WO2011095656A1 - Method for the selective adsorption of phenols - Google Patents
Method for the selective adsorption of phenols Download PDFInfo
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- WO2011095656A1 WO2011095656A1 PCT/ES2011/000019 ES2011000019W WO2011095656A1 WO 2011095656 A1 WO2011095656 A1 WO 2011095656A1 ES 2011000019 W ES2011000019 W ES 2011000019W WO 2011095656 A1 WO2011095656 A1 WO 2011095656A1
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- Prior art keywords
- selective
- catalytic
- phenols
- phenol
- oxide
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 17
- 150000002989 phenols Chemical class 0.000 title claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000002427 irreversible effect Effects 0.000 claims abstract description 13
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003463 adsorbent Substances 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 230000008030 elimination Effects 0.000 claims description 5
- 238000003379 elimination reaction Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004182 chemical digestion Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims 2
- 238000011084 recovery Methods 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 1
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- 239000011852 carbon nanoparticle Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000002077 nanosphere Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical class [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 241000252073 Anguilliformes Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 1
- 238000000619 electron energy-loss spectrum Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001239 high-resolution electron microscopy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/30—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
Definitions
- the scope of the present invention is the application of catalytic nanotechnology to the water purification sector, in particular the elimination of toxic organic compounds, such as phenol and its derivatives (chlorine and nitro phenols), in liquid effluents and operating in mild reaction conditions. It is also about applying the same fundamentals of phenol elimination in the formation of carbon nanoparticles.
- adsorption processes The removal of organic pollutants using different adsorbents is recognized as one of the most effective methods, commonly used in drinking water treatment plants. Active carbon is one of the most versatile adsorbents, given its good adsorbent properties for a wide range of organic pollutants (RG Peel and A. Benedek: Environmental Science & Technology, 14, 66, (2002); LR Radovic, C. Moreno -Castilla, and J. Rivera-Utrilla: Chem.Phys.Carbon, 27, 227, (2000)). However, after saturation of the adsorbent, it loses its properties and its regeneration can be expensive.
- Figure 1 shows the removal of total carbon per gram of catalyst as a function of time in tests where different ratios of initial phenol concentration and amount of a CeMnO x catalyst were used. It can be seen that in all cases, with the exception of the test carried out with 500 ppm of phenol, similar results are obtained indicating that the catalyst can only remove about 1000 ppm of the phenol present in the solution.
- Figure 2 shows the milligrams of carbon found per grams of catalyst after the tests shown in Figure 1. It is obvious that the sample is capable of adsorbing a maximum carbon content per gram of catalyst of 255 mg (equivalent to about 1000 ppm of phenol), producing its subsequent deactivation. On the other hand, the study by electron microscopy of the sample after reaction allowed to observe how all the catalyst particles are completely covered with an amorphous film, about 20 nm thick, which corresponds to the carbonaceous deposit (Figure 3).
- Figure 3 represents a catalytic activity test of the fresh sample and the deactivated and subsequently regenerated sample. It can be seen that the sample is fully regenerated. Therefore it is logical to propose a phenol elimination system in which this regeneration phase is included, in which the actual combustion of organic matter would take place.
- Table 1 shows the maximum carbon content expressed as a percentage and in mg of carbon per gram of catalyst that was obtained by using different cerium-manganese composites with various compositions.
- Figure 1 Reduction of the total carbon concentration per gram of catalyst as a function of time in tests where the following ratios of initial phenol concentration and catalyst quantity were used: 500 ppm / 1 g ( ⁇ ), 1900 ppm / 1 g ( ⁇ ), 3800 ppm / 1 g ( ⁇ ) and 3800 ppm / 2 g ( ⁇ ).
- the catalyst used was CM50, the operating conditions being 90 ° C and 0.5 MPa.
- Figure 3 High resolution electron microscopy image of the CM50 catalyst after a wet oxidation test of phenol with an initial concentration of 5000 ppm at 90 ° C and 0.5 MPa of partial oxygen pressure.
- Figure 4 Diagrams of different mass-load ratios obtained in an OTP experience, after a pretreatment in He at 125 ° C, of the solid recovered after a CWO test, where 500 ppm of carbon was used, the CM50 sample and the operating conditions were 90 ° C and 0.5 MPa of P02. Figure 5.
- - Evolution of the total carbon concentration using the fresh CM50 sample ( A ) and another regenerated at 500 0 C ( ⁇ ). Said catalyst comes from a test carried out under the following conditions: 90 ° C, 0.5 MPa of P02 and Cfo / CCat ratio 3800/2.
- Figure 6. Spherical carbon nanoparticles generated by exposure to manganese oxides dispersed in silica and previously reduced to the reaction medium.
- Figure 7. Spherical carbon nanoparticles generated by exposing cerium-manganese composites and previously reduced to the reaction medium.
- An EDS spectrum is included inside which indicates that the nanoparticles are formed of ultradispersed manganese and activated carbon.
- Figures 8 and 9. - Typical spectrum of EELS in the area of C 1s and O 1s corresponding to the spherical carbon nanoparticles obtained and comparison with activated carbon and graphite.
Abstract
The invention relates to the use of manganese oxides or mixed systems based on same for the catalytic, selective and irreversible adsorption of phenol dissolved in water. The invention also relates to the possibility of using said catalytic, selective and irreversible adsorption process for eliminating phenol from liquid effluents, with recuperation of the adsorbent, and for the synthesis of spherical nanoparticles of homogeneous size. The invention further relates to the nanoparticles obtained by said method and to the use thereof in various applications.
Description
PROCEDIMIENTO PARA LA ADSORCIÓN SELECTIVA DE FENOLES. PROCEDURE FOR THE SELECTIVE ADSORTION OF PHENOLS.
SECTOR DE LA TÉCNICA SECTOR OF THE TECHNIQUE
El ámbito de aplicación de la presente invención es la aplicación de nanotecnología de catalizadores al sector de la depuración de aguas, en concreto a la eliminación de compuestos orgánicos tóxicos, como el fenol y sus derivados (cloro y nitro fenoles), en efluentes líquidos y operando en condiciones suaves de reacción. Asimismo se trata de aplicar los mismos fundamentos de la eliminación del fenol en la formación nanopartículas de carbón. The scope of the present invention is the application of catalytic nanotechnology to the water purification sector, in particular the elimination of toxic organic compounds, such as phenol and its derivatives (chlorine and nitro phenols), in liquid effluents and operating in mild reaction conditions. It is also about applying the same fundamentals of phenol elimination in the formation of carbon nanoparticles.
ANTECEDENTES DE LA INVENCIÓN BACKGROUND OF THE INVENTION
El empleo de ciertos abonos y plaguicidas en la agricultura intensiva, así como los vertidos incontrolados de la actividad industrial, están provocando la progresiva contaminación de los principales recursos hídricos mundiales. Esta situación, unida a las actuales normativas medioambientales, ha provocado un creciente interés por el desarrollo de nuevas tecnologías para el tratamiento integral de aguas residuales. Cabe resaltar que el método más común es la degradación biológica. Este método consiste en transformar la materia orgánica del efluente en biomasa y finalmente en dióxido de carbono y agua. Para ello se emplean lodos activos, lechos bacterianos y biodiscos. La gran variedad de compuestos que se pueden tratar convierten a esta técnica en la más adecuada para el tratamiento de aguas residuales con orígenes diversos, como es el caso de las aguas residuales urbanas. No obstante, determinados compuestos con alto poder bacteriostático y bactericida, como es el caso del fenol, reducen drásticamente su efectividad
hasta el punto de hacerlos inviables. Así, por ejemplo, en el caso del fenol se ha observado que concentraciones por encima de 70-200 ppm resultan tóxicas para la población microbiana (R. Guerra: Chemosphere, 44, 1737, (2001 ); F. Luck: Catal.Today, 27, 195, (1996); F. Luck: Catal.Today, 53, 81 , (1999); A. Santos, P. Yustos, A. Quintanilla, F. García Ochoa, J. A. Casas, and J. J. Rodrigues: Environ.Sci.Technol. , 38, 133, (2004)). No obstante, estos métodos pueden ser empleados como complemento a otras técnicas previas que reduzcan la toxicidad y la concentración de este tipo de contaminantes. The use of certain fertilizers and pesticides in intensive agriculture, as well as uncontrolled discharges of industrial activity, are causing the progressive contamination of the world's main water resources. This situation, together with the current environmental regulations, has caused a growing interest in the development of new technologies for the integral treatment of wastewater. It should be noted that the most common method is biological degradation. This method consists of transforming the organic matter of the effluent into biomass and finally carbon dioxide and water. For this, active sludge, bacterial beds and biodisks are used. The great variety of compounds that can be treated make this technique the most suitable for the treatment of wastewater with diverse origins, as is the case of urban wastewater. However, certain compounds with high bacteriostatic and bactericidal power, such as phenol, drastically reduce their effectiveness to the point of making them unfeasible. Thus, for example, in the case of phenol it has been observed that concentrations above 70-200 ppm are toxic to the microbial population (R. Guerra: Chemosphere, 44, 1737, (2001); F. Luck: Catal.Today , 27, 195, (1996); F. Luck: Catal.Today, 53, 81, (1999); A. Santos, P. Yustos, A. Quintanilla, F. García Ochoa, JA Casas, and JJ Rodrigues: Environ .Sci.Technol., 38, 133, (2004)). However, these methods can be used as a complement to other prior techniques that reduce the toxicity and concentration of this type of contaminants.
Entre los procesos que pueden llegar a reducir la toxicidad de los efluentes se encuentran los procesos de adsorción. La eliminación de contaminantes orgánicos empleando distintos adsorbentes es reconocido como uno de los métodos más eficaces, empleándose comúnmente en las plantas de tratamiento de agua potable. El carbón activo es uno de los adsorbentes más versátiles, dada sus buenas propiedades adsorbentes para una amplia gama de contaminantes orgánicos (R. G. Peel and A. Benedek: Environmental Science & Technology, 14, 66, (2002); L. R. Radovic, C. Moreno-Castilla, and J. Rivera-Utrilla: Chem.Phys.Carbon, 27, 227, (2000)). No obstante, tras la saturación del adsorbente, éste pierde sus propiedades y su regeneración puede ser costosa. Uno de los procesos más comunes de regeneración supone la desorción de los compuestos previamente adsorbidos empleando un efluente líquido caliente. No obstante, tras dicho proceso debe de incluirse otro para eliminar el flujo pre-concentrado de contaminante. Por otra parte, los procesos de regeneración suelen conllevar pérdidas de actividad notable debido a la perdida de fase activa o la modificación de la misma (Y. I. Matatov-Meytal, M. Sheintuch, G. E. Shter, and G. S. Grader: Carbón, 35, 1527, (1997); N. Roostaei and F. H. Tezel: Journal of Environmental Management, 70, 157, (2004); M. Sheintuch and Y. I. Matatov-Meytal: Catalysis Today, 53, 73, (1999)).
Cabe destacar que algunos autores han encontrado que las capacidades de adsorción de fenol aumentan notablemente por la presencia de distintas impurezas en los carbones activos y condiciones oxidantes (L. J. Uranowski, C. H. Tessmer, and R. D. Vidic: Water Res., 32, 1841 , (1998)). En estos casos se observa que una parte de la adsorción es reversible, mientras que la otra es irreversible. Por tanto, esta adsorción irreversible es un proceso deseable puesto que aumenta notablemente la capacidad de eliminar el fenol en nuestro efluente. Sin embargo, las dificultades de eliminar dicho fenol adsorbido irreversiblemente en el adsorbente hacen imposible su reutilización y disminuye las posibilidades de su aplicabilidad en procesos reales. Among the processes that can reduce the toxicity of effluents are adsorption processes. The removal of organic pollutants using different adsorbents is recognized as one of the most effective methods, commonly used in drinking water treatment plants. Active carbon is one of the most versatile adsorbents, given its good adsorbent properties for a wide range of organic pollutants (RG Peel and A. Benedek: Environmental Science & Technology, 14, 66, (2002); LR Radovic, C. Moreno -Castilla, and J. Rivera-Utrilla: Chem.Phys.Carbon, 27, 227, (2000)). However, after saturation of the adsorbent, it loses its properties and its regeneration can be expensive. One of the most common regeneration processes involves the desorption of previously adsorbed compounds using a hot liquid effluent. However, after this process another one must be included to eliminate the pre-concentrated flow of contaminant. On the other hand, the regeneration processes usually lead to significant losses of activity due to the loss of active phase or the modification thereof (YI Matatov-Meytal, M. Sheintuch, GE Shter, and GS Grader: Coal, 35, 1527, (1997); N. Roostaei and FH Tezel: Journal of Environmental Management, 70, 157, (2004); M. Sheintuch and YI Matatov-Meytal: Catalysis Today, 53, 73, (1999)). It should be noted that some authors have found that the adsorption capacities of phenol are markedly increased by the presence of different impurities in the active carbons and oxidizing conditions (LJ Uranowski, CH Tessmer, and RD Vidic: Water Res., 32, 1841, (1998 )). In these cases it is observed that one part of the adsorption is reversible, while the other is irreversible. Therefore, this irreversible adsorption is a desirable process since it greatly increases the ability to eliminate phenol in our effluent. However, the difficulties of eliminating said irreversibly adsorbed phenol in the adsorbent make its reuse impossible and diminishes the possibilities of its applicability in real processes.
DESCRIPCIÓN DE LA INVENCIÓN DESCRIPTION OF THE INVENTION
Los datos obtenidos en nuestro laboratorio indican los óxidos de manganeso y sistemas mixtos basados en el mismo, bien sea soportados o formando composites, trabajando a temperaturas del orden de los 90-120°C y presiones parciales de oxígeno del orden de 0.1-2 MPa., son capaces de catalizar la polimerización del fenol, así como del nitrofenol, del clorofenol o de una mezcla de los mismos, y la adsorción selectiva de los compuestos formados sobre la superficie del sólido. Esta adsorción es irreversible y es similar a la observada en carbones activos, la cual se describió anteriormente. Una vez dispuestos sobre la superficie, dichos compuestos pueden ser mineralizados simplemente por combustión in-situ. Este mecanismo en dos etapas podría constituirse en la base de una nueva tecnología de depuración de aguas basada en: The data obtained in our laboratory indicate manganese oxides and mixed systems based on it, whether supported or forming composites, working at temperatures of the order of 90-120 ° C and partial oxygen pressures of the order of 0.1-2 MPa ., are capable of catalyzing the polymerization of phenol, as well as nitrophenol, chlorophenol or a mixture thereof, and selective adsorption of the compounds formed on the surface of the solid. This adsorption is irreversible and is similar to that observed in active carbons, which was described above. Once arranged on the surface, said compounds can be simply mineralized by in-situ combustion. This two-stage mechanism could be the basis of a new water purification technology based on:
1 ) Adsorción irreversible por polimerización en la superficie del catalizador y 2) Combustión, in-situ, por calcinación a temperaturas inferiores a 200°C.
Nuestros datos indican que la segunda etapa de calcinación produce la combustión total de la materia orgánica adsorbida en la superficie del catalizador, sin afectar sus propiedades, sirviendo de esta manera para la regeneración completa del mismo. Esta sería la principal ventaja del método propuesto, debido a que en los métodos de depuración de aguas empleando carbones activos los procesos de regeneración de estos materiales son complicados y costosos. Además, en este último caso no se eliminan realmente los residuos, sino que sólo se concentran en volúmenes inferiores de líquidos, siendo necesario un proceso de depuración posterior. 1) Irreversible adsorption by polymerization on the catalyst surface and 2) Combustion, in-situ, by calcination at temperatures below 200 ° C. Our data indicates that the second stage of calcination produces the total combustion of the organic matter adsorbed on the surface of the catalyst, without affecting its properties, thus serving for its complete regeneration. This would be the main advantage of the proposed method, because in the methods of water purification using active carbons the regeneration processes of these materials are complicated and expensive. In addition, in the latter case, the waste is not really eliminated, but only concentrated in lower volumes of liquids, and a subsequent purification process is necessary.
Actualmente disponemos de datos de la efectividad del método al emplear sistemas basados en los distintos óxidos de manganeso soportados en varios materiales como Si02, Al203, Ce02, CeZrOx. Igualmente, también se han estudiado nano-composites de óxidos de Ce-Mn. No obstante, similares resultados son esperables al emplear otros materiales como soportes o composites. Son especialmente interesantes los sólidos con altas superficie específica del tipo de carbones activos, la SB15 y otros soportes nano- estructurados. We currently have data on the effectiveness of the method when using systems based on the different manganese oxides supported in various materials such as Si0 2 , Al 2 0 3 , Ce0 2 , CeZrO x . Similarly, nano-composites of Ce-Mn oxides have also been studied. However, similar results are expected when using other materials such as media or composites. Especially interesting are solids with high specific surface area of the type of active carbon, the SB15 and other nanostructured supports.
En la figura 1 , a modo de ejemplo, se muestra la eliminación de carbono total por gramo de catalizador en función del tiempo en ensayos donde se emplearon distintas relaciones de concentración inicial de fenol y cantidad de un catalizador CeMnOx. Puede observarse que en todos los casos, con la excepción del ensayo realizado con 500 ppm de fenol, se consiguen resultados similares que indican que el catalizador sólo puede eliminar unos 1000 ppm del fenol presente en la disolución. En la Figura 2 se muestran los miligramos de carbono encontrados por gramos de catalizador tras los ensayos mostrados en la figura 1. Es obvio que la muestra es capaz de adsorber un contenido máximo de carbono por gramo de catalizador de 255 mg (equivalente a unos 1000 ppm de fenol), produciéndose su posterior desactivación. Por otra parte, el estudio mediante microscopía electrónica
de la muestra tras reacción permitió observar cómo todas las partículas del catalizador se encuentran completamente cubiertas de una película amorfa, de unos 20 nm de espesor, la cual se corresponde con el depósito carbonoso (Figura 3). Figure 1, by way of example, shows the removal of total carbon per gram of catalyst as a function of time in tests where different ratios of initial phenol concentration and amount of a CeMnO x catalyst were used. It can be seen that in all cases, with the exception of the test carried out with 500 ppm of phenol, similar results are obtained indicating that the catalyst can only remove about 1000 ppm of the phenol present in the solution. Figure 2 shows the milligrams of carbon found per grams of catalyst after the tests shown in Figure 1. It is obvious that the sample is capable of adsorbing a maximum carbon content per gram of catalyst of 255 mg (equivalent to about 1000 ppm of phenol), producing its subsequent deactivation. On the other hand, the study by electron microscopy of the sample after reaction allowed to observe how all the catalyst particles are completely covered with an amorphous film, about 20 nm thick, which corresponds to the carbonaceous deposit (Figure 3).
Por su parte, estudios de oxidación térmica programada han permitido determinar que este depósito carbonoso puede eliminarse fácil y rápidamente mediante un tratamiento de oxidación al aire a temperaturas inferiores a 250 °C (Figura 3). La figura 4 representa un ensayo de actividad catalítica de la muestra fresca y de la muestra desactivada y posteriormente regenerada. Puede observarse que la muestra es totalmente regenerada. Por consiguiente es lógico proponer un sistema de eliminación de fenol en el que se incluya esta fase de regeneración, en la cual tendría lugar la combustión real de la materia orgánica. Se trataría, por tanto, de procesos combinados que implicarían una primera fase donde los contaminantes tras sufrir un proceso de polimerización se adsorberían en el óxido, y una segunda etapa en la cual se sometería al catalizador a un tratamiento de calcinación que conduciría a la oxidación del residuo carbonoso. On the other hand, studies of programmed thermal oxidation have allowed to determine that this carbonaceous deposit can be removed easily and quickly by means of an oxidation treatment in the air at temperatures below 250 ° C (Figure 3). Figure 4 represents a catalytic activity test of the fresh sample and the deactivated and subsequently regenerated sample. It can be seen that the sample is fully regenerated. Therefore it is logical to propose a phenol elimination system in which this regeneration phase is included, in which the actual combustion of organic matter would take place. It would be, therefore, combined processes that would involve a first phase where the contaminants after undergoing a polymerization process would be adsorbed on the oxide, and a second stage in which the catalyst would be subjected to a calcination treatment that would lead to oxidation of the carbonaceous residue.
En la tabla 1 se muestra los contenidos máximos de carbono expresado en tanto por ciento y en mg de carbono por gramo de catalizador que se obtuvo al emplear distintos composites de cerio-manganeso con varias composiciones. Table 1 shows the maximum carbon content expressed as a percentage and in mg of carbon per gram of catalyst that was obtained by using different cerium-manganese composites with various compositions.
Carbono Carbon
Muestra Cdc D Sample Cdc D
(ppm) (%) (ppm) (mg C/g cat) (ppm) (%) (ppm) (mg C / g cat)
CM0 620 14,81 615 174 CM0 620 14.81 615 174
CM15 1022 18,79 986 256 CM15 1022 18.79 986 256
CM50 986 18,72 960 250 CM50 986 18.72 960 250
CM85 792 15,49 770 200 CM85 792 15.49 770 200
Tabla 1
Similares resultados se muestran en la tabla 2, pero en este caso las muestras empleadas fueron óxidos de manganeso disperso sobre distintos soportes. Table 1 Similar results are shown in Table 2, but in this case the samples used were manganese oxides dispersed on different supports.
Carbono D Carbon D
Muestra Sample
(%) (ppm) (mg C/g cat) (%) (ppm) (mg C / g cat)
5% MnOx/Ce02 cale 500°C 8.1 345.99 89.9574 5% MnO x / Ce0 2 cale 500 ° C 8.1 345.99 89.9574
5% MnOx/Si02 cale 500°C 2.0 76.19 19.8094 5% MnO x / Si0 2 cale 500 ° C 2.0 76.19 19.8094
20% MnOx/Ce02 cale 500°C 7.3 326.8 84.968 20% MnO x / Ce0 2 cale 500 ° C 7.3 326.8 84.968
20% MnOx/Si02 cale 500°C 3.4 140.03 36.4078 20% MnO x / Si0 2 cale 500 ° C 3.4 140.03 36.4078
Tabla 2 Table 2
Cabe indicarse que valores entorno a 100 mg de fenol/g han sido obtenidos por distintos autores empleando carbones activos con elevadas superficies específicas (1000 m2/g frente a los 100 m2/g de nuestros sistemas). Por otra parte valores superiores aunque inferiores a los nuestros fueron obtenidos por por Vidic et al (L.J. Uranowski, C.H. Tessmer y R.D. Vidic; Water Res., 32, 1841 , (1998).) para distintos carbones activos, a pesar de que estos últimos muestran una superficie específica mucho mayor (1000 m2/g) que los óxidos que se han empleado en el presente estudio. Debemos recordar que son numerosos los inconvenientes existentes en la regeneración del adsorbente, el cual no deja de ser considerado un elemento altamente contaminante hasta que el contaminante es eliminado o desorbido. Entre los principales problemas existentes en los procesos de regeneración se encuentra la pérdida del carbón activo por combustión y los efluentes de contaminante altamente concentrados que se generan y que deben de ser tratados posteriormente. It should be noted that values around 100 mg of phenol / g have been obtained by different authors using active carbons with high specific surfaces (1000 m 2 / g compared to 100 m 2 / g of our systems). On the other hand, higher values than ours were obtained by Vidic et al (LJ Uranowski, CH Tessmer and RD Vidic; Water Res., 32, 1841, (1998).) For different active carbons, although these The latter show a specific surface area much larger (1000 m 2 / g) than the oxides used in the present study. We must remember that there are numerous disadvantages in the regeneration of the adsorbent, which is still considered a highly polluting element until the contaminant is removed or desorbed. Among the main problems in regeneration processes is the loss of activated carbon by combustion and the highly concentrated pollutant effluents that are generated and should be treated later.
La necesidad de eliminar el depósito carbonoso para recuperar las propiedades adsorbentes de los sistemas catalíticos descritos, indicaría que podrían emplearse en reactores discontinuos, o bien empleando dos
reactores paralelos que funcionarían alternativamente para eliminar el fenol y la posterior regeneración del catalizador. The need to eliminate the carbonaceous deposit to recover the adsorbent properties of the catalytic systems described, would indicate that they could be used in discontinuous reactors, or using two parallel reactors that would work alternately to eliminate phenol and subsequent catalyst regeneration.
Cuando se emplean sistemas basados en óxidos de manganeso soportados o masivo (incluidos los composites de Ce-Mn) previamente reducidos (por ejemplo en fase gaseosa a 150-350 °C en presencia de hidrógeno) y se introducen estos materiales en disoluciones acuosas de fenol (500-5000 ppm) a presiones y temperaturas moderadas (0.5-4.0 MPa y 80-200°C), se observa que parte del manganeso se disuelve y se forman nanopartículas esféricas de diámetro homogéneo debido a la polimerización del fenol. Estas nanopartículas se purifican por cualquiera de los procedimientos habituales de digestión química. When systems based on supported or massive manganese oxides (including Ce-Mn composites) previously used (for example in the gas phase at 150-350 ° C in the presence of hydrogen) are used and these materials are introduced into aqueous solutions of phenol (500-5000 ppm) at moderate pressures and temperatures (0.5-4.0 MPa and 80-200 ° C), it is observed that part of the manganese dissolves and spherical nanoparticles of homogeneous diameter are formed due to the polymerization of the phenol. These nanoparticles are purified by any of the usual chemical digestion procedures.
En la fig. 6 y 7 se muestras algunas de estas nanopartículas carbonosas obtenidas empleando distintos materiales conteniendo manganeso. En la figura 7 se incluye un espectro EDS que confirma que las nanopartículas esféricas están constituidas de manganeso y carbón. Por otra parte en las figuras 8 y 9 se muestra el espectro EELS típico de las muestras correspondientes a la zona del carbón y del oxígeno. Se han incluido los espectros obtenidos para carbón amorfo y grafito para poder compararlos. Se puede observar que la microestructura de estas nano-esferas carbonosas tiene una estructura amorfa similar al carbón activo empleado en el análisis como carbón amorfo. Por otra parte, es de interés señalar que las nano- esferas obtenidas muestran un alto contenido de oxígeno, el cual puede tener interés en catálisis, así como en otras aplicaciones como sustitutivo del carbón activo. In fig. 6 and 7 show some of these carbon nanoparticles obtained using different materials containing manganese. An EDS spectrum is included in Figure 7 confirming that the spherical nanoparticles are made of manganese and carbon. On the other hand, the typical EELS spectrum of the samples corresponding to the carbon and oxygen zone is shown in Figures 8 and 9. The spectra obtained for amorphous carbon and graphite have been included to compare them. It can be seen that the microstructure of these carbonaceous nanospheres has an amorphous structure similar to active carbon used in the analysis as amorphous carbon. On the other hand, it is of interest to note that the obtained nanospheres show a high oxygen content, which may have an interest in catalysis, as well as in other applications as a substitute for active carbon.
Actualmente los procesos de síntesis de nanoesferas de carbón se consideran con potenciales aplicaciones en separación de gases, como tamices moleculares, soportes de catalizadores y electrodos en baterías de
ion litio (M. G. Stevens and H. C. Foley: Chem.Commun., 6, 519, (1997); S. Tang, Y. Tang, S. Vongehr, X. Zhao, and X. Meng: Applied Surface Science, 255, 6011 , (2009); R. Yang, X. Qiu, H. Zhang, J. Li, W. Zhu, Z. Wang, X. Huang, and L Chen: Carbón, 43, 1 1 , (2005)). Currently the processes of synthesis of carbon nanospheres are considered with potential applications in gas separation, such as molecular sieves, catalyst supports and electrodes in batteries of lithium ion (MG Stevens and HC Foley: Chem.Commun., 6, 519, (1997); S. Tang, Y. Tang, S. Vongehr, X. Zhao, and X. Meng: Applied Surface Science, 255, 6011 , (2009); R. Yang, X. Qiu, H. Zhang, J. Li, W. Zhu, Z. Wang, X. Huang, and L Chen: Coal, 43, 1 1, (2005)).
BREVE DESCRIPCIÓN DE LAS FIGURAS BRIEF DESCRIPTION OF THE FIGURES
Figura 1.- Reducción de la concentración de carbono total por gramo de catalizador en función del tiempo en ensayos donde se emplearon las siguientes relaciones de concentración inicial de fenol y cantidad de catalizador: 500 ppm/1 g (·), 1900 ppm/1 g (♦), 3800 ppm/1 g (▼) y 3800 ppm/2 g (■). El catalizador usado fue el CM50, siendo las condiciones de operación de 90 °C y 0,5 MPa. Figure 1.- Reduction of the total carbon concentration per gram of catalyst as a function of time in tests where the following ratios of initial phenol concentration and catalyst quantity were used: 500 ppm / 1 g (·), 1900 ppm / 1 g ( ♦ ), 3800 ppm / 1 g (▼) and 3800 ppm / 2 g (■). The catalyst used was CM50, the operating conditions being 90 ° C and 0.5 MPa.
Figura 2.- Contenido en carbono total de las muestras tras ensayos con distintas concentraciones iniciales de fenol. Figure 2.- Total carbon content of the samples after tests with different initial concentrations of phenol.
Figura 3.- Imagen de microscopía electrónica de alta resolución del catalizador CM50 tras un ensayo de oxidación húmeda de fenol con una concentración inicial de 5000 ppm a 90 °C y 0,5 MPa de presión parcial de oxígeno. Figure 3.- High resolution electron microscopy image of the CM50 catalyst after a wet oxidation test of phenol with an initial concentration of 5000 ppm at 90 ° C and 0.5 MPa of partial oxygen pressure.
Figura 4.- Diagramas de distintas relaciones masa-carga obtenidas en una experiencia de OTP, tras un pretratamiento en He a 125 °C, del sólido recuperado tras un ensayo de CWO, donde se empleó 500 ppm de carbono, la muestra CM50 y las condiciones de operación fueron 90 °C y 0,5 MPa de P02.
Figura 5.- Evolución de la concentración de carbono total empleando la muestra CM50 fresca (A ) y otra regenerada a 500 0 C (·). Dicho catalizador proviene de un ensayo realizado en las siguientes condiciones: 90 °C, 0,5 MPa de P02 y relación Cfo/CCat = 3800/2. Figure 4.- Diagrams of different mass-load ratios obtained in an OTP experience, after a pretreatment in He at 125 ° C, of the solid recovered after a CWO test, where 500 ppm of carbon was used, the CM50 sample and the operating conditions were 90 ° C and 0.5 MPa of P02. Figure 5.- Evolution of the total carbon concentration using the fresh CM50 sample ( A ) and another regenerated at 500 0 C (·). Said catalyst comes from a test carried out under the following conditions: 90 ° C, 0.5 MPa of P02 and Cfo / CCat ratio = 3800/2.
Figura 6.- Nanopartículas esféricas de carbón generadas al exponer a óxidos manganeso disperso en sílice y previamente reducidas al medio de reacción. Figura 7.- Nanopartículas esféricas de carbón generadas al exponer a composites de cerio-manganeso y previamente reducidas al medio de reacción. Se incluye en el interior un espectro EDS que indica que las nanopartículas están formadas de manganeso ultradisperso y carbón activo. Figuras 8 y 9.- Espectro típico de EELS en la zona del C 1s y O 1s correspondiente a las nanopartículas esféricas de carbón obtenidas y comparación con carbón activo y grafito.
Figure 6.- Spherical carbon nanoparticles generated by exposure to manganese oxides dispersed in silica and previously reduced to the reaction medium. Figure 7.- Spherical carbon nanoparticles generated by exposing cerium-manganese composites and previously reduced to the reaction medium. An EDS spectrum is included inside which indicates that the nanoparticles are formed of ultradispersed manganese and activated carbon. Figures 8 and 9.- Typical spectrum of EELS in the area of C 1s and O 1s corresponding to the spherical carbon nanoparticles obtained and comparison with activated carbon and graphite.
Claims
1.- Procedimiento para la adsorción catalítica, selectiva e irreversible de fenoles disueltos en agua caracterizada por el empleo como adsorbente de óxidos de manganeso o sistemas mixtos basados en los mismos, bien sean soportados o formando composites. 1.- Procedure for catalytic, selective and irreversible adsorption of phenols dissolved in water characterized by the use as adsorbent of manganese oxides or mixed systems based on them, whether supported or forming composites.
2.- Procedimiento para la adsorción catalítica, selectiva e irreversible de fenoles disueltos en agua que comprende: 2. Procedure for the catalytic, selective and irreversible adsorption of phenols dissolved in water comprising:
o La puesta en contacto de la disolución con un óxido de manganeso o un sistema mixto basado en el mismo, bien sea soportado o formando composites, en un reactor a temperaturas del orden de los 90-120°C y presiones parciales de oxígeno del orden de 0.1-2 MPa. o La adsorción irreversible del fenol por polimerización en la superficie del oxido. o The solution is brought into contact with a manganese oxide or a mixed system based on it, whether supported or forming composites, in a reactor at temperatures of the order of 90-120 ° C and partial oxygen pressures of the order 0.1-2 MPa. o Irreversible adsorption of phenol by polymerization on the surface of the oxide.
3.- Procedimiento para la adsorción catalítica, selectiva e irreversible de fenoles disueltos en agua según reivindicaciones 1 y 2, caracterizado porque el óxido utilizado es un óxido de manganeso masivo o soportado sobre un material que se selecciona entre S¡02, Al203, Ce02, CeZrOx o carbón activo. 3. Procedure for catalytic, selective and irreversible adsorption of phenols dissolved in water according to claims 1 and 2, characterized in that the oxide used is a massive or supported manganese oxide on a material selected from S0 2 , Al 2 0 3 , Ce0 2 , CeZrO x or activated carbon.
4. - Procedimiento para la adsorción catalítica, selectiva e irreversible de fenoles disueltos en agua según reivindicaciones 1 y 2, caracterizado porque el catalizador utilizado es un nanocomposite de oxido de Ce-Mn. 4. - Process for catalytic, selective and irreversible adsorption of phenols dissolved in water according to claims 1 and 2, characterized in that the catalyst used is a nanocomposite of Ce-Mn oxide.
5. - Procedimiento para la adsorción catalítica, selectiva e irreversible de fenoles disueltos en agua según reivindicaciones 1 a 4, caracterizado porque la sustancia fenólica que se adsorbe sobre el óxido es un fenol, un nitrofenol, un clorofenol o una mezcla de los mismos. 5. - Procedure for catalytic, selective and irreversible adsorption of phenols dissolved in water according to claims 1 to 4, characterized in that the phenolic substance adsorbed on the oxide is a phenol, a nitrophenol, a chlorophenol or a mixture thereof.
6. - Procedimiento de eliminación selectiva de fenoles en efluentes líquidos que comprende: 6. - Procedure for the selective elimination of phenols in liquid effluents comprising:
o La adsorción catalítica selectiva e irreversible de los mismos según reivindicaciones 1 a 2 o The selective and irreversible catalytic adsorption thereof according to claims 1 to 2
o La combustión, in-situ, por calcinación del residuo carbonoso a temperaturas inferiores a 200°C y recuperación de las propiedades adsorbentes. o Combustion, in-situ, by calcination of the carbonaceous residue at temperatures below 200 ° C and recovery of adsorbent properties.
7. - Procedimiento de eliminación selectiva de fenoles en efluentes líquidos según reivindicación 6, caracterizado porque para la recuperación de las propiedades adsorbentes pueden emplearse bien reactores discontinuos, bien reactores paralelos que funcionen alternativamente. 7. - Method of selective elimination of phenols in liquid effluents according to claim 6, characterized in that for the recovery of the adsorbent properties it is possible to use either discontinuous reactors, or parallel reactors that work alternately.
8. - Procedimiento para la síntesis de nanopartículas esféricas de Mn y carbón con una distribución homogénea de tamaño que comprende: 8. - Method for the synthesis of spherical nanoparticles of Mn and carbon with a homogeneous distribution of size comprising:
o Reducir un sólido basado en óxido de manganeso, soportado o masivo (incluidos los composites de Ce-Mn), mediante un tratamiento con hidrógeno hasta conversión total a monóxido de manganeso. o Introducir este material en una disolución acuosa de fenol (500-5000 ppm) a presiones y temperaturas moderadas (0.5-4.0 MPa y 80- o Reduce a solid based on manganese oxide, supported or massive (including Ce-Mn composites), by hydrogen treatment until total conversion to manganese monoxide. o Introduce this material in an aqueous phenol solution (500-5000 ppm) at moderate pressures and temperatures (0.5-4.0 MPa and 80-
200°C). 200 ° C).
o Purificación de las nanopartículas obtenidas mediante digestión química. o Purification of the nanoparticles obtained by chemical digestion.
9.- Nanopartículas obtenidas mediante el procedimiento descrito en la reivindicación 8 9. Nanoparticles obtained by the method described in claim 8
10.- Uso de las nanopartículas obtenidas mediante el procedimiento descrito en la reivindicación 8 como catalizadores, como soporte de catalizadores, como tamices moleculares o como sustitutivo de carbón activo. 10. Use of the nanoparticles obtained by the method described in claim 8 as catalysts, as catalyst support, as molecular sieves or as a substitute for activated carbon.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021043256A1 (en) * | 2019-09-04 | 2021-03-11 | 有研稀土高技术有限公司 | Rare earth manganese/cerium-zirconium-based composite compound, preparation method therefor and application thereof |
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| ES2364013B1 (en) | 2012-07-02 |
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