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US20050060985A1 - Combustion method with integrated CO2 separation by means of carbonation - Google Patents

Combustion method with integrated CO2 separation by means of carbonation Download PDF

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Publication number
US20050060985A1
US20050060985A1 US10/946,319 US94631904A US2005060985A1 US 20050060985 A1 US20050060985 A1 US 20050060985A1 US 94631904 A US94631904 A US 94631904A US 2005060985 A1 US2005060985 A1 US 2005060985A1
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US
United States
Prior art keywords
separation
calciner
carbonation
sorbent
integrated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/946,319
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English (en)
Inventor
Juan Carlos Abanades Garcia
John Oakey
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CONSEIO SUPERIOR DE INVESTIGACIONES CIENTIFICAS
Cranfield University
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Individual
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Assigned to CRANFIELD UNIVERSITY, CONSEIO SUPERIOR DE INVESTIGACIONES CIENTIFICAS reassignment CRANFIELD UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OAKEY, JUAN, ABANDES GARCIA, JUAN CARLOS
Publication of US20050060985A1 publication Critical patent/US20050060985A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/343—Heat recovery
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the UN's International Panel for Climate Change (IPCC, 2001) considers the capturing of CO 2 generated from large stationary sources and its subsequent containment in a variety of geological formations as a very interesting middle and long-term option. Use of these technologies require previous obtainment of a highly concentrated stream of CO 2 (Herzog et al., 1997).
  • the CO 2 content of the combustion gases in different types of thermal power stations varies between 3 and 17% by volume, which makes a previous separation stage necessary.
  • the method proposed in this invention differs from said proposals and attempts to make use of the equilibrium: CaO+CO 2 ⁇ CaCO 3 (1) for separating CO 2 from combustion gases.
  • This equilibrium has already been used previously in methods of separating CO 2 in the reforming of hydrocarbons and/or production of H 2 .
  • (Gorin et al. 1963, 1980) have patented and carried out on a demonstrative scale methods based on CO 2 “acceptors” that use the previous equilibrium.
  • López Ortiz and Harrison (2001) have also studied the use of the equilibrium (1) for the production of hydrogen in a single reactor starting from methane and steam and have a good number of patents and references in this field of CO 2 separation in reducing environments, that date back to 1868.
  • Shimizu et al. (1999) propose for the first time use of the equilibrium (1) for separating CO 2 from combustion gases. They suggest contacting CaO with the combustion gases of a thermal power station at temperatures around 600° C. to carry out the capture of CO 2 by means of the carbonation reaction. The partially carbonated solids are regenerated in a fluidized bed reactor where they are calcined at temperatures higher than 950° C., burning part of the fuel in the presence of O 2 /CO 2 . The O 2 necessary for calcination comes from an air separating plant. The authors claim with this method a large saving in the air separating plant with respect to the use of O 2 /CO 2 mixtures for all the fuel (technology described, among others in Herzog et al., 1997).
  • the object of the invention comprises a combustion chamber (1) wherein any type of fuel is burnt with air, preferably at temperatures higher than 1,000° C. generating heat and a stream of combustion gases at a high temperature with a CO 2 content between 3 and 17% by volume depending on the fuel and the excess air used in the combustion.
  • the combustion chamber may be of any type, a fluidized bed, a conventional powdered carbon combustion boiler, or natural gas burner or burner of other liquid fuels. Combustion can be done at atmospheric pressure or at a high pressure.
  • the invention is based on the fact that part of the heat (Q) generated in (1) must be transferred to the calciner (2) in order to maintain the endothermic reaction of calcination and to regenerate the CO 2 sorbent (CaO).
  • the calciner (2) operates at temperatures lower than 900° C. in atmospheres of pure CO 2 or of CO 2 /H 2 O.
  • the partial pressure of CO 2 in the calciner can be reduced by applying a certain vacuum to (2) and/or injecting steam into (2).
  • the heat exchange between (1) and (2) may be direct through metal walls or indirect by means of using an inert solid (sand, alumina or others) that continuously circulate through (1) and (2) and that is easily separable from the active solids in CO 2 capture.
  • Heat is removed from gases G 1 in order to condition them to a temperature (between 200 and 650° C.) suitable for treatment thereof in the carbonator (3). Electricity can be generated with this heat removed from G 1 , and if the combustion in (1) is carried out under pressure, the combustion gases G 1 can expand into a gas turbine in order to generate additional electricity.
  • the cooled combustion gases enter the carbonation unit (3) at atmospheric pressure.
  • the carbonator may be of any type, such as a circulating, drawing, cyclonic fluidized bed depending on the size of the CaO particle and the reaction rate.
  • the carbonation reaction is produced in the carbonator at 600-750° C. and at atmospheric pressure, which are suitable conditions for a sufficiently rapid reaction between the CaO and the CO 2 . This reaction is exothermic for which reason heat should be removed from (3) or the input temperature of G 1 and/or of s 2 must be adjusted below 550° C. in order to maintain the reactor (3) at the desired temperature.
  • the combustion gases G 3 that leave the unit (3) at temperatures between 600-750° C. contain a reduced amount of CO 2 (ideally close to the one of equilibrium at the operating temperature in (3)).
  • the remaining CO 2 that was present in G 1 is found in the form of CaCO 3 and leaves the calciner (3) in the solid stream s 3 , that contains the mixture of CaO and CaCO 3 .
  • the solid stream s 3 is directed towards the calciner (2) in order to be regenerated as CaO and CO 2 .
  • the calciner should be operated to generate a pure stream of CO 2 at a pressure lower than atmospheric pressure, or a mixture of CO 2 /steam easily separable by condensation of the steam (not included in FIG. 1 for the purpose of simplicity.)
  • a stream of regenerated solids (s 2 ) that mainly contain CaO, capable of recarbonating again in (3) leaves the calciner.
  • s 2 regenerated solids
  • the calciner can be a fluidized bed to take advantage of high heat transmission coefficients. It may also be a drawn or pneumatic transported bed comprised of a bed of pipes through which the stream s 3 is made to pass.
  • the combustion atmosphere (1) would be outside the pipes with nominal flame temperatures that may be higher than 1,300° C.
  • the object of the invention is shown schematically in FIG. 1 .
  • It comprises a combustion chamber (1) wherein the fuel is burnt with air at temperatures higher than 1,000° C. generating heat and a stream of high temperature gases with a CO 2 content between 3 and 17% by volume depending on the fuel and the excess air used in combustion.
  • the combustion chamber may be a fluidized bed, a conventional powdered carbon combustion boiler, or a natural gas burner or a burner of other liquid fuels. Combustion can be done at atmospheric pressure or at a high pressure.
  • Part of the heat (Q) generated in (1) should be transferred to the calciner (2) in order to maintain the endothermic reaction of calcination and to regenerate the CO 2 sorbent (CaO).
  • the calciner (2) operates at temperatures lower than 900° C.
  • the partial pressure of CO 2 in the calciner can be reduced by applying a certain vacuum to (2) and/or injecting steam into (2).
  • the heat exchange between (1) and (2) may be direct through metal walls or indirect by means of using an inert solid (sand, alumina or others) that continuously circulates between (1) and (2) and that is easily separable from the active solids in CO 2 capture. For the purpose of simplicity, this circulating stream of inert solids capable of transporting heat Q between (1) and (2) has not been drawn in FIG. 1 .
  • coal combustion chamber in a fluidized bed operating at 1,100° C. It could be another type of combustion chamber (gas or powder burners) with nominal flame temperatures higher than 1,300° C. It is supposed that there are no losses of heat and that the combustion of the fuel is complete.
  • calciner operating as a fluidized bed at 850° C. It operates at a partial pressure of CO 2 of 0.3 atm by applying a vacuum and/or injecting a certain amount of steam. In these conditions, calcination of the solids with CaCO 3 (s 3 ) is rapid and complete.
  • the solids that leave the calciner (s 3 ) only contain CaO in the example (although they may contain other inert materials if dolomites or other calcareous sorbents are used as CO 2 acceptors).
  • the coal of the example has a heating capacity of 25 MJ/kg and a coal content of 65% by weight. For each 100 MW of power of the power station, 2.6 kg/s of ° C. in the form of CO 2 that are present in the stream of combustion gases G 1 (15.4% vol. CO 2 ) are generated (20% excess air). In the example, an effectiveness in capturing the CO 2 in the combustion gases of 80% is sought, for which purpose, a total of 32.4 kg/s of CaO (stream s 2 and s 3 ) circulating between the calciner (2) and the carbonator is required. Only 30% thereof are carbonated in (3). The calculations have been done assuming a heating capacity of 900 J/kg for all the solid streams and of 1250 J/kg for all the gaseous streams. The reference temperature in the heat balances is 20° C. It is assumed that there are no heat losses in any of the units.
  • the example has been designed so that the carbonator operates at autothermic conditions when the stream of combustion gases (G 1 at 270° C.) is put in contact with the solids s 2 (from which 16.8 MS of useful heat have been removed to cool them, arbitrarily, at the same temperature of 270° C). Therefore, the 29.2 MW that are generated during the carbonation reaction manage to keep the carbonator temperature at 650° C. In the conditions of the example, 50.1 MW leave the carbonator as sensible heat of gases and solids at 650° C. (27.4 MW as heat in the gases, from which useful heat can be removed in order to generate electricity in the steam cycle and 22.7 MW in the stream of solids s 3 ).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Gas Separation By Absorption (AREA)
  • Separation Of Gases By Adsorption (AREA)
US10/946,319 2002-03-22 2004-09-21 Combustion method with integrated CO2 separation by means of carbonation Abandoned US20050060985A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ESP-200200684 2002-03-22
ES200200684A ES2192994B1 (es) 2002-03-22 2002-03-22 Procedimiento de combustion con separacion integrada de co2 mediante carbonatacion.
PCT/ES2003/000118 WO2003080223A1 (fr) 2002-03-22 2003-03-14 Procede de combustion integrant une separation de co2 realisee par carbonatation

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/ES2003/000118 Continuation WO2003080223A1 (fr) 2002-03-22 2003-03-14 Procede de combustion integrant une separation de co2 realisee par carbonatation

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US20050060985A1 true US20050060985A1 (en) 2005-03-24

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US10/946,319 Abandoned US20050060985A1 (en) 2002-03-22 2004-09-21 Combustion method with integrated CO2 separation by means of carbonation

Country Status (8)

Country Link
US (1) US20050060985A1 (fr)
EP (1) EP1495794A1 (fr)
JP (1) JP2005520678A (fr)
CN (1) CN1642620B (fr)
AU (1) AU2003216925B2 (fr)
CA (1) CA2479886C (fr)
ES (1) ES2192994B1 (fr)
WO (1) WO2003080223A1 (fr)

Cited By (17)

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US20070032380A1 (en) * 2003-11-14 2007-02-08 Anthony Edward J Reactivation of lime-based sorbents by co2
WO2007045048A1 (fr) * 2005-10-21 2007-04-26 Calix Pty Ltd Systeme et methode pour un traitement de recyclage de calcination/carbonisation
WO2008097666A1 (fr) * 2007-02-10 2008-08-14 Vast Power Portfolio, Llc Récupération d'huile lourde par fluide chaud à l'aide de vapeur et de dioxyde de carbone
US20090169462A1 (en) * 2006-03-31 2009-07-02 Consejo Superior De Investigaciones Cientificas Precalcination method with production of pure or easily purified co2 originating from the decomposition of carbonates
WO2009137886A1 (fr) * 2008-05-15 2009-11-19 Calix Limited Système et procédé de traitement de gaz de carneau
US20100000446A1 (en) * 2006-11-09 2010-01-07 L'Air Liquide Soceiete Anonyme Pour L'Etude Et L'Exploitation Des Procedes Georges Claude Process for Manufacturing Clinker with Controlled CO2 Emission
US20100086456A1 (en) * 2008-10-08 2010-04-08 Bernd Epple Method and arrangement for separation of CO2 from combustion flue gas
AU2006303828B2 (en) * 2005-10-21 2010-11-18 Calix Limited System and method for calcination/carbonation cycle processing
WO2011047409A1 (fr) * 2009-10-24 2011-04-28 Calix Limited Système et procédé de traitement d'un gaz combustible d'entrée et de vapeur pour la production de dioxyde de carbone et d'un gaz combustible de sortie
US8383072B2 (en) 2008-06-05 2013-02-26 Industrial Research Limited Gas separation process
US8757072B2 (en) 2008-11-21 2014-06-24 Gas Natural Sdg, S.A. Method and device for biomass combustion without carbon dioxide emission
US8807993B2 (en) 2006-03-31 2014-08-19 Calix Ltd. System and method for the calcination of minerals
US20150157978A1 (en) * 2013-12-11 2015-06-11 Industrial Technology Research Institute Loop tower co2 capture system, carbonator, calciner and operating method thereof
US9586827B2 (en) 2013-09-06 2017-03-07 David LeRoy Hagen CO2 producing calciner
CN108619896A (zh) * 2018-05-16 2018-10-09 安徽建筑大学 一种基于切换式填充床反应器的co2循环脱除装置及方法
US11047601B2 (en) * 2016-12-09 2021-06-29 Nanjing Tech University Method and system of high-temperature calcium looping thermochemical energy storage
WO2025099734A1 (fr) * 2023-11-09 2025-05-15 Pi Green Innovations Pvt. Ltd Procédé de capture de composants multi-gaz et système associé

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US7618606B2 (en) 2003-02-06 2009-11-17 The Ohio State University Separation of carbon dioxide (CO2) from gas mixtures
US20070092427A1 (en) * 2003-11-14 2007-04-26 Anthony Edward J Pre-treatment of lime-based sorbents using hydration
EP1899049A4 (fr) * 2005-06-28 2010-12-08 Univ Ohio State Separation de dioxyde de carbone (co2) de melange de gaz par processus de separation par reaction a base de calcium ( cars-co2)
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FR2944217B1 (fr) * 2009-04-08 2011-04-01 Inst Francais Du Petrole Procede de captage du dioxyde de carbone avec integration thermique de la regeneration avec la chaine de compression
DE102009039055A1 (de) * 2009-08-28 2011-03-10 Technische Universität Darmstadt Verfahren und Einrichtung zur Abscheidung von CO2 aus Abgas
US20120164032A1 (en) * 2009-09-18 2012-06-28 Wormser Energy Solutions, Inc. Systems, devices and methods for calcium looping
US8647413B2 (en) * 2009-10-30 2014-02-11 General Electric Company Spray process for the recovery of CO2 from a gas stream and a related apparatus
ES2370619B1 (es) * 2010-04-27 2012-10-26 Fundación Investigación E Innovación Para El Desarrollo Social Procedimiento para la obtención de hidrogeno, a partir de la biomasa y carbón vegetal.
ES2401294B1 (es) * 2011-06-24 2014-05-09 Consejo Superior De Investigaciones Científicas (Csic) DISPOSITIVO Y PROCEDIMIENTO PARA LA CAPTURA DE CO2 POR CARBONATACION DE CaO
EP2756068B1 (fr) 2011-09-15 2015-11-25 Energy Knowledge Group BV Procédé de préparation de biocarburant au moyen d'algues
KR101863967B1 (ko) * 2011-09-30 2018-06-04 한국전력공사 저에너지 소비형 이산화탄소의 회수방법
NO343140B1 (no) * 2013-06-14 2018-11-19 Zeg Power As Fremgangsmåte for bærekraftig energiproduksjon i et kraftverk som omfatter en fastoksid brenselcelle
KR101529823B1 (ko) * 2014-05-21 2015-06-29 현대중공업 주식회사 석탄가스화 복합발전 시스템
EP2959966B1 (fr) * 2014-06-24 2018-09-05 General Electric Technology GmbH Four de calcination et procédé de calcination d'un adsorbant riche en dioxyde de carbone
CN104841363A (zh) * 2015-04-22 2015-08-19 马鞍山市顺达环保设备有限公司 一种矿热炉用吸附剂及其制备方法
US9956517B2 (en) * 2016-05-23 2018-05-01 General Electric Company Gmbh System and method for reducing carbon dioxide emissions from a flue gas generated via combusting a fossil fuel
EP3592451A4 (fr) 2017-03-09 2020-12-30 Hot Lime Labs Limited Procédé et appareil perfectionnés de capture et de libération de dioxyde de carbone
NO345216B1 (en) 2019-08-28 2020-11-09 Zeg Power As Hydrogen-fuelled gas turbine power system and method for its operation
US11572518B2 (en) 2019-11-25 2023-02-07 Wormser Energy Solutions, Inc. Char preparation system and gasifier for all-steam gasification with carbon capture
CN115307149B (zh) * 2022-08-26 2025-08-08 中国科学院广州能源研究所 一种蓄热式可燃固废气化处置系统及co2富集方法

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Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070032380A1 (en) * 2003-11-14 2007-02-08 Anthony Edward J Reactivation of lime-based sorbents by co2
US7879139B2 (en) 2003-11-14 2011-02-01 Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Reactivation of lime-based sorbents by CO2 shocking
US8603222B2 (en) 2005-10-21 2013-12-10 Calix Ltd. System and method for calcination/carbonation cycle processing
WO2007045048A1 (fr) * 2005-10-21 2007-04-26 Calix Pty Ltd Systeme et methode pour un traitement de recyclage de calcination/carbonisation
US8951493B2 (en) 2005-10-21 2015-02-10 Calix Ltd. Material compound and a method of fabricating the same
AU2006303828C1 (en) * 2005-10-21 2011-04-14 Calix Limited System and method for calcination/carbonation cycle processing
AU2006303828B2 (en) * 2005-10-21 2010-11-18 Calix Limited System and method for calcination/carbonation cycle processing
US20100329963A1 (en) * 2005-10-21 2010-12-30 Calix Pty Ltd. System and Method for Calcination/Carbonation Cycle Processing
US20110011142A1 (en) * 2005-10-21 2011-01-20 Calix Pty Ltd. Material Compound and a Method of Fabricating the Same
US20090169462A1 (en) * 2006-03-31 2009-07-02 Consejo Superior De Investigaciones Cientificas Precalcination method with production of pure or easily purified co2 originating from the decomposition of carbonates
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CA2479886A1 (fr) 2003-10-02
AU2003216925A1 (en) 2003-10-08
ES2192994A1 (es) 2003-10-16
JP2005520678A (ja) 2005-07-14
CN1642620A (zh) 2005-07-20
CA2479886C (fr) 2011-05-17
CN1642620B (zh) 2011-08-10
ES2192994B1 (es) 2005-02-16
AU2003216925B2 (en) 2008-09-11
WO2003080223A1 (fr) 2003-10-02

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