CN112179046B - Liquid air energy storage and ammonia synthesis integrated device and method - Google Patents
Liquid air energy storage and ammonia synthesis integrated device and method Download PDFInfo
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- CN112179046B CN112179046B CN202011089104.6A CN202011089104A CN112179046B CN 112179046 B CN112179046 B CN 112179046B CN 202011089104 A CN202011089104 A CN 202011089104A CN 112179046 B CN112179046 B CN 112179046B
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 472
- 239000007788 liquid Substances 0.000 title claims abstract description 225
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 183
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 164
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 149
- 238000004146 energy storage Methods 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 449
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 223
- 238000000926 separation method Methods 0.000 claims abstract description 115
- 238000003860 storage Methods 0.000 claims abstract description 102
- 230000005611 electricity Effects 0.000 claims abstract description 47
- 238000010248 power generation Methods 0.000 claims abstract description 31
- 239000003570 air Substances 0.000 claims description 530
- 239000007789 gas Substances 0.000 claims description 157
- 239000001257 hydrogen Substances 0.000 claims description 107
- 229910052739 hydrogen Inorganic materials 0.000 claims description 107
- 238000005338 heat storage Methods 0.000 claims description 75
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 74
- 238000007906 compression Methods 0.000 claims description 61
- 230000002000 scavenging effect Effects 0.000 claims description 49
- 230000006835 compression Effects 0.000 claims description 40
- 150000002431 hydrogen Chemical class 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 230000009467 reduction Effects 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000012080 ambient air Substances 0.000 claims description 9
- 239000011232 storage material Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000013529 heat transfer fluid Substances 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000002912 waste gas Substances 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 2
- 239000012774 insulation material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002803 fossil fuel Substances 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 basalt and Shouo VLT Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
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- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
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- F25J1/0015—Nitrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2240/00—Processes or apparatus involving steps for expanding of process streams
- F25J2240/90—Hot gas waste turbine of an indirect heated gas for power generation
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Abstract
The invention discloses a liquid air energy storage and ammonia synthesis integrated device and a method. In the electricity consumption valley period, redundant electric power drives the air separation liquefaction unit to obtain liquid nitrogen and store the liquid nitrogen in the liquid air storage tank; the source of nitrogen in the ammonia synthesis circulation system can utilize liquid nitrogen in a liquid air storage tank on one hand, and can also utilize gaseous nitrogen separated from an air separation plant on the other hand. During the peak period of electricity consumption, after being pressurized and preheated, liquid nitrogen in the liquid air storage tank can be directly supplied to the ammonia synthesis circulation system as a raw material on one hand, and can enter the air turbine set for expansion power generation after being heated on the other hand, and then is pressurized and supplied to the ammonia synthesis circulation system.
Description
Technical Field
The invention relates to a novel liquid air energy storage and ammonia synthesis integrated device and method, and belongs to the technical field of liquid air energy storage, ammonia synthesis and air separation.
Background
The liquid air energy storage technology is a cryogenic energy storage technology which utilizes liquid air or nitrogen as an energy storage medium. In the electricity consumption valley period, liquid air or nitrogen is produced by utilizing electric energy, and meanwhile, compression heat generated in the air or nitrogen compression process is stored; during the peak period of electricity utilization, liquid air or nitrogen is pressurized by a pressurizing pump, low-temperature cold energy is recovered and further preheated, and then the liquid air or nitrogen drives an air turbine to do work and generate electricity. Liquid air energy storage is used as a new large-scale energy storage technology, has the characteristics of high energy storage density, short response time, no geographic condition limit, no environmental pollution and the like, and is widely concerned.
Ammonia gas, as a carrier of hydrogen gas, is one of the most potential long-term hydrogen storage media. In addition, ammonia can be used for producing ammonia water, compound fertilizer, nitric acid, soda ash and the like, and is widely applied to the fields of chemical industry, light industry, pharmacy, synthetic fiber and the like. Liquid ammonia can also be used as a green refrigerant and applied to the field of refrigeration and air conditioning. Ammonia is commercially produced by the haber process by direct combination of nitrogen and hydrogen at high temperature and pressure in the presence of a catalyst. Nitrogen is one of the important raw materials in ammonia synthesis, and is generally obtained by air separation device preparation. The air separation unit needs to be operated all day long to provide the high-purity nitrogen needed for ammonia synthesis, which is one of the reasons for high energy consumption and high cost in the ammonia synthesis process.
In conclusion, nitrogen is a working medium which is required by both liquid air energy storage and ammonia synthesis, so that the nitrogen has a good combination point. The liquid nitrogen can be stored in the liquid air in the electricity consumption valley period (with low electricity price), and the liquid nitrogen can be released by the liquid air in the electricity consumption peak period (with high electricity price) to supply ammonia for synthesis, so that the consumption of high-price electricity to produce nitrogen and supply ammonia for synthesis is avoided. Therefore, how to efficiently integrate the liquid air energy storage with the ammonia synthesis has important significance for reducing the operation and investment cost of the ammonia synthesis and improving the power generation efficiency of the liquid air energy storage.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of the prior art and provides a liquid air energy storage and ammonia synthesis integrated device and a method, the device stores nitrogen by using liquid air energy storage at the electricity consumption valley time period and releases the nitrogen to supply ammonia synthesis at the electricity consumption peak time period, thereby avoiding consuming peak electricity to produce the nitrogen, realizing the purposes of reducing the operation and investment cost of ammonia synthesis by using the peak-valley electricity price, improving the liquid air energy storage efficiency, realizing the independent operation of liquid air energy storage and ammonia synthesis and the like, and being an efficient and reasonable liquid air energy storage and ammonia synthesis integrated mode.
In order to achieve the purpose, the invention adopts the following technical scheme:
an integrated device for liquid air energy storage and ammonia synthesis, comprising: a liquid air energy storage circulating system and an ammonia synthesis circulating system;
the liquid air energy storage and circulation system comprises: an air separation liquefaction unit and an air power generation unit; wherein the air separation liquefaction unit comprises: an air compressor unit having a right side input, a left side output, a lower input, and a lower output; the left output end of the first air three-way valve is connected with the right input end of the air compressor unit; the right side input end of the first air three-way valve is connected with the purified ambient air; the right side input end of the low-temperature cooler is connected with the left side output end of the air compressor unit; the input end of the low-temperature turbo expander is connected with the left output end of the low-temperature cooler; the upper input end of the liquid air separator is connected with the output end of the low-temperature turbo expander; the upper input end of the second air three-way valve is connected with the lower output end of the liquid air separator; the upper input end of the third air three-way valve is connected with the lower output end of the second air three-way valve; the input end of the liquid air storage tank is connected with the right output end of the third air three-way valve; a right input end of the fourth air three-way valve is connected with a left output end of the liquid air separator; a lower input end of the fifth air three-way valve is connected with an upper output end of the fourth air three-way valve; the right output end of the fifth air three-way valve is connected with the left upper input end of the cryocooler; the lower input end of the sixth air three-way valve is connected with the right upper side output end of the cryocooler; the right side input end of the sixth air three-way valve is connected with the right side input end of the air compressor unit; the left output end of the sixth air three-way valve is connected with the environment; a cold storage unit having a right port and a left port; a first low-temperature three-way valve, a right port of which is connected with a left port of the cold storage unit; the input end of the first low-temperature circulating pump is connected with the upper output end of the first low-temperature three-way valve; the output end of the first low-temperature circulating pump is connected with the input end of the lower left side of the cryocooler; the upper input end of the second low-temperature three-way valve is connected with the right lower side output end of the cryocooler; the left port of the second low-temperature three-way valve is connected with the right port of the cold storage unit; the medium-temperature heat storage unit is provided with a right side port and a left side port; the right port of the first medium-temperature three-way valve is connected with the left port of the medium-temperature heat storage unit; the input end of the first medium-temperature circulating pump is connected with the upper output end of the first medium-temperature three-way valve; the output end of the first medium-temperature circulating pump is connected with the lower input end of the air compressor unit; the upper input end of the second medium-temperature three-way valve is connected with the lower output end of the air compressor unit; the left port of the second medium-temperature three-way valve is connected with the right port of the medium-temperature heat storage unit; the right upper side output end of the rectifying tower is connected with the left side input end of the fifth air three-way valve; the right upper side input end of the rectifying tower is connected with the left side output end of the second air three-way valve; the right lower side input end of the rectifying tower is connected with the lower output end of the fourth air three-way valve; the right lower side output end of the rectifying tower is connected with the left side input end of the third air three-way valve; the air power generation unit with air separation liquefaction unit sharing liquid air storage tank, cold storage unit, first low temperature three-way valve, second low temperature three-way valve, medium temperature heat-retaining unit, first medium temperature three-way valve and the medium temperature three-way valve of second still include: the input end of the low-temperature pressure pump is connected with the output end of the liquid air storage tank; the left input end of the evaporator is connected with the output end of the low-temperature pressure pump; the left output end of the evaporator is connected with the lower input end of the first low-temperature three-way valve; the left input end of the first nitrogen three-way valve is connected with the right output end of the evaporator; the upper input end of the third low-temperature three-way valve is connected with the lower output end of the second low-temperature three-way valve; the left output end of the third low-temperature three-way valve is connected with the right input end of the evaporator; the input end of the second low-temperature circulating pump is connected with the lower output end of the third low-temperature three-way valve; the output end of the second low-temperature circulating pump is connected with the right input end of the evaporator; the input end of the second medium-temperature circulating pump is connected with the lower output end of the second medium-temperature three-way valve; the upper input end of the third medium-temperature three-way valve is connected with the output end of the second medium-temperature circulating pump; the left input end of the third medium-temperature three-way valve is connected with the right port of the medium-temperature heat storage unit; the left side input end of the air turbine set is connected with the right side output end of the first nitrogen three-way valve; the upper output end of the air turbine unit is connected with the lower input end of the first medium-temperature three-way valve; the upper input end of the air turbine unit is connected with the lower output end of the third medium-temperature three-way valve;
the ammonia synthesis circulation system comprises: an air separation plant having a nitrogen output and an oxygen output; the lower input end of the second nitrogen three-way valve is connected with the nitrogen output end of the air separation plant; the upper output end of the second air three-way valve is connected with the lower input end of the first air three-way valve; the right side input end of the first mixing chamber is connected with the left side output end of the second nitrogen three-way valve; the upper input end of the first mixing chamber is connected with the right output end of the air turbine set; the hydrogen output end of the hydrogen generator is connected with the lower input end of the first mixing chamber; the upper input end of the second mixing chamber is connected with the lower output end of the first nitrogen three-way valve; the right side input end of the preheater is connected with the left side output end of the second mixing chamber; the input end of the normal-temperature cooler is connected with the right output end of the preheater; the upper input end of the liquid ammonia separator is connected with the output end of the normal temperature cooler; the input end of the liquid ammonia throttle valve is connected with the lower output end of the liquid ammonia separator; the input end of the liquid ammonia storage tank is connected with the output end of the liquid ammonia throttling valve; the left input end of the scavenging unit is connected with the right output end of the liquid ammonia separator; the upper output end of the scavenging unit is connected with the lower input end of the second mixing chamber; the left input end of the hydrogen separation unit is connected with the right output end of the scavenging unit; the lower output end of the hydrogen separation unit is connected with an external waste gas treatment unit, and the waste gas is discharged into the atmospheric environment after being qualified; the input end of the third medium-temperature circulating pump is connected with the lower left output end of the air turbine unit; a high temperature heat storage unit having an upper port and a lower port; the upper port of the first high-temperature three-way valve is connected with the lower port of the high-temperature heat storage unit; the input end of the first high-temperature circulating pump is connected with the right output end of the first high-temperature three-way valve; the lower port of the second high-temperature three-way valve is connected with the upper port of the high-temperature heat storage unit; the upper output end of the second high-temperature three-way valve is connected with the lower right input end of the air turbine unit; the output end of the second high-temperature circulating pump is connected with the left input end of the first high-temperature three-way valve; the input end of the second high-temperature circulating pump is connected with the output end of the lower middle part of the air turbine unit; the right input end of the mixed gas compressor unit is connected with the left output end of the first mixing chamber; the upper output end of the mixed gas compressor unit is connected with the lower middle input end of the air turbine unit; the upper input end of the mixed gas compressor unit is connected with the output end of the third medium-temperature circulating pump; the left output end of the mixed gas compressor unit is connected with the right input end of the second mixing chamber; the lower input end of the mixed gas compressor unit is connected with the upper output end of the hydrogen separation unit; the upper input end of the ammonia synthesis unit is connected with the left output end of the preheater; the lower output end of the ammonia synthesis unit is connected with the left input end of the preheater; the left input end of the ammonia synthesis unit is connected with the output end of the first high-temperature circulating pump; and the left output end of the ammonia synthesis unit is connected with the right input end of the second high-temperature three-way valve.
Further, the air compressor set comprises one or more stages of air compressors and air coolers; the air turbine set comprises a first-stage or multi-stage medium-temperature heater, a high-temperature heater, a turbine and a medium-temperature three-way valve; the mixed gas compressor unit comprises one-stage or multi-stage mixed gas compressors and a mixed gas cooler; the ammonia synthesis unit comprises a one-stage or multi-stage ammonia reactor and an ammonia cooler.
Further, the rectifying column includes: a high pressure chamber having an upper input, an upper output, a lower output, an upper right input and a lower right input; the right upper side input end of the high-pressure chamber is connected with the right upper side input end of the rectifying tower; the right lower side input end of the high-pressure chamber is connected with the right lower side input end of the rectifying tower; a packing located inside the high pressure chamber; the input end of the liquid oxygen throttle valve is connected with the lower output end of the high-pressure chamber; a low pressure chamber located at a top of the high pressure chamber; the left side input end of the low-pressure chamber is connected with the output end of the liquid oxygen throttle valve; the upper output end of the low-pressure chamber is connected with the upper right output end of the rectifying tower; an evaporative condenser located inside the low pressure chamber; the input end of the evaporative condenser is connected with the upper output end of the high-pressure chamber; the output end of the evaporative condenser is divided into two paths: one path is connected with the upper input end of the high-pressure chamber, and the other path is connected with the right lower side output end of the rectifying tower.
Further, the cold storage unit, the medium-temperature heat storage unit and the high-temperature heat storage unit respectively adopt latent heat, sensible heat or thermochemical energy storage materials with working temperature ranges of at least-195-20 ℃ (sensible heat cold storage materials such as basalt and Shouo VLT, phase change cold storage materials such as sodium salt aqueous solution and ethylene glycol aqueous solution, thermochemical cold storage materials such as silica gel and fluorite), 20-300 ℃ (sensible heat storage materials such as Shouo T55 and T66, phase change materials such as high-density polyethylene, sugar alcohols or nitrate) and 20-500 ℃ (sensible heat storage materials such as cast iron, cobblestone, molten salt and the like, sensible heat storage materials such as chlorate and carbonate and the like), can be operated in a single-stage or multi-stage series mode, and adopt heat insulation materials for heat insulation.
Preferably, the air separation liquefaction unit can adopt air or nitrogen as a working medium; the heat transfer fluid of the cold storage unit can be methanol, propane or air and the like; the heat transfer fluid of the medium-temperature heat storage unit can be heat transfer oil or silicone oil and the like; the heat transfer fluid of the high-temperature heat storage unit can be molten salt and the like; the hydrogen generator can be an electrolytic water tank or a hydrogen preparation device for producing hydrogen by using mineral fuel and the like.
Furthermore, the invention also provides an integrated method for storing liquid air energy and synthesizing ammonia by adopting the device, during the electricity consumption valley period, the air separation liquefaction unit and the ammonia synthesis circulating system work, and the device runs in two modes:
in the first mode, one part of gaseous nitrogen produced by the air separation plant is supplied to the air separation liquefaction unit to obtain and store liquid nitrogen, and the other part of gaseous nitrogen is supplied to the ammonia synthesis circulation system, and the method specifically comprises the following steps:
an air separation liquefaction unit: a part of gaseous nitrogen produced by the air separation plant enters the air compressor unit through the second nitrogen three-way valve and the first air three-way valve, the gaseous nitrogen is compressed to high pressure, and meanwhile, compression heat generated in the compression process is recovered and stored in the medium-temperature heat storage unit; the high-pressure gaseous nitrogen gas of air compressor unit export gets into the cryocooler, is cooled to low temperature by the low temperature cold energy of cold storage unit storage and the gaseous nitrogen gas of backward flow, then gets into the expansion of low temperature turboexpander and steps down, and wherein some gaseous nitrogen liquefies, separates gaseous state and liquid nitrogen gas through liquid air separator: liquid nitrogen enters the liquid air storage tank through the second air three-way valve and the third air three-way valve, and gaseous nitrogen enters the air compressor unit through the fourth air three-way valve, the fifth air three-way valve, the cryocooler and the sixth air three-way valve;
an ammonia synthesis circulating system: the other part of gaseous nitrogen produced by the air separation plant enters the first mixing chamber through the second nitrogen three-way valve, is fully mixed with the hydrogen produced by the hydrogen generator, enters the mixed gas compressor unit to be pressurized to the medium pressure, is then mixed with the unreacted hydrogen recycled by the hydrogen separation unit and is further pressurized to the high pressure, and simultaneously, the compression heat generated in the compression process is recycled and stored in the medium-temperature heat storage unit; high-pressure gas at the outlet of the mixed gas compressor unit enters a second mixing chamber, is fully mixed with unreacted gas recovered from the scavenging unit, enters an ammonia synthesis unit after being preheated by a preheater to synthesize ammonia, and simultaneously stores reaction heat generated in the ammonia synthesis reaction process in a high-temperature heat storage unit; the mixed gas after the reaction is cooled to normal temperature sequentially through a preheater and a normal temperature cooler, ammonia gas in the mixed gas is condensed, and then the mixed gas enters a liquid ammonia separator to separate liquid ammonia and unreacted gas: liquid ammonia enters a liquid ammonia storage tank after throttling and pressure reduction through a liquid ammonia throttle valve, and unreacted gas is discharged finally after completing scavenging and hydrogen recovery through a scavenging unit and a hydrogen separation unit in sequence;
in a second mode, the air separation liquefaction unit separates and liquefies nitrogen from air, one part of liquid nitrogen is stored in a liquid air storage tank, and the other part of liquid nitrogen is pressurized and preheated and then is supplied to an ammonia synthesis circulation system, and the method specifically comprises the following steps:
air separation liquefaction unit: after the ambient air is purified, the ambient air enters an air compressor unit through a first air three-way valve to be pressurized to high pressure, and meanwhile, compression heat generated in the air compression process is recovered and stored in a medium-temperature heat storage unit; the high-pressure air at the outlet of the air compressor unit passes through the low-temperature cooler, is cooled to low temperature by low-temperature cold energy stored in the cold storage unit and returned oxygen-enriched air, enters the low-temperature turboexpander for expansion and pressure reduction, wherein part of air is liquefied, and then enters the liquid air separator for separating gaseous air and liquid air: liquid air enters the high-pressure chamber of the rectifying tower through a second air three-way valve and is sprayed from top to bottom, and gaseous air enters the high-pressure chamber of the rectifying tower through a fourth air three-way valve and is blown and swept from bottom to top; the gaseous air and the liquid air finish heat and mass exchange in the filler, high-purity gaseous nitrogen is gathered at the top of the high-pressure chamber, and oxygen-enriched liquid air is gathered at the bottom of the high-pressure chamber; the oxygen-enriched liquid air at the bottom of the high-pressure chamber is cooled and depressurized through the liquid oxygen throttle valve, enters the low-pressure chamber to release cold energy to become gaseous oxygen-enriched air, and is discharged into the environment through the fifth air three-way valve, the low-temperature cooler and the sixth air three-way valve; the high-purity gaseous nitrogen at the top of the high-pressure chamber enters an evaporative condenser of the low-pressure chamber, the oxygen-enriched liquid air after throttling and pressure reduction is condensed into liquid nitrogen, one part of the liquid nitrogen flows back to the high-pressure chamber for spraying, and the other part of the liquid nitrogen enters a liquid air storage tank through a third air three-way valve; one part of liquid nitrogen in the liquid air storage tank is stored, the other part of the liquid nitrogen is pressurized by a low-temperature pressurizing pump and then enters an evaporator for preheating, and meanwhile, released cold energy is stored in a cold storage unit; the normal-temperature high-pressure gaseous nitrogen at the outlet of the evaporator is supplied to the ammonia synthesis circulating system through the first nitrogen three-way valve;
an ammonia synthesis circulating system: hydrogen produced by the hydrogen generator enters a mixed gas compressor unit through a first mixing chamber, is primarily compressed to medium pressure, is mixed with unreacted hydrogen recycled from a hydrogen separation unit, is further compressed to high pressure, and simultaneously recovers compression heat generated in the hydrogen compression process and stores the compression heat in a medium-temperature heat storage unit; high-pressure hydrogen at the outlet of the mixed gas compressor unit enters a second mixing chamber, is fully mixed with high-pressure nitrogen supplied by a liquid air storage tank and unreacted gas recovered by the scavenging unit, is preheated by a preheater and enters an ammonia synthesis unit to complete ammonia synthesis reaction, and meanwhile, reaction heat is recovered and stored in a high-temperature heat storage unit; the mixed gas after the full reaction is cooled to normal temperature through a preheater and a normal temperature cooler in turn, ammonia gas in the mixed gas is condensed, and then the mixed gas enters a liquid ammonia separator to separate liquid ammonia and unreacted gas: liquid ammonia enters a liquid ammonia storage tank after being throttled and depressurized by a liquid ammonia throttle valve, and unreacted gas is finally discharged after being subjected to scavenging and hydrogen recovery by a scavenging unit and a hydrogen separation unit in sequence.
Further, during the electricity consumption valley period, if the air separation plant is unavailable, the air separation liquefaction unit can utilize a rectifying tower to separate and liquefy nitrogen from air, one part is stored, and the other part is supplied to the ammonia synthesis circulation system; the air separation liquefaction unit may directly liquefy and store gaseous nitrogen provided by the air separation plant if available.
Furthermore, the invention also provides an integrated method for liquid air energy storage and ammonia synthesis by adopting the device, wherein the air power generation unit and the ammonia synthesis circulating system work at the peak time of electricity consumption, and the integrated method specifically comprises the following steps:
an air power generation unit: liquid nitrogen stored in the liquid air storage tank is pressurized to high pressure through a low-temperature pressurizing pump and then enters an evaporator for preheating, the liquid nitrogen is evaporated and vaporized into gaseous nitrogen, and cold energy released by the evaporation of the liquid nitrogen is stored in a cold storage unit; the normal-temperature high-pressure gaseous nitrogen at the outlet of the evaporator is divided into two paths through a first nitrogen three-way valve: one part of the mixed gas enters a second mixing chamber and is supplied to an ammonia synthesis circulating system, and the other part of the mixed gas enters an air turbine set, is subjected to two-stage preheating and then is subjected to expansion power generation, and then enters a first mixing chamber and is supplied to the ammonia synthesis circulating system;
an ammonia synthesis circulating system: hydrogen produced by the hydrogen generator enters a first mixing chamber, is fully mixed with nitrogen at the outlet of the air turbine unit, then enters a mixed gas compressor unit to be preliminarily compressed to medium pressure, is further compressed to high pressure after being mixed with unreacted hydrogen recycled by the hydrogen separation unit, and simultaneously, compression heat generated in the compression process is recycled to be used for preliminarily preheating the nitrogen in the air turbine unit; high-pressure gas at the outlet of the mixed gas compressor unit enters a second mixing chamber, is fully mixed with a part of nitrogen shunted at the outlet of the evaporator and unreacted gas recovered in the scavenging unit, enters an ammonia synthesis unit to synthesize ammonia after being preheated by a preheater, and simultaneously recovers reaction heat generated in the ammonia synthesis reaction process for further preheating the nitrogen in the air turbine unit; the mixed gas after the reaction is cooled to normal temperature sequentially through a preheater and a normal temperature cooler, ammonia gas in the mixed gas is condensed, and then the mixed gas enters a liquid ammonia separator to separate liquid ammonia and unreacted gas: liquid ammonia enters a liquid ammonia storage tank after being throttled and depressurized by a liquid ammonia throttle valve, and unreacted gas is finally discharged after being subjected to scavenging and hydrogen recovery by a scavenging unit and a hydrogen separation unit in sequence.
Further, during the peak period of power consumption, the air turbine unit preheats the nitrogen to the intermediate temperature primarily by using the compression heat stored by the intermediate-temperature heat storage unit and the compression heat generated by the mixed gas compressor unit in real time, and then preheats the nitrogen to the high temperature further by using the reaction heat stored by the high-temperature heat storage unit and the reaction heat generated by the ammonia synthesis unit in real time, so that the power generation capacity and the efficiency of the liquid air energy storage circulation system are improved; when the heat demand for the air turbine unit is reduced, redundant compression heat generated by the mixed gas compressor unit in real time can be stored in the medium-temperature heat storage unit, and redundant reaction heat generated by the ammonia synthesis unit in real time can be stored in the high-temperature heat storage unit.
Further, during the peak period of electricity utilization, the air power generation unit in the liquid air energy storage circulation system provides nitrogen for the ammonia synthesis circulation system in two ways: the first type can supply the liquid nitrogen stored in the liquid air storage tank to an ammonia synthesis circulating system after pressurization, preheating and expansion power generation, and does not influence the operation of the liquid air energy storage circulating system; and secondly, liquid nitrogen stored in a liquid air storage tank can be pressurized to the pressure required by the ammonia synthesis reaction, and then heated and vaporized to be supplied to an ammonia synthesis circulating system, so that the power consumption of mixed gas compression in a mixed gas compressor set is reduced.
Further, the liquid air energy storage circulation system and the ammonia synthesis circulation system can independently operate; the liquid nitrogen is stored by the liquid air energy storage circulation system at the electricity consumption valley time period, and the nitrogen required by ammonia synthesis is supplied at the electricity consumption peak time period, so that the nitrogen production process is transferred to the electricity consumption valley time period, and the operation and investment cost of the ammonia synthesis circulation system is reduced.
Compared with the prior art, the invention has the following beneficial effects:
1) according to the invention, the liquid air is used for storing the nitrogen produced by the air separation plant during the electricity consumption valley period, and the liquid air is used for storing the energy and releasing the nitrogen to supply ammonia for synthesis during the electricity consumption peak period, so that the air separation plant is prevented from running during the electricity consumption peak period, and the running cost of an ammonia synthesis circulating system is reduced.
2) The invention combines the rectifying tower to improve the air liquefaction process of liquid air energy storage, realizes the direct separation and liquefaction of nitrogen from air, and does not need additional investment to build an air separation plant, thereby reducing the investment cost of an ammonia synthesis circulating system.
3) According to the invention, through reasonably recovering the compression heat of the medium-temperature gas and the synthesis reaction heat of the high-temperature ammonia gas, the nitrogen before expansion in the air turbine set is heated to high temperature in two stages, so that the energy storage and power generation capacity of the liquid air can be obviously increased, and the overall efficiency of the system is improved.
4) The liquid air energy storage and ammonia synthesis can be operated independently without mutual influence, and a feasible effective scheme is provided for realizing the high-efficiency integration of the liquid air energy storage and the ammonia synthesis.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
Fig. 1 is a schematic diagram of the overall structure of the integrated device for liquid air energy storage and ammonia synthesis according to the present invention.
Fig. 2 is a schematic diagram of a first embodiment of the integrated liquid air energy storage and ammonia synthesis apparatus shown in fig. 1.
Fig. 2-1 is a schematic diagram of the operation of the first embodiment of the integrated device for liquid air energy storage and ammonia synthesis shown in fig. 2 during the electricity consumption valley period.
Fig. 2-2 is a schematic diagram of the operation of the integrated liquid air energy storage and ammonia synthesis apparatus shown in fig. 2 during peak periods of electricity consumption.
Fig. 3 is a schematic diagram of a second embodiment of the integrated liquid air energy storage and ammonia synthesis apparatus shown in fig. 1.
Fig. 3-1 is a schematic diagram of the operation of the liquid air energy storage and ammonia synthesis integrated device shown in fig. 3 in the power consumption valley period according to the second embodiment.
Fig. 3-2 is a schematic diagram of the second embodiment of the integrated liquid air energy storage and ammonia synthesis apparatus shown in fig. 3 during peak hours of electricity consumption.
Wherein, the air compressor set 100, the nth stage air compressor 101, the nth stage air cooler 102, the first air three-way valve 201, the cryocooler 202, the low temperature turboexpander 203, the liquid air separator 204, the second air three-way valve 205, the third air three-way valve 206, the liquid air storage tank 207, the fourth air three-way valve 208, the fifth air three-way valve 209, the sixth air three-way valve 210, the cold storage unit 211, the first low temperature three-way valve 212, the first low temperature circulating pump 213, the second low temperature three-way valve 214, the medium temperature unit 215, the first medium temperature three-way valve 216, the first medium temperature circulating pump 217, the second medium temperature three-way valve 218, the rectifying tower 300, the high pressure chamber 301, the packing 302, the liquid oxygen throttle valve 303, the low pressure chamber 304, the evaporative condenser 305, the low temperature pressurizing pump 401, the evaporator 402, the first nitrogen 403, the third low temperature three-way valve 404, the second low temperature circulating pump 405, the second medium temperature circulating pump 406, a third intermediate-temperature three-way valve 407, an air turbine unit 500, an nth stage intermediate-temperature heater 501, an nth stage high-temperature heater 502, an nth stage turbine 503, a fourth intermediate-temperature three-way valve 504, a fifth intermediate-temperature three-way valve 505, an air separation plant 601, a second nitrogen three-way valve 602, a first mixing chamber 603, a hydrogen generator 604, a second mixing chamber 605, a preheater 606, a normal-temperature cooler 607, a liquid ammonia separator 608, a liquid ammonia throttle valve 609, a liquid ammonia storage tank 610, a scavenging unit 611, a hydrogen separation unit 612, a third intermediate-temperature circulating pump 613, a high-temperature heat storage unit 614, a first high-temperature three-way valve 615, a first high-temperature circulating pump 617, a second high-temperature three-way valve 618, a mixed gas compressor unit 700, an nth stage mixed gas compressor 701, an nth stage mixed gas cooler 702, an ammonia synthesis unit 800, an nth stage ammonia reactor 801, and an nth stage ammonia cooler 802.
Detailed Description
The invention will be better understood from the following examples.
The structures, proportions, and dimensions shown in the drawings and described in the specification are for understanding and reading the present disclosure, and are not intended to limit the scope of the present disclosure, which is defined in the claims, and are not essential to the skilled in the art. In addition, the terms "upper", "lower", "front", "rear" and "middle" used in the present specification are for clarity of description, and are not intended to limit the scope of the present invention, and the relative relationship between the terms and the relative positions may be changed or adjusted without substantial technical changes.
As shown in fig. 1, the integrated device for liquid air energy storage and ammonia synthesis of the present invention comprises a liquid air energy storage circulation system and an ammonia synthesis circulation system:
the liquid air energy storage circulation system comprises: air separation liquefaction unit and air power generation unit:
wherein the air separation liquefaction unit includes: the system comprises an air compressor set 100, an nth-stage air compressor 101, an nth-stage air cooler 102, a first air three-way valve 201, a low-temperature cooler 202, a low-temperature turbo expander 203, a liquid air separator 204, a second air three-way valve 205, a third air three-way valve 206, a liquid air storage tank 207, a fourth air three-way valve 208, a fifth air three-way valve 209, a sixth air three-way valve 210, a cold storage unit 211, a first low-temperature three-way valve 212, a first low-temperature circulating pump 213, a second low-temperature three-way valve 214, a medium-temperature heat storage unit 215, a first medium-temperature three-way valve 216, a first medium-temperature circulating pump 217, a second medium-temperature three-way valve 218, a rectifying tower 300, a high-pressure chamber 301, a filler 302, a liquid oxygen throttle valve 303, a low-pressure chamber 304 and an evaporative condenser 305;
specifically, the air compressor package 100 has a right input, a left output, a lower input, and a lower output; the left output end of the first air three-way valve 201 is connected with the right input end of the air compressor unit 100, and the right input end of the first air three-way valve 201 is connected with the purified ambient air; the right input end of the cryocooler 202 is connected with the left output end of the air compressor unit 100; the input end of the low-temperature turboexpander 203 is connected with the left output end of the cryocooler 202; the upper input end of the liquid air separator 204 is connected with the output end of the low-temperature turbo-expander 203; the upper input end of the second air three-way valve 205 is connected with the lower output end of the liquid air separator 204; the upper input end of the third air three-way valve 206 is connected with the lower output end of the second air three-way valve 205; the input end of the liquid air storage tank 207 is connected with the right output end of the third air three-way valve 206; the right input end of the fourth air three-way valve 208 is connected with the left output end of the liquid air separator 204; the lower input end of the fifth air three-way valve 209 is connected with the upper output end of the fourth air three-way valve 208, and the right output end of the fifth air three-way valve 209 is connected with the left upper input end of the cryocooler 202; the lower input end of the sixth air three-way valve 210 is connected with the upper right output end of the cryocooler 202, the right input end of the sixth air three-way valve 210 is connected with the right input end of the air compressor set 100, and the left output end of the sixth air three-way valve 210 is connected with the environment; the cold storage unit 211 has a right side port and a left side port; a right port of the first low temperature three-way valve 212 is connected with a left port of the cold storage unit 211; the input end of the first low-temperature circulating pump 213 is connected with the upper output end of the first low-temperature three-way valve 212, and the output end of the first low-temperature circulating pump 213 is connected with the left lower input end of the cryocooler 202; the upper input end of the second low-temperature three-way valve 214 is connected with the right lower output end of the cryocooler 202, and the left port of the second low-temperature three-way valve 214 is connected with the right port of the cold storage unit 211; the medium-temperature heat storage unit 215 has a right port and a left port; the right port of the first medium-temperature three-way valve 216 is connected with the left port of the medium-temperature heat storage unit 215; the input end of the first intermediate-temperature circulating pump 217 is connected with the upper output end of the first intermediate-temperature three-way valve 216, and the output end of the first intermediate-temperature circulating pump 217 is connected with the lower input end of the air compressor unit 100; the upper input end of the second medium-temperature three-way valve 218 is connected with the lower output end of the air compressor unit 100, and the left port of the second medium-temperature three-way valve 218 is connected with the right port of the medium-temperature heat storage unit 215; the right upper side output end of the rectifying tower 300 is connected with the left side input end of the fifth air three-way valve 209, the right upper side input end of the rectifying tower 300 is connected with the left side output end of the second air three-way valve 205, the right lower side input end of the rectifying tower 300 is connected with the lower output end of the fourth air three-way valve 208, and the right lower side output end of the rectifying tower 300 is connected with the left side input end of the third air three-way valve 206;
the air power generation unit and the air separation liquefaction unit share the liquid air storage tank 207, the cold storage unit 211, the first low-temperature three-way valve 212, the second low-temperature three-way valve 214, the medium-temperature heat storage unit 215, the first medium-temperature three-way valve 216, and the second medium-temperature three-way valve 218, and further include: a low-temperature booster pump 401, an evaporator 402, a first nitrogen three-way valve 403, a third low-temperature three-way valve 404, a second low-temperature circulating pump 405, a second medium-temperature circulating pump 406, a third medium-temperature three-way valve 407, an air turbine unit 500, an nth-stage medium-temperature heater 501, an nth-stage high-temperature heater 502, an nth-stage turbine 503, a fourth medium-temperature three-way valve 504, and a fifth medium-temperature three-way valve 505;
specifically, the input end of the cryogenic booster pump 401 is connected with the output end of the liquid air storage tank 207; the left input end of the evaporator 402 is connected with the output end of the low-temperature booster pump 401, and the left output end of the evaporator 402 is connected with the lower input end of the first low-temperature three-way valve 212; the left input end of the first nitrogen three-way valve 403 is connected with the right output end of the evaporator 402; the upper input end of the third low-temperature three-way valve 404 is connected with the lower output end of the second low-temperature three-way valve 214, and the left output end of the third low-temperature three-way valve 404 is connected with the right input end of the evaporator 402; the input end of the second low-temperature circulating pump 405 is connected with the lower output end of the third low-temperature three-way valve 404, and the output end of the second low-temperature circulating pump 405 is connected with the right input end of the evaporator 402; the input end of the second medium-temperature circulating pump 406 is connected with the lower output end of the second medium-temperature three-way valve 218; the upper input end of the third medium-temperature three-way valve 407 is connected with the output end of the second medium-temperature circulating pump 406, and the left input end of the third medium-temperature three-way valve 407 is connected with the right port of the medium-temperature heat storage unit 215; the left input end of the air turbine set 500 is connected to the right output end of the first nitrogen three-way valve 403, the upper output end of the air turbine set 500 is connected to the lower input end of the first medium temperature three-way valve 216, and the upper input end of the air turbine set 500 is connected to the lower output end of the third medium temperature three-way valve 407;
the ammonia synthesis circulation system comprises: an air separation plant 601, a second nitrogen three-way valve 602, a first mixing chamber 603, a hydrogen generator 604, a second mixing chamber 605, a preheater 606, a normal-temperature cooler 607, a liquid ammonia separator 608, a liquid ammonia throttle valve 609, a liquid ammonia storage tank 610, a scavenging unit 611, a hydrogen separation unit 612, a third medium-temperature circulating pump 613, a high-temperature heat storage unit 614, a first high-temperature three-way valve 615, a first high-temperature circulating pump 616, a second high-temperature three-way valve 617, a second high-temperature circulating pump 618, a mixed gas compressor unit 700, an nth-stage mixed gas compressor 701, an nth-stage mixed gas cooler 702, an ammonia synthesis unit 800, an nth-stage ammonia reactor 801 and an nth-stage ammonia cooler 802;
specifically, the air separation plant 601 has a nitrogen output and an oxygen output; the lower input end of the second nitrogen three-way valve 602 is connected with the nitrogen output end of the air separation plant 601, and the upper output end of the second nitrogen three-way valve 602 is connected with the lower input end of the first air three-way valve 201; the right input end of the first mixing chamber 603 is connected to the left output end of the second nitrogen three-way valve 602, and the upper input end of the first mixing chamber 603 is connected to the right output end of the air turbine unit 500; the hydrogen output end of the hydrogen generator 604 is connected with the lower input end of the first mixing chamber 603; the upper input end of the second mixing chamber 605 is connected with the lower output end of the first nitrogen three-way valve 403; the right input end of the preheater 606 is connected with the left output end of the second mixing chamber 605; the input end of the normal temperature cooler 607 is connected with the right output end of the preheater 606; the upper input end of the liquid ammonia separator 608 is connected with the output end of the normal temperature cooler 607; the input end of the liquid ammonia throttling valve 609 is connected with the lower output end of the liquid ammonia separator 608; the input end of the liquid ammonia storage tank 610 is connected with the output end of the liquid ammonia throttling valve 609; the left input end of the scavenging unit 611 is connected with the right output end of the liquid ammonia separator 608, and the upper output end of the scavenging unit 611 is connected with the lower input end of the second mixing chamber 605; the left input end of the hydrogen separation unit 612 is connected with the right output end of the scavenging unit 611, and the lower output end of the hydrogen separation unit 612 is connected with the external environment; the input end of the third medium temperature circulating pump 613 is connected to the lower left output end of the air turbine group 500; the high temperature heat storage unit 614 has an upper port and a lower port; an upper port of the first high-temperature three-way valve 615 is connected with a lower port of the high-temperature heat storage unit 614; the input end of the first high-temperature circulating pump 616 is connected with the right output end of the first high-temperature three-way valve 615; the lower port of the second high-temperature three-way valve 617 is connected to the upper port of the high-temperature heat storage unit 614, and the upper output end of the second high-temperature three-way valve 617 is connected to the lower right input end of the air turbine unit 500; the output end of the second high temperature circulation pump 618 is connected with the left side input end of the first high temperature three-way valve 615, and the input end of the second high temperature circulation pump 618 is connected with the lower middle output end of the air turbine unit 500; the right input end of the mixed gas compressor group 700 is connected to the left output end of the first mixing chamber 603, the upper output end of the mixed gas compressor group 700 is connected to the lower middle input end of the air turbine group 500, the upper input end of the mixed gas compressor group 700 is connected to the output end of the third medium temperature circulating pump 613, the left output end of the mixed gas compressor group 700 is connected to the right input end of the second mixing chamber 605, and the lower input end of the mixed gas compressor group 700 is connected to the upper output end of the hydrogen separation unit 612; the upper input of ammonia synthesis unit 800 is connected with the left side output of preheater 606, and the lower part output of ammonia synthesis unit 800 is connected with the left side input of preheater 606, and the left side input of ammonia synthesis unit 800 is connected with the output of first high temperature circulating pump 616, and the left side output of ammonia synthesis unit 800 is connected with the right side input of second high temperature three-way valve 617.
The method for liquid air energy storage and ammonia synthesis by adopting the device comprises the following steps:
during the electricity consumption trough period, the air separation liquefaction unit and the ammonia synthesis circulation system work, and the device operation divides two kinds of modes:
in the first mode, a part of gaseous nitrogen produced by the air separation plant 601 is supplied to the air separation liquefaction unit to acquire and store liquid nitrogen, and the other part is supplied to the ammonia synthesis circulation system, and the method specifically comprises the following steps: the air separation liquefaction unit works: a part of gaseous nitrogen produced by the air separation plant 601 enters the air compressor unit 100 through the second nitrogen three-way valve 602 and the first air three-way valve 201, the gaseous nitrogen is compressed to a high pressure, and meanwhile, compression heat generated in the compression process is recovered and stored in the medium-temperature heat storage unit 215; the high-pressure gaseous nitrogen at the outlet of the air compressor unit 100 enters the low-temperature cooler 202, is cooled to low temperature by the low-temperature cold energy stored in the cold storage unit 211 and the returned gaseous nitrogen, then enters the low-temperature turboexpander 203 to be expanded and decompressed, wherein a part of the gaseous nitrogen is liquefied, and the gaseous nitrogen and the liquid nitrogen are separated by the liquid air separator 204: the liquid nitrogen enters the liquid air storage tank 207 through the second air three-way valve 205 and the third air three-way valve 206, and the gaseous nitrogen enters the air compressor set 100 through the fourth air three-way valve 208, the fifth air three-way valve 209, the cryocooler 202 and the sixth air three-way valve 210; the ammonia synthesis circulating system works: another part of gaseous nitrogen produced by the air separation plant 601 enters the first mixing chamber 603 through the second nitrogen three-way valve 602, is fully mixed with hydrogen produced by the hydrogen generator 604, enters the mixed gas compressor unit 700 to be pressurized to the medium pressure, is mixed with unreacted hydrogen recycled by the hydrogen separation unit 612 and is further pressurized to the high pressure, and simultaneously recovers compression heat generated in the compression process and stores the compression heat in the medium-temperature heat storage unit 215; high-pressure gas at the outlet of the mixed gas compressor unit 700 enters the second mixing chamber 605, is fully mixed with unreacted gas recovered from the scavenging unit 611, is preheated by the preheater 606, enters the ammonia synthesis unit 800 to synthesize ammonia, and stores reaction heat generated in the ammonia synthesis reaction process in the high-temperature heat storage unit 614; the mixed gas after the reaction is cooled to normal temperature sequentially through a preheater 606 and a normal temperature cooler 607, ammonia gas in the mixed gas is condensed, and then the mixed gas enters a liquid ammonia separator 608 to separate liquid ammonia and unreacted gas: liquid ammonia enters a liquid ammonia storage tank 610 after throttling and pressure reduction through a liquid ammonia throttle valve 609, and unreacted gas is discharged finally after completing scavenging and hydrogen recovery through a scavenging unit 611 and a hydrogen separation unit 612 in sequence;
in the second mode, the air separation liquefaction unit separates and liquefies nitrogen from air, one part of liquid nitrogen is stored in the liquid air storage tank 207, and the other part of liquid nitrogen is pressurized and preheated and then is supplied to the ammonia synthesis circulation system, and the method specifically comprises the following steps: the air separation liquefaction unit works: after the ambient air is purified, the ambient air enters the air compressor unit 100 through the first air three-way valve 201 to be pressurized to a high pressure, and meanwhile, the compression heat generated in the air compression process is recovered and stored in the medium-temperature heat storage unit 215; the high-pressure air at the outlet of the air compressor unit 100 passes through the low-temperature cooler 202, is cooled to a low temperature by the low-temperature cold energy stored in the cold storage unit 211 and the returned oxygen-enriched air, enters the low-temperature turbo expander 203 for expansion and decompression, wherein a part of air is liquefied, and then enters the liquid air separator 204 for separating gaseous and liquid air: liquid air enters the high-pressure chamber 301 of the rectifying tower 300 through the second air three-way valve 205 and is sprayed from top to bottom, and gaseous air enters the high-pressure chamber 301 of the rectifying tower 300 through the fourth air three-way valve 208 and is blown from bottom to top; the gaseous air and the liquid air complete heat and mass exchange in the filler 302, the high-purity gaseous nitrogen is gathered at the top of the high-pressure chamber 301, and the oxygen-enriched liquid air is gathered at the bottom of the high-pressure chamber 301; the oxygen-enriched liquid air at the bottom of the high-pressure chamber 301 is cooled and depressurized through the liquid oxygen throttle valve 303, enters the low-pressure chamber 304 to release cold energy to become gaseous oxygen-enriched air, and is discharged into the environment through the fifth air three-way valve 209, the cryocooler 202 and the sixth air three-way valve 210; the high-purity gaseous nitrogen at the top of the high-pressure chamber 301 enters an evaporative condenser 305 of the low-pressure chamber 304, the oxygen-enriched liquid air after throttling and pressure reduction is condensed into liquid nitrogen, one part of the liquid nitrogen flows back to the high-pressure chamber 301 for spraying, and the other part of the liquid nitrogen enters a liquid air storage tank 207 through a third air three-way valve 206; one part of liquid nitrogen in the liquid air storage tank 207 is stored, the other part of the liquid nitrogen is pressurized by a low-temperature pressurizing pump 401 and then enters an evaporator 402 for preheating, and meanwhile, released cold energy is stored in a cold storage unit 211; the normal-temperature high-pressure gaseous nitrogen at the outlet of the evaporator 402 is supplied to the ammonia synthesis circulation system through a first nitrogen three-way valve 403; the ammonia synthesis circulating system works: hydrogen produced by the hydrogen generator 604 enters the mixed gas compressor unit 700 through the first mixing chamber 603, is primarily compressed to medium pressure, is mixed with unreacted hydrogen recovered from the hydrogen separation unit 612, is further compressed to high pressure, and simultaneously recovers compression heat generated in the hydrogen compression process and stores the compression heat in the medium-temperature heat storage unit 215; the high-pressure hydrogen at the outlet of the mixed gas compressor unit 700 enters the second mixing chamber 605, is fully mixed with the high-pressure nitrogen supplied by the liquid air storage tank 207 and the unreacted gas recovered by the scavenging unit 611, is preheated by the preheater 606, enters the ammonia synthesis unit 800 to complete the ammonia synthesis reaction, and recovers the reaction heat and stores the reaction heat in the high-temperature heat storage unit 614; the fully reacted mixed gas is cooled to normal temperature through a preheater 606 and a normal temperature cooler 607 in sequence, ammonia gas in the mixed gas is condensed, and then the mixed gas enters a liquid ammonia separator 608 to separate liquid ammonia and unreacted gas: liquid ammonia enters a liquid ammonia storage tank 610 after being throttled and depressurized by a liquid ammonia throttle valve 609, and unreacted gas is discharged finally after being subjected to scavenging and hydrogen recovery by a scavenging unit 611 and a hydrogen separation unit 612 in sequence.
During the peak period of electricity utilization, the air power generation unit and the ammonia synthesis circulating system work, and the method specifically comprises the following steps:
the air power generation unit works: liquid nitrogen stored in the liquid air storage tank 207 is pressurized to high pressure by a low-temperature pressurizing pump 401, then enters an evaporator 402 for preheating, is evaporated and vaporized into gaseous nitrogen, and simultaneously stores cold energy released by evaporation of the liquid nitrogen in a cold storage unit 211; the normal-temperature high-pressure gaseous nitrogen at the outlet of the evaporator 402 is divided into two paths by a first nitrogen three-way valve 403: one part of the mixed gas enters a second mixing chamber 605 to be supplied to the ammonia synthesis circulation system, the other part of the mixed gas enters an air turbine unit 500 to be subjected to two-stage preheating and then expansion power generation, and then the mixed gas enters a first mixing chamber 603 to be supplied to the ammonia synthesis circulation system; the ammonia synthesis circulating system works: hydrogen produced by the hydrogen generator 604 enters the first mixing chamber 603, is fully mixed with nitrogen at the outlet of the air turbine unit 500, then enters the mixed gas compressor unit 700 for preliminary compression to a medium pressure, is further compressed to a high pressure after being mixed with unreacted hydrogen recovered by the hydrogen separation unit 612, and simultaneously recovers compression heat generated in the compression process for preliminary preheating of nitrogen in the air turbine unit 500; the high-pressure gas at the outlet of the mixed gas compressor unit 700 enters the second mixing chamber 605, is fully mixed with a part of nitrogen shunted at the outlet of the evaporator 402 and the unreacted gas recovered in the scavenging unit 611, enters the ammonia synthesis unit 800 to synthesize ammonia after being preheated by the preheater 606, and recovers the reaction heat generated in the ammonia synthesis reaction process for further preheating the nitrogen in the air turbine unit 500; the mixed gas after the reaction is cooled to normal temperature sequentially through a preheater 606 and a normal temperature cooler 607, ammonia gas in the mixed gas is condensed, and then the mixed gas enters a liquid ammonia separator 608 to separate liquid ammonia and unreacted gas: liquid ammonia enters the liquid ammonia storage tank 610 after throttling and pressure reduction through the liquid ammonia throttling valve 609, and unreacted gas is discharged finally after completing scavenging and hydrogen recovery through the scavenging unit 611 and the hydrogen separation unit 612 in sequence.
During the electricity consumption peak period, the air turbine set 500 preheats the nitrogen to the intermediate temperature primarily by using the compression heat stored in the intermediate-temperature heat storage unit 215 and the compression heat generated in real time by the mixed gas compressor set 700, and then preheats the nitrogen to the high temperature further by using the reaction heat stored in the high-temperature heat storage unit 614 and the reaction heat generated in real time by the ammonia synthesis unit 800, so that the power generation amount and the efficiency of the liquid air energy storage circulation system are improved; when the demand for heat for the air turbine unit 500 is reduced, the excess compression heat generated in real time by the mixed gas compressor unit 700 may be stored in the medium temperature heat storage unit 215, and the excess reaction heat generated in real time by the ammonia gas synthesizing unit 800 may be stored in the high temperature heat storage unit 614.
Fig. 2 is a first embodiment of the integrated liquid air energy storage and ammonia synthesis apparatus shown in fig. 1. The embodiment is suitable for the situation that the air separation plant 601 is already built, the liquid air energy storage circulation system only provides the liquefaction function (does not have the rectifying tower 300), and the operation cost of the ammonia synthesis circulation system can be reduced; the ammonia synthesis circulation system supplies nitrogen through the air separation plant 601 during the electricity consumption valley period and supplies nitrogen through the liquid air energy storage circulation system during the electricity consumption peak period.
Specifically, the liquid air energy storage circulation system includes: an air separation liquefaction unit and an air power generation unit. The air separation liquefaction unit comprises: the system comprises an air compressor set 100, an nth stage air compressor 101, an nth stage air cooler 102, a first air three-way valve 201, a low-temperature cooler 202, a low-temperature turboexpander 203, a liquid air separator 204, a second air three-way valve 205, a third air three-way valve 206, a liquid air storage tank 207, a fourth air three-way valve 208, a fifth air three-way valve 209, a sixth air three-way valve 210, a cold storage unit 211, a first low-temperature three-way valve 212, a first low-temperature circulating pump 213, a second low-temperature three-way valve 214, a medium-temperature heat storage unit 215, a first medium-temperature three-way valve 216, a first medium-temperature circulating pump 217 and a second medium-temperature three-way valve 218; the air power generation unit and the air separation liquefaction unit share the liquid air storage tank 207, the cold storage unit 211, the first low-temperature three-way valve 212, the second low-temperature three-way valve 214, the medium-temperature heat storage unit 215, the first medium-temperature three-way valve 216, and the second medium-temperature three-way valve 218, and further include: a low-temperature booster pump 401, an evaporator 402, a first nitrogen three-way valve 403, a third low-temperature three-way valve 404, a second low-temperature circulating pump 405, a second medium-temperature circulating pump 406, a third medium-temperature three-way valve 407, an air turbine unit 500, an nth-stage medium-temperature heater 501, an nth-stage high-temperature heater 502, an nth-stage turbine 503, a fourth medium-temperature three-way valve 504, and a fifth medium-temperature three-way valve 505; the ammonia synthesis circulation system comprises: an air separation plant 601, a second nitrogen three-way valve 602, a first mixing chamber 603, a hydrogen generator 604, a second mixing chamber 605, a preheater 606, a normal-temperature cooler 607, a liquid ammonia separator 608, a liquid ammonia throttle valve 609, a liquid ammonia storage tank 610, a scavenging unit 611, a hydrogen separation unit 612, a third medium-temperature circulating pump 613, a high-temperature heat storage unit 614, a first high-temperature three-way valve 615, a first high-temperature circulating pump 616, a second high-temperature three-way valve 617, a second high-temperature circulating pump 618, a mixed gas compressor unit 700, an nth-stage mixed gas compressor 701, an nth-stage mixed gas cooler 702, an ammonia synthesis unit 800, an nth-stage ammonia reactor 801 and an nth-stage ammonia cooler 802;
during the electricity consumption valley period, the air separation liquefaction unit and the ammonia synthesis circulation system work, as shown in figure 2-1:
one part of the gaseous nitrogen produced by the air separation plant 601 is supplied to the air separation liquefaction unit to obtain and store liquid nitrogen, and the other part of the gaseous nitrogen is supplied to the ammonia synthesis circulation system, and the method specifically comprises the following steps: the air separation liquefaction unit works: a part of gaseous nitrogen produced by the air separation plant 601 enters the air compressor unit 100 through the second nitrogen three-way valve 602 and the first air three-way valve 201, the gaseous nitrogen is compressed to a high pressure (about 120 bar), and meanwhile, compression heat (about 220 ℃) generated in the compression process is recovered and stored in the medium-temperature heat storage unit 215; the high-pressure gaseous nitrogen at the outlet of the air compressor unit 100 enters the low-temperature cooler 202, is cooled to low temperature by the low-temperature cold energy stored in the cold storage unit 211 and the returned gaseous nitrogen, and then enters the low-temperature turbo expander 203 to be expanded and decompressed (1bar), wherein a part of the gaseous nitrogen is liquefied, and the gaseous nitrogen and the liquid nitrogen are separated by the liquid air separator 204: the liquid nitrogen enters the liquid air storage tank 207 through the second air three-way valve 205 and the third air three-way valve 206, and the gaseous nitrogen enters the air compressor set 100 through the fourth air three-way valve 208, the fifth air three-way valve 209, the cryocooler 202 and the sixth air three-way valve 210; the ammonia synthesis circulating system works: the other part of gaseous nitrogen produced by the air separation plant 601 enters the first mixing chamber 603 through the second nitrogen three-way valve 602, is fully mixed with the hydrogen produced by the hydrogen generator 604, enters the mixed gas compressor unit 700 to be pressurized to the middle pressure (about 28 bar), is mixed with the unreacted hydrogen recovered by the hydrogen separation unit 612 and is further pressurized to the high pressure (about 150 bar), and meanwhile, the compression heat (about 230 ℃) generated in the compression process is recovered and is stored in the medium-temperature heat storage unit 215; high-pressure gas at the outlet of the mixed gas compressor unit 700 enters the second mixing chamber 605, is fully mixed with unreacted gas recovered from the scavenging unit 611, enters the ammonia gas synthesis unit 800 to synthesize ammonia gas after being preheated by the preheater 606, and simultaneously stores reaction heat (about 500 ℃) generated in the ammonia gas synthesis reaction process in the high-temperature heat storage unit 614; the mixed gas after the reaction is cooled to normal temperature sequentially through a preheater 606 and a normal temperature cooler 607, ammonia gas in the mixed gas is condensed, and then the mixed gas enters a liquid ammonia separator 608 to separate liquid ammonia and unreacted gas: liquid ammonia enters a liquid ammonia storage tank 610 after throttling and pressure reduction through a liquid ammonia throttle valve 609, and unreacted gas is discharged finally after completing scavenging and hydrogen recovery through a scavenging unit 611 and a hydrogen separation unit 612 in sequence;
during the peak period of electricity utilization, the air power generation unit and the ammonia synthesis circulation system work, as shown in the figure 2-2:
the air power generation unit works: liquid nitrogen stored in the liquid air storage tank 207 is pressurized to a high pressure (about 150 bar) by a low-temperature pressurizing pump 401, then enters an evaporator 402 for preheating, is evaporated and vaporized into gaseous nitrogen, and simultaneously stores cold energy released by evaporation of the liquid nitrogen in a cold storage unit 211; the normal-temperature high-pressure gaseous nitrogen at the outlet of the evaporator 402 is divided into two paths by a first nitrogen three-way valve 403: one part of the mixed gas enters a second mixing chamber 605 to be supplied to the ammonia synthesis circulation system, the other part of the mixed gas enters an air turbine unit 500 to be subjected to two-stage preheating and then expansion power generation, and then the mixed gas enters a first mixing chamber 603 to be supplied to the ammonia synthesis circulation system; the ammonia synthesis circulating system works: hydrogen produced by the hydrogen generator 604 enters the first mixing chamber 603, is fully mixed with nitrogen at the outlet of the air turbine unit 500, then enters the mixed gas compressor unit 700 to be preliminarily compressed to a medium pressure (about 28 bar), is further compressed to a high pressure (about 150 bar) after being mixed with unreacted hydrogen recycled by the hydrogen separation unit 612, and simultaneously recovers compression heat (about 230 ℃) generated in the compression process for preliminarily preheating the nitrogen in the air turbine unit 500; the high-pressure gas at the outlet of the mixed gas compressor unit 700 enters the second mixing chamber 605, is fully mixed with a part of nitrogen shunted at the outlet of the evaporator 402 and unreacted gas recovered from the scavenging unit 611, enters the ammonia synthesis unit 800 to synthesize ammonia after being preheated by the preheater 606, and simultaneously recovers reaction heat (about 500 ℃) generated in the ammonia synthesis reaction process for further preheating the nitrogen in the air turbine unit 500; the mixed gas after the reaction is cooled to normal temperature sequentially through a preheater 606 and a normal temperature cooler 607, ammonia gas in the mixed gas is condensed, and then the mixed gas enters a liquid ammonia separator 608 to separate liquid ammonia and unreacted gas: liquid ammonia enters the liquid ammonia storage tank 610 after throttling and pressure reduction through the liquid ammonia throttling valve 609, and unreacted gas is discharged finally after completing scavenging and hydrogen recovery through the scavenging unit 611 and the hydrogen separation unit 612 in sequence.
To further illustrate the operational performance of the first embodiment (fig. 2), thermodynamic and economic analyses were performed on the entire system. According to the electricity price for saving labor in Jiangsu (as shown in Table 1, wherein the flat period and the low valley period are electricity consumption low valley periods), the power generation efficiency of the liquid air energy storage circulation system is improved by about 30% (absolute value), and as shown in Table 2, the corresponding ammonia synthesis circulation system can save the operation cost by about 100 yuan per ton of ammonia produced in the electricity consumption peak period.
TABLE 1 Utility price of electricity for Jiangsu province
Table 2 performance of the liquid air energy storage cycle system in the first embodiment
Fig. 3 is a second embodiment of the integrated liquid air energy storage and ammonia synthesis apparatus shown in fig. 1. The embodiment is suitable for the condition that the air separation plant 601 is not built (or not available), and the liquid air energy storage circulation system is combined with the rectifying tower 300 to realize the air separation and liquefaction functions, so that the operation and investment cost of the ammonia synthesis circulation system can be reduced; the ammonia synthesis circulation system supplies nitrogen and stores liquid nitrogen through liquid air energy storage circulation system at the electricity consumption valley time period, and supplies ammonia synthesis circulation system through the liquid nitrogen that liquid air energy storage circulation system stored at the electricity consumption peak time period, and the concrete operation steps are as follows:
during the electricity consumption valley period, the air separation liquefaction unit and the ammonia synthesis circulation system work, as shown in figure 3-1:
the air separation liquefaction unit works: after being purified, the ambient air enters the air compressor unit 100 through the first air three-way valve 201 to be pressurized to a high pressure, and meanwhile, the compression heat generated in the air compression process is recovered and stored in the medium-temperature heat storage unit 215; the high-pressure air at the outlet of the air compressor unit 100 passes through the low-temperature cooler 202, is cooled to low temperature by the low-temperature cold energy stored in the cold storage unit 211 and the returned oxygen-enriched air, enters the low-temperature turboexpander 203 for expansion and pressure reduction, wherein a part of air is liquefied, and then enters the liquid air separator 204 for separating gas air and liquid air: liquid air enters the high-pressure chamber 301 of the rectifying tower 300 through the second air three-way valve 205 and is sprayed from top to bottom, and gaseous air enters the high-pressure chamber 301 of the rectifying tower 300 through the fourth air three-way valve 208 and is blown from bottom to top; the gaseous air and the liquid air complete heat and mass exchange in the filler 302, the high-purity gaseous nitrogen is gathered at the top of the high-pressure chamber 301, and the oxygen-enriched liquid air is gathered at the bottom of the high-pressure chamber 301; the oxygen-enriched liquid air at the bottom of the high-pressure chamber 301 is cooled and depressurized through the liquid oxygen throttle valve 303, enters the low-pressure chamber 304 to release cold energy to become gaseous oxygen-enriched air, and is discharged into the environment through the fifth air three-way valve 209, the cryocooler 202 and the sixth air three-way valve 210; the high-purity gaseous nitrogen at the top of the high-pressure chamber 301 enters an evaporative condenser 305 of the low-pressure chamber 304, the oxygen-enriched liquid air after throttling and pressure reduction is condensed into liquid nitrogen, one part of the liquid nitrogen flows back to the high-pressure chamber 301 for spraying, and the other part of the liquid nitrogen enters a liquid air storage tank 207 through a third air three-way valve 206; one part of liquid nitrogen in the liquid air storage tank 207 is stored, the other part of the liquid nitrogen is pressurized by a low-temperature pressurizing pump 401 and then enters an evaporator 402 for preheating, and meanwhile, released cold energy is stored in a cold storage unit 211; the normal-temperature high-pressure gaseous nitrogen at the outlet of the evaporator 402 is supplied to the ammonia synthesis circulation system through a first nitrogen three-way valve 403; the ammonia synthesis circulating system works: hydrogen produced by the hydrogen generator 604 enters the mixed gas compressor unit 700 through the first mixing chamber 603, is primarily compressed to medium pressure, is mixed with unreacted hydrogen recovered from the hydrogen separation unit 612, is further compressed to high pressure, and simultaneously recovers compression heat generated in the hydrogen compression process and stores the compression heat in the medium-temperature heat storage unit 215; the high-pressure hydrogen at the outlet of the mixed gas compressor unit 700 enters the second mixing chamber 605, is fully mixed with the high-pressure nitrogen supplied by the liquid air storage tank 207 and the unreacted gas recovered by the scavenging unit 611, is preheated by the preheater 606, enters the ammonia synthesis unit 800 to complete the ammonia synthesis reaction, and recovers the reaction heat and stores the reaction heat in the high-temperature heat storage unit 614; the fully reacted mixed gas is cooled to normal temperature through a preheater 606 and a normal temperature cooler 607 in sequence, ammonia gas in the mixed gas is condensed, and then the mixed gas enters a liquid ammonia separator 608 to separate liquid ammonia and unreacted gas: liquid ammonia enters the liquid ammonia storage tank 610 after throttling and pressure reduction through the liquid ammonia throttling valve 609, and unreacted gas is discharged finally after completing scavenging and hydrogen recovery through the scavenging unit 611 and the hydrogen separation unit 612 in sequence.
During peak electricity consumption, the air power generation unit and the ammonia synthesis circulation system are operated as shown in fig. 3-2, and the specific steps are the same as those of the first embodiment (fig. 2-2).
The invention provides a device and a method for integrating liquid air energy storage and ammonia synthesis, and a method and a device for integrating liquid air energy storage and ammonia synthesis, and a plurality of methods and ways for implementing the technical scheme are provided. All the components not specified in this embodiment can be implemented by the prior art.
Claims (10)
1. The utility model provides a liquid air energy storage and ammonia synthesis integrated device, its characterized in that, the device includes liquid air energy storage circulating system and ammonia synthesis circulating system, wherein:
the liquid air energy storage circulation system comprises: an air separation liquefaction unit and an air power generation unit;
the air separation liquefaction unit comprises:
an air compressor package (100), the air compressor package (100) having a right side input, a left side output, a lower input, and a lower output;
the left output end of the first air three-way valve (201) is connected with the right input end of the air compressor unit (100); the right input end of the first air three-way valve (201) is connected with the purified ambient air;
the right input end of the low-temperature cooler (202) is connected with the left output end of the air compressor unit (100);
a low temperature turboexpander (203), an input of the low temperature turboexpander (203) being connected to a left side output of the cryocooler (202);
a liquid air separator (204), wherein the upper input end of the liquid air separator (204) is connected with the output end of the low-temperature turbo-expander (203);
a second three-way air valve (205), wherein the upper input end of the second three-way air valve (205) is connected with the lower output end of the liquid air separator (204);
a third air three-way valve (206), wherein the upper input end of the third air three-way valve (206) is connected with the lower output end of the second air three-way valve (205);
the input end of the liquid air storage tank (207) is connected with the right output end of the third air three-way valve (206);
a fourth air three-way valve (208), wherein the right input end of the fourth air three-way valve (208) is connected with the left output end of the liquid air separator (204);
a fifth air three-way valve (209), wherein the lower input end of the fifth air three-way valve (209) is connected with the upper output end of the fourth air three-way valve (208); the right output end of the fifth air three-way valve (209) is connected with the left upper input end of the cryocooler (202);
a sixth air three-way valve (210), wherein the lower input end of the sixth air three-way valve (210) is connected with the upper right output end of the cryocooler (202); the right input end of the sixth air three-way valve (210) is connected with the right input end of the air compressor unit (100); the left output end of the sixth air three-way valve (210) is connected with the environment;
a cold storage unit (211), the cold storage unit (211) having a right side port and a left side port;
a first low temperature three-way valve (212), a right port of the first low temperature three-way valve (212) being connected with a left port of the cold storage unit (211);
the input end of the first low-temperature circulating pump (213) is connected with the upper output end of the first low-temperature three-way valve (212); the output end of the first low-temperature circulating pump (213) is connected with the lower left input end of the cryocooler (202);
a second low-temperature three-way valve (214), wherein the upper input end of the second low-temperature three-way valve (214) is connected with the lower right output end of the cryocooler (202); a left port of the second low-temperature three-way valve (214) is connected with a right port of the cold storage unit (211);
a medium temperature thermal storage unit (215), the medium temperature thermal storage unit (215) having a right side port and a left side port;
a first medium-temperature three-way valve (216), wherein a right port of the first medium-temperature three-way valve (216) is connected with a left port of the medium-temperature heat storage unit (215);
the input end of the first medium-temperature circulating pump (217) is connected with the upper output end of the first medium-temperature three-way valve (216); the output end of the first medium-temperature circulating pump (217) is connected with the lower input end of the air compressor unit (100);
the upper input end of the second medium-temperature three-way valve (218) is connected with the lower output end of the air compressor unit (100); the left port of the second medium-temperature three-way valve (218) is connected with the right port of the medium-temperature heat storage unit (215);
the right upper side output end of the rectifying tower (300) is connected with the left side input end of the fifth air three-way valve (209); the right upper side input end of the rectifying tower (300) is connected with the left side output end of the second air three-way valve (205); the right lower side input end of the rectifying tower (300) is connected with the lower output end of the fourth air three-way valve (208); the right lower side output end of the rectifying tower (300) is connected with the left side input end of the third air three-way valve (206);
the air power generation unit with air separation liquefaction unit sharing liquid air storage tank (207), cold storage unit (211), first low temperature three-way valve (212), second low temperature three-way valve (214), medium temperature heat-retaining unit (215), first medium temperature three-way valve (216) and second medium temperature three-way valve (218), still include:
the input end of the low-temperature booster pump (401) is connected with the output end of the liquid air storage tank (207);
the left input end of the evaporator (402) is connected with the output end of the low-temperature booster pump (401); the left output end of the evaporator (402) is connected with the lower input end of the first low-temperature three-way valve (212);
a first nitrogen three-way valve (403), wherein the left input end of the first nitrogen three-way valve (403) is connected with the right output end of the evaporator (402);
a third low-temperature three-way valve (404), wherein the upper input end of the third low-temperature three-way valve (404) is connected with the lower output end of the second low-temperature three-way valve (214); the left output end of the third low-temperature three-way valve (404) is connected with the right input end of the evaporator (402);
the input end of the second low-temperature circulating pump (405) is connected with the lower output end of the third low-temperature three-way valve (404); the output end of the second low-temperature circulating pump (405) is connected with the right input end of the evaporator (402);
the input end of the second medium-temperature circulating pump (406) is connected with the lower output end of the second medium-temperature three-way valve (218);
a third medium-temperature three-way valve (407), wherein the upper input end of the third medium-temperature three-way valve (407) is connected with the output end of the second medium-temperature circulating pump (406); the left input end of the third medium-temperature three-way valve (407) is connected with the right port of the medium-temperature heat storage unit (215);
an air turbine set (500), wherein the left input end of the air turbine set (500) is connected with the right output end of the first nitrogen three-way valve (403); the upper output end of the air turbine unit (500) is connected with the lower input end of the first medium-temperature three-way valve (216); the upper input end of the air turbine unit (500) is connected with the lower output end of the third medium-temperature three-way valve (407);
the ammonia synthesis circulation system comprises:
an air separation plant (601), the air separation plant (601) having a nitrogen output and an oxygen output;
the lower input end of the second nitrogen three-way valve (602) is connected with the nitrogen output end of the air separation plant (601); the upper output end of the second nitrogen three-way valve (602) is connected with the lower input end of the first air three-way valve (201);
a first mixing chamber (603), wherein the right input end of the first mixing chamber (603) is connected with the left output end of the second nitrogen three-way valve (602); the upper input end of the first mixing chamber (603) is connected with the right output end of the air turbine set (500);
a hydrogen gas generator (604), wherein the hydrogen gas output end of the hydrogen gas generator (604) is connected with the lower input end of the first mixing chamber (603);
the upper input end of the second mixing chamber (605) is connected with the lower output end of the first nitrogen three-way valve (403);
the right side input end of the preheater (606) is connected with the left side output end of the second mixing chamber (605);
the input end of the normal-temperature cooler (607) is connected with the right output end of the preheater (606);
the upper input end of the liquid ammonia separator (608) is connected with the output end of the normal temperature cooler (607);
an input end of the liquid ammonia throttling valve (609) is connected with a lower output end of the liquid ammonia separator (608);
the input end of the liquid ammonia storage tank (610) is connected with the output end of the liquid ammonia throttling valve (609);
a scavenging unit (611), a left input of the scavenging unit (611) being connected to a right output of the liquid ammonia separator (608); the upper output end of the scavenging unit (611) is connected with the lower input end of the second mixing chamber (605);
a hydrogen separation unit (612), wherein a left input end of the hydrogen separation unit (612) is connected with a right output end of the scavenging unit (611); the lower output end of the hydrogen separation unit (612) is connected with an external waste gas treatment unit;
a third medium temperature circulating pump (613), an input end of the third medium temperature circulating pump (613) being connected to a lower left output end of the air turbine group (500);
a high temperature heat storage unit (614), the high temperature heat storage unit (614) having an upper port and a lower port;
a first high-temperature three-way valve (615), wherein the upper port of the first high-temperature three-way valve (615) is connected with the lower port of the high-temperature heat storage unit (614);
the input end of the first high-temperature circulating pump (616) is connected with the right output end of the first high-temperature three-way valve (615);
a second high-temperature three-way valve (617), wherein the lower port of the second high-temperature three-way valve (617) is connected with the upper port of the high-temperature heat storage unit (614); the upper output end of the second high-temperature three-way valve (617) is connected with the lower right input end of the air turbine unit (500);
the output end of the second high-temperature circulating pump (618) is connected with the left input end of the first high-temperature three-way valve (615); the input end of the second high-temperature circulating pump (618) is connected with the lower middle output end of the air turbine set (500);
a mixed gas compressor set (700), wherein the right input end of the mixed gas compressor set (700) is connected with the left output end of the first mixing chamber (603); the upper output end of the mixed gas compressor unit (700) is connected with the lower middle input end of the air turbine unit (500); the upper input end of the mixed gas compressor unit (700) is connected with the output end of the third medium-temperature circulating pump (613); the left output end of the mixed gas compressor set (700) is connected with the right input end of the second mixing chamber (605); the lower input end of the mixed gas compressor unit (700) is connected with the upper output end of the hydrogen separation unit (612);
the upper input end of the ammonia synthesis unit (800) is connected with the left output end of the preheater (606); the lower output end of the ammonia synthesis unit (800) is connected with the left input end of the preheater (606); the left input end of the ammonia synthesis unit (800) is connected with the output end of the first high-temperature circulating pump (616); and the left output end of the ammonia synthesis unit (800) is connected with the right input end of the second high-temperature three-way valve (617).
2. The integrated liquid air energy storage and ammonia synthesis plant according to claim 1, characterized in that said air compressor group (100) comprises one or more stages of air compressors and air coolers; the air turbine set (500) comprises a one-stage or multi-stage medium-temperature heater, a high-temperature heater, a turbine and a medium-temperature three-way valve; the mixed gas compressor set (700) comprises one or more stages of mixed gas compressors and mixed gas coolers; the ammonia synthesis unit (800) comprises one or more stages of ammonia reactors and ammonia coolers.
3. The integrated device for liquid air energy storage and ammonia synthesis according to claim 1, characterized in that said rectifying column (300) comprises:
a high pressure chamber (301), said high pressure chamber (301) having an upper input, an upper output, a lower output, an upper right input and a lower right input; the right upper side input end of the high-pressure chamber (301) is connected with the right upper side input end of the rectifying tower (300); the right lower side input end of the high-pressure chamber (301) is connected with the right lower side input end of the rectifying tower (300);
a filler (302), the filler (302) being located inside the high pressure chamber (301);
the input end of the liquid oxygen throttle valve (303) is connected with the lower output end of the high-pressure chamber (301);
a low pressure chamber (304), the low pressure chamber (304) being located on top of the high pressure chamber (301); the left input end of the low-pressure chamber (304) is connected with the output end of the liquid oxygen throttle valve (303); the upper output end of the low-pressure chamber (304) is connected with the upper right output end of the rectifying tower (300);
an evaporative condenser (305), the evaporative condenser (305) located inside the low pressure chamber (304); the input end of the evaporative condenser (305) is connected with the upper output end of the high-pressure chamber (301); the output end of the evaporative condenser (305) is divided into two paths: one path is connected with the upper input end of the high-pressure chamber (301), and the other path is connected with the right lower output end of the rectifying tower (300).
4. The integrated device for liquid air energy storage and ammonia synthesis as claimed in claim 1, wherein the cold storage unit (211), the medium temperature heat storage unit (215) and the high temperature heat storage unit (614) respectively adopt latent heat, sensible heat or thermochemical energy storage materials with working temperature ranges of at least-195-20 ℃, 20-300 ℃ and 20-500 ℃, operate in single-stage or multi-stage series, and adopt heat insulation materials for heat insulation.
5. The integrated device for liquid air energy storage and ammonia synthesis according to claim 1, wherein the air separation liquefaction unit uses air or nitrogen as a working medium; the heat transfer fluid of the cold storage unit (211) is methanol, propane or air; the heat transfer fluid of the medium-temperature heat storage unit (215) is heat conduction oil or silicone oil; the heat transfer fluid of the high-temperature heat storage unit (614) is molten salt; the hydrogen generator (604) is an electrolytic water tank or a fossil fuel hydrogen production device.
6. An integrated method for liquid air energy storage and ammonia synthesis by using the device of any one of claims 1 to 5, wherein during the electricity consumption valley period, the air separation liquefaction unit and the ammonia synthesis circulation system work, and the device operates in two modes:
in the first mode, one part of gaseous nitrogen produced by the air separation plant (601) is supplied to the air separation liquefaction unit to acquire and store liquid nitrogen, and the other part of gaseous nitrogen is supplied to the ammonia synthesis circulation system, and the method specifically comprises the following steps:
air separation liquefaction unit: a part of gaseous nitrogen produced by an air separation plant (601) enters an air compressor unit (100) through a second nitrogen three-way valve (602) and a first air three-way valve (201), the gaseous nitrogen is compressed to high pressure, and meanwhile, compression heat generated in the compression process is recovered and stored in a medium-temperature heat storage unit (215); high-pressure gaseous nitrogen at the outlet of the air compressor unit (100) enters a low-temperature cooler (202), is cooled to low temperature by low-temperature cold energy stored in a cold storage unit (211) and returned gaseous nitrogen, then enters a low-temperature turboexpander (203) to be expanded and depressurized, wherein a part of gaseous nitrogen is liquefied, and gaseous and liquid nitrogen are separated by a liquid air separator (204): the liquid nitrogen enters a liquid air storage tank (207) through a second air three-way valve (205) and a third air three-way valve (206), and the gaseous nitrogen enters the air compressor unit (100) through a fourth air three-way valve (208), a fifth air three-way valve (209), a cryocooler (202) and a sixth air three-way valve (210);
an ammonia synthesis circulating system: the other part of gaseous nitrogen produced by the air separation plant (601) enters a first mixing chamber (603) through a second nitrogen three-way valve (602), is fully mixed with the hydrogen produced by a hydrogen generator (604), enters a mixed gas compressor unit (700) to be pressurized to the medium pressure, is mixed with unreacted hydrogen recycled by a hydrogen separation unit (612) and is further pressurized to the high pressure, and meanwhile, compression heat generated in the compression process is recycled and stored in a medium-temperature heat storage unit (215); high-pressure gas at the outlet of the mixed gas compressor unit (700) enters a second mixing chamber (605), is fully mixed with unreacted gas recovered from the scavenging unit (611), enters an ammonia synthesis unit (800) to synthesize ammonia after being preheated by a preheater (606), and simultaneously stores reaction heat generated in the ammonia synthesis reaction process in a high-temperature heat storage unit (614); the mixed gas after the reaction is cooled to normal temperature sequentially through a preheater (606) and a normal temperature cooler (607), ammonia gas in the mixed gas is condensed, and then the mixed gas enters a liquid ammonia separator (608) to separate liquid ammonia and unreacted gas: liquid ammonia enters a liquid ammonia storage tank (610) after throttling and pressure reduction through a liquid ammonia throttle valve (609), unreacted gas passes through a scavenging unit (611) and a hydrogen separation unit (612) in sequence to complete scavenging and hydrogen recovery, and then is discharged finally;
in a second mode, the air separation liquefaction unit separates and liquefies nitrogen from air, one part of liquid nitrogen is stored in a liquid air storage tank (207), and the other part of liquid nitrogen is pressurized and preheated and then is supplied to an ammonia synthesis circulation system, and the method specifically comprises the following steps:
air separation liquefaction unit: after being purified, ambient air enters an air compressor unit (100) through a first air three-way valve (201) to be pressurized to high pressure, and meanwhile, compression heat generated in the air compression process is recovered and stored in a medium-temperature heat storage unit (215); the high-pressure air at the outlet of the air compressor unit (100) passes through the low-temperature cooler (202), is cooled to low temperature by the low-temperature cold energy stored in the cold storage unit (211) and the returned oxygen-enriched air, enters the low-temperature turbo expander (203) for expansion and pressure reduction, wherein a part of air is liquefied, and then enters the liquid air separator (204) for separating gaseous air and liquid air: liquid air enters a high-pressure chamber (301) of the rectifying tower (300) through a second air three-way valve (205) and is sprayed from top to bottom, and gaseous air enters the high-pressure chamber (301) of the rectifying tower (300) through a fourth air three-way valve (208) and is blown from bottom to top; the gaseous air and the liquid air complete heat and mass exchange in the packing (302), the high-purity gaseous nitrogen is gathered at the top of the high-pressure chamber (301), and the oxygen-enriched liquid air is gathered at the bottom of the high-pressure chamber (301); oxygen-enriched liquid air at the bottom of the high-pressure chamber (301) is cooled and depressurized through the liquid oxygen throttle valve (303), enters the low-pressure chamber (304) to release cold energy and is changed into gaseous oxygen-enriched air, and then is discharged into the environment through the fifth air three-way valve (209), the cryocooler (202) and the sixth air three-way valve (210); high-purity gaseous nitrogen at the top of the high-pressure chamber (301) enters an evaporative condenser (305) of the low-pressure chamber (304), oxygen-enriched liquid air after being throttled and depressurized is condensed into liquid nitrogen, a part of liquid nitrogen flows back to the high-pressure chamber (301) for spraying, and the other part of liquid nitrogen enters a liquid air storage tank (207) through a third air three-way valve (206); one part of liquid nitrogen in the liquid air storage tank (207) is stored, the other part of the liquid nitrogen is pressurized by a low-temperature pressurizing pump (401) and then enters an evaporator (402) for preheating, and meanwhile, released cold energy is stored in a cold storage unit (211); the normal-temperature high-pressure gaseous nitrogen at the outlet of the evaporator (402) is supplied to the ammonia synthesis circulating system through a first nitrogen three-way valve (403);
an ammonia synthesis circulating system: hydrogen produced by a hydrogen generator (604) enters a mixed gas compressor unit (700) through a first mixing chamber (603), is primarily compressed to medium pressure, then is mixed with unreacted hydrogen recovered from a hydrogen separation unit (612), is further compressed to high pressure, and simultaneously recovers compression heat generated in the hydrogen compression process and stores the compression heat in a medium-temperature heat storage unit (215); high-pressure hydrogen at the outlet of the mixed gas compressor unit (700) enters a second mixing chamber (605), is fully mixed with high-pressure nitrogen supplied by a liquid air storage tank (207) and unreacted gas recovered by a scavenging unit (611), is preheated by a preheater (606) and enters an ammonia synthesis unit (800) to complete ammonia synthesis reaction, and meanwhile, reaction heat is recovered and stored in a high-temperature heat storage unit (614); the fully reacted mixed gas is cooled to normal temperature through a preheater (606) and a normal temperature cooler (607) in sequence, ammonia gas in the mixed gas is condensed, and then the mixed gas enters a liquid ammonia separator (608) to separate liquid ammonia and unreacted gas: liquid ammonia enters a liquid ammonia storage tank (610) after throttling and pressure reduction through a liquid ammonia throttle valve (609), and unreacted gas is discharged finally after completing scavenging and hydrogen recovery through a scavenging unit (611) and a hydrogen separation unit (612) in sequence.
7. The integrated method for liquid air energy storage and ammonia synthesis as claimed in claim 6, wherein in the electricity consumption valley period, when the air separation plant (601) is unavailable, the air separation liquefaction unit separates and liquefies nitrogen from air by using the rectifying tower (300), one part is stored, and the other part is supplied to the ammonia synthesis circulation system; when the air separation plant (601) is available, the air separation liquefaction unit directly liquefies and stores gaseous nitrogen provided by the air separation plant (601).
8. The integrated method for liquid air energy storage and ammonia synthesis by using the device of any one of claims 1 to 5, wherein the air power generation unit and the ammonia synthesis circulation system work during peak electricity utilization period, and the method comprises the following steps:
an air power generation unit: liquid nitrogen stored in a liquid air storage tank (207) is pressurized to high pressure through a low-temperature pressurizing pump (401), then enters an evaporator (402) to be preheated, the liquid nitrogen is evaporated and vaporized into gaseous nitrogen, and cold energy released by evaporation of the liquid nitrogen is stored in a cold storage unit (211); the normal-temperature high-pressure gaseous nitrogen at the outlet of the evaporator (402) is divided into two paths through a first nitrogen three-way valve (403): one part of the mixed gas enters a second mixing chamber (605) to be supplied to an ammonia synthesis circulation system, the other part of the mixed gas enters an air turbine unit (500), is subjected to two-stage preheating and then is subjected to expansion power generation, and then enters a first mixing chamber (603) to be supplied to the ammonia synthesis circulation system;
an ammonia synthesis circulating system: hydrogen produced by a hydrogen generator (604) enters a first mixing chamber (603), is fully mixed with nitrogen at the outlet of an air turbine unit (500), then enters a mixed gas compressor unit (700) for preliminary compression to medium pressure, is further compressed to high pressure after being mixed with unreacted hydrogen recycled by a hydrogen separation unit (612), and meanwhile, compression heat generated in the compression process is recycled for preliminary preheating of nitrogen in the air turbine unit (500); high-pressure gas at the outlet of the mixed gas compressor unit (700) enters a second mixing chamber (605), is fully mixed with a part of nitrogen shunted at the outlet of the evaporator (402) and unreacted gas recovered in the scavenging unit (611), enters an ammonia synthesis unit (800) to synthesize ammonia after being preheated by a preheater (606), and simultaneously recovers reaction heat generated in the ammonia synthesis reaction process for further preheating the nitrogen in the air turbine unit (500); the mixed gas after the reaction is cooled to normal temperature sequentially through a preheater (606) and a normal temperature cooler (607), ammonia gas in the mixed gas is condensed, and then the mixed gas enters a liquid ammonia separator (608) to separate liquid ammonia and unreacted gas: liquid ammonia enters a liquid ammonia storage tank (610) after being throttled and depressurized by a liquid ammonia throttle valve (609), and unreacted gas is discharged finally after being subjected to scavenging and hydrogen recovery by a scavenging unit (611) and a hydrogen separation unit (612) in sequence.
9. The integrated method for liquid air energy storage and ammonia synthesis of claim 8, wherein during peak electricity consumption periods, the air turbine set (500) preheats nitrogen to medium temperature primarily by using the heat of compression stored by the medium temperature heat storage unit (215) and the heat of compression generated by the mixed gas compressor set (700) in real time, and then preheats nitrogen to high temperature further by using the heat of reaction stored by the high temperature heat storage unit (614) and the heat of reaction generated by the ammonia synthesis unit (800) in real time, so as to improve the power generation and the efficiency of the liquid air energy storage circulation system; when the heat demand of the air turbine unit (500) is reduced, the excess compression heat generated in real time by the mixed gas compressor unit (700) can be stored in the medium-temperature heat storage unit (215), and the excess reaction heat generated in real time by the ammonia synthesis unit (800) can be stored in the high-temperature heat storage unit (614).
10. The integrated liquid air energy storage and ammonia synthesis method according to claim 8, wherein during peak electricity consumption, the air power generation unit in the liquid air energy storage circulation system provides nitrogen to the ammonia synthesis circulation system in two ways: the first method is that liquid nitrogen stored in a liquid air storage tank (207) is pressurized, preheated, expanded and generated and then is supplied to an ammonia synthesis circulating system, and the operation of the liquid air energy storage circulating system is not influenced; the second method is that liquid nitrogen stored in a liquid air storage tank (207) is pressurized to the pressure required by the ammonia synthesis reaction, and then heated and vaporized to be supplied to an ammonia synthesis circulation system, so that the power consumption of mixed gas compression in a mixed gas compressor unit (700) is reduced.
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| CN113686187B (en) * | 2021-07-24 | 2023-07-04 | 华北电力大学（保定） | Low-temperature waste heat enthalpy-increasing heat storage system based on chemical quality improvement and heat storage |
| CN113739516B (en) * | 2021-08-17 | 2024-05-28 | 西安交通大学 | System and method for air separation energy storage coupling oxygen-enriched combustion |
| WO2023033748A1 (en) * | 2021-09-06 | 2023-03-09 | Vattanapuripakorn Wenich | Conceptual design for new method of power generation plant using pressurized gaseous nitrogen |
| CN113958933B (en) * | 2021-09-26 | 2022-06-07 | 西安交通大学 | Composite energy system integrating multi-energy storage and hydrocarbon fuel preparation and method |
| CN113865160B (en) * | 2021-10-29 | 2023-04-21 | 势加透博（上海）能源科技有限公司 | Air circulation system |
| CN114777413B (en) * | 2022-03-14 | 2023-11-17 | 中国石油大学(华东) | System and method for co-production of ammonia electricity by using renewable energy sources |
| CN114414705B (en) * | 2022-03-29 | 2022-07-01 | 南京霍普斯科技有限公司 | Gas chromatography detection system and method for constant nitrogen and hydrogen in synthetic ammonia |
| CN115451647B (en) * | 2022-08-29 | 2023-08-11 | 北京科技大学 | Hydrogen liquefaction system integrated with liquefied air energy storage system |
| WO2024058660A1 (en) | 2022-09-12 | 2024-03-21 | Stamicarbon B.V. | Method and plant for the production of ammonia with renewable energy |
| CN116161676A (en) * | 2023-01-09 | 2023-05-26 | 中国长江三峡集团有限公司 | Comprehensive energy system for generating electricity, storing energy and preparing ammonia |
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