Industrial strong brine hydrogen production and energy supply system and method

Abstract

The invention discloses an industrial strong brine hydrogen production and energy supply system which comprises a strong brine treatment system, and the strong brine treatment system is connected with a hydrogen production system and an energy supply system through pipelines. The invention further discloses a hydrogen production and energy supply method. The method comprises the steps that S1, condensate needed for hydrogen production is output; s2, preparing, storing and distributing the prepared hydrogen and oxygen; and S3, generating electric energy and hot water from the hydrogen and the oxygen through the fuel cell unit, transmitting the electric energy to the coal mine area power utilization unit, and supplying the hot water to the coal mine area heat utilization unit. The industrial strong brine hydrogen production and energy supply system and method provided by the invention solve the problem that detection can be carried out only by manually turning over in sound wave water immersion detection in the prior art.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparing hydrogen and supplying energy from industrial wastewater, and specifically relates to an industrial concentrated brine hydrogen production and energy supply system, and also relates to a hydrogen production and energy supply method of the industrial concentrated brine hydrogen production and energy supply system. Background Art

[0002] At present, the green hydrogen industry is an important part of the future national energy system. As an emerging energy carrier, hydrogen has the characteristics of high combustion calorific value and stable use. Hydrogen is produced by electrolyzing water with wind energy and solar energy, and wind energy and solar energy are converted into hydrogen energy, giving full play to the advantages of hydrogen in energy storage, and promoting the development and large-scale application of wind energy and solar energy. Modern coal chemical industry is a typical high-carbon emission industry. The introduction of hydrogen-rich and green hydrogen resources and coal for carbon-hydrogen complementation can improve the efficiency of coal utilization, and the use of gas and electricity to replace coal, especially the use of abandoned wind and abandoned electricity, can significantly reduce carbon emissions and process production costs, and realize clean production of coal chemical industry. Summary of the invention

[0004] The first purpose of the present invention is to provide an industrial brine hydrogen production energy supply system, which solves the problem of treating brine in industrial waste liquid, and at the same time converts hydrogen energy into electrical energy and thermal energy through fuel cells for production use in coal mines.

[0005] Another object of the present invention is to provide a method for producing hydrogen for energy supply.

[0006] The first technical solution adopted by the present invention is an industrial brine hydrogen production and energy supply system, which includes a brine treatment system, and the brine treatment system is connected to a hydrogen production system and an energy supply system through pipelines.

[0007] The first technical solution of the present invention is also characterized in that: The brine treatment system includes a pretreatment unit, which is connected to a reverse osmosis unit, an MVR evaporation concentration unit and an evaporation crystallization salt separation unit in sequence through pipelines. The reverse osmosis unit and the evaporation crystallization salt separation unit are both connected to a hydrogen production system, and the pretreatment unit is respectively connected to a hydrogen production system and an energy supply system through pipelines.

[0008] The hydrogen production system includes a clean power supply unit and a salt water electrolyzer unit, the clean power supply unit is connected to an electrochemical energy storage unit through a pipeline, the clean power supply unit and the electrochemical energy storage unit are both connected to the salt water electrolyzer unit through a wire, the salt water electrolyzer unit is respectively connected to a gas-liquid separation unit and a purification unit through pipelines, the purification unit is connected to a first heat exchange unit through a pipeline, the first heat exchange unit is respectively connected to a reverse osmosis unit, an evaporation crystallization salt separation unit and a salt water electrolyzer unit through pipelines, and the purification unit is connected to a pretreatment unit through a pipeline; The gas-liquid separation unit includes an oxygen gas-liquid separator and a hydrogen gas-liquid separator, both of which are connected to the brine electrolyzer unit through pipelines, the hydrogen gas-liquid separator is connected to the hydrogen purification unit through pipelines, the oxygen gas-liquid separator is connected to the oxygen purification unit through pipelines, the hydrogen purification unit is connected to the hydrogen storage unit through pipelines, the hydrogen storage unit is connected to the coal chemical synthesis unit through pipelines, the oxygen purification unit is connected to the oxygen storage unit through pipelines, the oxygen storage unit is connected to the coal chemical gasification unit through pipelines, and both the hydrogen storage unit and the oxygen storage unit are connected to the energy supply system through pipelines.

[0009] The energy supply system includes a fuel cell unit, which is connected to a hydrogen storage unit and an oxygen storage unit through a pipeline. The fuel cell unit is respectively connected to electrical equipment in a coal mine area and a heat unit in a coal mine area. The fuel cell unit is connected to a second heat exchange unit through a pipeline, and the second heat exchange unit is connected to the heat unit in the coal mine area.

[0010] Another technical solution adopted by the present invention is a hydrogen production and energy supply method, which adopts an industrial brine hydrogen production and energy supply system, comprising the following steps: S1, preparing crystalline salt through a pretreatment unit, a reverse osmosis unit, an MVR evaporation concentration unit and an evaporation crystallization salt separation unit, and the reverse osmosis concentrated water outputs the condensate required for hydrogen production through a first heat exchange unit; S2, preparing, storing and distributing the prepared hydrogen and oxygen respectively by passing the condensate through a clean power supply unit, an electrochemical energy storage unit, a salt water electrolyzer, a purification unit, a first heat exchange unit, a gas-liquid separation unit, a hydrogen purification unit, an oxygen purification unit, a hydrogen storage unit and an oxygen storage unit; S3, hydrogen and oxygen are used to generate electricity and hot water through fuel cell units, the electricity is transmitted to the electricity unit in the coal mine area, and the hot water is supplied to the heat unit in the coal mine area.

[0011] Another technical solution of the present invention is also characterized in that: The specific process of S1 is: the produced water treated by the pretreatment unit is transported to the reverse osmosis unit, and the produced water is reused after being concentrated by the reverse osmosis unit. Part of the concentrated water is sent to the MVR evaporation and concentration unit for concentration, and part of the concentrated water is sent to the first heat exchange unit to prepare concentrated liquid and condensate. The concentrated liquid produced by the MVR evaporation and concentration unit and the first heat exchange unit is sent to the evaporation crystallization salt separation unit for evaporation, concentration and salt separation to produce sodium chloride, sodium sulfate and miscellaneous salts.

[0012] S2 specifically includes the following steps: S2.1, sending the condensate prepared in S1 to a salt water electrolyzer unit; S2.2, supplying the electric energy generated by the clean power supply unit to the electrochemical energy storage unit and the salt water electrolyzer unit, wherein the salt water electrolyzer unit receives the electric energy from the clean power supply unit or the electrochemical energy storage unit, and the salt water electrolyzer unit electrolyzes the condensate to generate a gas-liquid mixture; S2.3, transporting the gas-liquid mixture obtained in S2.2 to a hydrogen gas-liquid separator and an oxygen gas-liquid separator, and the hydrogen gas-liquid separator and the oxygen gas-liquid separator separate the gas-liquid mixture into oxygen, hydrogen and a salt-containing electrolyte; S2.4, transporting oxygen to the oxygen purification unit, and then to the oxygen storage unit after purification; transporting hydrogen to the hydrogen purification unit, and then to the hydrogen storage unit after purification; adjusting the amount of hydrogen sent to the coal chemical gasification unit and the fuel cell unit through the oxygen storage unit, and adjusting the amount of hydrogen sent to the coal chemical synthesis unit and the fuel cell unit through the hydrogen storage unit; S2.5, transporting the salt-containing electrolyte obtained in S2.3 to the purification unit, sending it to the first heat exchange unit through the purification unit to exchange heat and lower the temperature, returning to the purification unit for purification treatment, and returning the purified electrolyte to the salt-containing electrolytic cell unit for continuous concentration. When the salt concentration in the salt-containing electrolyte exceeds 10%, it is sent to the pretreatment unit through the purification unit for treatment and reuse.

[0013] S3 specifically includes the following steps: S3.1, passing the hydrogen and oxygen produced in S2 into the fuel cell unit to generate electric current and hot water through redox reaction; S3.2, sending the current generated by the fuel cell unit to the coal mine area power unit through an external power supply device; and sending the hot water generated by the fuel cell unit to the coal mine area heat unit through the second heat exchange unit or directly to the coal mine area heat unit without passing through the second heat exchange unit; S3.3, the wastewater generated after the hot water in the coal mine is used is sent to the pretreatment unit for recycling treatment.

[0014] The concentration multiple of the MVR evaporation concentration unit is 1.5-3 times, and the crystallization method of the evaporation crystallization salt separation unit is one or more of single-effect crystallization, double-effect crystallization, triple-effect evaporation crystallization or freezing crystallization. The salt ion corrosion resistance of the salt water electrolyzer unit electrode is 1mg / L-10000 mg / L, the COD resistance is 1-1000 mg / L, the service life of the electrode is 1-100000h, and the hydrogen production capacity of the salt water electrolyzer unit is 1 Nm 3 / h-2000Nm 3 / h.

[0015] The beneficial effects of the present invention are: The industrial brine hydrogen production energy supply system and method provided by the present invention couple the industrial wastewater zero-discharge treatment process, the condensed water electrolysis hydrogen production process and the coal mine mining area energy supply, optimize the existing industrial wastewater treatment overall process route, and reduce the brine treatment cost and investment in the whole process; the brine is passed through a heat exchange system, and the generated condensed water is recycled to prepare hydrogen and oxygen, and the hydrogen is used in the coal chemical synthesis unit, which simplifies the coal chemical process flow and investment cost, reduces the use of raw coal in the coal chemical project, and reduces the carbon emission of the overall coal chemical process; oxygen is used in the coal chemical gasification unit as a combustion aid, reduces the scale of the air separation unit, and reduces the investment cost and operation cost of the coal chemical project; at the same time, the excess hydrogen and oxygen are converted into electricity and hot water through a fuel cell to supply electricity and heat to the coal mine mining area. The whole system and method provided by the present invention concentrates part of the concentrated water through a heat exchange system and recycles part of the water, which greatly reduces the investment and operation costs of the industrial wastewater treatment unit, and uses the condensed water as a raw material to generate hydrogen and oxygen, providing hydrogen energy and production raw materials for coal chemical projects, and providing electricity and heat energy for coal mining areas, which has a significant impact on the energy supply of coal mining areas, the transformation and upgrading of the industrial wastewater treatment industry and the coal chemical industry, and on the entire social and economic development and ecological benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is a structural schematic diagram of the industrial concentrated brine hydrogen production energy supply system of the present invention.

[0017] In the figure, 1. pretreatment unit, 2. reverse osmosis unit, 3. MVR evaporation concentration unit, 4. evaporation crystallization salt separation unit, 5. first heat exchange unit, 6. clean power supply unit, 7. electrochemical energy storage unit, 8. salt water electrolyzer unit, 9. gas-liquid separation unit, 10. purification unit, 11. hydrogen purification unit, 12. hydrogen storage unit, 13. coal chemical synthesis unit, 14. oxygen purification unit, 15. oxygen storage unit, 16. coal chemical gasification unit, 17. fuel cell unit, 18. coal mine area electricity unit, 19. second heat exchange unit, 20. coal mine area heat unit. DETAILED DESCRIPTION

[0018] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0019] The industrial brine hydrogen production and energy supply system provided by the present invention is as follows: Figure 1As shown, it includes a brine treatment system, a hydrogen production system and an energy supply system. The brine treatment system is connected to the hydrogen production system and the energy supply system through pipelines. The brine treatment system includes a pretreatment unit 1, a reverse osmosis unit 2, an MVR evaporation concentration unit 3 and an evaporation crystallization salt separation unit 4. The brine treatment system includes a pretreatment unit 1, which is sequentially connected to the reverse osmosis unit 2, the MVR evaporation concentration unit 3 and the evaporation crystallization salt separation unit 4 through pipelines. The reverse osmosis unit 2 and the evaporation crystallization salt separation unit 4 are both connected to the hydrogen production system. The pretreatment unit 1 is connected to the hydrogen production system and the energy supply system through pipelines.

[0020] The hydrogen production system includes a clean power supply unit 6 and a salt water electrolyzer unit 8, the clean power supply unit 6 is connected to an electrochemical energy storage unit 7 through a pipeline, the clean power supply unit 6 and the electrochemical energy storage unit 7 are both connected to the salt water electrolyzer unit 8 through a wire, the salt water electrolyzer unit 8 is respectively connected to a gas-liquid separation unit 9 and a purification unit 10 through pipelines, the purification unit 10 is connected to a first heat exchange unit 5 through a pipeline, the first heat exchange unit 5 is respectively connected to a reverse osmosis unit 2, an evaporation crystallization salt separation unit 4 and a salt water electrolyzer unit 8 through pipelines, the generated condensate is used as a replenishing liquid for the salt water electrolyzer unit 8, and the purification unit 10 is connected to a pretreatment unit 1 through a pipeline connection; The gas-liquid separation unit 9 includes an oxygen gas-liquid separator and a hydrogen gas-liquid separator, both of which are connected to the salt water electrolyzer unit 8 through pipelines, the hydrogen gas-liquid separator is connected to the hydrogen purification unit 11 through a pipeline, and is sent to the hydrogen storage unit 12 after purification, the oxygen gas-liquid separator is connected to the oxygen purification unit 14 through a pipeline, the hydrogen purification unit 11 is connected to the hydrogen storage unit 12 through a pipeline, the hydrogen storage unit 12 is connected to the coal chemical synthesis unit 13 through a pipeline, the oxygen purification unit 14 is connected to the oxygen storage unit 15 through a pipeline, the oxygen storage unit 15 is connected to the coal chemical gasification unit 16 through a pipeline, and the hydrogen storage unit 12 and the oxygen storage unit 15 are both connected to the energy supply system through pipelines.

[0021] The energy supply system includes a fuel cell unit 17, which is connected to the hydrogen storage unit 12 and the oxygen storage unit 15 through pipelines. The fuel cell unit 17 is respectively connected to the coal mine area electrical equipment connection 18 and the coal mine area heat unit 20. The fuel cell unit 17 is connected to the second heat exchange unit 19 through a pipeline, and the second heat exchange unit 19 is connected to the coal mine area heat unit 20.

[0022] The hydrogen production and energy supply method proposed in the present invention adopts an industrial concentrated brine hydrogen production and energy supply system, comprising the following steps: S1, preparing crystalline salt through the pretreatment unit 1, the reverse osmosis unit 2, the MVR evaporation concentration unit 3 and the evaporation crystallization salt separation unit 4, and the reverse osmosis concentrated water outputs the condensate required for hydrogen production through the first heat exchange unit 5; The specific process of S1 is as follows: the produced water treated by the pretreatment unit 1 is transported to the reverse osmosis unit 2, and the produced water is reused after being concentrated by the reverse osmosis unit 2. Part of the concentrated water is sent to the MVR evaporation and concentration unit 3 for concentration, and part of the concentrated water is sent to the first heat exchange unit 5 to prepare concentrated liquid and condensate. The concentrated liquid produced by the MVR evaporation and concentration unit 3 and the first heat exchange unit 5 is sent to the evaporation crystallization salt separation unit 4 for evaporation, concentration and salt separation to produce sodium chloride, sodium sulfate and miscellaneous salts. S2, the condensate is passed through the clean power supply unit 6, the electrochemical energy storage unit 7, the salt water electrolyzer 8, the purification unit 10, the first heat exchange unit 5, the gas-liquid separation unit 9, the hydrogen purification unit 11, the oxygen purification unit 14, the hydrogen storage unit 12 and the oxygen storage unit 15 to prepare, store and distribute the prepared hydrogen and oxygen respectively; S2 specifically includes the following steps: S2.1, sending the condensate prepared in S1 to the brine electrolyzer unit 8; S2.2, supplying the electric energy generated by the clean power supply unit 6 to the electrochemical energy storage unit 7 and the salt water electrolyzer unit 8, the salt water electrolyzer unit 8 receives the electric energy from the clean power supply unit 6 or the electrochemical energy storage unit 7, and the salt water electrolyzer unit 8 electrolyzes the condensate to generate a gas-liquid mixture; S2.3, transporting the gas-liquid mixture obtained in S2.2 to a hydrogen gas-liquid separator and an oxygen gas-liquid separator, and the hydrogen gas-liquid separator and the oxygen gas-liquid separator separate the gas-liquid mixture into oxygen, hydrogen and a salt-containing electrolyte; S2.4, oxygen is transported to the oxygen purification unit 14, and after purification, it is sent to the oxygen storage unit 15; hydrogen is transported to the hydrogen purification unit 11, and after purification, it is sent to the hydrogen storage unit 12; the amount sent to the coal chemical gasification unit 16 and the fuel cell unit 17 is adjusted by the oxygen storage unit 15, and the amount sent to the coal chemical synthesis unit 13 and the fuel cell unit 17 is adjusted by the hydrogen storage unit 12; S2.5, the salt-containing electrolyte obtained in S2.3 is transported to the purification unit 10, sent to the first heat exchange unit 5 through the purification unit to exchange heat and reduce the temperature, and returned to the purification unit 10 for purification treatment. The purified electrolyte is returned to the salt-containing electrolytic cell unit 8 for continuous concentration. When the salt concentration in the salt-containing electrolyte exceeds 10%, it is sent to the pretreatment unit 1 through the purification unit 10 for treatment and reuse.

[0023] S3, hydrogen and oxygen are used to generate electricity and hot water through the fuel cell unit 17, the electricity is transmitted to the coal mine area electricity unit 18, and the hot water is supplied to the coal mine area heat unit 20.

[0024] S3 specifically includes the following steps: S3.1, passing the hydrogen and oxygen produced in S2 into the fuel cell unit 17 to generate electric current and hot water through redox reaction; S3.2, the current generated by the fuel cell unit 17 is sent to the coal mine area power unit 18 through an external power supply device; and the hot water generated by the fuel cell unit 17 is sent to the coal mine area heat unit 20 through the second heat exchange unit 19 or directly sent to the coal mine area heat unit 20 without passing through the second heat exchange unit 19; S3.3, the wastewater generated after the hot water in the coal mine is used is sent to the pretreatment unit 1 for recycling treatment.

[0025] The water from the pretreatment unit 1 is mine drainage, coal chemical wastewater or desulfurization wastewater, with a total dissolved solids content of 1 mg / L to 1000 mg / L, a chemical oxygen demand of 1 mg / L to 500 mg / L, and a pH value of 6 to 10. The operating pressure of the reverse osmosis unit is 1 Mpa~1.0Mpa, the interception rate of the reverse osmosis membrane for soluble salts in water is between 80% and 100%, and the recovery rate of the reverse osmosis unit 2 is between 50% and 100%; the concentration multiple of the MVR evaporation concentration unit 3 is 1.5 to 3 times, and the crystallization method of the evaporation crystallization salt separation unit 4 is one or more of single-effect crystallization, double-effect crystallization, triple-effect evaporation crystallization or freezing crystallization. The purity of the crystallized salt of sodium chloride and sodium sulfate is between 80% and 100%; the heat exchange method of the first heat exchange unit 5 is partition type, and the specific forms are immersion type, spray type, plate type, shell and tube type, and shell and tube type heat exchanger. The heat exchange form is countercurrent contact type, and the material of the concentrated water heat exchanger is 2205 duplex stainless steel and Hastelloy alloy. The salt ion corrosion resistance is 1mg / L~100000mg / L, and the heat exchange parameter is 100~10000 W / m 2 ·℃, there is a condensate recovery elbow above the concentrated water heat exchanger, the condensate enters the condensate tank through the recovery elbow and is sent to the subsequent salt water electrolyzer unit 8, the total soluble solids TDS in the condensate is 1 mg / L~1000 mg / L, the pH value is between 5 and 9, the COD is 1 mg / L~100 mg / L, the BOD is 1 mg / L~50 mg / L, the ammonia nitrogen is 1 mg / L~100 mg / L, and the oil is 1 mg / L~1 mg / L; The salt ion corrosion resistance of the electrode of the salt water electrolyzer unit 8 is 1 mg / L to 10000 mg / L, the COD resistance is 1 to 1000 mg / L, the service life of the electrode is 1 to 100000 hours, and the hydrogen production capacity of the salt water electrolyzer unit is 1 Nm 3 / h~2000 Nm 3 / h; the hydrogen production adjustment range of the salt water electrolyzer unit 8 is 60-200%, the hydrogen output pressure of the salt water electrolyzer unit 8 is 0 Mpa-5.0 Mpa, and the rated power consumption of the salt water electrolyzer unit 8 is 3.0 kWh / Nm 3 H2~5.0kWh / Nm 3 H2, the NaOH content in the electrolyte solution of the salt water electrolyzer unit 8 is between 0% and 31%, and the TDS of the electrolyte of the salt water electrolyzer unit 8 is 0 mg / L to 10000 mg / L; the length of the ceramic membrane of the hydrogen / oxygen liquid-liquid separator is between 100 mm and 1000 mm, the pore size of the ceramic membrane is between 0.1 mm and 100 mm, the pore size of the ceramic membrane surface is between 0.01 μm and 100 μm, and the ceramic membrane material is one or more composite materials such as alumina, silicon dioxide, zirconium oxide, etc. The purity of hydrogen / oxygen discharged from the hydrogen / oxygen liquid-liquid separator is not less than 99.9%; the purification unit 10 adopts an advanced oxidation process to remove organic matter, ammonia nitrogen, oils and phenols in the alkaline electrolyte, and the oxidation removal efficiency is 50% to 100%, the electrolyte salt ion concentration in the purification unit 10 is 1 to 10000 mg / L, and the salt ion concentration in the electrolyte exceeds 10000 mg / L, discharged into the pretreatment unit 1 in the concentrated brine treatment system for cyclic treatment, the electrolyte (inlet) temperature of the purification unit 10 is 50-100°C, and the electrolyte (return liquid) temperature is 50-100°C; The fuel cell unit 17 uses a hydrogen fuel cell with a rated power of 0 to 1 MW, a volume power density of 0 to 10 kW / L, an operating temperature of -30 to 150°C, a power generation efficiency of 50 to 80%, a voltage of 0 to 5 V, and a response time of 0 to 600 s.

[0026] Example 1 This embodiment provides an industrial brine hydrogen production energy supply system, such as Figure 1 As shown, it includes a concentrated brine treatment system, which is connected to a hydrogen production system and an energy supply system through pipelines.

[0027] Example 2 This embodiment provides an industrial brine hydrogen production energy supply system, such as Figure 1 As shown, it includes a concentrated brine treatment system, which is connected to a hydrogen production system and an energy supply system through pipelines.

[0028] The concentrated brine treatment system includes a pretreatment unit 1, which is sequentially connected to a reverse osmosis unit 2, an MVR evaporation concentration unit 3 and an evaporation crystallization salt separation unit 4 through pipelines. The reverse osmosis unit 2 and the evaporation crystallization salt separation unit 4 are both connected to the hydrogen production system, and the pretreatment unit 1 is respectively connected to the hydrogen production system and the energy supply system through pipelines. The hydrogen production system includes a clean power supply unit 6 and a salt water electrolyzer unit 8, the clean power supply unit 6 is connected to an electrochemical energy storage unit 7 through a pipeline, the clean power supply unit 6 and the electrochemical energy storage unit 7 are both connected to the salt water electrolyzer unit 8 through a wire, the salt water electrolyzer unit 8 is respectively connected to a gas-liquid separation unit 9 and a purification unit 10 through pipelines, the purification unit 10 is connected to a first heat exchange unit 5 through a pipeline, the first heat exchange unit 5 is respectively connected to the reverse osmosis unit 2, the evaporation crystallization salt separation unit 4 and the salt water electrolyzer unit 8 through pipelines, and the purification unit 10 is connected to the pretreatment unit 1 through a pipeline; the gas-liquid separation unit 9 includes an oxygen gas The liquid separator and the hydrogen gas-liquid separator, the oxygen gas-liquid separator and the hydrogen gas-liquid separator are all connected to the brine electrolyzer unit 8 through pipelines, the hydrogen gas-liquid separator is connected to the hydrogen purification unit 11 through a pipeline, the oxygen gas-liquid separator is connected to the oxygen purification unit 14 through a pipeline, the hydrogen purification unit 11 is connected to the hydrogen storage unit 12 through a pipeline, the hydrogen storage unit 12 is connected to the coal chemical synthesis unit 13 through a pipeline, the oxygen purification unit 14 is connected to the oxygen storage unit 15 through a pipeline, the oxygen storage unit 15 is connected to the coal chemical gasification unit 16 through a pipeline, and the hydrogen storage unit 12 and the oxygen storage unit 15 are both connected to the energy supply system through pipelines. The energy supply system includes a fuel cell unit 17, which is connected to the hydrogen storage unit 12 and the oxygen storage unit 15 through pipelines. The fuel cell unit 17 is respectively connected to the coal mine area electrical equipment connection 18 and the coal mine area heat unit 20. The fuel cell unit 17 is connected to the second heat exchange unit 19 through a pipeline, and the second heat exchange unit 19 is connected to the coal mine area heat unit 20.

[0029] Example 3 This embodiment provides a hydrogen production and energy supply method, using the industrial concentrated brine hydrogen production and energy supply system provided in the above embodiment, such as Figure 1 As shown, the following steps are included: Step 1, the water discharged from industrial wastewater, with a TDS of 500 mg / L, a COD content of 39 mg / L, and a pH of 7.8; is sent to the reverse osmosis unit 2 through the pretreatment unit 1, desalinated by the reverse osmosis membrane, the reverse osmosis operating pressure is 0.6 Mpa, the retention rate of soluble salt ions is 99.2%, the recovery rate is 75%, the TDS of the reverse osmosis concentrated water is 1956 mg / L, the COD content is 152 mg / L, and the pH is 6.9, part of the concentrated water is sent to the first heat exchange unit 5, and part of the concentrated water is sent to the MVR evaporation and concentration unit 3 for evaporation and concentration, the MVR concentration multiple is 3 times, and sodium sulfate crystalline salt is produced with a purity of 98.5%, and sodium chloride crystalline salt is produced with a purity of 98.2%; Step 2, the concentrated water output by the reverse osmosis unit 2 is transported to the first heat exchange unit 5. The heat exchange mode of the first heat exchange unit 5 is a countercurrent contact shell and tube heat exchanger. The concentrated water flows through the shell side and the electrolyte flows through the tube side. The first heat exchange unit 5 is made of 2205 duplex stainless steel. After the concentrated water passes through the first heat exchange unit 5, 50% of the condensate is generated and sent to the salt water electrolyzer unit 8. The total soluble solids TDS in the condensate is 560 mg / L, the pH value is 7.9, the COD is 20 mg / L, the BOD is 5 mg / L, the ammonia nitrogen is 25 mg / L, and the oil is 0.05 mg / L. 50% of the concentrated liquid returns to the evaporation crystallization salt separation unit 4 in S1 for double-effect crystallization.

[0030] Step 3: The clean power supply unit 6 supplies the generated electric energy to the electrochemical energy storage unit 7 and the salt water electrolyzer unit 8. The salt water electrolyzer unit 8 receives the electric energy from the clean power supply unit 6 and the electrochemical energy storage unit 7. The salt water electrolyzer unit 8 electrolyzes the condensate to produce a gas-liquid mixture. The power consumption of the electrolyzer is 5.0 kWh / Nm 3 H2, NaOH concentration in electrolyte solution is 17%, initial TDS of electrolyte is 560 mg / L, and hydrogen production is 1 Nm 3 / h, hydrogen output pressure 1.6Mpa; Step 4, transporting the gas-liquid mixture to the hydrogen gas-liquid separator and the oxygen gas-liquid separator, the hydrogen gas-liquid separator and the oxygen gas-liquid separator separate the gas-liquid mixture into oxygen, hydrogen and salt-containing electrolyte; transporting oxygen to the oxygen purification unit 14, and sending it to the oxygen storage unit 15 after purification; transporting hydrogen to the hydrogen purification unit 11, and sending it to the hydrogen storage unit 12 after purification; adjusting the amount sent to the coal chemical gasification unit 16 and the fuel cell unit 17 through the oxygen storage unit 15, and adjusting the amount sent to the coal chemical synthesis unit 13 and the fuel cell unit 17 through the hydrogen storage unit 12, the length of the ceramic membrane used in the hydrogen gas-liquid separator and the oxygen gas-liquid separator is 500 mm, the pore size of the ceramic membrane is 1 mm, the pore size of the ceramic membrane surface is 10 μm, the ceramic membrane material is a silicon dioxide composite material, the purity of the hydrogen discharged from the hydrogen gas-liquid separator is 99.92%, and the purity of the oxygen discharged from the oxygen gas-liquid separator is 99.95%; Step 5, the 95°C salt-containing electrolyte is transported to the purification unit 10, and is sent to the first heat exchange unit 5 through the purification unit 10 to exchange heat and reduce the temperature to 80°C, and is returned to the purification unit 10 for purification treatment. The purified electrolyte is returned to the salt-containing electrolytic cell unit 8 for continuous concentration. When the salt concentration in the salt-containing electrolyte is 11%, it is sent to the pretreatment unit 1 in the concentrated brine treatment system through the purification unit 10 for treatment and reuse. The purification unit 10 adopts an ozone catalytic oxidation process, and the oxide removal rate is 80%; Step 6, the hydrogen and oxygen delivered by the hydrogen production system are introduced into the fuel cell unit 17 to generate current and hot water through redox reaction; the current generated by the fuel cell unit 17 is sent to the coal mine power unit 18 through an external power supply device; the hot water generated by the fuel cell unit 17 is sent to the coal mine heat unit 20 through the second heat exchange unit 19, or directly sent to the coal mine heat unit 20; the waste water generated after the hot water in the coal mine heat unit 20 is used up is sent to the pretreatment unit 1 in the concentrated brine treatment system for cyclic treatment and use. The rated power of the fuel cell is 500 kW, the volume power density is 6 kW / L, the operating temperature is 80°C, the power generation efficiency is 60%, the voltage is 4V, and the response time is 60 s.

[0031] Example 4 This embodiment provides a hydrogen production and energy supply method, using the industrial concentrated brine hydrogen production and energy supply system provided in the above embodiment, such as Figure 1 As shown, the following steps are included: Step 1, the water discharged from industrial wastewater, with a TDS of 650 mg / L, a COD content of 28 mg / L, and a pH of 7.5; is sent to the reverse osmosis unit 2 through the pretreatment unit 1, desalinated by the reverse osmosis membrane, the reverse osmosis operating pressure is 0.75 MPa, the retention rate of soluble salt ions is 99.5%, the recovery rate is 76%, the TDS of the reverse osmosis concentrated water is 2159 mg / L, the COD content is 103 mg / L, and the pH is 6.5, part of the concentrated water is sent to the first heat exchange unit 5, and part of the concentrated water is sent to the MVR evaporation and concentration unit 3 for evaporation and concentration, the MVR concentration multiple is 2.5 times, and sodium sulfate crystalline salt is produced with a purity of 99.2%, and sodium chloride crystalline salt is produced with a purity of 98.5%; Step 2, the concentrated water output by the reverse osmosis unit 2 is transported to the first heat exchange unit 5. The heat exchange mode of the first heat exchange unit 5 is a countercurrent contact tube spray heat exchanger. The concentrated water goes through the shell side and the electrolyte goes through the tube side. The first heat exchange unit 5 uses Hastelloy 276. After the concentrated water passes through the first heat exchange unit 5, 60% of the condensate is generated and sent to the salt water electrolyzer unit 8. The total soluble solids TDS in the condensate is 369 mg / L, the pH value is 7.3, the COD is 32 mg / L, the BOD is 12 mg / L, the ammonia nitrogen is 23 mg / L, and the oil is 0.2 mg / L. 40% of the concentrated liquid returns to the evaporation crystallization salt separation unit 4 in S1 for single-effect crystallization.

[0032] Step 3: The clean power supply unit 6 supplies the generated electric energy to the electrochemical energy storage unit 7 and the salt water electrolyzer unit 8. The salt water electrolyzer unit 8 receives the electric energy from the clean power supply unit 6 and the electrochemical energy storage unit 7. The salt water electrolyzer unit 8 electrolyzes the condensate to produce a gas-liquid mixture. The power consumption of the electrolyzer is 4.6 kWh / Nm 3 H2, NaOH concentration in electrolyte solution is 18%, initial TDS of electrolyte is 369 mg / L, and hydrogen production is 1000 Nm 3 / h, hydrogen output pressure 2.0 Mpa; Step 4, transporting the gas-liquid mixture to the hydrogen gas-liquid separator and the oxygen gas-liquid separator, the hydrogen gas-liquid separator and the oxygen gas-liquid separator separate the gas-liquid mixture into oxygen, hydrogen and salt-containing electrolyte; transporting oxygen to the oxygen purification unit 14, and sending it to the oxygen storage unit 15 after purification; transporting hydrogen to the hydrogen purification unit 11, and sending it to the hydrogen storage unit 12 after purification; adjusting the amount sent to the coal chemical gasification unit 16 and the fuel cell unit 17 through the oxygen storage unit 15, and adjusting the amount sent to the coal chemical synthesis unit 13 and the fuel cell unit 17 through the hydrogen storage unit 12, the length of the ceramic membrane used in the hydrogen gas-liquid separator and the oxygen gas-liquid separator is 600 mm, the pore size of the ceramic membrane is 15 mm, the pore size of the ceramic membrane surface is 20 μm, the ceramic membrane material is alumina material, the purity of hydrogen discharged from the hydrogen gas-liquid separator is 99.92%, and the purity of oxygen discharged from the oxygen gas-liquid separator is 99.95%; Step 5, the 90°C salt-containing electrolyte is transported to the purification unit 10, and is sent to the first heat exchange unit 5 through the purification unit 10 to exchange heat and reduce the temperature to 76°C, and is returned to the purification unit 10 for purification treatment. The purified electrolyte is returned to the salt-containing electrolytic cell unit 8 for continuous concentration. When the salt concentration in the salt-containing electrolyte is 12%, it is sent to the pretreatment unit 1 in the concentrated brine treatment system through the purification unit for treatment and reuse. The purification unit 10 adopts an ozone catalytic oxidation process, and the oxide removal rate is 65%; Step 6, the hydrogen and oxygen delivered by the hydrogen production system are introduced into the fuel cell unit 17 to generate current and hot water through redox reaction; the current generated by the fuel cell unit 17 is sent to the coal mine power unit 18 through an external power supply device; the hot water generated by the fuel cell unit 17 is sent to the coal mine heat unit 20 through the second heat exchange unit 19, or directly sent to the coal mine heat unit 20; the waste water generated after the hot water in the coal mine heat unit 20 is used up is sent to the pretreatment unit 1 in the concentrated brine treatment system for cyclic treatment and use. The rated power of the fuel cell is 600 kW, the volume power density is 7 kW / L, the operating temperature is 85°C, the power generation efficiency is 65%, the voltage is 5V, and the response time is 100 s.

[0033] Example 5 This embodiment provides a hydrogen production and energy supply method, using the industrial concentrated brine hydrogen production and energy supply system provided in the above embodiment, such as Figure 1 As shown, the following steps are included: Step 1, the water discharged from industrial wastewater has a TDS of 820 mg / L, a COD content of 36 mg / L, and a pH of 7.2; it is sent to the reverse osmosis unit 2 through the pretreatment unit 1, desalinated by the reverse osmosis membrane, the reverse osmosis operating pressure is 0.82Mpa, the retention rate of soluble salt ions is 99.1%, the recovery rate is 80%, the TDS of the reverse osmosis concentrated water is 3157 mg / L, the COD content is 126 mg / L, and the pH is 6.3, part of the concentrated water is sent to the first heat exchange unit, and part of the concentrated water is sent to the MVR evaporation and concentration unit for evaporation and concentration, the MVR concentration multiple is 1.5 times, and sodium sulfate crystalline salt is produced with a purity of 99.5%, and sodium chloride crystalline salt is produced with a purity of 98.9%; Step 2, the concentrated water output from the reverse osmosis unit 2 is transported to the first heat exchange unit 5. The heat exchange mode of the first heat exchange unit 5 is a countercurrent contact shell-and-tube heat exchanger. The concentrated water flows through the shell side and the electrolyte flows through the tube side. The first heat exchange unit 5 is made of Hastelloy 276. After the concentrated water passes through the first heat exchange unit 5, 55% of the condensate is generated and sent to the salt water electrolyzer unit 8. The total soluble solids TDS in the condensate is 651 mg / L, the pH value is 7.7, the COD is 52 mg / L, the BOD is 23 mg / L, the ammonia nitrogen is 30 mg / L, and the oil is 0.3 mg / L. 40% of the concentrated liquid is returned to the evaporation crystallization salt separation unit 4 in S1 for triple-effect evaporation crystallization or freezing crystallization; Step 3: The clean power supply unit 6 supplies the generated electric energy to the electrochemical energy storage unit 7 and the salt water electrolyzer unit 8. The salt water electrolyzer unit 8 receives the electric energy from the clean power supply unit 6 and the electrochemical energy storage unit 7. The salt water electrolyzer unit 8 electrolyzes the condensate to produce a gas-liquid mixture. The power consumption of the electrolyzer is 4.3 kWh / Nm 3 H2, NaOH concentration in electrolyte solution is 20%, initial TDS of electrolyte is 651 mg / L, and hydrogen production is 2000 Nm 3 / h, hydrogen output pressure 2.5 Mpa; Step 4, transporting the gas-liquid mixture to the hydrogen gas-liquid separator and the oxygen gas-liquid separator, the hydrogen gas-liquid separator and the oxygen gas-liquid separator separate the gas-liquid mixture into oxygen, hydrogen and salt-containing electrolyte; transporting oxygen to the oxygen purification unit 14, and sending it to the oxygen storage unit 15 after purification; transporting hydrogen to the hydrogen purification unit 11, and sending it to the hydrogen storage unit 12 after purification; adjusting the amount sent to the coal chemical gasification unit 16 and the fuel cell unit 17 through the oxygen storage unit 15, and adjusting the amount sent to the coal chemical synthesis unit 13 and the fuel cell unit 17 through the hydrogen storage unit 12, the length of the ceramic membrane used in the hydrogen gas-liquid separator and the oxygen gas-liquid separator is 800 mm, the pore size of the ceramic membrane is 32 mm, the pore size of the ceramic membrane surface is 30 μm, the ceramic membrane material is a silicon dioxide composite material, the purity of hydrogen discharged from the hydrogen gas-liquid separator is 99.99%, and the purity of oxygen discharged from the oxygen gas-liquid separator is 99.96%; Step 5, the 95°C salt-containing electrolyte is transported to the purification unit 10, and is sent to the first heat exchange unit 5 through the purification unit 10 to exchange heat and reduce the temperature to 73°C, and then returns to the purification unit 10 for purification treatment. The purified electrolyte is returned to the salt-containing electrolytic cell unit 8 for continuous concentration. When the salt concentration in the salt-containing electrolyte is 11.6%, it is sent to the pretreatment unit 1 in the concentrated brine treatment system through the purification unit 10 for treatment and reuse. The purification unit 10 adopts an ozone catalytic oxidation process, and the oxide removal rate is 72%; Step 6, the hydrogen and oxygen delivered by the hydrogen production system are introduced into the fuel cell unit 17 to generate current and hot water through redox reaction; the current generated by the fuel cell unit 17 is sent to the coal mine power unit 18 through an external power supply device; the hot water generated by the fuel cell unit 17 is sent to the coal mine heat unit 20 through the second heat exchange unit 19, or directly sent to the coal mine heat unit 20; the waste water generated after the hot water in the coal mine heat unit 20 is used up is sent to the pretreatment unit 1 in the concentrated brine treatment system for cyclic treatment and use. The rated power of the fuel cell is 800 kW, the volume power density is 8.6 kW / L, the operating temperature is 93°C, the power generation efficiency is 79%, the voltage is 3.5V, and the response time is 120 s.

[0034] It can be seen that the industrial brine hydrogen production energy supply system and method provided by the present invention are used to couple the industrial wastewater zero-discharge treatment process, the condensed water electrolysis hydrogen production process and the coal mine area energy supply, thereby optimizing the overall process route of existing industrial wastewater treatment and reducing the brine treatment cost and investment in the entire process; the brine is passed through a heat exchange system, and the condensed water generated is recycled to prepare hydrogen and oxygen, and the hydrogen is used in the coal chemical synthesis unit, thereby simplifying the coal chemical process flow and investment cost, reducing the use of raw coal in coal chemical projects, and reducing the carbon emissions of the overall coal chemical process; at the same time, the excess hydrogen and oxygen are converted into electricity and hot water through fuel cells to supply electricity and heat to the coal mine area.

Claims

1. Industrial brine hydrogen production energy supply system, characterized in that: It comprises a concentrated brine treatment system, which is respectively connected to a hydrogen production system and an energy supply system through pipelines.

2. The industrial brine hydrogen production energy supply system according to claim 1, characterized in that: The concentrated brine treatment system comprises a pretreatment unit (1), wherein the pretreatment unit (1) is sequentially connected to a reverse osmosis unit (2), an MVR evaporation concentration unit (3) and an evaporation crystallization salt separation unit (4) via pipelines, wherein the reverse osmosis unit (2) and the evaporation crystallization salt separation unit (4) are both connected to a hydrogen production system, and the pretreatment unit (1) is respectively connected to a hydrogen production system and an energy supply system via pipelines.

3. The industrial brine hydrogen production energy supply system according to claim 2, characterized in that: The hydrogen production system comprises a clean power supply unit (6) and a salt water electrolyzer unit (8), wherein the clean power supply unit (6) is connected to an electrochemical energy storage unit (7) via a pipeline, and the clean power supply unit (6) and the electrochemical energy storage unit (7) are both connected to the salt water electrolyzer unit (8) via a wire, and the salt water electrolyzer unit (8) is respectively connected to a gas-liquid separation unit (9) and a purification unit (10) via pipelines, and the purification unit (10) is connected to a first heat exchange unit (5) via a pipeline, and the first heat exchange unit (5) is respectively connected to a reverse osmosis unit (2), an evaporation crystallization salt separation unit (4) and a salt water electrolyzer unit (8) via pipelines, and the purification unit (10) is connected to a pretreatment unit (1) via a pipeline; The gas-liquid separation unit (9) comprises an oxygen gas-liquid separator and a hydrogen gas-liquid separator, the oxygen gas-liquid separator and the hydrogen gas-liquid separator are both connected to the salt water electrolyzer unit (8) via a pipeline, the hydrogen gas-liquid separator is connected to a hydrogen purification unit (11) via a pipeline, the oxygen gas-liquid separator is connected to an oxygen purification unit (14) via a pipeline, the hydrogen purification unit (11) is connected to a hydrogen storage unit (12) via a pipeline, the hydrogen storage unit (12) is connected to a coal chemical synthesis unit (13) via a pipeline, the oxygen purification unit (14) is connected to an oxygen storage unit (15) via a pipeline, the oxygen storage unit (15) is connected to a coal chemical gasification unit (16) via a pipeline, and the hydrogen storage unit (12) and the oxygen storage unit (15) are both connected to an energy supply system via pipelines.

4. The industrial brine hydrogen production energy supply system according to claim 3 is characterized in that: The energy supply system comprises a fuel cell unit (17), wherein the fuel cell unit (17) is connected to a hydrogen storage unit (12) and an oxygen storage unit (15) via a pipeline, wherein the fuel cell unit (17) is respectively connected to a coal mine area electrical equipment connection (18) and a coal mine area heat unit (20), wherein the fuel cell unit (17) is connected to a second heat exchange unit (19) via a pipeline, and wherein the second heat exchange unit (19) is connected to the coal mine area heat unit (20).

5. A method for producing hydrogen and supplying energy, characterized in that: The industrial brine hydrogen production energy supply system as claimed in claim 4 is adopted, and the specific steps are as follows: S1, preparing crystalline salt through a pretreatment unit (1), a reverse osmosis unit (2), an MVR evaporation concentration unit (3) and an evaporation crystallization salt separation unit (4), and outputting condensate required for hydrogen production through a first heat exchange unit (5); S2, the condensate is passed through a clean power supply unit (6), an electrochemical energy storage unit (7), a salt water electrolyzer (8), a purification unit (10), a first heat exchange unit (5), a gas-liquid separation unit (9), a hydrogen purification unit (11), an oxygen purification unit (14), a hydrogen storage unit (12) and an oxygen storage unit (15) to respectively prepare, store and distribute the prepared hydrogen and oxygen; S3, hydrogen and oxygen are used to generate electric energy and hot water through a fuel cell unit (17), the electric energy is transmitted to a coal mine area electric energy unit (18), and the hot water is supplied to a coal mine area heat unit (20).

6. The method for producing hydrogen and supplying energy according to claim 5, characterized in that: The specific process of S1 is as follows: the produced water treated by the pretreatment unit (1) is transported to the reverse osmosis unit (2); the produced water is reused after being concentrated by the reverse osmosis unit (2); part of the concentrated water is transported to the MVR evaporation and concentration unit (3) for concentration; part of the concentrated water is transported to the first heat exchange unit (5) to prepare a concentrated liquid and a condensate; the concentrated liquid produced by the MVR evaporation and concentration unit (3) and the first heat exchange unit (5) is transported to the evaporation crystallization salt separation unit (4) for evaporation, concentration and salt separation to produce sodium chloride, sodium sulfate and miscellaneous salts.

7. The method for producing hydrogen and supplying energy according to claim 5, characterized in that: The S2 specifically includes the following steps: S2.1, sending the condensate prepared in S1 to a salt water electrolyzer unit (8); S2.2, supplying the electric energy generated by the clean power supply unit (6) to the electrochemical energy storage unit (7) and the salt water electrolyzer unit (8), wherein the salt water electrolyzer unit (8) receives the electric energy from the clean power supply unit (6) or the electrochemical energy storage unit (7), and the salt water electrolyzer unit (8) electrolyzes the condensate to generate a gas-liquid mixture; S2.3, transporting the gas-liquid mixture obtained in S2.2 to a hydrogen gas-liquid separator and an oxygen gas-liquid separator, wherein the hydrogen gas-liquid separator and the oxygen gas-liquid separator separate the gas-liquid mixture into oxygen, hydrogen and a salt-containing electrolyte; S2.4, transporting oxygen to an oxygen purification unit (14), and after purification, transporting it to an oxygen storage unit (15); transporting hydrogen to a hydrogen purification unit (11), and after purification, transporting it to a hydrogen storage unit (12); adjusting the amount of oxygen transported to a coal chemical gasification unit (16) and a fuel cell unit (17) through the oxygen storage unit (15), and adjusting the amount of hydrogen transported to a coal chemical synthesis unit (13) and a fuel cell unit (17) through the hydrogen storage unit (12); S2.5, conveying the salt-containing electrolyte obtained in S2.3 to the purification unit (10), through the purification unit, sending it to the first heat exchange unit (5) to exchange heat to reduce the temperature, returning to the purification unit (10) for purification treatment, and the purified electrolyte returns to the salt-containing electrolytic cell unit (8) for continuous concentration. When the salt concentration in the salt-containing electrolyte exceeds 10%, it is sent to the pretreatment unit (1) through the purification unit (10) for treatment and reuse.

8. The method for producing hydrogen and supplying energy according to claim 5, characterized in that: The S3 specifically includes the following steps: S3.1, passing the hydrogen and oxygen produced in S2 into a fuel cell unit (17) to generate electric current and hot water through redox reaction; S3.2, sending the current generated by the fuel cell unit (17) to the coal mine area power unit (18) through an external power supply device; and sending the hot water generated by the fuel cell unit (17) to the coal mine area heat unit (20) through the second heat exchange unit (19) or directly to the coal mine area heat unit (20) without passing through the second heat exchange unit (19); S3.3, the wastewater generated after the hot water in the coal mine is used is sent to the pretreatment unit (1) for recycling treatment.

9. The method for producing hydrogen and supplying energy according to claim 5, characterized in that: The concentration multiple of the MVR evaporation and concentration unit (3) is 1.5-3 times, and the crystallization method of the evaporation crystallization and salt separation unit (4) is one or more of single-effect crystallization, double-effect crystallization, triple-effect evaporation crystallization or freezing crystallization.

10. The method for producing hydrogen and supplying energy according to claim 5, characterized in that: The salt water electrolyzer unit (8) has an electrode with a salt ion corrosion resistance of 1 mg / L-10000 mg / L, a COD resistance of 1-1000 mg / L, an electrode service life of 1-100000 h, and a hydrogen production capacity of 1 Nm 3 / h-2000 Nm 3 / h.

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