EP1786726A2 - Nitrure de bore mesoporeux, a porosite homogene et ordonnee, presentant une surface specifique elevee, et procede de preparation - Google Patents
Nitrure de bore mesoporeux, a porosite homogene et ordonnee, presentant une surface specifique elevee, et procede de preparationInfo
- Publication number
- EP1786726A2 EP1786726A2 EP05793400A EP05793400A EP1786726A2 EP 1786726 A2 EP1786726 A2 EP 1786726A2 EP 05793400 A EP05793400 A EP 05793400A EP 05793400 A EP05793400 A EP 05793400A EP 1786726 A2 EP1786726 A2 EP 1786726A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- boron nitride
- mold
- mesoporous
- precursor
- specific surface
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
- C01B21/0646—Preparation by pyrolysis of boron and nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
- C01P2006/12—Surface area
-
- 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
- C01P2006/12—Surface area
- C01P2006/13—Surface area thermal stability thereof at high temperatures
-
- 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
- C01P2006/14—Pore volume
-
- 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
- C01P2006/16—Pore diameter
-
- 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
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter 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
Definitions
- the invention relates to the technical field of nanostructured compounds. More specifically, the subject of the invention is a process for the preparation of mesoporous compounds, with homogeneous and ordered porosity, of boron nitride, the boron nitride compounds obtainable by such a process, as well as the uses of these boron nitride compounds. compounds, in catalysis and adsorption in particular.
- the mesoporous materials can be defined as those having a three-dimensional pore arrangement with average pore diameters between 2 nm and 50 nm. These materials have potential applications as catalysts, catalyst supports, adsorbents or host matrices.
- mesoporous carbons have been developed in which thermal, hydrothermal and chemical resistance are superior to oxides.
- This new class of mesoporous carbon, the CMK-1s (Ryoo R. et al., J. Phys Chem., 1999, 103, 7743-7746, Ryoo R. et al., 2000, US 6,585,948, S. Jun et al. J. Am Chem Soc, 2000, 122, 10712-10713, J. Lee et al J. Mater Chem, 2004, 14, 478) was developed from cubic or hexagonal mesoporous silica templates.
- the method generally used consists of charring a sucrose in the pores of a mesoporous silica, and removing the silica with a solution of hydrofluoric acid or sodium hydroxide.
- Boron nitrides (BN) exhibit higher temperature oxidation resistance than carbons (RT Paine et al., Chem Rev., 1990, 90, 73).
- RT Paine et al., Chem Rev., 1990, 90, 73 Some studies have been conducted on the preparation of porous boron nitride. Mesoporous forms were obtained by reaction between the trichloroborazine and hexamethyldisilazane (DA Lindquist et al., Mat Soc Symp Proc 180, 1990, 73, DA Lindquist et al J.
- boron nitride which is treated at 1800 ° C., has a specific surface area of 500 m 2 / g and pores with a diameter of between 1 and 2 nm. Nevertheless, the boron nitrides prepared during these two studies do not exhibit porosity organization.
- the present invention proposes to provide a new process for the production of boron nitride, of high specific surface area, and especially having a homogeneous and organized porosity and comprising the following successive steps: a) Impregnation of a mold mesoporous, with homogeneous and ordered porosity, and having a high specific surface, with a precursor of boron nitride, b) ceramization by thermal decomposition of the precursor, so as to form boron nitride, c) removal of the mold.
- the subject of the invention is also boron nitride, which can be obtained by the process as defined above, which has a high specific surface area and a homogeneous and ordered porosity.
- boron nitride as defined above, as catalysts, catalyst support, adsorbent or host matrix, is also an integral part of the invention.
- Figure 1 shows the X-ray diffractogram (at small angles) of BN-2 boron nitride.
- FIG. 2 presents a BN-2 boron nitride transmission electron microscope.
- Figure 3 shows the adsorption isotherms ( ⁇ ) // nitrogen desorption (o) and pore size distributions of boron nitride BN-I and BN-2.
- Figure 4 shows the X-ray diffractogram (at small angles) of BN-4 boron nitride before (fat) and after removal of the carbon mold.
- FIG. 5 presents a BN-4 boron nitride transmission electron microscope.
- FIG. 7 presents a BN-7 boron nitride transmission electron microscopy and FIG. 8 shows the associated EDX spectrum.
- FIG. 9 presents a BN-9 boron nitride transmission electron microscope.
- mesoporous compounds solids having, within their structure, pores with a mean diameter of between 2 and 50 nm.
- mesoporous compounds known as "of ordered porosity” are, in turn, compounds having pores arranged periodically in space. This local organization of porosity is characterized experimentally by the fact that they exhibit at least one coherent diffusion peak in a scattering pattern of diffusion-type radiation by X-rays or by neutrons. Such scattering diagrams and their method of obtaining are described in particular in Small Angle X-Ray Scattering (Glatter and Kratky-Academic Press London-1982). The scattering peak observed in this type of diagram may be associated with a repetition distance characteristic of the compound in question, which will be referred to hereinafter as the "repetition spatial period" (dioo) of the structured system.
- mesoporous compounds of homogeneous porosity
- the average pore diameter can be obtained from the nitrogen desorption isotherms, exploited at the same time. using the BJH algorithm (Barrett-Joyner-Halenda). In the case of compounds with homogeneous and ordered porosity, it can be considered that the pores are arranged to form channels of substantially identical diameter, extending parallel to each other.
- the orifices of the channels are placed on lines spaced a substantially constant distance, which corresponds to the "repetition spatial period".
- specific surface is meant the BET specific surface area determined by nitrogen adsorption according to ASTM D 3663-78 established from the method BRUNAUER-EMMETT-TELLER described in the journal 'The Journal of the American Chemical Society, 60,309 (1938)
- the specific method used in the context of the present invention is detailed below:
- the present invention provides mesoporous boron nitrides which have a regular and organized porous structure, which makes them usable as catalysts, adsorbents, sensors,
- the inventors have developed a preparation process for the preparation of such a mesoporous BN boron nitride structure.
- the first step of the process consists in impregnating a mold with a mesoporous structure, exhibiting a high surface area, in particular greater than 400 m 2 / g, as well as homo
- the porous structure of this "template” is chosen according to the porous structure that it is desired to confer on the boron nitride.
- the impregnation makes it possible to fill the pores of the mold with the precursor of boron nitride.
- the mold used is, for example, silica or, preferably, carbon.
- mesoporous silicas or carbons with hexagonal porosity such as SBA-15 or CMK-3.
- Such silica or mesoporous carbon compounds, having a high specific surface area, as well as homogeneous and ordered porosity, are described in the prior art, as mentioned above.
- the mold may in particular be in the form of a molecular sieve.
- the impregnation is carried out from a molecular precursor in solution in a solvent such as, for example, toluene, removed in an intermediate drying step.
- a solvent such as, for example, toluene
- Any solvent capable of solubilizing the BN precursors is suitable in the context of the present invention: by way of example, THF or DMF.
- THF trifluoride
- DMF dimethyl methacrylate
- any molecular precursor known to form boron nitride is suitable in the context of the present invention.
- boron and nitrogen-based molecular precursors which can be used in the context of the present invention, mention may be made of borazine-type organic compounds, and in particular aminoborazine-type compounds, as described by US Pat. RT Paine, et al. in Chem. Rev., 90, 1990, 73. and Chemtech 1994, 29, by Y. Kimura et al. in Composite Sciences and Technology, 51, 1994, pp. 173-179 and by T. Wideman et al. in Chem. Mater., 1996, vol.8, pages 3-5.
- tris (isopropylamino) borazine or, preferably, tris (monomethylamino) borazine Y. Kimura, et al., Composites Science and Technology 51, 1994, 173-179, B. Toury, et al. Sol.Stat., Chem., 154, 2000, 137-140, S. Bernard, et al., J.
- a haloborazine such as trichloroborazine (TCB ) alone or in combination with a disilazane such as hexamethyldisilazane or heptamethyldisilazane (CK Narula, et al Materials Research Society Symposium Proceedings, 1986, 73 (Better Ceram Chem, 2), 383-8).
- TCB trichloroborazine
- disilazane such as hexamethyldisilazane or heptamethyldisilazane
- An intermediate polymerization stage of the molecular precursor may be provided by heating under reduced pressure.
- the next step consists of a ceramization step by thermal decomposition of the precursor, so as to form boron nitride.
- This ceramization is carried out between 500 ° C. and 1400 ° C. for 1 to 12 hours under reduced pressure, under inert atmosphere (rare gas or nitrogen), or under NH 3 atmosphere.
- the temperatures, the heating rates, the durations and the atmosphere used are chosen according to the precursor used, the mold used and the structure that it is desired to obtain. In particular, in the case of a carbon mold, it will operate, preferably under an inert atmosphere, for example under nitrogen, because the carbon hardly withstands a ceramization step ammonia.
- the last step of the process consists in eliminating the mold.
- treatment with ammonia is used, while washing with hydrofluoric acid or sodium hydroxide is used, in the case of a silica mold.
- ceramization and mold removal can be achieved in a single heat treatment.
- the process as defined above makes it possible to obtain a boron nitride, which has a high specific surface area and a homogeneous and ordered porosity.
- the boron nitride compounds thus produced have a specific surface area greater than 400 m 2 / g.
- the boron nitride according to the invention has a spatial repetition period (dioo) deduced from the small angle x-ray scattering diagram included in the gamma from 5 to 10 nm, preferably from 6 to 8 nm.
- the porosity is regular and the average pore diameter is generally in the range of 2 to 10 nm, preferably in the range of 3 to 5 nm.
- the mesoporous volume, boron nitrides produced in the context of the present invention is in the range of 0.2 cm 3 / g to 1 cmVg, preferably in the range of 0, 3 cm 3 / g to 0.6 cm 3 / g.
- the boron nitrides obtained according to the process of the invention have a high purity greater than or equal to 95%, and preferably greater than or equal to 98%.
- the boron nitride compounds according to the invention are obtained in the form of a powder of particles having a diameter of between 0.5 and 2 ⁇ m, for example of approximately 1 ⁇ m, preferably monodispersed.
- boron nitride compounds according to the present invention are chemically stable, in air, up to temperatures of 800 ° C. This stability, demonstrated by thermogravimetric analysis, is much higher than that of a molecular sieve of carbon (400 ° C.). Moreover, we observe the conservation of the mesostructural characteristics
- the variation factor of the BET surface area to which reference is made is calculated by the ratio (Si-Sf) / (Si), where "Si” denotes the BET specific surface area measured before heat treatment; and where Sf denotes the BET specific surface area measured after heat treatment at 1400 ° C. under an inert atmosphere
- Si-Sf the BET specific surface area measured before heat treatment
- Sf the BET specific surface area measured after heat treatment at 1400 ° C. under an inert atmosphere
- the compounds according to the invention are mainly boron nitride, have excellent resistance to oxidation at high temperature, as well as specific properties of interaction with gases from their morphology and orderly organization.
- X-ray diffractograms were recorded on a Siemens D500 instrument at 30 kV and 40 mA using Cu Ka radiation. The small angle diffractograms were recorded between 1 ° and 5 °, with a step of 0.01 ° and a collection time in steps of 4 s.
- Infrared spectra were recorded on a Nicolet Magna-IR 550 spectrometer between 400 and 4000 cm -1, 1 H NMR spectra were recorded in CDCl 3 on a Br ⁇ ker AM 300 MHz spectrometer, and 11 B NMR spectra were recorded. recorded on a DRX 300 Avance spectrometer with an external reference and 2 O-BF 3 in C 6 D 6.
- the nitrogen adsorption isotherms were measured on a Sorptomatic 1900 (Fisons) analyzer. were degassed for 4 h at 423 K. Specific surface area was calculated from nitrogen adsorption data for relative pressures between 0.05 and 0.3 The pore size distribution was analyzed from the desorption branch according to the algorithm of BJH. The total mesoporous volume corresponds to the volume BJH measured for a relative pressure of between 0.4 and 0.95.
- MET (Transmission Electron Microscopy) images were obtained on a TOPCON EM002B microscope with an acceleration voltage of 200 kV. The samples were deposited on a carbon-coated copper grid.
- HNBCl 2,4,6-Trichloroborazine
- TCB 2,4,6-Trichloroborazine
- Mesoporous silica S BA-15 is synthesized with the structuring agent EO 20 PO 70 EO 20 (Pluronic P123, BASF).
- the structuring agent E0 2 oP ⁇ 7 oE ⁇ 20 (4 g) was dissolved in 2M HCl (120 g) and H 2 O (30 g) at 35 0 C.
- Si (OEt) 4 (8.5 g) was added to the surfactant solution. Stirring is maintained for 20 h, then the solution is aged for 24 h at 80 ° C.
- the silica is then filtered, washed and then calcined in air at 500 ° C. for 6 hours. For more details, see D.Zhao et al. Science, 1998, 279, 548-552.
- the SBA-silica then undergoes silylation treatment to render it hydrophobic (De Juan et al., Mater, 2000, 12, 6). It is treated at 150 ° C. for 3 h under reduced pressure. Then 1 g of silica is reacted in 50 ml of toluene under reflux for 24 hours with trimethylchlorosilane (CH 3 ) 3 SiCl (10 ml) in the presence of pyridine (5 ml). The silica is then filtered, rinsed with toluene and with ethanol, dried in air and then treated at 150 ° C. under reduced pressure for 3 hours.
- silica is then filtered, rinsed with toluene and with ethanol, dried in air and then treated at 150 ° C. under reduced pressure for 3 hours.
- the CMK-3 carbon is prepared by impregnating the SBA-15 silica in a sucrose solution.
- SBA-silica (1 g) is placed in the presence of a solution of sucrose (1.25 g), water (5 g) in sulfuric acid medium (0.14 g).
- Polymerization in air for 6 hours at 100 ° C. and 6 hours at 160 ° C. is carried out, followed by a second impregnation (0.8 g sucrose, 5 g H 2 O and 0.09 g d sulfuric acid), a second air polymerization for 6 h at 100 ° C and 6 h at 160 ° C, and a ceramization step at 900 ° C under reduced pressure.
- X-ray diffraction patterns (at small angles) of SBA-15 and CMK-3 were recorded.
- Transmission electron microscopy (TEM) micrographs of SBA-15 and CMK-3 were also made.
- the TEM silica image shows that the channel openings are on lines 10 nm apart in accordance with the inter-lattice distance measured at 9.9 nm in X-ray diffraction.
- the MET carbon image shows that the orifices of the channels are placed on lines 8.4 nm apart in agreement with the inter-reticular distance measured at 8.0 nm in X-ray diffraction.
- the nitrogen adsorption / desorption isotherms are of type IV with a hysteresis loop in the case of silica (790 m 2 / g and pore size 4.9 nm (diameter)) and carbon (760 m 2 / g and pore size 3.3 nm (diameter)) (Table 1).
- the concentration in the impregnating solution of the precursor is measured by 1 H NMR.
- the CMK-3 carbon is passive at 500 ° C for 4 h under reduced pressure before impregnation.
- Table 2 Data relating to boron nitride BN-I and BN-2 (prepared by ceramization of MAB in a carbon screen at 1000 ° C. under NH 3 ).
- the boron nitrides obtained have a high porosity and an organization of this porosity.
- Figure 3 shows the nitrogen adsorption / desorption isotherms and the pore size distribution of mesoporous boron nitrides.
- the isotherms are of type IV.
- the measured surface area, the mesoporous volume and the average pore diameter obtained are shown in Table 2.
- Table 3 Data for boron nitride BN-4 to BN-6 (made by ceramizing MAB in a carbon screen under nitrogen).
- the boron nitrides obtained have a high and orderly porosity.
- the X-ray diffraction patterns (at small angles) and the BN-4 TEM shot are presented, respectively in FIGS. 4 and 5.
- Figure 6 shows the nitrogen adsorption / desorption isotherms and the pore size distribution of mesoporous boron nitrides.
- the isotherms are of type IV.
- the measured surface area, the mesoporous volume and the average pore diameter obtained are shown in Table 3.
- the nitrogen adsorption / desorption isotherms before (BN-4c to BN-6c) and after (BN-4 to BN -6) carbon removal were compared:
- Example 6 the filling seems to have been less effective than in Examples 4 and 5, since the mesoporous volume of the BN-carbon composite is not zero.
- BN-2 boron nitride treated only with ammonia, has a specific surface area of 790 m 2 / g and a mesoporous volume of 0.38 cm 3 / g.
- the pore size is 3.2 nm (diameter) (Table 2).
- the porosity of the order of 40% is a little lower than that obtained in Example 2.
- the mesoporous volumes are lower than those measured in Example 2. Nevertheless, it may be noted that in the case of treatment under nitrogen at 1000 ° C (BN-4 and BN-5), the pore size distribution is particularly narrow.
- MOLECULAR MAB - CERAMIZATION UNDER AMMONIA.
- Table 4 Data relating to boron nitride BN-7 (produced by ceramization of MAB in a silica sieve under NH 3 ).
- the infrared spectrum reveals the characteristic vibration bands of boron nitride at v
- Table 6 Data relating to boron nitride BNi-h obtained after a thermal treatment under nitrogen at 1400 ° C for 1 h of BN-i.
- the X-ray diffraction patterns of boron nitride BN-xh (x -1, 5, 8 and 9) after heat treatment at 1400 ° C under N 2 for 1 h show that the crystalline organization is almost unchanged compared to BN-x boron nitrides prepared at 1000 ° C.
- the boron nitride remains turbostratic, with crystallite sizes Lc measured at around 1.5 nm.
- the nitrogen adsorption / desorption isotherms show that the specific surface area decreases, the mesoporous volume and the pore size hardly change. The decrease of the surface is due to the disappearance of the microporosity while the mesoporosity remains intact.
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Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0408364A FR2873676B1 (fr) | 2004-07-29 | 2004-07-29 | Nitrure de bore mesoporeux, a porosite homogene et ordonnee, presentant une surface specifique elevee, et procede de preparation |
PCT/FR2005/001965 WO2006018545A2 (fr) | 2004-07-29 | 2005-07-27 | Nitrure de bore mesoporeux, a porosite homogene et ordonnee, presentant une surface specifique elevee, et procede de preparation |
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EP1786726A2 true EP1786726A2 (fr) | 2007-05-23 |
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EP05793400A Withdrawn EP1786726A2 (fr) | 2004-07-29 | 2005-07-27 | Nitrure de bore mesoporeux, a porosite homogene et ordonnee, presentant une surface specifique elevee, et procede de preparation |
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EP (1) | EP1786726A2 (fr) |
FR (1) | FR2873676B1 (fr) |
WO (1) | WO2006018545A2 (fr) |
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CN100460314C (zh) * | 2007-01-22 | 2009-02-11 | 华东师范大学 | 一次性真空灌注合成金属氧化物介孔材料的方法 |
US8889225B2 (en) * | 2012-12-21 | 2014-11-18 | The Gillette Company | Chemical vapor deposition of fluorocarbon polymers |
CN110586022A (zh) * | 2019-09-18 | 2019-12-20 | 沈阳航空航天大学 | 一种用酸碱改性的多孔氮化硼从纺织工业废水中去除脂肪酸的方法 |
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GB1313174A (en) * | 1969-06-02 | 1973-04-11 | Exxon Research Engineering Co | High surface area nitride catalysts of boron aluminium and silicon for hydrocarbon conversion reactions |
US5399535A (en) * | 1993-08-17 | 1995-03-21 | Rohm And Haas Company | Reticulated ceramic products |
CA2467703A1 (fr) * | 2001-11-21 | 2003-06-05 | University Of Massachusetts | Materiaux mesoporeux et procedes de fabrication |
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2004
- 2004-07-29 FR FR0408364A patent/FR2873676B1/fr not_active Expired - Fee Related
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- 2005-07-27 WO PCT/FR2005/001965 patent/WO2006018545A2/fr active Application Filing
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FR2873676A1 (fr) | 2006-02-03 |
FR2873676B1 (fr) | 2007-02-09 |
WO2006018545A2 (fr) | 2006-02-23 |
WO2006018545A3 (fr) | 2007-03-15 |
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