CN117365700A - Flexible and efficient carbon dioxide power generation coupling ammonia alcohol co-production system and method - Google Patents
Flexible and efficient carbon dioxide power generation coupling ammonia alcohol co-production system and method Download PDFInfo
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- CN117365700A CN117365700A CN202311604946.4A CN202311604946A CN117365700A CN 117365700 A CN117365700 A CN 117365700A CN 202311604946 A CN202311604946 A CN 202311604946A CN 117365700 A CN117365700 A CN 117365700A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 286
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 199
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 143
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 143
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 101
- 238000010248 power generation Methods 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 230000008878 coupling Effects 0.000 title claims abstract description 18
- 238000010168 coupling process Methods 0.000 title claims abstract description 18
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 254
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 109
- 238000000926 separation method Methods 0.000 claims abstract description 101
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 53
- 238000002360 preparation method Methods 0.000 claims abstract description 52
- 230000006835 compression Effects 0.000 claims abstract description 47
- 238000007906 compression Methods 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims description 79
- 238000003860 storage Methods 0.000 claims description 78
- 239000001257 hydrogen Substances 0.000 claims description 63
- 229910052739 hydrogen Inorganic materials 0.000 claims description 63
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 62
- 239000001301 oxygen Substances 0.000 claims description 53
- 229910052760 oxygen Inorganic materials 0.000 claims description 53
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 51
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 42
- 230000015572 biosynthetic process Effects 0.000 claims description 39
- 238000003786 synthesis reaction Methods 0.000 claims description 39
- 238000005338 heat storage Methods 0.000 claims description 31
- 239000003345 natural gas Substances 0.000 claims description 21
- 230000001105 regulatory effect Effects 0.000 claims description 21
- 238000002485 combustion reaction Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K13/00—General layout or general methods of operation of complete plants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K21/00—Steam engine plants not otherwise provided for
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
- F01K25/08—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours
- F01K25/10—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours the vapours being cold, e.g. ammonia, carbon dioxide, ether
- F01K25/103—Carbon dioxide
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23D—BURNERS
- F23D14/00—Burners for combustion of a gas, e.g. of a gas stored under pressure as a liquid
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
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Abstract
The invention discloses a flexible and efficient carbon dioxide power generation coupling ammonia alcohol co-production system and method, and relates to the technical field of energy and chemical treatment. The supercritical carbon dioxide power generation system comprises a combustor, a turbine expander, a generator, a first heat regenerator, a precooler, a water separation device and a circulating medium conveying passage, wherein the air compression separation system, the ammonia preparation system and the methanol preparation system are connected with the supercritical carbon dioxide power generation system, the air separation device is connected with the combustor, the turbine expander, the first heat regenerator, the precooler, the water separation device and the circulating medium conveying passage, the circulating medium conveying passage is connected with the first heat regenerator and the air compression separation system, and the first heat regenerator and the air compression separation system are connected with the combustor. According to the invention, the supercritical carbon dioxide power generation system, the ammonia preparation system and the methanol preparation system are coupled, so that the power generation efficiency is improved, and the problems of nitrogen source in ammonia preparation and carbon dioxide source in methanol preparation are solved.
Description
Technical Field
The invention relates to the technical field of energy and chemical treatment, in particular to a flexible and efficient carbon dioxide power generation coupling ammonia alcohol co-production system and method.
Background
In face of the increasingly serious global problems such as climate change, environmental risk challenges, energy resource constraint and the like, a green energy technology innovation system is constructed, the energy science and technology and equipment level are comprehensively improved, a healthy green low-carbon cyclic development economic system is established, the problem of resource environment ecology in China is solved, and the method is also a main direction of world energy development.
The supercritical carbon dioxide power generation technology is a technology for realizing high-efficiency power generation by taking carbon dioxide fluid above a critical point as fluid working medium and utilizing the characteristic of high energy density, has the technical advantages of simplified system, high efficiency, small volume, easy realization of modularized assembly and the like, and has good application prospect and research value.
Ammonia is an important component of all foods and fertilizers on earth, as well as a direct or indirect component in many pharmaceutical and commercial cleaning products. Methanol is a common organic chemical raw material, and is applied to various fields such as chemical industry, pharmacy, light industry, spinning, transportation and the like. At present, the raw material sources for synthesizing ammonia and methanol are mainly petroleum, and petroleum resources have nonrenewability, so that along with the continuous reduction of the resources, other suitable raw materials are actively searched, the problem of energy consumption is very critical, and the ecological environment can be optimized.
Carbon dioxide capture is a core part of carbon capture, utilization and sequestration technologies, and high capture energy consumption is a current technical bottleneck. The method takes the nitrogen obtained by separating the green hydrogen prepared by the renewable energy electrolyzed water from the low-temperature air as the raw material to synthesize ammonia, and takes the split carbon dioxide and the green hydrogen prepared by the renewable energy electrolyzed water as the raw materials to synthesize the methanol, so that the method not only can realize the localized effective absorption of new energy, but also is an important way of chemical green transformation, can obviously reduce the carbon emission in the chemical industry, and has huge scale potential.
At present, related equipment for coupling a carbon dioxide power generation system, an ammonia preparation system and a methanol preparation system is lacking in the market, so that a flexible and efficient carbon dioxide power generation coupling ammonia alcohol co-production system and method are necessary to be provided.
Disclosure of Invention
In order to solve the technical problems, the invention adopts the following technical scheme:
a flexible and efficient carbon dioxide power generation coupling ammonia alcohol co-production system comprises:
the air compression separation system comprises an air compressor, an air compression heat storage device, an air separation device, a nitrogen storage tank and an oxygen storage tank, wherein the air compressor is sequentially connected with the air compression heat storage device and the air separation device, and an outlet of the air separation device is respectively connected with the nitrogen storage tank and the oxygen storage tank;
the supercritical carbon dioxide power generation system is connected with the air compression separation system and comprises a combustor, a turbine expander, a generator, a first heat regenerator, a precooler, a water separation device and a circulating medium conveying passage, wherein an oxygen storage tank is sequentially connected with the combustor, the turbine expander, the first heat regenerator, the precooler, the water separation device and the circulating medium conveying passage through an oxygen compressor, the combustor is provided with a natural gas inlet, the circulating medium conveying passage is respectively connected with the first heat regenerator and the air compression heat storage device, the first heat regenerator and the air compression heat storage device are respectively connected with the combustor, and the turbine expander is connected with the generator;
the ammonia preparation system is connected with the nitrogen storage tank;
and the methanol preparation system is connected with the supercritical carbon dioxide power generation system.
Further, the circulating medium conveying passage comprises a carbon dioxide compressor and a second three-way valve, the water separation device is connected with the carbon dioxide compressor through a first three-way valve, the carbon dioxide compressor is respectively connected with the first heat regenerator and the air compression heat storage device through a second three-way valve, and the first heat regenerator and the air compression heat storage device are respectively connected with the burner.
Further, the water separation device is connected with the carbon dioxide compressor and the methanol preparation system through a first three-way valve, and the precooler is connected with the methanol preparation system and the second hydrogen storage tank respectively.
Further, the methanol preparation system comprises a pressure regulating valve, a fifth three-way valve, a hydrogen compressor, a sixth three-way valve, a third heat regenerator, a methanol synthesis device, a methanol separation device and a second hydrogen storage tank, wherein the water separation device is connected with the first three-way valve, the first three-way valve is sequentially connected with the pressure regulating valve, the fifth three-way valve, the third heat regenerator and the methanol synthesis device, a discharge hole of the methanol synthesis device is sequentially connected with the third heat regenerator and the methanol separation device, the second hydrogen storage tank is sequentially connected with a precooler and the sixth three-way valve, the methanol separation device is connected with one port of the sixth three-way valve, the other port of the sixth three-way valve is connected with an inlet of the hydrogen compressor, and an outlet of the hydrogen compressor is connected with one port of the fifth three-way valve.
Further, a carbon dioxide storage tank is connected between the first three-way valve and the pressure regulating valve.
Further, the ammonia preparation system comprises a third three-way valve, a fourth three-way valve, a mixed gas compressor, a second heat regenerator, an ammonia synthesis device and an ammonia separation device, wherein the third three-way valve is connected with the fourth three-way valve, the other two ports of the third three-way valve are respectively connected with a first hydrogen storage tank and a nitrogen storage tank, one port of the fourth three-way valve is sequentially connected with the mixed gas compressor, the second heat regenerator and the ammonia synthesis device, the air outlet end of the ammonia synthesis device is sequentially connected with the second heat regenerator and the ammonia separation device, and the ammonia separation device is connected with one port of the fourth three-way valve.
A combined production method of a flexible and efficient carbon dioxide power generation coupling ammonia alcohol combined production system comprises the following steps:
air compression separation system: the air at normal temperature and normal pressure is compressed by an air compressor and then is boosted and heated, then the air at high pressure and high temperature flows through an air compression heat storage device to store compression heat for cooling, the air at high pressure and normal temperature enters an air separation device to generate nitrogen and oxygen, the oxygen is stored in an oxygen storage tank, and the nitrogen is stored in a nitrogen storage tank;
generating electricity by carbon dioxide: oxygen from an oxygen storage tank is compressed to a specified pressure by an oxygen compressor and then enters a combustor, the oxygen is combusted together with the introduced natural gas in the combustor, high-temperature gas generated by combustion is mixed with carbon dioxide introduced into the combustor, the formed high-temperature and high-pressure mixed gas mainly comprising carbon dioxide enters a turbine expander from an outlet of the combustor to be matched with a generator to do work and generate power, the exhaust of the turbine expander is subjected to heat recovery by a first regenerator, a precooler cooling and water separation device is used for separating moisture in the exhaust, and then is split by a first three-way valve, the split carbon dioxide is compressed to the specified pressure by a carbon dioxide compressor and then is separated again by a second three-way valve, one carbon dioxide is heated by the first regenerator to enter the combustor to be mixed with combustion products of oxygen and natural gas and then to be circulated, and the other carbon dioxide is heated by the air compression heat storage device to enter the combustor to be mixed with combustion products of oxygen and natural gas and then to be circulated;
ammonia preparation: the nitrogen from the nitrogen storage tank is mixed with the hydrogen through a third three-way valve, the mixed gas of the nitrogen and the hydrogen is further mixed with the gas separated by the ammonia separation device through a fourth three-way valve, the mixed gas is compressed to a specified pressure through a mixed gas compressor, then the mixed gas is heated through a second heat regenerator and then enters the ammonia synthesis device to react to generate ammonia, an outlet of the ammonia synthesis device is connected with a high-temperature gas inlet of the second heat regenerator, the mixed gas is cooled through the second heat regenerator and then enters the ammonia separation device to separate ammonia, and the mixed gas after ammonia separation then flows into the fourth three-way valve to be mixed with the hydrogen and the nitrogen and then is continuously circulated to prepare ammonia;
preparation of methanol: the carbon dioxide split by the first three-way valve is stored in a carbon dioxide storage tank, and the carbon dioxide output from the carbon dioxide storage tank flows into a fifth three-way valve to be mixed with hydrogen according to a certain proportion after the pressure of the carbon dioxide is regulated by a pressure regulating valve; after the temperature of the hydrogen is raised by the precooler, the hydrogen is further mixed with the gas separated by the methanol separation device, compressed to the specified pressure by the hydrogen compressor, and then enters the fifth three-way valve to be mixed with carbon dioxide according to a certain proportion; the mixed gas is heated by a third heat regenerator and then enters a methanol synthesis device to react to generate methanol, an outlet of the methanol synthesis device is connected with a high-temperature gas inlet of the third heat regenerator, the mixed gas is cooled by the third heat regenerator and then enters a methanol separation device to separate methanol, and the mixed gas after separating the methanol then flows into a sixth three-way valve to be mixed with hydrogen and then is continuously circulated.
The invention has the beneficial effects that:
according to the flexible and efficient carbon dioxide power generation coupling ammonia alcohol co-production system and method provided by the invention, natural gas is used as fuel, full capture of carbon dioxide is realized through an oxygen-enriched combustion mode, high-energy-density carbon dioxide is used as working medium to perform power generation in a turbine expander, so that the heat-power conversion efficiency is improved, and when the working medium is in a supercritical state, the change of the phase state of the working medium is avoided, so that the consumption of compression power is reduced.
The nitrogen separated by the air separation device required by oxygen-enriched combustion is used as a nitrogen source of the ammonia preparation system, so that the localized effective absorption of the separated nitrogen can be realized, and the green production of ammonia synthesis chemical industry can be realized.
By diverting the carbon dioxide collected by the supercritical carbon dioxide power generation system to the methanol preparation system, the difficult problem of high energy consumption of carbon dioxide capture is solved, and meanwhile, the localized effective utilization of the carbon dioxide and the chemical green production of methanol synthesis are realized.
Through reasonable operation regulation and control, the single modules and the coupling operation among the modules for generating power, synthesizing ammonia and synthesizing methanol and the simultaneous operation of the whole co-production system can be realized, and the net zero emission and high economical operation of the whole co-production system are realized.
Drawings
FIG. 1 is a schematic diagram of a flexible and efficient carbon dioxide power generation coupled ammonia alcohol cogeneration system of the invention.
FIG. 2 is a schematic diagram of the operation of a supercritical carbon dioxide power generation system coupled with an ammonia production system.
FIG. 3 is a schematic diagram of the operation of a supercritical carbon dioxide power generation system coupled to a methanol production system.
FIG. 4 is a schematic diagram of a supercritical carbon dioxide power generation system operating alone.
FIG. 5 is a schematic diagram of an ammonia production system operating alone.
Wherein, in the figure:
1-an air compressor; 2-air compression heat storage device; 3-an air separation device; 4-nitrogen storage tank; a 5-oxygen storage tank; a 6-oxygen compressor; 7-a natural gas compressor; 8-a burner; 9-a turbo expander; a 10-generator; 11-a first regenerator; 12-precooler; 13-water separation means; 14-a first three-way valve; 15-a carbon dioxide compressor; 16-a carbon dioxide storage tank; 17-a second three-way valve; 18-a first hydrogen storage tank; 19-a third three-way valve; 20-a fourth three-way valve; 21-a mixed gas compressor; 22-a second regenerator; a 23-ammonia synthesis device; 24-ammonia separation device; 25-a second hydrogen storage tank; 26-a sixth three-way valve; a 27-hydrogen compressor; 28-a fifth three-way valve; 29-a pressure regulating valve; 30-a third regenerator; a 31-methanol synthesis device; 32-methanol separation unit.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to fig. 1 to 5 of the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a flexible and efficient carbon dioxide power generation coupling ammonia alcohol co-production system which comprises an air compression separation system, a supercritical carbon dioxide power generation system, an ammonia preparation system and a methanol preparation system.
The air compression separation system comprises an air compressor 1, an air compression heat storage device 2, an air separation device 3, a nitrogen storage tank 4 and an oxygen storage tank 5, wherein the air compressor 1 is sequentially connected with the air compression heat storage device 2 and the air separation device 3, and an outlet of the air separation device 3 is respectively connected with the nitrogen storage tank 4 and the oxygen storage tank 5.
The air compression heat storage device 2 is provided with an air inlet, an air outlet, a carbon dioxide inlet and a carbon dioxide outlet, and the pressure bearing range is not less than 300bar; the heat accumulating medium is one or several of water, paraffin, biomass oil, inorganic crystalline hydrated salt, molten salt, metal and its alloy, organic fatty acid and concrete.
The supercritical carbon dioxide power generation system is connected with the air compression separation system, the supercritical carbon dioxide power generation system comprises a combustor 8, a turbine expander 9, a generator 10, a first heat regenerator 11, a precooler 12, a water separation device 13 and a circulating medium conveying passage, the oxygen storage tank 5 is sequentially connected with the combustor 8, the turbine expander 9, the first heat regenerator 11, the precooler 12, the water separation device 13 and the circulating medium conveying passage through the oxygen compressor 6, the combustor 8 is provided with a natural gas inlet, the natural gas inlet is connected with a natural gas compressor 7, natural gas is introduced into the combustor 8 through the natural gas compressor 7, the circulating medium conveying passage is respectively connected with the first heat regenerator 11 and the air compression heat storage device 2, the first heat regenerator 11 and the air compression heat storage device 2 are respectively connected with the combustor 8, the turbine expander 9 is connected with the generator 10 through a coupler, the ammonia preparation system is connected with the nitrogen storage tank 4, and the methanol preparation system is connected with the supercritical carbon dioxide power generation system; the supercritical carbon dioxide power generation system is coupled with the ammonia preparation system and the methanol preparation system through the air separation device 3, nitrogen separated by the air separation device 3 is used as a nitrogen source of the ammonia preparation system, separated oxygen is used by the supercritical carbon dioxide power generation system, and carbon dioxide generated by power generation acts on methanol preparation and circulating media.
The air separation device 3 is provided with an air inlet, an oxygen outlet, a nitrogen outlet and corresponding control valves, and the air separation process also comprises air purification and purification to remove solid matters and impurity gases in the air; the air purification and purification device is integrated in the air separation unit.
The combustor 8 is provided with a natural gas inlet, an oxygen inlet, a carbon dioxide inlet, a mixed gas outlet after combustion and corresponding control valves, and the pressure bearing range of the combustor 8 is not less than 300bar.
The turbine expander 9 adopts one of a piston type, an axial flow type, a centrifugal type, a screw type or a mixed type, the pressure bearing range is not less than 300bar, and the inlet fluid temperature range is 500-1200 ℃.
The first regenerator 11 is a printed circuit board type heat exchanger, and the pressure bearing range is not less than 300bar.
The precooler 12 with heat accumulating function is provided with a hydrogen inlet, a hydrogen outlet, a carbon dioxide inlet and a carbon dioxide outlet, the pressure bearing range is not less than 100bar, and the heat accumulating medium adopted by the precooler 12 is one or a combination of more of water, paraffin, biomass oil, inorganic crystalline hydrated salt, molten salt, metal and alloy thereof, organic fatty acid or concrete.
The circulating medium conveying passage comprises a carbon dioxide compressor 15 and a second three-way valve 17, the water separation device 13 is connected with the carbon dioxide compressor 15 through a first three-way valve 14, the carbon dioxide compressor 15 is respectively connected with a first heat regenerator 11 and the air compression heat storage device 2 through a second three-way valve 17, and the first heat regenerator 11 and the air compression heat storage device 2 are respectively connected with the combustor 8; the carbon dioxide conveyed by the circulating medium conveying passage can be shunted and conveyed to the first heat regenerator 11 and the air compression heat storage device 2 for heating, and the heated carbon dioxide is reflowed into the combustor 8 again, so that the heat energy in the system is fully utilized.
The water separation device 13 is respectively connected with a carbon dioxide compressor 15 and a methanol preparation system through a first three-way valve 14, and the precooler 12 is respectively connected with the methanol preparation system and a second hydrogen storage tank 25.
The methanol preparation system comprises a pressure regulating valve 29, a fifth three-way valve 28, a hydrogen compressor 27, a sixth three-way valve 26, a third heat regenerator 30, a methanol synthesis device 31, a methanol separation device 32 and a second hydrogen storage tank 25, wherein the water separation device 13 is connected with the first three-way valve 14, the first three-way valve 14 is sequentially connected with the pressure regulating valve 29, the fifth three-way valve 28, the third heat regenerator 30 and the methanol synthesis device 31, a discharge port of the methanol synthesis device 31 is sequentially connected with the third heat regenerator 30 and the methanol separation device 32, the second hydrogen storage tank 25 is sequentially connected with the precooler 12 and the sixth three-way valve 26, the methanol separation device 32 is sequentially connected with one port of the sixth three-way valve 26, the other port of the sixth three-way valve 26 is connected with an inlet of the hydrogen compressor 27, an outlet of the hydrogen compressor 27 is sequentially connected with one port of the fifth three-way valve 28, and a carbon dioxide storage tank 16 is connected between the first three-way valve 14 and the pressure regulating valve 29.
The pressure regulating valve 29 is a self-operated regulating valve, and the pressure regulating range is 50-100bar.
The carbon dioxide collected by the supercritical carbon dioxide power generation system is split through the first three-way valve 14, one part is used as a circulating medium of the supercritical carbon dioxide power generation system, the other part is stored in the carbon dioxide storage tank 16 and used as a carbon dioxide raw material of the methanol preparation system, and the carbon dioxide in the carbon dioxide storage tank 16 can be stored.
The ammonia preparation system comprises a third three-way valve 19, a fourth three-way valve 20, a mixed gas compressor 21, a second heat regenerator 22, an ammonia synthesis device 23 and an ammonia separation device 24, wherein the third three-way valve 19 is connected with the fourth three-way valve 20, the other two ports of the third three-way valve 19 are respectively connected with a first hydrogen storage tank 18 and a nitrogen storage tank 4, one port of the fourth three-way valve 20 is sequentially connected with the mixed gas compressor 21, the second heat regenerator 22 and the ammonia synthesis device 23, the air outlet end of the ammonia synthesis device 23 is sequentially connected with the second heat regenerator 22 and the ammonia separation device 24, the ammonia separation device 24 is connected with one port of the fourth three-way valve 20, and nitrogen in the nitrogen storage tank 4 is used as a nitrogen source of the ammonia preparation system.
The second regenerator 22 and the third regenerator 30 are both shell-and-tube heat exchangers or brazing sheet heat exchangers.
The hydrogen sources of the first hydrogen tank 18 and the second hydrogen tank 25 are preferably green hydrogen produced by electrolysis of water from renewable energy sources.
In this embodiment, each gas compressor may be one of a piston type, an axial flow type, a centrifugal type, a screw type, or a hybrid type, and the pressure bearing range of each gas compressor is not less than 300bar; each three-way valve can adopt a mass flow controller flow dividing valve, the pressure bearing range of the first three-way valve 14, the third three-way valve 19, the fourth three-way valve 20, the fifth three-way valve 28 and the sixth three-way valve 26 is not less than 100bar, and the pressure bearing range of the second three-way valve 17 is not less than 300bar; each gas storage tank is provided with a gas inlet, a gas outlet and an inlet valve, and the gas bearing range of each gas storage tank is not less than 100bar.
Example two
A combined production method of a flexible and efficient carbon dioxide power generation coupling ammonia alcohol combined production system comprises the following steps:
air compression separation system: the air with normal temperature and normal pressure is compressed by the air compressor 1 and then is boosted and heated, then the air with high pressure and high temperature flows through the air compression heat storage device 2 to store compression heat for cooling, the air with high pressure and normal temperature enters the air separation device 3 to generate nitrogen and oxygen, the oxygen is stored in the oxygen storage tank 5, and the nitrogen is stored in the nitrogen storage tank 4;
generating electricity by carbon dioxide: oxygen from an oxygen storage tank 5 is compressed to a specified pressure by an oxygen compressor 6 and then enters a combustor 8 to be combusted together with natural gas introduced into the combustor 8, high-temperature gas generated by combustion is mixed with carbon dioxide introduced into the combustor 8, the formed high-temperature and high-pressure mixed gas mainly comprising carbon dioxide enters a turbine expander 9 from an outlet of the combustor to be matched with a generator 10 to do work and generate power, the exhaust gas of the turbine expander 9 is subjected to heat recovery by a first regenerator 11 and precooler 12 cooling and water separation device 13 to separate moisture in the gas, then is split by a first three-way valve 14, the split carbon dioxide is compressed to the specified pressure by a carbon dioxide compressor 15 and then is separated again by a second three-way valve 17, one carbon dioxide is heated by the first regenerator 11 to enter the combustor 8 to be mixed with combustion products of oxygen and natural gas and then is continuously circulated, and the other carbon dioxide is heated by the air compressed heat storage device 2 and enters the combustor 8 to be mixed with combustion products of oxygen and natural gas and then is continuously circulated.
Ammonia preparation: the nitrogen from the nitrogen storage tank 4 is mixed with the hydrogen through a third three-way valve 19, the mixed gas of the nitrogen and the hydrogen is further mixed with the gas separated by the ammonia separation device through a fourth three-way valve 20, then the mixed gas is compressed to a specified pressure through a mixed gas compressor 21, the mixed gas is heated through a second heat regenerator 22 and then enters an ammonia synthesis device 23 to react to generate ammonia, an outlet of the ammonia synthesis device 23 is connected with a high-temperature gas inlet of the second heat regenerator 22, the mixed gas is cooled through the second heat regenerator 22 and then enters an ammonia separation device 24 to separate the ammonia, and the mixed gas after the ammonia separation flows into the fourth three-way valve 20 to be mixed with the hydrogen and the nitrogen and then is continuously recycled to prepare the ammonia.
Preparation of methanol: the carbon dioxide split by the first three-way valve 14 is stored in the carbon dioxide storage tank 16, and the carbon dioxide output from the carbon dioxide storage tank 16 flows into the fifth three-way valve 28 to be mixed with the hydrogen according to a certain proportion after the pressure is regulated by the pressure regulating valve 29; the hydrogen is heated by the precooler 12, is further mixed with the gas separated by the methanol separation device 32, is compressed to the specified pressure by the hydrogen compressor 27, and then enters the fifth three-way valve 28 to be mixed with carbon dioxide according to a certain proportion; the mixed gas is heated by the third heat regenerator 30 and then enters the methanol synthesis device 31 to react to generate methanol, the outlet of the methanol synthesis device 31 is connected with the high-temperature gas inlet of the third heat regenerator 30, the mixed gas is cooled by the third heat regenerator 30 and then enters the methanol separation device 32 to separate the methanol, and the mixed gas after the methanol separation flows into the sixth three-way valve 26 to be mixed with hydrogen and then is continuously circulated.
The carbon dioxide source of the methanol preparation system is the carbon dioxide separated by the supercritical carbon dioxide power generation system, and the supercritical carbon dioxide power generation system, the ammonia preparation system and the methanol preparation system are coupled and connected, so that the efficiency of the supercritical carbon dioxide power generation system is improved, the problems of the nitrogen source of the ammonia preparation system and the carbon dioxide source of the methanol preparation system are solved, the raw materials for synthesizing ammonia and synthesizing methanol are provided while the clean zero-emission efficient power generation is realized, the problem of high carbon dioxide capture energy consumption is solved, and the clean zero emission and high economical operation of the whole co-production system are realized through reasonable operation regulation and control.
Example III
The embodiment is a working condition that a supercritical carbon dioxide power generation system, an ammonia gas preparation system and a methanol preparation system are coupled and run simultaneously.
The air compressor 1 pressurizes and heats air, then enters the air compression heat storage device 2 to cool the compressed air and store heat in the device, then enters the air separation device 3 to perform gas separation, the separated nitrogen is stored in the nitrogen storage tank 4, and the separated oxygen is stored in the oxygen storage tank 5; oxygen from an oxygen storage tank 5 enters a combustor 8 after being compressed to a specified pressure by an oxygen compressor 6, and is combusted with the introduced natural gas in the combustor 8, high-temperature gas generated by combustion is mixed with the introduced carbon dioxide, and the formed high-temperature high-pressure mixed gas enters a turbine expander 9 from an outlet of the combustor 8 to be matched with a generator 10 for power generation; the exhaust gas of the turbine expander 9 is subjected to heat recovery through a first heat regenerator 11 and water separation by a heat energy cooling and water separation device 13 stored in a precooler 12, and then is subjected to split flow through a first three-way valve 14; the carbon dioxide which is shunted into the supercritical carbon dioxide power generation system is compressed to a specified pressure by the carbon dioxide compressor 15 and then flows through the second three-way valve 17 to continue to be shunted, part of the carbon dioxide which is shunted by the second three-way valve 17 flows through the first heat regenerator 11 to absorb heat and raise temperature, and the rest of the carbon dioxide which is shunted by the second three-way valve 17 flows through the air compression heat storage device 2 to absorb heat and raise temperature, and the carbon dioxide after temperature raising enters the combustor 8 to be mixed with combustion products of oxygen and natural gas to be heated and then to continue to circulate; a portion of the carbon dioxide split through the first three-way valve 14 is stored in the carbon dioxide storage tank 16.
The nitrogen from the nitrogen storage tank 4 is mixed with the hydrogen from the first hydrogen storage tank 18 according to a certain proportion through a third three-way valve 19, the mixed gas is further mixed with the gas separated by the ammonia separation device 24 through a fourth three-way valve 20 and then compressed to a specified pressure through a mixed gas compressor 21, the mixed gas is heated through a second heat regenerator 22 and then enters an ammonia synthesis device 23 to react to generate ammonia, an outlet of the ammonia synthesis device 23 is connected with a high-temperature gas inlet of the second heat regenerator 22, the mixed gas is cooled through the second heat regenerator 22 and then enters the ammonia separation device 24 to separate ammonia, and the mixed gas after ammonia separation flows into the fourth three-way valve 20 to be mixed with the hydrogen and the nitrogen and then is recycled.
The carbon dioxide from the carbon dioxide storage tank 16 flows into the fifth three-way valve 28 to be mixed with the hydrogen according to a certain proportion after the pressure is regulated by the pressure regulating valve 29; the hydrogen from the second hydrogen storage tank 25 flows through the precooler 12 to absorb heat and raise temperature, and then is mixed with the gas separated by the methanol separation device 32 through the sixth three-way valve 26, enters the hydrogen compressor 27 to be boosted to a specified pressure, and then enters the fifth three-way valve 28 to be mixed with carbon dioxide according to a certain proportion; the mixed gas is heated by the third heat regenerator 30 and then enters the methanol synthesis device 31 to react to generate methanol, the outlet of the methanol synthesis device 31 is connected with the high-temperature gas inlet of the third heat regenerator 30, the mixed gas is cooled by the third heat regenerator 30 and then enters the methanol separation device 32 to separate the methanol, and the mixed gas after the methanol separation flows into the sixth three-way valve 26 to be mixed with hydrogen and then is continuously circulated.
Example IV
The difference between this embodiment and the third embodiment is that, as shown in fig. 2, the supercritical carbon dioxide power generation system is coupled with the ammonia production system to operate, the methanol production system is stopped, and the carbon dioxide stored in the carbon dioxide storage tank 16 can be stored or transported out for application in the fields of industry, food, chemical industry, etc.
Example five
The difference between this embodiment and the third embodiment is that, as shown in fig. 3, the supercritical carbon dioxide power generation system is coupled to the operation of the methanol preparation system, the operation of the ammonia preparation system is stopped, and the nitrogen gas stored in the nitrogen gas storage tank 4 can be externally transported and applied to the fields of industry, medical treatment, agriculture, aerospace, scientific research, etc.
Example six
The difference between this embodiment and the third embodiment is that, as shown in fig. 4, the supercritical carbon dioxide power generation system is operated independently, the methanol production system and the ammonia production system are stopped simultaneously, the nitrogen gas stored in the nitrogen gas storage tank 4 can be used for the fields of industry, medical treatment, agriculture, aerospace, scientific research, etc., and the carbon dioxide stored in the carbon dioxide storage tank 16 can be stored or used for the fields of industry, food, chemical industry, etc.
Example seven
This embodiment differs from embodiment three in that the ammonia production system is operated alone as shown in fig. 5. Air is pressurized and heated by an air compressor 1 and then enters an air compression heat storage device 2 to be cooled and stored in the air compression heat storage device 2, then air enters an air separation device 3, separated nitrogen flows through a nitrogen storage tank 4 and then enters an ammonia synthesis system to complete ammonia preparation, and separated oxygen stored in an oxygen storage tank 5 can be externally transported and applied to the fields of industry, medical treatment, scientific research and the like.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to the embodiments described above will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A flexible and efficient carbon dioxide power generation coupling ammonia alcohol co-production system is characterized by comprising:
the air compression separation system comprises an air compressor, an air compression heat storage device, an air separation device, a nitrogen storage tank and an oxygen storage tank, wherein the air compressor is sequentially connected with the air compression heat storage device and the air separation device, and an outlet of the air separation device is respectively connected with the nitrogen storage tank and the oxygen storage tank;
the supercritical carbon dioxide power generation system is connected with the air compression separation system and comprises a combustor, a turbine expander, a generator, a first heat regenerator, a precooler, a water separation device and a circulating medium conveying passage, wherein an oxygen storage tank is sequentially connected with the combustor, the turbine expander, the first heat regenerator, the precooler, the water separation device and the circulating medium conveying passage through an oxygen compressor, the combustor is provided with a natural gas inlet, the circulating medium conveying passage is respectively connected with the first heat regenerator and the air compression heat storage device, the first heat regenerator and the air compression heat storage device are respectively connected with the combustor, and the turbine expander is connected with the generator;
the ammonia preparation system is connected with the nitrogen storage tank;
and the methanol preparation system is connected with the supercritical carbon dioxide power generation system.
2. The flexible and efficient carbon dioxide power generation coupling ammonia alcohol cogeneration system of claim 1, wherein the circulating medium conveying path comprises a carbon dioxide compressor and a second three-way valve, the water separation device is connected with the carbon dioxide compressor through a first three-way valve, the carbon dioxide compressor is respectively connected with a first regenerator and the air compression heat storage device through a second three-way valve, and the first regenerator and the air compression heat storage device are respectively connected with the burner.
3. The flexible and efficient carbon dioxide power generation coupling ammonia alcohol co-production system according to claim 2, wherein the water separation device is respectively connected with the carbon dioxide compressor and the methanol preparation system through a first three-way valve, and the precooler is respectively connected with the methanol preparation system and the second hydrogen storage tank.
4. The flexible and efficient carbon dioxide power generation coupling ammonia-alcohol co-production system according to claim 3, wherein the methanol preparation system comprises a pressure regulating valve, a fifth three-way valve, a hydrogen compressor, a sixth three-way valve, a third heat regenerator, a methanol synthesis device, a methanol separation device and a second hydrogen storage tank, the water separation device is connected with the first three-way valve, the first three-way valve is sequentially connected with the pressure regulating valve, the fifth three-way valve, the third heat regenerator and the methanol synthesis device, a discharge port of the methanol synthesis device is sequentially connected with the third heat regenerator and the methanol separation device, the second hydrogen storage tank is sequentially connected with a precooler and the sixth three-way valve, the methanol separation device is connected with one port of the sixth three-way valve, the other port of the sixth three-way valve is connected with an inlet of the hydrogen compressor, and an outlet of the hydrogen compressor is connected with one port of the fifth three-way valve.
5. The flexible and efficient carbon dioxide power generation coupling ammonia alcohol co-production system according to claim 4, wherein a carbon dioxide storage tank is connected between the first three-way valve and the pressure regulating valve.
6. The flexible and efficient carbon dioxide power generation coupling ammonia-alcohol cogeneration system according to claim 5, wherein the ammonia preparation system comprises a third three-way valve, a fourth three-way valve, a mixed gas compressor, a second heat regenerator, an ammonia synthesis device and an ammonia separation device, wherein the third three-way valve is connected with the fourth three-way valve, the other two ports of the third three-way valve are respectively connected with a first hydrogen storage tank and a nitrogen storage tank, one port of the fourth three-way valve is sequentially connected with the mixed gas compressor, the second heat regenerator and the ammonia synthesis device, the air outlet end of the ammonia synthesis device is sequentially connected with the second heat regenerator and the ammonia separation device, and the ammonia separation device is connected with one port of the fourth three-way valve.
7. The co-production method of the flexible and efficient carbon dioxide power generation coupled ammonia alcohol co-production system according to any one of claims 1 to 6, comprising the following steps:
air compression separation system: the air at normal temperature and normal pressure is compressed by an air compressor and then is boosted and heated, then the air at high pressure and high temperature flows through an air compression heat storage device to store compression heat for cooling, the air at high pressure and normal temperature enters an air separation device to generate nitrogen and oxygen, the oxygen is stored in an oxygen storage tank, and the nitrogen is stored in a nitrogen storage tank;
generating electricity by carbon dioxide: oxygen from an oxygen storage tank is compressed to a specified pressure by an oxygen compressor and then enters a combustor, the oxygen is combusted together with the introduced natural gas in the combustor, high-temperature gas generated by combustion is mixed with carbon dioxide introduced into the combustor, the formed high-temperature and high-pressure mixed gas mainly comprising carbon dioxide enters a turbine expander from an outlet of the combustor to be matched with a generator to do work and generate power, the exhaust of the turbine expander is subjected to heat recovery by a first regenerator, a precooler cooling and water separation device is used for separating moisture in the exhaust, and then is split by a first three-way valve, the split carbon dioxide is compressed to the specified pressure by a carbon dioxide compressor and then is separated again by a second three-way valve, one carbon dioxide is heated by the first regenerator to enter the combustor to be mixed with combustion products of oxygen and natural gas and then to be circulated, and the other carbon dioxide is heated by the air compression heat storage device to enter the combustor to be mixed with combustion products of oxygen and natural gas and then to be circulated;
ammonia preparation: the nitrogen from the nitrogen storage tank is mixed with the hydrogen through a third three-way valve, the mixed gas of the nitrogen and the hydrogen is further mixed with the gas separated by the ammonia separation device through a fourth three-way valve, the mixed gas is compressed to a specified pressure through a mixed gas compressor, then the mixed gas is heated through a second heat regenerator and then enters the ammonia synthesis device to react to generate ammonia, an outlet of the ammonia synthesis device is connected with a high-temperature gas inlet of the second heat regenerator, the mixed gas is cooled through the second heat regenerator and then enters the ammonia separation device to separate ammonia, and the mixed gas after ammonia separation then flows into the fourth three-way valve to be mixed with the hydrogen and the nitrogen and then is continuously circulated to prepare ammonia;
preparation of methanol: the carbon dioxide split by the first three-way valve is stored in a carbon dioxide storage tank, and the carbon dioxide output from the carbon dioxide storage tank flows into a fifth three-way valve to be mixed with hydrogen according to a certain proportion after the pressure of the carbon dioxide is regulated by a pressure regulating valve; after the temperature of the hydrogen is raised by the precooler, the hydrogen is further mixed with the gas separated by the methanol separation device, compressed to the specified pressure by the hydrogen compressor, and then enters the fifth three-way valve to be mixed with carbon dioxide according to a certain proportion; the mixed gas is heated by a third heat regenerator and then enters a methanol synthesis device to react to generate methanol, an outlet of the methanol synthesis device is connected with a high-temperature gas inlet of the third heat regenerator, the mixed gas is cooled by the third heat regenerator and then enters a methanol separation device to separate methanol, and the mixed gas after separating the methanol then flows into a sixth three-way valve to be mixed with hydrogen and then is continuously circulated.
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