WO2018115345A1 - Solide porteur d'oxygène macroporeux avec feldspath/felpdspathoïde réfractaire, son procédé de préparation, son utilisation dans un procédé d'oxydo-réduction en boucle chimique - Google Patents
Solide porteur d'oxygène macroporeux avec feldspath/felpdspathoïde réfractaire, son procédé de préparation, son utilisation dans un procédé d'oxydo-réduction en boucle chimique Download PDFInfo
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- WO2018115345A1 WO2018115345A1 PCT/EP2017/084209 EP2017084209W WO2018115345A1 WO 2018115345 A1 WO2018115345 A1 WO 2018115345A1 EP 2017084209 W EP2017084209 W EP 2017084209W WO 2018115345 A1 WO2018115345 A1 WO 2018115345A1
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- Prior art keywords
- oxygen
- particles
- solid
- zeolite
- ceramic matrix
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- 239000007787 solid Substances 0.000 title claims abstract description 219
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 153
- 239000001301 oxygen Substances 0.000 title claims abstract description 144
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 238000000034 method Methods 0.000 title claims abstract description 99
- 230000033116 oxidation-reduction process Effects 0.000 title claims abstract description 56
- 239000010433 feldspar Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 255
- 239000010457 zeolite Substances 0.000 claims abstract description 141
- 239000011159 matrix material Substances 0.000 claims abstract description 116
- 239000000919 ceramic Substances 0.000 claims abstract description 98
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 82
- 239000002243 precursor Substances 0.000 claims abstract description 74
- 239000013078 crystal Substances 0.000 claims abstract description 35
- 238000002844 melting Methods 0.000 claims abstract description 23
- 230000008018 melting Effects 0.000 claims abstract description 23
- 238000002485 combustion reaction Methods 0.000 claims abstract description 22
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 17
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims description 85
- 230000008569 process Effects 0.000 claims description 83
- 238000009826 distribution Methods 0.000 claims description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 54
- 239000010949 copper Substances 0.000 claims description 54
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 51
- 239000000126 substance Substances 0.000 claims description 49
- 229910052802 copper Inorganic materials 0.000 claims description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 41
- 238000001354 calcination Methods 0.000 claims description 41
- 238000007254 oxidation reaction Methods 0.000 claims description 36
- 230000009467 reduction Effects 0.000 claims description 36
- 230000003647 oxidation Effects 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 31
- 229910052753 mercury Inorganic materials 0.000 claims description 31
- 239000011230 binding agent Substances 0.000 claims description 29
- 239000000377 silicon dioxide Substances 0.000 claims description 29
- 238000002459 porosimetry Methods 0.000 claims description 27
- 150000002500 ions Chemical class 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
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- 239000004927 clay Substances 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
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- 238000007493 shaping process Methods 0.000 claims description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 18
- 238000005470 impregnation Methods 0.000 claims description 18
- 229910052788 barium Inorganic materials 0.000 claims description 17
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- 238000005406 washing Methods 0.000 claims description 16
- 125000002091 cationic group Chemical group 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 150000004645 aluminates Chemical class 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000005751 Copper oxide Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
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- 229910052596 spinel Inorganic materials 0.000 claims description 8
- 239000011029 spinel Substances 0.000 claims description 8
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- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 claims description 6
- 230000002468 redox effect Effects 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000005341 cation exchange Methods 0.000 claims description 4
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- 238000004320 controlled atmosphere Methods 0.000 claims description 4
- 229910001462 kalsilite Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 229910001597 celsian Inorganic materials 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 53
- 239000007789 gas Substances 0.000 description 40
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- 238000006243 chemical reaction Methods 0.000 description 35
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- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000010586 diagram Methods 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 13
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- 238000005755 formation reaction Methods 0.000 description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 9
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000013507 mapping Methods 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 239000012690 zeolite precursor Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052664 nepheline Inorganic materials 0.000 description 7
- 239000010434 nepheline Substances 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 5
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- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 4
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
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- 229910052712 strontium Inorganic materials 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
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- 238000004438 BET method Methods 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000000177 wavelength dispersive X-ray spectroscopy Methods 0.000 description 1
- 238000005550 wet granulation Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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Definitions
- the present invention relates to an oxygen carrier solid, its preparation and its use in an oxidation-reduction process in chemical loop on active mass, commonly known as "Chemical Looping" according to the English terminology.
- the new type of oxygen carrier solid according to the invention can be used in a chemical looping combustion process (Chemical Looping Combustion).
- Chemical mass-based oxidation-reduction processes are known in the field of energy production, gas turbines, boilers and furnaces, particularly for the oil, glass and cement industry.
- the production of electricity, heat, hydrogen or steam can be achieved by this type of process, typically the CLC process, implementing oxidation-reduction reactions of an active mass, called mass oxidation reduction, conventionally a metal oxide, to produce a hot gas from a fuel, for example natural gas, carbon monoxide CO, hydrogen H 2 , coals or petroleum residues, a mixture of hydrocarbons, and isolate the carbon dioxide CO2 produced.
- a fuel for example natural gas, carbon monoxide CO, hydrogen H 2 , coals or petroleum residues, a mixture of hydrocarbons, and isolate the carbon dioxide CO2 produced.
- a fuel for example natural gas, carbon monoxide CO, hydrogen H 2 , coals or petroleum residues, a mixture of hydrocarbons, and isolate the carbon dioxide CO2 produced.
- a fuel for example natural gas, carbon monoxide CO, hydrogen H 2 , coals or petroleum residues, a mixture of hydrocarbons, and isolate the carbon dioxide CO2 produced.
- a second reduction reaction of the oxidized active mass with the aid of a gas, a liquid or a reducing solid (hydrocarbon feedstock) then makes it possible to obtain a reusable active mass and a gaseous mixture comprising essentially CO2 and water, even
- FIRE I LLE OF REM PLACEM ENT (RULE 26) synthesis gas containing CO and ⁇ 2 , depending on the conditions operated during the reduction step.
- the energy can be produced in the form of steam or electricity for example.
- the heat of combustion of the hydrocarbon feedstock is similar to that encountered in conventional combustion. This corresponds to the sum of the heats of reduction and oxidation in the chemical loop.
- the heat is generally extracted by exchangers located inside, wall or appendage of the fuel and / or air reactors, on the flue lines, or on the transfer lines of the active mass.
- a major advantage of these oxidation-reduction processes in chemical loop on active mass is then to allow to easily isolate the CO 2 (or synthesis gas) contained in the gaseous mixture without oxygen and nitrogen constituting the effluent from the reduction reactor.
- Another advantage is the production of a flow of nitrogen N 2 (and argon) containing almost no oxygen, and corresponding to the effluent from the oxidation reactor, when the air is used as oxidizing gas.
- the CLC process thus provides an attractive solution for C0 2 capture with a view to its sequestration or recovery for other processes, in order to limit the emission of greenhouse gases. greenhouse that is detrimental to the environment.
- US Pat. No. 5,447,024 for example 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 an oxidation reaction with moist air.
- the circulating fluidized bed technology is used to allow the continuous passage of the active mass of the reduction reactor to the oxidation reactor and vice versa.
- Patent application WO 2006/123925 describes another implementation of the CLC process using one or more fixed-bed reactors containing the active mass, the redox rings being carried out by permutation of the gases in order to successively carry out the oxidation and reduction of the active mass.
- the active mass passing alternately from its oxidized form to its reduced form and vice versa, describes an oxidation-reduction cycle. 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 active mass is oxidized and the reduction reactor is the reactor in which the active mass is reduced.
- the active mass usually a metal oxide (M x Oy) is first reduced to the state M x O y 2n-m / 2, via a hydrocarbon C n H m , which is correlatively oxidized to C0 2 and H 2 0, according to reaction (1), or optionally in CO + H 2 mixture according to the nature of the active mass and the proportions used.
- M x Oy metal oxide
- M represents a metal
- the active mass has a role of oxygen carrier in the chemical loop redox process.
- solid oxygen carrier solid comprising the active mass, typically comprising the metal oxide or oxides capable of exchanging oxygen under the redox conditions of the oxidation-reduction process in a chemical loop.
- the oxygen carrier solid may further comprise a binder or a support in association with the active mass, in particular to ensure good reversibility of oxidation and reduction reactions, and improve the mechanical strength of the particles.
- the active masses chosen, for example, from the redox couples of copper, nickel, iron, manganese and / or cobalt, are generally not used in pure form since the successive oxidation / reduction cycles at high temperature lead to a significant and rapid decrease in the oxygen transfer capacity, due to the sintering of the particles.
- the oxygen carrier solid comprises a NiO / Ni redox couple as an active mass, associated with a YSZ binder which is yttrium-stabilized zirconia, also called yttria zirconia.
- binders and supports in addition to yttria YSZ zirconia, have been studied in the literature to increase the mechanical strength of particles at a lower cost than YSZ.
- the effectiveness of the oxidation-reduction process in a chemical loop depends mainly on the physicochemical properties of the oxygen-carrying solid.
- the lifetime of the particles in the process has a preponderant impact on the operating cost of the process, particularly in the case of circulating fluidized bed process.
- the attrition rate of the particles makes it necessary to compensate for the loss of oxygen-carrying solid in the form of fines, typically particles of the oxygen-carrying solid with a diameter of less than 40. ⁇ , with new oxygen carrier solid.
- the rate of renewal of the oxygen-carrying solid therefore strongly depends on the mechanical strength of the particles as well as their chemical stability under the process conditions, which includes many successive oxidation / reduction cycles.
- the porosity of ilmenite ore particles increases strongly with redox cycles and results in their sputtering, potentially challenging the adequacy of this ore to the process, while early studies on the use of ilmenite concluded at its conclusion. good suitability for the CLC process.
- the increase in porosity observed by the minute characterization of the particles after the test is concomitant with the migration of ferrous and / or ferric ions by diffusion within the particles. According to the authors, segregation of iron within the particles precedes its migration to the surface, creating the porosity that results in the disaggregation of the particles in the form of fines.
- the appearance of porosity is the main mechanism for the formation of fine particles during the process, considerably limiting the lifetime of the particles, and therefore the potential value of the ore for the CLC application. Indeed, the estimated lifespan of ilmenite particles is of the order of only 200 hours ("Emerging C0 2 Capture Systems", JC Abanades, B. Arias, A. Lyngfelt, T. Mattisson, DE Wiley, H Li, MT Ho, E. Mangano, S. Brandani, J. Int Greenhouse Gas Control 40 (2015), 126).
- the attrition phenomenon of the oxygen-carrying solid is thus mainly due to a morphological evolution linked to the consecutive redox cycles experienced by the particles rather than to shocks on the walls and between particles, usually considered as the main source of attrition in fluidized bed processes.
- the patent application WO 2012/155059 discloses the use of oxygen carrier solids consisting of an active mass (20 to 70% by weight), a primary support material of the ceramic or clay type (5 to 70% by weight). , and a secondary support material (1 to 35% by weight), also of ceramic or clay type.
- An improved mechanical stability related to the control of the volume expansion is advanced for these solid oxygen carriers. It is explained that a diffusion movement of the iron ions towards the outside of the particles causes the volume expansion of the particles, which leads to embrittlement of the particles.
- the primary support material would make it possible to disperse the metallic active mass and prevent its agglomeration, preserving the redox activity, whereas the secondary support material would serve to reduce the speed of volume expansion by forming a phase stabilizing solid that would prevent iron migration to the surface.
- Lyngfelt et al. performed a 1000h test with nickel-based particles (40% NiO / 60% NiAl 2 O 4 ) in a 10kWth circulating fluidized bed plant (Linderholm, C., Mattisson, T. & Lyngfelt, A., "Long-term integrity testing of spray-dried particles in a 10-kW chemical-looping combustor using natural gas as fuel", Fuel, 88 (1 1),
- the present invention aims to overcome the problems of the prior art described above, and generally aims to provide an oxygen carrier solid for a chemical loop redox process which has a long life when its use in the process, in particular to reduce investment costs and / or operation for such processes.
- the present invention provides, in a first aspect, a particulate oxygen carrier solid for a method of combustion of a hydrocarbon feedstock by oxido.
- chemical loop reduction comprising: an oxidation-reduction active mass constituting between 5% and 75% by weight of the oxygen-carrying solid, the oxidation-reduction active mass comprising a metal oxide or a mixture of metal oxides and being capable of carrying oxygen in the chemical-loop oxidation-reduction combustion process;
- a ceramic matrix in which the oxidation-reduction active mass is dispersed the ceramic matrix constituting between 25% and 95% by weight of the oxygen-carrying solid, and the ceramic matrix comprising between 60% and 100%; % by weight of at least one feldspar or feldspathoid having a melting temperature above 1500 ° C and between 0% and 40% of at least one oxide;
- a porosity such that: the total pore volume of the oxygen-carrying solid, measured by mercury porosimetry, is between 0.05 and 0.9 ml / g,
- the pore volume of the macropores constitutes at least 10% of the total pore volume of the oxygen-carrying solid
- the size distribution of the macropores within the oxygen carrier solid, measured by mercury porosimetry, is between 50 nm and 7 ⁇ .
- the total pore volume of the oxygen-carrying solid is between 0.1 and 0.5 ml / g.
- the total pore volume of macropores constituting macropores constitutes at least 50% of the pore volume at least 50% of the pore volume of the oxygen-bearing solid.
- the size distribution of the macropores within the oxygen-carrying solid is between 50 nm and 4 ⁇ .
- the oxidation-reduction active mass preferably comprises at least one metal oxide included in the list consisting of Fe, Cu, Ni, Mn and / or Co oxides, a perovskite with redox properties, preferably a perovskite of formula CaMnO 3 , a metal aluminate spinel having redox properties, preferably a metal aluminate spinel of formula CuAl 2 O 4 or a Cuprospinelle of formula CuFe 2 O 4 .
- the oxidation-reduction active mass comprises at least one copper oxide.
- said at least one feldspar or feldspathoid has a melting temperature greater than 1700 ° C.
- said at least one feldspar or feldspathoid of the ceramic matrix is a feldspar chosen from the list consisting of celsiane, slawsonite, anorthite, or a feldspathoid being kalsilite, and is preferably celsiane.
- Said at least one oxide of the ceramic matrix may be chosen from the list consisting of alumina, metal aluminates, silica, silicates, aluminosilicates, titanium dioxide, perovskites and zirconia.
- the particles have a particle size such that more than 90% of the particles have a size of between 50 ⁇ and 600 ⁇ .
- the invention relates to a process for preparing the oxygen-carrying solid according to the invention, comprising the following steps:
- a1) the preparation of a macroporous zeolite material, the macroporous zeolite material comprising zeolite crystals with a mean diameter of less than or equal to 3 ⁇ , and preferably a number-average diameter of between 0.4 ⁇ and 2 ⁇ ; and
- step (C) forming particles of the precursor of the ceramic matrix during step (a1) or at the end of step (B); (D) drying the precursor of the impregnated ceramic matrix in particle form obtained at the end of all of the steps (A), (B) and (C); and
- step (E) calcining the precursor of the impregnated and dried ceramic matrix obtained in step (D) to obtain the particulate oxygen carrier solid.
- step a1) comprises: - a'1) agglomeration of the zeolite crystals with a clay binder to form a zeolite agglomerate;
- step a'2 the shaping of the zeolite agglomerate obtained in step a'1) to produce particles, followed by drying of said particles, and possibly followed by a sieving and / or cycloning step ; - a'3) calcining the particles of the zeolite agglomerate obtained in step a'2) at a temperature between 500 ° C and 600 ° C to produce the macroporous zeolite material in particulate form;
- step a'4 optionally the zeolitization of the clay binder by contacting the product resulting from step a'3) with an alkaline basic aqueous solution, followed by washing.
- the zeolitic crystals comprise at least one zeolite with an Si / Al molar ratio of between 1.00 and 1.5, preferably zeolitic crystals comprising at least one zeolite chosen from zeolites A, X, LSX and low-silica EMT. EMT low-silica having a Si / Al ratio of between 1.0 and 1.4.
- the cation exchange in step a2) is carried out with a solution comprising alkaline ions, preferably K +, or alkaline earth ions, and preferably with a solution comprising alkaline earth ions.
- the cationic exchange in step a2) is carried out with a solution comprising ions chosen from Ba 2+ , Sr 2 " -, Ca 2+ ions, and preferably with a solution containing Ba 2+ ions. .
- step (A) further comprises a heat treatment step a3) of the macroporous zeolite material obtained in step a2), the heat treatment comprising a drying step at a temperature of between 100 ° C. and 400 ° C.
- step (C) the precursor of the ceramic matrix is placed in the form of particles having a particle size such that more than 90% of the particles have a size of between 50 ⁇ and 600 ⁇ .
- the impregnation in step (B) is carried out with an aqueous or organic solution containing at least one soluble precursor compound of copper, nickel, cobalt, iron or manganese, preferably with a aqueous solution containing at least one precursor compound of the oxidation-reduction active mass chosen from the list consisting of the nitrates of the following formulas: Cu (N0 3 ) 2.xH 2 0, Ni (N0 3 ) 2 .xH 2 0 , Co (NO 3 ) 2 .xH 2 O, Fe (NO 3 ) 3 .xH 2 O, Mn (NO 3 ) 2 ⁇ xH 2 0.
- the impregnation in step (B) can be carried out in one or more successive stages, and preferably comprises intermediate stages of drying at a temperature of between 30 ° C. and 200 ° C. and / or calcination at a temperature of between between 200 ° C and 600 ° C when the impregnation is carried out in several successive stages.
- the drying in step (D) is carried out in air or in a controlled atmosphere, at a temperature between 30 ° C and 200 ° C, and preferably in air at a temperature between 100 ° C and 150 ° C.
- the calcination in step (E) is carried out under air between 450 ° C. and 1400 ° C., preferably between 600 ° C. and 1000 ° C., more preferably between 700 ° C. and 900 ° C, and is carried out for a period of 1 to 24 hours, and preferably for a period of 5 to 15 hours.
- the zeolite crystals are mixed with at least one oxide selected from the list consisting of alumina, metal aluminates, silica, silicates, aluminosilicates, titanium dioxide, perovskites, zirconia, and / or a pore-forming agent intended to increase the macroporosity of the macroporous zeolite material.
- the invention relates to a method of combustion of a hydrocarbon feedstock by oxido-reduction in a chemical loop using an oxygen carrier solid according to the invention or prepared according to the preparation method according to the invention.
- the invention relates to a CLC process, preferably in which the oxygen carrier solid circulates between at least one reduction zone and an oxidation zone both operating in a fluidized bed, the temperature in the reduction zone. and in the oxidation zone being between 400 ° C and 1400 ° C, preferably between 600 ° C and 1100 ° C, and more preferably between 800 ° C and 1100 ° C.
- FIGS. 1A, 1B, 1C and 1D relate to an oxygen carrier solid according to Example 2 (example not in accordance with the invention).
- FIG. 1A is a diagram giving information on the porosity of the oxygen carrier solid.
- Fig. 1B is a diagram showing the conversion of methane as a function of oxidation-reduction cycles in a CLC process using the oxygen-carrying solid.
- Fig. 1C is a diagram showing the particle size distribution of the oxygen carrier solid before and after its use in a CLC process.
- Figure 1D is a scanning electron microscope (SEM) photograph of a polished section of a sample of the oxygen-carrying solid after its use in a CLC process.
- SEM scanning electron microscope
- FIGS. 2A, 2B, 2C and 2D relate to an oxygen carrier solid according to Example 3 (example not in accordance with the invention).
- Fig. 2A is a diagram giving information on the porosity of the oxygen carrier solid.
- Figure 2B is a diagram showing the conversion of methane versus oxidation-reduction cycles in a CLC process using the oxygen-carrying solid.
- FIG. 2C shows in (a) a SEM image and (b) an energy dispersive X-ray spectrometry (EDX) mapping of the oxygen-carrying solid prior to its use in a CLC process.
- Figure 2D is a SEM image of a polished section of a sample of the oxygen-carrying solid after its use in a CLC process.
- EDX energy dispersive X-ray spectrometry
- FIGS. 3A, 3B, 3C, 3D and 3E relate to an oxygen carrier solid according to Example 4 (example according to the invention).
- FIG. 3A is a diffractogram obtained by X-ray diffractometry (XRD) of the oxygen carrier solid.
- Figure 3B shows in (a) a SEM backscattered electron micrograph and (b) an EDX mapping of a polished section of the oxygen carrier solid prior to its use in a CLC process.
- FIG. 3C is a diagram giving information on the porosity of the oxygen carrier solid.
- FIG. 3D represents in (a) a SEM backscattered electron micrograph and (b) an EDX mapping of a polished section of the oxygen carrier solid after its use in a CLC process.
- Figure 3E is a SEM image of a polished section of a sample of the oxygen-carrying solid after its use in a CLC process.
- FIGS. 4A, 4B and 4C relate to an oxygen-carrying solid according to Example 5 (example not in accordance with the invention).
- FIG. 4A is a diagram giving information on the porosity of the oxygen carrier solid.
- Figure 4B shows a SEM picture of the oxygen-carrying solid prior to its use in a CLC process.
- FIG. 4C shows in (a) a SEM backscattered electron micrograph and (b) an EDX mapping of a polished section of the oxygen carrier solid after its use in a CLC process.
- FIGS. 5A, 5B and 5C relate to an oxygen carrier solid according to Example 6 (example not in accordance with the invention).
- FIG. 5A is a diagram giving information on the porosity of the oxygen carrier solid.
- Figure 5B shows a polished section SEM of the oxygen-carrying solid prior to its use in a CLC process.
- Figure 5C shows a polished section SEM of the oxygen-carrying solid after its use in a CLC process.
- FIGS. 6A and 6B relate to an oxygen carrier solid according to Example 7 (example according to the invention).
- Fig. 6A is a diagram giving information on the porosity of the oxygen carrier solid.
- Figure 6B shows a polished section SEM of the oxygen carrier solid prior to use in a CLC process.
- the object of the invention is to propose an oxygen-carrying solid for a chemical-loop oxidation-reduction process, such as a CLC process, but also for other active mass chemical loop oxidation reduction methods such as a chemical loop reforming process (CLR with reference to the term “Chemical Looping Reforming”) or a method of CLOU (with reference to the expression “Chemical Looping Oxygen Uncoupling ").
- CLR chemical loop reforming
- CLOU with reference to the expression "Chemical Looping Oxygen Uncoupling”
- the present invention also relates to the preparation and use of the oxygen-carrying solid in such processes.
- the CLC processes generally use two separate reactors to perform on the one hand in a reduction reactor, the reduction of the active mass by means of a fuel, or more generally a gas, liquid or reducing solid.
- the effluents from the reduction reactor mainly contain CO 2 and water, allowing easy capture of CO 2 .
- the oxidation reactor the restoration of the active mass to its oxidized state by contact with air or any other oxidizing gas makes it possible to correlatively generate a hot energy vector effluent and a nitrogen stream. poor or free of nitrogen (where air is used).
- oxygen carrier solid in a circulating fluidized bed CLC process
- oxygen carrier solid according to the invention can also be used in any other type of process.
- chemical loop reduction CLC, CLR, CLOU
- CLC, CLR, CLOU chemical loop reduction
- the oxygen carrier comprises: an oxidation-reduction active mass constituting between 5% and 75% by weight of the oxygen-carrying solid, preferably between 10% and 40% by weight, the oxidation-reduction active mass comprising a metal oxide or a mixture of metal oxides and being capable of exchanging oxygen under the redox conditions of said chemical loop-redox process; a ceramic matrix in which is dispersed the oxidation-reduction active mass, the ceramic matrix constituting between 25% and 95% by weight of the oxygen-carrying solid, preferably between 60% and 90% by weight, and the ceramic matrix comprising between 60% and 100% by weight, and preferably between 80% and 100% by weight, of at least one tectosilicate having a melting temperature above 1500 ° C, and preferably a melting temperature above 1700 ° C, and between 0% and 40% by weight of at least one oxide, of preferably between 0% and 20% by weight of at least one oxide.
- the ceramic matrix consists essentially of at least one tectosilicate having a melting point greater than 1500 ° C., and preferably a melting temperature greater than 1700 ° C. Essentially constituted is understood to comprise 100% of said tectosilicate, to 1%.
- the oxygen-carrying solid according to the invention has a particular porosity. which, unexpectedly, makes it possible to limit the migration phenomenon of the active mass within the oxygen carrier particles.
- This initial texture significantly improves the lifetime of the particles in the chemical loop combustion process and is characterized in that: the total pore volume of the oxygen carrier solid Vtot, measured by mercury porosimetry, is between 0 , 05 and 0.9 ml / g; the total pore volume Vtot of the oxygen carrier solid comprises at least 10% of macropores.
- the pore volume of the macropores constitutes at least 10% of the total pore volume Vtot of the oxygen-carrying solid; the size distribution of the macropores within the oxygen carrier solid, measured by mercury porosimetry, is between 50 nm and 7 ⁇ .
- initial texture is meant the texture prior to any use in a chemical loop-redox process such as CLC.
- the total pore volume of the solid is measured by mercury porosimetry, more precisely the measurement relates to the volume of mercury injected when the pressure exerted increases from 0.22 MPa to 413 MPa.
- the total pore volume Vtot of the oxygen-carrying solid is preferably between 0.1 and 0.5 ml / g, and preferably between 0.1 and 0.4 ml / g.
- the total pore volume Vtot of the particles is constituted for at least 50% by macropores.
- the pore volume of the macropores constitutes at least 50% of the total pore volume Vtot of the oxygen-carrying solid.
- the remainder of the total pore volume may be indifferently constituted by microporosity or mesoporosity in any proportion whatsoever.
- the size distribution of the macropores within the particles is more preferably between 50 nm and 4 ⁇ , and even more preferably between 200 nm and 1 ⁇ .
- the ceramic matrix comprises at least one tectosilicate which is preferably a feldspar or a feldspathoid, and can be formed solely by such a tectosilicate.
- Tectosilicates are silicates whose arrangement of [Si0 4 ] 4 " tetrahedra is made up of a three-dimensional framework where each oxygen of the tops of the tetrahedra is shared with the neighboring tetrahedrons.
- [Si0 4 ] 4" base tetrahedra that we find in all silicates are welded by their four vertices and each oxygen is bound to two cations.
- Feldspathoids are tectosilicates with a high silica deficit.
- the ceramic matrix comprises at least one feldspar selected from the list consisting of celsiana, slawsonite, anorthite, or feldspathoid, kalsilite.
- the ceramic matrix consists essentially of at least one feldspar selected from the list consisting of the celsian, the slawsonite, anorthite.
- Feldspars containing alkaline earth cations (Ca 2+, Si 2 * and Ba 2+), such as celsian, the slawsonite, anorthite, have mechanical, thermal and electrical interesting.
- their coefficient of thermal expansion is very low, for example of 2.29 ⁇ 10 -6 K -1 for the monoclinic celsiane, which makes it possible to limit the mechanical stresses of deformation for use at high temperature, in particular in high temperature processes.
- the ceramic matrix comprises celsiane.
- the ceramic matrix consists essentially of celsiane.
- Celsiane is a feldspar which advantageously has a high mechanical strength and a very low coefficient of thermal expansion. It also has a high melting point (1760 ° C).
- Table 1 below lists the feldspars and feldspathoids mentioned that can make up the ceramic matrix, as well as examples of other feldspathoids whose melting point is below 1500 ° C.
- the ceramic matrix of the solid carrier of oxygen according to the invention may also consist of a mixture of one or more tectosilicates and other oxides typically used as supports for catalysts in petroleum refining processes.
- the ceramic matrix may comprise at least one oxide chosen from the list constituted by alumina, metal aluminates, silica, silicates, aluminum silicates, aluminosilicates, titanium dioxide, perovskites, zirconia.
- oxide covers a mixed oxide, that is to say a solid resulting from the combination of oxide ions O 2 " with at least two cationic elements (for example calcium aluminate CaAl 2 0 4 or magnesium aluminate MgAl 2 0 4 )
- mixing oxides is meant at least two distinct solid compounds each being an oxide.
- the ceramic matrix is obtained from a precursor based on zeolite.
- Zeolites are crystallized microporous solids of the family of aluminosilicates that can be found frequently in nature. These materials can also be synthesized, such as frequently for use as adsorbents or catalysts in the chemical industry. Zeolites have three-dimensional structures formed by the arrangement of [Si0 4 ] 4 ⁇ and [Al0 4 ] 5 ⁇ tetrahedra bonded by bridging oxygen atoms. The electroneutrality of the assembly is ensured by the presence of one or more exchangeable compensation cations.
- the general formula of a zeolite is M x / m Al x S 9 2-x 0 3 e 4 , y H 2 0 with M m + the extra-network charge cation + m.
- celsiane can be obtained from a zeolite exchanged with barium.
- a high temperature treatment that is to say higher than 1000 ° C, causes the formation of celsiane, according to the following sequence: zeolite ⁇ amorphous phase ⁇ hexagonal celsiane ⁇ monoclinic celsiane.
- the formation of monoclinic celsiane from pure BaX ("BaX" for zeolite X exchanged with barium) requires a heat treatment of 24 ° to 1550 ° C. (S. Esposito et al., A comparative study of the thermal transformations of Ba-exchanged zeolites A, X and LSX, J.
- the oxygen carrier solid according to the invention is prepared from various zeolites of low Si / Al ratio, impregnated with a precursor of an oxidation-reduction active mass, typically a metal nitrate, which decompose by calcination, preferably in air and at a temperature of between 450 ° C. and 1400 ° C., to form the oxidation-reduction active mass (eg a metal nitrate oxide) dispersed in a ceramic matrix composed of tectosilicates or mixtures of tectosilicates, depending on the nature of the cation or cation mixture in the zeolite cages and the Si / Al ratio of the zeolite.
- a precursor of an oxidation-reduction active mass typically a metal nitrate, which decompose by calcination, preferably in air and at a temperature of between 450 ° C. and 1400 ° C.
- the melting temperature of the ceramic matrix depends on the nature of the cation M m + , the Si / Al ratio and the arrangement of the tetrahedra in the crystallographic phase.
- the preparation of the oxygen carrier solid according to the invention is detailed later in the description.
- the oxygen-carrying solid according to the invention comprises an oxidation-reduction active mass which comprises, and preferably consists of, at least one metal oxide included in the list consisting of Fe, Cu, Ni and Mn oxides. and Co, a perovskite having redox properties, preferably a perovskite of formula CaMnO 3 , a metal aluminate spinel having redox properties, preferably a metal aluminate spinel of formula CuAl 2 O 4 or of formula CuFe 2 4 .
- the spinel of formula CuFe 2 O 4 is a cuprospinelle.
- the oxidation-reduction active mass comprises at least one copper oxide, for example of formula CuO, and is more preferably constituted by at least one copper oxide, for example of formula CuO.
- the oxygen-carrying solid advantageously has a dispersed active mass within the ceramic matrix, typically an initial distribution of the relatively homogeneous active mass, and the migration of the active mass within the particles of the solid carrier. Oxygen is minimized during the redox cycles of the chemical-loop oxidation-reduction process as exemplified by some examples later in the description.
- the oxido-reducing active mass is capable of exchanging oxygen under the redox conditions of the chemical loop redox process.
- the active mass is reduced according to the reaction (1) already described above, during a contact reduction step a hydrocarbon feedstock, and is oxidized according to the reaction (2) or (3) already described above, during an oxidation step in contact with an oxidizing gas.
- the oxygen storage capacity of the oxido-reducing active mass is advantageously, depending on the type of material, between 1% and 15% by weight.
- the amount of oxygen effectively transferred by the metal oxide is between 1 and 3% by weight, which makes it possible to use only a fraction of the oxygen transfer capacity.
- the oxygen carrier solid according to the invention is preferably in the form of particles, which can be fluidized in the oxidation-reduction process in a chemical loop, in particular be implemented in a circulating fluidized bed.
- They may be fluidizable particles (fluidizable powder, generally called “fluidisable carrier” in English) belonging to groups A, B or C of the Geldart classification (D. Geldart, "Types of gas fluidization", Powder Technol. (5), 285-292, 1973), and preferably the particles belong to group A or group B of the Geldart classification, and preferably to group B of the Geldart classification.
- the particles of the oxygen-carrying solid have a particle size such that more than 90% of the particles have a size of between 50 ⁇ and 600 ⁇ , more preferably a particle size such that more than 90% of the particles have a size of between 80 ⁇ and 400 ⁇ , more preferably a particle size such that more than 90% of the particles have a size of between 100 ⁇ and 300 ⁇ , and even more preferably a particle size such that more than 95% of the particles have a size between 100 ⁇ and 300 ⁇ .
- the particles of the oxygen-carrying solid have a grain density of between 500 kg / m 3 and 5000 kg / m 3 , preferably a grain density of between 800 kg / m 3 and 4000 kg / m 3 , and even more preferably a grain density of between 1000 kg / m 3 and 3000 kg / m 3 .
- the particles of the oxygen-bearing solid are preferably substantially spherical.
- Size distribution and morphology of particles for use in another type of chemical loop process (CLC, CLR, CLOU) in fixed bed, moving bed or rotating reactor are adapted to the envisaged process.
- the preferred size of the particles is greater than 400 ⁇ , in order to minimize the pressure losses.
- the morphology of the particles is not necessarily spherical.
- the morphology is dependent on the shaping mode, for example in the form of extrudates, beads, monoliths or particles of any geometry obtained by grinding larger particles.
- the solid carrier of oxygen in the form of particles, is deposited on the surface of the ceramic monolith channels by the coating methods known to those skilled in the art. or the monolith itself consists of the particles according to the invention.
- Particle size can be measured by laser particle size.
- the size distribution of the particles is preferably measured using a laser granulometer, for example Malvern Mastersizer 3000, preferably in a liquid path, and using the Fraunhofer theory.
- a laser granulometer for example Malvern Mastersizer 3000, preferably in a liquid path, and using the Fraunhofer theory.
- Step (A): Preparation of a Precursor of a Ceramic Matrix Step (A) comprises: - a1) the preparation of a macroporous zeolite material said material comprising zeolite crystals with a mean diameter of less than or equal to 3 ⁇ , and preferably a number-average diameter of between 0.4 ⁇ and 2 ⁇ , and even more preferably a number-average diameter of between 0 , 5 ⁇ and 1, 7 ⁇ ; and - a2) a cationic exchange of said macroporous zeolite material with a solution of precursor ions, the precursor ions being chosen to form a tectosilicate with a melting point> 1500 ° C. of the ceramic matrix at the end of step (D ), said cation exchange being followed by a washing of said macroporous zeolite material to obtain said precursor of the ceramic matrix.
- step a1) for preparing a macroporous zeolite material comprises the following steps:
- step a'2 the shaping of the zeolite agglomerate obtained in step a'1) to produce particles, followed by drying of said particles, and possibly followed by a sieving and / or cycloning step ;
- step a'3 calcination of the zeolite agglomerate particles obtained in step a'2) at a temperature between 500 ° C and 600 ° C to produce the macroporous zeolite material in particulate form.
- the particles produced have sufficient mechanical strength for their subsequent use;
- step a'4 optionally the zeolitization of the clay binder by contacting the product resulting from step a'3) with an alkaline basic aqueous solution, followed by washing.
- the clay binder is an agglomeration binder intended to ensure the cohesion of the crystals in the form of particles. This binder can also contribute to imparting mechanical resistance to the particles so that they can withstand the mechanical stresses to which they are subjected during their implementation within the chemical loop redox units.
- the proportions of agglomeration binder and zeolite employed can be typically from 5 parts to 20 parts by weight of binder per 95 parts to 80 parts by weight of zeolite.
- the zeolite crystals may be mixed with at least one oxide selected from the list consisting of alumina, metal aluminates, silica, silicates, aluminum silicates, aluminosilicates, titanium dioxide, perovskites, zirconia.
- alumina metal aluminates
- silica silicates
- aluminum silicates aluminum silicates
- aluminosilicates titanium dioxide, perovskites, zirconia.
- such an oxide may be formed, in the desired quantities, at the end of the treatments of the zeolite agglomerate and the precursor of the ceramic matrix, without adding said oxide to the zeolite crystals during step (A). ).
- step a1) it is also possible to mix the zeolite crystals with a pore-forming agent intended to increase the macroporosity of the macroporous zeolite material.
- step a1) it is also possible to mix the zeolite crystals with at least one of the abovementioned oxides and with a pore-forming agent.
- step a1) other additives may also be used, intended to facilitate the agglomeration and / or to improve the hardening and / or increase the macroporosity of the agglomerates formed.
- the zeolitic crystals comprise at least one zeolite with an Si / Al molar ratio of between 1.00 and 1.5, and preferably at least one zeolite chosen from zeolites A, X, LSX and low-silica EMT.
- X zeolites are of structural type FAU and Si / Al ratio of between 1 and 1.5, as is the case for the LSX zeolite (Low Silica X).
- the low-silica EMT zeolites are of structural type EMT and Si / Al ratio of between 1.0 and 1.4 (Mintova et al., Chem Mater 24, 4758-4765, 2012, and Science, Jan.
- the zeolite crystals A, X, LSX and low-silica EMT can be derived from synthesis and the compensating cations are mainly, or even exclusively, sodium cations (for example NaX (or 13X), NaA (or 4A) crystals), but it is not beyond the scope of the invention using crystals having undergone one or more cationic exchanges, between the synthesis in sodium form and their implementation in step a1).
- the estimation of the number average diameter of the zeolite X crystals used in step a1) and the zeolite X crystals contained in the agglomerates is preferably carried out by observation under a scanning electron microscope (SEM) or by observation under an electron microscope in transmission (MET).
- a set of images is carried out at a magnification of at least 5000.
- the diameter of at least 200 crystals is then measured using dedicated software. for example the Smile View software from the LoGraMi editor.
- the accuracy is of the order of 3%.
- the optional step a'4) of zeolitization of the clay binder makes it possible to convert all or part of the binder into zeolite, preferably into zeolite with an Si / Al molar ratio of between 1.00 and 1.5, and preferably zeolite A , X, LSX or low-silica EMT, in order to obtain a macroporous zeolite material consisting essentially of zeolite, the non-zeolite phase being typically in an amount of less than 5%, and corresponding to non-zeolite residual binder or any other amorphous phase after zeolitization, while maintaining or even improving the mechanical strength of the macroporous zeolite material, as taught by patents FR 2 903 978 and FR 2 925 366.
- the clay agglomeration binder used in step a '1) comprises, and preferably consists of, a clay or a mixture of clays, to which a source of silica may be added.
- These clays are preferably chosen from kaolins, kaolinites, nacrites, dickites, halloysites, attapulgites, sepiolites, montmorillonites, bentonites, illites and metakaolins, as well as mixtures of two or more of them in all proportions.
- the clay agglomeration binder used in step a'1) contains at least 80%, preferably at least 90%, more preferably at least 95% more particularly at least 96% by weight of zeolitizable clay and may also contain other minerals such as bentonite, attapulgite, and the like.
- zeolitic clay is meant a clay or a mixture of clays which are capable of being converted into zeolite material, most often by the action of an alkaline basic solution.
- Zeolizable clay generally belongs to the family of kaolin, kaolinite, nacrite, dickite, halloysite and / or metakaolin. Kaolin is preferred and most commonly used.
- step a'3 After drying in step a'2), the calcination in step a'3) is carried out at a temperature in general of between 500 ° C. and 600 ° C., for example at 550 ° C., and makes it possible to transform zeolitic clay, typically kaolin, in meta-kaolin which can after being converted to zeolite during the optional zeolitization step (step a'4)).
- zeolitic clay typically kaolin
- meta-kaolin which can after being converted to zeolite during the optional zeolitization step (step a'4).
- the principle is exposed in "Zeolite Molecular Sieves" by DW Breck, John Wiley and Sons, New York, (1973), p. 314-315.
- the zeolitization of the agglomeration binder is carried out according to any method now well known to those skilled in the art and may for example be carried out by immersion of the product of step a'3) in an alkaline basic solution, generally aqueous, by an aqueous solution of sodium hydroxide and / or potassium hydroxide.
- the macroporous zeolite material contains alkaline or alkaline earth cations, and more generally sodium and / or potassium cations.
- the macroporous zeolite material at the end of step a1) can also be obtained, alternatively with the succession of steps a'1) to a'4) described above, by any alternative method leading to zeolite particles, and in particular by the method described in US Pat. No. 4,818,508 starting from agglomerates of zeolitic clay subjected to zeolitization by the action of an alkaline basic solution.
- the cationic exchange (step a2) can be carried out with a solution comprising alkaline ions, preferably K + , or alkaline earth ions, and preferably with a solution comprising alkaline earth ions.
- the cationic exchange is more preferably carried out with a solution comprising ions selected from Ba 2+ , Sr 2+ , Ca 2+ ions, and even more preferably with a solution comprising Ba 2+ ions.
- the solution used is an aqueous solution in which a salt is dissolved, preferably a barium salt such as barium chloride BaCl 2 , a strontium salt such as strontium chloride SrCl 2 or a calcium salt such as chloride calcium CaCl 2 , and preferably BaCl 2 barium salt.
- Step a2) of cationic exchange of the zeolite is carried out by contacting the macroporous zeolite material resulting from step a1), in particular the macroporous zeolite material in the form of particles resulting from step a'3) or a'4), with an alkali or alkaline earth metal salt, such as BaCl 2 , in aqueous solution, preferably at a temperature between room temperature and 100 ° C, and preferably at a temperature between 80 ° C and 100 ° C.
- an exchange rate in cation eg barium, high, ie greater than 90%, it is preferred to operate with a large excess of the cation exchange with respect to the cations of the zeolite that is to be exchanged.
- step a2) The chemical analysis of the precursor of the ceramic matrix resulting from step a2) or zeolite crystals used in step a1) is carried out according to conventional techniques, in particular by X-ray fluorescence as described in standard NF EN ISO 12677: 201 1 on a wavelength dispersive spectrometer (WDXRF), for example Tiger S8 from Bruker, or by inductively coupled plasma atomic emission spectrometry (ICP-OES for Inductively Coupled Plasma-Optical Spectroscopy emission according to the English terminology) according to the UOP 961-12 standard.
- WDXRF wavelength dispersive spectrometer
- ICP-OES Inductively coupled plasma atomic emission spectrometry
- the cationic exchange of zeolites can be done without destroying the zeolite structure.
- the precursor of the ceramic matrix obtained at the end of the optional thermal treatment step a3) can be totally or partially amorphous, in particular in the case where the zeolite A is used in step a1), or when the temperature of the heat treatment of step a3) is too high to maintain the zeolite structure.
- the preparation of the precursor of the ceramic matrix during step (A) may further comprise an additional step a3) of heat treatment of the macroporous zeolite material obtained in step a2). This heat treatment comprises a drying step at a temperature of between 100 ° C. and 400 ° C.
- the precursor of the ceramic matrix obtained in step (A) is impregnated with a precursor compound of an oxidation-reduction active mass.
- the impregnation may be carried out with an aqueous or organic solution containing at least one soluble precursor compound of copper, nickel, cobalt, iron or manganese.
- the impregnation is carried out with an aqueous solution containing at least one precursor compound of the oxidation-reduction active mass chosen from the list consisting of the nitrates of the following formulas: Cu (N0 3 ) 2.xH 2 0, Ni (N0 3 ) 2 .xH 2 O, Co (NO 3 ) 2.xH 2 O, Fe (NO 3 ) 3 .xH 2 O, Mn (NO 3 ) 2 .xH 2 0.
- the copper nitrate of Copper Cu (N0 3 ) 2 .xH 2 0 is chosen to carry out this impregnation, in order to obtain an oxido-reducing active mass of copper oxide (s), for example a copper oxide of formula CuO, to form the solid carrier of oxygen.
- the amount of precursor of the oxidation-reduction active mass used for the impregnation stage is chosen so that the active redox mass constitutes between 5% and 75% by weight of the solid carrier substance. oxygen.
- the impregnation can be carried out in one or more successive stages.
- the precursor of the ceramic matrix is formed into particles during step (a1) or after step (B).
- step a1) has been described above.
- step a'2) the shaping is followed by a drying of the particles, which is optionally followed by a sieving and / or cycloning step.
- the precursor of the ceramic matrix is shaped so as to obtain particles having a particle size such that more than 90% of the particles have a size of between 100 ⁇ and 500 ⁇ . If a circulating fluidized bed implementation is envisaged for the chemical loop oxidation-reduction process using the oxygen-carrying solid, it will be preferred to perform a shaping so as to obtain a size distribution of the particles of the zeolite agglomerate, or precursor of the ceramic matrix from step (B), such that said particles belong to class A or class B of the Geldart classification.
- the shaping is carried out so as to produce particles having the following particle size: more than 90% of the particles have a size of between 100 ⁇ and 500 ⁇ , and a grain density of between 500 kg / m 3 and 5000 kg / m 3 .
- the shaping is carried out so as to produce particles of the following particle size: more than 90% of the particles have a size of between 100 ⁇ and 300 ⁇ , and a grain density of between 800 kg / m 3 and 4000 kg / m 3 .
- the shaping is carried out so as to produce particles having the following particle size: more than 95% of the particles have a size of between 100 ⁇ and 300 ⁇ , and a grain density of between 1000 kg / m 3 and 3000 kg / m 3 .
- the shaping which can directly follow the agglomeration stage a '1), can be carried out by any techniques known to those skilled in the art, such as extrusion, compaction, agglomeration on a granulating plate. , granulator drum, wet or dry granulation, etc., and preferably by granulation or any other technique making it possible to obtain particles of spherical shape.
- the shaping may optionally comprise a sieving and / or cycloning step, in order to obtain agglomerates of the desired particle size.
- the precursor of the impregnated ceramic matrix in the form of particles obtained at the end of all of the steps (A), (B) and (C) is subjected to a drying step.
- This drying is preferably carried out in air or in a controlled atmosphere (controlled relative humidity, under nitrogen), at a temperature of between 30 ° C. and 200 ° C.
- controlled atmosphere is meant for example with a controlled relative humidity or under nitrogen.
- the drying is carried out in air at a temperature of between 100 ° C. and 150 ° C.
- the precursor of the impregnated and dried ceramic matrix obtained in step (D) is calcined to obtain the particulate oxygen carrier solid.
- This calcination is preferably carried out in air between 450 ° C. and 1400 ° C., more preferably between 600 ° C. and 1000 ° C., and even more preferably between 700 ° C. and 900 ° C.
- This calcination can be carried out for a period of 1 to 24 hours, and preferably for a period of 5 to 15 hours.
- a ramp for increasing the temperature between 1 ° C./min and 50 ° C./min, and preferably between 5 ° C./min and 20 ° C./min, is applied to reach the given calcination temperature.
- the time to implement this temperature ramp is not included in the calcination time ranges indicated above.
- the calcination enables the formation of the tectosilicate (s) of the solid ceramic matrix carrying oxygen in the form of particles, a matrix in which the redox active mass is dispersed.
- the calcination step (E) has a limited impact on the initial macroporous structure of the particles, and all the more limited when the calcination is carried out at a temperature between 700 ° C and 900 ° C. A small increase in macropore diameter and a small decrease in total pore volume can be observed.
- the preparation of an oxygen carrier of formula CuO / BaAl 2 Si 2 O 8 according to the invention is carried out according to the following steps: Firstly, step (A) of preparation of a precursor of a ceramic matrix of celsiana in the form of particles.
- the precursor of the ceramic matrix BaAl 2 Si 2 O 8 is a macroporous zeolite agglomerate consisting essentially of zeolite with a low Si / Al atomic ratio, that is to say with an Si / Al ratio of less than 1.5 (and greater than 1).
- the zeolitic crystals may comprise a zeolite chosen from zeolites A, X, LSX and low-silica EMT, alone or as a mixture.
- the zeolites of the agglomerate are exchanged with barium.
- the precursor of the BaAl 2 Si 2 O 8 ceramic matrix is prepared according to the following steps: a1) the preparation of a macroporous zeolite material comprising an agglomeration of zeolite crystals with an Si / Al atomic ratio of between 1.00 and 1, 50, by example of zeolite A, X, LSX, low-silica EMT, alone or as a mixture, with a mean diameter less than or equal to 3 ⁇ , preferably between 0.4 ⁇ and 2 ⁇ , and preferably between 0 , 5 ⁇ and 1, 7 ⁇ , with a binder based on a clay or a mixture of clays (step a'1), and a shaping to form particles, then a drying of the particles (step a'2), followed by calcination
- step a'3 A possible zeolitization of the clay binder by the action of an alkaline basic solution can be carried out (step a'4).
- the shaping in the form of particles is carried out subsequently, after the impregnation step (B); a2) the cationic exchange of the particles of the macroporous zeolite material resulting from step a1) by contacting with a solution of barium ions, followed by washing of the product thus treated.
- the barium exchange of the cations of the zeolite is carried out by contacting the macroporous zeolite material from step a1), in particular the macroporous zeolite material in particulate form resulting from step a'3) or 4), with a barium salt, such as BaCl 2 , in aqueous solution at a temperature between room temperature and 100 ° C, and preferably between 80 ° C and 100 ° C.
- a barium salt such as BaCl 2
- 0 3 is of the order of 10 to 12 by proceeding by successive exchanges.
- the degree of exchange by the barium ions is determined by the ratio between the number of moles of barium oxide, BaO, and the number of moles of all the oxides of alkaline and alkaline-earth ions (typically the number of moles of BaO + K 2 O + Na 2 O).
- the barium exchange of zeolites X, LSX, or A or low-silica EMT, is done without destruction of the zeolite structure.
- the precursor of the ceramic matrix obtained at the end of this step a3) may be totally or partially amorphous, especially in the case where zeolite A is used in step a1).
- step (B) is carried out for impregnating the precursor of the ceramic celsiane matrix: the precursor of the ceramic matrix, preferably shaped according to step (C) already described, is impregnated with an aqueous solution or organic containing at least one soluble precursor of copper, nickel, cobalt, iron and / or manganese, as described in detail above.
- drying step (D) of the precursor of the ceramic matrix of celsiana impregnated in the form of particles is carried out.
- This drying step is in accordance with what has been described generally above.
- step (E) is carried out with particles from step (D), in order to form the oxygen carrier comprising a celsiana matrix BaAl 2 Si 2 0 8 within from which is dispersed the active mass of CuO oxidation reduction, and having the specific porous texture described above. It appears that the impregnation of zeolite shaped and exchanged by barium, by one or more metal precursors of the active redox active mass, such as precursors of Cu, Ni, Co, Fe and / or Mg does not modify the transformation sequence of the zeolite structure mentioned by Esposito et al. 2004, but phase transition temperatures are lowered.
- the oxygen-carrying solid is intended to be used in a chemical loop-redox process.
- the invention thus relates to a chemical loop redox process using the oxygen carrier solid as described, or prepared according to the method of preparation as described.
- the oxygen-bearing solid described is used in a CLC process of a hydrocarbon feedstock, in which the oxygen-carrying solid is in the form of particles and circulates between at least one reduction zone and an oxidation zone all operating both in a fluidized bed.
- the temperature in the reduction zone and in the oxidation zone is between 400 ° C. and 1400 ° C., and preferably between 600 ° C. and 1100 ° C., and even more preferentially between 800 ° C. and 1100 ° C. ° C.
- the hydrocarbon feedstock treated can be a solid, liquid or gaseous hydrocarbon feedstock: gaseous fuels (eg natural gas, syngas, biogas), liquids (eg fuel oil, bitumen, diesel, gasoline, etc.), or solids (ex. : coal, coke, pet-coke, biomass, oil sands, etc.).
- gaseous fuels eg natural gas, syngas, biogas
- liquids eg fuel oil, bitumen, diesel, gasoline, etc.
- solids e. : coal, coke, pet-coke, biomass, oil sands, etc.
- the operating principle of the CLC process in which the oxygen-bearing solid described is used is as follows: a reduced oxygen-carrying solid is brought into contact with an air flow, or any other oxidizing gas, in a zone reaction called air reactor (or oxidation reactor). This results in a depleted airflow and a particle stream of the reoxidized oxygen carrier.
- the stream of oxidized oxygen carrier particles is transferred to a reduction zone called a fuel reactor (or reduction reactor).
- the flow of particles is brought into contact with a fuel, typically a hydrocarbon feedstock. This results in a combustion effluent and a stream of reduced oxygen carrier particles.
- the CLC installation may include various equipment for heat exchange, pressurization, separation or possible recirculation of material around the air and fuel reactors.
- the hydrocarbon feedstock is brought into contact, for example cocurrently, with the particulate oxygen-carrying solid comprising the oxido-reducing active mass in order to carry out the combustion of said feedstock by reducing the oxido-reducing active mass.
- the redox active mass M x O y, M representing a metal is reduced to the state M x O y 2n-m / 2, through the hydrocarbon feedstock C n H m which is correlatively oxidized in C0 2 and H 2 0, according to the reaction (1) already described, or optionally in mixture CO + H 2 according to the proportions used and the nature of the metal M.
- the combustion of the charge in contact with the active mass is carried out at a temperature generally between 400 ° C.
- the contact time varies depending on the type of fuel load used. It typically varies between 1 second and 10 minutes, for example preferably between 1 and 5 minutes for a solid or liquid charge, and for example preferably from 1 to 20 seconds for a gaseous charge.
- a mixture comprising the gases from the combustion and the particles of the oxygen-carrying solid is removed, typically at the top of the reduction zone.
- Gas / solid separation means such as a cyclone, make it possible to separate the combustion gases from the solid particles of the oxygen carrier in their most reduced state.
- the active mass is restored to its oxidized state M x O y in contact with the air, according to reaction (2) already described (or according to reaction (3) if the oxidizing gas is H 2 0), before returning to the reduction zone, and after being separated from the depleted oxygen air evacuated at the top of the oxidation zone 100.
- the active mass passing alternately from its oxidized form to its reduced form and vice versa, describes an oxidation-reduction cycle.
- the disclosed oxygen carrier solid may also be used in another chemical loop redox process such as a CLR process or a CLOU process.
- the technology used in the chemical loop oxidation reduction process is preferably that of the circulating fluidized bed, but is not limited to this technology, and can be extended to other technologies such as fixed bed, mobile or bubbling bed , or rotating reactor. Examples
- Examples 1 to 7 relate to oxygen-carrying solids not in accordance with the invention.
- Examples 4 and 7 relate to oxygen-carrying solids in accordance with the invention.
- Example 1 Aging test for oxygen-carrying solids in a batch fluidized bed
- the aging of the oxygen carrier solids in a batch fluidized bed was carried out in a unit consisting of a quartz reactor, an automated system for supplying the gas reactor and a system for analyzing the gases leaving the reactor. reactor.
- This aging test approximates the conditions of use of the oxygen-carrying solid in a chemically-looped oxidation-reduction process, in particular of a chemical-reduction oxidation-reduction loop.
- the distribution of gases (CH 4 , CO 2 , N 2 , air) is ensured by mass flow meters. For safety reasons, a nitrogen sweep is carried out after each period of reduction and oxidation.
- the height of the quartz reactor is 30 cm, with a diameter of 4 cm in its lower part (on 24 cm high), and 7 cm in its upper part.
- a quartz sinter is placed at the bottom of the reactor to ensure the distribution of the gases and a good fluidization of the particles.
- Another sinter is placed in the upper part of the reactor to prevent the loss of fines during the test.
- the reactor is heated using an electric oven. Part of the gas leaving the reactor is pumped to the gas analyzers, cooled to condense most of the water formed during the reduction and then dried with calcium chloride.
- the gas concentrations are measured using non-dispersive infrared analyzers for CO, CO 2 and CH 4 , a paramagnetic analyzer for oxygen, and a TCD detector for hydrogen.
- Standard test conditions 100 grams of particles are introduced into the quartz reactor and then heated to 900 ° C under air flow (60 Nl / h). When the temperature of the bed is stabilized at 900 ° C. in air, 250 cycles are carried out according to the following steps:
- Particle size distribution was measured using a Malvern particle size analyzer, using Fraunhofer's theory.
- the granulometer is a Malvern Mastersizer 3000 particle size analyzer, and the measurement is carried out in a liquid way.
- the mercury porosimetry measurements were performed on the Autopore IV device marketed by Micromeritics, considering a mercury surface tension of 485 dyn / cm and a contact angle of 140 °.
- the minimum pore size measurable by mercury porosimetry is 3.65 nm.
- the nitrogen adsorption isotherms were carried out on the ASAP 2420 device marketed by Micromeritics.
- an oxygen-carrying solid is formed from alumina as a support matrix for an active oxide-reduction mass of copper oxide (s).
- the alumina used for this example is Puralox SCCa 150-200 marketed by Sasol.
- the pore volume of the particles measured by mercury porosimetry is 0.450 ml / g, and the pore size distribution is between 5 and 15 nm, centered on 9 nm.
- the macroporous volume of the support measured by mercury porosimetry is 0.007 ml / g (1.5% of the total pore volume).
- the nitrogen adsorption isotherm of Puralox makes it possible to measure a specific surface area of 199 m 2 / g, a microporous volume (pores ⁇ 2 nm) of zero and a mesoporous volume (2 nm ⁇ pores ⁇ 50 nm) of 0.496.
- ml / g. 233 g of Puralox alumina was impregnated according to the dry impregnation method, with 96.5 g of copper nitrate trihydrate dissolved in the necessary volume of demineralized water. After drying at 120 ° C. and calcination at 850 ° C. for 12 hours, a solid containing 12% by weight of CuO is obtained; the crystallographic phases detected by XRD are ⁇ - ⁇ 203 and CuO. The distribution of copper within the particles is homogeneous.
- the pore volume of the particles of the solid obtained, measured by mercury porosimetry, is 0.367 ml / g, of which 0.015 ml / g (ie 4% of the total pore volume measured by mercury porosimetry) is due to the macroporosity.
- the pore size distribution is between 5 and 20 nm and centered on 11.25 nm, as can be seen in the diagram of FIG.
- the nitrogen adsorption isotherm of the oxygen-carrying solid according to this example makes it possible to measure a surface area of 135 m 2 / g, a microporous volume (pore size ⁇ 2 nm) and a mesoporous volume (2 nm ⁇ pores ⁇ 50 nm) of 0.404 ml / g.
- FIG. 1B is a diagram showing the normalized conversion rate Xc of methane as a function of the number N of oxidation-reduction rings in a CLC process using the oxygen carrier solid according to Example 2.
- the conversion of methane is of the order of 98% at the beginning of the test, it increases until reaching 100%, then a progressive deactivation is observed after the hundredth cycle. The conversion then stabilizes around 95%.
- the nature of the active mass used causes the appearance of oxygen during the nitrogen sweeping step.
- the particles can therefore be used indifferently in a CLC or CLOU type process.
- the sample underwent a very significant attrition, with almost all the particles having a size of less than 100 ⁇ , as can be seen in the diagram of the FIG. 1C, representing the particle size distribution ( ⁇ ) of the oxygen carrier solid according to this example before (curve 10) and after (curve 1 1) its use in a CLC process, that is to say before and after the aging test according to Example 1.
- SEM slices on a polished section of the particles after the aging test according to Example 1, such as the plate of FIG. 1D, show that the constitutive aluminic matrix of the particles did not resist the 250 successive redox cycles. Most of the particles are actually in the form of small fragments (a few tens of ⁇ ).
- additional SEM-EDX analyzes show that the finest particles observed (some ⁇ in size) consist almost exclusively of copper and oxygen. This example shows that when the active mass is deposited on a purely mesoporous alumina, the accumulation of redox cycles leads to the cracking of said aluminum matrix, and to the migration of copper within the aluminum matrix to form aggregates composed essentially of copper. The mechanical strength of the cracked ceramic matrix is then insufficient and the life of the particles is drastically reduced.
- Example 3 Carbohydrate carrying solid CuO / Silica Alumina at 5% SiO 2
- an oxygen-carrying solid is formed from silicified alumina at 5% of SiO 2 as a support matrix for an active oxide-reduction mass of copper oxide (s) (CuO and CuAl 2 O 4 ).
- the siliceous alumina used is Siralox 5 sold by Sasol and which contains 5% by weight of silica (SiO 2 ).
- the pore volume measured by mercury porosimetry of the alumino-silicic support is 0.549 ml / g, and the pore size distribution is between 5 and 30 nm, centered on 13 nm.
- the macroporous volume is 0.033 ml / g, ie 6% of the total pore volume measured by mercury porosimetry.
- the nitrogen adsorption isotherm of Siralox 5 makes it possible to measure a specific surface area of 173 m 2 / g, a microporous volume (pore size ⁇ 2 nm) and a mesoporous volume (2 nm ⁇ pores ⁇ 50 nm) of 0.601 ml. /boy Wut.
- the pore volume of the particles measured by mercury porosimetry is 0.340 ml / g, of which 0.029 ml / g (8.5%) is due to macroporosity.
- the pore size distribution is between 7 and 50 nm and centered on 15 nm, as can be seen in the diagram of FIG. 2A representing the volume of mercury injected Vi (ml / g) in the porosity, as well as the ratio dV / dD, as a function of the pore diameter (nm), for the oxygen carrier solid according to this example.
- the particles after impregnation / calcination are essentially mesoporous.
- the specific surface area measured by nitrogen adsorption is 77 m 2 / g.
- the oxygen carrier solid according to Example 3 was aged under the conditions described in Example 1.
- the nature of the active mass used causes the appearance of oxygen during the nitrogen sweeping step.
- the particles can therefore be used indifferently in a CLC or CLOU type process.
- the partial conversion of methane relative to Example 2 is not a problem with respect to the CLC or CLOU process on an industrial scale, the total conversion of the fuel can be achieved by modifying the residence times of the particles. , gas velocities and / or inventory in the reduction reactor.
- the size distribution of the particles after the aging test is similar to that of the material before testing, which indicates a better mechanical strength of the alumina-silica matrix compared to the particles on pure alumina.
- the zone of particles whose morphology is relatively unchanged with respect to the initial silica-alumina consists mainly of alumina and contains only traces of copper, as well as almost all of silicon.
- the presence of silicon in the ceramic matrix thus makes it possible to stabilize said ceramic matrix.
- all the copper initially well dispersed in the mesoporous matrix migrated to the periphery of the particles during successive redox cycles.
- EXAMPLE 4 CuO / Celsiane Oxygen-Bearing Solid
- an oxygen-carrying solid is formed comprising a ceramic matrix of Celsiane in which is dispersed an oxidation-reduction active mass of oxide (s). of copper.
- BaX means zeolite X exchanged with barium
- a zeolitization of the binder by contact of the obtained particles placed in a glass reactor with an aqueous solution of sodium hydroxide concentration 100 g / l at a temperature of 100 ° C with stirring for 3 h.
- the particles are then washed in 3 successive water-washing operations followed by reactor emptying.
- the effectiveness of the washing is ensured by measuring the final pH of the washing water which is between 10 and 10.5.
- barium exchange using a solution of 0.5 M barium chloride at 95 ° C in four steps. At each step, the volume ratio of solution to solid mass is 20 ml / g and the exchange is continued for 4 hours each time.
- the barium exchange rate of this zeolite precursor is 95%.
- the pore volume of the precursor of the shaped ceramic matrix which is a particulate macroporous BaX zeolite material measured by mercury porosimetry, is 0.206 ml / g.
- the macroporous volume (pore size> 50 nm) is 0.191 ml / g, and the mesoporous volume (3.65 nm ⁇ pore ⁇ 50 nm) is 0.015 ml / g.
- the size distribution of the macropores is between 100 nm and 1000 nm, centered on 330 nm. This distribution is visible in FIG. 3C, where Vi Z refers to the porosity of the precursor of the ceramic matrix (macroporous BaX zeolite material formed).
- the nitrogen adsorption isotherm of this precursor of the ceramic matrix makes it possible to measure a specific surface area of 676 m 2 / g, a microporous volume (pore size ⁇ 2 nm) of 0.24 ml / g and a mesoporous volume ( 2 nm ⁇ pores ⁇ 50 nm) of 0.04 ml / g.
- the macroporous volume (pore size> 50 nm) is 0.145 ml / g (94.8%), and the mesoporous volume is 0.008 ml / g.
- the size distribution of the macropores is between 100 nm and 4000 nm, centered on 400 nm.
- the grain density is 2086 kg / m 3 . This distribution is visible in FIG. 3C, where Vi S refers to the porosity of the initial oxygen-carrying solid (before aging test).
- the specific surface area of the oxygen carrier according to the invention measured by nitrogen adsorption according to the BET method, is 5 m 2 / g.
- the nature of the active mass used causes the appearance of oxygen during the nitrogen sweeping step.
- the particles can therefore be used indifferently in a CLC or CLOU type process.
- the partial conversion of methane relative to Example 2 is not a problem with respect to the CLC or CLOU process on an industrial scale, the total conversion of the fuel can be achieved by modifying the residence times of the particles. , gas velocities and / or inventory in the reduction reactor.
- Example 3 the particle size distribution after the aging test is similar to that of the pre-test material. Contrary to the observations of Example 3, the copper distribution after 250 cycles in a batch fluidized bed within the particles of the oxygen carrier according to the invention remains generally homogeneous, with a markedly minimized tendency for copper to migrate towards the periphery of the particles, as visible on the SEM image (a) and the EDX map (b) of the 3D figure. The presence of cuprous nodules of size between 0, 1 ⁇ and 5 ⁇ in the porosity. This texture is clearly visible in the SEM backscattered electron micrograph of FIG. 3E relating to a detail of a particle of the oxygen-carrying solid after aging.
- the main crystalline phases detected by DRX after aging are tenorite (CuO) and monoclinic celsiane. Some very low intensity peaks characteristic of hexagonal celsiane and copper aluminate (CuAl 2 0 4 ) are also present.
- the oxygen carrier solid according to this example 4 has a good sintering resistance.
- the oxygen-carrying solid after 250 oxidation-reduction cycles nevertheless retains a pore size distribution and a pore volume sufficient to limit the migration of copper within the particles.
- the morphological evolution of the oxygen-carrying solid according to the invention thus makes it possible to envisage the prolonged use of these particles in an industrial process in a circulating fluidized bed.
- an oxygen carrier solid comprising a ceramic matrix of nepheline (feldspathoid) within which is dispersed an active oxide redox oxide (s) active mass.
- the zeolitization steps of the binder and exchange with barium have not been realized.
- the pore volume of the precursor of the ceramic matrix (zeolite material macroporous NaX) shaped, measured by mercury porosimetry, is 0.336 ml / g.
- the macroporous volume (pore size> 50 nm) is 0.296 ml / g, and the mesoporous volume is 0.040 ml / g.
- the size distribution of the macropores is between 100 nm and 1000 nm, centered on 330 nm. This distribution is visible in FIG. 4A where Vi Z refers to the porosity of the precursor of the ceramic matrix.
- the nitrogen adsorption isotherm of the precursor of the ceramic matrix makes it possible to measure a specific surface area of 749 m 2 / g, a microporous volume (pores ⁇ 2 nm) of 0.260 ml / g and a mesoporous volume (2 nm ⁇ pores ⁇ 50 nm) of 0.12 ml / g.
- tenorite (CuO) and nepheline of formula Na 3 . 6 AI 3 . 6 Si4.4Oi 6 are the only two phases detected by DRX.
- the pore volume of the particles of Example 5, measured by mercury porosimetry, is 0.103 ml / g, with a wide pore size distribution (130 nm to 4.7 ⁇ m) centered on 750 nm.
- the pore volume consists of 100% macropores. This distribution is visible in FIG. 4A, where Vi refers to the porosity of the initial oxygen-carrying solid (before aging test).
- the conversion of methane to water and carbon dioxide is stable, but only around 30% over the entire test.
- the partial conversion of methane relative to Example 2 is not a problem with respect to the CLC or CLOU process on an industrial scale, the total conversion of the fuel can be achieved by modifying the residence times of the particles. , the gas velocities and / or the inventory in the reduction reactor, but the solid according to Example 5 is less efficient than that of Example 4 and would require a higher inventory.
- the second morphology consists of macroporous particles in which copper forms micrometric nodules (SEM image (a) of Figure 4C).
- the relatively low melting temperature of nepheline (1230 ° C) relative to celsian (1760 °) may be responsible for the higher densification observed. It is likely that some of the copper trapped in particles with a dense matrix is not accessible to gas, hence the conversion of methane lower than in Example 4. In addition to decreased reactivity compared to Example 4, the formation of a metal oxide crust at the periphery of a high proportion particles makes the use of this type of particles unthinkable in a fluidized bed circulating on an industrial scale (risk of agglomeration and loss of copper by attrition too large).
- the pore volume of the particles measured by mercury porosimetry (0.088 ml / g) is of the same order of magnitude as before, as is the pore size distribution (1 10 nm - 4.7 ⁇ m).
- an oxygen-carrying solid comprising a ceramic matrix of albite (feldspathoid) within which an oxidation-reduction active mass is dispersed. copper oxide (s).
- a zeolitization of the binder by contact of the obtained particles placed in a glass reactor with an aqueous solution of sodium hydroxide concentration 100 g / l at a temperature of 100 ° C with stirring for 3 h.
- the particles are then washed in three successive operations of washing with water followed by the emptying of the reactor. The effectiveness of the washing is ensured by measuring the final pH of the washing water which is between 10 and 10.5.
- the pore volume of the precursor of the shaped ceramic matrix (macroporous NaY zeolite material), measured by mercury porosimetry, is 0.376 ml / g.
- Volume macroporous (pore size> 50 nm) is 0.319 ml / g, and the mesoporous volume (3.65 nm ⁇ pores ⁇ 50 nm) is 0.057 ml / g.
- the size distribution of the macropores is between 100 nm and 1000 nm, centered on 330 nm. This distribution is visible in Figure 5A where Vi Z refers to the porosity of the precursor of the ceramic matrix.
- the precursor nitrogen adsorption isotherm of the ceramic matrix makes it possible to measure a specific surface area of 676 m 2 / g, a microporous volume (pore size ⁇ 2 nm) of 0.24 ml / g and a mesoporous volume (2 nm). ⁇ pores ⁇ 50 nm) of 0.04 ml / g.
- the porosity of the particles of the oxygen-bearing solid is only 9% and the pore size distribution is very wide (from 30 nm to 5000 nm, or even Figure 5A curve Vi S), reflecting the presence of very large cavities created during the calcination and observed by SEM, as well as a densification of the amorphous matrix of silica-alumina (SEM image of Figure 5B).
- the total pore volume is 0.043 ml / g.
- the macroporous volume (pore size> 50 nm) is 0.038 ml / g (88.4%), and the mesoporous volume is 0.005 ml / g.
- the porosity of the particles is only 4%, consisting essentially of large cavities still present within the particles (size centered around 3700 nm).
- the low conversion of methane can be directly related to the lack of porosity of the matrix, which encapsulates a large proportion of copper and makes it inaccessible to different gases.
- the gradual increase in conversion is probably due to the migration of copper to the periphery of the particles over the redox cycles.
- the SEM analysis after aging shows that a copper crust has accumulated on the surface of the particles during the test (SEM image of FIG. 5C). This accumulation of copper on the surface is responsible for the agglomeration of the particles. A significant proportion of the copper is still trapped inside the matrix at the end of the test.
- the XRD analysis shows that the initially amorphous matrix formed a crystalline phase, the albite (NaAISi 3 0 8 ), whose melting point (1120 ° C.) is weak relative to the celsiane.
- the presence of tenorite (CuO), quartz, cuprite (Cu 2 O) and traces of nepheline is also observed.
- Example 7 CuO / Slawsonite oxygen carrier solid
- an oxygen carrier solid comprising a slawsonite ceramic matrix (feldspar) in which is dispersed an active oxide redox oxide (s) active mass.
- SrLSX means zeolite LSX exchanged with strontium
- a zeolitization of the binder by contact of the obtained particles placed in a glass reactor with an aqueous solution of sodium hydroxide concentration 100 g / l at a temperature of 100 ° C with stirring for 3 h.
- the particles are then washed in 3 successive operations of washing with water followed by the emptying of the reactor.
- the effectiveness of the washing is ensured by measuring the final pH of the washing water which is between 10 and 10.5.
- an exchange with strontium by means of a solution of 0.5 M strontium chloride at 95 ° C. in 4 steps. At each step, the volume ratio of solution to solid mass is 20 ml / g and the exchange is continued for 4 hours each time. Between each exchange, the solid is washed several times in order to rid it of excess salt.
- the strontium exchange rate of this zeolite precursor is 94%.
- the pore volume of the precursor of the shaped ceramic matrix (macroporous SrLSX zeolite material), measured by mercury porosimetry, is 0.195 ml / g.
- the macroporous volume (pore size> 50 nm) is 0.183 ml / g, and the mesoporous volume is 0.012 ml / g.
- the size distribution of the macropores is between 50 nm and 950 nm, centered on 300 nm. This distribution is visible in Figure 6A where Vi Z refers to the porosity of the precursor of the ceramic matrix.
- the porous volume of the oxygen carrier solid according to the invention measured by mercury porosimetry, is 0.093 ml / g.
- the macroporous volume (pore size> 50 nm) is 0.091 ml / g, and the mesoporous volume is 0.002 ml / g.
- the size distribution of the macropores is between 50 nm and 3500 nm, centered on 350 nm. This distribution is visible in FIG. 6A where Vi S refers to the porosity of the initial oxygen-carrying solid (before aging test).
- the specific surface area of the oxygen carrier according to the invention measured by nitrogen adsorption according to the BET method, is 3 m 2 / g.
- the nature of the active mass used causes the appearance of oxygen during the nitrogen sweeping step.
- the particles can therefore be used indifferently in a CLC or CLOU type process.
- the partial conversion of methane relative to Example 2 is not a problem with respect to the CLC or CLOU process on an industrial scale, the total conversion of the fuel can be achieved by modifying the residence times of the particles. , gas velocities and / or inventory in the reduction reactor.
- Example 3 the particle size distribution after the aging test is similar to that of the pre-test material. Contrary to the observations of Example 3, the copper distribution after 250 cycles in a batch fluidized bed within the particles of the oxygen carrier according to the invention remains generally homogeneous, with a markedly minimized tendency for copper to migrate towards the periphery of the particles. The presence of copper-bearing nodules is still observed between 0, 1 ⁇ and 5 ⁇ in the porosity.
- FIG. 6B which is an SEM image of a portion of a particle of the oxygen-carrying solid after aging, shows this texture.
- the main crystalline phases detected by DRX after aging are tenorite (CuO) and monoclinic slawsonite. Some very weak peaks characteristic of hexagonal slawsonite and copper aluminate (CUAI2O4) are also present.
- the porous particle volume measured by mercury porosimetry decreased by 23% (0.072 ml / g) during aging, and the pore size increased (pore size distribution centered on 550 nm). A slight sintering of the slawsonite matrix therefore took place.
- the oxygen-carrying solid after 250 oxidation-reduction cycles nevertheless retains a pore size distribution and a pore volume sufficient to limit the migration of copper within the particles.
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16/471,403 US11071971B2 (en) | 2016-12-23 | 2017-12-21 | Macroporous oxygen carrier solid with a refractory feldspar/feldspathoid, method for the preparation thereof, and use thereof in a chemical-looping oxidation-reduction method |
AU2017383046A AU2017383046A1 (en) | 2016-12-23 | 2017-12-21 | Macroporous oxygen carrier solid with a refractory feldspar/felpdspathoid, method for the preparation thereof, and use thereof in a chemical-looping oxidation-reduction method |
EP17838128.1A EP3558518A1 (fr) | 2016-12-23 | 2017-12-21 | Solide porteur d'oxygène macroporeux avec feldspath/felpdspathoïde réfractaire, son procédé de préparation, son utilisation dans un procédé d'oxydo-réduction en boucle chimique |
CN201780079817.4A CN110214055B (zh) | 2016-12-23 | 2017-12-21 | 具有难熔长石/似长石的大孔氧载体固体,其制备方法及其在化学链氧化还原方法中的用途 |
CA3045289A CA3045289A1 (fr) | 2016-12-23 | 2017-12-21 | Solide porteur d'oxygene macroporeux avec feldspath/felpdspathoide refractaire, son procede de preparation, son utilisation dans un procede d'oxydo-reduction en boucle chimique |
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FR1663302A FR3061037B1 (fr) | 2016-12-23 | 2016-12-23 | Solide porteur d'oxygene a base de tectosilicates, son procede de preparation et son utilisation pour un procede d'oxydo-reduction en boucle chimique |
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EP (1) | EP3558518A1 (fr) |
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CA (1) | CA3045289A1 (fr) |
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FR3061036B1 (fr) * | 2016-12-23 | 2021-07-02 | Ifp Energies Now | Solide porteur d'oxygene macroporeux a matrice ceramique d'oxydes, son procede de preparation et son utilisation pour un procede d'oxydo-reduction en boucle chimique |
US11433385B1 (en) * | 2019-09-13 | 2022-09-06 | Energy, United States Department Of | Encapsulation method for preparation of pellets with high attrition resistance |
CN111996060B (zh) * | 2020-09-15 | 2022-06-24 | 中国石油化工股份有限公司 | 一种钙钛矿结构氧化物修饰的钛铁矿石载氧体及其制备方法 |
FR3125441B1 (fr) | 2021-07-23 | 2023-07-14 | Ifp Energies Now | Procédé et installation CLC avec récupération d’oxygène gazeux produit par un porteur d’oxygène |
CN114133274B (zh) * | 2021-12-17 | 2023-06-13 | 福建省德化县邦威陶瓷有限公司 | 一种长余辉荧光釉陶瓷制品及其制备方法 |
CN116409794B (zh) * | 2023-06-09 | 2024-01-19 | 山东理工大学 | 一种锶长石转晶合成高硅ssz-13分子筛的方法 |
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- 2017-12-21 CN CN201780079817.4A patent/CN110214055B/zh active Active
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Publication number | Publication date |
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FR3061037A1 (fr) | 2018-06-29 |
AU2017383046A1 (en) | 2019-07-25 |
FR3061037B1 (fr) | 2021-07-02 |
EP3558518A1 (fr) | 2019-10-30 |
CN110214055A (zh) | 2019-09-06 |
CN110214055B (zh) | 2022-07-12 |
US11071971B2 (en) | 2021-07-27 |
US20190381488A1 (en) | 2019-12-19 |
CA3045289A1 (fr) | 2018-06-28 |
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