Method for producing hydrogen through continuous electrolysis of organic matter

Abstract

The invention provides an organic matter continuous electrolysis hydrogen production method, which relates to the field of electrolysis hydrogen production, and comprises a hydrogen production system, and the hydrogen production system mainly comprises a reaction kettle, a separation assembly composed of a fine screen and an ultrafiltration membrane, an electrolytic bath and a hydrogen collection system. The process for producing hydrogen by using the system comprises the following steps: firstly, adding a strong acid solution, an oxidation reduction medium and an organic matter into a reaction kettle, heating to 50 DEG C to reflux temperature, and oxidizing and degrading the organic matter for 0.5-1.0 hour; then organic matters are continuously added through a feeding device, materials are continuously discharged through a discharging pipe, the discharged materials are separated through a fine screen and an ultrafiltration membrane, and an obtained solution is input into an electrolytic bath at a certain flow speed for electrolysis. The medium solution regenerated by anodic oxidation is continuously conveyed to the reaction kettle for recycling, and meanwhile, protons entering the cathode through the proton exchange membrane obtain electrons and release hydrogen. By adopting the system and the method to produce hydrogen, the energy consumption, the cost and the investment of hydrogen production can be remarkably reduced, the hydrogen production efficiency is improved, and the system and the method are almost suitable for organic matters.

Description

Technical Field

[0001] This invention relates to a continuous electrolytic hydrogen production method for organic compounds, specifically a system for hydrogen production by indirect electro-oxidation coupled with direct electrolytic electrolysis, consisting of a reaction vessel, separation components, an electrolyzer, and a hydrogen collection device, and a method for producing hydrogen using the same, belonging to the field of hydrogen production. Background Technology

[0002] Hydrogen energy, as a green, low-carbon, and widely applicable secondary energy source, is gradually becoming one of the important carriers for global energy transformation and development. my country has identified hydrogen energy as an important component of the future national energy system, a key carrier for green and low-carbon transformation, and a key development direction for strategic emerging industries and future industries [Liu Xiaojie, Liu Jun, Zhou Zuxu, et al. Current development and future trends of green hydrogen production technology based on new energy sources, Modern Chemical Industry, 2025, 45(7): 33-39; Zhu Qiaoqiao, Cheng Jihua. Research progress on hydrogen energy production technology, New Energy, 2015, (12): 51-54]. Natural gas reforming is currently the most mainstream method for hydrogen production, accounting for about 95% of global hydrogen production. The second most common method is coal gasification reaction for hydrogen production. The two methods for producing hydrogen using fossil fuels have advantages such as low cost, mature technology, and large scale, but they also have high carbon emissions. During the production process, a large amount of carbon dioxide is directly emitted into the atmosphere, which runs counter to the goal of a low-carbon economy [Liu Xiaojie, Liu Jun, Zhou Zuxu, et al. Current development and future trend of green hydrogen production technology based on new energy, Modern Chemical Industry, 2025, 45(7): 33-39; Zhu Qiaoqiao, Cheng Jihua. Research progress of hydrogen energy production technology, New Energy, 2015, (12): 51-54; Li Jianlin, Li Guanghui, Ma Suliang, et al. Review of the progress and development prospects of key technologies for hydrogen production under the carbon neutrality target, Thermal Power Generation, 2021, 50(6): 1-6]. The hydrogen produced by the above methods is called gray hydrogen. Hydrogen that basically does not produce greenhouse gases during the preparation process is called green hydrogen, also known as "zero-carbon hydrogen". Green hydrogen is perfectly in line with the global carbon neutrality target. Therefore, green hydrogen is the development direction and ultimate form of hydrogen energy. In order to find efficient and inexpensive green hydrogen production methods, countries around the world have carried out a lot of research. The main methods reported are photocatalytic hydrogen production, photoelectrocatalytic hydrogen production, biomass hydrogen production, and renewable energy water electrolysis hydrogen production. Hydrogen production by electrolysis of water using renewable energy sources such as photovoltaic power generation, wind power and solar energy basically does not produce greenhouse gases. Therefore, the hydrogen produced is green hydrogen, but the cost is high and it depends on renewable energy. The method of using waste renewable energy to electrolyze water to produce hydrogen has been industrialized, but the waste renewable energy is limited. Photocatalytic hydrogen production and photoelectrocatalytic hydrogen production are still in the laboratory research stage and still face problems such as immature technology, low efficiency and high cost [Liu Xiaojie, Liu Jun, Zhou Zuxu, et al. Current development and future development trend of green hydrogen production technology based on new energy, Modern Chemical Industry, 2025, 45(7): 33-39; Huang Gesheng, Yan Jie, Shi Xiaoyu, et al. Current status and prospect analysis of new energy hydrogen production technology, Petrochemical Technology and Application, 2019, 37(5): 289-296].

[0003] Biomass is a general term for organisms derived from animals, plants, microorganisms, and the organisms they produce, excrete, and metabolize. Simply put, biomass is organic material derived from life [Luo Zhongyang. Principles and Technological Applications of Biomass Liquefaction. Beijing: Chemical Industry Press, 2013]. It is a form of energy stored in biomass as chemical energy, or energy carried by organic matter. The key characteristics of biomass are its renewability and carbon neutrality. As long as sunlight exists, biomass can be continuously produced through photosynthesis by plants; theoretically, the carbon dioxide absorbed during the growth process is roughly equivalent to the carbon dioxide released during combustion or decomposition, and it does not additionally increase the total amount of carbon dioxide in the atmosphere. In addition, biomass reserves are extremely large. According to estimates by the International Energy Agency (IEA) and other organizations, the world produces about 170-200 billion tons of biomass annually through photosynthesis. The energy contained therein is equivalent to 10-20 times the current global annual energy consumption, while the utilization rate is less than 3% [Wang Xiaohui. Clean and efficient preparation of furfural from bagasse and efficient utilization of furfural residue. Doctoral dissertation of South China University of Technology, 2019-10-15].

[0004] Based on the above characteristics of biomass and its high hydrogen content, biomass hydrogen production, as a sustainable hydrogen production technology, has received widespread attention and research in recent years. Early research on biomass hydrogen production technology involved pre-treating biomass through crushing, drying, and chemical or physical modification, and then using gasification (thermochemical hydrogen production) or microbial catalytic deoxygenation (biological hydrogen production) to produce hydrogen-rich syngas from biomass resources.

[0005] Thermochemical hydrogen production technology has attracted much attention due to its ability to efficiently process biomass with low water content and specific types of waste, while biological hydrogen production technology is more suitable for biomass or waste with higher water content, especially organic waste such as kitchen waste and feces. However, both have some problems: Thermochemical methods have the following problems: the water content of biomass is generally as high as 50-90%, so the thermochemical method requires pre-drying of this biomass, which consumes a lot of energy; the temperature and pressure of the production process are as high as 300-1100℃ and 15-50 atmospheres, respectively, resulting in large equipment investment and high operating costs; it produces pollutants such as tar, flue gas, and fly ash, leading to secondary pollution; and a certain scale is required to achieve economic benefits, but large-scale supply of raw materials is difficult. Biological methods mainly produce biogas, but have problems such as slow reaction rate and hydrogen production rate of less than 20% [Liu Xiaojie, Liu Jun, Zhou Zuxu, et al. Current development and future trend of green hydrogen production technology based on new energy, Modern Chemical Industry, 2025, 45(7): 33-39; Huang Gesheng, Yan Jie, Shi Xiaoyu, et al. Analysis of the current status and prospects of new energy hydrogen production technology, Petrochemical Technology and Application, 2019, 37(5): 289-296].

[0006] To address the problems existing in biomass thermochemical and biological hydrogen production technologies, Deng Yulin et al. invented a method and system for direct electrolysis of biomass to produce hydrogen. This method is a novel biomass hydrogen production process that utilizes a redox couple (also known as a medium) as an electrocatalyst. The oxidized medium oxidizes and degrades the biomass, while the reduced medium acts as a charge carrier, transferring its electrons to the anode. Under the influence of an applied electric field, the anode loses electrons and regenerates the oxidized medium (the regenerated medium is recycled). Simultaneously, hydrogen protons captured from the biomass are released. These protons pass through a proton exchange membrane into the cathode, where they gain electrons and are released as hydrogen gas. Compared to water electrolysis, biomass-based electrolysis does not require the addition of any precious metal catalysts at the anode, and boasts low energy consumption and high hydrogen evolution efficiency. It can directly electrolyze almost all biomass raw materials to obtain high-purity hydrogen (over 99.99%), possessing significant application value [Deng Yulin, Liu Wei, Du Xu, et al. A method and system for direct electrolysis of biomass to produce hydrogen, Chinese Patent, CN106676564B, 2019-04-23]. This method can be used not only for biomass electrolysis to produce hydrogen but also for various organic materials, especially organic waste and wastewater containing organic matter, such as garbage [Liu Wei, Shao Xuxin, Zhao Yongdong, et al. A method and system for two-step oxidation electrochemical degradation of garbage and / or its leachate to produce hydrogen, Chinese Patent, CN115254870B, 2024-03-19], biomass refining organic waste, and flue gas [Liu Wei. A dual-catalyst system and method for electrochemical degradation of biomass refining organic waste to produce hydrogen]. [Chinese Patent, CN114182294B, 2023-11-14; Liu Wei, Yin Xinbin, Zhao Yongdong. Method for combined electro-chemical graded treatment of biomass refining flue gas to produce hydrogen, Chinese Patent, CN117385415A, 2024-01-12], and electrolytic hydrogen production from organic wastewater [Liu Wei, Yin Xinbin, Zhao Yongdong, et al. Method for producing hydrogen from organic waste in ethylene glycol production by electrochemical degradation, Chinese Patent, CN120138649A, 2025.06.13], etc.

[0007] Despite this, the method also suffers from problems such as high investment, high total energy consumption, and low overall efficiency. The main reason is that the current process is asynchronous and intermittent; that is, the oxidative degradation of biomass and other organic matter and the electrolytic hydrogen production are not simultaneous and continuous. Instead, the solution after the material's oxidative degradation is completed enters the electrolysis system for hydrogen production and media regeneration, and the oxidation degradation temperature is inconsistent with the electrolysis temperature. This asynchronous intermittent process has the following disadvantages: due to the influence of various factors such as solubility, the concentration of the oxidized medium generally cannot be too high. Therefore, for each reaction, the amount of organic matter that can be oxidized and degraded is limited, resulting in a very low concentration of biomass and other organic matter during oxidative degradation, mostly around 1%, and a single-stage degradation rate of only about 50%. Some organic matter, especially biomass, is insoluble in water and degrades incompletely, thus the degraded material contains many fine and colloidal particles. To prevent these particles from clogging the electrodes and proton exchange membranes, the degraded material must be filtered before entering the electrolysis system for electrolysis. Due to the presence of colloidal particles, filtration is difficult and time-consuming, resulting in a low temperature of the mother liquor (anolyte), mostly below 50°C. Furthermore, the proton exchange membrane has poor temperature resistance, with electrolysis temperatures generally below 50°C, while oxidative degradation temperatures are generally above 90°C, creating a mismatch. The medium is essentially an electrocatalyst, and the intermittent operation means that although the medium can be regenerated, it cannot be regenerated in a timely manner, and its catalytic characteristics are not fully realized. As oxidation proceeds, the concentration of the oxidized medium decreases, slowing down the rate of organic matter oxidation and degradation. These drawbacks lead to high equipment investment, high energy consumption, and low efficiency. Currently, the energy consumption of the process is mainly consumed in heating and filtering the material during oxidative degradation, with approximately 99% of the heating energy consumption used to heat the reaction medium—water [Wang Guizhou. 4E Evaluation of Biomass Direct Electrolysis Hydrogen Production Technology Based on the Whole Life Cycle, Master's Thesis, North China Electric Power University, 2020-04]. Summary of the Invention

[0008] To address the above problems, a detailed theoretical analysis and calculation were conducted. The conclusion is that if the oxidative degradation and electrolysis of biomass and other organic matter are carried out simultaneously and continuously, the above problems can be solved. The specific reasons are as follows: Using a simultaneous and continuous process, and replacing conventional filtration devices with fine sieves and ultrafiltration membrane separation components, the reaction medium does not need repeated heating and filtration, thus significantly reducing the energy consumption of oxidative degradation; with a simultaneous and continuous process, the medium can be regenerated in a timely manner, resulting in a high and essentially constant concentration of the medium throughout the reaction process, thus significantly increasing the rate of oxidative degradation and the degree of material degradation; continuous feeding significantly increases the concentration of biomass and other organic matter during oxidative degradation, thus significantly improving equipment utilization efficiency and reducing equipment investment. Based on the above analysis, this invention provides a method for continuous electrolytic hydrogen production from organic matter.

[0009] To achieve the aforementioned technical features, the present invention aims to provide a continuous electrolytic hydrogen production method for organic matter, comprising an electrolytic hydrogen production system. The electrolytic hydrogen production system consists of a reaction vessel (which also serves as an anolyte storage tank) equipped with a continuous feed device and a discharge pipe, a separation assembly consisting of a fine screen and an ultrafiltration membrane, an electrolytic cell, a catholyte storage tank, and a hydrogen collection device. The separation assembly consisting of the fine screen and ultrafiltration membrane replaces conventional filtration devices. The reactants pass through the fine screen and ultrafiltration membrane sequentially, respectively trapping fine particles and colloidal particles to obtain a clear oxidative degradation solution. The fine screen effectively traps fine particles primarily to prevent them from clogging the ultrafiltration membrane. The process of continuous hydrogen production using an electrolytic hydrogen production system is as follows: First, a strong acid solution, an oxidized medium, and organic matter are added to a reactor and heated to 50°C to reflux temperature (approximately 103°C) to oxidize and degrade the organic matter for 0.5 to 1.0 hours. Then, organic matter is continuously added through a continuous feeding device at a rate consistent with the rate of oxidation and degradation. The material is continuously discharged through an upper discharge pipe. The discharged material is separated by a fine screen and ultrafiltration membrane of the separation component or, before being discharged, is separated into fine and colloidal particles by a fine screen and ultrafiltration membrane of the built-in separation component. The resulting clear solution is pumped into the anode area of ​​the electrolytic cell at a certain flow rate. At the same time, a strong acid solution of the same concentration is supplied to the cathode area of ​​the electrolytic cell. The medium solution regenerated by the anode oxidation is continuously pumped back to the reactor for recycling. Meanwhile, protons released from the anode enter the cathode area through a proton exchange membrane and gain electrons at the cathode to release hydrogen. The released hydrogen is collected using conventional methods.

[0010] Preferably, the continuous feeding device is a conventional feeding device. For powder materials, a single screw feeder is preferred, and for liquid materials, a high-level tank or metering pump is preferred.

[0011] Preferably, the upper discharge pipe is located at the top of the reactor, close to the liquid surface of the material.

[0012] Preferably, the fine screen is a corrosion-resistant screen of 400 to 1500 mesh, more preferably an 800-1000 mesh polyurethane screen, and the ultrafiltration membrane is a high-temperature resistant ultrafiltration membrane. When the material temperature is below 95 ℃, an ultrafiltration membrane made of polysulfone or polyethersulfone is preferred, while when the material temperature is above 95 ℃, a ceramic ultrafiltration membrane is preferred.

[0013] Preferably, the fine screen and ultrafiltration membrane separation assembly can be installed inside the reactor or in an overflow tank outside the reactor. If installed inside the reactor, it is preferably fixed to the upper part of the inner wall of the reactor, but below the liquid level of the material, and installed horizontally around the inner wall of the reactor. A discharge pipe with a valve is installed in the area of ​​the reactor wall where the separation assembly is installed. If installed outside the reactor, it can be installed vertically in the middle of the overflow tank, dividing the overflow tank into two zones, each equipped with a discharge pipe with a valve. The area of ​​the screen and ultrafiltration membrane is determined according to the feed rate of the anolyte (oxidative degradation solution). The total rate at which the oxidative degradation solution permeates through the screen and ultrafiltration membrane must be greater than the feed rate of the anolyte (oxidative degradation solution), and this rate is the product of the flux of the ultrafiltration membrane and the ultrafiltration membrane itself. Preferably, the electrolytic cell is a dual-chamber electrolytic cell consisting of an anode, a proton exchange membrane, and a cathode. When the electrolyte temperature is less than 80 °C, a perfluorosulfonic acid resin proton exchange membrane is used, while when the electrolyte temperature is greater than 80 °C, a perfluorosulfonic acid resin proton exchange membrane composed of nanoparticles is used.

[0014] Preferably, all devices used in the system must have good resistance to strong acid solutions, and the reaction vessel, overflow tank, electrolytic cell, cathode liquid storage tank, and liquid conveying pipeline must have good thermal insulation performance.

[0015] Preferably, the organic matter is various biomass, domestic waste, and industrial organic waste.

[0016] Preferably, the strong acid solution is a sulfuric acid solution, a phosphoric acid solution, a hydrochloric acid solution, or a nitric acid solution, with a molar concentration of 1–8 mol / L. Sulfuric acid and phosphoric acid solutions with a molar concentration of 2–5 mol / L are preferred.

[0017] Preferably, the redox medium includes various metallic media, non-metallic media, organic media, and organometallic compound media, such as Fe. 3+ / Fe 2+ Ag + / Ag、Mn 4+ / Mn 2+ Mn 3+ / Mn 2+ Co 3+ / Co 2+ Ce 4+ / Ce 3+ Cr 6+ / Cr 3+ POM (polyoxometalate) / H-POM, TEMPO + / TEMPO (2,2,6,6-Tetramethylpiperidine N-oxide), AQ + / AQ (anthraquinone), Br - / Br2、 I- / I2, and the above-mentioned media composition, wherein the molar ratio of acid to media is 1:0.01 to 0.5, and the mass ratio of media to organic matter at the time of initial feeding is 1:0.2 to 2.0.

[0018] Preferably, the current density during the electrolysis process is 20–200 mA / cm². 2 .

[0019] The present invention has the following beneficial effects: The present invention discloses a continuous electrolytic hydrogen production method for organic matter. By simultaneously and continuously coupling the oxidative degradation of organic matter with the electrolytic regeneration of the medium, and with the aid of suitable separation components, it fundamentally solves the technical defects of existing intermittent electrolytic hydrogen production processes, such as high energy consumption, low efficiency, large equipment investment, and insufficient medium utilization. Simultaneously, it achieves a green, continuous, and large-scale hydrogen production process. Specific beneficial effects are as follows: 1. Significantly reduce total system energy consumption and reduce energy waste.

[0020] In existing batch processes, the oxidative degradation of organic matter requires temperatures above 90°C. After degradation, the material must be filtered and cooled to below 50°C before entering the electrolyzer. The regenerated medium solution after electrolysis then needs to be reheated back into the reactor. This repeated heating and cooling of the reaction medium (water) results in approximately 99% energy waste. This invention employs a simultaneous continuous process. The oxidative degradation liquid in the reactor directly enters the electrolyzer after passing through a separation component. Furthermore, the reactor, electrolyzer, and transport pipelines within the system all possess excellent insulation properties, enabling heat recycling. Simultaneously, this invention uses a fine screen + ultrafiltration membrane separation component instead of traditional filtration devices, eliminating the need for cooling and filtration of the material, avoiding heat loss during filtration, and significantly reducing the repeated energy consumption of material heating. In addition, the continuous process allows the medium to be regenerated in the electrolyzer and returned to the reactor in a timely manner, maintaining a high concentration and stable state of the oxidized medium in the reactor, increasing the rate of organic matter oxidative degradation, shortening the reaction time, and further reducing the energy consumption per unit of hydrogen production.

[0021] 2. Improve the degradation rate of organic matter and the efficiency of hydrogen production, and increase the utilization rate of equipment.

[0022] In existing batch processes, the concentration of the oxidized medium gradually decreases as the reaction proceeds, leading to a continuous decline in the degradation rate of organic matter. Furthermore, due to limitations in medium solubility, the organic matter concentration in the reactor is typically only around 1%, resulting in a single-pass degradation rate of only about 50%. Simultaneously, batch operations require alternating start-ups and shutdowns of the reactor and electrolyzer, resulting in long periods of equipment downtime. This invention, through synchronous continuous coupling, allows the oxidized medium regenerated from the electrolyzer anode to be returned to the reactor in real time, maintaining a consistently high concentration of oxidized medium within the reactor. This provides sufficient oxidant for the oxidative degradation of organic matter, significantly improving the degradation reaction rate. In continuous feeding mode, the organic matter concentration in the reactor can be increased to 5%–10%, greatly increasing the throughput per unit volume of the reactor. Moreover, continuous operation enables uninterrupted operation of the entire process, from reactor degradation and separation component filtration to hydrogen production in the electrolyzer, eliminating downtime caused by equipment start-ups and shutdowns.

[0023] 3. Optimize separation effect and extend the service life of key components of electrolytic cell.

[0024] In existing batch processes, the degraded material contains a large number of fine and colloidal particles, which are difficult to remove efficiently using traditional filtration methods. This easily leads to electrode blockage and proton exchange membrane contamination in the electrolyzer, resulting in decreased operational stability and frequent replacement of key components. This invention employs a composite separation component consisting of a fine sieve and an ultrafiltration membrane. The fine sieve pre-retains larger solid particles, while the ultrafiltration membrane further retains colloidal particles, achieving precise purification of the degradation solution. Simultaneously, the separation component can be integrated or overflow-type to adapt to the separation requirements of different material systems, and the separation process is carried out at the original temperature of the material, avoiding colloidal particle aggregation caused by temperature changes and improving separation efficiency. Furthermore, the purified anolyte enters the electrolyzer, effectively preventing electrode and proton exchange membrane blockage and contamination.

[0025] 4. Improve media utilization and reduce catalyst costs.

[0026] As electrocatalysts, redox media rely on the efficient cycling of oxidized and reduced states for catalytic performance. In existing batch processes, the oxidative degradation and electrolytic regeneration of the media are not synchronized, and the reduced media cannot be regenerated into the oxidized state in time, leading to a decrease in catalytic activity in the later stages of the reaction. Furthermore, in batch operations, the media is easily lost with filter residue. The simultaneous continuous process of this invention achieves a closed-loop circulation of the media: after the reduced media is anolyzed and regenerated into the oxidized state in the electrolytic cell, it is immediately returned to the reactor to participate in the degradation of organic matter, with no retention or loss throughout the process, maintaining the high catalytic activity of the media; and during the continuous circulation process, the media loss is only less than 5% of that in batch processes.

[0027] 5. Expand the scope of application of raw materials to realize the resource utilization of organic waste.

[0028] The continuous process of this invention is adaptable to organic raw materials of different forms and concentrations, including various biomass, municipal solid waste, and industrial organic waste. The synergistic effect of the strongly acidic reaction system and the high-concentration oxidizing medium can effectively degrade recalcitrant organic waste that is difficult to treat with traditional processes. Simultaneously, the continuous feeding and discharging modes allow for flexible adjustment of the raw material processing volume to meet different scales of hydrogen production needs. Furthermore, during the hydrogen production process, the hydrogen element in the organic matter is efficiently converted into high-purity hydrogen gas, realizing the transformation of organic waste into valuable resources. Attached Figure Description To more clearly describe the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 This invention provides a schematic diagram of a system structure for continuous electrolytic hydrogen production from organic matter.

[0030] In the attached diagram, the components represented by each number are as follows: 1 is a continuous feeder, 2 is a stirrer, 3 is a pipeline, 4 is an electrolytic cell, 5 is a power switch, 6 is a power supply, 7 is a gas-liquid separator, 8 is a safety valve, 9 is a hydrogen detector, 10 is a gas flow meter, 11 is a hydrogen purification column, 12 is a gas collecting bottle, 13 is a reaction vessel, 14 is a valve, 15 is a separation component, 16 is a diaphragm pump, 17 is a pressure gauge, 18 is a thermometer, 19 is a diaphragm pump, 20 is a liquid flow meter, 21 is a level switch, and 22 is a cathode liquid storage tank. Figure 2 This is a schematic diagram of the process flow.

[0031] Figure 3 A schematic diagram of a reactor for installing a fine screen and an ultrafiltration membrane separation assembly.

[0032] In the attached diagram, the components represented by each number are as follows: 1 is the continuous feeder, 2 is the agitator, 3 is the reactor, 4 is the separation assembly, 5 is the upper discharge valve, 6 is the ultrafiltration membrane, 7 is the support material, 8 is the fine screen, 9 is the jacket, and 10 is the upper discharge valve. Figure 4 A schematic diagram of an overflow tank for installing a fine screen and an ultrafiltration membrane separation assembly.

[0033] In the attached diagram, the components represented by each number are as follows: 1 is the overflow trough, 2 and 4 are the feed pipes, 3 and 5 are the discharge pipes, 6 is the fine screen, 7 is the ultrafiltration membrane, and 8 is the support material. Detailed Implementation

[0034] The preferred embodiments of the present invention are described below. It should be understood that the preferred embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0035] Unless otherwise stated, all percentages used in this invention are mass percentages.

[0036] The ethylene glycol distillation residue was provided by Sino-Korean (Wuhan) Petrochemical Co., Ltd. It contains approximately 85% tetraethylene glycol, approximately 10% pentaethylene glycol, and approximately 5% other substances, with a total carbon content of 49.5% and a hydrogen content of 9.25%.

[0037] The bagasse was provided by Pingxiang Huatan New Energy Technology Co., Ltd. The dry basis has a total carbon content of 47.8%, a hydrogen content of 5.95%, and a fineness of -80 mesh.

[0038] The oxidative degradation rate of organic matter was determined using the COD method.

[0039] The hydrogen content of the product was analyzed by gas chromatography using a Shimadzu GC-14C gas chromatograph equipped with a thermal conductivity detector (TCD) and a gas injection valve. The analytical conditions were as follows: feed was via a gas injection valve, with helium as the carrier gas at a flow rate of 35 mL / min; a 2 m x 1 / 8" x 2.0 mm (length x outer diameter x inner diameter) 5A molecular sieve column was used; the injection port temperature was 120℃, the detection temperature was 130℃, and the column temperature was 60℃; the bridge current was 120 mA; and the data acquisition time was 35 min. Chromatographic data were processed using a Zhejiang University Intelligent N2000 data workstation, and the hydrogen content was calculated using the area normalization method.

[0040] The hydrogen yield is the ratio of actual hydrogen production to input materials. The mass of hydrogen produced is calculated based on the volume of H2 collected. Under standard atmospheric pressure, 1g of hydrogen has a volume of 11.2L.

[0041] Example 1: A continuous electrolytic hydrogen production method for organic compounds comprises the following components: a reaction flask (which also serves as an anolyte storage tank), a 250 mL four-necked flask equipped with a mechanical stirrer, condenser, thermometer, dropping funnel, or a glass single-screw feed pipe and discharge pipe; and a separation assembly consisting of an 800-mesh polyurethane screen and a polyethersulfone ultrafiltration membrane, separated by graphite felt and fixed with plastic parts and metal plates. Both metal plates are equipped with inlets and outlets. The screen and ultrafiltration membrane have an area of ​​20 cm². 2 The fuel cell stack consists of a cathode electrode plate, an anode electrode plate, a proton selective membrane, a current collector plate, and end plates. Graphite plate electrodes are used, with the anode filled with graphite felt and the cathode plated with platinum, approximately 1 µm thick. The electrode plate area is 38.5 cm². 2A 250mL glass bottle with a stopper serves as both a cathode liquid storage tank and a dehydrogenation tank. The stopper is equipped with an inlet pipe, an outlet pipe, and a hydrogen exhaust pipe. H2 is collected by water displacement. The oxidative degradation solution (anolyte) and cathode liquid are transported using a peristaltic pump, with the transport pipe being a 4×6mm silicone rubber tube.

[0042] Example 2: A method for continuous electrolytic hydrogen production from organic matter, using the hydrogen production system of Example 1, is as follows: First, 200 mL of a 5 mol / L sulfuric acid solution is added to the reaction flask, then 0.2 mol (17.4 g) of MnO2 is slowly added (the molar ratio of acid to medium is 1:0.20), followed by 8 g of ethylene glycol distillation residue (the mass ratio of medium to residue is 1:0.73). The mixture is heated to 70℃~80℃ to oxidize and degrade the ethylene glycol distillation residue. After 0.5 hours, the material changed from black to pink and transparent. Then, ethylene glycol distillation residue was continuously added through a dropping funnel at a rate of 3g per hour. Simultaneously, the valve of the discharge pipe of the reaction flask was opened, and the outflowing material passed through a fine sieve / ultrafiltration membrane separation unit, which retained very few fine and colloidal particles. The resulting clear material was fed into the anode zone of the electrolytic cell via a peristaltic pump at a flow rate of approximately 0.5 L / min. Simultaneously, a 4 mol / L sulfuric acid solution was fed into the cathode zone via a peristaltic pump at a flow rate of approximately 0.5 L / min. The electrolyte temperature was 75±5℃ and the current density was 200±0.2 mA / cm². 2 Electrolysis was performed under specific conditions. During electrolysis, the medium regenerated at the anolyte was pumped to the reaction flask via a peristaltic pump. The protons produced gained electrons at the cathode and released hydrogen. Hydrogen was collected by water displacement. The above process was carried out continuously for 24 hours, with a total of 80g of ethylene glycol distillation residue added. The measured oxidation degradation rate of the ethylene glycol distillation residue was 98.6%. A total of 76.2L of hydrogen was collected, with a mass of 6.8g (theoretical hydrogen production was 7.4g), and the hydrogen production rate was 91.9%. Gas chromatography analysis showed that the hydrogen content was 99.95%.

[0043] Example 3: A method for continuous electrolytic hydrogen production from organic matter, using the hydrogen production system of Example 1, is as follows: First, 200 mL of a 2 mol / L phosphoric acid solution is added to the reaction flask, then 0.01 mol (18.25 g) of phosphomolybdic acid (POM) is slowly added (the molar ratio of acid to POM is 1:0.025), followed by 8 g of bagasse (dry basis, the mass ratio of medium to bagasse is 1:0.73). The mixture is heated to 70℃~80℃ to oxidize and degrade the bagasse for 0.5 h, during which the material changes from yellowish-brown to a dark blue solution. Subsequently, bagasse is continuously added through a glass single-screw feed pipe at a rate of 3 g per hour. At the same time, the valve of the discharge pipe of the reaction flask is opened, and the outflowing material is separated by a screen / ultrafiltration membrane separation component to retain fine and colloidal particles. The resulting clear material is fed into the anode area of ​​the electrolytic cell at a flow rate of 0.5 L / min by a peristaltic pump, while a 2 mol / L phosphoric acid solution is fed into the cathode area at a flow rate of approximately 0.5 L / min by a peristaltic pump. At an electrolyte temperature of 75±5℃ and a current density of 200±0.2mA / cm² 2 Electrolysis was performed under specific conditions. During electrolysis, the medium regenerated at the anolyte was pumped to the reaction vessel via a peristaltic pump, and the protons produced gained electrons at the cathode, releasing hydrogen. Hydrogen was collected by water displacement. The above process was carried out continuously for 24 hours, with a total of 80g of sugarcane bagasse (dry basis) added. The measured oxidative degradation rate of sugarcane was 70.6%, and a total of 34.6L of hydrogen was collected, with a mass of 3.09g (theoretical hydrogen production of 4.76g), resulting in a hydrogen production rate of 64.9%. Gas chromatography analysis showed that the hydrogen content was 99.95%.

[0044] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for producing hydrogen by continuous electrolysis of an organic substance, characterized by, The electrolytic hydrogen production system comprises a reaction kettle with a continuous feeding device and an upper discharge pipe, a separation assembly composed of a fine screen and an ultrafiltration membrane, an electrolytic cell, a cathode liquid storage tank and a hydrogen collecting device. The process of continuously producing hydrogen by the system is as follows: first, strong acid solution, oxidized medium and organic matter are added into the reaction kettle, heated to 50 DEG C to reflux temperature, and the organic matter is oxidized and degraded for 0.5-1.0 h, then the organic matter is continuously added through the continuous feeding device at a rate consistent with the oxidation and degradation rate, and discharged continuously through the upper discharge pipe, the discharged material is separated or removed through the fine screen and the ultrafiltration membrane of the separation assembly, the obtained clear solution is pumped into the anode area of the electrolytic cell at a certain flow rate, and the same concentration of strong acid solution is supplied to the cathode area of the electrolytic cell, the anode oxidized and regenerated medium solution is continuously supplied to the reaction kettle through the pump for recycling, at the same time, the protons released by the anode enter the cathode area through the proton exchange membrane, and the hydrogen is released in the cathode by obtaining electrons, and the released hydrogen is collected by using conventional methods.

2. The method of claim 1, wherein the organic material is selected from the group consisting of methanol, ethanol, propanol, butanol, acetone, acetic acid, formic acid, and mixtures thereof. The upper discharge pipe is located at the upper part of the reaction kettle and is close to the liquid surface of the material.

3. The method of claim 1, wherein the organic material is selected from the group consisting of methanol, ethanol, propanol, butanol, acetone, acetic acid, formic acid, and mixtures thereof. The fine screen is a corrosion-resistant screen with a mesh size of 400-1500, and the ultrafiltration membrane is a high-temperature resistant ultrafiltration membrane. The separation assembly composed of the fine screen and the ultrafiltration membrane can be installed in the reaction kettle or in the overflow tank outside the reaction kettle. If installed in the reaction kettle, it is fixed to the upper part of the inner wall of the reaction kettle below the liquid surface of the material, and is installed horizontally around the inner wall of the reaction kettle. A discharge pipe with a valve is installed in the area of the kettle wall where the separation assembly is installed. If installed outside the reaction kettle, it is installed vertically in the middle part of the overflow tank, which divides the overflow tank into two areas, each of which is provided with a discharge pipe with a valve. The area of the fine screen and the ultrafiltration membrane is determined according to the feeding rate of the anode electrolyte. The total rate of the oxidized and degraded liquid passing through the fine screen and the ultrafiltration membrane must be greater than the feeding rate of the anode electrolyte, and the rate is the product of the flux of the ultrafiltration membrane and the area of the ultrafiltration membrane.

4. The method of claim 1, wherein the organic material is selected from the group consisting of methanol, ethanol, propanol, butanol, acetone, acetic acid, formic acid, and mixtures thereof. The electrolytic cell is a double-chamber electrolytic cell composed of an anode, a proton exchange membrane and a cathode. When the temperature of the electrolyte is less than 80 DEG C, a perfluorosulfonic acid resin proton exchange membrane is used, and when the temperature of the electrolyte is greater than 80 DEG C, a nano-particle composite perfluorosulfonic acid resin proton exchange membrane is used.

5. The method of claim 1, wherein the organic material is selected from the group consisting of methanol, ethanol, propanol, butanol, acetone, acetic acid, formic acid, and mixtures thereof. All devices used in the electrolytic hydrogen production system must have good corrosion resistance to strong acid solution. The reaction kettle, the overflow tank, the electrolytic cell and the cathode liquid storage tank and the liquid conveying pipeline must have good heat preservation performance.

6. The method of claim 1, wherein the organic material is selected from the group consisting of methanol, ethanol, propanol, butanol, acetone, acetic acid, formic acid, and mixtures thereof. The organic matter is various biomass, household garbage and industrial organic waste.

7. The method of claim 1, wherein the organic material is selected from the group consisting of methanol, ethanol, propanol, butanol, acetone, acetic acid, formic acid, and mixtures thereof. The strong acid solution is sulfuric acid solution, phosphoric acid solution, hydrochloric acid solution and nitric acid solution, and the molar concentration is 1-8 mol / L.

8. The method of claim 1, wherein the organic material is selected from the group consisting of methanol, ethanol, propanol, butanol, acetone, acetic acid, formic acid, and mixtures thereof. The oxidation-reduction medium includes various metal media, non-metal media, organic media and metal-organic compound media, as well as combinations of the above media. The molar ratio of acid to medium is 1:0.01-0.5, and the mass ratio of medium to organic matter at the first feeding is 1:0.2-2.

0.

9. The method of claim 1, wherein the organic material is selected from the group consisting of methanol, ethanol, propanol, butanol, acetone, acetic acid, formic acid, and mixtures thereof. The current density in the electrolysis process is 20-200 mA / cm 2 .

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