WO2009100937A2 - Matériau convenant comme absorbant de co2 et utilisable comme matériau dans des lits fluidisés et sa production - Google Patents

Matériau convenant comme absorbant de co2 et utilisable comme matériau dans des lits fluidisés et sa production Download PDF

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Publication number
WO2009100937A2
WO2009100937A2 PCT/EP2009/001043 EP2009001043W WO2009100937A2 WO 2009100937 A2 WO2009100937 A2 WO 2009100937A2 EP 2009001043 W EP2009001043 W EP 2009001043W WO 2009100937 A2 WO2009100937 A2 WO 2009100937A2
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WIPO (PCT)
Prior art keywords
particles
carbonate
material according
oxide
core
Prior art date
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PCT/EP2009/001043
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German (de)
English (en)
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WO2009100937A3 (fr
Inventor
Tonja MARQUARD-MÖLLENSTEDT
Peter Sichler
Michael Specht
Ulrich ZUBERBÜHLER
Original Assignee
Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg
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Priority to EP09711423A priority Critical patent/EP2303429A2/fr
Publication of WO2009100937A2 publication Critical patent/WO2009100937A2/fr
Publication of WO2009100937A3 publication Critical patent/WO2009100937A3/fr

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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
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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
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0996—Calcium-containing inorganic materials, e.g. lime
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to a material which is particularly suitable for CO 2 absorption and / or for use as a bed material in fluidized beds, a method for producing such a material, a method for producing a CO 2 -lower gas with such a material and other uses of the material, in particular in the field of gas purification.
  • Natural, carbonate-containing minerals such as lime or dolomite are suitable as starting material for absorbents, which can be used in industrial processes, for example for desulfurization or as catalysts, but especially for the separation of CO 2 , for example from flue gases or from synthesis gases.
  • the carbonate-containing minerals are generally subjected to a thermal treatment in which the carbonate is converted under CO 2 release into an oxide, for example CaO.
  • the oxides produced can reversibly take up and release CO 2 , for example in the case of CaO according to the following equation:
  • the oxides can bind sulfur oxide as occurring in flue gases.
  • the separation of CO 2 from gases or their desulfurization is often carried out under fluidizing conditions in fluidized bed reactors, in which ensures a particularly intensive contact between the absorbent and the gas to be treated.
  • a bed of solid particles, in this case the absorbent is caused to flow by an upward flow of a fluid, for example a CO 2 -containing gas.
  • the ability of the oxidic absorbents to absorb CO 2 or SO 2 is of course limited. In the case of CO 2 , however, the absorbents can be regenerated in a simple manner. The regeneration is generally carried out by thermal treatment of the "spent" absorbent, in which the bound CO 2 is liberated again according to the above equation The thermal treatment for regeneration can also take place in a fluidized-bed reactor.
  • the absorbent is frequently allowed to circulate continuously in one cycle, the CO 2 absorption taking place in a first fluidized-bed reactor, and the CO 2 desorption in a second fluidized bed, ie the regeneration of the absorbent.
  • Such a circuit is known for example from DE 199 46 381.
  • the absorbent particles in fluidized-bed reactors are subject to high thermal and in particular also mechanical stresses, the latter resulting in particular from constant collisions with other particles and with the inner walls of the reactors.
  • the chemical composition of the absorbent particles changes as a result of CO 2 uptake or release, which further impairs their structural integrity.
  • a gas cyclone for separating solids with a return line can be installed in fluidized-bed reactors to recycle the particles discharged with the gas stream.
  • the gas cyclone at least partially separates the fine attrition from the gas stream which is then e.g. can be returned to the bottom zone of the fluidized bed.
  • the object of the present invention is to find a way of optimizing the operation of a fluidized bed reactor plant with regard to the described problems.
  • Suitable technical measures are to be provided by which the operation can be kept as trouble-free as possible and in particular also low in maintenance. These measures should in particular _
  • the material according to the present invention is preferably present as bulk material. It can be used in particular as CO 2 absorber and / or as bed material in fluidized beds, in particular as a reactive bed material, and also referred to as such. It consists essentially of at least one metal oxide and / or at least one carbonate. The at least one metal oxide and the at least one carbonate are preferably convertible into each other under CC uptake and release.
  • the material is characterized in preferred embodiments in particular by the fact that it is substantially free of particles having a particle size ⁇ 100 .mu.m, in particular ⁇ 200 .mu.m.
  • fine, volatile particles can be discharged from a fluidized bed by means of a gas flow.
  • particles with a size of up to several hundred micrometers can be discharged.
  • the particles In powdered absorbents based on conventional Be obtained by a thermal treatment of carbonate minerals manner, the particles have a broad particle size distribution, including a proportion of such fine, volatile particles.
  • this portion is discharged from the gas stream and at least partially dragged into downstream equipment parts.
  • the material according to the invention is preferably substantially free of particles having particle sizes ⁇ 100 ⁇ m, preferably ⁇ 200 ⁇ m (also referred to below as undersize), which usually make up a large part of the abrasion which is carried out at normal gas velocities. Accordingly, when using a material according to the invention as an absorbent, the amount of abrasion occurring is markedly lower than with conventional absorbents. The proportion of particularly fine abrasion, which can no longer be detected by gas cyclones, is at least greatly reduced at this stage of the process.
  • the material according to the invention is in particular also with regard to the accumulation of abrasion due to thermal, mechanical and chemical stress in the case of multiple use, ie when used as an absorbent in a cycle with a periodic sequence of CO 2 absorption and regeneration of the absorbent, optimized.
  • the material according to the invention preferably has mechanically particularly stable particles which can withstand the described loads better, so that correspondingly less abrasion results in the CO 2 absorption and the regeneration.
  • the material according to the invention is produced in particular from carbonate-containing materials, in particular by thermal and / or mechanical treatment of at least one carbonate.
  • the mechanical The stability of the absorbent particles is attributable in particular to a mechanical and / or thermal treatment step which can be carried out within the scope of the method according to the invention for producing a material for CO 2 absorption.
  • a starting material is micritic lime.
  • lime should be understood to mean lime which consists at least for the most part of a micrit matrix, in particular a matrix of interconnected carbonate grains with particle sizes ⁇ 100 ⁇ m, preferably ⁇ 10 ⁇ m, in particular ⁇ 5 ⁇ m, particularly preferably ⁇ 4 microns.
  • the material according to the invention is composed in preferred embodiments of individual, interconnected grains with the dimensions given.
  • the material according to the invention may consist of only the at least one metal oxide and only of the at least one carbonate. Preferably, however, it consists essentially of particles which have a core of at least one carbonate and a shell surrounding the core (or shell) of at least one metal oxide.
  • the material according to the invention is largely resistant (passivated) against the influence of atmospheric moisture and accordingly has improved storage and transportability. So the carbonate layer can _ _
  • the particles with the core of at least one carbonate and the shell surrounding the core (or shell) may also be passivated from at least one metal oxide.
  • the core of the carbonate is surrounded by two shells, namely an inner sheath of the at least one metal oxide and an outer sheath of carbonate.
  • sheath or shell substantially completely surrounds the core.
  • the weight ratio of metal oxide to carbonate in the material is preferably between 100: 1 and 1: 100, preferably between 100: 1 and 1: 1, in particular about 10: 1 (oxide to carbonate).
  • a material according to the invention consists essentially of particles which in particular have an average particle size in the range between 0.3 mm and 3 mm, particularly preferably between 0.5 mm and 1.5 mm.
  • it consists essentially of porous particles.
  • the at least one metal oxide is preferably at least one metal oxide of the type M x O y , where M denotes a metal, for example Mg, Ca, Sr, Ba, La, Mn or Y and x and y in the usual way suitable integers describe.
  • the at least one metal oxide is particularly preferably at least one alkaline earth oxide, in particular CaO or a mixture of CaO and MgO.
  • the at least one metal oxide may comprise a portion of iron oxide and / or silicon dioxide. Possibly. it can also contain alumina.
  • the proportion of iron oxide in preferred embodiments is less than 10% by weight (residue on ignition, based on the total mass of the material according to the invention).
  • the proportion of silicon dioxide in preferred embodiments is less than 5% by weight (incineration residue, based on the total mass of the material according to the invention). In particular, this value should not be too high in order not to promote the formation of calcium silicates in operation.
  • cement clinker phases eg 3 CaO • SiO 2 , 2 CaO • SiO 2 , 2 CaO • (Al 2 O 3 , Fe 2 O 3 ), etc. ], which can lead to deposits in various plant components (such as heat exchangers).
  • the proportion of iron oxide, silicon dioxide and aluminum oxide in the material according to the invention is preferably less than 10% by weight, in particular less than 5% by weight (residue on ignition, based on the total mass of the material according to the invention).
  • the at least one carbonate is preferably at least one carbonate of the type M x (CO 3 ) y , where M denotes a metal such as, for example, Mg 1 Ca 1 Sr, Ba, La, Mn or Y and x and y in the customary manner designate suitable integers.
  • the at least one carbonate is particularly preferably at least one alkaline earth carbonate, in particular CaCO 3 or a mixture of CaCO 3 and MgCO 3 .
  • the at least one carbonate may comprise at least one metal oxocarbonate, in particular at least one metal oxocarbonate of the type M x Oy (CO 3 ) 2 , where M denotes a metal, eg Mg, Ca 1 Sr, Ba, La 1 Mn or Y and x , y and z denote suitable integers in the usual way.
  • MgO is contained in the inventive material in preferred embodiments in a proportion of ⁇ 3 wt .-% (incineration residue, based on the total mass of the material according to the invention).
  • the present invention is a process for the preparation of a material as described above.
  • carbonate particles are subjected to a heat treatment in which a thermal desorption reaction takes place under CO 2 release.
  • the method is characterized in that after or during the heat treatment essentially all particles with particle sizes ⁇ 100 ⁇ m, in particular ⁇ 200 ⁇ m, are separated off.
  • the heat treatment is carried out in favor of a large pore surface in the interior of the particles particularly preferably over the shortest possible time at the highest possible temperatures, preferably at a temperature in the range between 1000 0 C and 1500 0 C, in particular between 1100 0 C and 1300 0 C.
  • the temperature during the heat treatment is selected so that the particles during the heat treatment of a - -
  • the material according to the invention is therefore in preferred embodiments a material which has been subjected to a sintering process.
  • an initial material preferably a natural carbonate, such as lime and / or dolomite, see below
  • a lime standard of> 400, in particular> 2000.
  • the lime standard is a measure of the proportion of oxidic impurities. It indicates the total CaO content of the raw material in relation to the CaO content, which can be bound to SiO 2 , Al 2 O 3 and Fe 2 O 3 by formation of cement clinker phases:
  • KSt (2.8 • SiO 2 ) + (1.18 • Al 2 O 3 ) + (0.65 • Fe 2 O 3 )
  • Such a starting material in preferred embodiments has a high sinterability (i.e., the density of the particle increases significantly in the sintering process).
  • Sintering usually refers to the process of "compacting a powder or porous body by a temperature treatment below the melting point of the material", which process can be observed macroscopically as a decrease in length, volume and porosity or density increase.
  • the sinterability increases with increasing lime standard.
  • the material according to the invention has a bulk density> 900 kg / m 3 , in particular> 1200 kg / m 3 .
  • Such a material could be obtained in particular from an initial matehal having a lime standard> 400, in particular> 2000, in the context of the process according to the invention.
  • the resulting material according to the invention has a bulk density> 900 kg / m 3 , in particular> 1200 kg / m 3 .
  • the heat treatment is carried out until the thermal desorption reaction is complete and the carbonate particles are essentially completely converted into oxide particles.
  • the heat treatment is stopped before the thermal desorption reaction is complete and the carbonate particles are substantially completely converted to oxide particles. This results in the material described above with a core of carbonate and a surrounding oxidic layer.
  • the heat treatment can be carried out, for example, under conditions such as occur in a fluidized-bed reactor.
  • particles as already mentioned above, are exposed to mechanical stresses, including, in particular, collisions with other particles and with reactor internals, in fluidized-bed reactors, in particular with the inner walls of the reactors.
  • the carbonate particles to be converted at least partially into oxide particles are therefore subject to the same loads which are also exposed to a "finished" bed material during operation of a fluidized-bed reactor.
  • the heat treatment can be carried out in a rotary kiln.
  • the material according to the invention has an abrasion resistance which is comparable to that of quartz sand.
  • the material according to the invention preferably has an HGI value (Hardgrove Index, determined according to the American ASTM Standard D 409) ⁇ 60, in particular ⁇ 50. This applies in particular if it has the above-mentioned preferred values for the bulk density. - -
  • the material produced according to the described preferred embodiments (thermal treatment or sintering and possibly additional mechanical treatment, ie separation of the particles with a particle size ⁇ 100 ⁇ m, in particular ⁇ 200 ⁇ m) of the method according to the invention differs in summary in two respects from Conventional Absorbenzien: Firstly, it is freed of very fine particles and on the other hand, it has particularly stable particles. From the first use of the material according to the invention as a CO 2 -Absorbens falls to significantly less wear than conventional absorbents, which has a positive effect on the operating stability, reliability and economy (including less bed material consumption, lower number of required maintenance of a fluidized bed reactor per unit time). The small amounts of accumulating abrasion are largely problem-free by means of conventional particle separation, for example by means of a gas cyclone, separable.
  • the particles with particle sizes ⁇ 100 ⁇ m, in particular ⁇ 200 ⁇ m can be separated using a gas cyclone.
  • the separation can thus be carried out continuously during the heat treatment, so that a separate separation step can be omitted.
  • the carbonate particles used are particularly preferably particles of natural carbonates, in particular of lime and / or dolomite. They therefore consist essentially of CaCO 3 or a mixture of CaCO 3 and MgCO 3 . _ _
  • the heat-treated particles are subjected to CC> 2 treatment in a gas atmosphere (recarbonation) so that a layer of carbonate, for example CaCO 3 , can be formed at least on the particle surface.
  • a layer of carbonate for example CaCO 3
  • the chemical composition of the particles below the surface ie in particular the oxidic structure of the particle core
  • the recarbonation is preferably carried out before the separation of the particles having particle sizes ⁇ 100 .mu.m, in particular ⁇ 200 .mu.m.
  • Such treatment may result in the already mentioned passivated particles having on their surface a layer of at least one carbonate.
  • the parameters temperature, pressure, duration of the treatment and / or composition of the gas atmosphere are carefully selected during the CO 2 treatment.
  • the setting of the mentioned parameters depends on many factors, including, but not limited to, the average particle size of the particles to be treated and their other nature.
  • the mean particle size of the particles to be treated ranges, in some preferred embodiments, between 0.7 mm and 1.5 mm.
  • the CO 2 treatment is preferably carried out at temperatures in the range between 600 0 C and 800 0 C, in particular between 650 0 C and 750 0 C. • * "
  • a CO 2 partial pressure between 100 and 700 mbar is preferably set in the CO 2 treatment.
  • the gas atmosphere has a vapor fraction.
  • the H 2 O partial pressure is preferably set to values between 100 mbar and 500 mbar, preferably between 100 mbar and 300 mbar.
  • the duration of a CO 2 treatment is generally between 1 and 10 hours.
  • the CO 2 treatment can be carried out both before and after the separation of the undersize.
  • the CO 2 treatment is carried out directly after the heat treatment (CO 2 desorption), wherein the particles are cooled to a corresponding temperature (preferably ⁇ 800 0 C) and brought into contact with a CO 2 vapor mixture.
  • CO 2 desorption heat treatment
  • a final fractionation eg sieving
  • a finely porous recarbonate can be prepared from a coarse-pore oxide again, the structure of which approaches the original structure of the starting material.
  • This fine porosity is with greater inner Surface, which explains the higher activity.
  • a fine-pored microstructure is mechanically more stable, since many small “bridges” react more elastically to mechanical stresses than a few large “connecting bridges” (which rather act as predetermined breaking points).
  • the inventive material has excellent characteristics with regard to the parameters CO 2 uptake rate, and CO 2 - absorption capacity, in particular if it consists essentially of the above-described particles comprising a core of at least one carbonate, and a cladding surrounding the core of at least one metal oxide or consists of the particles already described with a core of at least one metal oxide and a shell surrounding the core of at least one carbonate.
  • the material has a CO 2 absorption capacity of> 0.05 g C ⁇ 2 / go ⁇ id-
  • the material may have a CO 2 take -up rate of> 0.01 gCO 2 / (goid ⁇ min) (at a CO 2 partial pressure of from 0.01 to 0.3 bar in the raw gas, based on Normal pressure, and an absorption temperature between 600 0 C and 700 0 C).
  • the present invention also includes a method of producing a low-CO 2 gas.
  • a method of producing a low-CO 2 gas in this method, in a first process step, CO 2 is separated from a raw gas (for example, a flue gas or product gas) by means of a material as described above.
  • a second process step the material is then regenerated under CO 2 release.
  • the first and the second process step can also be repeated periodically, it being then preferred for the material to circulate continuously in a circuit as already mentioned at the outset.
  • both the first use of the CC 2 absorbent according to the invention and, if appropriate, in the later periodic operation generally produce less abrasion than with conventional absorbents. The reasons for this have already been explained in detail.
  • the above corresponding statements, in particular with regard to the material according to the invention are hereby incorporated by reference.
  • a material which consists essentially of particles which have at least one core of at least one metal oxide (as is the case, for example, with quicklime).
  • process parameters are selected under which the chemical composition of the core is substantially retained.
  • the core itself participates only limitedly in the reaction happening.
  • the conversion is then reversed again under CO 2 release and the original state is restored.
  • a material which consists essentially of particles which have at least one core of at least one carbonate (as is the case, for example, with limestones which are still untreated).
  • process parameters are selected for the second process step, among which the _ _
  • the process parameters are selected in the second process step so that essentially only the layer surrounding the core is converted into an oxide with CO 2 release.
  • the nucleus itself participates in the reaction process at best only to a limited extent.
  • the conversion is then reversed again and the original state at least approximately restored.
  • the process control according to the two described preferred embodiments ensures that the mechanical stability and thus the abrasion behavior of the particles of the CO 2 absorbent used remains largely the same even after many absorption and regeneration cycles. Presumably, this is due to the fact that in both cases the core participates only limitedly in the reaction process and therefore retains its properties, in particular its mechanical stability.
  • the transition from carbonate to oxide and vice versa is usually accompanied by a change in the crystalline structure of the absorbent particle. Associated with this may be tensions that weaken the structural integrity of the entire particle. If the core does not participate in the reaction process, the tensions occurring in a particle are presumably much lower, so that the particle as a whole retains its stability.
  • the choice of process parameters includes in particular a coordinated adjustment of process temperature, CO 2 - partial pressure and / or process duration.
  • the duration of the process is to be understood as meaning, in particular, the residence time of the CO 2 absorbent in the respective process step.
  • the process parameters in the first process step are selected in particular as a function of the average particle size of the absorbent particles and / or the nature of the raw gas, in particular its CO 2 content.
  • the crude gas used is preferably a hydrogen-containing synthesis gas, in particular a synthesis gas obtained from biomass. Furthermore, smoke and process gases can be used as raw gas.
  • the CCV content in the raw gas usually fluctuates between 10 and 30% by volume and can be reduced to less than 10% by volume (dry gas composition).
  • the first process step is seen as a process temperature under atmospheric conditions, preferably a temperature between 600 0 C and 750 0 C is selected.
  • the process time is usually in the WS in the range of a few minutes.
  • the second process step (regeneration) is preferably selected as the process temperature un- ter atmospheric conditions at a temperature between 800 0 C and 950 0 C.
  • the process duration is usually in the range of a few seconds to less minutes.
  • both process steps are performed without applying an external pressure.
  • the first and / or the second process step are particularly preferably carried out in a fluidized-bed reactor in which the CO 2 -absorbing material correspondingly exists as a fluidized bed.
  • the process according to the invention can also be carried out in other reactors known to the person skilled in the art.
  • the material according to the invention described above can be used not only for the "downstream" removal of CO 2 from a synthesis gas, but also directly in a gasification process step, for example in the presence of a carbonaceous feedstock in the production of synthesis gas from biomass Material can not only absorb CO 2 , but also is able to adsorb on its surface so-called tars (cyclic and polycyclic aromatics) In a further process step, these tars can be used for heat generation by combustion for the thermal desorption reaction, as For example, it is already known from DE 10 2004 045 772.
  • the material according to the invention generally has a catalytic activity with respect to tar degradation which, compared with quartz sand, is less than 0.5 times the tar concentration in the gasification of biogenic input materials under otherwise identical reaction conditions.
  • the catalytic activity is more than twice that of silica sand.
  • the described material according to the invention is outstandingly suitable as an oxide catalyst, in particular for the catalytic tar reforming. Accordingly, the use of the described inventive material as oxide catalyst, in particular for the catalytic tar reforming, the subject of the present invention.
  • iron oxide-containing material according to the invention.
  • the described material according to the invention is also suitable for the separation of sulfur compounds and other impurities contained in gases.
  • the corresponding use is also included in the present invention.
  • the preparation takes place in two stages in preferred embodiments: In a first rotary tubular reactor, carbonate is fired at temperatures above 900 ° C., CO 2 being released. In a second rotary reactor, the intermediate product (oxide) at 650 0 C to 750 0 C again takes CO 2 (Recarbonatmaschine).
  • the separation of particles with a particle size ⁇ 100 microns can be done continuously or after completion of treatment.
  • the starting material e.g., limestone
  • the starting material is preferably added continuously to the first rotary tube reactor.
  • shrinkage of the particles as a result of sintering must be taken into account (approx. 10% under the conditions recommended below).
  • the product falls continuously into a collecting container.
  • the residence time of the material in the rotary tube should be about 30 minutes.
  • the material sinters, increasing its strength but also changing the particle size (the grain shrinks).
  • the material may lose chemical reactivity, ie, for example, the back reaction to the carbonate (recarbonation) or the hydroxide formation generally proceed more slowly, the more the material has been sintered.
  • This sintering process is intensified by long residence times and / or high temperatures (in the lime industry, a distinction is made between soft, medium and hard fires during the sintering process).
  • the Recarbonattician is procedurally much more difficult to implement than the burning process, since the CO 2 uptake proceeds only in a narrow temperature window. Ideally, the material passes through an isothermal rotary tube reactor within about 1 h, through which flue gases pass. Good gas-solid contact is a prerequisite for favorable reaction conditions.
  • the temperature window of Recarbonattician is bounded below by the reaction rate: At temperatures below 600 0 C, the C ⁇ is 2 uptake even at a CO 2 partial pressure of 1 bar very slow and thus not technically relevant. If the temperature is too high, the thermodynamic equilibrium of the CaO-CaCO 3 -CO 2 system is reached, ie the recarbonation reaction is very slow or does not run off any more - in the worst case even calcination conditions are even reached again.
  • the possible / favorable temperature window for the recarbonation depends on the CO 2 partial pressure.
  • the temperature can be increased if the CO 2 partial pressure in the gas phase is greater, ie if, for example, flue gas is enriched with CO 2 .
  • Higher temperatures and partial pressures increase the reaction rate of CO 2 uptake.
  • water vapor has a catalytic effect on the rec- bonatleiters Anlagen and improves the overall material properties.
  • a CC> 2 partial pressure of 0.3 bar and a water vapor partial pressure of 0.1-0.3 bar is recommended.
  • the cooling of the product is preferably carried out in a dry gas atmosphere with a low CO 2 content (eg 5 mol.%) In order to avoid calcination and hydroxide formation.
  • a fluidized bed is suitable for this purpose.
  • the intermediate (oxide) thus occurs e.g. from the calcination rotary kiln and is fed directly into a fluidized bed. Recarbonated particles sink downwards due to their greater specific gravity and can be discharged here.

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Abstract

L'invention concerne un matériau convenant à l'absorption de CO2 et/ou utilisable comme matériau dans des lits fluidisés, un procédé pour produire un tel matériau, un procédé pour produire un gaz pauvre en CO2 à l'aide d'un tel matériau, ainsi que d'autres utilisations de ce matériau, en particulier dans le domaine de la purification des gaz. Le matériau selon l'invention se compose pratiquement d'au moins un oxyde métallique et/ou d'au moins un carbonate et est pratiquement exempt de particules ayant une taille inférieure à 100 μm.
PCT/EP2009/001043 2008-02-13 2009-02-13 Matériau convenant comme absorbant de co2 et utilisable comme matériau dans des lits fluidisés et sa production WO2009100937A2 (fr)

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EP09711423A EP2303429A2 (fr) 2008-02-13 2009-02-13 MATÉRIAU CONVENANT COMME ABSORBANT DE CO2 ET UTILISABLE COMME MATÉRIAU DANS DES LITS FLUIDISÉS ET SA PRODUCTION& xA;

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DE102008010349.7 2008-02-13
DE102008010349A DE102008010349A1 (de) 2008-02-13 2008-02-13 Als CO2-Absorbens und zur Anwendung als Bettmaterial in Wirbelschichten geeignetes Material und dessen Herstellung

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US11718558B2 (en) 2019-08-13 2023-08-08 California Institute Of Technology Process to make calcium oxide or ordinary Portland cement from calcium bearing rocks and minerals

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