Preparation and processing integrated innovative hydrogen energy preparation method

Abstract

The invention discloses a preparation and processing integrated innovative hydrogen energy preparation method, which relates to the technical field of hydrogen energy preparation, and comprises the following steps: purifying hydrogen in by-products of an industrial park by using a pressure swing adsorption technology, producing hydrogen by using biomass gasification-reforming, compressing the purified hydrogen, feeding the compressed hydrogen into a hydrogenation system, and feeding the compressed hydrogen into a hydrogen storage system. After the whole electrolytic tank is assembled, renewable energy sources are used for driving electrolysis of water to produce hydrogen, and automatic control and an intelligent algorithm are used for monitoring, regulating and controlling the hydrogen production and hydrogenation process in real time. The yield and the operation state of the hydrogen production link are adjusted in real time, when the hydrogen demand quantity of the hydrogen refueling station is increased, the system can automatically increase the load of the hydrogen production equipment and improve the hydrogen yield, when the demand quantity is reduced, the operation power of the hydrogen production equipment is properly reduced, excessive production is avoided, and the operation efficiency of the whole hydrogen energy system can be improved through the cooperative control mechanism.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen energy preparation, and in particular to an innovative hydrogen energy preparation method integrating production and processing. Background Art

[0002] As the global demand for clean energy grows to cope with climate change and reduce dependence on traditional fossil energy, hydrogen energy, as a clean, efficient and high-energy-density energy carrier, has received widespread attention. The energy density of hydrogen energy is as high as 142MJ / kg, which is about three times that of gasoline (about 46MJ / kg), and the product after combustion or reaction is mainly water, with almost zero emissions. Under the general trend of energy transformation, hydrogen energy is regarded as an important bridge connecting renewable energy and traditional energy systems, and is expected to play a key role in transportation, distributed power generation, energy storage and other fields.

[0003] The existing integrated hydrogen production lacks an effective intelligent control system, making it difficult to accurately regulate the output and operating status of the hydrogen production process based on the real-time hydrogen demand of the hydrogen refueling station. When the hydrogen refueling demand changes, the load of the hydrogen production equipment cannot be adjusted in time, which can easily lead to overproduction or insufficient supply, resulting in energy waste and low operating efficiency. To this end, we propose an innovative hydrogen production method that integrates production and refueling. Summary of the invention

[0004] The purpose of the present invention is to provide an innovative hydrogen energy preparation method with integrated production and addition.

[0005] In order to solve the problems raised in the above background technology, the present invention provides the following technical solutions: an innovative hydrogen energy preparation method with integrated production and addition, comprising purifying hydrogen from by-products generated in an industrial park, using biomass as a hydrogen raw material, and utilizing renewable energy to drive water electrolysis to produce hydrogen. The specific operating steps of the innovative hydrogen energy preparation method with integrated production and addition are as follows: Step 1: Purify hydrogen from by-products in industrial parks using pressure swing adsorption technology; Step 2: Produce hydrogen by biomass gasification-reforming, compress the purified hydrogen and send it to the hydrogenation system; Step 3: preparing bipolar plate flow field and proton exchange membrane; Step 4: coating the prepared nanocatalyst on the electrode surface; Step 5: After the electrolyzer is assembled as a whole, renewable energy is used to drive water electrolysis to produce hydrogen; Step 6: Use automated control and intelligent algorithms to monitor and regulate the hydrogen production and hydrogenation processes in real time.

[0006] As a further solution of the present invention: in the step 1, in the industrial park, the by-products of industrial production contain 50%-80% hydrogen, and are also mixed with nitrogen, carbon monoxide, carbon dioxide and methane impurity gases. The gas in the by-products is separated by pressure swing adsorption technology, and the by-products are added to an adsorption tower filled with an adsorbent. The adsorption tower adopts a multi-tower series connection method, the pressure in the adsorption tower is set to 1MPa-3MPa, the temperature is set to 40°C-60°C, the adsorbent is selected from activated carbon, molecular sieve and activated alumina, and the adsorbent is filled in the adsorption tower bed layer using a mixed filling method. When the by-product passes through the adsorbent bed layer, the adsorbent can The nitrogen, carbon monoxide, carbon dioxide and methane in the by-products are selectively adsorbed, and the hydrogen can be discharged from the top of the adsorption tower through the adsorbent bed to obtain purified hydrogen. When the adsorbent reaches saturation for the adsorption of impurity gases, the pressure equalization and pressure reduction operation is started to reduce the pressure in the adsorption tower to 0.1MPa-0.3MPa at a rate of 0.05MPa / min-0.1MPa / min, and the high-pressure gas is pressure-balanced with other low-pressure adsorption towers. After the pressure is balanced, the release valve of the adsorption tower is opened to discharge the remaining hydrogen in the tower under its own pressure. The purified high-purity hydrogen is pressurized and added to the high-pressure hydrogen storage tank for storage.

[0007] As a further solution of the present invention: In the step 2, crop straw and wood chips are added to the fluidized bed gasifier by a screw feeder for gasification reaction, the feeding speed is set to 100kg / h-500kg / h, the temperature in the fluidized bed gasifier is set to 800℃-1000℃, and the gasifier is evenly distributed in the furnace at a speed of 1m / s-3m / s through the air distribution plate, the gasifier is selected from oxygen-water vapor mixed gas, the ratio of water vapor to oxygen is set to 2-5:1, and the oxidation reaction formula of oxygen in the gasifier contacting the coke produced by pyrolysis is: ; Under the high temperature environment provided by the oxidation reaction, the reduction reaction formula of water vapor contacting the coke produced by pyrolysis is: ; The conversion reaction formula of carbon monoxide generated by the reduction reaction and water vapor is: ; The reaction generates a synthesis gas rich in hydrogen, carbon monoxide and carbon dioxide, which is then added to a fixed-bed reforming reactor filled with a Ni / Al2O3 catalyst with a particle size of 2mm-5mm. The temperature is set to 300℃-500℃, the pressure is set to 1MPa-3MPa, and the space velocity of the synthesis gas in the fixed-bed reforming reactor is set to 1000h -1 -3000h -1, so that the carbon monoxide in the synthesis gas reacts with water vapor to generate hydrogen and carbon dioxide, and then the reformed synthesis gas is added to the water scrubber for purification. The water scrubber is filled with ball ring packing, and the spray volume is set to 1m 3 / h-5m 3 / h, the solid particles in the synthesis gas are removed after 20s-30s of gas-liquid contact, and then the membrane separation technology is used to remove the residual carbon monoxide, carbon dioxide and methane in the synthesis gas. The membrane material is a ceramic-polyimide composite membrane. The pressure difference on both sides of the membrane is set to 0.5MPa-5MPa, the temperature is set to 30℃-80℃, and the flow rate of the synthesis gas is set to 0.1m / s-1m / s. High-purity hydrogen is obtained after membrane separation. The high-purity hydrogen is pressurized and added to the high-pressure hydrogen storage tank for storage.

[0008] As a further scheme of the present invention: in the step three, a perfluorosulfonic acid membrane is selected as a proton exchange membrane, and the proton exchange membrane is immersed in deionized water at 20°C-30°C for 2h-4h. Titanium is selected as the material of the bipolar plate, the titanium plate is cleaned with acetone, and then the titanium plate is pickled with a hydrofluoric acid-nitric acid mixture, and then rinsed with deionized water after pickling. The pattern of the serpentine flow field is designed using computer design software, the flow channel width of the serpentine flow field is 1mm-3mm, the depth is 0.5mm-2mm, the bending angle is between 90°-150°, the bending radius is 3mm-10mm, and the flow channel spacing is 2mm-5mm. The designed serpentine flow field pattern is imported into a CNC engraving machine, the feed speed of the CNC engraving machine is set to 500mm / min-1000mm / min, the speed of the tool is set to 10000r / min-20000r / min, and the serpentine flow field is engraved on the titanium bipolar plate according to the designed pattern.

[0009] As a further solution of the present invention: in the step 4, the chloroplatinic acid H2PtCl6 solution and the activated carbon carrier are added to an electric stirrer for mixing, stirred at a speed of 300r / min-500r / min for 30min-60min, the concentration of chloroplatinic acid is set to 0.1mol / L-0.5mol / L, and then sodium borohydride NaBH4 reducing agent with a concentration of 0.5mol / L-1mol / L is added to the mixed solution, and the molar ratio of sodium borohydride to chloroplatinic acid is set to 3-5:1, and the mixture is stirred at a temperature of 20-40°C. The reaction was carried out for 1-2 hours. After the reaction was completed, the catalyst suspension was added to a high-speed centrifuge for separation and centrifuged at a speed of 3000r / min-5000r / min for 10min-20min. After the centrifugation was completed, the supernatant was removed and the precipitate was washed with deionized water. The volume of the deionized water was 5-10 times the volume of the precipitate. The washed catalyst precipitate was then added to a vacuum drying oven for drying. The vacuum degree of the vacuum drying oven was set to -0.08MPa to -0.1MPa and the temperature was 60℃-80℃. The platinum-carbon cathode catalyst powder is dried for 12h-24h to obtain the platinum-carbon cathode catalyst powder, the platinum-carbon cathode catalyst powder is added to the isopropanol solvent, and dispersed by an ultrasonic disperser, the ultrasonic power is generally set at 100W-300W, the ultrasonic time is 30-60 minutes, the platinum-carbon cathode catalyst powder is uniformly dispersed in the isopropanol solvent to form a suspension, the concentration of the suspension is set to 5mg / mL-20mg / mL, and the platinum-carbon catalyst suspension is sprayed on the surface of the cathode electrode using a spray gun. The material of the cathode electrode is titanium, and the spraying pressure is set to 0.2 MPa-0.5MPa, the nozzle diameter of the spray gun is set to 0.5mm-1mm, the distance between the electrode and the nozzle is set to 10cm-20cm, wait for 5min-10min after each spraying to allow the isopropanol solvent to evaporate, spray 3-5 layers repeatedly, and the thickness of the coating is controlled between 20um-30um. The electrode with the platinum-carbon catalyst sprayed on the surface is placed in a heating box for heat treatment, and the temperature is increased to 200℃-500℃ at 5℃ / min-10℃ / min. After treating for 1h-3h, a cathode electrode coated with the platinum-carbon catalyst is obtained.

[0010] As a further scheme of the present invention: in the step 4, chloroiridic acid H2IrCl6 is selected as the precursor salt of iridium, and the chloroiridic acid is dissolved in a propanol solvent at a temperature of 30-50°C, and the concentration of the chloroiridic acid is set to 0.1mol / L-0.5mol / L. The chloroiridic acid solution is sprayed on the surface of the anode electrode using a spray gun. The material of the anode electrode is titanium metal, the nozzle diameter of the spray gun is set to 0.5mm-1mm, and the spraying pressure is set to 0.2MPa-0.5MPa. After spraying, it is naturally dried, and the anode electrode sprayed with the chloroiridic acid solution is placed in a high-temperature furnace for thermal decomposition reaction. The high-temperature furnace is heated to 400°C-600°C at a heating rate of 5°C / min-10°C / min. After a reaction time of 2h-4h, the chloride ion impurities in the chloroiridic acid will gradually volatilize to obtain an anode electrode coated with an iridium dioxide catalyst.

[0011] As a further scheme of the present invention: in the step five, the prepared anode and cathode electrodes are respectively assembled with the pretreated proton exchange membrane, a layer of perfluorosulfonic acid binder is added between the electrode and the proton exchange membrane, the electrode and the proton exchange membrane are aligned, and then hot pressed on a hot press, the hot pressing temperature is 100°C-150°C, and the electrode and the proton exchange membrane are pressed for 2min-5min at a pressure of 1MPa-3MPa to make the electrode and the proton exchange membrane fit tightly to form an electrode-proton exchange membrane assembly (MEA), the titanium bipolar plate with a serpentine flow field is assembled with the MEA, the flow field of the titanium bipolar plate is fully in contact with the catalyst on the electrode surface, the MEA is placed between the two titanium bipolar plates to form a sandwich structure, a rubber sealing ring is placed between the bipolar plate and the MEA, the sealing ring is made of fluororubber with a thickness of 1mm-3mm, the bipolar plate and the MEA are fixed together with bolts, and the torque of the bolts is set to 2N·m-5N·m.

[0012] As a further solution of the present invention: in the step five, the assembled electrolyzer is coupled with solar photovoltaic power generation and wind power generation through an energy management system EMS. The solar photovoltaic power generation system and the wind power generation system are connected to the electrolyzer through their respective power output lines. The voltage is adjusted through a transformer so that the output voltage of the power generation system matches the rated voltage of the electrolyzer. The EMS can dispatch and optimize the energy of the entire coupled system, monitor the power generated and the working state of the electrolyzer, dynamically adjust the operating parameters of the electrolyzer, and set a confluence device in the entire coupled system to gather the electric energy generated by the solar photovoltaic power generation and the wind power generation, and then distribute it according to the operating state of the electrolyzer and the energy demand.

[0013] As a further solution of the present invention: in the step six, intelligent monitoring and control are adopted in the whole hydrogen production and hydrogenation process. In the hydrogen production process, temperature, pressure and current sensors are installed on various hydrogen production equipment. In the hydrogenation process, pressure and liquid level sensors are installed on high-pressure hydrogen storage tanks to monitor the pressure and liquid level of high-pressure hydrogen storage tanks. Flow sensors are installed at hydrogenation machines to accurately measure the amount of hydrogenation and reasonably arrange hydrogenation operations according to vehicle demand and hydrogenation station inventory. Wireless sensor networks are used to transmit data collected by sensors to the central automatic control system. The central automatic control system can adjust the operating load of hydrogen production equipment according to hydrogen demand. Machine learning algorithms are used to establish prediction models for hydrogen production and hydrogenation processes, and based on the prediction models, the prediction models can be used to accurately predict the amount of hydrogenation. According to the number of hydrogen refueling vehicles and hydrogen refueling amounts in different historical time periods, as well as external information such as surrounding traffic flow and corporate production plans, a hydrogen refueling demand prediction model is established to predict future peak and trough periods of hydrogen refueling demand, so as to prepare for hydrogen production and storage in advance. The particle swarm optimization algorithm is used to deeply optimize the hydrogen production and hydrogenation process, determine the hydrogenation sequence and time for different hydrogen refueling vehicles, and reduce the waiting time for vehicles in queues. When renewable energy is used to drive hydrogen production, since the output power of renewable energy is intermittent and volatile, when the power of renewable energy is too high, the intelligent control system can increase the number of operating electrolyzers and increase the operating current of a single electrolyzer. When the power is insufficient, the load of the electrolyzer can be appropriately reduced and the operation of some electrolyzers can be suspended.

[0014] By adopting the above technical solution, compared with the prior art, the beneficial effects of the present invention are: The integrated production and addition system of the present invention can adjust the output and operating status of the hydrogen production link in real time according to the hydrogen demand of the hydrogen filling station through an intelligent control system. When the hydrogen demand of the hydrogen filling station increases, the system can automatically increase the load of the hydrogen production equipment to increase the hydrogen output. When the demand decreases, the operating power of the hydrogen production equipment is appropriately reduced to avoid overproduction. This collaborative control mechanism can improve the operating efficiency of the entire hydrogen energy system and reduce energy waste. Through the comprehensive utilization of multiple hydrogen production methods and the optimization of integrated production and addition, the production cost of hydrogen is reduced. The lower hydrogen cost can attract more users to use hydrogen energy.

[0015] The present invention closely combines the production, purification, storage and filling of hydrogen through integrated production and filling, thereby realizing the coordinated optimization of the industrial chain. In the industrial park, hydrogen produced by various hydrogen production methods, such as hydrogen purification from by-products, hydrogen production from biomass, and hydrogen production from electrolysis of water with renewable energy, can be directly transported to the hydrogen filling station for processing and filling, reducing the loss and transportation cost in the intermediate links. Purifying hydrogen in the industrial park reduces the direct emission of by-products, which helps to improve the environmental quality of the park and surrounding areas. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a schematic diagram of the steps of the innovative hydrogen energy preparation method with integrated production and addition in an embodiment of the present invention. DETAILED DESCRIPTION

[0017] The specific embodiments of the present invention are further described below in conjunction with the accompanying drawings. It should be noted that the description of these embodiments is used to help understand the present invention, but does not constitute a limitation of the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0018] The present invention discloses an innovative hydrogen energy preparation method integrating production and addition, which comprises purifying hydrogen from byproducts generated in an industrial park, using biomass as a hydrogen raw material, and utilizing renewable energy to drive water electrolysis to produce hydrogen. The specific operation steps of the innovative hydrogen energy preparation method integrating production and addition are as follows: Step 1: Purify hydrogen from by-products in industrial parks using pressure swing adsorption technology; Step 2: Produce hydrogen by biomass gasification-reforming, compress the purified hydrogen and send it to the hydrogenation system; Step 3: preparing bipolar plate flow field and proton exchange membrane; Step 4: coating the prepared nanocatalyst on the electrode surface; Step 5: After the electrolyzer is assembled as a whole, renewable energy is used to drive water electrolysis to produce hydrogen; Step 6: Use automated control and intelligent algorithms to monitor and regulate the hydrogen production and hydrogenation processes in real time.

[0019] In one embodiment of the present invention: in step 1, in the industrial park, the by-products in industrial production contain 50%-80% hydrogen, and are also mixed with nitrogen, carbon monoxide, carbon dioxide and methane impurity gases. The gas in the by-products is separated by pressure swing adsorption technology, and the by-products are added to an adsorption tower filled with an adsorbent. The adsorption tower adopts a multi-tower series mode, the pressure in the adsorption tower is set to 1MPa-3MPa, the temperature is set to 40°C-60°C, the adsorbent is selected from activated carbon, molecular sieve and activated alumina, and the adsorbent is filled in the adsorption tower bed layer using a mixed filling method. When the by-product passes through the adsorbent bed layer, the adsorbent can The nitrogen, carbon monoxide, carbon dioxide and methane in the by-products are selectively adsorbed, and the hydrogen can be discharged from the top of the adsorption tower through the adsorbent bed to obtain purified hydrogen. When the adsorbent reaches saturation for the adsorption of impurity gases, the pressure equalization and pressure reduction operation is started to reduce the pressure in the adsorption tower to 0.1MPa-0.3MPa at a rate of 0.05MPa / min-0.1MPa / min, and the high-pressure gas is pressure-balanced with other low-pressure adsorption towers. After the pressure is balanced, the release valve of the adsorption tower is opened to discharge the remaining hydrogen in the tower under its own pressure. The purified high-purity hydrogen is pressurized and added to the high-pressure hydrogen storage tank for storage.

[0020] In one embodiment of the present invention: In step 2, crop straw and wood chips are added to a fluidized bed gasifier using a screw feeder for gasification reaction, the feeding rate is set to 100kg / h-500kg / h, the temperature in the fluidized bed gasifier is set to 800℃-1000℃, and the gasifier is evenly distributed in the furnace at a speed of 1m / s-3m / s through an air distribution plate. The gasifier is an oxygen-water vapor mixed gas, and the ratio of water vapor to oxygen is set to 2-5:1. The oxidation reaction formula of oxygen in the gasifier contacting the coke produced by pyrolysis is: ; Under the high temperature environment provided by the oxidation reaction, the reduction reaction formula of water vapor contacting the coke produced by pyrolysis is: ; The conversion reaction formula of carbon monoxide generated by the reduction reaction and water vapor is: ; The reaction generates a synthesis gas rich in hydrogen, carbon monoxide and carbon dioxide, which is then added to a fixed-bed reforming reactor filled with a Ni / Al2O3 catalyst with a particle size of 2mm-5mm. The temperature is set to 300℃-500℃, the pressure is set to 1MPa-3MPa, and the space velocity of the synthesis gas in the fixed-bed reforming reactor is set to 1000h -1 -3000h -1, so that the carbon monoxide in the synthesis gas reacts with water vapor to generate hydrogen and carbon dioxide, and then the reformed synthesis gas is added to the water scrubber for purification. The water scrubber is filled with ball ring packing, and the spray volume is set to 1m 3 / h-5m 3 / h, the solid particles in the synthesis gas are removed after 20s-30s of gas-liquid contact, and then the membrane separation technology is used to remove the residual carbon monoxide, carbon dioxide and methane in the synthesis gas. The membrane material is a ceramic-polyimide composite membrane. The pressure difference on both sides of the membrane is set to 0.5MPa-5MPa, the temperature is set to 30℃-80℃, and the flow rate of the synthesis gas is set to 0.1m / s-1m / s. High-purity hydrogen is obtained after membrane separation. The high-purity hydrogen is pressurized and added to the high-pressure hydrogen storage tank for storage.

[0021] In one embodiment of the present invention: in step three, a perfluorosulfonic acid membrane is selected as a proton exchange membrane, and the proton exchange membrane is immersed in deionized water at 20°C-30°C for 2h-4h. Titanium is selected as the material of the bipolar plate, the titanium plate is cleaned with acetone, and then the titanium plate is pickled with a hydrofluoric acid-nitric acid mixture, and then rinsed with deionized water after pickling. The pattern of the serpentine flow field is designed using computer design software, the flow channel width of the serpentine flow field is 1mm-3mm, the depth is 0.5mm-2mm, the bending angle is between 90°-150°, the bending radius is 3mm-10mm, and the flow channel spacing is 2mm-5mm. The designed serpentine flow field pattern is imported into a CNC engraving machine, the feed speed of the CNC engraving machine is set to 500mm / min-1000mm / min, the speed of the tool is set to 10000r / min-20000r / min, and the serpentine flow field is engraved on the titanium bipolar plate according to the designed pattern.

[0022] In one embodiment of the present invention: in step 4, chloroplatinic acid H2PtCl6 solution and activated carbon carrier are added to an electric stirrer for mixing, stirred at a speed of 300r / min-500r / min for 30min-60min, the concentration of chloroplatinic acid is set to 0.1mol / L-0.5mol / L, and then sodium borohydride NaBH4 reducing agent with a concentration of 0.5mol / L-1mol / L is added to the mixed solution, and the molar ratio of sodium borohydride to chloroplatinic acid is set to 3-5:1, and the mixture is stirred at a temperature of 20-40°C. The reaction was carried out for 1-2 hours. After the reaction was completed, the catalyst suspension was added to a high-speed centrifuge for separation and centrifuged at a speed of 3000r / min-5000r / min for 10min-20min. After the centrifugation was completed, the supernatant was removed and the precipitate was washed with deionized water. The volume of the deionized water was 5-10 times the volume of the precipitate. The washed catalyst precipitate was then added to a vacuum drying oven for drying. The vacuum degree of the vacuum drying oven was set to -0.08MPa to -0.1MPa and the temperature was 60℃-80℃. The platinum-carbon cathode catalyst powder is dried for 12h-24h to obtain the platinum-carbon cathode catalyst powder, the platinum-carbon cathode catalyst powder is added to the isopropanol solvent, and dispersed by an ultrasonic disperser, the ultrasonic power is generally set at 100W-300W, the ultrasonic time is 30-60 minutes, the platinum-carbon cathode catalyst powder is uniformly dispersed in the isopropanol solvent to form a suspension, the concentration of the suspension is set to 5mg / mL-20mg / mL, and the platinum-carbon catalyst suspension is sprayed on the surface of the cathode electrode using a spray gun. The material of the cathode electrode is titanium, and the spraying pressure is set to 0.2 MPa-0.5MPa, the nozzle diameter of the spray gun is set to 0.5mm-1mm, the distance between the electrode and the nozzle is set to 10cm-20cm, wait for 5min-10min after each spraying to allow the isopropanol solvent to evaporate, spray 3-5 layers repeatedly, and the thickness of the coating is controlled between 20um-30um. The electrode with the platinum-carbon catalyst sprayed on the surface is placed in a heating box for heat treatment, and the temperature is increased to 200℃-500℃ at 5℃ / min-10℃ / min. After treating for 1h-3h, a cathode electrode coated with the platinum-carbon catalyst is obtained.

[0023] In one embodiment of the present invention: in step 4, chloroiridic acid H2IrCl6 is selected as the precursor salt of iridium, and the chloroiridic acid is dissolved in a propanol solvent at a temperature of 30-50°C, and the concentration of the chloroiridic acid is set to 0.1mol / L-0.5mol / L. The chloroiridic acid solution is sprayed on the surface of the anode electrode using a spray gun. The material of the anode electrode is titanium metal, the nozzle diameter of the spray gun is set to 0.5mm-1mm, and the spraying pressure is set to 0.2MPa-0.5MPa. After spraying, it is naturally dried, and the anode electrode sprayed with the chloroiridic acid solution is placed in a high-temperature furnace for thermal decomposition reaction. The high-temperature furnace is heated to 400°C-600°C at a heating rate of 5°C / min-10°C / min. After a reaction time of 2h-4h, the chloride ion impurities in the chloroiridic acid will gradually volatilize to obtain an anode electrode coated with an iridium dioxide catalyst.

[0024] In one embodiment of the present invention: in step five, the prepared anode and cathode electrodes are respectively assembled with the pretreated proton exchange membrane, a layer of perfluorosulfonic acid binder is added between the electrode and the proton exchange membrane, the electrode and the proton exchange membrane are aligned, and then hot pressed on a hot press, the hot pressing temperature is 100°C-150°C, and the electrode and the proton exchange membrane are pressed for 2min-5min at a pressure of 1MPa-3MPa to make the electrode and the proton exchange membrane fit tightly to form an electrode-proton exchange membrane assembly (MEA), and a titanium bipolar plate with a serpentine flow field is assembled with the MEA so that the flow field of the titanium bipolar plate is in full contact with the catalyst on the electrode surface, and the MEA is placed between two titanium bipolar plates to form a sandwich structure, and a rubber sealing ring is placed between the bipolar plate and the MEA, the sealing ring is made of fluororubber with a thickness of 1mm-3mm, and the bipolar plate and the MEA are fixed together with bolts, and the torque of the bolts is set to 2N·m-5N·m.

[0025] In one embodiment of the present invention: in step five, the assembled electrolyzer is coupled with solar photovoltaic power generation and wind power generation through an energy management system EMS. The solar photovoltaic power generation system and the wind power generation system are connected to the electrolyzer through their respective power output lines. The voltage is adjusted through a transformer so that the output voltage of the power generation system matches the rated voltage of the electrolyzer. The EMS can dispatch and optimize the energy of the entire coupled system, monitor the power generated and the working state of the electrolyzer, dynamically adjust the operating parameters of the electrolyzer, and set a confluence device in the entire coupled system to gather the electric energy generated by the solar photovoltaic power generation and the wind power generation, and then distribute it according to the operating state of the electrolyzer and the energy demand.

[0026] In one embodiment of the present invention: in step six, in the entire hydrogen production and hydrogenation process, intelligent monitoring and control are adopted. In the hydrogen production process, temperature, pressure and current sensors are installed on various types of hydrogen production equipment. In the hydrogenation process, pressure and liquid level sensors are installed on high-pressure hydrogen storage tanks to monitor the pressure and liquid level of high-pressure hydrogen storage tanks. Flow sensors are installed at hydrogenation machines to accurately measure the amount of hydrogenation, and to reasonably arrange hydrogenation operations according to vehicle demand and hydrogenation station inventory. Wireless sensor networks are used to transmit data collected by sensors to the central automatic control system, which can adjust the operating load of hydrogen production equipment according to hydrogen demand conditions, and use machine learning algorithms to establish prediction models for hydrogen production and hydrogenation processes, and according to The number of hydrogen refueling vehicles and hydrogen refueling volumes in different historical time periods, as well as external information such as surrounding traffic flow and corporate production plans, are used to establish a hydrogen refueling demand prediction model to predict future peak and trough periods of hydrogen refueling demand, so as to prepare for hydrogen production and storage in advance. The particle swarm optimization algorithm is used to deeply optimize the hydrogen production and hydrogenation process, determine the hydrogenation sequence and time for different hydrogen refueling vehicles, and reduce the waiting time for vehicles in queues. When renewable energy is used to drive hydrogen production, since the output power of renewable energy is intermittent and volatile, when the power of renewable energy is too high, the intelligent control system can increase the number of operating electrolyzers and increase the operating current of a single electrolyzer. When the power is insufficient, the load of the electrolyzer can be appropriately reduced and the operation of some electrolyzers can be suspended.

[0027] Embodiment 1: When the by-product gas passes through the adsorbent bed, the adsorbent uses its selective adsorption characteristics for different gas molecules to adsorb impurity gases (such as carbon dioxide, carbon monoxide, nitrogen, etc.). The molecular sieve adsorbent can preferentially adsorb impurity gases according to molecular size and polarity. Hydrogen molecules are relatively small and chemically stable. In this case, they are relatively difficult to be adsorbed, so they can be discharged from the top of the adsorption tower. As the mixed gas flows in the adsorbent bed, the impurity gas molecules are gradually adsorbed on the active sites on the adsorbent surface, while hydrogen can smoothly pass through the adsorbent bed and be discharged from the top of the adsorption tower, thereby achieving separation of hydrogen and impurity gases. When the adsorbent adsorbs impurity gases to a certain extent, the adsorption tower needs to be regenerated, such as pressure equalization and decompression, forward placement, reverse placement and flushing processes, so that the adsorbent can restore its adsorption capacity for the next round of adsorption.

[0028] Embodiment 2: By optimizing the bipolar plate flow field design, the serpentine flow field is designed with a flow channel width of 2 mm, a depth of 1 mm, a bending angle of 90°, a bending radius of 5 mm, and a flow channel spacing of 4 mm, so that the distribution of the electrolyte on the surface of the proton exchange membrane can be more uniform, which can ensure that more water molecules are in full contact with the catalyst, thereby increasing the hydrogen generation rate. After the flow field optimization design, the hydrogen production rate of the electrolyzer can be increased by 20%. This is because the uniform electrolyte distribution can reduce the local concentration polarization phenomenon, so that the electrolysis reaction can be carried out under more ideal conditions. The serpentine flow field design helps to separate and collect the generated hydrogen and oxygen in time, thereby improving the purity of the product.

[0029] Embodiment 3: EMS analyzes the relationship between the total power of solar photovoltaic power generation and wind power generation and the power demand of the electrolyzer in real time based on the collected data. When the total power generation is greater than the power demand of the electrolyzer, EMS can adopt a variety of strategies to optimize power matching. By adjusting the operating parameters of the electrolyzer (such as increasing the current density of the electrolyzer or increasing the number of electrolyzers in operation), the electrolyzer consumes more electricity and increases the hydrogen production; or the excess electricity is stored through batteries or other energy storage devices (such as supercapacitors, pumped storage, etc.) for use when the power generation is insufficient. When the total power generation is less than the power demand of the electrolyzer, EMS can reduce the load of the electrolyzer and reduce the hydrogen production, or supplement part of the electricity from the external power grid to maintain the basic operation of the electrolyzer. During the peak period of hydrogenation demand, the intelligent control system increases the current of water electrolysis to produce hydrogen or increases the feed rate of raw materials for biomass gasification-reforming to produce hydrogen to increase the hydrogen production; during the trough period of hydrogenation demand, the operating load of the hydrogen production equipment is appropriately reduced to save energy and raw materials.

[0030] As attached Figure 1 As shown, by using a large amount of hydrogen-containing by-products, crop straw, forestry residues and organic waste generated in the production process of industrial parks as hydrogen raw materials, and using renewable energy to drive water electrolysis to produce hydrogen, the comprehensive utilization of multiple hydrogen production methods and the optimization of integrated production and processing have reduced the production cost of hydrogen.

[0031] The embodiments of the present invention are described in detail above with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions and variations of these embodiments are made without departing from the principles and spirit of the present invention, and still fall within the scope of protection of the present invention.

[0032] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0033] The above contents are merely examples and explanations of the present invention. Various modifications or additions to the specific embodiments described or replacements in similar ways by technicians in the technical field shall fall within the protection scope of the present invention as long as they do not deviate from the invention or exceed the scope defined by the claims.

[0034] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. An innovative hydrogen production method with integrated production and processing, comprising purifying hydrogen from by-products produced in an industrial park, using biomass as a hydrogen raw material, and utilizing renewable energy to drive water electrolysis to produce hydrogen, characterized in that: The specific operation steps of the innovative hydrogen energy preparation method with integrated production and addition are as follows: Step 1: Purify hydrogen from by-products in industrial parks using pressure swing adsorption technology; Step 2: Produce hydrogen by biomass gasification-reforming, compress the purified hydrogen and send it to the hydrogenation system; Step 3: preparing bipolar plate flow field and proton exchange membrane; Step 4: coating the prepared nanocatalyst on the electrode surface; Step 5: After the electrolyzer is assembled as a whole, renewable energy is used to drive water electrolysis to produce hydrogen; Step 6: Use automated control and intelligent algorithms to monitor and regulate the hydrogen production and hydrogenation processes in real time.

2. The method for preparing hydrogen energy by integrating production and addition according to claim 1, characterized in that: In the step 1, in the industrial park, the by-products of industrial production contain 50%-80% hydrogen, and are also mixed with nitrogen, carbon monoxide, carbon dioxide and methane impurity gases. The gas in the by-products is separated by pressure swing adsorption technology, and the by-products are added to an adsorption tower filled with an adsorbent. The adsorption tower adopts a multi-tower series mode, the pressure in the adsorption tower is set to 1MPa-3MPa, the temperature is set to 40°C-60°C, the adsorbent is selected from activated carbon, molecular sieve and activated alumina, and the adsorbent is filled in the adsorption tower bed by a mixed filling method. When the by-product passes through the adsorbent bed, the adsorbent can Nitrogen, carbon monoxide, carbon dioxide and methane are selectively adsorbed, and hydrogen can be discharged from the top of the adsorption tower through the adsorbent bed to obtain purified hydrogen. When the adsorbent reaches saturation for the impurity gas, the pressure equalization and pressure reduction operation begins, and the pressure in the adsorption tower is reduced to 0.1MPa-0.3MPa at a rate of 0.05MPa / min-0.1MPa / min. The high-pressure gas is pressure-balanced with other low-pressure adsorption towers. After the pressure is balanced, the release valve of the adsorption tower is opened to discharge the remaining hydrogen in the tower under its own pressure. The purified high-purity hydrogen is pressurized and added to the high-pressure hydrogen storage tank for storage.

3. The method for preparing hydrogen energy by integrating production and addition according to claim 1, characterized in that: In the step 2, crop straw and wood chips are added to the fluidized bed gasifier by a spiral feeder for gasification reaction, the feeding speed is set to 100kg / h-500kg / h, the temperature in the fluidized bed gasifier is set to 800°C-1000°C, and the gasifier is evenly distributed in the furnace at a speed of 1m / s-3m / s through the air distribution plate. The gasifier is an oxygen-water vapor mixed gas, and the ratio of water vapor to oxygen is set to 2-5:

1. The oxidation reaction formula of oxygen in the gasifier contacting the coke produced by pyrolysis is: ； Under the high temperature environment provided by the oxidation reaction, the reduction reaction formula of water vapor contacting the coke produced by pyrolysis is: ； The conversion reaction formula of carbon monoxide generated by the reduction reaction and water vapor is: ； The reaction generates a synthesis gas rich in hydrogen, carbon monoxide and carbon dioxide, which is then added to a fixed-bed reforming reactor filled with a Ni / Al2O3 catalyst with a particle size of 2mm-5mm. The temperature is set to 300℃-500℃, the pressure is set to 1MPa-3MPa, and the space velocity of the synthesis gas in the fixed-bed reforming reactor is set to 1000h -1 -3000h -1 , so that the carbon monoxide in the synthesis gas reacts with water vapor to generate hydrogen and carbon dioxide, and then the reformed synthesis gas is added to the water scrubber for purification. The water scrubber is filled with ball ring packing, and the spray volume is set to 1m 3 / h-5m 3 / h, the solid particles in the synthesis gas are removed after 20s-30s of gas-liquid contact, and then the membrane separation technology is used to remove the residual carbon monoxide, carbon dioxide and methane in the synthesis gas. The membrane material is a ceramic-polyimide composite membrane. The pressure difference on both sides of the membrane is set to 0.5MPa-5MPa, the temperature is set to 30℃-80℃, and the flow rate of the synthesis gas is set to 0.1m / s-1m / s. High-purity hydrogen is obtained after membrane separation. The high-purity hydrogen is pressurized and added to the high-pressure hydrogen storage tank for storage.

4. The method for preparing hydrogen energy by integrating production and addition according to claim 1, characterized in that: In the step three, a perfluorosulfonic acid membrane is selected as a proton exchange membrane, and the proton exchange membrane is immersed in deionized water at 20°C-30°C for 2h-4h. Titanium is selected as the material of the bipolar plate, the titanium plate is cleaned with acetone, and then the titanium plate is pickled with a hydrofluoric acid-nitric acid mixture, and then rinsed with deionized water after pickling. The pattern of the serpentine flow field is designed using computer design software. The flow channel width of the serpentine flow field is 1mm-3mm, the depth is 0.5mm-2mm, the bending angle is between 90°-150°, the bending radius is 3mm-10mm, and the flow channel spacing is 2mm-5mm. The designed serpentine flow field pattern is imported into a CNC engraving machine, the feed speed of the CNC engraving machine is set to 500mm / min-1000mm / min, the speed of the tool is set to 10000r / min-20000r / min, and the serpentine flow field is engraved on the titanium bipolar plate according to the designed pattern.

5. The innovative hydrogen energy preparation method of claim 1, characterized in that: In the step 4, the chloroplatinic acid H2PtCl6 solution and the activated carbon carrier are added to an electric stirrer for mixing, stirred at a speed of 300r / min-500r / min for 30min-60min, the concentration of chloroplatinic acid is set to 0.1mol / L-0.5mol / L, and then sodium borohydride NaBH4 reducing agent with a concentration of 0.5mol / L-1mol / L is added to the mixed solution, and the molar ratio of sodium borohydride to chloroplatinic acid is set to 3-5:1, and the reaction is carried out at a temperature of 20-40°C for 1-2h. After completion, the catalyst suspension is added to a high-speed centrifuge for separation, and centrifuged at a speed of 3000r / min-5000r / min for 10min-20min. After the centrifugation, the supernatant is removed, and the precipitate is washed with deionized water. The volume of the deionized water is 5-10 times the volume of the precipitate. Wash 3-5 times, and then add the washed catalyst precipitate to a vacuum drying oven for drying. The vacuum degree of the vacuum drying oven is set to -0.08MPa ~ -0.1MPa, and dry at a temperature of 60℃-80℃ for 12h-2. 4h, to obtain platinum-carbon cathode catalyst powder, the platinum-carbon cathode catalyst powder is added to isopropanol solvent, and dispersed by ultrasonic disperser, the ultrasonic power is generally set at 100W-300W, the ultrasonic time is 30-60 minutes, the platinum-carbon cathode catalyst powder is evenly dispersed in the isopropanol solvent to form a suspension, the concentration of the suspension is set to 5mg / mL-20mg / mL, and the platinum-carbon catalyst suspension is sprayed on the surface of the cathode electrode using a spray gun, the material of the cathode electrode is titanium, and the spraying pressure is set to 0.2MPa -0.5MPa, the nozzle diameter of the spray gun is set to 0.5mm-1mm, the distance between the electrode and the nozzle is set to 10cm-20cm, wait for 5min-10min after each spraying to allow the isopropanol solvent to evaporate, spray 3-5 layers repeatedly, and the thickness of the coating is controlled between 20um-30um. The electrode with the platinum-carbon catalyst sprayed on the surface is placed in a heating box for heat treatment, and the temperature is increased to 200℃-500℃ at 5℃ / min-10℃ / min. After treating for 1h-3h, a cathode electrode coated with the platinum-carbon catalyst is obtained.

6. The innovative hydrogen energy preparation method of claim 1, characterized in that: In the step 4, chloroiridic acid H2IrCl6 is selected as the precursor salt of iridium, and the chloroiridic acid is dissolved in a propanol solvent at a temperature of 30-50°C, the concentration of the chloroiridic acid is set to 0.1mol / L-0.5mol / L, and the chloroiridic acid solution is sprayed on the surface of the anode electrode using a spray gun. The material of the anode electrode is titanium metal, the nozzle diameter of the spray gun is set to 0.5mm-1mm, and the spraying pressure is set to 0.2MPa-0.5MPa. After spraying, it is naturally dried, and the anode electrode sprayed with the chloroiridic acid solution is placed in a high-temperature furnace for thermal decomposition reaction, and the high-temperature furnace is heated to 400°C-600°C at a heating rate of 5°C / min-10°C / min. After a reaction time of 2h-4h, the chloride ion impurities in the chloroiridic acid will gradually volatilize to obtain an anode electrode coated with an iridium dioxide catalyst.

7. The innovative hydrogen energy preparation method of claim 6, characterized in that: In the step 5, the prepared anode and cathode electrodes are respectively assembled with the pretreated proton exchange membrane, a layer of perfluorosulfonic acid adhesive is added between the electrode and the proton exchange membrane, the electrode and the proton exchange membrane are aligned, and then hot pressed on a hot press, the hot pressing temperature is 100°C-150°C, and the electrode and the proton exchange membrane are pressed for 2min-5min at a pressure of 1MPa-3MPa to make the electrode and the proton exchange membrane fit tightly to form an electrode-proton exchange membrane assembly (MEA), and a titanium bipolar plate with a serpentine flow field is assembled with the MEA so that the flow field of the titanium bipolar plate is in full contact with the catalyst on the electrode surface, and the MEA is placed between the two titanium bipolar plates to form a sandwich structure, and a rubber sealing ring is placed between the bipolar plate and the MEA, the sealing ring is made of fluororubber with a thickness of 1mm-3mm, and the bipolar plate and the MEA are fixed together with bolts, and the torque of the bolts is set to 2N·m-5N·m.

8. The innovative hydrogen energy preparation method of claim 7, characterized in that: In the step five, the assembled electrolyzer is coupled with the solar photovoltaic power generation and wind power generation through the energy management system EMS. The solar photovoltaic power generation system and the wind power generation system are connected to the electrolyzer through their respective power output lines. The voltage is adjusted through the transformer so that the output voltage of the power generation system matches the rated voltage of the electrolyzer. The EMS can dispatch and optimize the energy of the entire coupled system, monitor the power generated and the working state of the electrolyzer, dynamically adjust the operating parameters of the electrolyzer, and set a confluence device in the entire coupled system to gather the electric energy generated by the solar photovoltaic power generation and the wind power generation, and then distribute it according to the operating state of the electrolyzer and the energy demand.

9. The innovative hydrogen energy preparation method of claim 8, characterized in that: In step 6, intelligent monitoring and control are adopted in the whole hydrogen production and hydrogenation process. In the hydrogen production process, temperature, pressure and current sensors are installed on various hydrogen production equipment. In the hydrogenation process, pressure and liquid level sensors are installed on high-pressure hydrogen storage tanks to monitor the pressure and liquid level of high-pressure hydrogen storage tanks. Flow sensors are installed at hydrogenation machines to accurately measure the amount of hydrogenation and reasonably arrange hydrogenation operations according to vehicle demand and hydrogenation station inventory. Wireless sensor networks are used to transmit data collected by sensors to the central automation control system. The central automation control system can adjust the operating load of hydrogen production equipment according to hydrogen demand conditions. Machine learning algorithms are used to establish prediction models for hydrogen production and hydrogenation processes, and based on different historical periods, the prediction models are automatically adjusted. Based on the number of hydrogen refueling vehicles and hydrogen refueling amounts in the interval as well as the surrounding traffic flow and the company's production plan external information, a hydrogen refueling demand prediction model is established to predict the future peak and trough periods of hydrogen refueling demand, so as to prepare for hydrogen production and storage in advance. The particle swarm optimization algorithm is used to deeply optimize the hydrogen production and hydrogenation process, determine the hydrogenation sequence and hydrogenation time of different hydrogenation vehicles, and reduce the waiting time of vehicles in queues. When renewable energy is used to drive hydrogen production, due to the intermittent and volatile output power of renewable energy, when the power of renewable energy is too high, the intelligent control system can increase the number of operating electrolyzers and increase the operating current of a single electrolyzer. When the power is insufficient, the load of the electrolyzer is appropriately reduced and the operation of some electrolyzers is suspended.

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