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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Prior art keywords
separation
calciner
carbonation
sorbent
integrated
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Abandoned
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US10/946,319
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English (en)
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Juan Carlos Abanades Garcia
John Oakey
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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
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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 ).
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
ES200200684A ES2192994B1 (es) 2002-03-22 2002-03-22 Procedimiento de combustion con separacion integrada de co2 mediante carbonatacion.
ESP-200200684 2002-03-22
PCT/ES2003/000118 WO2003080223A1 (es) 2002-03-22 2003-03-14 Procedimiento de combustión con separación integrada de co2 mediante carbonatación

Related Parent Applications (1)

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PCT/ES2003/000118 Continuation WO2003080223A1 (es) 2002-03-22 2003-03-14 Procedimiento de combustión con separación integrada de co2 mediante carbonatación

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

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US20070032380A1 (en) * 2003-11-14 2007-02-08 Anthony Edward J Reactivation of lime-based sorbents by co2
WO2007045048A1 (en) * 2005-10-21 2007-04-26 Calix Pty Ltd System and method for calcination/carbonation cycle processing
WO2008097666A1 (en) * 2007-02-10 2008-08-14 Vast Power Portfolio, Llc Hot fluid recovery of heavy oil with steam and carbon dioxide
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 (en) * 2008-05-15 2009-11-19 Calix Limited System and method for processing flue gas
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 (en) * 2009-10-24 2011-04-28 Calix Limited System and method for processing an input fuel gas and steam to produce carbon dioxide and an output fuel gas
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

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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
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Cited By (38)

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Publication number Priority date Publication date Assignee Title
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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 (en) * 2005-10-21 2007-04-26 Calix Pty Ltd System and method for calcination/carbonation cycle processing
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
US8807993B2 (en) 2006-03-31 2014-08-19 Calix Ltd. System and method for the calcination of minerals
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
US8187374B2 (en) * 2006-11-09 2012-05-29 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for manufacturing clinker with controlled CO2 emission
WO2008097666A1 (en) * 2007-02-10 2008-08-14 Vast Power Portfolio, Llc Hot fluid recovery of heavy oil with steam and carbon dioxide
US20100276148A1 (en) * 2007-02-10 2010-11-04 Vast Power Portfolio, Llc Hot fluid recovery of heavy oil with steam and carbon dioxide
US8561702B2 (en) * 2007-02-10 2013-10-22 Vast Power Portfolio, Llc Hot fluid recovery of heavy oil with steam and carbon dioxide
US8894743B2 (en) 2008-05-15 2014-11-25 Calix Limited Method for processing flue gas
US8632626B2 (en) 2008-05-15 2014-01-21 Calix Limited System and method for processing flue gas
WO2009137886A1 (en) * 2008-05-15 2009-11-19 Calix Limited System and method for processing flue gas
AU2009246062B2 (en) * 2008-05-15 2014-07-17 Calix Limited System and method for processing flue gas
US20110113957A1 (en) * 2008-05-15 2011-05-19 Calix Limited System and method for processing flue gas
US8383072B2 (en) 2008-06-05 2013-02-26 Industrial Research Limited Gas separation process
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CN1642620B (zh) 2011-08-10
CA2479886C (en) 2011-05-17
EP1495794A1 (en) 2005-01-12
ES2192994A1 (es) 2003-10-16
AU2003216925A1 (en) 2003-10-08
WO2003080223A1 (es) 2003-10-02
JP2005520678A (ja) 2005-07-14

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