• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention presents an integrated system of production of na2 hco3 from co2 captured from industries or power plants by a process of dry carbonate starting from trona as raw material (na2 co3º nahco3º 2H2 o) and converting it to sodium carbonate (na2 co3). The optimized integration of the assembly allows the coupling with renewable energies at a medium temperature> 220º c, such as biomes or solar thermal systems at medium temperature. The use of these results in a global system of almost zero co2 emissions, being able to satisfy the heat needs of the integrated assembly, minimizing the energy consumption of the co capture system2 and conversion to bicarbonate. This optimized integration reduces the energy and economic penalty of the integration of the system of capture of co2 and conversion to chemical product of added value. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2650840A1
    申请号:ES201600616
    申请日:2016-07-19
    公开日:2018-01-22
    发明作者:Ricardo CHACARTEGUI RAMÍREZ；José Antonio BECERRA VILLANUEVA；José Manuel VALVERDE MILLÁN；Davide BONAVENTURA
    申请人:Universidad de Sevilla；
    IPC主号:
    专利说明:

     Integrated CO2 capture system and production of sodium bicarbonate (NaHC03) from high chair (Na2C03 '2H20 · NaHC03) 5 TECHNICAL SECTOR The invention falls within the technical sector of CO2 capture and storage (CCS), specifically with regard to the capture of CO2 in power plants and industrial processes and their subsequent use (CCU) for the production of chemical products of industrial interest. This invention integrates the processes of CO2 capture and production of sodium bicarbonate with the support of renewable energy, biomass or medium temperature solar energy «220 ° C), resulting in a global system of almost-zero emissions with an energy penalty Reduced at low cost. STATE OF THE TECHNIQUE 15 The capture and storage of CO2 has a great potential for growth on a global scale due to the urgent need to reduce emissions of effect gases in order to mitigate global warming. The CO2 capture processes developed in recent years at the level of research and development (1 + D) have as main objectives the reduction of costs and the energy requirements of them, so as to reduce or eliminate energy penalties and economic factors associated with the integration of CO2 capture systems. At present, the only post-combustion CO2 capture technology that operates on a commercial scale is based on the chemical absorption of CO2 through amines [1). The CO2 capture process using dry sodium carbonate (dry carbonation process) is based on the chemical adsorption of CO2 into sodium carbonate. By adsorption, sodium carbonate (Na2C03) is converted into sodium bicarbonate (NaHC03) or an intermediate salt (Na2C03. 3NaHC03) through the chemical reaction with CO2 and water vapor [2]. The sorbent is regenerated back to its carbonate form (Na2C03) when heated, thereby releasing an almost pure flow of CO2 after steam condensation. CO2 adsorption occurs at a low operating temperature (T <80 o C) while the regeneration of the sorbent is carried out at higher temperatures but also at relatively low temperatures (T> DESCRIPTION100 o C). For the complete regeneration of the sorbent quickly enough, it is enough to operate with temperatures of the order of 200 o C. Different patents describe processes and improvements to optimize the carbonation of Na2C03, which is exothermic [3,4], The management of this heat released in the reactor it is essential to effectively implement the process in a commercial system minimizing the energy penalty of the process in which it is integrated. On the other hand, there are different production processes of sodium bicarbonate, intermediate solvent in the dry carbonate process. The SOL VA Y patent for the production of sodium bicarbonate ES2409084 (A 1) [5] describes a process for producing sodium bicarbonate from a stream carrying sodium carbonate, a part of which is generated by a crystallizer, where said stream carries sodium carbonate (A) with at least 2% by weight of sodium chloride and / or sodium sulfate. The process comprises an aqueous dissolution process, generation of sodium bicarbonate crystals and separation thereof. In US2015175434 (A 1) [6] a process is described for the joint production of sodium bicarbonate and other alkaline compounds in which CO2 is generated as an intermediate product that can be used to feed back the production phase of sodium bicarbonate . Na2C03 can be obtained from the decomposition of the natural highchair ore (Na2C03. NaHC03. 2H20), composed of approximately 20% sodium carbonate (Na2C03) and sodium bicarbonate (NaHC03) by 35% by weight and available galore. The region with the highest production of this mineral in the world is Wyoming (United States) whose mines produced more than 17 million tons of highchair. The US Geological Survey In 1997, he estimated that the total highchair reserve is 127 million tons, although only 40 million tons are 25 recoverable [7]. La Trona is stable up to 57 oC dry, and creates intermediate compounds such as wegschiderite (Na2C03. 3NaHC03) and sodium monohydrate (Na2C03. H20) between 57 o C and 160 o C [8]. Above 160 o C, the highchair decomposes to Na2C03 [9]. A relevant technological challenge is the development of a method for converting the fraction of Na2C03 in the high chair into a commercial value-added product such as sodium bicarbonate (NaHC03) that is cost effective. The generation of sodium bicarbonate from highchair is described in different patents [10-11]. A process for the production of sodium carbonate and sodium bicarbonate from highchair is described in US2013095011 (A 1) [12]. Includes themilling of the high chair and its dissolution in a solution with sodium carbonate and an additive that generates solid particles suspended in the aqueous solution and that can be separated. As regards the generation of sodium bicarbonate crystals from highchair in W02013106294 (A1) [13], a process for producing sodium bicarbonate crystals from highchair and water is described; US2011 064637 (A 1) [14] describes a process for the joint production of sodium carbonate and sodium bicarbonate crystals from sodium sesquicarbonate powder. In the process a suspension of water and a gas containing CO2 is used. In US2009238740 (A 1) [15] 10 a method of preparing sodium bicarbonate from highchair containing sodium floride as an impurity is presented by preparing a highchair solution and introducing CO2 until the solution reaches a pH in the range from 7.5 to 8.75 by precipitating the sodium carbonate in the high chair solution. In US2006182675 (A1) [16] a process for the production of bicarbonate obtained from 15 highchair is collected including the stages of purification, evaporation-decarbonation, crystallization, centrifugation and drying. US2004057892 (A 1) [17] patents a method to produce sodium bicarbonate from highchair ore. The process uses the effluent water stream from the conversion of highchair to sodium carbonate as a supply for the conversion of sodium carbonate to sodium bicarbonate. 20 The current state of the art for the production of NaHC03 from Trona can be summarized as follows. A vertical tubular reactor with a perforated bottom that separates the upper fluidization chamber from a lower backwater chamber is fed from ground natural highchair. A stream of gas is passed through the backwater chamber upwards through the bottom drilled into the fluidization chamber at a speed high enough to keep a portion of the load in suspension, and to drag the decomposition gases , such as water vapor and CO2, which are generated during the reaction. The fluid bed reactor acts both as a calciner for the high chair and as a separator for the fine highchair particles of the thick portion of the remaining load suspended in the fluid bed. The thermal energy required to convert the raw material (highchair) into raw sodium carbonate can be supplied by heating the fluidization gas or by placing internal heating devices or around the fluid bed, preferably within the fluid bed. same. The temperature of5 fluid bed should be found in the range of 140 or -220 o C (8). The reaction that takes place in the fluid bed reactor is: K]!: J.H298K = 133,9-l [9] m or For the production of sodium bicarbonate the intermediate Na2C03 solution is centrifuged, to separate the liquid from the crystals. The crystals are then dissolved in a carbonate solution (a solution of Na2C03) in a rotating dilutor, thus becoming a saturated solution. This solution is filtered to remove any non-soluble material and is then pumped through a feed tank to the top of a carbonation tower. The purified CO2 is introduced into the lower part of the carbonation tower and is pressurized. As the saturated sodium solution evolves through the carbonator, it cools and reacts with the CO2 to form sodium bicarbonate crystals. These crystals are collected in the lower part of the reactor and transferred to another centrifuge, where the excess solution is filtered off. The crystals are then washed in a bicarbonate solution, forming a cake-like substance ready for drying in the filtrate. The filtrate that is removed from the centrifuge is recycled to the rotary solution vessel, where it is used to saturate more intermediate Na2C03 crystals. The washed filter cake 20 is then dried, either in a continuous belt conveyor or in an instant vertical tube dryer (flash dryer). In the carbonation tower, the saturated Na2C03 solution evolves from the top to the bottom. As it falls, the solution cools and reacts with CO2 25 to form NaHC03 crystals. After filtration, washing and drying, the crystals are sorted by particle size and packaged properly. The reaction that takes place in the carbonation tower is: Na2C03 (S) + CO2 (g) + H20 (g) H 2NaHC03 k]!: J.H298K = 129.09-l [11] moThe heat required in this endothermic process can be supplied by fossil fuels or renewable sources such as solar energy or biomass could be used. Since the operating temperature is moderate (200 ° C), a low-cost parabolic trough system (PTC) could be used to supply the heat required for endothermic reactions. The parabolic trough concentrator (PTC) is a solar concentration technology that converts solar radiation into thermal energy in the receiver using a linear focusing system. The applications of the PTC parabolic cylinder systems can be divided into two main groups. The first and most developed is associated with concentrated solar power plants 10 (CSP) for the generation of electricity using temperatures relatively around 300-400 ° C. The second group of applications is associated with the supply of thermal energy in applications that require temperatures in the range 85 -250 o C. These applications, which mainly use industrial process heat, can be cleaning, drying, evaporation, distillation, pasteurization, sterilization, among others, as well as applications with low temperature heat demand and high consumption rates (domestic hot water, heating, heated pools), as well as heat-based cooling [18]. Currently the term medium temperature collectors is used to refer to the collectors operating in the range of 80-250 o C. 20 Regarding CO2 capture systems with sodium bicarbonate production, in US20100028241A1 [20) and W02009029292A1 [21) a system of reactions for the partial capture of carbon (C02 and CO) in coal plants and hydrogen production and hydrogenated compounds from NaCI sodium chloride, coal and water is presented. The sodium hydroxide generated from the chloride is used to produce sodium carbonate and bicarbonate. Chemical reactions between gases, hydroxide, carbon or natural gas produce solid carbonate and hydrogen, valuable substances that can be sold or used to generate electricity. In W02011 075680A 1 [22) a process is described by which C02 is absorbed by an aqueous caustic mixture to subsequently react with a hydroxide and form carbonate / bicarbonate. This implies the use of a process of separation of the liquid mixture and use of an electrolysis process. In US20060185985A 1 [23) this same process of using hydroxide and electrolysis to obtain carbonate and bicarbonate from CO2 captured by an aqueous mixture is presented. These aqueous solutions for CO2 capture are described in patent US201 00051859A 1 [24) in which water is processed to generate an acid solution and an alkaline solution that captures CO2.The invention presented in this document consists in the synergistic integration of: i) a CO2 capture system based on the use of highchair as a precursor to Na2C03 that will be used as a CO2 sorbent; ii) CO2 capture of effluent gases through a dry carbonate capture process (dry carbonation process), therefore not based on aqueous solutions such as the aforementioned patents; iii) sodium bicarbonate production process as a product partly reused in the capture process and partly intended for sale. This synergistic integration of both processes yields several advantages such as: i) energy consumption allows integration with heat sources for the regeneration of the sorbent based on renewable energies such as biomass or medium temperature solar energy «220 ° C); ii) sorbent: the bicarbonate produced in the process in turn allows the regeneration of the raw material used in the C02 capture process while the excess bicarbonate produced is a product of economic value whose sale reduces the economic penalty of the plant ; iii)) the proposed integration 15 using renewable energy sources (solar, biomass, wind) as sources of heat gives rise to global systems of zero CO2 emissions with a reduced penalty of performance of the integrated system and low energy penalty References 20 [1] Spigarelli BP, Kawatra SK. Opportunities and challenges in carbon dioxide capture. J C02 Useful 2013; 1: 69-87. doi: 10.1016 / j.jcou. 2013.03.002. [2] Nelson, T. O., Coleman, L. J., Green, D. A, & Gupta, R. P. (2009). The dry carbonate process: carbon dioxide recovery from power plant flue gas. Energy Procedia, 1 (1), 1305-1311. [3] Krieg, J.P., and Winston, AE. 1984. Dry Carbonation Process. U.S. Patent 4,459,272, 25 assigned to Church & Dwight Co., Inc., filed April 26, 1983, and issued July 10, 1984. [4] Falotico, AJ. 1993. Dry Carbonation of Trona. PCT Application No .: PCT / US19921006321 (W01993 / 011070), assigned to Church & Dwight Company, Inc., June 10. [5] WALRAVENS HUGO; ALLEN KURT; CHAU THOI-DAI; VANDENDOREN ALAIN, "PROCEDURE TO PRODUCE BICARBONE TO SODIUM" Spanish Patent ES2409084 30 (A 1), [6] KISIELEWSKI JAMES C; HANSEN DAVID M, PRODUCTLON OF CRYSTALLlNE SODIUM BICARBONA TE USING C02 RECOVERED FROM ANOTHER ALKALI PRODUCTlON PROCESS U. S. Patent No. US2015175434 (A 1) [7] Harris RE. Fifty Years of Wyoming Highchair Mining 1997: 177-82. 35 [8] Gartner RS, Witkamp GJ. Wet calcining of trona (sodium sesquicarbonate) and bicarbonate in a mixed solvent. J Cryst Growth 2002; 237: 2199-204. doi: 10.1016 / S0022-0248 (01) 02275-8. [9] Kim NK, Srivastava R, Lyon J. Simulation of an industrial rotary calciner with trona ore decomposition 2002.[10J Sproul, Jared Sanford, and Eric Rau. "Process for producing sodium carbonate from trona." US. Patent No. 3,869,538. 4 Mar. 1975. [11JTurner, A / lan L. "Process for producing sodium carbonate from trona ore." U S. Patent No. 6,010,672. 4 Jan. 2000. 5 [12J BRETON CLAUOE; CHAU THOI-OAI; PIET JOFFREY, PROCESS FOR THE JOINT PROOUCTlON OF SOOIUM CARBONA TE ANO SOOIUM BICARBONA TE, U S. Patent No. US2013095011 (A1) [13J BRACILOVIC ORAGOMIR M; KURTZ ANOREW O; PALUZZI JOSEPH A; SENK ZBIGNlEW M BOUNOARY LA YER CARBONA TlON OF TRONA, WO Patent No. 10 W02013106294 (A 1) [14J DA VOINE PERRINE; COUSTRY FRANCIS M; OETOURNA and JEANPAUL; ALLEN KURT, PROCESS FOR THE JOINT PROOUCTlON OF SOOIUM CARBONA TE ANO SOO / UM BICARBONATE, US. Patent No. US2011064637 (A 1) [15J SENSARMA SOUMEN; PHAOTARE SUMANT; SASTRY MURAL /, METHOO OF 15 REMOVING FLUORIOE IMPURITIES FROM TRONA YEAR PREPARES TlON OF SOOIUM BICARBONATE, US. Patent No. US2009238740 (A 1) [16J CEYLAN ISMAIL; UGURELL / A L /; OILEK NOYAN, PROCESS FOR PROOUCTlON OF DENSE SODA, L / GHT SODA, SOOIUM BICARBONA TE ANO SOOIUM SIL / CA TE FROM SOLUTlONS CONTAINING BICARBONATE, U S. Patent No. US2006182675 (A 1 20 [17J KURTZ ANOREW B, SOO / BICARO BICARO OICARO B, PROOUCTLON METHOO, US Patent No. US2004057892 (A 1) [18J Fernández-García A, Zarza E, Valenzuela L, Pérez M. Parabolic-trough solar co / readers and their applications. Renew Sustain Energy Rev 2010; 14: 1695- 721. [191 Hal BH Cooper Robert E. Tang Oonald E. Oegling Thomas K. Ewan Sam M. Ewan, 25 Process and apparatus for carbon capture and elimination of multi-po / lutants in fuel gas from hydrocarbon fuel sources and recovery of multiple by-products, U S. Patent No. US20080250715A 1 [201 Surendra Saxena, Hydrogen Production and Carbon Sequestration in Coal and Natural Gas-Burning Power Plants, US. Patent No. US20100028241A 1 30 [211 Surendra Saxena, Hydrogen production with carbon sequestration in coal and / natural gas-burning power plants, WO Patent No. W02009029292A 1 [221 Joe David Jones, Séquestration du dioxyde de carbone par formation de carbonates du groupe 2 et de silicium dioxyde, WO Patent No. W02011 075680A 1 [231 Joe Jones, Removing carbon dioxide from waste streams through co-generation of 35 carbonate and / or bicarbonate minerals, U S. Patent No. US20060185985A 1 40 [24J Kurt Z. House Christopher H. House Michael J. Aziz Daniel Paul Schrag, Carbon Oioxide Capture and Related Processes, U S. Patent No. US201 00051859A 1DESCRIPTION OF THE FIGURES Figure 1. Schematic representation of the invention with representation of the different streams of solids and gases and interaction between the CO2 capture and NaHC03 generation subsystems. 5 Figure 2. Schematic representation of the CO2 capture and storage subsystem through the dry carbonation process. The figure illustrates a possible configuration for the CO2 capture subsystem. The different reaction process units, heat exchange, separation and compression are shown. 10 Components 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. F1 flows. F2 F3 F4 F5 F6 F7 F8 F9 F10 F11 Meaning Electric power production plant Water-smoke heat exchanger CO2 capture reactor Solid-gas separator Heat exchanger NaHC03-Na2C03 Sorbent regenerator Solid-gas separator CO2 cooler (20 ° C) CO2 compressor (1-10 bar ) CO2 Cooler (20 ° C) CO2 Compressor (10-25 bar) CO2 Cooler (20 ° C) CO2 Compressor (25-75 bar) CO2 Cooler (20 ° C) Meaning Fumes at the exit of the power plant Water for the CO2 capture reactor Make-up of the sorbent needed each cycle Product at the exit of the carbonator Smoke at the exit of the carbonator Solids at the exit of the carbonator (60 ° C) Solids at the entrance to the regenerator (140 ° C ) CO2 recovered from the regenerated Na2C03 system (80 ° C) Regenerated Na2C03 (200 ° C) CO2 sent to the storage system (20 oC, 75 bar) Figure 3. Schematic representation of the sodium bicarbonate production subsystem. The figure illustrates a possible configuration for the production of NaHC03. Used natural mineral Trona and CO2 from the capture subsystem (C02 EN). The excess Na2C03 is sent to the capture subsystem for sorbent makup. The5 different reaction process units, heat exchange and product separation is shown. Components 15. 16. 17. 18. 19. 20. F12 flows. F13 F14. F15 F16 F17 F18 F19 F20 F3 F21 F11 F22 F23 F24 Meaning Heat exchanger Highchair -Na2C03 Fluid bed reactor Solid-gas separator Heat exchanger Water -Water + C02 CO2 capture reactor and production NaHC03 Solid-liquid separator Meaning Crushed highchair Hot highchair at the entrance to the fluid bed reactor ( 125 ° C) Product at the outlet of the CO2 fluid bed reactor and water vapor (220 ° C) CO2 and water (95 oC) Water (35 oC) Superheated water vapor (205 ° C) Hot Na2C03 (220 ° C) Chilled Na2C03 (40 OC) Make up of the sorbent needed each cycle Product at the entrance to the production reactor of NaHC03 CO2 capture system Product at the exit of the production reactor of NaHC03 Process water NaHC03 product of the system DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an integrated system for the production of sodium bicarbonate (Na2HC03) from CO2 captured by a dry carbonation process starting from highchair (Na2C03. NaHC03. 2H20) com or raw material and converting it into sodium carbonate (Na2C03). Part of the Na2C03 is recycled as a sorbent in the CO2 capture process and the rest is used together with part of the C02 captured for the production of sodium bicarbonate as a chemical of commercial value. 15 The optimized integration of the assembly allows the coupling of a medium temperature heat supply system, which can be based on solar thermal energy at medium temperature or biomass, capable of satisfying the heat needs of the integrated assembly, thereby minimizing the energy consumption of the systemCO2 capture and bicarbonate production. This optimized integration reduces the energy and especially economic penalty of CO2 capture. Depending on the configuration adopted, the thermal energy to be provided for the capture of CO2 is of the order of 915 kWhth per ton of captured CO2, while the consumption of 5 thermal energy for the conversion of CO2 to sodium bicarbonate would have a thermal energy consumption of the order of 250 kWhth per ton of NaHC03 produced. To these consumptions is added the energy consumption associated with the compression of CO2 for storage, which in the case of an increase in pressure from atmospheric pressure to 75 bar is of the order of 112 kWhel per ton of CO2. 10 The proposed system consists of two subsystems, one associated with the dry carbonation process for CO2 capture, based on the use of sodium carbonate as a CO2 sorbent and another related to the production of sodium bicarbonate from highchair . The conceptual scheme of the integrated system is shown in Figure 1 where it illustrates the logical structure of current integration between both processes of capture and generation of sodium bicarbonate with part of the captured CO2. The process also allows its regeneration and control of the amount of CO2 captured and recirculated Na2C03 to optimize the mode of operation, energy consumption and the economic return of the system as a whole. The main units of the first subsystem (CO2 capture) are shown in Figure 2 and consist of a CO2 capture reactor (carbonator), a desorption reactor (regenerator), two separation units, heat exchangers for recovery of heat, water condensing unit at the end of the process and compressors for pure CO2. 25 The elements that make up the second subsystem, conversion of CO2 to sodium bicarbonate use (Figure 3) similar units: a fluid bed reactor for the conversion of highchair into sodium carbonate, a carbonation tower for the production of sodium bicarbonate, two separation units and heat exchangers for heat recovery and energy optimization of processes. 30 In the CO2 capture subsystem (Figure 2), combustion gases, from fossil fuel power plants or an industrial application, are sent to the carbonation tower. In the carbonator, CO2, H20 and Na2C03 react exothermically to form NaHC03. This reactor operates at low temperature (T = 60 o C) and atmospheric pressure (p = 1 atm), so that the heat released can be used for thermal storage at low temperature. The system integrates a separator that allows dividing the bicarbonate solution stream from the streamof residual combustion gas. With this configuration 90% of CO2 input can be captured. The outgoing bicarbonate stream is sent to a regenerator. In it, the inverse reaction (endothermic) takes place, leading to the formation of Na2C03, H20 and CO2 from NaHC03. This heat can be supplied by a moderate temperature source of both fossil and renewable origin. In order not to introduce new CO2 emissions with fossil fuel, heat from either biomass or solar energy can be supplied by a system based on parabolic cylinders especially suitable for medium temperature operation (200 OC). In the regenerator the output currents are separated: the Na2C03 is sent back to the carbonation tower, while the CO2 not used in the bicarbonate generation is sent to a stage of water condensation and subsequent compression for storage. To reduce the driving power of these compressors, intermediate cooling is necessary. The system will need a certain amount of sorbent to replace the deactivated Na2C03 with irreversible reactions associated with the reaction with S02 and HCI that are normally present in the flue gases. The second subsystem (Fig. 2) uses a fraction of the CO2 captured in the first subsystem and highchair to produce NaHC03. The ground highchair ore is introduced into the fluid bed reactor along with superheated steam at 200 ° C. The fluid bed reactor operates in the range of 200-220 ° C and atmospheric pressure. Under these operating conditions the high chair becomes Na2C03. An additional flow of CO2 and water vapor is generated during the conversion of the highchair that is separated from the flow of Na2C03. Part of the Na2C03 flow is sent to the capture subsystem by dry carbonate as a fresh replacement sorbent, while the rest is sent to a carbonation tower along with the CO2 and H20 stream, and additional pure CO2 from the capture subsystem ( Fig. 1) in order to produce NaHC03, a product with added value for the chemical industry and suitable for sale. In the proposed invention, CO2 from either fossil fuel power plants (coal, natural gas or fuel oil), or from industrial processes (refineries, cement plants, metallurgical industry, etc.) is captured by the process of Dry carbonate using a mineral that is abundant in nature and of relatively low cost (highchair ore) as raw material. The optimized integration of CO2 capture and sodium bicarbonate production gives rise to a synergistic configuration in terms of energy consumption and associated costs of CO2 capture processes and conversion to high chemical productadded value (sodium bicarbonate). The integration of both presents an energy penalty of the power plant (or CO2 emitting industry to which it is applied) moderate compared to what it has with other CO2 capture systems. This energy penalty is associated with the extra energy consumed in the processes. The heat supplied both in the sorbent regenerator in the CO2 capture subsystem and in the fluid bed reactor in the sodium bicarbonate production subsystem can have as much fossil fuel origin, with the corresponding penalty in terms of emissions of Additional CO2 and operating cost or renewable sources that allow virtually zero emissions of 10 CO2. This can be achieved either by using biomass or by solar energy at medium temperature. In both cases and thanks to the optimization of the subsystem integration carried out in this invention in terms of operating conditions and fraction of CO2 captured in the exhaust gases used for the production of a chemical with added value (NaHC03). In addition, the process itself generates the replacement sorbent for the capture process in the plant. Therefore there is a synergy of the integrated set against the behavior of isolated systems. This translates into a clear energy, environmental and economic benefit of the integration of non-expected systems of the analysis of the isolated behavior of them and with a clear advantage over other capture systems (or capture 20 and use of CO2). The CO2 capture and storage subsystem shown in Fig. 2 uses a solid-solid heat exchanger (HEATEXCH) between the two reactors to reduce the total amount of heat required in the regenerator. This heat exchanger allows an increase in the temperatures in the regenerator, which improves the reaction speed, with a small additional cost of thermal energy. The diagram of a possible configuration for the production of sodium bicarbonate is shown in Figure 3. Before entering the fluid bed reactor, the high chair, in ambient conditions, passes through a solid-solid heat exchanger (HEATEXT) where it exchanges heat with the Na2C03 current flowing out of the fluid bed reactor 30. Another heat exchanger (HEATEXW) is used to heat the water entering the fluid bed from the outgoing gases thereof, which allows superheated water vapor to be supplied to the reactor. The synergy obtained by integrating both systems is reflected in the flow chart of Figure 1. 35 • For the production of NaHC03 from highchair, the necessary CO2 is supplied by the CO2 capture subsystem (x * C02 in the diagram). Therefore use is given topart of the captured CO2 and the rest is stored, giving rise to a new application of CCUS (carbon dioxide capture, use and storage) not identified to date 5 • For the capture of CO2 in the dry carbonate process, a contribution of fresh Na2C03, which with the proposed integration is supplied by the Trona production subsystem (MAKEUP in Figure 1). This substantially lowers the capture system, this being novel. 10 The advantages of this technology are: 15 20 25 30 35 CO2 capture technology in fossil fuel thermal plants and industrial plants with reduced energy and economic penalties for the whole. CO2 capture technology and conversion to chemical with added value, sodium bicarbonate, both for fossil fuel thermal plants and for other CO2-emitting industrial plants with an important economic return because the energy penalty effect is supplied by the sale from NaHC03. It also generates the amount of fresh sorbent that needs to be replaced due to its deactivation. A fraction of the captured CO2 is integrated into the production of bicarbonate, which reduces / eliminates storage requirements. This increases the sustainability of the CO2 capture process. In the case of integration of renewable energy sources (medium temperature biomass or solar), a global system of almost zero CO2 emissions is obtained for both fossil fuel power plants and other industrial plants. It includes industrial sectors such as coal, steelworks, cement. It allows to optimize the integration configuration and the fraction of recirculated Na2C03 and CO2 stored in the form of bicarbonate depending on the production requirements from the environmental point of view depending on the characteristics of the integration. It can be incorporated into existing thermal and industrial plants without relevant penalty in their performance.EMBODIMENT OF THE INVENTION As an example of the invention, the process of production of sodium bicarbonate using the CO2 captured by a dry carbonation process in a coal power plant (150 MWel) is shown. The combustion gases of the plant have a CO2 concentration (-15% vol). The main data of the coal power plant are shown in Table 1. 10 Item Magnitude Units Coal consumption 61 ton / hr Air flow 692 ton / hr Gross power contributed 447 MWth Net power contributed 397 MWth Net power produced 150 MW Net yield 33.5% Table 1: Data of the invention example. Reference thermal power plant. 150 MWel coal plant Table 2 shows the molar fluxes of the flue gases taken to illustrate the invention. 20 Compound of the current Molar flow (kmol / hr) Mass expenditure (tons / hr) output N2 17154.21 529.71 CO2 3085.62 135.96 H20 1471.86 29.4 O2 781.8 27.57 CO 140.7 3.93 NO 135.36 4.47 S02 37.53 2.64 Table 2: Composition of the exhaust gases in the coal-fired thermal power plant5 10 Other parameters used in the analysis are shown in Table 3 while Table 4 shows the energy consumption associated with the different components. Regenerator temperature 200 oC Fluid bed reactor temperature 220 oC Carbonation temperature e 60 oC Na2C03 activity 0.75 Minimum temperature difference at 15 oC heat exchangers Transport consumption of solids 5.5 kwheltn Solar reference hours 12 Isentropic performance of comyresors 0.9 CO2 storage pressure 75 bar ------ Table 3: Reference parameters for the invention example Power Generated power consumption CFFP 150 MWel 447 MWth Heat Regenerator 114 MWth CO2 compression power 13.3 MWel Power Solids transport 2.47 MWel Net power 134.23 MWel Fluid bed reactors 51 MW Total heat required 612 MWth Table 4: Energy consumption in the reference plant of the example of the invention with the C02 capture system and NaHC03 production. The capture subsystem has a yield of 90%. For this use 430 ton! hr of Na2C03 as a sorbent to remove 125 tons! hr of CO2 in a continuous cycle. The replacement sorbent flow is close to 3 ton! hr. As shown in Table 4, the heat required for regeneration of the sorbent after CO2 capture is 114 MWth. The energy consumption for the compression of CO2 and transport of solids amounts to 16 MWel. The total performance of the integrated plant (coal combustion plant + capture) considering the required heat input the power consumed is reduced from 33.5% to 24%. Considering only the effect of the power 20 required for compression and transport, for this example the reduction inavailable electrical energy is 10% which has an effect on the overall performance of 3%. Taking into account that the temperatures in the reactors allow the integration of solar energy input, the whole system could operate with a penalty on the economic performance (available energy / purchased energy) of less than 3%, achieving almost zero emissions. In the NaHC03 production subsystem (Fig 3), the heat required in the fluid bed reactor to decompose 192 ton / hr (53.3 kg / sec) of highchair is 51 MWth at T = 220 o C to produce 135, 5 ton / hr of Na2C03 (in addition to 18.5 ton / hr of CO2 and 40 ton / h of water). 3 tn / h of Na2C03 is used as a replacement sorbent for the CO2 capture process. The rest (132.5 ton / hr) is sent to the carbonation tower where it reacts with 37.5 ton / hr of CO2 from the CO2 capture system (in addition to CO2 effluent from the fluid bed) to produce NaHC03. From the reaction Na2 C03 + H20 + CO2 -> 2NaHC03 it turns out that 207.5 ton / hr of NaHC03 are produced with a total flow rate of approximately 95 m3 / hr. In this way, a chemical of high economic value (NaHC03) is obtained from a raw material such as high chair, abundant and relatively low cost and part of the captured CO2 (from thermal power plants or industrial processes). This integrated capture and conversion process to NaHC03 reduces (and eliminates, depending on the mode of operation chosen) the need for total CO2 storage, with the requirements of the energy compression and penalization system involved. The overall performance of the system, and the available electrical energy required, is reduced by the integration of sodium bicarbonate production, which in turn captures CO2 that does not need to be compressed. The economic income associated with the new product 25 compensates for the penalty associated with this process. The total heat requirements are increased taking into account the 51 MW thermal required in the fluid bed reactor. 30 35 
    权利要求:
    Claims (1)
    [1]
    5 CLAIMS 1. Integrated system for capturing CO2 and producing sodium bicarbonate (Na2HC03) characterized in that it comprises: a. CO2 capture through a dry carbonation process b. Conversion of trona (Na2C03. NaHC03. 2H20) to sodium carbonate (Na2C03) c. Generation of sodium bicarbonate from generated Na2C03 and captured CO2. 2. Integrated system for capturing CO2 and generating NaHC03 according to claim 1, characterized in that it is integrated into the output stream of fossil fuel thermal plants and CO2-emitting industrial facilities. 3. Integrated system for capturing CO2 and generating NaHC03 according to claim 1, characterized in that the CO2 capture subsystem is through the dry carbonation process. 4. Integrated system according to claims 1 to 3 characterized by the supply of heat at medium temperature (140-230 o C) for the regeneration of the sorbent and dissociation of the trona in the process of capturing CO2 is from renewable energies. , biomass or medium temperature solar thermal technology. 25 30 5. Integrated system for capturing CO2 and generating NaHC03 according to claims 1 to 4, characterized in that it allows generating systems with almost-zero CO2 emissions, with a capture efficiency> 90%, in technologies based on fossil fuel by means of the support of renewable energies that for coal plants is of the order of 10% of the total heat contributed in the set. 6. Integrated system for capturing CO2 and generating NaHC03 according to claims 1 to 5, characterized in that for the production of NaHC03 from Trona, the necessary CO2 is supplied by the CO2 capture subsystem. 7. Integrated system for capturing CO2 and generating NaHC03 according to claim 6, characterized in that the CO2 necessary for the production of sodium bicarbonate comes from the captured CO2 and in turn the conversion to sodium bicarbonate permanently fixes the captured CO2 35 8. Integrated system capture of CO2 and generation of NaHC03 according to claims 1 to 7 characterized in that it internally generates the sorbentfresh (NaZC03) that must be replaced to keep the CO2 capture process active and allows the generation of the replacement Na2C03 necessary for the dry carbonation process from the calcination of the trona for bicarbonate production. S 9. Integrated system for capturing CO2 and generating NaHC03 according to 10 claims 1 to 8 characterized in that it allows reducing the energy requirements of the whole: composition and temperature of currents in the sodium carbonate regenerator in the CO2 capture process and the calciner of the trona (150-2200C), and currents in both carbonation towers (60 ° C).
    类似技术:
    公开号 | 公开日 | 专利标题
    US8702847B2|2014-04-22|Systems and methods for extraction of carbon dioxide from air
    US7699909B2|2010-04-20|Systems and methods for extraction of carbon dioxide from air
    ES2671444T3|2018-06-06|Calcination / carbonation cycle processing system and procedure
    ES2599411T3|2017-02-01|Method and system to convert carbon dioxide into chemical starting materials
    Bonaventura et al.2017|Carbon capture and utilization for sodium bicarbonate production assisted by solar thermal power
    ES2592703T3|2016-12-01|Steam generation system that has multiple combustion chambers and dry combustion gas purification
    ES2719780T3|2019-07-16|Regenerable sorbent for carbon dioxide removal
    ES2838727T3|2021-07-02|System for capturing CO2 from a combustion gas through the carbonation-calcination cycles CaO / CaCO3
    WO2003080223A1|2003-10-02|Combustion method with integrated co2 separation by means of carbonation
    US20100196244A1|2010-08-05|Method and device for binding gaseous co2 to sea water for the flue gas treatment with sodium carbonate compounds
    CN107108247B|2020-06-19|Process for the production of sodium carbonate/bicarbonate
    ES2650840B2|2018-05-14|Integrated CO2 capture system and production of sodium bicarbonate | from Trona |
    CN106268183A|2017-01-04|Carbon dioxide and global thermostat is removed from air
    US9464010B2|2016-10-11|Systems, methods and devices for the capture and hydrogenation of carbon dioxide with thermochemical Cu—Cl and Mg—Cl—Na/K—CO2 cycles
    CN102773006A|2012-11-14|Device and process for cyclic capture of carbon dioxide by taking CaO as carrier
    CN104284707A|2015-01-14|Carbon dioxide sequestration involving two-salt-based thermolytic processes
    CN106975341A|2017-07-25|A kind of devices and methods therefor of the calcium-base absorbing agent circularly removing carbon dioxide of carrying vapour activated reactor
    CN102786236B|2014-05-07|Device and method for capturing carbon dioxide in lime production process
    WO2015097674A1|2015-07-02|Method for carbonating industrial and urban waste and regenerating reagents
    CN104321125A|2015-01-28|Separation device for carbon dioxide, method for the operation thereof, and separating unit
    DK2359925T3|2015-06-29|METHOD AND DEVICE FOR BIOMASS BURNING AND SIMULTANEOUS CAPTURE OF CARBON DIOXIDE In a combustor-carbonator
    CA2891185A1|2014-05-15|Systems, methods and devices for the capture and hydrogenation of carbon dioxide with thermochemical cu-cl and mg-cl-na/k-co2 cycles
    ES2595443B1|2017-11-07|Integrated calcination-carbonation system and closed loop CO2 cycle for thermochemical energy storage and electric power generation
    CZ31029U1|2017-09-19|A device for capturing CO2 from a gas generator using the method of high-temperature sorption
    ES2799178T3|2020-12-15|Sodium carbonate manufacturing process integrated with carbon dioxide capture through ammonia process
    同族专利:
    公开号 | 公开日
    EP3485963A4|2019-07-03|
    ES2650840B2|2018-05-14|
    WO2018015581A1|2018-01-25|
    EP3485963A1|2019-05-22|
    US20200002183A1|2020-01-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2007003013A1|2005-07-05|2007-01-11|Greensols Australia Pty Ltd|Preparation and use of cationic halides, sequestration of carbon dioxide|
    WO2009029292A1|2007-08-27|2009-03-05|Surendra Saxena|Hydrogen production with carbon sequestration in coal and/natural gas-burning power plants|
    US20120275987A1|2011-04-26|2012-11-01|Hiza Michael D|Systems and methods for carbon sequestration of synthesis gas|
    US9051188B2|2011-06-01|2015-06-09|Solvay Chemicals, Inc.|Sodium bicarbonate product with excellent flowability and its method of manufacture|
    KR20150036864A|2013-09-30|2015-04-08|한국전력공사|Solid sorbent composition to remove CO2 from fossile fuel combustion and Solid sorbent containing the same|CN108993128A|2018-07-17|2018-12-14|江苏智锐环保科技有限公司|For the treatment process and its conveying device of acid waste gas|
    GB2576762B|2018-08-31|2021-05-05|Tata Chemicals Europe Ltd|Sodium bicarbonate production|
    法律状态:
    2018-05-14| FG2A| Definitive protection|Ref document number: 2650840 Country of ref document: ES Kind code of ref document: B2 Effective date: 20180514 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201600616A|ES2650840B2|2016-07-19|2016-07-19|Integrated CO2 capture system and production of sodium bicarbonatefrom Trona |ES201600616A| ES2650840B2|2016-07-19|2016-07-19|Integrated CO2 capture system and production of sodium bicarbonatefrom Trona |
    US16/319,105| US20200002183A1|2016-07-19|2017-07-13|Integrated system for capturing co2 and producing sodium bicarbonatefrom trona |
    EP17830525.6A| EP3485963A4|2016-07-19|2017-07-13|INTEGRATED CO2 CAPTURE SYSTEM AND PRODUCTION OF SODIUMFROM TRONA |
    PCT/ES2017/000091| WO2018015581A1|2016-07-19|2017-07-13|Integrated system for capturing co2 and producing sodium bicarbonatefrom trona |
    [返回顶部]