conjunction with claim 2, wherein the fixed-bed reactor comprises a catalyst configured to selectively decompose intermediate organic molecules such as alcohols, acetic acid, aldehydes, and ketones into gaseous molecules such as CH4, CO2, and H2 under supercritical water conditions.

13. The system according to the preceding claim, wherein the fixed-bed reactor catalyst is selected from the group consisting of metals or bimetals supported on a catalyst support, the metals including Ni, Ru, Fe, Pt, Pd, Rh, Cu, Co, and bimetals such as Ni-Ru, the catalyst support including carbon-based materials, alumina, zirconium oxide, titanium dioxide, cerium oxide, magnesium oxide, zeolite, calcium oxide, zinc oxide, silicates, and optionally the fixed catalyst is doped with a promoter selected from the group consisting of Mo, K, Cu, Sn, Ce, Na, Y, Au, La.

14. The system according to any of the preceding claims, wherein the solid extraction system (8) includes a collector (17) coupled to a solid outlet via a collector inlet valve (V1, V9, V12, V14).

15. The system according to the preceding claim, wherein the solid extraction system further comprises a gas feed circuit (35) connected to the collector via a gas supply valve (V5), the gas supply valve being operable to be opened to extract solid residues and particles in the collector to a solid output tank (20, 21, 21b), the solid output tank being connected to the collector via a collector solid output valve (V6, V10).

16. The system of claim 14 or 15, wherein the moving bed solid particle tank (21, 21b) is connected to a collector (17) via valves (V6, V13) and a solid particle pump (P3), the collector being configured to pump solid particles from the solid particle tank into the collector. Furthermore, the water source (15) is coupled to a high-pressure pump (P2), which is coupled to a collector via a collector valve (V7) configured to inject water into the collector and inject solid particles from the collector into the reactor chamber via the solid particle feed inlet.

17. The system according to the preceding claims, wherein the bottom wall (43) of each moving bed reactor chamber (41) has a funnel shape.

18. The system according to the preceding claim, wherein the solid extraction system (8) includes a loop configured to recycle moving bed solid particles to a moving bed solid particle tank (21, 21b) connected to the solid particle feed inlet (36) of each moving bed reactor.

19. An aqueous effluent treatment system (1) comprising a supercritical reactor system (2), an aqueous effluent source (3) connected upstream to the supercritical reactor system via a waste feed pump (P1), a fluid extraction system (4) connected downstream to the supercritical reactor system, and a solids extraction system (8) connected downstream to the supercritical reactor system, the supercritical reactor system comprising one or more reactors, each reactor having a vessel having a reactor chamber therein, each reactor being operable to generate a pressure exceeding 22.1 MPa and a temperature exceeding 374 °C, configured to generate a supercritical zone in the reactor chamber, wherein at least one reactor is a first moving bed reactor, the first moving bed reactor comprising: - Fluid effluent outlet (25) at the top of the first moving bed reactor chamber. - A solid particle feed inlet (36) at the top of the first moving bed reactor chamber is used to inject moving bed solid particles into the reactor chamber, and - A solids outlet (30) connected to the bottom of the first moving bed reactor chamber of the solids extraction system for extracting bulk particles from the first moving bed reactor chamber. The solid extraction system (8) includes a loop configured to recycle moving bed solid particles to a moving bed solid particle tank (21, 21b) connected to the solid particle feed inlet (36) of each moving bed reactor.

20. The system according to the preceding claim further includes a second moving bed reactor (7b) downstream of the first moving bed reactor (7), the second moving bed reactor including a solid particle feed inlet (36) at the top of the reactor chamber of the second moving bed reactor for injecting solid particles into the reactor chamber, an input at the lower portion of the reactor chamber connected to the fluid effluent outlet (25) of the first moving bed reactor, and a solid outlet (30b) at the bottom of the reactor chamber of the second moving bed connected to a solid extraction system for extracting solid particles from the second moving bed reactor chamber.

21. The system according to claim 19 or 20, wherein the supercritical reactor system comprises at least one separation reactor (6) configured to generate a supercritical region (38) in the upper portion of the separation reactor chamber and a subcritical region (39) in the lower portion of the separation reactor chamber, the separation reactor comprising: - Inlet (23) at the lower part of the separation reactor chamber connected to the aqueous effluent source (3). - The liquefied fluid outlet (24) at the upper portion of the separation reactor chamber connected to the fluid effluent inlet of the first moving bed reactor, and - Solid outlet (29) at the bottom of the separation reactor chamber connected to the solid extraction system for extracting solid residues from the subcritical zone of the separation reactor chamber.

22. The system according to the preceding claim, wherein the solids outlet of the separation reactor and the solids outlet of the moving bed reactor are connected to the solids extraction system via a valve (V1), such as a three-way valve.

23. The system according to any one of claims 17-20, wherein the moving bed solid particles comprise sulfur removal materials configured to remove sulfur substances such as H2S, simple organosulfur compounds and complex organosulfur compounds.

24. The system according to the preceding claim, wherein the sulfur removal material is selected from the group consisting of metals or metal oxides, wherein the metal is a transition metal or a lanthanide element, such as Fe, Co, Mo, Ni, Cu, Zn, Mn, Ce, La, Cr, W, optionally wherein the sulfur removal metal is supported on a catalyst support selected from the group consisting of carbon-based materials, alumina, zirconium oxide, titanium dioxide, cerium oxide, and magnesium oxide.

25. The system according to the preceding claim, wherein the particle size of the moving bed solid particles is less than 1 mm, preferably in the range of about 20 to 500 micrometers.

26. The system according to any one of claims 17-23, wherein the moving bed solid particles comprise a catalyst configured to selectively decompose intermediate organic molecules (e.g., alcohols, acetic acid, aldehydes, ketones) into gaseous molecules, such as hydrogen, carbon dioxide, methane, ethane, butane, and / or propane, under supercritical water conditions.

27. The system according to the preceding claim, wherein the catalyst configured to selectively decompose intermediate organic molecules is selected from the group consisting of metals or bimetals supported on a catalyst support, such as Ni, Ru, Fe, Pt, Pd, Rh, Cu, Co, and bimetals such as Ni-Ru, and the catalyst support is selected from the group consisting of carbon-based materials, alumina, zirconium oxide, titanium dioxide, cerium oxide, magnesium oxide, zeolite, calcium oxide, zinc oxide, silicates, or combinations thereof.

28. The system according to the preceding claims, wherein the carbon-based material is selected from the group consisting of activated carbon, graphene, carbon nanotubes, carbon nanofibers, or combinations thereof.

29. The system according to the preceding claim, wherein the catalyst is doped with a promoter selected from the group consisting of Mo, K, Cu, Sn, Ce, Na, Y, Au, and La.

30. The system according to any one of claims 17-27, wherein the supercritical reactor system comprises a fixed-bed reactor (9) comprising: - A fluid effluent outlet connected to the first moving bed reactor (7), or an inlet connected to the fluid effluent outlet of the second moving bed reactor (7b) in conjunction with claim 2, and - Fluid product outlet (26) connected to the fluid extraction system (4).

31. The system according to the preceding claims, wherein the fixed-bed reactor includes a catalyst configured to selectively decompose intermediate organic molecules such as alcohols, acetic acid, aldehydes, and ketones into gaseous molecules such as CH4, CO2, and H2 under supercritical water conditions.

32. The system according to the preceding claim, wherein the fixed-bed reactor catalyst is selected from the group consisting of metals or bimetals supported on a catalyst support, the metals including Ni, Ru, Fe, Pt, Pd, Rh, Cu, Co, and bimetals such as Ni-Ru, the catalyst support including carbon-based materials, alumina, zirconium oxide, titanium dioxide, cerium oxide, magnesium oxide, zeolite, calcium oxide, zinc oxide, silicates, and optionally the fixed catalyst is doped with a promoter selected from the group consisting of Mo, K, Cu, Sn, Ce, Na, Y, Au, La.

33. The system according to any one of claims 17-31, wherein the solid extraction system (8) comprises a collector (17) coupled to a solid outlet via a collector inlet valve (V1, V9), and the solid extraction system further comprises a gas feed circuit (35) connected to the collector via a gas supply valve (V5), the gas supply valve being operable to be opened to extract solid residues and particles in the collector to solid output tanks (20, 21, 21b), the solid output tanks being connected to the collector via collector solid output valves (V6, V10).

34. The system according to any one of claims 19-31, wherein the bottom wall (43) of each moving bed reactor chamber (41) has a funnel shape.

35. An aqueous effluent treatment system (1) comprising a supercritical reactor system (2), an aqueous effluent source (3) connected upstream to the supercritical reactor system via a waste feed pump (P1), a fluid extraction system (4) connected downstream to the supercritical reactor system, moving bed solids tanks (21, 21b), a water feed loop (34) including a water source (15), and a solids extraction system (8) connected downstream to the supercritical reactor system, the supercritical reactor system comprising at least one reactor, each reactor having a vessel having a reactor chamber therein, each reactor being operable to generate a pressure exceeding 22.1 MPa and a temperature exceeding 374 °C, configured to generate a supercritical zone in the reactor chamber, wherein at least one reactor is a first moving bed reactor, the first moving bed reactor comprising: - Fluid effluent outlet (25) at the top of the first moving bed reactor chamber. - A solid particle feed inlet (36) at the top of the first moving bed reactor chamber is used to inject moving bed solid particles into the reactor chamber, and - A solids outlet (30) connected to a solids extraction system for extracting solid particles from the first moving bed reactor chamber. The solid extraction system (8) includes a collector (17) coupled to the solid outlet via collector inlet valves (V1, V9, V12, V14). Furthermore, the moving bed solid particle tanks (21, 21b) are connected to the collector (17) via valves (V6, V13) and a solid particle pump (P3), which is configured to pump solid particles from the solid particle tanks into the collector. Furthermore, the water source (15) is coupled to a high-pressure pump (P2), which is coupled to a collector via a collector valve (V7) configured to inject water into the collector and inject solid particles from the collector into the reactor chamber via the solid particle feed inlet.

36. The system according to the preceding claims, wherein the supercritical reactor system further comprises at least a second reactor (7b, 9) downstream of the first moving bed reactor (7), the inlet of the second reactor being connected to the fluid effluent outlet of the first moving bed reactor.

37. The system according to claim 35 or 36, further comprising any one or more of the additional features of claims 2-13, 15, 17-19.

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