• 专利附录
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    • 专利摘要:
    Procedure of preparation of transporters of O2 , product thus obtained and its use. The present invention relates to a process for producing an oxygen carrier material by mixing CuO and Mn3O4 , prepared by fluidized bed granulation. The material thus obtained has high reactivity, high mechanical strength, low attrition rate and low attrition rate. This material is applied in a CLOU process of solid combustion with inherent capture of CO2 . (Machine-translation by Google Translate, not legally binding)
    公开号:ES2682049A1
    申请号:ES201730355
    申请日:2017-03-16
    公开日:2018-09-18
    发明作者:Juan Adanez Elorza；Luis Francisco De Diego Poza；Francisco Garcia Labiano；Pilar Gayan Sanz；Alberto Abad Secades；María Teresa IZQUIERDO PANTOJA；Iñaki ADANEZ RUBIO
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

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    Preparation procedure for O2 transporters, product thus obtained and
    its use
    DESCRIPTION
    Technical sector
    The present invention relates to a process for preparing O2 transport materials, from CuO and Mn3O4. The material thus obtained is applied in the combustion of solids (coal, biomass, coke, oil, solid waste, etc.) using an indirect combustion process (with solid oxygen generators) to produce energy without CO2 emissions into the atmosphere.
    Therefore, the present invention is framed within the chemical sector, particularly the energy sector.
    State of the art
    The climatic changes that the planet is suffering have caused the need to reduce greenhouse gas emissions, mainly CO2, to the atmosphere. The high cost that currently involves the separation of CO2 from combustion fumes for later storage has generated in recent years the emergence of new combustion systems that produce concentrated currents of CO2. To avoid the costs associated with the separation of CO2, a new technology has been developed, such as indirect combustion with solid oxygen transporters (CLC). This process is based on carrying out the transfer of oxygen from the air to the fuel by an oxygen transporter in the form of metallic oxide, without at any time bringing the fuel into contact with the air. This system has no energy penalty because there is no separation of CO2 from any other gas (except H2O) and therefore the energy efficiency does not decrease. This is the main advantage of the CLC system over any other CO2 capture system (chemical, physical absorption, membrane reactors, adsorption systems, etc.). In addition, the energy generated in combustion is equivalent to that obtained in conventional combustion.
    The metal oxide particles that are used to transport oxygen in CLC combustion must have acceptable oxidation and reduction rates,
    as well as sufficient mechanical resistance to limit its breakage and attrition, since they must be circulating continuously between two interconnected fluidized beds.
    To be able to use solid fuels in a CLC system, prior gasification is necessary, since it is necessary that the fuel is in gaseous form, which entails an energy and economic penalty in the system.
    To avoid this slow reaction of gasification of the fuel and the need for another reactor, a process called “Chemical Looping with Oxygen Uncoupling” (CLOU), SE200500249, based on the strategy of using oxygen transporters that are capable of releasing oxygen has been patented in gaseous form in the reduction reactor and therefore the solid fuel can react directly with gaseous oxygen.
    In the CLOU process the oxidation of solid fuel occurs in two steps. First, the oxygen transporter decomposes and releases gaseous oxygen according to the reaction (r.1):
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    MexOy ^ MexOy_i +1/2 O2 (r.1)
    Next, the fuel reacts with oxygen, as in normal combustion, to produce a pure stream of CO2 and H2O, reaction (r.2):
    CnH2m + (n + m / 2) O2 ^ nCO2 + mH (r 2)
    2 0 The reduced conveyor of the reduction reactor is transported to the reactor of
    oxidation, where it reacts with the oxygen in the air (r.3):
    1 / 2O2 + MexOy_i ^ MexOy (r.3)
    The total enthalpy released in the reduction and oxidation reactors is the same as in conventional combustion. The advantage is that CO2 and H2O are inherently separated from N2 in the air, therefore there is no separation energy expenditure (see Figure 1). The oxygen transporters for the CLOU process must have special characteristics necessary to react reversibly with the oxygen at high temperature, so that they are capable of releasing oxygen in the reduction reactor and recovering it in the oxidation reactor. The process
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    CLOU uses the fact that some metal oxides are capable of generating O2 at high temperature, between 800 ° C and 1200 ° C, and subsequently regenerated with air.
    So far, the main methods that have been applied in the preparation of oxygen transporters for use in CLOU processes are: impregnation, cryogenic granulation, spray drying, mass mixing and extrusion, co-precipitation, sol-gel and combustion.
    Granulation is a process by which the primary particles of raw materials or a heterogeneous mixture of fine powders are transformed into a uniform granulate, of greater size and density.
    Mattison et al. [Mattisson T, Lyngfelt A, Leion H. "Chemical-looping oxygen uncoupling for combustion of solid fuels", Int J. Greenhouse Gas Control (2009); 3: 119] developed a conveyor with 60% CuO on alumina prepared by cryogenic granulation and analyzed it in a fluidized bed reactor for a small number of cycles with methane / air at 950 ° C. Also Mattisson et al. [Mattisson T, Leion H, Lyngfelt A. "Chemical-Looping with Oxygen Uncopling using CuO / ZrO2 with petroleum coke", Fuel (2009); 88: 683-690] developed a 40% CuO transporter on zirconium oxide prepared by cryogenic granulation and analyzed it in a fluidized bed reactor for a small number of cycles at various temperatures. However, the mechanical resistance of this conveyor was low (0.8 N) and they detected some problems of agglomeration at some moments of experimentation. These copper-based transporters presented in the literature have been prepared using the freeze granulation method. With this method, conveyors with sufficient mechanical strength for the industrial process (> 1 N) are not obtained and, in addition, it is difficult to extrapolate on an industrial scale.
    In other documents found, [Abad A, Adánez-Rubio I, Gayán P, García-Labiano F, by Diego LF, Adánez J. “Demonstration of chemical-looping with oxygen uncoupling (CLOU) process in a 1,5 kWth continuously operating unit using a Cu-based oxygen-carrier ', International journal of greenhouse gas control (2012); 6: 189-200], [Adánez- Rubio I, Abad A, Gayán P, by Diego LF, García-Labiano F, Adánez J. “Performance of CLOU process in the combustion of different types of coal with CO2 capture”, International Journal of Greenhouse Gas Control (2013); 12: 430-440] and [Adánez-Rubio I, Abad A, Gayán P, by Diego LF, García-Labiano F, Adánez J. “Biomass combustion
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    with CO2 capture by Chemical looping with oxygen uncoupling (CLOU) ", Fuel Processing Technology (2014); 124: 104-114], oxygen transporters obtained by a spray drying method are used. These works showed a significant decrease in resistance mechanics of the conveyor, being necessary an improvement of the half-life of the particles for the CLOU process.Today the main effort to continue with the development of the CLOU process is to find a conveyor with high reactivity with solid fuels and high mechanical resistance .
    None of the bibliographic sources and patent bases consulted are based on a method of preparation by granulation of Cu-Mn transporters. Thus, the present invention relates to the method of obtaining a high reactivity conveyor, which does not agglomerate, with high mechanical resistance and with a low attrition rate, which allows the complete combustion of a solid fuel with inherent CO2 capture. With low conveyor inventory.
    Brief Description of the Invention
    A first aspect of the present invention relates to a process for the preparation of oxygen transporters, which comprises the following steps:
    a) mix 30-50% by weight of CuO and 70-50% by weight of Mn3O4
    b) classify the particles of the mixture by size up to 0.4-0.8 mm
    c) prepare a suspension with solids concentration of 70-75%, 25-30% water,
    and additives binders, surfactants, dispersants and deflocculants
    d) classify suspension particles by size up to 0.6-1 mm
    e) subject the mixture obtained in the previous stage to granulation
    f) calcine the particles at a temperature of 1100-1150 ° C.
    The mixture of step a) can preferably be carried out with a proportion of 34% by weight of CuO and 66% by weight of Mn3O4.
    The mixture obtained in step a) can be classified by particle size of 0.40.8 mm, preferably rejecting particles larger than 0.6 mm, more preferably rejecting particles larger than 0.4 mm to remove possible agglomerates.
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    A suspension with a solids concentration of 70-75%, 25-30% water, additives with binding properties, surfactants, dispersants and deflocculants can be prepared. This preparation includes the following sub-stages:
    - prepare a 10% binder solution with half the water to use
    keeping stirring
    - heat the second half of the water
    - add the binder solution prepared above to the water with
    constant stirring until completely dissolved
    - add: surfactant, dispersant and deflocculant while maintaining constant agitation
    - add the solids mixture while maintaining constant stirring.
    The suspension prepared in step c) can be classified by particle size of 0.6-1 mm, preferably rejecting those greater than 0.8 mm, more preferably rejecting those greater than 0.6 mm to avoid stoppers in the injector.
    The granulation step can be carried out at a temperature of 70-90 ° C, preferably at 80 ° C until obtaining particles with a size of 90-350 microns.
    The calcination can be carried out at a temperature of 1100-1150 ° C, preferably 1125 ° C by heating ramp of 12 ° C / min in an air flask, and for a time of 2 h.
    Another aspect of the present invention is the product obtained by the process described above. The product of the invention has the following properties:
    - high reactivity
    - density of 4.0 g / cm3
    - porosity of 12%
    - mechanical resistance of 2.0 N
    - AJI 3.0% attrition value,
    - attrition rate of 0.005% / h
    - 20,000 h half-life of particles of transport material
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    Another aspect of the present invention is the use of the product of the invention in a Chemical Looping with Oxygen Uncoupling (CLOU) process of solid combustion with inherent capture of CO2 in fluidized bed.
    The product of the invention can be applied in a CLOU process comprising the following steps:
    - decomposition of the oxygen transporter releasing gaseous oxygen
    - reaction of the fuel with oxygen, producing a pure stream of CO2 and H2O
    - the reduced conveyor of the reduction reactor is transported to the oxidation reactor, where it reacts with the oxygen in the air.
    The preparation method of the present invention is extrapolated on an industrial scale and produces materials with the necessary mechanical strength to operate in a fluidized bed, density of 4.0 g / cm3, porosity of 12%, attrition value AJI 3.0%, low speed of attrition, 20,000 h of average life of particles of carrier material, as well as high reactivity.
    Brief description of the figures
    In order to complete the description and in order to help a better understanding of the features of the invention, the following figures are described by way of illustration and not limiting.
    Figure 1.- It shows a scheme, described in the state of the art, of the process of combustion of solids with oxygen-generating oxygen transporters (CLOU) and with inherent CO2 capture.
    Figure 2.- Shows a graph that represents the conversion of the oxygen transport material as a function of the time for the decomposition reaction in N2 at 950 ° C and the oxidation reaction with air of the transporter reduced to 950 ° C.
    Figure 3.- Shows a diagram of a discontinuous fluidized bed in which the process of reduction or oxidation of the O2 transport material takes place.
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    Figure 4.- Shows a graph that represents the attrition rate of the oxygen transport material in percentage of mass elutriated per redox cycle, obtained after successive reduction-oxidation cycles in the discontinuous fluidized bed of Figure 3.
    Figure 5.- It shows a diagram of the continuous fluidized bed pilot plant for the combustion of solids with the oxygen transport material.
    Figure 6 (a), (b) and (c) .- They show the CO2 capture efficiency, char conversion and combustion efficiency as a function of the reduction reactor temperature, the coal feed rate and the solids circulation speed.
    Detailed description of the invention
    The present invention relates to a process for preparing oxygen transport materials based on the mixture of CuO and Mn3O4, which is carried out by fluidized bed granulation. The material thus obtained has good properties for application in a solid combustion process with inherent CO2 capture.
    The process of obtaining the oxygen transport material comprises the following stages:
    a) mix 30-50% by weight of CuO and 70-50% by weight of Mn3O4
    b) classify the particles of the mixture by size up to 0.4-0.8 mm
    c) prepare a suspension with solids concentration of 70-75%, 25-30% water,
    and additives binders, surfactants, dispersants and deflocculants
    d) classify suspension particles by size up to 0.6-1 mm
    e) subject the mixture obtained in the previous stage to granulation
    f) calcine the particles at a temperature of 1100-1150 ° C.
    In the first stage of the process, 30-50% by weight of CuO and 70-50% by weight of Mn3O4 can be mixed. Preferably, 34% by weight of CuO and 66% by weight of Mn3O4 are used.
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    The mixture obtained in step a) can be classified by particle size of 0.40.8 mm, preferably rejecting particles larger than 0.6 mm, more preferably rejecting particles larger than 0.4 mm to remove possible agglomerates.
    Step c) consists in preparing a suspension with a solids concentration of 70-75%, 25-30% water, and additives with binding properties, surfactants, dispersants and deflocculants. This stage includes the following sub-stages:
    - prepare a 10% binder solution with half the water to use
    keeping stirring
    - heat the second half of the water
    - add the previously prepared binder solution to the water with
    constant stirring until completely dissolved
    - add: surfactant, dispersant and deflocculant while maintaining constant agitation
    - add the solids mixture while maintaining constant stirring.
    The suspension prepared in step c) can be classified by particle size of 0.6-1 mm, preferably rejecting those greater than 0.8 mm, more preferably rejecting those greater than 0.6 mm to avoid stoppers in the injector.
    The obtained mixture is subjected to a fluidized bed granulation step at a temperature of 70-90 ° C, more preferably at a temperature of 80 ° C, until particles of size 90-350 microns are obtained.
    The calcination step is carried out at 1100-1150 ° C, preferably at a temperature of 1125 ° C by heating ramp of 12 ° C / min in an air flask, and for a time of 2 h.
    High reactivity is defined as the reduction reaction rate of Cu15Mn15Q4 to CuMnO2 that produces almost complete reductions of the oxygen transport material in less than three minutes at 950 ° C, or at a rate of the oxidation reaction of CuMnO2 with air that produces almost complete transport oxidation conversions in less than five minutes at 950 ° C.
    High mechanical strength is defined as the breaking strength of a carrier particle measured in a Shimpo FGN-5X dynamometer, where the particle is
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    placed on the flat surface of the dynamometer and pressure is exerted with a tip until breakage.
    The material prepared by the process of the invention has a high reactivity, both for the release of oxygen and for its regeneration during a high number of cycles, as well as a high mechanical resistance (of 2 N). The mechanical resistance value is obtained as the average of a minimum of 20 measures of the force exerted on the particles until their break expressed in Newtons.
    Low attrition rate is defined as the low breaking rate of a friction particle measured in the ATTRI-AS three-hole air jet attrition meter (Ma.Tec. Materials Technologies Snc) configured according to ASTM-D-5757 .
    The material prepared according to the process of the invention has an attrition value (AJI 3.0%). To know this value, the tests were performed with 50 g of oxygen transporter, with an air flow of 10 l / min, which was equivalent to a jet speed of 490 m / s, as specified in the ASTM method. The weight loss of the fines was recorded after 1 h and 5 h of operation, respectively.
    Low attrition rate is defined as a low rate of generation of fine particles that are elutriated from the reactor during fluidization of the particles of the oxygen transport material.
    The invention relates to the material prepared according to the method described above, which has the following properties:
    - high reactivity
    - density of 4.0 g / cm3
    - porosity of 12%
    - mechanical resistance of 2.0 N
    - AJI 3.0% attrition value,
    - attrition rate of 0.005% / h
    - 20,000 h half-life of particles of transport material
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    The present invention relates to the use of the product of the invention in a Chemical Looping with Oxygen Uncoupling (CLOU) process of combustion of solids with inherent capture of CO2 in fluidized bed.
    The product of the invention can be applied in a CLOU process comprising the following steps:
    - decomposition of the oxygen transporter releasing gaseous oxygen
    - reaction of the fuel with oxygen, producing a pure stream of CO2 and H2O
    - the reduced conveyor of the reduction reactor is transported to the oxidation reactor, where it reacts with the oxygen in the air.
    The material of the invention is applied in a solid combustion process with inherent CO2 capture. As shown in Figure 1, a CLOU plant is formed by two interconnected fluidized bed reactors. In the reduction reactor (1), the combustible solid (CnH2m) is oxidized to CO2 + H2O by the oxygen generated by a metal oxide (Cu15Mn15O4) which is reduced to (CuMnO2). The reduced oxide (CuMnO2) is transferred to the oxidation reactor (2) for oxidation in air and thus start a new cycle. The gas that leaves this reactor only contains N2 and O2 not used in oxidation. The exhaust gas from the reduction reactor (1) only contains CO2 and H2O as products of the solid's combustion reaction, which after condensation in a condenser (3) allows the separation of CO2 for later storage.
    Examples
    The examples described below should not be understood only as a limitation of the scope of the invention. On the contrary, the present invention seeks to cover all alternatives, variants, modifications and equivalences that may be included within the scope of the object of the invention.
    Example 1.- Scheme of the process for obtaining the oxygen transport material of Cu15Mn15O4 by granulation.
    5000 g of material were prepared, for this the following steps were carried out:
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    1. Mix kg in kg: 34% CuO (Panreac dp <10 microns) and 66% Mn3O4 (STREM dp <10 microns) in mill with 190 steel balls for 10 min.
    2. Sift the mixture with 0.6 mm sieve to remove possible agglomerates.
    For each batch a suspension with a solids concentration of 75% is prepared, with 3.7 kg of powder mixture that allows operation for 1-2 h according to the pump feed rate (15-30 rpm).
    3. Suspension preparation:
    3.a) Heat 1250 g of water
    3.b) Add the PEO (high molecular weight polyethylene oxide) to the water with constant stirring until completely dissolved
    3.c) Keeping the stirring constant add 13 g of Targon®
    3.d) Keeping stirring constantly add 45 g of Darvan®
    3.e) Keeping stirring constantly add 37 g of Dolapix®
    3. f) Keeping the stirring constant add the solids mixture little by little.
    4. Sift the suspension with a 0.8 mm sieve to avoid caps in the injector.
    5. Subject the above mixture to a fluidized bed granulation step at 80 ° C.
    6. Calcify the particles obtained in the previous stage, giving rise to an oxygen transport material. This calcination step is preferably carried out at 1125 ° C in an air flask by means of a heating ramp of 12 ° C / min, and for a period of 2 h.
    In this way, a solid oxygen transport material was obtained that has the following characteristics:
    - density of 4.0 g / cm3, measured with helium pycnometer in Micromeritics AccuPyc II 1340 equipment
    - 12% porosity, measured with Quantachrome PoreMaster33 mercury porosimeter
    - mechanical resistance of 2.0 N. The mechanical resistance was measured with a Shimpo FGN-5X dynamometer.
    Example 2.- Test of oxygen generation and regeneration of the solid in a fluidized bed with the oxygen transport material obtained from the process of the invention.
    This example reflects the appropriate properties of using O2 transport materials with the characteristics indicated in the description of the invention. Specifically, the oxygen transporter prepared in example 1 was used.
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    First, the reduction and oxidation rate of the conveyor using a thermobalance is shown. The characteristics of these tests are widely known to a person skilled in the art. Figure 2 shows the speed of the reduction reaction (thermogravimetric analysis, TGA, at 950 ° C and with 100% N2) and the oxidation reaction of the reduced transporter (thermogravimetric analysis, TGA, at 950 ° C and with 21% of O2). A high rate of oxygen generation and a high oxidation reactivity are observed (Figure 2).
    In addition, to study the behavior of solid oxygen transport materials with respect to oxygen generation, chemical resistance to cycles, attrition and agglomeration, the transporters were studied in discontinuous fluidized bed (LFB) in successive cycles (100 cycles) of reduction -oxidation at temperatures between 800 ° C and 925 ° C, with 100% N2 in the reduction and between 4-21 vol% O2 in N2 in the oxidation. Figure 3 shows a scheme of the installation used. This installation consists of a gas supply system formed by the reagent supply lines, the gas flow controllers and an automatic three-way valve (4). The fluidized bed is in a cylindrical reactor of Kantal walls that alternatively operates as a reduction (1) or oxidation reactor (2). Said fluidized bed reactor has measures of 5.4 cm internal diameter, 50 cm high and 30 cm preheating zone of the injected gases. The bed base is a plate (5) with 13 distribution hoods to fluidize the solid. The bed temperature is measured with a thermocouple (6) of type K. The reactor is surrounded by an electric furnace (7) with temperature control. The loss of load in the bed is measured with a water pressure gauge (8) and allows to determine if the bed fluidizes correctly or not. In the gas outlet line there are two heated filters (9), which are used alternately, with ceramic blanket and glass wool to collect the elutriated solids. The mass of fines collected is measured by weighing difference. A continuous O2 analyzer (10) is used for gas analysis.
    The experiments were carried out with loads of 400 grams of oxygen transport material with a particle size between 0.1 and 0.3 mm and a superficial velocity of the fed gas of 0.15 m / s.
    Figure 4 shows the attrition rate of the O2 transport material of the invention after successive reduction-oxidation cycles in the fluidized bed
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    discontinuous. After 10 h of operation the attrition value stabilizes at a low value, the final value being very low, 0.005% / h. The average life corresponding to the attrition values of these particles of transport material is very high, said time being 20,000 h. This attrition rate is lower than other oxygen transporters for CLOU previously studied and patented (CuO-MgAl2O4). In addition, an ASTM attrition test was performed on the oxygen transporter, yielding a 3% attrition result, lower than that obtained with the CuO-MgAl2O4 transporter (this being 5%). Therefore it can be affirmed that with respect to attrition resistance this oxygen transporter Cu1.5Mn1.5O4 is a substantial improvement of previous oxygen transporters for the CLOU process.
    In addition, during the operation with these materials no agglomeration problems were observed in the discontinuous fluidized bed of any kind.
    Example 3.- Combustion test with coal in a continuous pilot plant with the conveyor obtained from the process of the invention.
    This example demonstrates the properties of using O2 transport materials with the characteristics indicated in the report obtained from the process of the invention under more real conditions to the industrial process. Specifically, the oxygen transport material prepared in example 1 was used in a 1500 W thermal pilot plant with two interconnected fluidized beds for 62 h.
    Figure 5 shows a scheme of the installation used. The plant consists of two interconnected fluidized bed reactors. The reduction reactor (1) has 5 cm of internal diameter and a bed height of 20 cm. The oxidation reactor (2) has 8 cm of internal diameter and a height of 10 cm. The pneumatic transport reactor (11) for the transport of solids between reactors has 2 cm of internal diameter and a height of 1 m.
    Additionally, the installation consists of a solids valve (12) to control the flow of solids that circulates between the reactors, a closing bed (13) and a cyclone (14). The flow rate is measured by diversion of the solids to a tank (15). The solid fuel is fed with a worm screw (16) at the bottom of the reduction reactor. The fluidizing agent of the reduction reactor (1) and the air in the oxidation reactor (2) are fed from the bottom of the reactors with mass meters. The plant is equipped with temperature and pressure meters.
    For the analysis of the output gases of both reactors, continuous analyzers of CH4, CO2, H2O, CO, H2 and O2 are used.
    The experiments were carried out with an inventory of 2600 grams of 5-oxygen transporter with a particle size between 0.1 and 0.3 mm and a gas flow fed into the reduction reactor (1) of 186-550 lN / h of nitrogen The temperature of the reduction reactor (1) was varied between 800 ° C and 875 ° C and that of the oxidation reactor (2) was set at 800 ° C. As fuel a Chilean bituminous coal was used, with a particle size between 0.2 and 0.3 mm and a feed rate between 70 and 175 g / h.
    The following table shows the immediate and elementary analysis of bituminous coal used in the continuous pilot plant for the evaluation of the oxygen transporter.
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     Immediate analysis (wt.%)  Elementary analysis (wt.%)
     Humidity  14.2 C 52.4
     Ashes  15.3 H 5.24
     Volatile  34.6 N 0.77
     Fixed carbon  35.9 S 0.2
     O * 11.9
     PCI (kJ / kg)  18900
    Calculated by difference
    The steady state for the different operating conditions was maintained at 2 or less 1 hour in each condition for a total of 62 hours of operation with the O2 transport material.
    As an example of the excellent behavior of the conveyor in the combustion of coal, in Figure 6 (a), (b) and (c) show the efficiency of CO2 capture, and the combustion efficiency as a function of the reactor temperature of reduction, coal feed rate and solids flow rate. Complete combustion of coal to CO2 and H2O was observed in all experiments carried out at temperatures above 800 ° C. It can be seen that
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    obtained high CO2 capture values in all cases. The positive effect of the reduction reactor temperature on CO2 capture is remarkable, see Figure 6 (a). Thus, when the temperature of the reduction reactor was 875 ° C, 96.3% of the carbon in the carbon was captured, that is, only 3.7% of the incoming carbon exited with the oxidation reactor gases.
    An increase in the carbon feed rate caused the CO2 capture efficiency to decrease slightly as the amount of char lost to the air reactor increased; See figure 6 (b). In addition, it was observed that with carbon feed values of less than 0.1 kg / h, CO2 capture values greater than 99% were obtained (less than 1% of the coal fed was released as CO2 from the oxidation reactor) and also It obtained an excess of O2 gas in the exhaust gases of the reduction reactor. This is because at high values of the oxygen to fuel transporter ratio, the conversion reduction of the oxygen transporter was less than 50% and in these conditions the speed of generation of O2 by the transporter is very high, since This depends on the degree of reduction. By increasing the fuel feed rate, the ratio of oxygen to fuel transporter decreases, increasing the degree of reduction and decreasing the efficiency of CO2 capture, although complete combustion of coal was always maintained.
    Finally, Figure 6 (c) shows that increasing the speed of solids circulation causes an increase in CO2 capture efficiency. This is due to the fact that increasing the circulation speed of solids markedly decreases the conversion variation of the oxygen transporter by increasing the rate of generation of O2 for combustion and therefore improving the combustion rate. It should be noted that during the operation with the conveyor no agglomeration problems were observed in any of the pilot plant reactors during the 62 hours of experimentation. In addition, the material maintained its mechanical strength and its attrition rate at values similar to those measured with the unused material.
    Therefore, it is demonstrated with these tests that the material prepared according to the indicated procedure has suitable properties to be used as an oxygen transporter in a CLOU process.
    权利要求:
    Claims (19)
    [1]
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    1. Procedure for preparing O2 transport materials comprising the following stages:
    a) mix 30-50% by weight of CuO and 70-50% by weight of Mn3O4
    b) classify the particles of the mixture by size up to 0.4-0.8 mm
    c) prepare a suspension with solids concentration of 70-75%, 25-30% water,
    and additives binders, surfactants, dispersants and deflocculants
    d) classify suspension particles by size up to 0.6-1 mm
    e) subject the mixture obtained in the previous stage to granulation
    f) calcine the particles at a temperature of 1100-1150 ° C.
    [2]
    2. The method according to previous claim, wherein step a) is carried out using 34% by weight of CuO and 66% by weight of Mn3O4.
    [3]
    3. Method according to any of claims 1 and 2, wherein in step b) particles larger than 0.6 mm are rejected.
    [4]
    4. Method according to any one of claims 1 to 3, wherein in step b) particles with greater than 0.4 mm are rejected.
    [5]
    5. Method according to any one of claims 1 to 4, wherein step c) consists of a suspension with a solids concentration of 70-75%, 25-30% water, additives with binding properties, surfactants, dispersants and deflocculants and comprises The following sub-stages:
    [5]
    5.a) prepare a 10% binder solution with half the water to use
    keeping stirring
    [5]
    5.b) heat the second half of the water
    [5]
    5.c) add the previously prepared binder solution to the water with constant stirring until complete dissolution
    [5]
    5.d) add: surfactant, dispersant and deflocculant while maintaining constant agitation
    [5]
    5.e) add the solids mixture while maintaining constant stirring.
    [6]
    6. Method according to any of claims 1 to 5, wherein in step d) particles larger than 0.8 mm are rejected.
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    [7]
    7. Method according to any of claims 1 to 6, wherein in the
    step d) particles larger than 0.6 mm are rejected.
    [8]
    8. Method according to any of claims 1 to 7, wherein the step
    Granulation is carried out in a fluidized bed at a temperature of 70-90
    ° C.
    [9]
    9. Method according to any of claims 1 to 8, wherein step e) is carried out at a temperature of 80 ° C.
    [10]
    10. Method according to claim 1 to 9, wherein step f) is carried out at a temperature of 1125 ° C in an air flask by means of a heating ramp of 12 ° C / min and for a time of 2 h.
    [11]
    11. Product obtained by the procedure indicated in the preceding claims
    [12]
    12. Product obtained by the procedure described above that has the following properties:
    - high reactivity
    - density of 4.0 g / cm3
    - porosity of 12%
    - mechanical resistance of 2.0 N
    - AJI 3.0% attrition value,
    - attrition rate of 0.005% / h
    - 20,000 h half-life of particles of transport material
    [13]
    13. Use of the above product in a Chemical Looping with Oxygen Uncoupling (CLOU) process of solid combustion with inherent capture of CO2 in fluidized bed.
    [14]
    14. Use of the product described above for a CLOU process comprising the following steps:
    - decomposition of the oxygen transporter releasing gaseous oxygen
    - reaction of the fuel with oxygen, producing a pure stream of CO2 and H2O
    - The reduced conveyor of the reduction reactor is transported to the oxidation reactor, where it reacts with the oxygen in the air.
    DRAWINGS
    image 1
    The following figure is described in the state of the art
    Fig. 1
    image2
    image3
    Fig. 3
    image4
    image5
    AR 13
    n
    Air*-
    eleven
    L »
    li
    O », n2
    co2 + h2o
    .
    image6
    ¡Re N2 CO2 N2
    Fig. 5
    d
    C
    :2
    (/)
    3
    .Q
    AND
    or
    OR
    or
    ■ a
    .5
    or
    LU
    100
    95
    90
    85
    80
    75
    70
     --------- A A ------ A -------  - ** - ---------- A ------- A A ----------
     (to)  (b) (c)
     • _ ^
     • •  • ^ •
     --- = ► •
     • •
    840 860 880 0.00 0.05 0.10 0.15 0.20 0
    Temperature (° C) Feed rate
    of coal (kg / h)
    2 4 6 8 10 12
    Solids circulation speed (kg / h)
    100
    95
    90
    85
    80
    75
    70
    CO2 Capture Efficiency (%)
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    ES2682049B1|2019-07-10|O2 CONVEYOR PREPARATION PROCEDURE, PRODUCT AS OBTAINED AND ITS USE
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    ES2682049B1|2019-07-10|
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