A pre-homogeneous phase auxiliary organic matter coupling electrolysis and grading collection method and device

Abstract

This invention relates to the field of electrolytic hydrogen production technology, specifically to a pre-homogeneous assisted organic matter coupled electrolysis and graded collection method and apparatus. It combines the solubilizing and dispersing effects of subcritical, near-critical, or supercritical high-temperature and high-pressure water on complex organic matter with the organic matter coupled electrolysis process. In the pre-homogeneous stage, the material forms a continuous, quasi-homogeneous, or highly dispersed reaction phase in the high-temperature and high-pressure water, significantly reducing the mass transfer resistance of insoluble, multi-component, or suspended solid organic matter. This improves the continuity of feed for the anode organic matter oxidation reaction and reduces the tendency for oxygen evolution competition and non-target side reactions caused by insufficient feed, thus improving the feed conditions in the electrode reaction zone. Through a graded collection path that first collects gas, then liquid, and finally discharges residues, the products of each phase are sequentially discharged, reducing the separation difficulties caused by gas-liquid entrainment and residue mixing, and achieving the integration of the electrolysis reaction and the graded collection process of the products.

Description

Technical Field

[0001] This invention relates to the field of electrolytic hydrogen production technology, specifically to a method and apparatus for pre-homogeneous assisted organic matter coupled electrolysis and graded collection. Background Technology

[0002] With the increasing demand for clean energy and the resource utilization of organic waste, coupled electrolysis hydrogen production technology, which replaces the oxygen evolution reaction at the anode of traditional water electrolysis with an organic matter oxidation reaction, has attracted widespread attention. This technology can achieve the oxidation conversion of organic matter at the anode and efficient hydrogen evolution at the cathode at a lower theoretical voltage, thereby reducing energy consumption and increasing the added value of anode products.

[0003] However, existing coupled electrolytic hydrogen production schemes mainly focus on liquid-phase systems at room temperature or lower temperatures, and mostly use soluble small-molecule organic matter as substrates. For organic feeds with complex composition, poor solubility, multiphase or containing suspended solids, such as poorly soluble organic matter, multi-component organic waste liquid, organic slurry and organic waste liquid containing suspended solids, the following problems are common when directly applied to conventional electrochemical reactors: low homogenization of the reaction system, large mass transfer resistance between organic matter and electrolyte aqueous solution, resulting in low electrode reaction efficiency and uneven current density distribution; organic matter is difficult to effectively enrich and stably transform on the electrode surface, easily triggering competitive oxygen evolution reaction, reducing current efficiency; with the scale-up of reactor and the increase of substrate concentration, non-electrochemical conversion, non-target degradation of organic matter under high temperature or alkaline conditions, cross-contamination of products and generation of by-products often occur; after the reaction, the separation, collection and residue treatment of products lack a controllable path, and gaseous, liquid and solid products are often discharged mixed, increasing the difficulty of post-treatment and separation cost.

[0004] Supercritical water electrolysis hydrogen production systems already exist, capable of electrolysis reactions in high-temperature, high-pressure water environments. Organic slurries can also be added to supercritical water electrolyzers for electrochemical conversion. However, for systems containing sparingly soluble organic matter, suspended organic particles, colloidal organic matter, or multi-component organic waste liquid, simply heating the material to a supercritical state and directly applying electricity may still result in problems such as unstable material phase before electricity application, uneven supply of organic components near the electrodes, gas remaining dissolved or dispersed in the liquid or highly dispersed phase after electricity is stopped, liquid entrainment during depressurization, solid residues or precipitated salts blocking the outlet path, and mixed discharge of gas, liquid, and residue phases.

[0005] Therefore, an operating method is needed that differs from continuous flow supercritical water electrolysis systems and electrochemical measurement-type intermittent supercritical water electrolysis systems. The focus is not on the reactor body or the electrochemical measurement system, but on the pre-homogeneous construction of complex organic matter before energization, the stabilization by heat and pressure after energization, and the graded extraction of gas, liquid, and residue based on pressure and temperature sequence control after the reaction. Summary of the Invention

[0006] The purpose of this invention is to provide a pre-homogeneous assisted organic matter coupling electrolysis and graded collection method and apparatus to solve the technical problem of poor hydrogen production effect of existing complex organic matter electrolysis.

[0007] The solution of the present invention to the above-mentioned technical problems is as follows: A method for pre-homogeneous assisted organic matter coupled electrolysis and fractional collection includes the following steps: S1, adding materials containing organic matter and water into an intermittent high-temperature and high-pressure electrolysis reactor, wherein an anode and a cathode are provided inside the intermittent high-temperature and high-pressure electrolysis reactor; S2, under closed conditions, the material is heated and pressurized to the pre-homogeneous temperature and pre-homogeneous pressure, so that the material is in a subcritical, near-critical or supercritical high temperature and high pressure water state. S3, under conditions of no power supply or lower than the formal electrolysis current, the material is subjected to heat preservation and pressure pre-homogenization treatment to make the material form a continuous phase, quasi-homogeneous phase or highly dispersed reaction phase suitable for entering the electrode reaction zone; S4, maintain or adjust the system in the intermittent high temperature and high pressure electrolysis reactor to the electrochemical reaction window, start electrolysis, so that the organic matter or its hydrothermal conversion intermediates undergo an oxidation reaction at the anode and generate hydrogen-containing gaseous components at the cathode; S5, when the predetermined power-on time is reached or the reaction decay condition is reached, the power-on is stopped, and the heat and pressure are maintained after the power-on is stopped; S6, under the condition of retaining liquid products and residues in the batch high temperature and high pressure electrolysis reactor, the batch high temperature and high pressure electrolysis reactor is depressurized in a controlled manner, and gaseous products are preferentially exported and collected; S7, after cooling the intermittent high-temperature and high-pressure electrolysis reactor to the liquid phase collection temperature, the liquid phase product or condensed product is discharged and collected; S8 discharges residual slurry, sediment, precipitated salt, or solid residue from the intermittent high-temperature and high-pressure electrolysis reactor.

[0008] Further specified, the pre-homogenization temperature is 300℃~520℃, and the pre-homogenization pressure is 15MPa~35MPa; Preferably, the pre-homogenization temperature is 380℃~500℃, and the pre-homogenization pressure is 23MPa~30MPa.

[0009] Further specified, the temperature of the electrochemical reaction window is 250℃~430℃, and the pressure of the electrochemical reaction window is 8MPa~30MPa; Preferably, the temperature of the electrochemical reaction window is 300℃~400℃ and the pressure is 15MPa~28MPa.

[0010] Further specified, the volume of the material is 20% to 90% of the effective volume of the intermittent high-temperature and high-pressure electrolysis reactor, preferably 30% to 80%, so as to reserve buffer space in the intermittent high-temperature and high-pressure electrolysis reactor.

[0011] Further defined, the pre-homogenization treatment is to keep the material statically heated and pressurized under closed high temperature and high pressure conditions, or to keep the material heated and pressurized in conjunction with the heating and pressurization process; the conditions for completing the pre-homogenization treatment include at least one of the following: a decrease in the rate of change of pressure inside the vessel, a tendency for the conductivity to stabilize, no obvious macroscopic phase separation of the material, or a decrease in the solid sedimentation rate. The tendency to stabilize means that the rate of change of the corresponding parameter is lower than a preset threshold within 1 min to 30 min.

[0012] Further specifying, the material containing organic matter and water is at least one of the following: an aqueous solution containing oxidizable small molecule organic matter, a waste liquid containing multiple oxidizable organic components, an emulsion containing hydrophobic organic components, a slurry containing suspended organic particles, a waste liquid containing colloidal organic matter, or a solid-liquid mixture containing hydrothermally depolymerizable organic components.

[0013] Further specifying, the electrolysis in step S4 is carried out using constant current, constant voltage, constant anode potential, pulsed current, or a combination thereof; the current density is 10mA / cm² to 500mA / cm², preferably 50mA / cm² to 300mA / cm².

[0014] Further specifying, the reaction attenuation conditions include at least one of the following: the cell voltage increases to a preset upper limit, the system conductivity decreases to below a preset threshold, the cathode hydrogen production rate decreases to 30% to 70% of the initial hydrogen production rate, the anode potential reaches the oxygen evolution reaction enhancement threshold, the oxygen content in the gaseous products increases to a preset threshold, or the rate of change of pressure inside the reactor is lower than a preset value.

[0015] Further specified, the heat preservation and pressure holding time after the power is stopped in step S5 is 0.5min to 30min, preferably 0.5min to 10min, so that the gas phase components dissolved or dispersed in the continuous phase, quasi-homogeneous phase or highly dispersed phase are preferentially released or enriched in the buffer space when step S6 is performed.

[0016] Further specified, the controlled pressure reduction rate in step S6 is 0.1 MPa / min to 5 MPa / min, preferably 0.5 MPa / min to 2 MPa / min; the gaseous product is discharged when the pressure in the reactor drops to 3 MPa to 18 MPa, preferably at 8 MPa to 15 MPa.

[0017] Further specifying, the liquid phase collection temperature in step S7 is 20℃~150℃, preferably 40℃~100℃.

[0018] Further specified, a supporting electrolyte is added to the material to provide ionic conductivity within the electrochemical reaction window; When there is a risk of salting out or deposition in the system, the impact of deposits on the electrode reaction zone or the outlet path can be reduced by at least one of the following methods: reducing the concentration of the supporting electrolyte, reducing the electrolysis temperature, pulse energizing, controlled residue removal, or flushing the reactor.

[0019] An intermittent high-temperature and high-pressure electrolysis reactor device for implementing the above-mentioned pre-homogeneous assisted organic matter coupling electrolysis and graded collection method includes a reactor body, a reactor cover, a flange connection structure, a sealing gasket, a temperature measuring tube, a pressure measuring interface, a heating coil, a heat insulation layer, electrodes, and a control unit; The vessel body is provided with a reaction chamber, and the electrode and temperature measuring tube both extend into the reaction chamber. The vessel lid covers the vessel body, and the sealing gasket is located between the vessel lid and the vessel body. The heating coil is sleeved on the outside of the vessel body, and the heat insulation layer is sleeved on the outside of the heating coil. The pressure measuring interface is opened in the vessel lid and communicates with the reaction chamber. The temperature measuring tube is used to install the temperature measuring element, and the pressure measuring interface is used to connect the pressure measuring element. The temperature measuring element, pressure measuring element, heating coil, and electrode are all electrically connected to the control unit.

[0020] Furthermore, the intermittent high-temperature and high-pressure electrolysis reactor device also includes at least one outlet interface connected to a gas phase collection container, a liquid phase collection container, or a residue collection container. The outlet interface is used to sequentially export gas phase products, liquid phase products, or condensed products and residues under different pressure or temperature conditions.

[0021] The beneficial effects of this invention are as follows: 1. This invention combines the solubilizing and dispersing effects of subcritical, near-critical, or supercritical high-temperature and high-pressure water on complex organic matter with the organic matter coupled electrolysis process. In the pre-homogeneous stage, the material forms a continuous, quasi-homogeneous, or highly dispersed reaction phase in high-temperature and high-pressure water, significantly reducing the mass transfer resistance of insoluble, multi-component, or suspended solid organic matter. This is beneficial for improving the continuity of feed for the anodic organic matter oxidation reaction and reducing the tendency of oxygen evolution competition and non-target side reactions caused by insufficient feed, thus improving the feed conditions in the electrode reaction zone. Through a staged collection path of first collecting gas, then liquid, and finally discharging residues, the products of each phase are sequentially discharged under controlled conditions, reducing the separation difficulty caused by gas-liquid entrainment and residue mixing. This integrates the electrolysis reaction with the product staged collection process, improving the engineering adaptability and operability of the method for feeding complex organic matter. Attached Figure Description

[0022] Figure 1 This is a flowchart illustrating the steps of the pre-homogeneous assisted organic matter coupling electrolysis and fractional collection method of the present invention; Figure 2This is a structural diagram of the intermittent high-temperature and high-pressure electrolysis reactor device of the present invention; Figure 3 This is a schematic cross-sectional view of the vessel body of the present invention; Figure 4 This is a top view of the lid of the vessel according to the present invention; Figure 5 This is a cross-sectional view of the lid of the vessel according to the present invention; In the diagram, 10-vessel body; 11-vessel lid; 12-pressure measurement interface; 20-flange connection structure; 30-sealing gasket; 40-temperature measuring tube; 50-heating coil; 60-insulation layer; 70-electrode; 80-control unit. Detailed Implementation

[0023] In the description of the embodiments of the present invention, it should be noted that if terms such as "upper," "lower," "horizontal," or "inner" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product of the invention is in use, they are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of the present invention. Furthermore, terms such as "first" and "second" are only used to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0024] Example 1 refer to Figure 1 This invention provides a method for pre-homogeneous assisted organic matter coupling electrolysis and fractional collection, comprising the following steps: S1, add materials containing organic matter and water into an intermittent high-temperature and high-pressure electrolysis reactor. The intermittent high-temperature and high-pressure electrolysis reactor is equipped with an anode and a cathode, and a buffer space is reserved at the top of the reaction chamber. S2, under closed conditions, the material is heated and pressurized to the pre-homogeneous temperature and pre-homogeneous pressure, so that the material is in a subcritical, near-critical or supercritical high temperature and high pressure water state, preferably a supercritical high temperature and high pressure water state. S3, under conditions of no power supply or lower than the formal electrolysis current, the material is subjected to heat preservation and pressure pre-homogenization treatment to make the material form a continuous phase, quasi-homogeneous phase or highly dispersed reaction phase suitable for entering the electrode reaction zone; S4, after completing the pre-homogenization, the temperature and pressure can be maintained directly for energization, or the system can be adjusted to the electrochemical reaction window before energization based on the system conductivity, salting-out risk, electrode stability and gas production state; during the energization process, organic matter or its hydrothermal conversion intermediates undergo oxidation reaction at the anode, and hydrogen-containing gas phase components are generated at the cathode.

[0025] S5, when the predetermined energizing time is reached or the reaction decay condition is reached, the energizing is stopped, and the temperature and pressure are maintained after the energizing is stopped. After the electrochemical reaction is stopped, the system is kept stable to avoid immediate pressure release that could lead to flash evaporation, splashing and solid disturbance, thus providing a stable initial state for subsequent preferential gas phase release. S6, under the condition of retaining liquid products and residues in the batch high temperature and high pressure electrolysis reactor, the batch high temperature and high pressure electrolysis reactor is depressurized in a controlled manner. As the pressure decreases, the solubility of gas in high temperature and high pressure aqueous phase or highly dispersed phase decreases, and gaseous products are preferentially exported and collected; reducing the entrainment of liquid droplets, tar, salts and solid particles in gaseous products.

[0026] S7, after the gas phase is preferentially discharged, the intermittent high temperature and high pressure electrolysis reactor is cooled to the liquid phase collection temperature, so that water vapor, volatile organic compounds and liquid phase products are condensed, reducing the risk of high temperature discharge, and the liquid phase products or condensed products are discharged and collected to obtain relatively independent liquid phase products and reduce gas-liquid mixing. S8 discharges residual slurry, sediment, precipitated salt, or solid residue from the intermittent high-temperature and high-pressure electrolysis reactor, reducing the risk of clogging the gas phase outlet path and liquid phase collection path.

[0027] To further explain, in step S1, the material containing organic matter and water is at least one of the following: an aqueous solution containing oxidizable small molecule organic matter, a waste liquid containing multiple oxidizable organic components, an emulsion containing hydrophobic organic components, a slurry containing suspended organic particles, a waste liquid containing colloidal organic matter, or a solid-liquid mixture containing hydrothermally depolymerizable organic components.

[0028] To further explain, in step S1, the volume of the material is 20% to 90% of the reaction chamber volume of the intermittent high-temperature and high-pressure electrolysis reactor, preferably 30% to 80%, so as to reserve buffer space in the intermittent high-temperature and high-pressure electrolysis reactor.

[0029] Further explanation: In step S2, the pre-homogenization temperature is 300℃~520℃, and the pre-homogenization pressure is 15MPa~35MPa; preferably, the pre-homogenization temperature is 380℃~500℃, and the pre-homogenization pressure is 23MPa~30MPa.

[0030] To further explain, in step S3, the pre-homogenization treatment is a static heat preservation and pressure preservation treatment carried out under closed high temperature and high pressure conditions, or a heat preservation and pressure preservation treatment carried out in conjunction with the heating and pressurization process; the conditions for completing the pre-homogenization treatment include at least one of the following: a decrease in the rate of change of pressure inside the vessel, a tendency for the conductivity to stabilize, no obvious macroscopic phase separation of the material, or a decrease in the solid sedimentation rate. The tendency to stabilize means that the rate of change of the corresponding parameter is lower than a preset threshold within 1 min to 30 min. The pre-homogenization treatment is used to make the material undergo pre-dissolution, pre-dispersion, swelling, depolymerization, or phase reconstruction in a high temperature and high pressure water medium.

[0031] Further explanation: In step S4, the temperature of the electrochemical reaction window is 250℃~430℃, and the pressure of the electrochemical reaction window is 8MPa~30MPa; preferably, the temperature of the electrochemical reaction window is 300℃~400℃, and the pressure is 15MPa~28MPa.

[0032] To further explain, in step S4, electrolysis is carried out using constant current, constant voltage, constant anode potential, pulsed current, or a combination thereof; the current density is 10mA / cm² to 500mA / cm², preferably 50mA / cm² to 300mA / cm².

[0033] To further explain, in step S5, the reaction decay conditions include at least one of the following: the cell voltage increases to a preset upper limit, the system conductivity decreases to below a preset threshold, the cathode hydrogen production rate decreases to 30% to 70% of the initial hydrogen production rate, the anode potential reaches the oxygen evolution reaction enhancement threshold, the oxygen content in the gaseous products increases to a preset threshold, or the pressure change rate inside the reactor is lower than a preset value.

[0034] To further explain, in step S5, the heat preservation and pressure holding time after the power is turned off is 0.5 min to 30 min, preferably 0.5 min to 10 min, so that the gas phase components dissolved or dispersed in the continuous phase, quasi-homogeneous phase or highly dispersed phase are preferentially released or enriched in the buffer space when step S6 is performed.

[0035] To further explain, in step S6, the controlled pressure reduction rate is 0.1 MPa / min to 5 MPa / min, preferably 0.5 MPa / min to 2 MPa / min; the gaseous product is discharged when the pressure in the reactor drops to 3 MPa to 18 MPa, preferably at 8 MPa to 15 MPa.

[0036] To further explain, in step S7, the liquid phase collection temperature is 20℃~150℃, preferably 40℃~100℃.

[0037] To further explain, in step S1, a supporting electrolyte is added to the material. The supporting electrolyte is used to provide ionic conductivity within the electrochemical reaction window. When there is a risk of salting out or deposition in the system, the impact of the deposits on the electrode reaction zone or the outlet path is reduced by at least one of the following methods: reducing the concentration of the supporting electrolyte, reducing the electrolysis temperature, pulse energizing, controlled residue removal, or rinsing the reactor.

[0038] Example 2 Based on Example 1, the pre-homogeneous assisted organic matter coupling electrolysis and fractional collection method provided in this example uses an aqueous solution containing oxidizable small molecule organic matter as the material containing organic matter and water; wherein, the aqueous solution containing oxidizable small molecule organic matter is an aqueous solution containing ethylene glycol, glycerol, ethanol, glucose, formate, acetate or a combination thereof.

[0039] The type and concentration of the supporting electrolyte can be adjusted according to the conductivity of the material, corrosion risk, and salting-out risk. For example, the material is 2L of an aqueous solution containing 10wt% ethylene glycol. At the same time, 0.5mol / L KOH is added to the batch high-temperature and high-pressure electrolysis reactor as the supporting electrolyte. After sealing, the temperature is raised to 400℃ at a rate of about 5℃ / min, and the pressure is increased to 25MPa. This condition is maintained for pre-homogenization for 10min. Then, a constant current density of 150mA / cm² is applied for 30min. After stopping the energization, the temperature and pressure are maintained for 3min. Subsequently, the pressure is released to 12MPa at a rate of 1MPa / min, and hydrogen-rich gas is collected. After depressurization, the reactor is cooled to 50℃, and the liquid phase product is discharged. Finally, a small amount of residual liquid is discharged.

[0040] The gas phase, liquid phase, and residue composition can be determined by gas chromatography, liquid chromatography, ion chromatography, total organic carbon analysis, or COD analysis, respectively.

[0041] Example 3 Based on Example 1, the pre-homogeneous assisted organic matter coupling electrolysis and graded collection method provided in this example uses waste liquid containing organic acids, alcohols, aldehydes, ketones, aromatic organics, colloidal organics or suspended organic particles as the material containing organic matter and water.

[0042] For example, the material is pharmaceutical wastewater with a COD of approximately 50,000 mg / L, containing organic acids, aromatic compounds, and a small amount of suspended solids. 2 L of this wastewater is added to a reactor; the temperature is raised to 450℃, the pressure to 27 MPa, and pre-homogenized for 20 min; then energized at a current density of 200 mA / cm² for 45 min. After energization, the temperature and pressure are maintained for 5 min. The pressure is slowly released to 10 MPa to collect the gaseous products. The gaseous products can be analyzed by gas chromatography, and the liquid products can be determined by liquid chromatography, ion chromatography, total organic carbon analysis, or COD analysis. The reactor is then cooled to 60℃, and the liquid products are collected. This process achieves a high COD removal rate and recovers some small molecule acids. The residue consists of inorganic salts and a small amount of tar-like substances, which are discharged through the bottom.

[0043] For materials with high salt or solid content, dilution, filtration, sedimentation, or pre-desalination treatment can be performed before adding them to the reactor. Before energizing, pre-homogenization treatment should be carried out in subcritical, near-critical, or supercritical high-temperature and high-pressure water conditions. During energization, the current density or energizing method should be adjusted according to changes in tank voltage, conductivity, pressure, or gas generation status. After energization, the materials should be collected in stages according to the controlled pressure reduction for gas collection, cooling for liquid collection, and residue discharge sequence.

[0044] Example 4 Based on Example 1, the pre-homogeneous assisted organic matter coupling electrolysis and fractional collection method provided in this example uses a solid-liquid mixture containing organic matter and water, which is a mixture of cellulose, starch, lignin, protein, colloidal organic matter or other hydrothermally depolymerizable organic components.

[0045] For example, cellulose powder is mixed with water to form a 5wt% slurry, which is added to a reactor along with 0.3 mol / L Na₂SO₄ as the electrolyte. The mixture is heated to 500℃ and pressured at 30 MPa for 30 min to allow for complete hydrolysis and dispersion of the cellulose. Then, an electric current is applied at 150 mA / cm² for 50 min, followed by 8 min of pressure and temperature control after the current is stopped. The pressure is slowly released to 9 MPa to collect the gaseous product, which mainly contains hydrogen and a small amount of CO₂. The mixture is then cooled to 70℃ to collect the liquid product. Finally, the incompletely converted cellulose residue and inorganic salts are discharged. This method achieves a one-pot hydrolysis-electrolysis conversion of cellulose in supercritical water, which is beneficial for improving the direct utilization efficiency of solid biomass.

[0046] Before energizing, the material is first solubilized, depolymerized, and dispersed by a high-temperature and high-pressure water medium to form a highly dispersed reaction phase or a quasi-homogeneous system containing hydrothermal conversion intermediates. Then, an anodic organic matter oxidation coupled to a cathode hydrogen evolution reaction is carried out under an electrochemical reaction window. After the reaction, the gaseous products, liquid products or condensed products, as well as residual slurry or solid residues are discharged in stages according to the pressure and temperature control sequence.

[0047] Example 5 refer to Figures 2-5 This embodiment provides an intermittent high-temperature and high-pressure electrolysis reactor device for implementing the pre-homogeneous assisted organic matter coupling electrolysis and graded collection method in any of the embodiments 1 to 4. The device includes: reactor body 10, reactor cover 11, flange connection structure 20, sealing gasket 30, temperature measuring tube 40, pressure measuring interface 12, heating coil 50, heat insulation layer 60, electrode 70 and control unit 80. The electrode 70 includes an anode, a cathode and a reference electrode.

[0048] Specifically, the vessel body 10 is located beside the control unit 80 and is protected by a protective cover during use; a vessel cover 11 is provided on the top of the vessel body 10, and the vessel cover 11 is detachably connected to the vessel body 10 through a flange connection structure 20. The vessel body 10 has a reaction chamber, and the vessel cover 11 covers the reaction chamber to form a closed reaction space that can withstand high temperature and high pressure water environment; the reaction chamber is used to contain materials. In actual use, the materials occupy 20% to 90% of the volume of the reaction chamber, preferably 30% to 80%, so that a buffer space is reserved between the materials and the vessel cover 11; a sealing gasket 30 is provided between the vessel cover 11 and the vessel body 10 to maintain the sealing of the reactor during the heating and pressurization, electro-reaction, and depressurization collection processes.

[0049] Both electrode 70 and temperature measuring tube 40 are connected to the vessel lid 11. During use, the bottom ends of electrode 70 and temperature measuring tube 40 extend into the reaction chamber. Temperature measuring tube 40 is used to install temperature measuring elements. Temperature measuring elements and electrode 70 are electrically connected to control unit 80. Electrode 70 is connected to the power supply in control unit 80 through a power connection terminal. Control unit 80 controls the on / off state and current magnitude to form anodic and cathodic reaction zones under the electrochemical reaction window. Temperature measuring elements are used to obtain the current internal temperature in real time. A heating coil 50 is sleeved on the outside of vessel body 10. Heating coil 50 is electrically connected to control unit 80. Control unit 80 adjusts the temperature of the pre-homogeneous stage and electrochemical reaction stage according to the reaction progress. Combined with temperature measuring elements, precise temperature control can be achieved. Insulation layer 60 is sleeved on the outside of heating coil 50 to reduce heat loss, reduce energy consumption, and improve the reliability of temperature regulation.

[0050] The pressure measurement interface 12 is located in the vessel cover 11 and communicates with the reaction chamber. The pressure measurement interface 12 is used to connect the pressure measuring element, which is connected to the control unit 80 to acquire the real-time pressure. Optionally, a pressure relief interface connected to the safety valve interface is also provided on the vessel cover 11 to ensure the safety and reliability of the reaction.

[0051] The intermittent high-temperature and high-pressure electrolysis reactor also includes at least one outlet interface connected to a gas phase collection container, a liquid phase collection container or a residue collection container. The outlet interface is used to sequentially export gas phase products, liquid phase products or condensed products and residues under different pressure or temperature conditions. For example, a gas-liquid phase outlet is opened on the reactor cover 11, and a gas-liquid separator is used to export the gas phase and liquid phase. After the gas phase and liquid phase are exported, the solid phase is exported.

[0052] The intermittent high-temperature and high-pressure electrolysis reactor does not necessarily require a continuous flow supercritical water generator, a dual-tank product diversion structure, or a three-electrode electrochemical measurement structure. Its focus is on using the above methods to achieve pre-homogenization before energization, heat and pressure maintenance after energization, and graded collection of gas phase, liquid phase, and residue after the reaction.

[0053] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered illustrative and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the scope of the invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0054] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can be appropriately combined to form other embodiments that can be understood by those skilled in the art. The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

[0055] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A pre-homogeneous auxiliary organic matter coupling electrolysis and grading collection method, characterized in that, Includes the following steps: S1, adding materials containing organic matter and water into an intermittent high-temperature and high-pressure electrolysis reactor, wherein an anode and a cathode are provided inside the intermittent high-temperature and high-pressure electrolysis reactor; S2, under closed conditions, the material is heated and pressurized to the pre-homogeneous temperature and pre-homogeneous pressure, so that the material is in a subcritical, near-critical or supercritical high temperature and high pressure water state. S3, under conditions of no power supply or lower than the formal electrolysis current, the material is subjected to heat preservation and pressure pre-homogenization treatment to make the material form a continuous phase, quasi-homogeneous phase or highly dispersed reaction phase suitable for entering the electrode reaction zone; S4, maintain or adjust the system in the intermittent high temperature and high pressure electrolysis reactor to the electrochemical reaction window, start electrolysis, so that the organic matter or its hydrothermal conversion intermediates undergo an oxidation reaction at the anode and generate hydrogen-containing gaseous components at the cathode; S5, when the predetermined power-on time is reached or the reaction decay condition is reached, the power-on is stopped, and the heat and pressure are maintained after the power-on is stopped; S6, under the condition of retaining liquid products and residues in the batch high temperature and high pressure electrolysis reactor, the batch high temperature and high pressure electrolysis reactor is depressurized in a controlled manner, and gaseous products are preferentially exported and collected; S7, after cooling the intermittent high-temperature and high-pressure electrolysis reactor to the liquid phase collection temperature, the liquid phase product or condensed product is discharged and collected; S8 discharges residual slurry, sediment, precipitated salt, or solid residue from the intermittent high-temperature and high-pressure electrolysis reactor.

2. The pre-homogeneous auxiliary organic matter coupling electrolysis and grading collection method according to claim 1, characterized in that, The pre-homogenization temperature is 300℃~520℃, and the pre-homogenization pressure is 15MPa~35MPa; Preferably, the pre-homogenization temperature is 380℃~500℃, and the pre-homogenization pressure is 23MPa~30MPa.

3. The pre-homogeneous auxiliary organic matter coupling electrolysis and fractional collection method according to claim 1 or 2, characterized in that, The temperature of the electrochemical reaction window is 250℃~430℃, and the pressure of the electrochemical reaction window is 8MPa~30MPa; Preferably, the temperature of the electrochemical reaction window is 300℃~400℃ and the pressure is 15MPa~28MPa.

4. The pre-homogeneous auxiliary organic matter coupling electrolysis and grading collection method according to claim 1, characterized in that, The volume of the material is 20% to 90% of the effective volume of the intermittent high-temperature and high-pressure electrolysis reactor, preferably 30% to 80%, so as to reserve buffer space in the intermittent high-temperature and high-pressure electrolysis reactor.

5. The pre-homogeneous auxiliary organic matter coupling electrolysis and fractional collection method according to claim 1, characterized in that, The pre-homogeneous treatment is to keep the material statically heated and pressurized under closed high temperature and high pressure conditions, or to keep the material heated and pressurized in conjunction with the heating and pressurization process. The conditions for completing the pre-homogeneous treatment include at least one of the following: a decrease in the rate of change of pressure inside the vessel, a tendency for the conductivity to stabilize, no obvious macroscopic phase separation of the material, or a decrease in the solid sedimentation rate. The tendency to stabilize means that the rate of change of the corresponding parameter is lower than a preset threshold within 1 min to 30 min.

6. The pre-homogeneous auxiliary organic matter coupling electrolysis and grading collection method according to claim 1, characterized in that, The material containing organic matter and water is at least one of the following: an aqueous solution containing oxidizable small molecule organic matter, a waste liquid containing multiple oxidizable organic components, an emulsion containing hydrophobic organic components, a slurry containing suspended organic particles, a waste liquid containing colloidal organic matter, or a solid-liquid mixture containing hydrothermally depolymerizable organic components.

7. The pre-homogeneous auxiliary organic matter coupling electrolysis and grading collection method according to claim 1, characterized in that, In step S4, electrolysis is performed using constant current, constant voltage, constant anode potential, pulsed current, or a combination thereof; the current density is 10 mA / cm² to 500 mA / cm², preferably 50 mA / cm² to 300 mA / cm².

8. The pre-homogeneous auxiliary organic matter coupling electrolysis and grading collection method according to claim 1, characterized in that, The reaction attenuation conditions include at least one of the following: the cell voltage increases to a preset upper limit, the system conductivity decreases to below a preset threshold, the cathode hydrogen production rate decreases to 30% to 70% of the initial hydrogen production rate, the anode potential reaches the oxygen evolution reaction enhancement threshold, the oxygen content in the gaseous products increases to a preset threshold, or the rate of change of pressure inside the reactor is lower than a preset value.

9. The pre-homogeneous auxiliary organic matter coupling electrolysis and grading collection method according to claim 4, characterized in that, In step S5, the heat preservation and pressure holding time after the power is turned off is 0.5 min to 30 min, preferably 0.5 min to 10 min, so that the gas phase components dissolved or dispersed in the continuous phase, quasi-homogeneous phase or highly dispersed phase are preferentially released or enriched in the buffer space when step S6 is performed.

10. The method for pre-homogeneous assisted organic matter coupling electrolysis and fractional collection according to claim 1, characterized in that, In step S6, the controlled pressure reduction rate is 0.1 MPa / min to 5 MPa / min, preferably 0.5 MPa / min to 2 MPa / min; the gaseous product is discharged when the pressure in the reactor drops to 3 MPa to 18 MPa, preferably at 8 MPa to 15 MPa.

11. The method for pre-homogeneous assisted organic matter coupling electrolysis and fractional collection according to claim 1, characterized in that, In step S7, the liquid phase collection temperature is 20℃~150℃, preferably 40℃~100℃.

12. The method for pre-homogeneous assisted organic matter coupling electrolysis and fractional collection according to claim 1, characterized in that, A supporting electrolyte is added to the material to provide ionic conductivity within the electrochemical reaction window; When there is a risk of salting out or deposition in the system, the impact of deposits on the electrode reaction zone or the outlet path can be reduced by at least one of the following methods: reducing the concentration of the supporting electrolyte, reducing the electrolysis temperature, pulse energizing, controlled residue removal, or flushing the reactor.

13. An intermittent high-temperature and high-pressure electrolysis reactor apparatus for implementing the pre-homogeneous assisted organic matter coupling electrolysis and fractional collection method according to any one of claims 1 to 12, characterized in that, It includes a vessel body (10), a vessel cover (11), a flange connection structure (20), a sealing gasket (30), a temperature measuring tube (40), a pressure measuring interface (12), a heating coil (50), a heat insulation layer (60), an electrode (70), and a control unit (80). The vessel body (10) is provided with a reaction chamber. The electrode (70) and the temperature measuring tube (40) both extend into the reaction chamber. The vessel lid (11) covers the vessel body (10). The sealing gasket (30) is located between the vessel lid (11) and the vessel body (10). The heating coil (50) is sleeved on the outside of the vessel body (10). The heat insulation layer (60) is sleeved on the outside of the heating coil (50). The pressure measuring interface (12) is opened in the vessel lid (11) and communicates with the reaction chamber. The temperature measuring tube (40) is used to install the temperature measuring element. The pressure measuring interface (12) is used to connect the pressure measuring element. The temperature measuring element, the pressure measuring element, the heating coil (50) and the electrode (70) are all electrically connected to the control unit (80).

14. The intermittent high-temperature and high-pressure electrolysis reactor apparatus according to claim 13, characterized in that, The intermittent high-temperature and high-pressure electrolysis reactor also includes at least one outlet interface connected to a gas phase collection container, a liquid phase collection container, or a residue collection container. The outlet interface is used to export gas phase products, liquid phase products, or condensed products and residues under different pressure or temperature conditions.

Images