All-weather wind-solar-coke complementary stable hydrogen production and liquefaction cogeneration unit and its working method

Abstract

This invention discloses an all-weather, wind-solar-coke complementary stable hydrogen production and liquefaction co-production device and its operating method. The device includes a coke oven gas hydrogen production system, an electrolysis water hydrogen production system, and a hydrogen liquefaction system. The operating method of this invention sets up three operating modes for the stable production of liquid hydrogen products around the clock: a coke oven gas hydrogen production coupled with hydrogen liquefaction mode, an electrolysis water hydrogen production system coupled with hydrogen liquefaction mode, and a coke oven gas and electrolysis water hydrogen production coupled with hydrogen liquefaction mode. The coke oven gas hydrogen production system performs pretreatment, desulfurization, and pressure swing adsorption processes on the coke oven gas. The electrolysis water hydrogen production system uses direct current generated by wind and solar power generation to electrolyze water to produce hydrogen. The hydrogen liquefaction system compresses and cools the hydrogen to ultimately produce liquid hydrogen products. This invention fully utilizes the electricity generated by wind and solar power generation, supplemented by a stable supply of coke oven gas, to achieve the goal of uninterrupted liquid hydrogen co-production around the clock.

Description

Technical Field

[0001] This invention relates to a hydrogen production and hydrogen liquefaction system, and more particularly to an all-weather wind-solar-coke complementary stable hydrogen production and liquefaction co-production device and its operating method. Background Technology

[0002] my country has abundant coal resources, totaling 5.6 trillion tons, with proven reserves of 1 trillion tons, accounting for 11% of the world's total reserves; its annual coke production exceeds 400 million tons, and its annual output is nearly 1000 million tons. 8 m 3 Coke oven gas can be developed and utilized as a resource. In recent years, wind and solar power generation have developed rapidly, but due to the inability to consume the generated electricity in a timely manner, a lot of electricity has been wasted.

[0003] Hydrogen is the cleanest energy source, and with the development of technology, its applications in fine chemicals, powder metallurgy, and other fields are becoming increasingly widespread. Utilizing water electrolysis technology to produce hydrogen by converting electrical energy into hydrogen energy for storage not only alleviates the aforementioned problems but also has relatively low energy costs.

[0004] However, photovoltaic and wind power generation are intermittent and heavily dependent on the seasonality of the natural environment, exhibiting significant uncertainty. Relying solely on new energy sources like photovoltaics and wind for power generation would necessitate frequent start-ups and shutdowns for hydrogen liquefaction plants that require a stable supply of liquid hydrogen and long cooling times. This would obviously lead to a series of problems such as low energy utilization efficiency and low liquefaction output. For example, patent CN202210046797.3 (A Photovoltaic Hydrogen Production, Storage, and Cold Energy Recovery Coupled Dry Ice Production Device and Method of Use) mentions that intermittent photovoltaic power generation can be used to store liquid hydrogen and optimize the recovery of liquid hydrogen cold energy for liquid nitrogen and dry ice production, achieving energy conservation and emission reduction goals. However, for large-scale liquid hydrogen plants requiring a stable supply of liquid hydrogen, there is currently a lack of systems that couple new energy power generation for hydrogen production with industrial blue hydrogen, and then liquefy, store, and transport the hydrogen. Summary of the Invention

[0005] Purpose of the invention: In view of the above problems, the purpose of this invention is to provide an all-weather wind-solar-coke complementary stable hydrogen production and liquefaction cogeneration device, which can make full use of surplus coke oven gas and electricity generated by wind and solar power generation systems, generate clean energy hydrogen, solve the problem of resource waste, and provide its working method.

[0006] Technical solution: An all-weather wind-solar-coke complementary stable hydrogen production and liquefaction cogeneration unit, including a coke oven gas hydrogen production system, an electrolysis water hydrogen production system, and a hydrogen liquefaction system;

[0007] The inlet of the coke oven gas compressor in the coke oven gas to hydrogen production system is connected to the coke oven gas (COG) via ball valve one, and the outlet of the coke oven gas compressor is connected to the gas-liquid separator. A cooler is installed between the two. The gas phase outlet of the gas-liquid separator is connected to the desulfurization component. The desulfurization component is connected to the inlet of the pressure swing adsorption (PSA) decarbonization device via cooler two. The outlet of the PSA decarbonization device is divided into two paths: one is the desorbed gas end, which is directly connected to an external container, and the other is connected to the inlet of the PSA hydrogen production device. The outlet of the PSA hydrogen production device is also divided into two paths: the first outlet of the PSA hydrogen production device is connected to the inlet of the PSA decarbonization device, and the second outlet of the PSA hydrogen production device is connected to the water electrolysis hydrogen production system via ball valve two.

[0008] The inlet of the electrolyzer in the water electrolysis hydrogen production system is connected to DC power generated by ventilation and / or solar energy through a switch. The inlet of the electrolyzer is connected to the raw water through ball valve three. The first outlet of the electrolyzer is connected to the inlet of the dehydrogenation drying system through shut-off valve one. The second outlet of the electrolyzer is connected to the inlet of the deoxygenation drying system through shut-off valve two.

[0009] The hydrogen liquefaction system includes an oxygen liquefaction module and a hydrogen liquefaction module. The inlet of the Dewar tank of the hydrogen liquefaction system is connected to the liquid nitrogen pipeline through ball valve six. The Dewar tank is connected to the oxygen liquefaction module and the hydrogen liquefaction module. The outlet of the dehydrogenation drying system is connected to the oxygen liquefaction module through ball valve four. The outlet of the dehydrogenation drying system is connected to the hydrogen liquefaction module through ball valve five.

[0010] Furthermore, the oxygen liquefaction module includes an oxygen compressor. The outlet of ball valve four is connected to the inlet of the oxygen compressor. The outlet of the oxygen compressor is connected to the inlet C of the first heat exchanger. The outlet D of the first heat exchanger is connected to the inlet L of the second heat exchanger. The outlet Q of the second heat exchanger is connected to the inlet of the liquid oxygen storage tank through throttle valve one. The outlet of the liquid oxygen storage tank is connected to the inlet R of the second heat exchanger. The outlet M of the second heat exchanger is connected to the inlet F of the first heat exchanger. The outlet E of the first heat exchanger merges with the outlet of ball valve four and then enters the oxygen compressor together to enter the next oxygen liquefaction cycle.

[0011] Furthermore, the hydrogen liquefaction module includes hydrogen compressor one and hydrogen compressor two. The outlet of ball valve five is connected to the inlet of hydrogen compressor one, the outlet of hydrogen compressor one is connected to the inlet of hydrogen compressor two, the outlet of hydrogen compressor two is connected to the inlet I of the first heat exchanger, the outlet J of the first heat exchanger is connected to the inlet O of the second heat exchanger, the outlet T of the second heat exchanger has two parallel connections, one of which is connected to the inlet i of the third heat exchanger, the outlet j of the third heat exchanger is connected to the inlet k of the fourth heat exchanger, the outlet l of the fourth heat exchanger has two parallel connections, the first of which is connected to the inlet m of the fifth heat exchanger, the outlet n of the fifth heat exchanger is connected to the inlet o of the sixth heat exchanger, and the outlet p of the sixth heat exchanger is connected to the inlet of the liquid hydrogen storage tank through throttle valve two. The outlet of the liquid hydrogen storage tank is connected to the inlet h of the sixth heat exchanger. The second outlet of the fourth heat exchanger outlet l passes through the first and second turbine expanders and merges with the outlet g of the sixth heat exchanger, then connects with the inlet f of the fifth heat exchanger. The outlet e of the fifth heat exchanger is connected with the inlet d of the fourth heat exchanger. At this time, the second outlet of the second heat exchanger outlet T passes through the third turbine expander and merges with the outlet c of the fourth heat exchanger, then connects with the inlet b of the third heat exchanger. The outlet a of the third heat exchanger is connected with the inlet S of the second heat exchanger. The outlet N of the second heat exchanger is connected with the inlet H of the first heat exchanger. The outlet G of the first heat exchanger merges with the outlet of the ball valve five and then enters the hydrogen compressor one, entering the next hydrogen liquefaction cycle.

[0012] Ideally, the outlet of the Dewar flask is connected to the inlet P of the second heat exchanger. The outlet K of the second heat exchanger merges with the outlet of the Dewar flask and enters the first heat exchanger through the inlet B of the first heat exchanger. The outlet A of the first heat exchanger releases nitrogen into the air.

[0013] Furthermore, the first, second, third, fourth, fifth, and sixth heat exchangers are microchannel plate-fin heat exchangers, and the microchannels in the second, third, fourth, fifth, and sixth heat exchangers are filled with positive-negative hydrogen conversion catalyst particles.

[0014] Furthermore, the desulfurization assembly includes at least two desulfurization beds connected in parallel. The inlet of each desulfurization bed is connected to the gas phase outlet of the gas-liquid separator through a shut-off valve three, and the outlet is connected to the inlet of the cooler two through a shut-off valve four.

[0015] Ideally, the desulfurizing agent used in the desulfurization bed is one of iron oxide, zinc oxide, copper oxide, calcium oxide, manganese oxide, or activated carbon, or two or more composite oxides in any proportion.

[0016] Ideally, cooler one uses brine cooling, cooler two uses water cooling, and the liquid phase outlet of the gas-liquid separator is connected to an external storage container to collect low-boiling-point hydrocarbons.

[0017] The best deoxygenation drying system and dehydrogenation drying system use the principle of reacting with oxygen or hydrogen to produce water, thereby obtaining the desired gas through deoxygenation purification or dehydrogenation purification.

[0018] The electrolyzer of the water electrolysis hydrogen production system produces hydrogen by electrolyzing water through alkaline hydrolysis, proton exchange membrane hydrolysis, and high-temperature solid oxide hydrolysis.

[0019] A method for operating the aforementioned all-weather wind-solar-coke complementary stable hydrogen production and liquefaction co-production unit includes three operating modes:

[0020] When the wind power and solar power systems are short of electricity, switch to mode one;

[0021] Mode 1: Coke oven gas to hydrogen production coupled with hydrogen liquefaction mode:

[0022] Close the switch, ball valve 3, ball valve 4 and stop valve 2, and open ball valve 1, ball valve 2, ball valve 5 and ball valve 6;

[0023] Coke oven gas is pressurized by a coke oven gas compressor, then cooled by a cooler before entering a gas-liquid separator to separate free water and low-boiling-point substances. The gas exiting the gas-liquid separator enters a desulfurization unit for desulfurization. After desulfurization, the gas is cooled by a cooler and then enters a pressure swing adsorption (PSA) decarbonization unit to remove most of the weakly adsorbed components. After removing the desorbed gas, the gas enters a PSA hydrogen production unit. The flushing gas produced by the PSA hydrogen production unit is recycled in the PSA decarbonization unit. Another portion of the gas from the PSA hydrogen production unit enters a deoxygenation and drying system, and then enters a hydrogen liquefaction module through a ball valve. The hydrogen liquefaction module pressurizes, cools, liquefies, and reheats the gas. The gas then merges with the gas processed by the deoxygenation and drying system and re-enters the hydrogen liquefaction module, thus entering the next hydrogen liquefaction cycle.

[0024] When the wind power and solar power systems are generating electricity close to full capacity, switch to mode two.

[0025] Mode 2: Hydrogen production system coupled with hydrogen liquefaction:

[0026] Close ball valve 1 and ball valve 2; open switch, ball valve 3, ball valve 5, gate valve 2, ball valve 4, and ball valve 6.

[0027] Direct current generated by wind and / or solar power systems enters the inlet of the electrolyzer. Raw water enters the inlet of the electrolyzer to replenish the water consumed in the process of producing hydrogen through water electrolysis. The gas generated at the first outlet of the electrolyzer enters the dehydrogenation and drying system through a shut-off valve to remove small amounts of hydrogen and water from the oxygen. Then it enters the oxygen liquefaction module. The oxygen liquefaction module pressurizes, cools and liquefies, and reheats the gas. The gas then merges with the gas processed by the dehydrogenation and drying system and re-enters the oxygen liquefaction module, thus entering the next oxygen liquefaction cycle.

[0028] The gas generated from the second outlet of the electrolytic cell enters the deoxygenation and drying system through the second shut-off valve to remove the oxygen and moisture contained in the gas. Then, it enters the hydrogen liquefaction module from the outlet of the deoxygenation and drying system. After the hydrogen liquefaction module pressurizes, cools and liquefies the gas, and reheats it, the gas merges with the gas processed by the deoxygenation and drying system and re-enters the hydrogen liquefaction module, and then enters the next hydrogen liquefaction cycle.

[0029] When the wind power and solar power systems are insufficient to generate enough electricity, switch to mode three;

[0030] Mode 3: Coke oven gas and water electrolysis hydrogen production coupled with hydrogen liquefaction mode.

[0031] When this mode is in operation, all valves and switches are in the open state, and the systems in Mode 1 and Mode 2 operate continuously at the same time.

[0032] Beneficial effects: Compared with the prior art, the advantages of the present invention are:

[0033] 1. This invention provides an innovative technical approach that achieves the goal of producing and liquefying hydrogen by coupling coke oven gas hydrogen production technology, water electrolysis hydrogen production technology, and a low-temperature hydrogen liquefaction system.

[0034] 2. This invention obtains liquid oxygen as a byproduct, making full use of coke oven gas and promptly consuming the electricity generated by wind and solar power generation.

[0035] 3. The present invention arranges ortho- and para-hydrogen conversion catalyst particles in the microchannels of the second, third, fourth, fifth, and sixth heat exchangers, which saves the space occupied by traditional ortho- and para-hydrogen conversion devices and saves resources to a great extent.

[0036] 4. The invention fully utilizes the electricity generated by wind and solar power generation, supplemented by a stable supply of coke oven gas, to achieve the goal of continuous liquid hydrogen co-production around the clock. Attached Figure Description

[0037] Figure 1 This is a schematic diagram of the system structure of the present invention. Detailed Implementation

[0038] The present invention will be further illustrated below with reference to the accompanying drawings and specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0039] A weather-combined wind-solar-coke stable hydrogen production and liquefaction cogeneration unit, such as Figure 1 As shown, it includes a coke oven gas hydrogen production system, an electrolytic water hydrogen production system, and a hydrogen liquefaction system.

[0040] The inlet of the coke oven gas compressor 102 in the coke oven gas to hydrogen production system is connected to coke oven gas (COG) via ball valve 101. The outlet of the coke oven gas compressor 102 is connected to a gas-liquid separator 104, with a cooler 103 between them. The gas phase outlet 104c of the gas-liquid separator 104 is connected to a desulfurization component. The desulfurization component is connected to the inlet 109a of a pressure swing adsorption (PSA) hydrocarbon removal device 109 via a cooler 108. The outlet of the PSA hydrocarbon removal device 109... The outlet 109b is divided into two paths. One path is the desorption gas end, which is directly connected to the external container. The other path is connected to the inlet 110a of the pressure swing adsorption hydrogen production device 110. The outlet of the pressure swing adsorption hydrogen production device 110 is divided into two paths. The first outlet 110c of the pressure swing adsorption hydrogen production device 110 is connected to the inlet 109c of the pressure swing adsorption decarbonization device 109. The second outlet 110b of the pressure swing adsorption hydrogen production device 110 is connected to the water electrolysis hydrogen production system through ball valve 111.

[0041] The pressure swing adsorption decarbonization unit 109 and the pressure swing adsorption hydrogen production unit 110 are both composed of two or more adsorbers connected in parallel, ensuring that one adsorber is in adsorption state at any time, and matching the corresponding number of equalization and depressurization flushing desorption processes according to parameters such as the number of adsorbers.

[0042] The adsorbent in the pressure swing adsorption decarbonization unit 109 and the pressure swing adsorption hydrogen production unit 110 can be one of the following: activated alumina, activated carbon, silica gel, or molecular sieve adsorbents.

[0043] The inlet 203a of the electrolyzer 203 in the water electrolysis hydrogen production system is connected to DC power generated by ventilation and / or solar energy through switch 201. The inlet 203c of the electrolyzer 203 is connected to raw water through ball valve 202. The first outlet 203b of the electrolyzer 203 is connected to the inlet of the dehydrogenation drying system 212 through shut-off valve 206. The second outlet 203d of the electrolyzer 203 is connected to the inlet 205a of the deoxygenation drying system 205 through shut-off valve 204.

[0044] The hydrogen liquefaction system includes an oxygen liquefaction module and a hydrogen liquefaction module. The inlet end 308b of the Dewar canister 308 in the hydrogen liquefaction system is connected to a liquid nitrogen pipeline through a ball valve 307. The liquid nitrogen is connected to the inlet end of the ball valve 307. The outlet end of the ball valve 307 is connected to the inlet end 308b of the Dewar canister 308. The outlet end 308a of the Dewar canister 308 is connected to the inlet end P of the second heat exchanger 302. The outlet end K of the second heat exchanger 302 and the outlet end 308c of the Dewar canister 308 merge and enter the first heat exchanger 301 through the inlet end B of the first heat exchanger 301. The outlet end A of the first heat exchanger 301 releases nitrogen into the air.

[0045] In the oxygen liquefaction module, the outlet of ball valve 209 is connected to the inlet of oxygen compressor 208. The outlet of oxygen compressor 208 is connected to the inlet C of first heat exchanger 301. The outlet D of first heat exchanger 301 is connected to the inlet L of second heat exchanger 302. The outlet Q of second heat exchanger 302 is connected to the inlet of throttle valve 309. The outlet of throttle valve 309 is connected to the inlet of liquid oxygen storage tank 314. The outlet of liquid oxygen storage tank 314 is connected to the inlet R of second heat exchanger 302. The outlet M of second heat exchanger 302 is connected to the inlet F of first heat exchanger 301. The outlet E of first heat exchanger 301 merges with the outlet of ball valve 209 and enters oxygen compressor 208 together, then enters the next oxygen liquefaction cycle.

[0046] In the hydrogen liquefaction module, the outlet of ball valve 5 207 is connected to the inlet of hydrogen compressor 1 210. The outlet of hydrogen compressor 1 210 is connected to the inlet of hydrogen compressor 2 211. The outlet of hydrogen compressor 2 211 is connected to the inlet I of the first heat exchanger 301. The outlet J of the first heat exchanger 301 is connected to the inlet O of the second heat exchanger 302. The outlet T of the second heat exchanger 302 has two parallel connections: the first outlet is connected to the third heat exchanger 302. The inlet end i of heat exchanger 303 is connected to the outlet end j of heat exchanger 303, which is connected to the inlet end k of heat exchanger 304. The outlet end l of heat exchanger 304 has two parallel connections: the first outlet is connected to the inlet end m of heat exchanger 305, the outlet end n of heat exchanger 305 is connected to the inlet end o of heat exchanger 306, the outlet end p of heat exchanger 306 is connected to the inlet end of throttle valve 313, and the outlet end of throttle valve 313 is connected to liquid hydrogen storage tank 315. The inlet end of the liquid hydrogen storage tank 315 is connected to the inlet end h of the sixth heat exchanger 306. The second gas stream from the outlet end l of the fourth heat exchanger 304 passes through the turbine expander 1 311 and the turbine expander 2 312 in sequence and merges with the outlet end g of the sixth heat exchanger 306. Then it is connected to the inlet end f of the fifth heat exchanger 305. The outlet end e of the fifth heat exchanger 305 is connected to the inlet end d of the fourth heat exchanger 304. The second outlet from the outlet end T of the second heat exchanger 302 is connected to the second outlet. After passing through the turbine expander 310, it merges with the outlet c of the fourth heat exchanger 304, and then connects to the inlet b of the third heat exchanger 303. The outlet a of the third heat exchanger 303 is connected to the inlet S of the second heat exchanger 302. The outlet N of the second heat exchanger 302 is connected to the inlet H of the first heat exchanger 301. The outlet G of the first heat exchanger 301 merges with the outlet of the ball valve 207 and then enters the hydrogen compressor 210, and then enters the next hydrogen liquefaction cycle.

[0047] The first heat exchanger 301, the second heat exchanger 302, the third heat exchanger 303, the fourth heat exchanger 304, the fifth heat exchanger 305, and the sixth heat exchanger 306 are microchannel plate-fin heat exchangers. The microchannels in the second heat exchanger 302, the third heat exchanger 303, the fourth heat exchanger 304, the fifth heat exchanger 305, and the sixth heat exchanger 306 are filled with positive-negative hydrogen conversion catalyst particles.

[0048] The desulfurization assembly includes at least two desulfurization beds 106 connected in parallel. The inlet of each desulfurization bed 106 is connected to the gas phase outlet 104c of the gas-liquid separator 104 through a shut-off valve 3 105, and the outlet is connected to the inlet of the cooler 2 108 through a shut-off valve 4 107.

[0049] The desulfurizing agent used in the desulfurization bed 106 is one of iron oxide, zinc oxide, copper oxide, calcium oxide, manganese oxide, and activated carbon, or two or more composite oxides in any proportion.

[0050] Cooler 103 is cooled with brine, and cooler 2108 is cooled with water. The liquid phase outlet 104b of the gas-liquid separator 104 is connected to an external storage container to collect low-boiling-point hydrocarbons.

[0051] The deoxygenation drying system 205 and the dehydrogenation drying system 212 adopt the principle of reacting with oxygen or hydrogen to produce water, thereby obtaining the desired gas through deoxygenation purification or dehydrogenation purification.

[0052] The electrolyzer 203 of the water electrolysis hydrogen production system produces hydrogen by electrolyzing water through alkaline hydrolysis, proton exchange membrane hydrolysis, and high-temperature solid oxide hydrolysis.

[0053] The above-mentioned all-weather wind-solar-coke complementary stable hydrogen production and liquefaction cogeneration unit includes three operating modes:

[0054] When the wind power and solar power systems are short of electricity, switch to mode one.

[0055] Mode 1: Coke oven gas to hydrogen production coupled with hydrogen liquefaction mode:

[0056] Close switch 201, ball valve 3 202, ball valve 4 209 and stop valve 2 204, and open ball valve 1 101, ball valve 2 111, ball valve 5 207 and ball valve 6 307.

[0057] Coke oven gas (COG) is pressurized to 1.3 MPa by coke oven gas compressor 102, then cooled to 3-5°C by brine cooler 103, and enters gas-liquid separator 104. Here, low-boiling-point substances such as benzene and naphthalene are separated. The remaining gas passes through shut-off valve group 105 and enters desulfurization bed 106 for desulfurization. After passing through shut-off valve group 107 and water cooler 108, the temperature of the remaining gas drops to 20-25°C, and then enters pressure swing adsorption (PSA) decarbonization unit 109. At this point, HCN, CO2, NH3, NO, and most of CH4 and C are removed. O, N2, etc. are removed, and after the desorbed gas is released, the remaining gas enters the pressure swing adsorption (PSA) hydrogen production unit 110. At this time, the content of impurities such as CO meets the requirements. The flushing gas is returned to the PSA decarbonization unit 109 for recycling. The gas after passing through the PSA hydrogen production unit 110 enters the deoxygenation and drying system 205 to remove a small amount of oxygen and moisture contained in the hydrogen. At this time, the product hydrogen has met the quality requirements, with a hydrogen purity volume ratio of 99.999%, O2 ≤ 1 ppm, N2 + CH4 + CO + CO2 ≤ 10 ppm, and the total H2S content ≤ 1 ppm.

[0058] The pressure is 1.1 × 10⁻⁶. 5 Liquid nitrogen at a temperature of -195°C enters Dewar jar 308. The liquid nitrogen in Dewar jar 308 enters the second heat exchanger 302 through outlet 308a. Then, it exits from outlet K of the second heat exchanger 308 and merges with the low-temperature nitrogen gas exiting from outlet 308c of Dewar jar 308 before entering the first heat exchanger 301. Finally, the nitrogen gas is released into the air from outlet A of the first heat exchanger 301.

[0059] Hydrogen gas, after being processed by the deoxygenation and drying system 205, enters hydrogen compressor 210 and is pressurized to 1.5 MPa, then enters hydrogen compressor 211 and is pressurized to 2.5 MPa. It then enters the first heat exchanger 301 for cooling to -100°C. From the outlet J of the first heat exchanger 301, it enters the second heat exchanger 302 for cooling to -180°C. The outlet T of the second heat exchanger 302 has two parallel paths: the first path connects to the inlet i of the third heat exchanger 303 for cooling, and then exits from the... The outlet j of the third heat exchanger 303 enters the fourth heat exchanger 304 for cooling. The outlet l of the fourth heat exchanger 304 has two parallel connections. The first gas path connects to the inlet m of the fifth heat exchanger 305 for cooling. The outlet n of the fifth heat exchanger 305 enters the sixth heat exchanger 306 for cooling. The outlet p of the sixth heat exchanger 306 is connected to the second throttling valve 313. After the gas passes through the second throttling valve 313, its temperature drops to -253℃. At this point, the hydrogen gas is converted into liquid hydrogen and enters the liquid hydrogen storage tank from the outlet of the second throttling valve 313. In storage tank 315, hydrogen gas from liquid hydrogen storage tank 315 enters the sixth heat exchanger 306 for heat exchange via the outlet end of liquid hydrogen storage tank 315. At this time, the second gas from the outlet end l of the fourth heat exchanger 304 expands and cools to -243℃ via turbine expander 1 311 and turbine expander 2 312, and then merges with the outlet end g of the sixth heat exchanger 306 before entering the fifth heat exchanger 305 for reheating. The outlet end e of the fifth heat exchanger 305 enters the fourth heat exchanger 304 for reheating. At this time, the second gas from the outlet end T of the second heat exchanger 302... After being expanded and cooled to -202℃ by the turbine expander 310, it then merges with the outlet c of the fourth heat exchanger 304 and enters the third heat exchanger 303 for reheating. The outlet a of the third heat exchanger 303 enters the second heat exchanger 302 for reheating to -180℃. The outlet N of the second heat exchanger 302 enters the first heat exchanger 301 for reheating to -100℃. The outlet G of the first heat exchanger 301 merges with the outlet 205b of the deoxygenation drying system 205 and enters the hydrogen compressor 210 for pressurization, and then proceeds to the next hydrogen liquefaction cycle.

[0060] When the wind power and solar power systems are generating electricity close to full capacity, switch to mode two.

[0061] Mode 2: Hydrogen production system coupled with hydrogen liquefaction:

[0062] Close ball valve 1 (101) and ball valve 2 (111), and open switch 201, ball valve 3 (202), ball valve 5 (207), stop valve 2 (204), ball valve 4 (209), and ball valve 6 (307).

[0063] The pressure is 1.1 × 10⁻⁶. 5 Liquid nitrogen at a temperature of -195°C enters Dewar jar 308. The liquid nitrogen in Dewar jar 308 enters the second heat exchanger 302 through outlet 308a. Then, it exits from outlet K of the second heat exchanger 308 and merges with the low-temperature nitrogen gas exiting from outlet 308c of Dewar jar 308 before entering the first heat exchanger 301. Finally, the nitrogen gas is released into the air from outlet A of the first heat exchanger 301.

[0064] Direct current generated by wind and solar power systems enters electrolyzer 203 for water electrolysis. Raw water enters electrolyzer 203 to replenish the raw water consumed during hydrogen production. Electrolyzer 203 has two parallel outlets. The first outlet, 203b, is the oxygen outlet. After passing through shut-off valve 206, it enters dehydrogenation drying system 212 for dehydrogenation drying, removing trace amounts of hydrogen and moisture from the oxygen. Then, it is pressurized to 5.5 MPa by oxygen compressor 208 and cooled to -100°C by first heat exchanger 301. From outlet D of first heat exchanger 301, it enters second heat exchanger for further cooling to -180°C. Finally, from outlet Q of second heat exchanger 302, it enters throttle valve 309 for further cooling to -183°C, converting the oxygen into liquid oxygen. The oxygen enters the liquid oxygen storage tank 314, where it is reheated to -180°C in the second heat exchanger 302. Then, it enters the first heat exchanger 301 from outlet M of the second heat exchanger 302 and is reheated to -100°C. From outlet E of the first heat exchanger 301, it merges with the oxygen processed by the dehydrogenation drying system 212 and enters the oxygen compressor 208 for pressurization. It then enters the next oxygen liquefaction cycle. The second outlet 203d is the hydrogen outlet. After passing through the first shut-off valve 206, it enters the deoxygenation drying system 205 to remove trace amounts of oxygen and moisture. The hydrogen processed by the deoxygenation drying system 205 enters the hydrogen compressor 210 for pressurization to 1.5 MPa, and then enters the hydrogen compressor 211 for further pressurization to 2 MPa.The gas pressure is 5 MPa, then it enters the first heat exchanger 301 for cooling down to -100℃. From the outlet J of the first heat exchanger 301, it enters the second heat exchanger 302 for cooling down to -180℃. The outlet T of the second heat exchanger 302 has two parallel paths: the first path connects to the inlet iJ of the third heat exchanger 303 for cooling down, and then enters the fourth heat exchanger 304 from the outlet j of the third heat exchanger 303 for cooling down. The outlet of the fourth heat exchanger 304... Two parallel paths are connected at end l. The first path connects to the inlet m of the fifth heat exchanger 305, where the gas enters for cooling. The outlet n of the fifth heat exchanger 305 enters the sixth heat exchanger 306 for cooling. The outlet p of the sixth heat exchanger 306 is connected to throttle valve 313. After being throttled by throttle valve 313, the gas temperature drops to -253℃. At this point, the hydrogen gas is converted into liquid hydrogen and enters the liquid hydrogen storage tank 315 from the outlet of throttle valve 313. The hydrogen gas exiting the liquid hydrogen storage tank 315 then enters... Heat exchange occurs in the sixth heat exchanger 306. At this time, the second stream of gas from the outlet 1 of the fourth heat exchanger 304 expands and cools to -243℃ via turbine expander 1 311 and turbine expander 2 312, then merges with the outlet 2 g of the sixth heat exchanger 306 and enters the fifth heat exchanger 305 for reheating. The outlet 3e of the fifth heat exchanger 305 enters the fourth heat exchanger 304 for reheating. Meanwhile, the second stream of gas from the outlet 3T of the second heat exchanger 302 expands and cools to -243℃ via turbine expander 3 310. The gas temperature is 0.02℃, then it merges with the outlet c of the fourth heat exchanger 304 and enters the third heat exchanger 303 for reheating. The outlet a of the third heat exchanger 303 enters the second heat exchanger 302 for reheating to -180℃. The outlet N of the second heat exchanger 302 enters the first heat exchanger 301 for reheating to -100℃. The outlet G of the first heat exchanger 301 merges with the outlet 205b of the deoxygenation drying system 205 and enters the hydrogen compressor 210 for pressurization, then enters the next hydrogen liquefaction cycle.

[0065] When the wind power and solar power systems are insufficient to generate enough electricity, switch to mode three.

[0066] Mode 3: Coke oven gas and water electrolysis hydrogen production coupled with hydrogen liquefaction mode.

[0067] When this mode is in operation, all valves and switches are in the open state, and the systems in Mode 1 and Mode 2 operate continuously at the same time.

Claims

1. An all-weather, solar-wind, focus-complementary, stable hydrogen and liquefied co-production device, characterized in that: The hydrogen production system includes a coke oven gas hydrogen production system, an electrolytic water hydrogen production system, and a hydrogen liquefaction system. The inlet end of a coke oven gas compressor (102) of the coke oven gas hydrogen production system is connected to coke oven gas COG through a ball valve (101), the outlet end of the coke oven gas compressor (102) is connected to a gas-liquid separation tank (104), a cooler (103) is arranged between the two, the gas phase outlet end (104c) of the gas-liquid separation tank (104) is connected to a desulfurization assembly, the desulfurization assembly is connected to the inlet end (109a) of a pressure swing adsorption decarburization device (109) through a cooler (108), the outlet end (109b) of the pressure swing adsorption decarburization device (109) is divided into two paths, one path is a desorption gas end and is directly connected to an external container, the other path is connected to the inlet end (110a) of a pressure swing adsorption hydrogen production device (110), the outlet of the pressure swing adsorption hydrogen production device (110) is divided into two paths, the first path outlet (110c) of the pressure swing adsorption hydrogen production device (110) is connected to the inlet end (109c) of the pressure swing adsorption decarburization device (109), and the second path outlet (110b) of the pressure swing adsorption hydrogen production device (110) is connected to an electrolytic water hydrogen production system through a ball valve (111). The inlet end (203a) of an electrolytic tank (203) of the electrolytic water hydrogen production system is connected to direct current generated by wind energy and / or solar energy through a switch (201), the inlet end (203c) of the electrolytic tank (203) is connected to raw material water through a ball valve (202), the first path outlet (203b) of the electrolytic tank (203) is connected to the inlet end of a dehydrogenation drying system (212) through a stop valve (206), and the second path outlet (203d) of the electrolytic tank (203) is connected to the inlet end (205a) of a deoxygenation drying system (205) through a stop valve (204). The hydrogen liquefaction system includes an oxygen liquefaction module and a hydrogen liquefaction module, the inlet end (308b) of a Dewar flask (308) of the hydrogen liquefaction system is connected to a liquid nitrogen pipeline through a ball valve (307), the Dewar flask (308) is connected to the oxygen liquefaction module and the hydrogen liquefaction module, the outlet end of the dehydrogenation drying system (212) is connected to the oxygen liquefaction module through a ball valve (209), and the outlet end (205b) of the deoxygenation drying system (205) is connected to the hydrogen liquefaction module through a ball valve (207).

2. The all-weather sun and wind light focused complementary stable hydrogen and liquefied co-production device according to claim 1, characterized in that: The oxygen liquefaction module comprises an oxygen compressor (208), the outlet end of a ball valve four (209) is connected with the inlet end of the oxygen compressor (208), the outlet end of the oxygen compressor (208) is connected with the inlet end C of a first heat exchanger (301), the outlet end D of the first heat exchanger (301) is connected with the inlet end L of a second heat exchanger (302), the outlet end Q of the second heat exchanger (302) is connected with the inlet end of a liquid oxygen storage tank (314) through a throttle valve one (309), the outlet end of the liquid oxygen storage tank (314) is connected with the inlet end R of the second heat exchanger (302), the outlet end M of the second heat exchanger (302) is connected with the inlet end F of the first heat exchanger (301), and the outlet end E of the first heat exchanger (301) is connected with the outlet end of the ball valve four (209) and then enters the oxygen compressor (208) together to enter the next oxygen liquefaction cycle.

3. The all-weather sun and wind light focused complementary stable hydrogen and liquefied co-production device according to claim 2, characterized in that: The hydrogen liquefaction module comprises a hydrogen compressor I (210), a hydrogen compressor II (211), an outlet end of the ball valve V (207) is connected with an inlet end of the hydrogen compressor I (210), an outlet end of the hydrogen compressor I (210) is connected with an inlet end of the hydrogen compressor II (211), an outlet end of the hydrogen compressor II (211) is connected with an inlet end I of the first heat exchanger (301), an outlet end J of the first heat exchanger (301) is connected with an inlet end O of the second heat exchanger (302), an outlet end T of the second heat exchanger (302) is connected with an inlet end i of the third heat exchanger (303) in one way, an outlet end j of the third heat exchanger (303) is connected with an inlet end k of the fourth heat exchanger (304), an outlet end l of the fourth heat exchanger (304) is connected with an inlet end m of the fifth heat exchanger (305) in one way, an outlet end n of the fifth heat exchanger (305) is connected with an inlet end o of the sixth heat exchanger (306), an outlet end p of the sixth heat exchanger (306) is connected with an inlet end of the liquid hydrogen storage tank (315) through the throttle valve II (313), an outlet end of the liquid hydrogen storage tank (315) is connected with an inlet end h of the sixth heat exchanger (306), an outlet end l of the fourth heat exchanger (304) is connected with an outlet end g of the sixth heat exchanger (306) in the other way, then connected with an inlet end f of the fifth heat exchanger (305), an outlet end e of the fifth heat exchanger (305) is connected with an inlet end d of the fourth heat exchanger (304), at this time, an outlet end T of the second heat exchanger (302) is connected with an outlet end c of the fourth heat exchanger (304) in the other way through the turbine expander III (310), then connected with an inlet end b of the third heat exchanger (303), an outlet end a of the third heat exchanger (303) is connected with an inlet end S of the second heat exchanger (302), an outlet end N of the second heat exchanger (302) is connected with an inlet end H of the first heat exchanger (301), an outlet end G of the first heat exchanger (301) is connected with the outlet end of the ball valve V (207) and then enters the hydrogen compressor I (210) to enter the next hydrogen liquefaction cycle.

4. The all-weather sun and wind light focused complementary stable hydrogen and liquefied co-production device according to claim 3, characterized in that: An outlet end (308a) of the Dewar flask (308) is connected with an inlet end P of the second heat exchanger (302), an outlet end K of the second heat exchanger (302) is connected with an outlet end (308c) of the Dewar flask (308) and then enters the first heat exchanger (301) through an inlet end B of the first heat exchanger (301), and an outlet end A of the first heat exchanger (301) releases the nitrogen into the air.

5. The all-weather sun and wind light focused complementary stable hydrogen and liquefied co-production device according to claim 3, characterized in that: The first heat exchanger (301), the second heat exchanger (302), the third heat exchanger (303), the fourth heat exchanger (304), the fifth heat exchanger (305) and the sixth heat exchanger (306) are micro-channel plate fin heat exchangers, and the micro-channels in the second heat exchanger (302), the third heat exchanger (303), the fourth heat exchanger (304), the fifth heat exchanger (305) and the sixth heat exchanger (306) are filled with positive-para hydrogen conversion catalyst particles.

6. The all-weather sun and wind light focused complementary stable hydrogen and liquefied co-production device according to claim 1, characterized in that: The desulfurization assembly comprises at least two parallel desulfurization beds (106), the inlets of each desulfurization bed (106) are connected with the gas phase outlet end (104c) of the gas-liquid separation tank (104) through one stop valve three (105) respectively, and the outlets are connected with the inlet end of the cooler two (108) through one stop valve four (107) respectively.

7. The all-weather sun and wind light focused complementary stable hydrogen and liquefied co-production device according to claim 6, characterized in that: The desulfurizer used in the desulfurization bed (106) is one or any proportion of two or more composite oxides of iron oxide, zinc oxide, copper oxide, calcium oxide, manganese oxide and activated carbon.

8. The all-weather sun and wind light focused complementary stable hydrogen and liquefied co-production device according to claim 1, characterized in that: The cooler one (103) uses salt water cooling, the cooler two (108) uses water cooling, the liquid phase outlet end (104b) of the gas-liquid separation tank (104) is connected with an external storage container to collect low-boiling-point hydrocarbon substances.

9. The all-weather sun and wind light focused complementary stable hydrogen and liquefied co-production device according to claim 1, characterized in that: The deoxidation drying system (205) and the dehydrogenation drying system (212) use a principle system that reacts with oxygen or hydrogen to generate water, so as to obtain the required gas through deoxidation purification or dehydrogenation purification; The electrolytic tank (203) of the electrolytic water hydrogen production system electrolyzes water to produce hydrogen by the methods of alkaline hydrolysis, proton exchange membrane hydrolysis and high-temperature solid oxide hydrolysis.

10. The method of operation of the all-weather, sun and wind light focused complementary stable hydrogen and liquefied co-production device as claimed in any one of claims 1 to 9, characterized in that Three working modes are included: When the wind power generation and solar power generation system generates insufficient electricity, switch to mode one; Mode one: coke oven gas hydrogen production coupled with hydrogen liquefaction mode: Close the switch (201), the ball valve three (202), the ball valve four (209) and the stop valve two (204), and open the ball valve one (101), the ball valve two (111), the ball valve five (207) and the ball valve six (307); The coke oven gas enters the coke oven gas compressor (102) to be pressurized, and then enters the gas-liquid separation tank (104) after being cooled by the cooler I (103) to separate free water and low-boiling-point substances in the coke oven gas. The gas out of the gas-liquid separation tank (104) enters the desulfurization assembly to be desulfurized, and the gas after desulfurization is cooled by the cooler II (108), and then enters the pressure swing adsorption decarburization device (109) to remove most of the weakly adsorbed components. The gas after the pressure swing adsorption decarburization device (109) removes the desorption gas enters the pressure swing adsorption hydrogen production device (110), and the flushing gas produced by the pressure swing adsorption hydrogen production device (110) enters the pressure swing adsorption decarburization device (109) for recycling. Another part of the gas out of the pressure swing adsorption hydrogen production device (110) enters the deoxygenation drying system (205), and then enters the hydrogen liquefaction module through the ball valve V (207). The hydrogen liquefaction module pressurizes, cools and liquefies, and warms up the gas, and then the gas enters the next hydrogen liquefaction cycle after being combined with the gas treated by the deoxygenation drying system (205). When the wind power generation and solar power generation system generates power close to full load, switch to mode two. Mode two: electrolytic water hydrogen production system coupled with hydrogen liquefaction mode: Close the ball valve I (101) and the ball valve II (111), and open the switch (201), the ball valve III (202), the ball valve V (207), the stop valve II (204), the ball valve IV (209) and the ball valve VI (307). The direct current generated by the wind power and / or solar power generation system enters the inlet end (203a) of the electrolytic cell (203), and the raw water enters the inlet end (203c) of the electrolytic cell (203) to supplement the water consumed in the electrolytic water hydrogen production process. The gas generated by the first outlet (203b) of the electrolytic cell (203) enters the dehydrogenation drying system (212) through the stop valve I (206) to remove a small amount of hydrogen and water in the oxygen, and then enters the oxygen liquefaction module. The oxygen liquefaction module pressurizes, cools and liquefies, and warms up the gas, and then the gas enters the next oxygen liquefaction cycle after being combined with the gas treated by the dehydrogenation drying system (212). The gas generated by the second outlet (203d) of the electrolytic cell (203) enters the deoxygenation drying system (205) through the stop valve II (204) to remove oxygen and water in the gas, and then enters the hydrogen liquefaction module from the outlet end (205b) of the deoxygenation drying system (205). The hydrogen liquefaction module pressurizes, cools and liquefies, and warms up the gas, and then the gas enters the next hydrogen liquefaction cycle after being combined with the gas treated by the deoxygenation drying system (205). When the wind power generation and solar power generation system generates insufficient power, switch to mode three. Mode three: coke oven gas and electrolytic water hydrogen production coupled with hydrogen liquefaction mode: When the mode is running, all valves and switches are in the open state, and the system of mode one and mode two is continuously running at the same time.

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