WO2002096801A1 - Active carbon-based agglomerates, method for preparing same and uses thereof - Google Patents

Active carbon-based agglomerates, method for preparing same and uses thereof Download PDF

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Publication number
WO2002096801A1
WO2002096801A1 PCT/FR2002/001754 FR0201754W WO02096801A1 WO 2002096801 A1 WO2002096801 A1 WO 2002096801A1 FR 0201754 W FR0201754 W FR 0201754W WO 02096801 A1 WO02096801 A1 WO 02096801A1
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Prior art keywords
agglomerate
tar
equal
less
agglomerate according
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PCT/FR2002/001754
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French (fr)
Inventor
Serge Bordere
Hedi Lini
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Ceca S.A.
LINI, Chantal
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Publication of WO2002096801A1 publication Critical patent/WO2002096801A1/en

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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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • 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
    • B01J21/18—Carbon
    • B01J35/31—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/354—After-treatment
    • C01B32/384—Granulation

Definitions

  • the invention relates to the field of active carbon and more particularly active carbon agglomerated with a binder.
  • Activated charcoals are products resulting from the carbonization of various carbonaceous materials, such as vegetable materials (wood, fruit shells), mineral materials (coal), synthetic materials (polymers), having undergone an activation treatment which gives them high porosity and high adsorption capacity. These adsorbent properties have been used for a long time for the treatment, separation and purification of gases as well as for the discoloration, purification and deodorization of liquids.
  • One method of preparing agglomerated activated carbon consists in mixing a finely divided hydrocarbon solid material with a hydrocarbon binder, agglomerating the mixture by compacting or extrusion in the form of grains to the desired size.
  • the agglomerated products are then carbonized at a temperature of 400 to 700 ° C. and then activated by partial gasification in an oxidizing atmosphere (water vapor and / or CO 2 ) at a temperature of 700 to 1000 ° C.
  • the finely divided carbonaceous solid may be coal, peat, peat or lignite or coconut shell or charcoal.
  • the hydrocarbon binder preferably has the following characteristics: it is not very ashy; it has agglomerating properties which allow mechanical resistance to green of the yarns (resistance to transport, resistance to impact and abrasion) and - it has a good yield of coke in order to ensure the final product a good overall yield and a good mechanical strength, particularly in terms of resistance to crushing.
  • FR 2 228 031 discloses parts molded from material containing carbon and a binder based on a phenol and an aldehyde.
  • FR 2 219 114 and FR 2 215 461 describe processes for the preparation of agglomerates of carbonaceous material using thermosetting as binder.
  • application FR 2 780 052 discloses a process for the preparation of activated carbon agglomerates using in particular thermosetting and thermofusible binders.
  • the first object of the invention therefore relates to an agglomerate of activated carbon based on carbon of plant material (s) and of binder based on tar (s), characterized in that it has a lower sulfur content. or equal to 500 ppm, preferably less than or equal to 300 ppm, a packed density of between 0.3 and 0.6 g / cm 3 , preferably between 0.35 and 0.45 g / cm 3 , an index of benzene between 25 and 50, preferably between 30 and 45, a crush resistance> 2 kg, preferably> 4 kg, an attrition resistance according to ASTM D4058-96 ⁇ 10%, preferably ⁇ 5 % and an average particle size between 0.5 to 10mm, preferably between 0.8 to 6mm.
  • the judicious choice of binder and tar makes it possible to obtain such an agglomerate of activated carbon meeting the strict criteria applied to active carbon used in catalysis.
  • the quality of the tar is indeed an important element.
  • the tar used advantageously has an Dean Stark extract of less than 15%.
  • the Dean Stark extract indicates the water-soluble content by azeotropic entrainment with toluene.
  • it has a Dean Stark extract of less than 10% and in particular less than 5%.
  • the sulfur content of the tar used alone or as a mixture is less than 500 ppm, advantageously less than 300 ppm and in particular less than 100 ppm.
  • the charcoal of plant material (s) is a charcoal obtained from vegetable material, such as for example wood or fruit shells such as coconut shells.
  • the charcoal of plant material (s) preferably also has a low sulfur content.
  • the agglomerate may also include a hardening and / or activating additive.
  • a hardening and activating additive are, for example, K 2 CO 3 or phosphoric acid.
  • These additives make it possible to harden the agglomerates at the outlet of the press or the extruder and thus to make them more manipulable. Furthermore, they have an activation effect insofar as they accelerate the gasification kinetics. Finally, they make it possible to orient the spectrum of pore sizes towards a microporosity, namely a pore diameter less than 2nm.
  • one or the other of the two additives will be chosen, in particular according to the undesirable impurities (potassium or phosphorus).
  • the agglomerate is in particular in the form of yarn.
  • the second object of the invention is a process for the preparation of such an agglomerate. It includes the steps of:
  • the carbon of plant material (s) has a diameter d 50 of between 15 and 30 ⁇ m.
  • the charcoal of vegetable material (s) is a charcoal.
  • the tar or mixture of tars advantageously has an Dean Stark extract of less than 10%.
  • the tar or the mixture of tars has a sulfur content less than or equal to 300 ppm, preferably less than or equal to 100 ppm.
  • the kneaded mixture comprises 100 parts by weight of carbon of vegetable material (s) and 50 to 70 parts by weight of tar.
  • the mixture to be kneaded can also comprise up to 6 parts by weight of hardening and / or activation additive (s) per 100 parts of carbon of plant material (s). A one hour mixing will generally be sufficient.
  • the operation of shaping the mixture of charcoal and kneaded wood tar is also called “spinning". It can be produced by extrusion, molding or compacting, for example by means of devices such as a roller press, screw extruder, piston press, press mold or any other device allowing such shaping.
  • the average diameter of the agglomerates is typically between 0.5 and 10 mm.
  • the agglomerates are preferably in the form of yarns with a diameter generally between 0.8 and 6 mm and preferably between 1 and 5 mm.
  • the stage of carbonization of the agglomerates is preferably carried out at approximately 700 ° C., for example by combustion fumes. This step eliminates the volatiles contained in the tar and condenses the residue. It also has the advantage of hardening the agglomerates. Finally, the charred agglomerates are activated, preferably by heat treatment at 900 to 1000 ° C. in the presence of water vapor and / or carbon dioxide. , Uses
  • these agglomerates can be used with advantage in catalytic processes, for example as a catalyst or as a catalyst support.
  • the agglomerates according to the invention can also serve as adsorbents for separating the components of a mixture comprising at least two different compounds in an adsorption process comprising the following steps: - bringing the mixture into contact with the agglomerate under conditions allowing preferential adsorption of certain compounds of the mixture; separation of the agglomerate and of the compounds adsorbed by the latter from the mixture thus depleted in preferentially adsorbed compounds; and regeneration of the agglomerate by desorption of. adsorbed compounds.
  • Such a process can operate, for example, cyclically.
  • Another object of the invention relates to uses of the agglomerates described in the adsorption processes.
  • the agglomerates described can in particular be used in liquid phase adsorption processes, in particular water, such as the purification of chemical compounds resulting from synthesis reactions and polluted by by-products or even purification and / or cleaning up water.
  • the agglomerates described can also be used in gas phase adsorption processes, such as the depollution of air containing gaseous organic compounds.
  • pulverized charcoal about 5 or about 20 m
  • a 75% H 3 PO 4 solution is added.
  • the mixture is extruded into agglomerates with a diameter of 3mm with a roller press.
  • the agglomerates obtained are then charred at 650 ° C and finally activated in the presence of water vapor and CO 2 at 900 to 1000 ° C.
  • the activated carbon obtained is characterized by its packed density according to the following procedure.
  • a 250 ml graduated cylinder is installed on a tamping device comprising a fixed base which carries 6 rollers.
  • the product is then poured slowly into the test tube, so that the product reaches approximately the 200 ml graduation.
  • On this base rests horizontally a mobile steel plate provided with 6 saw teeth.
  • This plate while being able to move vertically by sliding on an axis receives a rotational movement of an endless screw, coupled to an electric motor at the rate of 30 rpm.
  • the movable plate by means of the ramps of its saw teeth raised by the rollers
  • the mass of packed product is weighed and the density is calculated.
  • the benzene index is determined by measuring the weight of benzene adsorbed at saturation at 20 ⁇ 1 ° C per 100 g of dry activated carbon crossed by a stream of dry air containing benzene vapors at a partial pressure of 0.1 .
  • Attrition makes it possible to determine the propensity of agglomerated products to produce fines during transport, handling and use. It is measured according to standard ASTM D4058-96.
  • the crush resistance is measured using an Indelco-Chatillon type device (ADS / 801) fitted with a TCM 200 support and a DFGS 50 dynamometer whose descent speed is set to 23 m / min.
  • the breaking load (expressed in kg) of an agglomerated product subjected to increasing pressure is measured.
  • the mechanical resistance to crushing R is defined by the arithmetic mean of 25 measurements.
  • the sulfur content of the samples is determined from the analysis of SO 2 (by UV fluorescence) emitted by combustion / oxidation of the sample at 1000 ° C.
  • the phosphorus and potassium contents of the samples are determined after complete mineralization and analysis by ICP. The results are collated in Table 1.
  • the agglomerates of activated carbon according to the invention have a considerably reduced sulfur content of equal or higher quality which allows them to be used in applications sensitive to the presence of sulfur such as catalysis.

Abstract

The invention concerns an active carbon agglomerate based on coal derived from vegetable matter and tar-based binder. The invention is characterised in that it has a sulphur content not more than 500 ppm, a packing density ranging between 0.3 and 0.6 g/cm3, a benzene index ranging between 25 and 30, a crush resistance ≥ 2 kg, an ASTM D4058-96 standard attrition strength ≤ 10 %, and an average particle-size distribution ranging between 0.5 and 10 mm. The invention also concerns the method for preparing said agglomerate. The invention is for use in catalysis as catalyst or catalyst support and in liquid-phase or gas-phase adsorption processes.

Description

AGGLOMERES A BASE DE CHARBON ACTIF LEUR PROCEDE DE PREPARATION ET LEURS UTILISATIONS ACTIVATED CARBON AGGLOMERATES, PROCESS FOR THEIR PREPARATION AND USES THEREOF
L'invention concerne le domaine des charbons actifs et plus particulièrement des charbons actifs agglomérés avec un liant.The invention relates to the field of active carbon and more particularly active carbon agglomerated with a binder.
Les charbons actifs sont des produits résultant de la carbonisation de matières carbonées diverses, telles que les matières végétales (bois, coques de fruits), matières minérales (houille), matières synthétiques (polymères), ayant subi un traitement d' activation qui leur confère une forte porosité et un grand pouvoir adsorbant. Ces propriétés adsorbantes ont été exploitées depuis longtemps pour le traitement, la séparation et l'épuration de gaz ainsi que pour la décoloration, l'épuration et la désodorisation de liquides.Activated charcoals are products resulting from the carbonization of various carbonaceous materials, such as vegetable materials (wood, fruit shells), mineral materials (coal), synthetic materials (polymers), having undergone an activation treatment which gives them high porosity and high adsorption capacity. These adsorbent properties have been used for a long time for the treatment, separation and purification of gases as well as for the discoloration, purification and deodorization of liquids.
Lorsque le charbon actif est mis en contact avec des gaz, par exemple dans un lit d'adsorbant, on évite les granulométries trop fines dont la perte de charge est trop élevée et qui augmentent les risques de colmatage des appareillages.When the activated carbon is brought into contact with gases, for example in an adsorbent bed, excessively fine particle sizes are avoided, the pressure drop of which is too high and which increase the risk of clogging of the equipment.
Une méthode de préparation de charbon actif aggloméré consiste à mélanger un matériau solide hydrocarboné finement divisé avec un liant hydrocarboné, d'agglomérer le mélange par compactage ou extrasion sous forme de grains à la dimension voulue. Les produits agglomérés sont ensuite carbonisés à une température de 400 à 700°C puis activés par gazéification partielle en atmosphère oxydante (vapeur d'eau et/ou CO2) à une température de 700 à 1000°C.One method of preparing agglomerated activated carbon consists in mixing a finely divided hydrocarbon solid material with a hydrocarbon binder, agglomerating the mixture by compacting or extrusion in the form of grains to the desired size. The agglomerated products are then carbonized at a temperature of 400 to 700 ° C. and then activated by partial gasification in an oxidizing atmosphere (water vapor and / or CO 2 ) at a temperature of 700 to 1000 ° C.
Le solide carboné finement divisé peut être de la houille, la tourbe, le coke de tourbe ou de lignite ou de coque de noix de coco ou le charbon de bois. Afin de permettre l'obtention d'un aggloméré de charbon actif utile, le liant hydrocarboné possède de préférence les caractéristiques suivantes : il est peu cendreux ; il a des propriétés agglomérantes qui permettent une tenue mécanique à vert des filés (tenue au transport, résistance aux chocs et à l'abrasion) et - il a un bon rendement en coke afin d'assurer au produit final un bon rendement global et une bonne tenue mécanique, notamment en résistance à l'écrasement. On connaît de FR 2 228 031 des pièces moulées à partir de matière contenant du carbone et d'un liant à base d'un phénol et d'un aldéhyde.The finely divided carbonaceous solid may be coal, peat, peat or lignite or coconut shell or charcoal. In order to allow a useful activated carbon agglomerate to be obtained, the hydrocarbon binder preferably has the following characteristics: it is not very ashy; it has agglomerating properties which allow mechanical resistance to green of the yarns (resistance to transport, resistance to impact and abrasion) and - it has a good yield of coke in order to ensure the final product a good overall yield and a good mechanical strength, particularly in terms of resistance to crushing. FR 2 228 031 discloses parts molded from material containing carbon and a binder based on a phenol and an aldehyde.
FR 2 219 114 et FR 2 215 461 décrivent des procédés de préparation d'agglomérés de matière carbonée utilisant comme liant des thermodurcissables.FR 2 219 114 and FR 2 215 461 describe processes for the preparation of agglomerates of carbonaceous material using thermosetting as binder.
Bien que ces résines puissent convenir, leur coût cependant est élevé. 18299PCAlthough these resins may be suitable, however, their cost is high. 18299PC
2 Enfin, on connaît de la demande FR 2 780 052 un procédé de préparation d'agglomérats de charbon actif utilisant en particulier des liants thermodurcissables et thermofusibles.2 Finally, application FR 2 780 052 discloses a process for the preparation of activated carbon agglomerates using in particular thermosetting and thermofusible binders.
Un des liants remplissant ces critères et économiquement plus avantageux est le goudron de houille. Cependant, on constate que l'utilisation de ces agglomérés de charbons actifs dans des procédés de catalyse conduit à une dégradation rapide du catalyseur.One of the binders fulfilling these criteria and economically more advantageous is coal tar. However, it is found that the use of these agglomerates of active carbon in catalysis processes leads to rapid degradation of the catalyst.
Il se présente donc le nouveau problème de proposer des agglomérés de charbon actif économiques et compatibles avec une mise en œuvre dans les procédés de catalyse.The new problem therefore arises of proposing economic activated carbon agglomerates which are compatible with use in catalysis processes.
Le premier objet de l'invention vise alors un aggloméré de charbon actif à base de charbon de matière(s) végétale(s) et de liant à base de goudron(s), caractérisé en ce qu'il présente une teneur en soufre inférieure ou égale à 500 ppm, de préférence inférieure ou égale à 300 ppm, une densité tassée comprise entre 0,3 et 0,6 g/cm3, de préférence entre 0,35 et 0,45 g/cm3, un indice de benzène compris entre 25 et 50, de préférence compris entre 30 et 45, une résistance à l'écrasement > 2 kg, de préférence > 4 kg, une résistance à l'attrition selon ASTM D4058-96 < 10 %, de préférence < 5 % et une granulométrie moyenne comprise entre 0,5 à 10mm, de préférence entre 0,8 à 6 mm.The first object of the invention therefore relates to an agglomerate of activated carbon based on carbon of plant material (s) and of binder based on tar (s), characterized in that it has a lower sulfur content. or equal to 500 ppm, preferably less than or equal to 300 ppm, a packed density of between 0.3 and 0.6 g / cm 3 , preferably between 0.35 and 0.45 g / cm 3 , an index of benzene between 25 and 50, preferably between 30 and 45, a crush resistance> 2 kg, preferably> 4 kg, an attrition resistance according to ASTM D4058-96 <10%, preferably <5 % and an average particle size between 0.5 to 10mm, preferably between 0.8 to 6mm.
L'aggloméréThe agglomerate
Le choix judicieux du liant et du goudron permet l'obtention d'un tel aggloméré de charbon actif répondant aux critères sévères appliqués aux charbons actifs utilisés en catalyse. La qualité du goudron constitue en effet un élément important. Le goudron utilisé présente avantageusement un extrait au Dean Stark inférieur à 15 %. L'extrait au Dean Stark indique la teneur en hydrosolubles par entraînement azéotropique au toluène. De préférence, il présente un extrait au Dean Stark inférieur à 10 % et en particulier inférieur à 5 %. La teneur en soufre du goudron utilisé seul ou en mélange est inférieure à 500 ppm, avantageusement inférieure à 300 ppm et en particulier inférieur à 100 ppm.The judicious choice of binder and tar makes it possible to obtain such an agglomerate of activated carbon meeting the strict criteria applied to active carbon used in catalysis. The quality of the tar is indeed an important element. The tar used advantageously has an Dean Stark extract of less than 15%. The Dean Stark extract indicates the water-soluble content by azeotropic entrainment with toluene. Preferably, it has a Dean Stark extract of less than 10% and in particular less than 5%. The sulfur content of the tar used alone or as a mixture is less than 500 ppm, advantageously less than 300 ppm and in particular less than 100 ppm.
Le charbon de matière(s) végétale(s) est un charbon obtenu à partir de matière végétale, telle que par exemple de bois ou de coques de fruits tels que des coques de noix de coco.The charcoal of plant material (s) is a charcoal obtained from vegetable material, such as for example wood or fruit shells such as coconut shells.
Le charbon de matière(s) végétale(s) présente de préférence également une faible teneur en soufre. On choisira de préférence le charbon de bois. Celui-ci peut être obtenu par exemple par carbonisation de bois à une température de 600 à 700°C dans les conditions classiques. Ensuite, le charbon de bois est broyé, de préférence à un diamètre d50 d'environ 20 μm.The charcoal of plant material (s) preferably also has a low sulfur content. We will preferably choose charcoal. This can be obtained for example by carbonization of wood at a temperature of 600 to 700 ° C under conventional conditions. Then, the charcoal is ground, preferably to a diameter d50 of about 20 μm.
L'aggloméré peut également comprendre un additif de durcissement et/ou d'activation. De tels additifs de durcissement et d'activation sont par exemple le K2CO3 ou l'acide phosphorique. Ces additifs permettent d'obtenir un durcissement des agglomérés à la sortie de la presse ou de l'extrudeuse et de les rendre ainsi plus manipulables. Par ailleurs, ils ont un effet d'activation dans la mesure où ils accélèrent la cinétique de gazéification. Enfin, ils permettent d'orienter le spectre des tailles des pores vers une microporosité, à savoir un diamètre de pores inférieur à 2nm. Selon l'application, on choisira l'un ou l'autre des deux additifs, notamment selon les impuretés indésirables (potassium ou phosphore). L'aggloméré est notamment sous forme de filé.The agglomerate may also include a hardening and / or activating additive. Such hardening and activating additives are, for example, K 2 CO 3 or phosphoric acid. These additives make it possible to harden the agglomerates at the outlet of the press or the extruder and thus to make them more manipulable. Furthermore, they have an activation effect insofar as they accelerate the gasification kinetics. Finally, they make it possible to orient the spectrum of pore sizes towards a microporosity, namely a pore diameter less than 2nm. Depending on the application, one or the other of the two additives will be chosen, in particular according to the undesirable impurities (potassium or phosphorus). The agglomerate is in particular in the form of yarn.
Le procédé de préparationThe preparation process
Le deuxième objet de l'invention est un procédé de préparation d'un tel aggloméré. Il comprend les étapes de :The second object of the invention is a process for the preparation of such an agglomerate. It includes the steps of:
(a) malaxage de charbon de matière(s) végétale(s) avec du goudron ou un mélange de goudrons présentant un extrait au Dean Stark inférieur à 15 % et une teneur en soufre inférieure ou égale à 500 ppm et le cas échéant avec les additifs de durcissement et/ou d'activation ;(a) kneading of carbon of plant material (s) with tar or a mixture of tars having an Dean Stark extract of less than 15% and a sulfur content of less than or equal to 500 ppm and, where appropriate, with the curing and / or activating additives;
(b) mise en forme du mélange issu de (a) ;(b) shaping the mixture resulting from (a);
(c) carbonisation de l'aggloméré issu de (b) ; et(c) carbonization of the agglomerate from (b); and
(d) activation de l'aggloméré carbonisé issu de (c). Selon un mode de réalisation, le charbon de matière(s) végétale(s) présente un diamètre d50 compris entre 15 et 30 μm.(d) activation of the charred agglomerate from (c). According to one embodiment, the carbon of plant material (s) has a diameter d 50 of between 15 and 30 μm.
Avantageusement, le charbon de matière(s) végétale(s) est un charbon de bois. Le goudron ou mélange de goudrons présente avantageusement un extrait au Dean Stark inférieur à 10 %. De préférence, le goudron ou le mélange de goudrons présente une teneur en soufre inférieure ou égale à 300 ppm, de préférence inférieure ou égale à 100 ppm.Advantageously, the charcoal of vegetable material (s) is a charcoal. The tar or mixture of tars advantageously has an Dean Stark extract of less than 10%. Preferably, the tar or the mixture of tars has a sulfur content less than or equal to 300 ppm, preferably less than or equal to 100 ppm.
De préférence, le mélange malaxé comprend 100 parties en poids de charbon de matière(s) végétale(s) et 50 à 70 parties en poids de goudron. Le mélange à malaxer peut en outre comprendre jusqu'à 6 parties en poids d'additif(s) de durcissement et/ou d'activation pour 100 parties de charbon de matière(s) végétale(s). Un malaxage d'une heure sera en général suffisant.Preferably, the kneaded mixture comprises 100 parts by weight of carbon of vegetable material (s) and 50 to 70 parts by weight of tar. The mixture to be kneaded can also comprise up to 6 parts by weight of hardening and / or activation additive (s) per 100 parts of carbon of plant material (s). A one hour mixing will generally be sufficient.
L'opération de mise en forme du mélange de charbon de bois et goudron de bois malaxé est aussi appelée « filage ». Elle peut être réalisée par extrusion, moulage ou compactage, par exemple par l'intermédiaire d'appareils tels qu'une presse à galets, extrudeuse à vis, presse piston, moule sous presse ou tout autre appareil permettant une telle mise en forme. Le diamètre moyen des agglomérés est typiquement compris entre 0.5 et 10 mm. Les agglomérés se présentent de préférence sous forme de filés de diamètre en général compris entre 0,8 et 6 mm et de préférence entre 1 et 5 mm.The operation of shaping the mixture of charcoal and kneaded wood tar is also called "spinning". It can be produced by extrusion, molding or compacting, for example by means of devices such as a roller press, screw extruder, piston press, press mold or any other device allowing such shaping. The average diameter of the agglomerates is typically between 0.5 and 10 mm. The agglomerates are preferably in the form of yarns with a diameter generally between 0.8 and 6 mm and preferably between 1 and 5 mm.
L'étape de carbonisation des agglomérés est de préférence réalisée à environ 700°C, par exemple par des fumées de combustion. Cette étape permet d'éliminer les volatiles contenus dans le goudron et de condenser le résidu. Elle a également comme avantage le durcissement des agglomérés. Enfin, les agglomérés carbonisés sont activés, de préférence par traitement thermique à 900 à 1000°C en présence de vapeur d'eau et/ou de dioxyde de carbone. , Les utilisationsThe stage of carbonization of the agglomerates is preferably carried out at approximately 700 ° C., for example by combustion fumes. This step eliminates the volatiles contained in the tar and condenses the residue. It also has the advantage of hardening the agglomerates. Finally, the charred agglomerates are activated, preferably by heat treatment at 900 to 1000 ° C. in the presence of water vapor and / or carbon dioxide. , Uses
En raison de leurs propriétés particulières, ces agglomérés peuvent être utilisés avec avantage dans les procédés catalytiques, par exemple comme catalyseur ou comme support de catalyseur.Due to their special properties, these agglomerates can be used with advantage in catalytic processes, for example as a catalyst or as a catalyst support.
Les agglomérés selon l'invention peuvent également servir d'adsorbants pour séparer les composants d'un mélange comprenant au moins deux composés différents dans un procédé par adsorption comprenant les étapes suivantes : - mise en contact du mélange avec l'aggloméré dans des conditions permettant l'adsorption préférentielle de certains composés du mélange ; séparation de l'aggloméré et des composés adsorbés par celui-ci du mélange ainsi appauvri en composés préférentiellement adsorbés ; et régénération de l'aggloméré par désorption des. composés adsorbés. Un tel procédé peut fonctionner par exemple de manière cyclique.The agglomerates according to the invention can also serve as adsorbents for separating the components of a mixture comprising at least two different compounds in an adsorption process comprising the following steps: - bringing the mixture into contact with the agglomerate under conditions allowing preferential adsorption of certain compounds of the mixture; separation of the agglomerate and of the compounds adsorbed by the latter from the mixture thus depleted in preferentially adsorbed compounds; and regeneration of the agglomerate by desorption of. adsorbed compounds. Such a process can operate, for example, cyclically.
Un autre objet de l'invention vise des utilisations des agglomérés décrits dans les procédés d' adsorption. Les agglomérés décrits .peuvent notamment être utilisés dans des procédés d'adsorption en phase liquide, en particulier l'eau, tels que la purification de composés chimiques issus de réactions de synthèse et pollués par des sous-produits ou encore l'épuration et/ou la dépollution de l'eau. Les agglomérés décrits peuvent également être mis en œuvre dans des procédés d'adsorption en phase gazeuse, tels que la dépollution de l'air contenant des composés organiques gazeux.Another object of the invention relates to uses of the agglomerates described in the adsorption processes. The agglomerates described can in particular be used in liquid phase adsorption processes, in particular water, such as the purification of chemical compounds resulting from synthesis reactions and polluted by by-products or even purification and / or cleaning up water. The agglomerates described can also be used in gas phase adsorption processes, such as the depollution of air containing gaseous organic compounds.
Cependant, ces agglomérés sont également utiles pour les applications classiques des charbons actifs. L'invention est décrite plus en détail dans les exemples qui suivent.However, these agglomerates are also useful for conventional applications of active carbon. The invention is described in more detail in the following examples.
EXEMPLESEXAMPLES
Exemple 1Example 1
On mélange 60 kg de charbon de bois pulvérisé (d5o environ 20 m) avec 37 kg de goudron de bois puis on ajoute 2,5 kg d'une solution de H3PO4 à 75 %. Après une heure de malaxage, le mélange est extradé en agglomérés d'un diamètre de 3mm avec une presse à galets. Les agglomérés obtenus sont ensuite carbonisés à 650°C et enfin activés en présence de vapeur d'eau et de CO2 à 900 à 1000°C.60 kg of pulverized charcoal (about 5 or about 20 m) are mixed with 37 kg of wood tar and then 2.5 kg of a 75% H 3 PO 4 solution is added. After one hour of kneading, the mixture is extruded into agglomerates with a diameter of 3mm with a roller press. The agglomerates obtained are then charred at 650 ° C and finally activated in the presence of water vapor and CO 2 at 900 to 1000 ° C.
Exemple 2Example 2
On mélange 60 kg de charbon de bois pulvérisé (às environ 20 μm) avec 37 kg de goudron de bois puis on ajoute 4 kg d'une solution de K2CO à 45 % en poids. Après une heure de malaxage, le mélange est extradé en agglomérés d'un diamètre de 3 mm avec une presse à galets. Les agglomérés obtenus sont ensuite carbonisés à 650°C et enfin activés en présence de vapeur d'eau et de CO2 à 900 à 1000°C.60 kg of pulverized charcoal (about 20 μm) are mixed with 37 kg of wood tar and then 4 kg of K 2 CO solution at 45% by weight are added. After one mixing time, the mixture is extruded into agglomerates with a diameter of 3 mm with a roller press. The agglomerates obtained are then charred at 650 ° C and finally activated in the presence of water vapor and CO 2 at 900 to 1000 ° C.
Exemple 3 (exemple de comparaisonExample 3 (comparison example
On mélange 60 kg de charbon de bois pulvérisé (d50 environ 20 μm) avec 9,5 kg de goudron de bois et 28 kg de goudron de houille puis on ajoute 2,5 kg d'une solution de H3PO4 à 75 %. Après une heure de malaxage, le mélange est extradé en agglomérés d'un diamètre de60 kg of pulverized charcoal (d 50 approximately 20 μm) are mixed with 9.5 kg of wood tar and 28 kg of coal tar and then 2.5 kg of a H 3 PO 4 solution at 75 is added %. After one hour of kneading, the mixture is extruded into agglomerates with a diameter of
3 mm avec une presse à galets. Les agglomérés obtenus sont ensuite carbonisés à 650°C et enfin activés en présence de vapeur d'eau et de CO2 à 900 à 1000°C.3 mm with a roller press. The agglomerates obtained are then charred at 650 ° C and finally activated in the presence of water vapor and CO 2 at 900 to 1000 ° C.
Les charbons actifs obtenus sont caractérisés par leur densité tassée selon la procédure suivante. Une éprouvette graduée de 250 ml est installée sur un appareil à tasser comprenant un socle fixe qui porte 6 galets. On verse alors le produit lentement dans l'éprouvette, de telle sorte que le produit atteigne environ la graduation 200 ml. Sur ce socle repose horizontalement un plateau mobile en acier muni de 6 dents de scie. Ce plateau, tout en pouvant se déplacer verticalement en coulissant sur un axe reçoit un mouvement de rotation d'une vis sans fin, accouplée à un moteur électrique à raison de 30 tr/min. En tournant sur lui- même, le plateau mobile (par l'intermédiaire des rampes de ses dents de scie soulevées par les galets) est soumis à une série de montées, suivies de chutes brusques de 4 ± 1 mm de hauteur. Ces chutes provoquent une série de chocs verticaux qui sont transmis à l'éprouvette graduée. Après 10 minutes de fonctionnement de la machine, on pèse la masse de produit tassé et on calcule la densité.The activated carbon obtained is characterized by its packed density according to the following procedure. A 250 ml graduated cylinder is installed on a tamping device comprising a fixed base which carries 6 rollers. The product is then poured slowly into the test tube, so that the product reaches approximately the 200 ml graduation. On this base rests horizontally a mobile steel plate provided with 6 saw teeth. This plate, while being able to move vertically by sliding on an axis receives a rotational movement of an endless screw, coupled to an electric motor at the rate of 30 rpm. By turning on itself, the movable plate (by means of the ramps of its saw teeth raised by the rollers) is subjected to a series of climbs, followed by sudden falls of 4 ± 1 mm in height. These falls cause a series of vertical shocks which are transmitted to the graduated cylinder. After 10 minutes of operation of the machine, the mass of packed product is weighed and the density is calculated.
On détermine l'indice de benzène par mesure du poids de benzène adsorbé à saturation à 20 ± 1°C par 100 g de charbon actif sec traversé par un courant d'air sec contenant des vapeurs de benzène à une pression partielle de 0, 1.The benzene index is determined by measuring the weight of benzene adsorbed at saturation at 20 ± 1 ° C per 100 g of dry activated carbon crossed by a stream of dry air containing benzene vapors at a partial pressure of 0.1 .
L'attrition permet de déterminer la propension des produits agglomérés à produire des fines au cours du transport, des manipulations et de l'utilisation. Elle est mesurée selon la norme ASTM D4058-96.Attrition makes it possible to determine the propensity of agglomerated products to produce fines during transport, handling and use. It is measured according to standard ASTM D4058-96.
La résistance à l'écrasement est mesurée à l'aide d'un appareil de type Indelco- Chatillon (ADS/801) muni d'un support TCM 200 et d'un dynamomètre DFGS 50 dont la vitesse de descente est réglée à 23 m/min. On mesure la charge de rupture (exprimée en kg) d'un produit aggloméré soumis à une pression croissante. La résistance mécanique à l'écrasement R est définie par la moyenne arithmétique de 25 mesures.The crush resistance is measured using an Indelco-Chatillon type device (ADS / 801) fitted with a TCM 200 support and a DFGS 50 dynamometer whose descent speed is set to 23 m / min. The breaking load (expressed in kg) of an agglomerated product subjected to increasing pressure is measured. The mechanical resistance to crushing R is defined by the arithmetic mean of 25 measurements.
La teneur en soufre des échantillons est déterminée à partir de l'analyse de SO2 (par fluorescence UV) émis par combustion/oxydation de l'échantillon à 1000°C, Les teneurs en phosphore et en potassium des échantillons sont déterminées après minéralisation complète et analyse par ICP. Les résultats sont rassemblés dans le tableau 1.The sulfur content of the samples is determined from the analysis of SO 2 (by UV fluorescence) emitted by combustion / oxidation of the sample at 1000 ° C. The phosphorus and potassium contents of the samples are determined after complete mineralization and analysis by ICP. The results are collated in Table 1.
On constate que les agglomérés de charbon actif selon l'invention présentent à qualité égale voire supérieure une teneur en soufre considérablement réduite qui permet leur mise en œuvre dans des applications sensibles à la présence de soufre tels que la catalyse.It can be seen that the agglomerates of activated carbon according to the invention have a considerably reduced sulfur content of equal or higher quality which allows them to be used in applications sensitive to the presence of sulfur such as catalysis.
Tableau 1Table 1
Figure imgf000007_0001
Figure imgf000007_0001

Claims

REVENDICATIONS
I. Aggloméré de charbon actif à base de charbon de matière(s) végétale(s) et de liant à base de goudron(s), caractérisé en ce qu'il présente une teneur en soufre inférieure ou égale à 500 ppm, une densité tassée comprise entre 0,3 et 0,6 g/cm , un indice de benzène compris entre 25 et 50, une résistance à l'écrasement > 2 kg, une résistance à l'attrition selon ASTM D4058-96 < 10 % et une granulométrie moyenne comprise entre 0,5 à 10 mm.I. Aggregate of activated carbon based on carbon of plant material (s) and of tar-based binder (s), characterized in that it has a sulfur content less than or equal to 500 ppm, a density packed between 0.3 and 0.6 g / cm, a benzene index between 25 and 50, a crush resistance> 2 kg, an attrition resistance according to ASTM D4058-96 <10% and a average particle size between 0.5 to 10 mm.
2. Aggloméré selon la revendication 1 présentant une teneur en soufre inférieure ou égale à 300 ppm.2. Agglomerate according to claim 1 having a sulfur content less than or equal to 300 ppm.
3. Aggloméré selon la revendication 1 ou 2 présentant une densité tassée comprise entre 0,35 et 0,45 g/cm3.3. Agglomerate according to claim 1 or 2 having a packed density of between 0.35 and 0.45 g / cm 3 .
4. Aggloméré selon l'une des revendications 1 à 3 présentant un indice de benzène compris entre 30 et 45.4. Agglomerate according to one of claims 1 to 3 having a benzene number between 30 and 45.
5. Aggloméré selon l'une des revendications 1 à 4 présentant une résistance à l'écrasement supérieure ou égale à 4 kg.5. Agglomerate according to one of claims 1 to 4 having a crushing strength greater than or equal to 4 kg.
6. Aggloméré selon l'une des revendications 1 à 5 présentant une résistance à l'attrition selon ASTM D4058-96 inférieure ou égale à 5 %.6. Agglomerate according to one of claims 1 to 5 having a resistance to attrition according to ASTM D4058-96 less than or equal to 5%.
7. Aggloméré selon l'une des revendications 1 à 6 présentant une granulométrie moyenne comprise entre 0,8 à 6 mm.7. Agglomerate according to one of claims 1 to 6 having an average particle size between 0.8 to 6 mm.
8. Aggloméré selon l'une des revendications 1 à 7 comprenant en outre au moins un additif de durcissement et/ou d'activation.8. Agglomerate according to one of claims 1 to 7 further comprising at least one curing and / or activating additive.
9. Aggloméré selon l'une des revendications 1 à 8, dans lequel au moins un des additifs de durcissement et/ou d'activation est le K CO3 ou l'acide phosphorique.9. Agglomerate according to one of claims 1 to 8, in which at least one of the hardening and / or activating additives is K CO 3 or phosphoric acid.
10. Aggloméré selon l'une des revendications 1 à 9, dans lequel le charbon de matière végétale est un charbon de bois.10. Agglomerate according to one of claims 1 to 9, wherein the vegetable material charcoal is a charcoal.
I I. Aggloméré selon l'une des revendications 1 à 10 sous forme de filé. I I. Agglomerate according to one of claims 1 to 10 in the form of a yarn.
12. Procédé de préparation d'un aggloméré selon l'une des revendications précédentes, comprenant les étapes de :12. Method for preparing an agglomerate according to one of the preceding claims, comprising the steps of:
(a) malaxage de charbon de matière(s) végétale(s) avec du goudron ou un mélange de goudrons présentant un extrait au Dean Stark inférieur à 15 % et une teneur en soufre inférieure ou égale à 500 ppm et le cas échéant avec les additifs de durcissement et/ou d'activation ;(a) kneading of carbon of plant material (s) with tar or a mixture of tars having an Dean Stark extract of less than 15% and a sulfur content of less than or equal to 500 ppm and, where appropriate, with the curing and / or activating additives;
(b) mise en forme du mélange issu de l'étape (a) ;(b) shaping the mixture from step (a);
(c) carbonisation de l'aggloméré issu de l'étape (b) ; et (d) activation de l'aggloméré carbonisé issu de l'étape (c).(c) carbonization of the agglomerate from step (b); and (d) activation of the charred agglomerate from step (c).
13. Procédé selon la revendication 12, dans lequel le charbon de matière(s) végétale(s) présente un diamètre d5o compris entre 15 et 30 μm.13. The method of claim 12, wherein the carbon material (s) plant (s) has a diameter d 5 o between 15 and 30 microns.
14. Procédé selon la revendication 12 ou 13, dans lequel le charbon de matière(s) végétale(s) est du charbon de bois.14. The method of claim 12 or 13, wherein the charcoal of plant material (s) is charcoal.
15. Procédé selon l'une des revendications 12 à 14, dans lequel le goudron ou le mélange de goudrons présente un extrait au Dean Stark inférieur à 10 %.15. Method according to one of claims 12 to 14, wherein the tar or the mixture of tars has a Dean Stark extract of less than 10%.
16. Procédé selon l'une des revendications 12 à 15, dans lequel le goudron ou le mélange de goudrons présente une teneur en soufre inférieure ou égale à 300 ppm et de préférence inférieure ou égale à 100 ppm.16. Method according to one of claims 12 to 15, wherein the tar or the mixture of tars has a sulfur content less than or equal to 300 ppm and preferably less than or equal to 100 ppm.
17. Procédé selon l'une des revendications 12 à 16, dans lequel on malaxe 100 parties en poids de charbon de matière(s) végétale(s) avec 50 à 70 parties en poids de goudron.17. Method according to one of claims 12 to 16, in which 100 parts by weight of carbon of vegetable material (s) are kneaded with 50 to 70 parts by weight of tar.
18. Procédé selon l'une des revendications 12 à 17, dans lequel le mélange à malaxer comprend jusqu'à 6 parties en poids d'additif(s) de durcissement et/ou d'activation pour 100 parties de charbon de matière(s) végétale(s).18. Method according to one of claims 12 to 17, wherein the mixture to be kneaded comprises up to 6 parts by weight of hardening and / or activation additive (s) per 100 parts of carbon of material (s) ) vegetable (s).
19. Procédé selon l'une des revendications 12 à 18 dans lequel la mise en forme est réalisée par extrusion, moulage ou compactage.19. Method according to one of claims 12 to 18 wherein the shaping is carried out by extrusion, molding or compacting.
20. Utilisation de l'aggloméré selon les revendications 1 à 11 en catalyse comme catalyseur. 20. Use of the agglomerate according to claims 1 to 11 in catalysis as a catalyst.
21. Utilisation de l'aggloméré selon les revendications 1 à 11 en catalyse comme support de catalyseur.21. Use of the agglomerate according to claims 1 to 11 in catalysis as a catalyst support.
22. Utilisation de l'aggloméré selon les revendications 1 à 11 dans des procédés d'adsorption en phase liquide.22. Use of the agglomerate according to claims 1 to 11 in liquid phase adsorption processes.
23. Utilisation de l'aggloméré selon les revendications 1 à 11 dans des procédés d'adsorption en phase gazeuse. 23. Use of the agglomerate according to claims 1 to 11 in gas phase adsorption processes.
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EP2523241A1 (en) * 2011-05-11 2012-11-14 Samsung SDI Co., Ltd. Negative active material, method of preparing the same, and lithium battery including the same
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US20120288766A1 (en) * 2011-05-11 2012-11-15 Samsung Sdi Co., Ltd. Negative active material, method of preparing the same, and lithium battery including the same
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