EP2274095A2

EP2274095A2 - Oxidation-reduction active mass and chemical-loop combustion method

Info

Publication number: EP2274095A2
Application number: EP09745914A
Authority: EP
Inventors: Arnold Lambert; Thierry Gauthier.
Original assignee: IFP Energies Nouvelles IFPEN; Total SE
Current assignee: IFP Energies Nouvelles IFPEN; TotalEnergies SE
Priority date: 2008-04-30
Filing date: 2009-04-29
Publication date: 2011-01-19
Also published as: WO2009138595A2; WO2009138595A3; US20110054049A1; FR2930733B1; FR2930733A1

Abstract

The invention relates to a method for chemical-loop oxidation-reduction combustion that uses an active mass including a binder in the form of a fluidised-bed catalytic-cracking catalyst containing silica and alumina, and a metal oxide active phase. The active mass is obtained by impregnating metal salts on a new or used catalytic-cracking catalyst. Advantageously, the invention pertains to the field of CO₂ trapping.

Description

ACTIVE OXYDO-REDUCTION MASS AND CHEMICAL LOOP COMBUSTION METHOD

FIELD OF THE INVENTION

The invention relates to an active mass and a process for capturing CO ₂ in a fluidized bed employing this active mass.

We have discovered that the catalyst that has been used in fluidized catalytic cracking plants, generally considered as a valuable industrial waste and usually incorporated into cements or road coatings, may after impregnation of a metal salt be used in a combustion process in a redox loop, in particular for CO ₂ sequestration.

The invention consists in using silica and alumina catalysts shaped to have facilitated flow and transport properties, such as the catalysts used in the catalytic cracking process, to impregnate these catalysts with solutions. of metal salts, preferably based on iron, nickel, copper, cobalt or manganese, and using these impregnated catalysts in a combustion process consisting of a zone in which the fuel is oxidized by the oxygen supplied by reduction of the impregnated catalyst, and an oxidation zone of the catalyst impregnated in the presence of air, the impregnated catalyst circulating continuously between these two zones of reduction and oxidation. The method makes it possible to carry out the combustion of the fuel and in particular to produce nitrogen-free concentrated CO ₂ fumes facilitating the sequestration of CO ₂ . The impregnated catalyst according to the invention (active mass) is particularly interesting because it has the physical properties facilitating its circulation (diameter, density) and the mechanical properties such as resistance to attrition facilitating its implementation in such a way. process.

Terminology

Catalytic cracking (FCC: "Fluid Catalytic Cracking"): Catalytic cracking is a process for converting heavy petroleum fractions without the addition of hydrogen, using a high temperature (generally of the order of 500 to 600 ^° C.) and a cracking catalyst (generally an acidic solid such a solid based on silica and alumina or a zeolite). The catalyst is in the form of a fine powder (approximately 50 to 100 microns in average diameter) which circulates in the fluidized state in the installation (catalytic cracking in a fluidized bed). The heavy charges are for example vacuum distillates, deasphalted oils or petroleum residues hydrotreated more or less severely, which are converted into light fractions (LPG, gasoline) by the catalytic cracking process.

Process of Chemical Looping Combustion or CLC: In the remainder of the text, the term CLC (Chemical Looping Combustion) is understood to mean a process of oxidation-reduction in loop on active mass. It should be noted that, in general, the terms oxidation and reduction are used in relation to the respectively oxidized or reduced state of the active mass. The oxidation reactor is one in which the redox mass is oxidized and the reduction reactor is the reactor in which the redox mass is reduced.

Prior art

In a context of increasing global energy demand, the capture of carbon dioxide for sequestration has become an unavoidable necessity in order to limit the emission of greenhouse gases that are harmful to the environment. The process of oxidation-reduction in active loop, or Chemical Looping Combustion (CLC) in the English terminology, makes it possible to produce energy from hydrocarbon fuels while facilitating the capture of the carbon dioxide emitted during of combustion.

The CLC process consists in carrying out oxidation-reduction reactions of an active mass in order to decompose the combustion reaction into two successive reactions. A first oxidation reaction of the active mass, with air or a gas acting as an oxidant, makes it possible to oxidize the active mass. A second reduction reaction of the active mass thus oxidized by means of a reducing gas then makes it possible to obtain a reusable active mass and a gaseous mixture essentially comprising carbon dioxide and water, or even gas synthesis product containing hydrogen and nitric oxide. This technique therefore makes it possible to isolate carbon dioxide or synthesis gas in a gaseous mixture that is substantially free of oxygen and nitrogen.

As combustion is generally exothermic, it is possible to produce energy from this process, in the form of steam or electricity, by exchange in the circulation loop of the active mass or on the gaseous effluents downstream of the combustion or oxidation reactions.

US Pat. No. 5,447,024 describes a CLC process comprising a first reactor for reducing an active mass using a reducing gas and a second oxidation reactor for restoring the active mass in its oxidized state by means of a reaction. oxidation with moist air. Circulating fluidized bed technology is used to allow the continuous passage of the active mass from its oxidized state to its reduced state.

The active mass, passing alternately from its oxidized form to its reduced form and vice versa, describes an oxidation-reduction cycle.

Thus, in the reduction reactor, the active mass (M _x O _y ) is first reduced to the state M _x Oy _-2n - _{m / 2} , via a hydrocarbon C _n H _m , which is correlatively oxidized to CO ₂ and H ₂ O, according to the reaction (1), or optionally in CO + H ₂ mixture according to the proportions used.

(1) C _n H _m + M _x O _y "* n CO ₂ + m / 2 H ₂ O + M _x O _{y-2n-m / 2}

In the oxidation reactor, the active mass is restored to its oxidized state (M _x O _y ) in contact with the air according to reaction (2), before returning to the first reactor.

(2) M _x O _{y-2n-m / 2} + (n + m / 4) O ₂ ^" * M _x O _y

The efficiency of the CLC process in circulating fluidized bed relies to a large extent on the physicochemical properties of the active redox active mass. The reactivity of the oxidation-reduction pair (s) involved as well as the associated oxygen transfer capacity are parameters that influence the design of the reactors and the particle circulation speeds. The lifetime of the particles as for it depends on the mechanical resistance of the particles as well as their chemical stability.

In order to obtain particles that can be used for this process, the particles used are generally composed of a pair or a set of oxido-reducing pairs chosen from CuO / Cu, Cu ₂ O / Cu, NiO / Ni, Fe ₂ O ₃ / Fe ₃ O ₄ , FeO / Fe, Fe ₃ O ₄ / FeO, MnO ₂ / Mn ₂ O ₃ , Mn ₂ O ₃ / Mn ₃ O ₄ , Mn ₃ O ₄ / MnO, MnO / Mn, Co ₃ O ₄ / CoO, CoO / Co, and a binder providing the necessary physicochemical stability. No. 5,447,024 claims as active mass the use of the redox / NiO / Ni pair, alone or in combination with the YSZ binder (which is defined by yttria-stabilized zirconia). In addition to improving the mechanical strength of the particles, yttria zirconia being ionic conductor O ^{2 '} ions at the temperatures of use, the reactivity of the NiO / Ni / YSZ system is improved.

Many types of binders in addition to the yttria zirconia (YSZ) already mentioned have been studied in the literature, in order to increase the mechanical strength of the particles at a lower cost than IΥSZ. Among these, there may be mentioned alumina, spinel of aluminate metal, titanium dioxide, silica, zirconia, kaolin.

The weight ratio of the oxido-reducing couple / binder is generally around 60/40 in order to obtain particles with good mechanical strength as well as sufficient redox properties (oxidation rate, reduction and oxygen transfer capacity). .

The document EP 1 747 813 describes, for its part, oxido-reducing masses comprising a pair or a set of oxidation-reduction pairs, chosen from the group formed by CuO / Cu, Cu ₂ O / Cu, NiO / Ni , Fe ₂ O ₃ ZFe ₃ O ₄ , FeO / Fe, Fe ₃ O ₄ / FeO, MnO ₂ ZMn ₂ O ₃ , Mn ₂ O ₃ ZMn ₃ O ₄ , Mn ₃ O ₄ ZMnO, MnO ₂ Mn, Co ₃ O ₄ ZCoO CoOZCo in combination with a ceria-zirconia type binder to increase the oxygen transfer capacity of said masses.

The use of a binder makes it possible to provide the necessary mechanical strength for the particles, but it also increases the cost price of the particles involved in the CLC process.

It is therefore important to find an optimized catalyst for the low-cost active-mass loop-oxidation process. To reduce the impact of the cost of particles on the price of CO ₂ capture by CLC, the possibility of using an ilmenite ore (FeTiO ₃ ) has been demonstrated by the Institute of Catalisis and Petroleoquimica (CSIC), Madrid ("Titania-supported iron oxide as oxygen carrier for chemical-looping combustion of methane, Corbella, Beatriz M. Palacios, Jose Maria, Fuel (2006), Volume Date 2007, 86 (1-2), 113-122).

We have discovered that the use of waste from the refining industry in the form of catalytic cracking catalysts used as a binder in combination with one or more metal oxides makes it possible to obtain an active mass for the CLC at a cost price. even weaker than the geometric and structural characteristics of the FCC catalyst particles are optimized for fluidization and attrition resistance and the amounts of spent catalyst generated by the fluidized catalytic cracking process are large.

Indeed, the catalytic cracking process is a process used worldwide to convert heavy petroleum fractions such as vacuum distillates, deasphalted oils or petroleum residues hydrotreated more or less severely, into light fractions (LPG, gasoline).

In the catalytic cracking process, the feedstock is converted by carrying out acid catalytic cracking reactions. The presence of metals on the catalyst is detrimental to the operation of the process. For these purposes, to maintain an acceptable level of performance, refiners routinely add fresh (non-metal-containing) cracking catalyst and draw off "spent" cracking catalyst from the unit to maintain a metal concentration. on the reasonable catalyst.

The addition of fresh catalyst in the units to maintain stable catalytic activity over time is therefore important. The more the refiner processes metallized fillers, the more catalyst must be added to maintain a reasonable metal content on the catalyst.

However, there is currently no noble use of this spent catalyst. it is usually sent to cement plants or used as a coating agent for road surfaces. On a worldwide scale, this material nevertheless represents very large quantities. Several hundred thousand tons are available annually worldwide, at a marginal cost since the spent catalyst has no noble use and can therefore be considered as a waste.

The catalysts used in the catalytic cracking units contain, after use, between 50 and 20000 ppm of metals which decrease their catalytic activity for this process, in particular Ni and V. Such a content is not sufficient to consider using these catalysts. materials currently considered as waste in a power plant by the active mass loop oxidation reduction process, because the flow rates of solid required for combustion would be too high. However, after impregnation of the catalyst with one or more metal salts and calcination, the particles obtained have interesting characteristics for their use in a circulating fluidized bed: granulometry adapted to fluidization, redox properties, resistance to attrition.

OBJECTS OF THE INVENTION

The invention relates to an active mass for combustion comprising a binder in the form of a fluidized catalytic cracking catalyst (new or spent) based on silica and alumina and a metal oxide active phase obtained by impregnation with metal salts on the catalyst.

The invention finally relates to a loop-type oxidation-reduction combustion method using as active mass said impregnated catalyst.

DESCRIPTION OF THE INVENTION

The invention consists in taking a catalyst used for the conversion of petroleum feeds, fresh or after use in a catalytic cracking unit, to impregnate it with one or more metal salts, and then using it in a process of oxidation-reduction loop on active mass Chemical Looping type.

Summary of the invention

The invention relates to a process for the combustion of solid, liquid or gaseous hydrocarbons by chemical loop-redox using an active mass comprising at least one binder based on silica and alumina in the form of a catalyst for catalytic cracking. fluidized bed and at least one metal oxide at a content of between 5 and 95% by weight.

Advantageously, the active mass is a catalytic cracking catalyst in a spent fluidized bed.

Preferably, the content of metal oxide is between 20 and 70% by weight, very preferably between 30 and 60%. Advantageously, the metal oxide is based on at least one element chosen from

Co, Fe, Mn, Cu, Ni, preferentially based on Fe.

The combustion can be total or partial. When the combustion is partial, the process allows the production of synthesis gas (CO + H2), which may constitute a gaseous feedstock that can be used in the Fischer-Tropsch liquid hydrocarbon synthesis process.

In this case, when the gas allowing the fluidization of the active mass comprises water vapor, a gas mixture comprising (CO2 + H2) is produced at the outlet. The process can then be used for the production of hydrogen.

The process according to the invention (partial or total combustion) can be used for the production of energy.

The invention relates to a process for capturing CO2 by total combustion in a chemical loop in a process according to the invention.

In the process according to the invention, the active mass can be prepared as follows: a. a step of impregnation with at least one metal salt of a catalytic cracking process catalyst in a fluidized bed; b. a step of drying and / or calcination of the impregnated catalyst. The active mass can be: b. dried, c. injected after drying in the oxidation reactor.

The active mass can be: b. calcined, c. injected after calcination in the reduction reactor.

Detailed description of the invention

Description of Catalyst catalyst

In the catalytic cracking process, the feedstock is converted by carrying out acid catalytic cracking reactions. It is well known that the acidity of the catalyst can be obtained by using silica and alumina solids, or complex crystalline structures such as zeolites. The catalytic cracking catalyst generally comprises one or more zeolites.

During the reaction, coke is formed, deposited on the catalyst and led to its rapid deactivation. It is therefore necessary to continuously regenerate the catalyst. The process is therefore generally composed of a reaction zone, in which the feedstock meets the catalyst under the appropriate conditions, and a regeneration zone, in which the coke deposited on the catalyst during the reaction is burned in the presence of oxygen. . The catalyst flows continuously between the reaction zone and the regeneration zone. After the regeneration, the catalyst has its catalytic activity restored by burning the coke. The catalyst therefore undergoes a succession of reaction-regeneration cycles.

In this process, the constraints related to the regeneration of the catalyst and the thermal balance of the unit are such that the circulation of catalyst is very important between the two enclosures. For a given charge rate, the circulation of catalyst is generally around 3 to 10 times the charge rate, generally 5 to 7 times, and for a unit processing about 40000 BPD, average capacity of the units currently in operation, the circulation The catalyst continuous rate is typically about 1300-1800 rpm, the average residence time of the catalyst to circumnavigate the unit generally being between 3 and 10 minutes.

Throughout the process, the catalyst is maintained in a fluid state by controlling the flow of fluidizing gas at any point in the unit. This is essential to ensure the operation of the process and this can only be achieved if the catalyst particles are shaped with particular properties: it is essential that the particles belong to Group A of the Geldart Periodic Table (Geldart D. Powder Technology, 7, p285-292 (1973)). Preferably, the average (Sauter) diameter of the particles will be between 50 and 100 microns, preferably around 70 microns, and the grain density will be between 1000 and 3500, or even 5000 kg / m3 if the diameter of the particles tends towards 50 microns. In addition, it is preferable that the particle size distribution of the powder is extended. This objective is achieved through the shaping of the catalyst by techniques such as spray drying. Under these conditions, it is possible to manufacture powders whose average diameter is between 50 and 100 microns, but which contain significant amounts of fine particles (preferably 5 to 20% by weight).

In fluidized catalytic cracking, the catalyst undergoes significant deactivation between each reaction cycle and each regeneration cycle associated with coke deposition. The type of charges processed in this process generally contains metals, for example nickel, vanadium, iron (Ni, V, Fe) in small amounts. These metals, during the contact between the charge and the catalyst, are deposited on the catalyst and accumulate gradually. During regeneration, driving according to technologies at temperatures ranging between 600 and 850 ⁰ C, typically around 750 ⁰ C, in contact with air and water vapor, the catalyst can undergo modifications, amplified if the metal load deposited on the catalyst is important. In general, the feedstock to be treated in the catalytic cracking unit ("Fluid Catalytic Cracking" or FCC) contains from 0 to 50 ppm, preferably from 0 to 20 ppm of nickel and vanadium (Ni + V). The iron content of the charges is more occasional, but perhaps significant in the treated charges. The concentration of metals on the catalyst in operation naturally depends on the concentration of metals in the feeds, it generally varies between 0 and 20000 ppm for nickel and vanadium, generally between 5 and 10,000 ppm. In an episodic manner, the concentration may be higher when constituents such as iron are encountered in the feeds to be converted.

The presence of metals on the catalyst is detrimental to the operation of the process. The hydrothermal stability of the acid catalyst (silica-alumina) is affected by the presence of metals, particularly vanadium. In addition, some metals such as nickel promote the dehydrogenation of hydrocarbons and thus lead to higher coke yields. Coke combustion is also sensitive to metal deposition on the catalyst. In the absence of oxygen, the CO / CO ₂ ratio varies a lot depending on these deposits.

Assuming that all the metals of the feed are deposited on the catalyst, the addition of fresh catalyst needed to maintain a reasonable metal concentration CMc on the catalyst as a function of the metal concentration in the feed CMf can be simply estimated. load flow FF: A = FF * CMf / CMc.

For a unit treating 6000 t / d of charge, if the metal content (Ni + V) of the charge is 4 ppm, it will be necessary to add 3 t / d of fresh catalyst to maintain a metal content of 8000 ppm on the catalyst. If the metal content is higher, for example 20 ppm of Ni and V, a case frequently encountered in the catalytic cracking residue units, the addition of catalyst required will then be 15 t / d.

In order to maintain a constant inventory in the unit, it will therefore be necessary to extract an equivalent quantity of catalyst from the unit, taking into account the catalyst entrainment with the products and the fumes, which are however relatively low (generally of the order of 1 t / d). This catalyst withdrawn from the unit represents a significant amount of catalyst still having satisfactory flow properties and high porosity (the specific surface is still greater than 50 m ² / g).

Advantageously, a fresh fluidized catalytic cracking catalyst is composed of zeolite and matrix. The zeolite most commonly used is the zeolite USY. In some cases, other zeolites are used, such as ZSM-5, often as an additive of 1 to 15% in the inventory of the catalytic cracking unit to give the catalyst particular properties and for example to maximize the production. of propylene. The zeolite content of the catalyst is generally between 10 and 50% by weight. Preferably, a catalytic cracking catalyst comprises a zeolite USY or ZSM5 integrated in a matrix of silica alumina of variable composition.

The specific surface area of the fresh catalyst is generally close to 300-350 m ² / g with the zeolite USY and 150 m ² / g with the ZSM5. With the zeolite USY, the specific surface area developed by the matrix is approximately 30 to 150 m ² / g _/ generally around 60 m ² / g and the specific surface area developed by the zeolite varies between 150 and 300 m ² / g. , generally around 250 m ² / g. In the spent catalyst, these properties are modified. The specific surface of the spent catalyst is generally close to 100-180 m ² / g with the zeolite USY. The specific surface area developed by the matrix is then approximately 20 to 70 m ² / g, typically 30 m ² / g, and the specific surface area developed by the zeolite varies between 50 and 150 m ² / g, generally around 100. -120 m ² / g. The molecular Si / Al ratio of the ultrastable zeolite varies from new catalyst to spent catalyst. Thus, in a new catalyst, the Si / Al ratio of the zeolite is generally close to 2 to 4. Due to dealumination linked to deactivation in the process, this ratio increases and is generally from 4 to 10, often close from 5-6. Rare earth oxides are sometimes incorporated into the catalyst to promote the hydrothermal stability of the zeolite at 0-5% wt.

Preparation of catalysts that can be used in the CLC process according to the invention

FCC catalysts from the catalytic cracking process contain between 0 and 20000 ppm nickel and vanadium, and sometimes iron. Nickel and iron have interesting redox properties for their use in the context of chemical loop combustion and have been extensively studied.

As the metal content of the used FCC catalysts is very low, the direct use of these catalysts in the chemical loop combustion technology would require a large mass flow of catalyst and practically unimaginable in the current state of circulating fluidized bed technology. . In order to make this waste from the refining industry useful for chemical loop combustion, the amount of metal contained in spent catalysts can be increased by impregnating metal salts. The traces of nickel, iron, and vanadium present in the catalyst of

Used FCCs contribute to the oxygen transfer capacity of the materials obtained after impregnation / calcification.

Similarly, a fresh FCC catalyst, having by its destination an optimized particle size and attrition resistance for fluidization, can be impregnated in order to obtain an oxidation-reduction active mass with an oxide content (s). ) metal (s) according to the invention.

The dry impregnation method is advantageously used (or "incipient wetness" according to the English terminology) in order not to modify the initial size distribution of the particles, but any other type of impregnation can be used, in particular excess impregnation.

After impregnation, the particles can be either dried or calcined. Depending on the initial pore volume of the catalyst particles, the concentration of the salt solution (s) metal (s) and the amount of oxide (s) to be deposited, the particles may undergo several impregnation / drying and / or successive impregnations / calcinations. The amount of impregnated metal salts is such that the particles contain between 5 and

95% by mass of active metal oxide (s) (Ni, Cu, Fe, Co, Mn) after calcination between

600 and 1400 ⁰ C, preferably between 20 and 80% by weight, and even more preferably between 40 and 70% by weight. The matrix composed of alumino-silicate and zeolite of the FCC catalyst (fresh or spent) then acts as a binder for the metal oxide (s).

After calcination, the metal salts impregnated on the particles are in oxidized form. The calcination step may optionally be carried out directly by introducing the FCC catalyst impregnated into the oxidation reactor, in which case the calcination effluents of the metal precursors used will be at the outlet of said oxidation reactor. The impregnation of the FCC catalyst is preferably carried out by water-soluble metal precursors, such as nitrates, sulphates, acetates, formates, halides or perchlorates. The metal salts soluble in organic solvents can also be used.

Description of the process for capturing CO2 in a fluidized bed by means of a chemical loop combustion

The active compounds according to the invention act as oxygen carriers for the oxidation-reduction loop combustion process and can be used to treat liquid gaseous fuels (eg natural gas, syngas) ( eg, fuel, bitumen ...), or solids (eg coal) in a circulating fluidized bed.

The impregnated catalyst is oxidized in a fluidized bed at a temperature between 600 and 1400 ⁰ C, preferably between 800 and 1000 ⁰ C. It is then transferred to another fluidized bed reactor where it is brought into contact with the fuel at a temperature between 600 and 1400 ⁰ C, preferably between 800 and 1000 ⁰ C. The contact time typically varies between 10 seconds and 10 minutes, preferably between 1 and 5 minutes. The ratio between the amount of solid active mass and of charge to be burned is between 1 and 1000, preferably between 10 and 500.

The combustion can be partial or total.

In the case of partial combustion, the active mass / fuel ratio is adjusted so as to achieve the partial oxidation of the fuel, producing a synthesis gas in the form of a CO + H ₂ mixture. The process can therefore be used for the production of synthesis gas.

This synthesis gas can be used as a feedstock for other chemical transformation processes, for example the Fischer Tropsch process making it possible to produce liquid hydrocarbons with long hydrocarbon chains which can subsequently be used as fuel bases from synthesis gas.

In the case where the fluidization gas used is water vapor or a mixture of water vapor and other gas (s), the reaction of CO gas with water (or water gas shift in English terms) Saxons, CO + H ₂ O <* ^• CO ₂ + H ₂ ) can also take place, resulting in the production of a CO ₂ + H ₂ mixture at the outlet of the reactor. In this case, the flue gas can be used for energy production purposes given its calorific value.

It is also possible to use this gas for the production of hydrogen, for example to supply hydrogenation units, hydrotreating units for refining or a hydrogen distribution network (after reaction of water gas shift).

In the case of total combustion, the gas flow at the outlet of the reduction reactor is composed essentially of CO ₂ and water vapor. A flow of CO ₂ ready to be sequestered is then obtained by condensation of the water vapor. The energy production is integrated in the Chemical Looping Combustion process by heat exchange in the reaction zone and on the fumes which are cooled.

Depending on the use of the flue gases, the process pressure will be adjusted. Thus, to achieve total combustion, it will be advantageous to work at low pressure to minimize the energy cost of compressing the gases and thus maximize the energy efficiency of the installation. In order to produce synthesis gas, pressure may be advantageously used in certain cases in order to avoid compression of the synthesis gas upstream of the downstream synthesis process: the Fischer Tropsch process working for example at pressures between 20 and 40 bars, there may be interest in producing the gas at a higher pressure.

Description of figures

Figures 1 to 7 illustrate the invention without limiting the scope.

Figure 1: Figure 1 shows the evolution of the particle size distribution between a fresh catalytic cracking catalyst (Figure IA) and the active mass obtained after impregnation of metal salts on said catalyst and calcination (Figure 1B) (Example 1).

FIG. 2 represents the evolution of the particle size distribution between a spent catalytic cracking catalyst constituting the binder of the active mass according to the invention (FIG. 2A) and the active mass according to the invention obtained after impregnation with metal salts on said spent catalyst and calcination (Figure 2B) (Example 2).

3 shows the evolution of the particle size distribution between a spent catalytic cracking catalyst constituting the binder of the active mass according to FIG. the invention (Figure 3A) and the active composition according to the invention obtained after impregnation of metal salts on said spent catalyst and calcination (Figure 3B) (Example 3) _^

Figure 4: Figure 4 shows the evolution of the loss and recovery of relative weight of the Ilmenite sample (non-compliant) as a function of time for 5 successive reduction / oxidation cycles. In accordance with the protocol described in Example 4, the nature of the gases used (air, nitrogen, gaseous mixture CH ₄ / CO ₂ ) as well as the temperature vary during the course of each cycle.

Figure 5: Figure 5 shows the evolution of the loss and recovery of relative weight of the sample of Example 1 (impregnated fresh catalytic cracking catalyst according to the invention) as a function of time for 5 cycles successive reduction / oxidation. In accordance with the protocol described in Example 4, the nature of the gases used (air, nitrogen, gaseous mixture CH ₄ / CO ₂ ) as well as the temperature vary during the course of each cycle.

Figure 6: Figure 6 shows the evolution of the loss and recovery of relative weight of the sample of Example 2 (according to the invention) as a function of time for 5 successive reduction / oxidation cycles. In accordance with the protocol described in Example 4, the nature of the gases used (air, nitrogen, gaseous mixture CH ₄ / CO ₂ ) as well as the temperature vary during the course of each cycle.

Figure 7: Figure 7 shows the evolution of the loss and recovery of relative weight of the sample of Example 3 (according to the invention) as a function of time for 5 successive reduction / oxidation cycles. In accordance with the protocol described in Example 4, the nature of the gases used (air, nitrogen, gaseous mixture CH ₄ / CO ₂ ) as well as the temperature vary during the course of each cycle.

Examples

The examples below illustrate the invention without limitation.

Example 1 Catalyst of FCC not used industrially An FCC catalyst not used industrially (fresh) having a BET surface area of 220 m ² / g and an initial pore volume of 0.8 ml / g is dry impregnated with a nitrate solution of iron containing 13.9% by weight equivalent Fe ₂ O ₃ . After calcination in air at 600 ^° C., the impregnated catalyst contains 12% by weight of iron oxide. The operations impregnation / drying / calcination are repeated three times, the particles of active mass obtained having a total content by weight of Fe ₂ O ₃ of 32%.

Example 2 Catalyst of FCC used industrially weakly loaded with metals

A spent FCC catalyst having been taken from an industrial unit containing 4000 ppm nickel (Ni) and 2000 ppm vanadium (V), with a BET surface area of 107 m ² / g and an initial pore volume of 0.67 ml / g is dry impregnated with a solution of iron nitrate containing 13.9% by weight equivalent Fe ₂ O ₃ . After calcination in air at 600 ^° C., the impregnated catalyst contains 11% by weight of iron oxide. The impregnation / drying / calcination operations are repeated three times, the particles of active mass obtained having a total content by weight of Fe ₂ O ₃ of 30%.

Example 3 Catalyst of FCC used industrially heavily loaded with metals

An industrially used FCC catalyst containing no nickel (Ni) but containing 100 ppm vanadium (V), with a BET surface area of 192 m ² / g and an initial pore volume of 0.64 ml / g is impregnated dry with a solution of iron nitrate containing 13.9% by weight equivalent Fe ₂ O ₃ . After calcination in air at 600 ^° C., the impregnated catalyst contains 12% by weight of iron oxide. The impregnation / drying / calcination operations are repeated three times, the particles of active mass obtained having a total content by weight of Fe ₂ O ₃ of 33%.

Particle size distribution

The size distribution of the particles was measured by wet laser particle size, and the results are collated in the table below.

Figures 1, 2 and 3 respectively represent the size distribution of the particles of Examples 1, 2 and 3. After dry impregnation and calcination, the particle size distribution is similar to the initial distribution, which allows the use of FCC catalyst particles in a circulating fluidized bed combustion process without additional shaping step.

Attrition measures

An ASTM attrition test D5757-00 simulating the attrition of fluidized bed particles was performed on the samples before and after impregnation / calcination. Impregnation and calcination slightly reduce the attrition resistance of the particles. The mechanical strength of the impregnated / calcined particles is suitable for use in a circulating fluidized bed.

The table below summarizes the inventory losses, in mass%, associated with attrition in the standard IFP test.

Example 4: Reactivity

A SETARAM thermobalance has been equipped with a gas supply automaton to simulate the successive reduction / oxidation and oxidation stages to which the particles are subjected in an active mass-based oxidation-reduction method, of the type "Chemical Looping Combustion".

The tests are carried out at a temperature of 900 ^° C., with 65 mg (± 2 mg) of sample contained in a platinum boat. In order to allow a comparison between the different samples, the size distribution of the particles is selected between 30 and 40 μm by sieving. The reducing gas used is composed of 10% CH ₄ , 25% CO ₂ and 65% N ₂ , and the oxidation gas is dry air.

For safety reasons, a nitrogen sweep of the thermobalance furnaces is carried out systematically between the oxidation and reduction steps.

For each sample, five successive reduction / oxidation cycles are carried out according to the following protocol:

1) temperature rise under air (50 ml / min): from 20 ^° C. to 800 ^° C.: 40 ° C./min of 800 ^° C. to 900 ^° C.: 5 ° C./min

2) Scanning with nitrogen for 5minl5s, flow rate 80ml / min 3) injection of a CH ₄ / CO ₂ mixture for 20min, at 50ml / min 4) Nitrogen sweep 5minl5s

5) air injection, 20min, 50ml / min

Steps 2 to 5 are then repeated four additional times, at 900 ^° C.

Ability to

Reduction rate Oxygen transfer rate of oxidation (mmol 0 ₂ / min g) (mmol 0 ₂ / min g) (%)

Example 1 2.6 0.37 ± 0.02 0.54 ± 0.03

Example 2 2.7 0.40 ± 0.02 0.55 ± 0.03

Example 3 3.0 0.40 ± 0.02 0.64 ± 0.03

Ilmenite 4.1 0.19 ± 0.02 1.08 ± 0.06

The rates of reduction and oxidation are calculated from the slopes related to the loss and the weight gain (respectively) observed, between the second and the third minute after the passage under reducing gas, and averaged over the last four cycles. redox.

The results obtained with an ilmenite sample and the active mass samples of Examples 1 to 3 are collated in Figures 4 to 7. In these figures is shown the evolution of the loss and recovery of relative weight of the sample versus time for five successive reduction / oxidation cycles. In accordance with the protocol described above, the nature of the gases used varies during the course of each cycle.

The reduction rates measured by thermobalance on the particles according to the invention are similar for the three examples, and higher than that observed with ilmenite. The oxidation rates measured are slower with the particles according to the invention than with ilmenite. Similarly, the oxygen transfer capacity of the materials according to the invention is lower than ilmenite, but it is possible to achieve the same transfer capacity by impregnating more metals.

The comparison with ilmenite is interesting because this material is a natural oxide available on a large scale and at a relatively low cost, the use of which can be envisaged on a large scale for the combustion of coal by CLC circulating fluidized bed, the objective being to minimize the cost of the metal oxide in the process. It can be seen that the use of a fresh catalytic cracking catalyst such as the use of a spent catalytic cracking catalyst, initially considered as waste from the refining industry, makes it possible to obtain similar performances at low cost also. .

Claims

A method for the combustion of solid, liquid or gaseous hydrocarbons by chemical loop-redox using an active mass comprising at least one binder based on silica and alumina in the form of a catalytic cracking catalyst in a fluidized bed and at least one metal oxide at a content of between 5 and 95% by weight.

The process of claim 1 wherein the binder is a spent fluidized catalytic cracking catalyst.

3. Method according to claim 1 or 2 wherein the metal oxide content is between 20 and 70% by mass.

4. The method of claim 3 wherein the metal oxide content is between 30 and 60%.

5. Method according to one of the preceding claims wherein the metal oxide is based on at least one element selected from Co, Fe, Mn, Cu, Ni.

6. The process of claim 5 wherein the metal oxide is Fe-based.

7. Method according to one of the preceding claims wherein the combustion is total.

8. Method according to one of claims 1 to 6 wherein the combustion is partial.

9. Process for producing syngas (CO + H2) according to claim 8.

10. The method of claim 8 wherein the gas for fluidization of the active mass comprises water vapor and wherein is output a gas mixture comprising (CO2 + H2).

11. Method according to one of the preceding claims for the production of energy.

12. Process according to claim 10 for the production of hydrogen.

13. Process according to claim 9 for the Fischer-Tropsch synthesis of liquid hydrocarbons from the synthesis gas (CO + H2).

14. The method of claim 7 for capturing CO2.

15. Method according to one of the preceding claims wherein the active mass is prepared by: a. a step of impregnation with at least one metal salt of a catalytic cracking process catalyst in a fluidized bed; b. a step of drying and / or calcination of the impregnated catalyst.

The method of claim 15 wherein the active mass is: b. dried, c. injected after drying in the oxidation reactor.

17. The method of claim 15 wherein the active mass is: b. calcined, c. injected after calcination in the reduction reactor.