EP1301435A1 - Colloidale dispersion einer ceriumverbindung oder einer ceriumhaltigen verbindung die ein weiteres element, ausgewählt aus den seltenerd- und übergangsmetallelementen und eine aminosäure enthält - Google Patents
Colloidale dispersion einer ceriumverbindung oder einer ceriumhaltigen verbindung die ein weiteres element, ausgewählt aus den seltenerd- und übergangsmetallelementen und eine aminosäure enthältInfo
- Publication number
- EP1301435A1 EP1301435A1 EP01940666A EP01940666A EP1301435A1 EP 1301435 A1 EP1301435 A1 EP 1301435A1 EP 01940666 A EP01940666 A EP 01940666A EP 01940666 A EP01940666 A EP 01940666A EP 1301435 A1 EP1301435 A1 EP 1301435A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dispersion
- cerium
- amino acid
- acid
- water
- 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- Withdrawn
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- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
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- B01D—SEPARATION
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0034—Additives, e.g. in view of promoting stabilisation or peptisation
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- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
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- C01F17/229—Lanthanum oxides or hydroxides
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- C10N2010/00—Metal present as such or in compounds
- C10N2010/06—Groups 3 or 13
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/055—Particles related characteristics
- C10N2020/06—Particles of special shape or size
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/01—Emulsions, colloids, or micelles
Definitions
- the present invention relates to a colloidal dispersion of a cerium compound or a cerium compound and at least one other element chosen from rare earths and transition metals and comprising an amino acid.
- Cerium soils especially tetravalent cerium soils, are well known. Furthermore, cerium soils in combination with another element can be of great interest, for example for cosmetic applications, such as anti-UV, optics or in the field of phosphors.
- the colloidal dispersion according to the invention is a dispersion of a cerium compound or a cerium compound and at least one other element M chosen from titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, gallium, zirconium and rare earths other than cerium, and it is characterized in that it comprises an amino acid, this acid being at least partly linked to the constituent particles of the dispersion.
- colloidal dispersion or sol of a cerium compound, or of a cerium compound and of another abovementioned element designates any system made up of fine solid particles of colloidal dimensions based on d oxide and / or hydrated oxide (hydroxide) of cerium and the other element, in suspension in a liquid phase, said species possibly also containing, possibly, residual quantities of bound or adsorbed ions such as for example acetates, citrates, nitrates, chlorides or ammoniums.
- the percentage of these ions bound X or possibly X + Y in the case of two ions, expressed in molar ratio X / Ce or (X + Y) / Ce can vary for example between 0.01 and 1.5, more particularly between 0,01 and 1. It will be noted that in such dispersions, the cerium and the other element can be either completely in the form of colloids, or simultaneously in the form of ions or polyions and in the form of colloids.
- rare earth is meant the elements of the group constituted by Pyttrium and the elements of the periodic classification of atomic number included inclusively between 57 and 71.
- the main characteristic of the dispersion of the invention is that it comprises an amino acid linked at least in part to the colloidal particles.
- bound is meant that there is a bond between the amino acid and the particles.
- This connection can be of different types. It may firstly be a bond by chemical complexation between the acid group of the amino acid in ionized form and a cation present at the surface of the colloidal particle. This connection can also be of electrostatic nature between the ionized COO " pattern of the amino acid and the surface of the colloidal particle of positive charge. Finally, this connection can be made by adsorption between the amino acid and the surface of the particle.
- bonds can also be demonstrated by different techniques, for example by determination of adsorption curves according to techniques known to those skilled in the art; chemical analyzes of supernatants of centrifugation or ultracentrifugation or by spectroscopic techniques of the Raman or infrared type on colloids separated from their liquid phase by ultracentrifugation.
- the NH 2 function of the acid is free and thus constitutes a protonizable function improving the colloidal stability of the dispers ion or again, this function, as such, may exhibit chemical reactivity for further processing.
- the amino acid is present in the dispersion as much as possible in the form bound to the particles which has just been described.
- at least 50 mol% and even more preferably at least 75 mol% of the amino acid must be present in bound form.
- the amino acid may more particularly be an aliphatic amino acid. It can in particular be a C 4 -C 10 acid and preferably a C - C 8 acid. It will be noted that the longer the acid chain, the more hydrophobic the colloidal particles which can adversely affect the stability of the dispersion in the case of aqueous dispersions.
- the total amino acid content in the dispersion is generally between 0.1 and 1 mole of amino acid per 1 mole of cerium.
- the dispersion can optionally contain cerium in the oxidation state III.
- the level of cerium III is generally at most 50%. It is expressed here and for the whole description by the atomic ratio Ce III / Ce total.
- the level of cerium III can more particularly be at most 35%, in particular in the case of a dispersion of cerium and another element M, and very particularly at most 10%. Furthermore, it is preferably at least 0.5%. This rate can more particularly be at least 1% and even more particularly at least 1.5%.
- the dispersion also contains in this case cerium in the form of cerium IV. The invention also applies of course to the case where all the cerium is present in form IV.
- the amount of this element is generally at most 50%, preferably at most 20%, this amount being expressed by the ratio moles of element M / sum of moles of element M and cerium.
- Element M can be present in different oxidation states. The invention obviously applies to dispersions containing several elements M.
- the dispersions of the invention have a pH value which can vary over a wide range, especially in the high pH range. They may for example have a pH value of between 4 and 8.5. These pH values, close to neutrality, allow interesting applications of the dispersions of the invention.
- the dispersions of the invention are particularly pure in nitrate anions. More specifically, the content of nitrates anions in the dispersions of this variant, measured by the content of nitrates anions by weight of the colloidal particles is less than 80ppm.
- the dispersions of the invention can also be pure as regards their content of chloride ions.
- the dispersion of the invention can have a concentration of at least 50 g / l.
- This concentration is expressed as oxide and taking into account the sum of cerium oxides and, where appropriate, the other or others of the foregoing.
- This concentration can more particularly be at least 80 g / l.
- the sizes of the colloidal particles which constitute the soils of the invention are also liable to vary over a wide range.
- the particles can have an average diameter of between 2 and 80 nm, more particularly between 3 and 50 nm. This diameter is determined by photometric counting from an analysis by METHR (High Resolution Transmission Electron Microscopy).
- the dispersions according to the invention can be aqueous dispersions, the continuous phase being water, or dispersions in a continuous phase which can be constituted by a water / organic solvent mixture miscible with water or alternatively dispersions in an organic solvent miscible with water.
- solvents that may be mentioned are alcohols such as methanol or ethanol, glycols such as ethylene glycol, acetate derivatives of glycols such as ethylene glycol monoacetate, glycol ethers, polyols or ketones.
- This process essentially consists in adding an amino acid to a starting colloidal dispersion of a cerium compound or a cerium compound and at least one other element M mentioned above.
- the amino acid can be added in solid form or in solution.
- the amount of amino acid added is adjusted according to the size of the colloidal particles and therefore their specific surface. The larger this area, the greater the amount of amino acid to be added to have a high level of acid in bound form.
- an amount of 2 to 8 will be targeted, more particularly from 2 to 5 amino acid molecules per nm 2 of surface of colloidal particles.
- any suitable colloidal dispersion can be used as the starting dispersion. Mention may thus be made, as suitable dispersions, of those described or obtained by the methods described in patent applications EP-A-206906, EP-A-208580, EP-A-208581, EP-A-239477 and EP-A-700870. It is possible to use very particularly the colloidal dispersions obtained by thermohydrolysis of an aqueous solution of a cerium IV salt such as a nitrate, in an acid medium in particular. Such a process is described in European patent applications EP-A-239477 or EP-A-208580.
- This process for the preparation of dispersions based on cerium and on an element M comprises a first step in which a mixture of at least one salt of cerium with at least one salt of an element M is reacted with a base.
- dispersions containing cerium III it is possible in particular to start from a cerium III salt or from a mixture comprising a cerium IV salt in addition to the cerium III salt.
- cerium III salts it is possible to use more particularly cerium III acetate, chloride or nitrate as well as mixtures of these salts such as mixed acetate / chloride.
- cerium IV cerium IV nitrate can be used and for the other elements chlorides and nitrates in particular. Salts of the same type can be used for the other element or elements M.
- products of the hydroxide type can be used in particular.
- the reaction of the cerium salt with the base takes place in the presence of an acid.
- acids which can be used there may be mentioned the mineral acids and more particularly those corresponding to the cerium salts, in particular of cerium III, used in the reaction. Mention may in particular be made of acetic acid, nitric acid or hydrochloric acid. It should be noted that the acid can also be provided by the solution of a salt in which it is incorporated. For example, an acidic titanium chloride solution such as TiOCI 2 , 2HCI can be used as the starting solution.
- the amount of acid present or used during the reaction is such that the atomic ratio H7 (Ce + M) is greater than 0.1, preferably 0.25.
- the reaction of the base with the salts can be carried out continuously, by this is meant a simultaneous addition of the reactants to the reaction medium.
- the pH of the reaction medium is usually between 7.5 and 9.5. It is possible to work under conditions such that the pH of the reaction medium is kept constant during the reaction.
- a precipitate is obtained at the end of the above-mentioned reaction. This precipitate can be separated from the liquid medium by any known method, for example by centrifugation. The precipitate thus obtained can then be resuspended in water so as to give the dispersion of the invention.
- the concentration of cerium in the dispersion thus obtained is generally between 0.005M and 2M, preferably between 0.05M and 0.25M.
- the precipitate resulting from the reaction can be washed.
- This washing can be done by putting the precipitate back into water and then, after stirring, by separating the solid from the liquid medium by centrifugation for example. This can be repeated several times if necessary.
- the dispersion obtained after resuspension in water can be purified and / or concentrated by ultrafiltration.
- Washing and ultrafiltration can be carried out in air or in an atmosphere of air and nitrogen or even under nitrogen.
- the atmosphere under which these operations take place plays a role in the transformation of cerium III into cerium IV.
- This oxidizing treatment can be done in two ways for example.
- a first way is to keep the dispersion under stirring and in air, and this for a period which can vary from 3 to 20 hours for example.
- the second way is to. add oxygenated water to the dispersion.
- the amount of hydrogen peroxide added is adjusted so as to obtain in the final dispersion the ratio Ce III / Ce total given above.
- This oxidation with addition of hydrogen peroxide is preferably carried out after stirring the dispersion in air for a period greater than 2 hours.
- the duration of the addition of hydrogen peroxide can be between 30 min and 6 hours.
- the process which has just been described above for the preparation of a dispersion of cerium and of another element M can be used in the case of the preparation of a dispersion of cerium alone and in which the cerium can be partly in Ce form III.
- the first step of the process consists in reacting the base with only a cerium III salt and in the presence of an acid. Everything that has been described elsewhere for the process also applies in this case; the amount of acid, measured here by the H + / Ce ratio, verifying the values given above.
- This process makes it possible, both for a starting dispersion of cerium alone and for that of a starting dispersion of cerium and of another element M, to obtain soils having a conductivity of at most 5 mS / cm, which is characteristic of a high purity, and a nitrate content of less than 80 ppm.
- this process involves the formation of a precipitate which is then redispersed in water to give the starting dispersion. It can be noted that it is possible to add the amino acid at the same time as water is added to redisperse the precipitate. This procedure makes it possible to obtain concentrated dispersions directly without going through a concentration step, for example by ultrafiltration.
- anionic resins are used.
- this type of resins of those with a backbone of styrene-divinylbenzene copolymers.
- Use may more particularly be made of those having quaternary ammonium, OH "functional groups.
- anionic resins which can be used are Amberlite IRN 78® or Duolite A 101® resins.
- the resin treatment is carried out in any suitable manner.
- the resins can be brought into direct contact with the colloidal dispersion.
- the quantity of anionic resin to be used is defined by the pH which it is desired to reach.
- One of the advantages of the dispersions of the invention is the possibility of obtaining a dispersion at high pH by treatment with an anionic resin whose duration or number of steps are reduced.
- this dispersion can be prepared from an aqueous dispersion as obtained by the methods described above and by addition of the organic solvent to this dispersion aqueous then distillation to remove the water or treatment with an ultrafiltration membrane for the progressive removal of the water.
- the dispersions of the invention also allow access to redispersible compositions in the form of colloidal dispersions.
- a dispersion according to the invention is subjected to evaporation, centrifugation, ultrafiltration or osmotic compression.
- Osmotic compression is a known method, the principle of which is to balance the chemical potential of water through a membrane.
- a dialysis bag for example made of cellulosic material
- This bag being placed in an aqueous solution whose chemical potential of water is different from that of the aqueous phase of the dispersion.
- This can be done, for example, using an aqueous solution of polyethylene glycol (PEG) or else dextran.
- PEG polyethylene glycol
- dextran dextran
- Evaporation, centrifugation and ultrafiltration can be done using any suitable device.
- the dispersion is dried by stoving at low temperature, preferably at a temperature below 50 ° C, or by using a rotavapor, the drying being moreover preferably carried out on dispersions after purification of the free amino acid. , unbound.
- the treatments which have just been mentioned are carried out alone or in combination and make it possible to pass continuously from a colloidal dispersion to a gel or paste and then to a powder. This paste or powder can optionally be dried.
- a redispersible composition is thus obtained in the form of a colloidal dispersion, which comprises particles based on cerium or cerium and on an element M as defined above and an amino acid at least partly linked to these particles.
- the cerium and the other element can be in the form of oxide and / or hydrated oxide (hydroxide).
- the other characteristics described above in particular with regard to the amino acid and its bond with the particles or with regard to the element M also apply to this composition.
- the composition can be in the form of a gel, a paste or a powder. This composition can be redispersed in a liquid medium and a colloidal dispersion identical to the colloidal dispersion of the invention described above is thus obtained.
- the dispersions of the invention can be used in many applications. Mention may be made of catalysis, especially for automotive post combustion, in which case the dispersions are used in the preparation of catalysts.
- the dispersions can also be used for lubrication, in ceramics, in the manufacture of phosphor compounds or in optics.
- the dispersions can also be used for their anti-UV properties, for example in the preparation of polymer films (of the acrylic or polycarbonate type for example) or of cosmetic compositions in particular in the preparation of anti-UV creams. Finally, they can be used on a substrate as anticorrosion agents.
- a colloidal dispersion of Ce ⁇ 2 with a colloid diameter of 5 nm is obtained by adding 1400 g of demineralized water to 460 g of cerium compound obtained by thermohydrolysis at 100 ° C of a ceric nitrate solution previously preneutralized and according to the method of the type described in Example 1 of patent application EP 208580. The whole is stirred.
- the CeO 2 concentration in the dispersion is 1M.
- a solution A is obtained, obtained by dissolving 39.3 g of 6-aminocaproic acid (i.e. 0.3 moles of amino acid, with a molecular mass of 131.2 g) in demineralized water, made up to 150 cm 3 .
- Solution A is added at room temperature, at a constant flow rate, for one hour, to 1000 ml of the colloidal dispersion of CeO 2 described above, stirred.
- the dispersion is left under agitation for 2 hours.
- 40 g of wet anionic resin, of the Amberlite IRN 78 Prolabo brand are added in forty minutes.
- the product is filtered on a frit under a primary vacuum.
- the pH of the dispersion is 4 and the equivalent concentration of CeO 2 , determined by steaming and calcination of an aliquot, is 0.98 M.
- An aqueous colloidal dispersion of CeO 2 , free of nitrate ions, is prepared as follows.
- the precipitation of the solid is carried out in a continuous assembly comprising:
- the precipitate is separated from the mother liquors by centrifugation at 4500 rpm for 10 min. On an aliquot, by calcination at 1000 ° C., a CeO 2 percentage of the precipitate of 23.4% in CeO 2 oxide is determined.
- the precipitate is dispersed by adding demineralized water to obtain a 0.25M Ce dispersion.
- the mixture is stirred for 15 min. Centrifuge again. Two successive operations are thus carried out.
- 100 ml of the 0.25 M Ce dispersion are diluted to 300 ml with demineralized water. Up to 100 ml are concentrated by ultrafiltration on 3 KD membranes. Three ultrafiltrations are thus carried out so as to obtain a colloidal dispersion having a clear appearance and at 0.12 M of Ce.
- the pH of the dispersion is 3.5.
- the NO 3 content is less than 80 ppm.
- the ratio Ce III / Ce total is 1.9% and the conductivity of the dispersion is 0.9 mS / cm.
- the size of the colloids is 3nm.
- Example 3 An aqueous colloidal dispersion of cerium and lanthanum particles is obtained as follows.
- a solution A is obtained by adding to water, with stirring, 525.6 g of Ce (CH 3 COO) 3 at 49.3% in CeO 2 and making up to 3000 ml.
- a solution B is obtained by adding 135 g of lanthanum acetate at 46.4% in La which is made up to 750 ml.
- a solid residue is separated by centrifugation at 4500 rpm for 10 min. Add solution B to solution A, then pour in 214.8 cc of 17.5 M acetic acid solution.
- Precipitation is then carried out in a continuous assembly comprising: a one-liter reactor equipped with a paddle stirrer, with a base of the water tank, and a control electrode
- the pH of the reaction medium is pH 8.5 for the entire duration of the reaction.
- a precipitate is obtained which is separated by centrifugation at 4500 rpm for 10 minutes, the solid product is redispersed in demineralized water. We recentrifuge again.
- the precipitate is evaluated at 34% as cerium and lanthanum oxide.
- the precipitate is dispersed by adding demineralized water to obtain a 0.15 M dispersion in Ce and La.
- the mixture is stirred for 15 min. Centrifuge again. Two successive operations are thus carried out.
- the dispersion is then stirred under an atmosphere of air overnight.
- 100ml of the 0.15M Ce and La dispersion are diluted to 300ml with water demineralized.
- By ultrafiltration on 3 KD membranes up to 100 ml are concentrated. Three ultrafiltrations are thus carried out so as to obtain a dispersion at 0.08M in CeO 2 and La.
- the pH is 4.1.
- the concentration of nitrate ions in the colloidal dispersion is less than 80 ppm.
- TEM cryometry particles of about 3 to 4 nm size are observed.
- the pH is 4.6. 4 cm 3 of 0.1 M NH 4 OH are added at a constant flow rate over a period of 8 min.
- the pH is 7.
- the dispersion remains stable over a period of at least 1 month.
- Example 4 An aqueous colloidal dispersion of cerium and aluminum particles is obtained as follows.
- the precipitation of the solid is carried out in the continuous assembly described in Example 2.
- a precipitate is obtained which is separated by centrifugation.
- the precipitate is dispersed by adding demineralized water to obtain a 0.25 M Ce and Al dispersion.
- the mixture is stirred for 15 min. Centrifuge again. Two successive operations are thus carried out.
- the cerium III content of the dispersion is 60%.
- the dispersion is then stirred under an atmosphere of air overnight. At the end of this treatment, the cerium III content is 31%.
- 100 ml of the 0.25 M Ce and Al dispersion are diluted to 300 ml with demineralized water. Up to 100 ml are concentrated by ultrafiltration on 3 KD membranes. Three ultrafiltrations are thus carried out so as to obtain a dispersion at 0.68 M in CeO 2 -AIO ⁇ , 5 .
- the pH of the dispersion is 4.2.
- 0.5 g of 6-aminocaproic acid (3.8 millimoles) is added to a first aliquot of 20 cm 3 of dispersion (13.6 millimoles).
- the pH of the dispersion is 4.5.
- An aqueous colloidal dispersion of cerium and titanium particles is obtained in the following manner. 562.8 g of Ce (CH 3 COO) 3 at 49.3% in CeO 2 are added with stirring
- the precipitation of the solid is carried out continuously in the assembly described in Example 1.
- the pH of the reaction medium is 8.5 throughout the duration of the reaction.
- a precipitate is obtained which is separated by centrifugation.
- the precipitate contains 15% of cerium and titanium oxide.
- the precipitate is dispersed by adding demineralized water to obtain a 0.12 M dispersion in Ce and Ti.
- the mixture is stirred for 15 min. Centrifuge again. Two successive operations are thus carried out.
- the cerium III content of the dispersion is 60%.
- the dispersion is then stirred under an atmosphere of air overnight. At the end of this treatment, the cerium III content of the dispersion is 6.5%, the total cerium content is 17.2 g / l.
- 100 ml of the 0.1 M dispersion in Ce and Ti are diluted to 300 ml with demineralized water.
- 3 KD membranes By ultrafiltration on 3 KD membranes, up to 100 ml are concentrated. Three ultrafiltrations are thus carried out so as to obtain a dispersion at 0.34 M in CeO 2 -TiO 2 .
- the pH is 3.8.
- the nitrate concentration of the colloidal dispersion is less than 80 ppm.
- TEM cryometry particles of about 3 to 4 nm size are observed.
- Example 3 The procedure is as in Example 3 until the precipitate evaluated at 34% in cerium and lanthanum oxide is obtained.
- a colloidal dispersion is obtained at pH 6.2.
- the CeO 2 - La concentration is 0.4M.
- the addition of the amino acid simultaneously with the resuspension in water of the precipitate leads to a more concentrated soil than that obtained in the case of Example 3.
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0007147 | 2000-06-05 | ||
FR0007147A FR2809637B1 (fr) | 2000-06-05 | 2000-06-05 | Dispersion colloidale d'un compose de cerium ou d'un compose de cerium et d'au moins un autre element choisi parmi les terres rares et des metaux de transition et comprenant un acide amine |
PCT/FR2001/001706 WO2001094262A1 (fr) | 2000-06-05 | 2001-06-01 | Dispersion colloidale d'un compose de cerium ou d'un compose de cerium et d'au moins un autre element choisi parmi les terres rares et des metaux de transition et comprenant un acide amine |
Publications (1)
Publication Number | Publication Date |
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EP1301435A1 true EP1301435A1 (de) | 2003-04-16 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP01940666A Withdrawn EP1301435A1 (de) | 2000-06-05 | 2001-06-01 | Colloidale dispersion einer ceriumverbindung oder einer ceriumhaltigen verbindung die ein weiteres element, ausgewählt aus den seltenerd- und übergangsmetallelementen und eine aminosäure enthält |
Country Status (9)
Country | Link |
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US (1) | US20030187077A1 (de) |
EP (1) | EP1301435A1 (de) |
JP (1) | JP2003535674A (de) |
KR (1) | KR20030036214A (de) |
CN (1) | CN1438970A (de) |
AU (1) | AU2001274178A1 (de) |
CA (1) | CA2411749A1 (de) |
FR (1) | FR2809637B1 (de) |
WO (1) | WO2001094262A1 (de) |
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FR2803224B1 (fr) * | 1999-12-30 | 2002-09-27 | Rhodia Chimie Sa | Dispersion colloidale aqueuse a base d'au moins un compose d'un metal et d'un complexant, procede de preparation et utilisation |
FR2831177B1 (fr) * | 2001-10-22 | 2005-02-18 | Rhodia Elect & Catalysis | Dispersion colloidale et poudre colorees de cerium ou de cerium et de titane, de zirconium, d'aluminium ou d'une terre rare, leur procede de preparation et leur utilisation |
FR2831176A1 (fr) * | 2001-10-22 | 2003-04-25 | Rhodia Elect & Catalysis | Composition pigmentaire a base d'un sulfure de terre rare, d'un colorant et, eventuellement, d'un agent de couplage, son procede de preparation et son utilisation |
FR2833862B1 (fr) | 2001-12-21 | 2004-10-15 | Rhodia Elect & Catalysis | Dispersion colloidale organique de particules de fer, son procede de preparation et son utilisation comme adjuvant de carburant pour moteurs a combustion interne |
WO2004041942A1 (fr) * | 2002-10-24 | 2004-05-21 | Rhodia Electronics And Catalysis | Dispersion colloidale et poudre colorees de cerium ou de cerium et de titane, de zirconium, d'aluminium ou d'une terre rare, leur procede de preparation et leur utilisation |
FR2853261B1 (fr) * | 2003-04-04 | 2006-06-30 | Rhodia Elect & Catalysis | Dispersion colloidale d'un compose d'une terre rare comprenant un agent anti-oxydant et son utilisation comme adjuvant de gazole pour moteurs a combustion interne |
CN1871087B (zh) * | 2003-08-28 | 2011-08-17 | 多摩-技术转让机关株式会社 | 贵金属胶体、贵金属微粒、组合物及贵金属微粒的制造方法 |
FR2884732B1 (fr) * | 2005-04-20 | 2007-08-24 | Rhodia Chimie Sa | Dispersion colloidale d'un compose de cerium et d'un autre element choisi parmi le zirconium, les terres rares, le titane et l'etain, solide dispersible a base de ce compose et procedes de preparation |
AU2006242541B2 (en) * | 2005-04-29 | 2011-12-08 | Board Of Regents Of The University Of Oklahoma | Inhibition of reactive oxygen species and protection of mammalian cells |
CN1876237B (zh) * | 2005-06-10 | 2011-01-26 | 上海天丰环保科技有限公司 | 三相催化氧化处理废水的复合型催化剂 |
JP2009149524A (ja) * | 2006-03-16 | 2009-07-09 | Kyushu Univ | アルツハイマー病の予防・治療剤 |
FR2899906B1 (fr) * | 2006-04-13 | 2008-06-27 | Eads Ccr Groupement D Interet | Utilisation d'un materiau nanostructure, comme revetement protecteur de surfaces metalliques |
US7959949B2 (en) | 2006-04-27 | 2011-06-14 | University Of Central Florida Research Foundation, Inc. | Functionalized nanoceria composition for ophthalmic treatment |
FR2905371B1 (fr) * | 2006-08-31 | 2010-11-05 | Rhodia Recherches & Tech | Composition a reductibilite elevee a base d'un oxyde de cerium nanometrique sur un support, procede de preparation et utilisation comme catalyseur |
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US9119391B1 (en) | 2007-07-16 | 2015-09-01 | University Of Central Florida Research Foundation, Inc. | Polymer coated ceria nanoparticles for selective cytoprotection |
US8916199B1 (en) | 2008-04-25 | 2014-12-23 | University of Central Florida Research Foundation, Ind. | Inhibition of angiogenesis associated with ovarian cancer by nanoparticles of cerium oxide |
EP2288258A4 (de) * | 2008-04-25 | 2012-10-31 | Univ Oklahoma | Inhibition of neovascularization by cerium oxide nanoparticles |
FR2933100B1 (fr) * | 2008-06-25 | 2010-08-13 | Commissariat Energie Atomique | Dispersions de particules d'oxydes de terres rares luminescents, vernis comprenant ces particules, leurs procedes de preparation et procede de marquage de substrats. |
US9127202B1 (en) | 2008-07-18 | 2015-09-08 | University Of Central Florida Research Foundation, Inc. | Biocompatible nano rare earth oxide upconverters for imaging and therapeutics |
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US9585840B1 (en) | 2009-07-10 | 2017-03-07 | University Of Central Florida Research Foundation, Inc. | Redox active cerium oxide nanoparticles and associated methods |
US8312053B2 (en) * | 2009-09-11 | 2012-11-13 | Oracle International Corporation | Dynamic atomic arrays |
US8795731B1 (en) | 2009-10-12 | 2014-08-05 | University Of Central Florida Research Foundation, Inc. | Cerium oxide nanoparticle-based device for the detection of reactive oxygen species and monitoring of chronic inflammation |
US8877207B2 (en) | 2010-09-17 | 2014-11-04 | University Of Central Florida Research Foundation, Inc. | Nanoparticles of cerium oxide targeted to an amyloid-beta antigen of Alzheimer's disease and associated methods |
US8951539B1 (en) | 2011-06-07 | 2015-02-10 | University Of Central Florida Research Foundation, Inc. | Methods of promoting angiogenesis using cerium oxide nanoparticles |
US9161950B2 (en) | 2011-09-21 | 2015-10-20 | University Of Central Florida Foundation, Inc. | Neuronal protection by cerium oxide nanoparticles |
WO2013158744A2 (en) * | 2012-04-17 | 2013-10-24 | Cerion Enterprises, Llc | Nanoparticles of cerium and amino acids |
JP6174692B2 (ja) | 2012-06-13 | 2017-08-02 | セリオン エンタープライジズ リミテッド ライアビリティ カンパニー | 酸化ストレスの処置のためのナノセリア |
US9463437B2 (en) | 2013-02-14 | 2016-10-11 | University Of Central Florida Research Foundation, Inc. | Methods for scavenging nitric oxide using cerium oxide nanoparticles |
CN108084735B (zh) * | 2017-12-19 | 2020-08-28 | 包头中科世纪科技有限责任公司 | 金属盐或铵盐及羧酸类有机物对稀土硫化物后处理的方法 |
CN112206776B (zh) * | 2020-07-28 | 2023-04-28 | 陕西延长石油(集团)有限责任公司 | 复合金属氧化物、原料组合物及其制备方法和应用 |
CN113373304B (zh) * | 2021-06-09 | 2022-05-13 | 江西理工大学 | 一种从稀土料液中络合-浊点萃取除铝的方法 |
CN115504454B (zh) * | 2022-09-13 | 2024-02-02 | 中国石油大学(华东) | 一种新型绿色稀土掺杂的碳点缓蚀剂的制备及离子液体对其进行改性的方法 |
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US4351735A (en) * | 1978-12-19 | 1982-09-28 | R.G.B. Laboratories Inc. | Mineral enrichment composition and method of preparing same |
US5234870A (en) * | 1988-07-21 | 1993-08-10 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Zirconia sol and method for production thereof |
WO1990009350A1 (en) * | 1989-02-10 | 1990-08-23 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Zirconia sol, preparation thereof, slurry for use in the production of porous ceramic, and porous ceramic produced from said slurry |
FR2829481B1 (fr) * | 2001-09-12 | 2003-12-19 | Rhodia Elect & Catalysis | Dispersion colloidale de particules d'un vanadate ou d'un phospho-vanadate d'une terre rare |
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2000
- 2000-06-05 FR FR0007147A patent/FR2809637B1/fr not_active Expired - Fee Related
-
2001
- 2001-06-01 WO PCT/FR2001/001706 patent/WO2001094262A1/fr not_active Application Discontinuation
- 2001-06-01 US US10/297,264 patent/US20030187077A1/en not_active Abandoned
- 2001-06-01 CA CA002411749A patent/CA2411749A1/fr not_active Abandoned
- 2001-06-01 KR KR1020027016592A patent/KR20030036214A/ko not_active Application Discontinuation
- 2001-06-01 CN CN01811946A patent/CN1438970A/zh active Pending
- 2001-06-01 JP JP2002501783A patent/JP2003535674A/ja active Pending
- 2001-06-01 AU AU2001274178A patent/AU2001274178A1/en not_active Abandoned
- 2001-06-01 EP EP01940666A patent/EP1301435A1/de not_active Withdrawn
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CA2411749A1 (fr) | 2001-12-13 |
FR2809637B1 (fr) | 2003-01-24 |
WO2001094262A1 (fr) | 2001-12-13 |
KR20030036214A (ko) | 2003-05-09 |
FR2809637A1 (fr) | 2001-12-07 |
AU2001274178A1 (en) | 2001-12-17 |
JP2003535674A (ja) | 2003-12-02 |
CN1438970A (zh) | 2003-08-27 |
US20030187077A1 (en) | 2003-10-02 |
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