FR2459211A1 - Fired clays doped with metals - used as catalyst supports and in biological water treatment - Google Patents
Fired clays doped with metals - used as catalyst supports and in biological water treatment Download PDFInfo
- Publication number
- FR2459211A1 FR2459211A1 FR7915632A FR7915632A FR2459211A1 FR 2459211 A1 FR2459211 A1 FR 2459211A1 FR 7915632 A FR7915632 A FR 7915632A FR 7915632 A FR7915632 A FR 7915632A FR 2459211 A1 FR2459211 A1 FR 2459211A1
- Authority
- FR
- France
- Prior art keywords
- clays
- cooked
- metal
- doped
- clay
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/04—Clay; Kaolin
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
Description
La présente invention a trait au domaine des argiles cuites ou chamottes et concerne tout particulièrement de nouvelles compositions chargées en éléments métalliques fortement électro-positifs ainsi que leur procédé de préparation et leurs applications. The present invention relates to the field of baked or chamotte clays and particularly relates to new compositions loaded with highly electro-positive metallic elements as well as their preparation process and their applications.
La chamotte ou argile cuite est un matériau très ancien (rentrant dans la catégorie plus générale des céramiques) obtenu par calcination de diverses argiles et traditionnellement utilisé pour ses propriétés réfractaires. Depuis plusieurs années cependant, de nouvelles voies d'utilisation ont été ouvertes grace à la mise au point de granulats d'argiles cuites dopées aptes a servir de supports en milieu chimique ou biologique.C'est ainsi, par exemple, que l'on a préconisé l'emploi d'argiles cuites comme supports de filtres biologiques dans le traitement des eaux, ces argiles ayant été chargées en éléments métalliques tels que Fe, Cu, Zn, Na, K, Ca, Mg, Mn.. jouant le rôle d'oligo-éléments qui servent de nutriments pour les microorganismes chargés de digérer les substances polluantes contenues dans les eaux usées (voir brevet français N076.03573 du 10 Février 1976)
Poursuivant ses travaux dans le domaine de la mise au point d'argiles cuites à propriétés de surface très spécifiques en vue des utilisations nouvelles comme supports actifs, la Demandtresse a mis au point de nouveaux produits qui, dopés par certains éléments métalliques, ont une structure électronique superficielle apte à favoriser des échanges spécifiques avec un milieu donné, notamment lorsque ce dernier présente une ionisation négative.Chamotte or baked clay is a very old material (falling into the more general category of ceramics) obtained by calcination of various clays and traditionally used for its refractory properties. For several years, however, new ways of use have been opened thanks to the development of doped cooked clay aggregates capable of serving as supports in chemical or biological medium. This is how, for example, recommended the use of cooked clays as supports for biological filters in water treatment, these clays having been loaded with metallic elements such as Fe, Cu, Zn, Na, K, Ca, Mg, Mn .. playing the role trace elements that serve as nutrients for the microorganisms responsible for digesting polluting substances contained in wastewater (see French patent N076.03573 of 10 February 1976)
Continuing its work in the field of developing baked clays with very specific surface properties for new uses as active supports, Demandtresse has developed new products which, doped with certain metallic elements, have a structure surface electronics capable of promoting specific exchanges with a given medium, in particular when the latter exhibits negative ionization.
Selon leur caractéristique principale, les argiles cuites dopées selon l'invention renferment au moins un métal fortement électropositif, de valence égale ou supérieure à 5. According to their main characteristic, the fired clays doped according to the invention contain at least one highly electropositive metal, of valence equal to or greater than 5.
Bien que d'autres éléments métalliques, généralement sous forme d'oxydes, puissent convenir s'ils présentent la valence minimum précitée, l'invention vise tout particulièrement les métaux du groupe constitué par : le tungstène, le vanadium, le tantale et l'uranium. Grâce à la présence de nombreux électrons célibataires ou électrons de valence dans l'orbite externe de ces métaux et a l'importante énergie d'activation ainsi créée, les argiles traitées sont réactives, en particulier à l'égard d'éléments ayant des charges négatives comme il sera expliqué plus loin. Although other metallic elements, generally in the form of oxides, may be suitable if they have the abovementioned minimum valency, the invention relates in particular to the metals of the group consisting of: tungsten, vanadium, tantalum and uranium. Thanks to the presence of numerous single electrons or valence electrons in the external orbit of these metals and to the important activation energy thus created, the treated clays are reactive, in particular with regard to elements having charges negative as will be explained later.
Les argiles selon l'invention sont obtenues par ajout des éléments métalliques susvisés, sous forme de sels ou d'oxydes, à des argiles naturelles telles que celles des types : illitique, kaolinique, halloysitique, montmorillonitique ou des mélanges de ces produits. Conformément à un mode de réalisation avantageux on utilise comme argile crue de départ un produit contenant le moins possible d'élénents faiblement électropositifs, comme par exemple des métaux alcalins, alcalino-terreux. A cet égard, les argiles kaoliniques conviennent spécialement bien comme produit de base.La quantité d'éléments à introduire dans l'argile crue est déterminée par comparaison entre la composition chimique (en % et en oxyde) de l'argile ayant subi une calcination a plus de 1000 C, avec les taux minimum des éléments métalliques précités qui doivent être présents dans le support final. En général, ces taux sont maintenus entre des fourchettes de 1 a 15 O/oo (pour mille) par rapport au poids d'argile cuite finale. La calcination de cette composition donne un matériau où, globalement et en surface (grâce au mécanisme d'agitation thermique) toutes les charges sont compensées, la surface étant donc électroniquement neu: tre.Après broyage à température ambiante, l'apparition de faces " fraîches donne lieu à des surfaces où les charges ne sont plus compensées et où les éléments métalliques présents sont accepteurs d'électrons ou de molécules ou encore d'organismes qui contribueront à la neutralité de la surface. The clays according to the invention are obtained by adding the above-mentioned metallic elements, in the form of salts or oxides, to natural clays such as those of the types: illitic, kaolinic, halloysitic, montmorillonitic or mixtures of these products. In accordance with an advantageous embodiment, a product containing as little as possible weak electropositive elements, such as, for example, alkali or alkaline earth metals, is used as the starting raw clay. In this respect, kaolinic clays are particularly suitable as a basic product. The quantity of elements to be introduced into the raw clay is determined by comparison between the chemical composition (in% and in oxide) of the clay having undergone calcination. has more than 1000 C, with the minimum levels of the aforementioned metallic elements which must be present in the final support. In general, these rates are maintained between ranges of 1 to 15 O / oo (per thousand) relative to the weight of final baked clay. The calcination of this composition gives a material where, overall and at the surface (thanks to the thermal agitation mechanism) all the charges are compensated, the surface therefore being electronically new: tre.After grinding at room temperature, the appearance of faces " fresh gives rise to surfaces where the charges are no longer compensated and where the metallic elements present are acceptors of electrons or molecules or of organisms which will contribute to the neutrality of the surface.
Selon un procédé de préparation préféré , on effectue le mélange de l'argile crue et des ajouts par voie seche, les matériaux étant mélangés sous forme broyée puis ensuite humidifiés et malaxés pour obtenir des boudins qui sont soumis à une cuisson à température de 1200 à 1300 C, par exemple dans un four rotatif.La chamotte récupérée est alors broyée et tamisée aux granulométries désirées selon les types d'emplois et les problèmes hydrauliques classiques (vitesse de passage, perte de charge.,.), par exemple avec des diamètres de grains compris entre 0,5 et 25 mm:
Selon un autre mode de préparation, on peut opérer par voie humide, les matières premières finement broyées étant mélangées en milieu de dispersion aqueux, la pâte obtenue après concentration de la suspension étant ensuite mise sous forme convenable (étirage, extrusion, etc..) avant cuisson au four. Bien entendu, des variantes peuvent être apportées à ces modes opératoires non limitatifs, conformément par exemple aux méthodes habituellement utilisées dans la fabrication connue des céramiques.Dans le cad?e de la présente invention, le terme céramique est pris selon son accep tion technologique la plus large à savoir : tout matériau manufacturé solide à température ambiante pourvu qu'il ne soit ni métallique ni organique.According to a preferred preparation process, the raw clay is mixed with dry additions, the materials being mixed in crushed form and then moistened and kneaded to obtain rolls which are subjected to cooking at a temperature of 1200 to 1300 C, for example in a rotary oven. The recovered chamotte is then crushed and sieved to the desired grain sizes according to the types of use and conventional hydraulic problems (speed of passage, pressure drop, etc.), for example with diameters grains between 0.5 and 25 mm:
According to another method of preparation, it is possible to operate by the wet route, the finely ground raw materials being mixed in an aqueous dispersion medium, the paste obtained after concentration of the suspension is then put into suitable form (drawing, extrusion, etc.) before baking. Of course, variants can be made to these nonlimiting operating methods, in accordance for example with the methods usually used in the known manufacture of ceramics. In the context of the present invention, the term ceramic is taken according to its technological acceptance. broader to know: any manufactured material solid at room temperature provided that it is neither metallic nor organic.
Les argiles cuites dopées selon l'invention se prêtent à de nombreuses et intéressantes applications, pour la plupart nouvelles ou récentes par rapport aux usages traditionnels des chamottes. Parmi ces emplois on peut citer tout particulièrement : les supports catalytiques pour réactions chimiques et les milieux d'accrochage pour microorganismes. The fired clays doped according to the invention lend themselves to numerous and interesting applications, most of which are new or recent compared to the traditional uses of chamottes. Among these uses, mention may be made most particularly of: catalytic supports for chemical reactions and attachment media for microorganisms.
On sait que les microorganismes exsudent des métabolites du type polysaccharldes (entre autres) qui sont chargés négativement indépendamment de la charge propre de la bactérie ou de la levure ; par ailleurs, ce sont ces polysaccharides (notamment) qui permettent l'accrochage des microorganismes sur la surface du matériau argileux. It is known that microorganisms exude metabolites of the polysaccharide type (among others) which are negatively charged independently of the specific charge of the bacteria or yeast; moreover, it is these polysaccharides (in particular) which allow the attachment of microorganisms to the surface of the clay material.
De ce fait, des utilisations particulièrement avantageuses des produits selon l'invention ont trait à des supports d'enzymes dans les usages de ces derniers sous forme immobilisée ou, mieux encore, à des supports pour la filtration biologique des eaux usées, industrielles ou à potabiliser ; en effet, les bactéries ou microorganismes étant chargés négativement, l'accrochage de la bête est considérablement facilité sur les grains d'argile cuite chargés en éléments métalliques fortement électropositifs. Therefore, particularly advantageous uses of the products according to the invention relate to enzyme supports in the uses of the latter in immobilized form or, better still, to supports for the biological filtration of waste water, industrial or make it drinkable; in fact, the bacteria or microorganisms being negatively charged, the attachment of the beast is considerably facilitated on the cooked clay grains loaded with highly electropositive metallic elements.
Enfin, parmi d'autres usages encore des nouvelles argiles dopées, on peut citer les supports activés pour l'industrie de la biere, du lactosérum et l'industrie pharmaceutique en général. Finally, among other uses of new doped clays, mention may be made of activated supports for the beer industry, whey and the pharmaceutical industry in general.
Claims (6)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR7915632A FR2459211A1 (en) | 1979-06-19 | 1979-06-19 | Fired clays doped with metals - used as catalyst supports and in biological water treatment |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR7915632A FR2459211A1 (en) | 1979-06-19 | 1979-06-19 | Fired clays doped with metals - used as catalyst supports and in biological water treatment |
Publications (1)
Publication Number | Publication Date |
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FR2459211A1 true FR2459211A1 (en) | 1981-01-09 |
Family
ID=9226773
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
FR7915632A Pending FR2459211A1 (en) | 1979-06-19 | 1979-06-19 | Fired clays doped with metals - used as catalyst supports and in biological water treatment |
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FR (1) | FR2459211A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018162208A3 (en) * | 2017-03-06 | 2019-08-22 | Sibelco Nederland N.V. | Particles for fluidised bed reaction methods and fluidised bed reaction methods |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2759899A (en) * | 1952-10-03 | 1956-08-21 | Union Oil Co | Conversion catalysts and processes for bonding the catalyst composites |
DE2113940A1 (en) * | 1971-03-23 | 1972-09-28 | Aloys Dr Wuestefeld | Increasing reactivity of solids - eg when acting as solid catalysts |
FR2340909A1 (en) * | 1976-02-10 | 1977-09-09 | Omnium Assainissement | BIOLOGICAL FERMENTATION SUPPORT MATERIALS |
FR2432485A1 (en) * | 1978-08-02 | 1980-02-29 | Omnium Assainissement | BIOLOGICAL WATER DENITRIFICATION PROCESS |
-
1979
- 1979-06-19 FR FR7915632A patent/FR2459211A1/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2759899A (en) * | 1952-10-03 | 1956-08-21 | Union Oil Co | Conversion catalysts and processes for bonding the catalyst composites |
DE2113940A1 (en) * | 1971-03-23 | 1972-09-28 | Aloys Dr Wuestefeld | Increasing reactivity of solids - eg when acting as solid catalysts |
FR2340909A1 (en) * | 1976-02-10 | 1977-09-09 | Omnium Assainissement | BIOLOGICAL FERMENTATION SUPPORT MATERIALS |
FR2432485A1 (en) * | 1978-08-02 | 1980-02-29 | Omnium Assainissement | BIOLOGICAL WATER DENITRIFICATION PROCESS |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018162208A3 (en) * | 2017-03-06 | 2019-08-22 | Sibelco Nederland N.V. | Particles for fluidised bed reaction methods and fluidised bed reaction methods |
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