FR3045415A1 - PROCESS FOR MANUFACTURING A SELF-SUPPORTED MONOLITHIC STRUCTURE ADSORBENT - Google Patents

PROCESS FOR MANUFACTURING A SELF-SUPPORTED MONOLITHIC STRUCTURE ADSORBENT Download PDF

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FR3045415A1
FR3045415A1 FR1562784A FR1562784A FR3045415A1 FR 3045415 A1 FR3045415 A1 FR 3045415A1 FR 1562784 A FR1562784 A FR 1562784A FR 1562784 A FR1562784 A FR 1562784A FR 3045415 A1 FR3045415 A1 FR 3045415A1
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monolith
dough
heat treatment
substep
zeolite
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Guludec Erwan Le
Raphael Faure
Pascal Del-Gallo
Thierry Chartier
Julie Bourret
Thibault Gadrat
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Centre National de la Recherche Scientifique CNRS
Air Liquide SA
Universite de Limoges
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Centre National de la Recherche Scientifique CNRS
Air Liquide SA
Universite de Limoges
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Priority to FR1562784A priority Critical patent/FR3045415A1/en
Publication of FR3045415A1 publication Critical patent/FR3045415A1/en
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Abstract

Procédé de fabrication d'un adsorbant structuré monolithique autosupporté comprenant les étapes successives suivantes : a) préparation de la pâte, b) maturation de la pâte, c) extrusion de la pâte mature de manière à former un monolithe, d) séchage du monolithe, e) traitement thermique du monolithe, et f) contrôle de la reprise en humidité du monolithe.Process for the production of a self-supporting monolithic structured adsorbent comprising the following successive stages: a) preparation of the dough, b) maturation of the dough, c) extrusion of the mature dough so as to form a monolith, d) drying of the monolith, e) heat treatment of the monolith, and f) control of the moisture recovery of the monolith.

Description

La présente invention est relative à un procédé de fabrication d'un adsorbant structuré monolithique.The present invention relates to a method for manufacturing a monolithic structured adsorbent.

Les adsorbants utilisés dans les procédés de purification ou de séparation des gaz se présentent généralement sous la forme de billes ou d'extrudés de quelques millimètres. Ces adsorbants dits « adsorbants en vrac » conduisent à une perte de charge relativement importante qui peut-être pénalisante en particulier lorsque l'on cherche à réduire le temps de cycle de ces procédés. Depuis quelques années, chercheurs et industriels s'intéressent à de nouvelles formes, ce sont les adsorbants dits « structurés » : l'adsorbant est mis en forme de manière à avoir un ensemble de canaux rectilignes et parallèles dans lesquels le gaz s'écoule. Cela conduit à des structures en nid d'abeille de plusieurs centimètres de long. Les canaux de ces structures peuvent avoir différentes formes (hexagone, carré, triangle, rond, etc.)The adsorbents used in the purification or gas separation processes are generally in the form of beads or extrudates of a few millimeters. These so-called adsorbents called "bulk adsorbents" lead to a relatively large pressure drop that can be detrimental especially when trying to reduce the cycle time of these processes. In recent years, researchers and industrialists are interested in new forms, they are so-called "structured" adsorbents: the adsorbent is shaped so as to have a set of rectilinear and parallel channels in which the gas flows. This leads to honeycomb structures several inches long. The channels of these structures can have different shapes (hexagon, square, triangle, round, etc.)

Ces adsorbants structurés sont susceptibles d'améliorer significativement les procédés d'adsorption. Ils présentent plusieurs avantages par rapport aux adsorbants «vrac»: une réduction des pertes de charge, l'absence de phénomènes d'attrition, la possibilité de nouvelles mises en œuvre, une amélioration de la cinétique d'adsorption.These structured adsorbents are likely to significantly improve the adsorption processes. They have several advantages over "bulk" adsorbents: a reduction of pressure drops, the absence of attrition phenomena, the possibility of new implementations, an improvement of the adsorption kinetics.

Il existe plusieurs types d'adsorbants structurés, les principaux étant: - les fibres creuses - les laminés - les monolithes.There are several types of structured adsorbents, the main ones being: - hollow fibers - laminates - monoliths.

Sur ces 3 types d'adsorbant, les monolithes sont des adsorbants structurés particulièrement intéressants car ils ont un coût compétitif et présentent les quantités d'adsorbant par unité de volume les plus élevées. Ces monolithes sont « autosupportés » c'est-à-dire que l'adsorbant n'est pas déposé sur un support monolithique, il constitue la base même du monolithe.Of these 3 types of adsorbent, monoliths are structured adsorbents particularly interesting because they have a competitive cost and have the highest amounts of adsorbent per unit volume. These monoliths are "self-supporting" that is to say that the adsorbent is not deposited on a monolithic support, it is the very basis of the monolith.

Les adsorbants ne sont pas des matériaux qui confèrent une résistance mécanique élevée aux objets fabriqués. Ainsi, l'enjeu de la fabrication de ce type de monolithe est de trouver un compromis entre la tenue mécanique et les performances en adsorption, ces deux propriétés étant antagonistes.Adsorbents are not materials that give high mechanical strength to manufactured objects. Thus, the challenge of manufacturing this type of monolith is to find a compromise between the mechanical strength and the adsorption performance, these two properties being antagonistic.

La zéolite est un adsorbant largement utilisé dans les procédés d'adsorption pour capter de l'eau, du C02 et d'autres impuretés.Zeolite is an adsorbent widely used in adsorption processes to capture water, CO 2 and other impurities.

Pour les monolithes à base de zéolite, un liant inorganique est ajouté afin de conférer au monolithe une tenue mécanique suffisante. Il est généralement utilisé des liants qui sont des argiles comme la bentonite, l'attalpugite, le kaolin, etc. Mais même avec ces liants, les monolithes fabriqués peuvent présenter une tenue mécanique insuffisante, l'une des raisons étant la présence de microfissures, ces microfissures les fragilisent et ne permettent pas l'utilisation de ces adsorbants dans des conditions industrielles qui sont exigeantes en termes de résistance mécanique et de durabilité.For zeolite-based monoliths, an inorganic binder is added to give the monolith sufficient mechanical strength. It is generally used binders that are clays such as bentonite, attalpugite, kaolin, etc. But even with these binders, the manufactured monoliths may have insufficient mechanical strength, one of the reasons being the presence of microcracks, these microcracks weaken them and do not allow the use of these adsorbents in industrial conditions that are demanding in terms mechanical strength and durability.

Partant de là un problème qui se pose est de fournir un adsorbant structuré monolithique amélioré.Starting from there a problem that arises is to provide an improved structured monolithic adsorbent.

Une solution de la présente invention est un procédé de fabrication d'un adsorbant structuré monolithique autosupporté comprenant les étapes successives suivantes : a) préparation de la pâte, b) maturation de la pâte, c) extrusion de la pâte mature de manière à former un monolithe, d) séchage du monolithe, e) traitement thermique du monolithe, et f) contrôle de la reprise en humidité du monolithe.A solution of the present invention is a method of manufacturing a self-supporting monolithic structured adsorbent comprising the following successive steps: a) preparation of the dough, b) maturation of the dough, c) extrusion of the mature dough so as to form a monolith, d) drying of the monolith, e) heat treatment of the monolith, and f) control of the moisture recovery of the monolith.

Selon le cas, le procédé selon l'invention peut présenter une ou plusieurs des caractéristiques suivantes : - le traitement thermique est effectué au moyen d'un four de calcination et l'étape f) de contrôle de la reprise en humidité comprend l'augmentation progressive de l'hygrométrie de l'atmosphère du four. - le contrôle de la reprise en humidité du monolithe est réalisé au moyen d'un ou plusieurs matériaux déposés à la surface du monolithe après l'étape d) de séchage ou l'étape e) de traitement thermique du monolithe. - le ou les matériaux déposés sont choisis parmi la zéolite, le gel de silice, l'alumine activée ou des dessicants à base de CaCI2 ou de CaS04. - le ou les matériaux déposés recouvrent entre 60% et 100% de la surface du monolithe. - l'étape d) comprend une première sous-étape de congélation du monolithe, et une deuxième sous-étape de lyophilisation du monolithe congelé, - la température de congélation est comprise entre -10°C et -20°C, - la première sous-étape présente une durée d'au moins lOh, - la deuxième sous-étape présente une durée comprise entre 8 et 16h, - la pâte préparée à l'étape a) comprend de la zéolite, un ou plusieurs liants inorganiques, un ou plusieurs composés organiques et de l'eau. - la pâte préparée à l'étape a) comprend entre 10 et 50%m d'eau, de préférence entre 20 et 40%m d'eau. - la pâte préparée à l'étape a) comprend entre 45 et 93%m de zéolite, entre 4.5 et 49%m de liant, entre 1 et 5%m de glycerol, et entre 1 et 5%m de methylcellulose. Le glycerol en plus de jouer le rôle de lubrifiant sert de plastifiant. - le liant est choisi parmi la bentonite, l'attalpugite, le kaolin et l'alloysite.Depending on the case, the method according to the invention may have one or more of the following characteristics: the heat treatment is carried out by means of a calcination furnace and the moisture recovery control step f) comprises the increase; progressive hygrometry of the furnace atmosphere. the control of the moisture recovery of the monolith is carried out by means of one or more materials deposited on the surface of the monolith after the drying step d) or the heat treatment step e) of the monolith. the deposited material or materials are chosen from zeolite, silica gel, activated alumina or desicants based on CaCl 2 or CaSO 4. the deposited material or materials cover between 60% and 100% of the surface of the monolith. step d) comprises a first sub-step of freezing the monolith, and a second sub-step of lyophilizing the frozen monolith, the freezing temperature is between -10 ° C and -20 ° C, the first sub-step has a duration of at least 10 h, - the second substep has a duration between 8 and 16 h, - the dough prepared in step a) comprises zeolite, one or more inorganic binders, one or several organic compounds and water. the dough prepared in step a) comprises between 10 and 50% of water, preferably between 20 and 40% of water. the paste prepared in step a) comprises between 45 and 93% by weight of zeolite, between 4.5 and 49% by weight of binder, between 1 and 5% by weight of glycerol, and between 1 and 5% by weight of methylcellulose. Glycerol in addition to acting as a lubricant serves as a plasticizer. - The binder is selected from bentonite, attalpugite, kaolin and alloysite.

Après traitement thermique, le monolithe comprend : - entre 50% et 95% m de zéolite, préférentiellement entre 60 et 90% m de zéolite, - entre 5% et 50% m de liant inorganique, préférentiellement entre 10 et 40% m de liant inorganique. Le monolithe pouvant comprendre un ou plusieurs liants inorganiques.After heat treatment, the monolith comprises: between 50% and 95% by weight of zeolite, preferably between 60 and 90% by weight of zeolite, between 5% and 50% by weight of inorganic binder, preferentially between 10 and 40% by weight of binder inorganic. The monolith may include one or more inorganic binders.

Une solution selon l'invention consiste à recouvrir les monolithes par des matériaux qui permettent de sécher l'air : zéolite, gel de silice, alumine activée, ou dessicants à base CaCh ou de CaS04. Ces matériaux peuvent être sous forme de poudre, de billes, d'extrudés ou de granulés. Ces matériaux sont déposés soit après l'étape de séchage des monolithes, soit après le traitement thermique.A solution according to the invention consists in covering the monoliths with materials which make it possible to dry the air: zeolite, silica gel, activated alumina, or desicants based on CaCl 2 or CaSO 4. These materials may be in the form of powder, beads, extrudates or granules. These materials are deposited either after the drying step of the monoliths or after the heat treatment.

Dans une variante de cette invention, dans le cas où on peut contrôler le taux d'humidité du four de calcination, on augmentera progressivement l'hygrométrie de l'atmosphère du four après le traitement thermique.In a variant of this invention, in the case where the moisture content of the calcining furnace can be controlled, the humidity of the furnace atmosphere will gradually be increased after the heat treatment.

Dans une variante de l'invention, dans le cas où on peut contrôler le taux d'humidité du four de calcination, on s'arrangera pour qu'il n'y ait pas de reprise en humidité des monolithes, on les stockera ensuite dans une enceinte étanche sous une atmosphère sèche.In a variant of the invention, in the case where it is possible to control the moisture content of the calcination furnace, it will be arranged so that there is no moisture recovery of the monoliths, they will then be stored in a sealed enclosure under a dry atmosphere.

Dans une variante de l'invention, après calcination, on placera les monolithes dans une enceinte à hygrométrie contrôlée pour une reprise en humidité progressive. En fin de calcination mais avant d'avoir atteint la température ambiante, les monolithes peuvent être disposés dans une enceinte fermée ou dans un contenant avec couvercle.In one variant of the invention, after calcination, the monoliths will be placed in a chamber with controlled hygrometry for a progressive moisture recovery. At the end of calcination but before having reached the ambient temperature, the monoliths can be arranged in a closed enclosure or in a container with lid.

Ce contrôle de la reprise en humidité permet d'éviter l'apparition de microfissures.This control of the moisture recovery makes it possible to avoid the appearance of microcracks.

La pâte préparée à l'étape a) comprend de la zéolite, un ou plusieurs liants inorganiques, un ou plusieurs composés organiques et de l'eau. L'adsorbant apporte les propriétés d'adsorption du monolithe, le liant inorganique les propriétés de résistance mécanique après traitement thermique, le liant organique les propriétés de résistance mécanique en cru avant traitement thermique et les autres additifs organiques peuvent servir de lubrifiant pour faciliter l'extrusion de la pâte ou de plastifiant ou de porogène.The paste prepared in step a) comprises zeolite, one or more inorganic binders, one or more organic compounds and water. The adsorbent provides the adsorption properties of the monolith, the inorganic binder the strength properties after heat treatment, the organic binder the mechanical strength properties in green before heat treatment and the other organic additives can serve as a lubricant to facilitate the extrusion of the paste or plasticizer or porogen.

Le liant organique peut être de la methylcellulose ou ses dérivés tels que le carboxyméthylcellulose (CMC), l'Hydroxyméthylcellulose (HMC), l'hydroxyéthylméthylcellulose (HEMC), l'hydroxypropylméthylcellulose (HPMC).Les autres additifs organiques peuvent être du glycérol, des glycols tels que le polyéthylène de glycol (PEG), de l'acide oléique ou de l'acide stéarique. A noter qu'il peut être utilisé plus d'un liant inorganique ou organique et plus d'un additif.The organic binder can be methylcellulose or its derivatives such as carboxymethylcellulose (CMC), hydroxymethylcellulose (HMC), hydroxyethylmethylcellulose (HEMC), hydroxypropylmethylcellulose (HPMC). Other organic additives can be glycerol, glycols such as polyethylene glycol (PEG), oleic acid or stearic acid. It should be noted that more than one inorganic or organic binder and more than one additive can be used.

Une fois que la pâte est préparée, elle est portée à maturation pendant 24h. La pâte est ensuite extrudée, i.e. elle passe à travers une filière avec une structure en nid d'abeille. Le monolithe extrudé est ensuite séché puis consolidé par une calcination entre 600 et 800 °C. Ce traitement thermique permet également d'éliminer les composés organiques.Once the dough is prepared, it is matured for 24 hours. The paste is then extruded, i.e. it passes through a die with a honeycomb structure. The extruded monolith is then dried and consolidated by calcination at 600 to 800 ° C. This heat treatment also makes it possible to eliminate the organic compounds.

Le contrôle de la reprise en humidité du monolithe permet de réduire significativement le nombre de microfissure.Controlling the moisture recovery of the monolith significantly reduces the number of microcracks.

Notons que la décomposition de l'étape de séchage en une première sous-étape de congélation du monolithe, et une deuxième sous-étape de lyophilisation du monolithe congelé permet d'avoir un séchage plus homogène et progressif et réduit les contraintes mécaniques qui s'exercent lors du séchage. Cela permet de réduire le nombre de fissure. Dans ce cas, une fois l’extrusion terminée, les monolithes sont placés dans un congélateur à des températures comprises entre -10°C et -20°C. Les étapes qui suivent la fin de l'extrusion doivent être réalisées le plus rapidement possible pour éviter le séchage à l'air libre des monolithes, idéalement en moins de 5 minutes. Le séjour des échantillons dans le congélateur est compris entre 10 et 24 heures pour assurer une congélation totale. Après congélation, les monolithes sont séchés dans un lyophilisateur. La durée de lyophilisation, de 12 heures environ, varie en fonction de la masse de monolithe à traiter. Les monolithes peuvent ensuite être traités thermiquement.It should be noted that the decomposition of the drying step into a first sub-step of freezing the monolith, and a second sub-step of lyophilization of the frozen monolith, makes it possible to have a more homogeneous and gradual drying and to reduce the mechanical stresses that occur. exercise during drying. This reduces the number of cracks. In this case, once the extrusion is complete, the monoliths are placed in a freezer at temperatures between -10 ° C and -20 ° C. The steps following the end of the extrusion should be carried out as quickly as possible to avoid the drying of the monoliths in the open air, ideally in less than 5 minutes. The samples stay in the freezer is between 10 and 24 hours to ensure complete freezing. After freezing, the monoliths are dried in a lyophilizer. The freeze-drying time, approximately 12 hours, varies according to the mass of monolith to be treated. The monoliths can then be heat treated.

Enfin, la présente invention a également pour objet l'utilisation d'un adsorbant structuré monolithique selon l'invention, au sein d'une unité de purification de type TSA ou VSA ou PSA.Finally, the subject of the present invention is also the use of a monolithic structured adsorbent according to the invention, within a purification unit of the TSA or VSA or PSA type.

Claims (14)

Revendicationsclaims 1. Procédé de fabrication d'un adsorbant structuré monolithique autosupporté comprenant les étapes successives suivantes : a) préparation de la pâte, b) maturation de la pâte, c) extrusion de la pâte mature de manière à former un monolithe, d) séchage du monolithe, e) traitement thermique du monolithe, et f) contrôle de la reprise en humidité du monolithe.A method of manufacturing a self-supporting monolithic structured adsorbent comprising the following successive steps: a) preparing the dough, b) maturing the dough, c) extruding the mature dough so as to form a monolith, d) drying the dough. monolith, e) heat treatment of the monolith, and f) control of the moisture recovery of the monolith. 2. Procédé selon la revendication 1, caractérisé en ce que le traitement thermique est effectué au moyen d'un four de calcination et l'étape f) de contrôle de la reprise en humidité comprend l'augmentation progressive de l'hygrométrie de l'atmosphère du four.2. Method according to claim 1, characterized in that the heat treatment is carried out by means of a calcination furnace and step f) of controlling the moisture recovery comprises the gradual increase of the hygrometry of the oven atmosphere. 3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que le contrôle de la reprise en humidité du monolithe est réalisé au moyen d'un ou plusieurs matériaux déposés à la surface du monolithe après l'étape d) de séchage ou l'étape e) de traitement thermique du monolithe.3. Method according to one of claims 1 or 2, characterized in that the control of the moisture recovery of the monolith is achieved by means of one or more materials deposited on the surface of the monolith after step d) drying or step e) heat treatment of the monolith. 4. Procédé de fabrication selon la revendication 3, caractérisé en ce que le ou les matériaux déposés sont choisis parmi la zéolite, le gel de silice, l'alumine activée ou des dessicants à base de CaCb ou de CaS04.4. The manufacturing method according to claim 3, characterized in that the deposited material or materials are selected from zeolite, silica gel, activated alumina or desicants based on CaCb or CaSO4. 5. Procédé selon l'une des revendications 3 ou 4, caractérisé en ce que le ou les matériaux recouvrent entre 60% et 100% de la surface du monolithe.5. Method according to one of claims 3 or 4, characterized in that the material or materials cover between 60% and 100% of the surface of the monolith. 6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'étape d) comprend : - une première sous-étape de congélation du monolithe, et - une deuxième sous-étape de lyophilisation du monolithe congelé.6. Method according to one of claims 1 to 5, characterized in that step d) comprises: - a first substep of freezing the monolith, and - a second substep of lyophilization of the frozen monolith. 7. Procédé selon la revendication 6, caractérisé en ce que la température de congélation est comprise entre -10°C et -20°C.7. Process according to claim 6, characterized in that the freezing temperature is between -10 ° C and -20 ° C. 8. Procédé selon l'une des revendications 6 ou 7, caractérisé en ce que la première sous-étape présente une durée d'au moins lOh.8. Method according to one of claims 6 or 7, characterized in that the first substep has a duration of at least 10h. 9. Procédé selon l'une des revendications 6 à 8, caractérisé en ce que la deuxième sous-étape présente une durée comprise entre 8 et 16h.9. Method according to one of claims 6 to 8, characterized in that the second substep has a duration of between 8 and 16h. 10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que la pâte préparée à l'étape a) comprend de la zéolite, un ou plusieurs liants inorganiques, un ou plusieurs composés organiques et de l'eau.10. Method according to one of claims 1 to 9, characterized in that the paste prepared in step a) comprises zeolite, one or more inorganic binders, one or more organic compounds and water. 11. Procédé selon l'une des revendications 1 à 10, caractérisé en ce que la pâte préparée à l'étape a) comprend entre 10 et 50%m d'eau, de préférence entre 20 et 40%m d'eau.11. Method according to one of claims 1 to 10, characterized in that the dough prepared in step a) comprises between 10 and 50% m water, preferably between 20 and 40% m water. 12. Procédé selon l'une des revendications 1 à 11, caractérisé en ce que la pâte préparée à l'étape a) comprend entre 45 et 93%m de zéolite, entre 4.5 et 49%m de liant, entre 1 et 5%m de glycerol, et entre 1 et 5%m de methylcellulose.12. Method according to one of claims 1 to 11, characterized in that the paste prepared in step a) comprises between 45 and 93% m of zeolite, between 4.5 and 49% m of binder, between 1 and 5% m of glycerol, and between 1 and 5% of methylcellulose. 13. Procédé selon la revendication 12, caractérisé en ce que le liant est choisi parmi la bentonite, l'attalpugite, le kaolin et l'alloysite.13. The method of claim 12, characterized in that the binder is selected from bentonite, attalpugite, kaolin and alloysite. 14. Utilisation d'un adsorbant structuré monolithique obtenu par le procédé selon l'une des revendications 1 à 13, au sein d'une unité de purification de type TSA ou VSA ou PSA.14. Use of a monolithic structured adsorbent obtained by the process according to one of claims 1 to 13, in a purification unit of TSA or VSA or PSA type.
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