CN116903441A - Integrated supercritical CO 2 Method for preparing methanol by using recycled green hydrogen coupled coal - Google Patents
Integrated supercritical CO 2 Method for preparing methanol by using recycled green hydrogen coupled coal Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 223
- 238000000034 method Methods 0.000 title claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 49
- 239000001257 hydrogen Substances 0.000 title claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000003245 coal Substances 0.000 title claims abstract description 39
- 239000007789 gas Substances 0.000 claims abstract description 91
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 41
- 230000008569 process Effects 0.000 claims abstract description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000001301 oxygen Substances 0.000 claims abstract description 39
- 238000010926 purge Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000010248 power generation Methods 0.000 claims abstract description 16
- 238000002309 gasification Methods 0.000 claims abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 14
- 230000008878 coupling Effects 0.000 claims abstract description 11
- 238000010168 coupling process Methods 0.000 claims abstract description 11
- 238000005859 coupling reaction Methods 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 10
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 239000002737 fuel gas Substances 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 56
- 238000002485 combustion reaction Methods 0.000 claims description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 28
- 239000001569 carbon dioxide Substances 0.000 claims description 19
- 230000001590 oxidative effect Effects 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 230000005611 electricity Effects 0.000 description 7
- 238000004088 simulation Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000183024 Populus tremula Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000012720 thermal barrier coating Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides an integrated supercritical CO 2 The method for preparing methanol by green hydrogen coupling coal through cyclic power generation comprises the following steps: renewable energy source water electrolysis device, coal gasification device, conversion device, purification device, methanol synthesis device and dioxygen deviceDevice for preparing methanol by carbon conversion hydrogenation, methanol rectifying device and supercritical CO 2 A circulation device; the renewable energy source water electrolysis device is used for generating hydrogen and oxygen required by the whole process, one part of the oxygen is input into the coal gasification device to meet gasification requirements, and the other part of the oxygen is input into the supercritical CO 2 The circulating device is used as combustion-supporting gas, and hydrogen generated by electrolysis and CO removed by the purifying device 2 Methanol is prepared, wherein, considering the resource utilization condition of the purge gas in the process of preparing the methanol from the green hydrogen coupled coal, the purge gas is taken as fuel gas to integrate supercritical CO 2 The cyclic power generation promotes the recycling of process materials, realizes the CO-production of methanol and power and CO 2 The device has the advantages of low cost, separation and collection, high efficiency, energy conservation and emission reduction.
Description
Technical Field
The invention belongs to the technical field of new energy coupling utilization, and particularly relates to an integrated supercritical CO 2 A method for preparing methanol by green hydrogen coupling coal through cyclic power generation.
Background
In green hydrogen coupling coal chemical industry, particularly in the process of preparing methanol from coal, attention has been paid in recent years, and the process of preparing methanol by hydrogenating the removed carbon dioxide is considered to be capable of well solving the problems of large carbon emission, low resource utilization rate and the like in the process.
Although the purge gas of this process occupies a relatively small proportion (5% -15%) in the recycle gas, in mass production, the unused purge gas is still an important component of resource waste and environmental pollution. The evacuation of purge gas can bring about a large amount of pollution and resource waste, the combustion of entering a torch can also cause a large amount of emission, the recovery of hydrogen through pressure swing adsorption to reduce resource waste is one of the effective utilization ways of the present purge gas, however, the cost of pressure swing adsorption is a limiting factor, and the utilization of other resources is not emphasized. Meanwhile, part of oxygen generated in the green hydrogen preparation process is used as gasifying agent, but still has surplus oxygen, which is usually sold as a byproduct, and the part of oxygen is not utilized effectively and reasonably in the process. Therefore, how to promote the utilization of purge gas and surplus oxygen is of great significance to resource recovery, emission reduction and system efficiency improvement.
The Allam cycle is performed by supercritical CO 2 (sCO 2) is a working medium, a regenerative Brayton cycle for burning and heating gaseous fuel and oxygen in a combustion chamber, and sCO for heating the working medium by indirect heat exchange 2 The main difference in thermodynamic cycle is thatThe temperature is raised by direct combustion. Due to combustion in CO 2 And NO is present in an oxygen atmosphere x And the like are beneficial to CO 2 Is low cost to capture, and sCO 2 Has obvious advantages in a larger temperature range. At present, part of the research has already been on sCO 2 The method is circularly combined into the traditional coal-to-methanol process, and the purge gas is used as a gas fuel for combustion power generation, so that the energy efficiency of the system is improved, the utilization of resources is promoted, and the cost of carbon capture is reduced.
The Allam cycle has high requirement on oxygen purity, an air separation oxygen generator is needed, an air separation device is not needed in the process of preparing methanol from green hydrogen, the purity of the rest oxygen can meet the requirement, and at present, the supercritical CO is lacking 2 (sCO 2 ) The Allam cycle is integrated to the green hydrogen coupling coal to prepare methanol process to form a design scheme for promoting the system resource to be consumed and utilized and further improving the system efficiency.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art, and integrating supercritical CO based on the process of preparing methanol from green hydrogen coupled coal 2 (sCO 2 ) Allam circulation promotes resource consumption, further utilizes and improves system efficiency, reduces carbon emission.
The technical proposal of the invention
To achieve the above object, the present invention provides an integrated supercritical CO 2 The green hydrogen coupled coal methanol preparation method for cyclic power generation comprises a renewable energy electrolysis water device, a coal gasification device, a conversion device, a purification device, a synthesis gas methanol preparation device, a carbon dioxide hydrogenation methanol preparation device, a methanol rectification device and a supercritical CO 2 A circulation device; the hydrogen and oxygen required by the whole process are generated by the renewable energy source water electrolysis device, the hydrogen enters the device for preparing methanol by hydrogenating carbon dioxide and is used for synthesizing the methanol, one part of the oxygen generated by electrolysis is input into the coal gasification device to meet the gasification requirement, and the other part of the oxygen enters into the supercritical CO 2 The circulating device is used as combustion-supporting gas, the gasified crude synthetic gas enters the conversion device, the reaction requirement of the synthetic gas for preparing methanol is met through conversion, and the carbon dioxide is removed in the purification device by the conversion gasAnd sulfide, wherein the removed carbon dioxide reacts with hydrogen in a device for preparing methanol by hydrogenation of carbon dioxide, the purified synthesis gas enters a device for preparing methanol from the synthesis gas to produce methanol, then methanol is purified by a methanol rectifying device, and unreacted purge gas in the two methanol preparation processes is conveyed to supercritical CO 2 And generating electricity in the circulating device.
Because of the instability of renewable energy sources, the renewable energy source water electrolysis device needs to comprise a hydrogen storage device and an oxygen storage device to ensure continuous and stable operation of the process flow.
Supercritical CO 2 The circulating device comprises a purge gas compressor, a combustion chamber, a gas turbine and a generator, an oxygen compressor, an oxidizing gas compressor, a high-temperature heat regenerator, a low-temperature heat regenerator, an oxidizing gas preheater, a water separator and CO 2 Primary compressor, interstage condenser and CO 2 Secondary compressor, condenser, primary booster pump and secondary booster pump
After the purge gas is compressed to 30.5MPa by a compressor, the purge gas and the compressed oxidizing gas enter a combustion chamber to be combusted, and the combusted gas and a cycle working medium CO 2 The working medium is converged into a gas turbine to do work together, the working medium after working is divided into two parts, one part of the working medium is preheated by an oxidizing gas preheater, the other part of the working medium is sequentially fed into a high-temperature heat regenerator and a low-temperature heat regenerator to heat the circulating working medium which is about to enter a combustion chamber, after leaving the low-temperature heat regenerator, the working medium is converged with the other circulating working medium, and then water is separated by a water separator to capture a small part of CO 2 Then compressed to 8MPa by a two-stage compressor, an interstage condenser is arranged by the two-stage compression, and the mixture is condensed by the condenser to lead the mixture to be higher than CO 2 Is pressurized to a certain pressure by a pressure pump, wherein a small amount of CO 2 The mixed gas enters a combustion chamber to serve as an oxidant after being mixed with oxygen, the other gas serves as a circulating working medium to be pressurized by a secondary pressurizing pump and then is preheated by a low-temperature regenerator and a high-temperature regenerator, a small gas serves as a turbine cooling flow to cool a turbine, and most of circulating flow enters the combustion chamber to adjust sintering temperature, so that a circulating process is completed. The condensation process is cooled by cooling water.
On the basis of ensuring the consumption of gasifying agent in the process of preparing methanol from green hydrogen coupled coal, the surplus oxygen is used for the system and is used as a pure oxygen source without an air separation device.
The fuel gas is purge gas in the methanol synthesis process, and the main components are CO and H 2 CO 2 The combustion product is H 2 O and CO 2 Is convenient for realizing the separation of water and CO 2 Wherein when the green hydrogen content is reduced, the purge gas is purged with incompletely reacted CO 2 Mainly, the low-order heat value is lower, and the generated energy is reduced.
The heat recovery device mainly comprises a high-temperature heat regenerator, a low-temperature heat regenerator and an oxidizing gas preheater
The working pressure of the whole cyclic power generation process is changed between 3 MPa and 30MPa, the span is large, and the cyclic power generation process is realized by connecting a plurality of compressors in series. The maximum operating temperature, i.e., turbine inlet temperature, is 1100 ℃, and turbine interstage cooling is provided.
The invention has the following beneficial effects: the invention comprehensively considers the problem of utilization of purge gas resources generated in the process of preparing methanol from green hydrogen coupled coal, takes the purge gas as fuel gas, and integrates supercritical CO 2 Cycle power generation, at the same time, supercritical CO 2 Pure oxygen required by the process is provided by cyclic power generation, an air separation device is removed, and supercritical CO is improved 2 The cyclic power generation efficiency realizes the CO-production of methanol and power and CO 2 The device has the advantages of low cost, separation and collection, high efficiency, energy conservation and emission reduction.
The process features of the present invention are described in detail below in terms of one example.
Drawings
FIG. 1 is a schematic view of the process of the present invention
FIG. 2 is a schematic diagram of an embodiment
In the figure: 1. the device comprises a photovoltaic water electrolysis device 2, a coal gasification device 3, a conversion device 4, a purification device 5, a device 6 for preparing methanol from synthetic gas, a device 7 for preparing methanol from carbon dioxide through hydrogenation, a methanol rectifying device 8-1, a purge gas compressor 8-2, a combustion chamber 8-3, a gas turbine and a generator 8-4, an oxygen compressor 8-5, an oxidizing gas compressor 8-6, a high-temperature regenerator 8-7, a low-temperature regenerator 8-8 and oxygenThe chemical gas preheater 8-9, the water separator 8-10, the CO2 primary compressor 8-11, the interstage condenser 8-12 and CO 2 The secondary compressor 8-13, the condenser 8-14, the primary booster pump 8-15 and the secondary booster pump
Detailed Description
Through adopting the photovoltaic water electrolysis device to produce the hydrogen and the oxygen required by the whole process and connecting a hydrogen pipeline with a device for preparing methanol by hydrogenating carbon dioxide, one part of the oxygen produced by electrolysis is input into a coal gasification device to meet gasification requirements, and the other part is input into supercritical CO 2 The circulating device is used as combustion-supporting gas, the coal gasification device is connected with the conversion device, the reaction requirement of preparing methanol from synthetic gas is met through conversion, the purification device is connected with the conversion device, carbon dioxide and sulfide are removed, the removed carbon dioxide and hydrogen react in the device for preparing methanol from carbon dioxide through hydrogenation, the purified synthetic gas enters the device for preparing methanol from synthetic gas to produce methanol, then methanol is purified through the methanol rectification device, and the purge gas which is not utilized in the two processes is conveyed to supercritical CO 2 And generating electricity in the circulating device.
After the purge gas is pressurized to 30.5MPa by a compressor, the purge gas is taken as fuel gas to enter a combustion chamber, pure oxygen required by combustion comes from surplus oxygen serving as a gasifying agent after the hydrogen production process of the photovoltaic electrolyzed water, the purge gas is compressed to meet the pressure condition, and part of cycle working medium (12 MPaCO is used for safety consideration 2 ) Mixing with oxygen, compressing to 30.5MPa, feeding into combustion chamber, and injecting large amount of supercritical CO 2 The circulating flow (accounting for 95% of the oxidizing gas) is used for regulating the combustion temperature (under the pressure, sCO2 can obviously strengthen the combustion process), the highest efficiency operation of the system can be ensured when the outlet temperature of the combustion chamber is 1150-1200 ℃, the combusted gas and the injected circulating working medium are converged into the gas turbine to do turbine work to generate electric energy, the inlet turbine pressure of the circulating working medium and the combustion gas is 30.5MPa, the cooling expansion is reduced to 3.4MPa, the increase of the outlet pressure of the turbine can reduce the generated energy, the compression work required by the subsequent compression link is reduced, and the energy efficiency is balanced, so that the system has good effects between 3.4 and 4 MPa; after expansion workOne is divided into two parts, and one part preheats oxygen and CO by means of an oxidizing gas preheater 2 The mixed gas is preheated to 720 ℃, the other part of the mixed gas sequentially enters a high-temperature heat regenerator and a low-temperature heat regenerator to heat circulating working media which are about to enter a combustion chamber, the mixed gas is heated to 720 ℃ as well, the exhaust gas after leaving the low-temperature heat regenerator is converged with another working medium for preheating the mixed gas, and then all water is condensed and separated by a water separator, and the residual CO with the purity of more than 95 percent is obtained 2 Ensuring stable working medium circulation quantity and generating CO in the combustion process 2 And (5) collecting and sealing. Then the circulating working medium is compressed to 8MPa by two stages, the two stages are compressed to set inter-stage cooling, and then condensed to 31 ℃ by a condenser, which is slightly higher than CO 2 In this state, CO 2 Can be compressed efficiently in the compressor without significant changes in temperature. The heat conductivity also reaches the maximum value at the critical density, greatly accelerating CO 2 The heat exchange process can fully exert the dramatic change advantage of the physical properties of the working medium. Then pressurizing to 12MPa by a pressure pump, wherein a small amount of CO 2 Mixing with oxygen, entering a combustion chamber to serve as an oxidant, pumping a circulating working medium to 30.5MPa through a secondary booster pump, recovering heat of the expanded gas through a low-temperature heat regenerator and a high-temperature heat regenerator, preheating to 720 ℃, wherein 20% of the circulating working medium is used as turbine cooling flow to cool the turbine, and the other part of the circulating working medium is used as circulating flow to adjust the combustion temperature, so that the circulating process is completed. The condensing process is cooled by cooling water at 20 ℃ so as to ensure that the compressor runs with low power consumption.
In the embodiment, the conversion device is reserved, green hydrogen is prepared by photovoltaic electrolyzed water only to be matched with the hydrogen-carbon ratio in the carbon dioxide hydrogenation process, and the generated oxygen meets two conditions: the coal gasification process is suitable for the ratio of oxygen to coal; supercritical CO 2 The fuel gas is completely combusted during the cycle. Therefore, the process should firstly meet the oxygen required by the gasification process, and the oxygen is blended as an oxidant according to the complete combustion of the combustible gas in the purge gas, and the rest of the oxygen outside the process can be sold as an industrial byproduct.
In the above example, 60 ten thousand tons of methanol are produced annually, and the coal consumption is reduced to 0.664 tons of coal/ton of methanol by replacing renewable energy green hydrogen.
The system electricity consumption is derived from the photovoltaic generator set, so that the system electricity consumption is clean and green, the carbon emission is reduced, the electricity consumption cost is reduced, and the system electricity consumption is reduced by supercritical CO 2 The circularly generated electricity, a part of which can be used for adjusting the fluctuation of the photovoltaic power generation.
The working pressure of the whole cycle is changed between 3 MPa and 30MPa, the span is large, and the working pressure is realized by connecting a plurality of compressors in series. The highest working temperature, namely the turbine inlet temperature is 1100 ℃, the material problem of the turbine needs to be considered, meanwhile, a turbine cooling system is arranged, a turbine shell can adopt CrMoV, a rotor center part adopts nickel-based materials, and a rotor tail end adopts CrMoV materials. The blade is protected by a thermal barrier coating and cooled by convection, wherein the cooling liquid adopts CO 2 。
The invention provides an integrated supercritical CO 2 The circulating green hydrogen coupling coal methanol preparation method has the advantages that the flow can stably run through Aspen Plus simulation, the temperature (1150 ℃) of fuel gas coming out of a combustion chamber is in the optimal running interval, a simplified model is adopted during simulation, a multi-flow heat exchanger is adopted to replace a high-temperature heat regenerator, a low-temperature heat regenerator and an oxidizing gas preheater in a heat recovery device, and circulating simulation parameters are set according to the description. Meanwhile, the clean generating capacity is used as a generating index, the Allam circulating efficiency is obtained through the low-level heat value of purge gas, and the key parameter results of the system are shown in table 1. By analysis, by integration of supercritical CO 2 The energy efficiency of the technology for preparing methanol by green hydrogen coupling coal is improved by 16.7 percent, and the total carbon emission is 1.59tCO 2 Reduction of/tMEOH to 1.28tCO 2 The cycle efficiency of the Allam cycle was increased to 66.89% by removing the air separation unit. In summary, the integrated system can effectively promote the resource consumption and utilization, further reduce the carbon emission and improve the system efficiency.
TABLE 1
Claims (9)
1. Integrated supercritical CO 2 Circulating green hydrogen coupled coalThe methanol method is characterized by comprising a green hydrogen coupling coal methanol preparation process and supercritical CO 2 A cyclic power generation process; the green hydrogen coupling coal methanol preparation process comprises a renewable energy source water electrolysis device (1), a coal gasification device (2), a conversion device (3), a purification device (4), a synthesis gas methanol preparation device (5), a carbon dioxide hydrogenation methanol preparation device (6) and a methanol rectification device (7); the technology for preparing methanol by green hydrogen coupling coal not only utilizes carbon dioxide to improve the production capacity of the methanol, but also is supercritical CO 2 The supercritical CO2 cycle power generation process comprises supercritical CO 2 A circulation device (8);
the renewable energy source water electrolysis device (1) is used for generating hydrogen and oxygen required by the whole process, the hydrogen enters the carbon dioxide hydrogenation methanol preparation device (6) for synthesizing methanol, one part of the oxygen generated by electrolysis is input into the coal gasification device (2) to meet the gasification requirement, and the other part of the oxygen enters the supercritical CO 2 The circulating device (8) is used as combustion-supporting gas, the gasified crude synthetic gas enters the conversion device (3), the reaction requirement of the synthetic gas for preparing methanol is met through conversion, the conversion gas removes carbon dioxide and sulfide in the purification device (4), the removed carbon dioxide reacts with hydrogen in the carbon dioxide hydrogenation methanol preparation device (6), the purified synthetic gas enters the synthetic gas methanol preparation device (5) for producing methanol, then methanol is purified through the methanol rectification device (7), and the unreacted purge gas in the two methanol preparation processes is conveyed to supercritical CO 2 The power generation is performed in the circulation device (8).
2. The integrated supercritical CO of claim 1 2 The method for preparing methanol by using recycled green hydrogen coupled coal is characterized in that the renewable energy source water electrolysis device also comprises a hydrogen storage device and an oxygen storage device.
3. The integrated supercritical CO of claim 1 2 The method for preparing methanol by using recycled green hydrogen coupled coal is characterized by comprising the following steps of 2 The circulating device (8) comprises a purge gas compressor (8-1), a combustion chamber (8-2), a gas turbine and a generator (8-3), an oxygen compressor (8-4) and oxidizing gasThe device comprises a compressor (8-5), a high-temperature heat regenerator (8-6), a low-temperature heat regenerator (8-7), an oxidizing gas preheater (8-8), a water separator (8-9), a CO2 primary compressor (8-10), an interstage condenser (8-11), a CO2 secondary compressor (8-12), a condenser (8-13), a primary booster pump (8-14) and a secondary booster pump (8-15).
4. An integrated supercritical CO according to claim 3 2 The method for preparing methanol by using recycled green hydrogen coupling coal is characterized in that purge gas is compressed to 30.5MPa step by a compressor (8-1), then the purge gas is mixed with oxidized gas compressed by an oxygen compressor (8-4) and an oxidized gas compressor (8-5) and a circulating working medium, the oxidized gas and the circulating working medium enter a combustion chamber (8-2) for combustion, the circulating working medium is used for adjusting combustion temperature, the combusted gas is converged into a gas turbine (8-3) for turbine power, the power is divided into two parts after the power is applied, one part of the gas is used for preheating mixed gas by an oxidized gas preheater (8-8), the other part of the gas is sequentially heated by a high-temperature regenerator (8-6) and a low-temperature regenerator (8-7), the circulating working medium which is about to enter the combustion chamber is heated by the other part of the gas enters the low-temperature regenerator (8-7), after leaving the low-temperature regenerator (8-7), water is separated from the other circulating working medium, a small part of the gas is compressed by a water separator (8-9), CO2 is captured, and then compressed by a two-stage compressor (8-12), and a condenser (8-11) is arranged after the two-stage compression, and the gas is condensed by a condenser (8-13) to make CO higher than CO 2 And then compressed to a certain pressure by a primary pressurizing pump (8-14), wherein part of CO2 and oxygen are mixed and enter a combustion chamber to serve as an oxidant, the other part of CO2 is pressurized to a working pressure by a secondary pressurizing pump (8-15) and then preheated by a low-temperature heat regenerator (8-7) and a high-temperature heat regenerator (8-6) by using a circulating working medium, a small part of CO2 serves as a turbine cooling flow to cool a turbine, most of circulating flow enters the combustion chamber (8-2) to adjust the firing temperature, the circulating process is completed, and the condensing process is cooled by using cooling water.
5. The integrated supercritical CO of claim 1 2 The method for preparing methanol by using recycled green hydrogen coupled coal is characterized in that on the basis of ensuring the consumption of gasifying agent in the process of preparing methanol by using green hydrogen coupled coal, the surplus oxygen is used for supercritical CO 2 Cycle power generation as pure oxygenThe source does not need a space division device.
6. The integrated supercritical CO of claim 1 2 The method for preparing methanol by using recycled green hydrogen coupled coal is characterized in that fuel gas is purge gas in the methanol synthesis process and the carbon dioxide hydrogenation process, and the main components are CO and H 2 CO 2 The combustion product is H 2 O and CO 2 The separation of water and the capture of CO2 are convenient to realize.
7. The integrated supercritical CO of claim 1 2 A method for preparing methanol by using recycled green hydrogen coupled coal, wherein when the green hydrogen content is reduced, the methanol yield is reduced, and purge gas is used for CO which is not completely reacted 2 Mainly, the generated energy is reduced.
8. The integrated supercritical CO of claim 1 2 The method for preparing methanol by using recycled green hydrogen coupled coal is characterized in that the heat recovery device comprises a high-temperature heat regenerator (8-6), a low-temperature heat regenerator (8-7) and an oxidizing gas preheater (8-8).
9. The integrated supercritical CO of claim 1 2 The method for preparing methanol by using circulating green hydrogen coupled coal is characterized by that the working pressure of whole circulating power generation process is changed between 3-30 MPa, its span is large, and several compressors are required to be series-connected, and its highest working temperature, i.e. turbine inlet temperature is 1150-1200 deg.C, and the turbine interstage cooling is set.
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