EP2032251A2 - Granulé carboné, son procédé de fabrication et son utilisation - Google Patents

Granulé carboné, son procédé de fabrication et son utilisation

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Publication number
EP2032251A2
EP2032251A2 EP07725308A EP07725308A EP2032251A2 EP 2032251 A2 EP2032251 A2 EP 2032251A2 EP 07725308 A EP07725308 A EP 07725308A EP 07725308 A EP07725308 A EP 07725308A EP 2032251 A2 EP2032251 A2 EP 2032251A2
Authority
EP
European Patent Office
Prior art keywords
carbon
granules
carbon granules
catalyst
mcc
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07725308A
Other languages
German (de)
English (en)
Inventor
Constant J. Van Lookeren Campagne
Wolfgang Hungerbach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Glatt Systemtechnik GmbH
Original Assignee
Glatt Systemtechnik GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Glatt Systemtechnik GmbH filed Critical Glatt Systemtechnik GmbH
Publication of EP2032251A2 publication Critical patent/EP2032251A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • 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
    • B01J37/0063—Granulating
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • 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
    • B01J33/00—Protection of catalysts, e.g. by coating
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/392—Metal surface area
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm

Definitions

  • the invention relates to a carbon granulate which is formed pyrolytically from microcrystalline cellulose. Furthermore, the invention relates to a method for producing these granules.
  • the granulate according to the invention is used in particular as a carrier structure for solid catalysts.
  • the performance of solid catalysts is essentially determined by two properties: activity and selectivity.
  • the activity of the catalyst is determined by the catalytically active surface and the accessibility of the active surface.
  • the selectivity of the catalyst defines how strongly the reaction to be catalyzed dominates over competing side reactions.
  • the properties of the catalytically active surface are the selectivity of a catalyst
  • the accessibility of the active surface can be decisive for the selectivity.
  • the catalytically active material is generally finely dispersed in order to achieve a sufficiently large active surface area of the catalyst.
  • a high activity of the solid catalyst requires that the catalytically active substance is not sintered into larger particles because this is accompanied by a smaller surface area.
  • the stability of solid catalysts is determined by the resistance of the small catalytically active particles to sintering during use as a catalyst.
  • the porous structure determines the transport properties of the catalyst.
  • the mechanical strength is important because fragments of the catalyst body can lead to an increased pressure drop of the gas flow through the fixed bed. With regard to catalyst bodies suspended in a liquid, mechanical strength is important because abrasion leads to the formation of fines which are difficult to separate from the reaction products by filtration or centrifugation.
  • the support structure determines the shape, size and mechanical strength of the catalyst body as well as the porous structure of the surface of the catalyst.
  • the support structure is not catalytically active, but provides a surface on which the catalytically active substance is finely dispersed.
  • the most widely used catalyst support structures are based on ⁇ -alumina, which is prepared by dehydrogenation of bayerite or gibbsite (Al (OH) 3 ) or boehmite (AlOOH).
  • Carrier structures of this type share the common drawback that the recovery of the catalytically active substances from the catalyst is cumbersome. The dissolution of the catalyst body and subsequent separation of the dissolved material is difficult and requires much caustic.
  • Another technique relies on melting the catalyst in a vacuum oven at very high temperatures. However, in view of the expensive equipment required for this purpose and the high energy consumption, this is only economically feasible for noble metal catalysts.
  • activated carbon Furthermore, support structures made of activated carbon are known from the prior art. These can be easily removed from the catalytically active substances by simple combustion of the carbon. Since activated carbon does not dissolve in an alkaline or acidic environment, activated carbon is the carrier structure of choice for noble metal catalysts in catalytic reactions in the liquid phase. During combustion of the activated carbon, only the catalytically active substance, eg the noble metal, remains available. back.
  • US Pat. No. 4,052,336 discloses a carrier structure of activated carbon having a particle size between 1 and 60 ⁇ m. This small particle size has the disadvantage that in a fixed bed reactor, a high pressure drop is the result and therefore the use of the catalysts described herein is severely limited.
  • WO 03/55599 A1 describes a catalyst composition containing an extruded carbon material.
  • the carbon particles can be obtained from products such as lignite or wood.
  • the shaping takes place here with the carbon particles, which brings considerable disadvantages in terms of mechanical strength with it.
  • various disadvantages are found. Since activated carbon is extracted from natural materials such as peat, wood or coconut shells, it is difficult to ensure a consistent and consistent quality of the raw material.
  • the mechanical strength of support structures made of activated carbon is usually problematic.
  • the abrasion of activated carbon is a previously unresolved
  • a granular carbon which contains 50 to 99.9% by weight of carbon. Furthermore, 0.1 to 50 wt .-% minerals and / or non-charred additives are included. At least 20% by weight of the carbon is formed pyrolytically from granulated microcrystallised cellulose (MCC) and optionally further binders and / or additives. In this case, the individual grains of the carbon granules have a porosity in the core which is greater than the porosity at the surface of the grains.
  • MCC microcrystallised cellulose
  • the surface has a lower porosity, the surface of the individual grains is smooth, which results in a high mechanical strength as well as a low abrasion of the granules according to the invention.
  • the abrasion resistance properties are particularly illustrated by the fact that the granules in the drum abrasion test according to ASTM D4058 preferably have an abrasion in the range from 0.2 to 5% by weight. Particularly preferably, the abrasion is in a range of 0.2 to 1.5 wt .-%.
  • the specific surface area of the carbon granules can be adjusted as desired, with the proportion by weight of MCC being greater than that of binders and other additives.
  • the specific one Surface can be controlled.
  • the specific surface is preferably in a range from 60 to 1200 m 2 / g.
  • Granules having a compressive strength according to D 7084-4 in the range of 2 to 20 wt .-%, wherein the compressive strength on the weight fraction of MCC is controllable.
  • the carbon granules can be present in any geometric form. Particularly preferred here is the spherical shape, since in this case a lower abrasion was found. This brings advantages in particular for the production of catalysts.
  • the spherical granules should preferably be uniform in size when reactions are carried out using catalyst bodies suspended in solutions. However, variations of up to 20% with respect to the diameter of the grains in spherical form are quite acceptable. Another advantage resulting from a uniform size of the grains is the easier loading and unloading of the catalyst bodies.
  • the carbon granulate in spherical form preferably has a length-to-width ratio of not more than 3: 1, preferably not more than 2: 1 and more preferably not more than 1.5: 1.
  • a variant according to the invention further provides that the porosity of the grains of the carbon granules decreases from the core to the surface.
  • a method for producing a carbon granulate comprising the following steps: i) mixing a powder consisting of at least 20% by weight of microcrystalline cellulose (MCC) and optionally further binders or additives with water,
  • the binder is preferably selected from the group consisting of carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, glucose or mixtures thereof.
  • a first provides that first the powder is mixed with the water in a weight ratio, so that a dough-like consistency results. This dough is then extruded and processed into a MCC granule of cylindrical shape. Likewise, however, tri-, quadro- or multilobal forms or ring shapes are also possible.
  • Another variant provides that an agglomeration by tabletting of the microcrystalline cellulose he follows.
  • a third preferred variant provides that the agglomeration takes place in a fluidized bed reactor to form a substantially spherical MCC granules.
  • a further variant according to the invention relates to the agglomeration in a raking apparatus, the formation of a substantially spherical MCC granulate.
  • the thermal treatment is preferably carried out at a temperature of at least 400 0 C. Generally, however, the temperature depends on the composition of the MCC granules, since the decomposition temperature can be determined by this. In a further preferred variant, the temperature is increased in the thermal treatment in stepped steps up to the decomposition temperature of the MCC granules.
  • the thermal treatment is preferably carried out in an inert gas, nitrogen and / or carbon dioxide being particularly preferably used here.
  • the invention also provides the use of the previously described carbon granules and at least one catalytically active substance for the preparation of a catalyst.
  • the catalytically active substance is preferably selected from group VIII of the Periodic Table of the Elements or the group of transition metals. These include, for example, platinum,
  • the first process variant is based on the fact that in the above-described step i) the catalytically active substance or a precursor thereof is added to the mixture of water and microcellulose. Likewise, it is of course also possible to first suspend the catalytically active substance or a precursor thereof in water and then add the microcrystalline cellulose to this suspension.
  • a second variant provides that the carbon granules are brought into contact with a solution or a suspension of the catalytically active substance or a precursor thereof. Particularly preferred here is the contacting with the catalytically active substance by spraying the carbon granules with the solution or suspension.
  • a further preferred variant provides that the catalyst described above is additionally provided with at least one further final coating, wherein this is preferably formed as an oxygen-protecting layer.
  • This coating preferably consists of a wax and / or a fatty constituent having a melting point of more than 50 ° C.
  • Fig. 1 shows an electron micrograph of the carbon granules according to the invention in spherical form.
  • Fig. 2 shows an electron micrograph of the surface of the carbon granules according to the invention.
  • Fig. 3 shows an electron micrograph (SEM) of the core of the carbon granules according to the invention.
  • TEM 4 shows an electron micrograph (TEM) of a catalyst according to the invention with nickel as the catalytically active substance at a magnification of a factor of 135,000.
  • TEM 5 shows an electron micrograph (TEM) of the catalyst according to the invention with nickel as the catalytically active substance at a magnification of a factor of 500,000.
  • FIG. 1 is based on an electron micrograph (SEM) with a magnification by a factor of 200, the different porosity in the core and on the surface of the granule grain clarified. It can be seen here that there is a significantly higher porosity in the core than at the surface of the granule grain. A smooth surface of the granule grain can be seen, which explains the good properties in terms of mechanical strength and abrasion.
  • FIG. 2 shows an electron micrograph (SEM) of the surface of the granule grain at a magnification of a factor of 5,000. Here is the small number of pores in the surface.
  • FIG. 3 shows an electron micrograph of the core at a magnification of a factor of 500.
  • a significantly higher porosity relative to the surface becomes apparent.
  • FIG. 4 shows a catalyst according to the invention on the basis of a transmission electron micrograph at a magnification of a factor of 135,000.
  • the dense coverage of the carbon structure with nickel particles becomes clear.
  • Fig. 6 which shows the same picture at a magnification of a factor of 500,000.
  • nickel particles with a size of about 5 nm can be seen. The difference in
  • MCC granules granules of microcrystalline cellulose
  • the fluidized bed reactor consisted of a vertical quartz tube with a diameter of 3 cm.
  • the temperature of the fluidized bed reactor could be controlled by a furnace surrounding the quartz tube up to tures of 57 0 C are set.
  • the bulk density of the MCC granules was 15.1 g / ml.
  • the minimum linear velocity of the gas flow of nitrogen to achieve turbulence was 4 cm / sec. at 70 ° C:
  • the MCC granules were filled with a gas flow at a linear speed of 5.4 cm / sec. swirled. Previously, the granules were dried at 100 0 C for 1 h and 14 min. The temperature was increased according to the following temperature scheme:
  • the results obtained were confirmed by a test in the thermobalance.
  • the invention Granules were kept in a nitrogen flow while the temperature was increased by 5 0 C per minute.
  • the weight loss started at about 250 ° C. and maximum weight loss was observed at 315 ° C.
  • the weight loss decreased noticeably, but a weight loss up to temperatures of 700 0 C could be observed.
  • the remaining weight was 21% of the original weight.
  • MCC powder was mixed with water to a dispersion having a solids content of about 30%. This dispersion was agglomerated in a fluidized bed rotor agglomerator and dried.
  • the spherical spherical agglomerates of the MCC powder had a particle size D50 of 300 ⁇ m. They were placed in an oven and preheated at 250 ° C. for 1 h in the absence of oxygen and then thermally treated at 450 ° C. for 2 h (also under reducing conditions) to initiate decomposition into carbon and gas components and a spherical one To form carbon granules.
  • the carbon granules had a carbon content of more than 98% by weight.
  • the grain size D50 of the carbon granules was reduced by the decomposition process to a value of 150 microns.
  • the coefficient of friction of the carbonaceous spheres was determined by a modified drum abrasion test according to ASTM D4058 with a Heubach tester. The result was an abrasion value of 1.7 wt .-%.
  • the MCC powder was mixed with water to form a dough having a moisture content between 30 and 40%.
  • This dough was extruded with a basket extruder Fuj i-Paudall).
  • the extruded particles were placed in a spheronizer (Smooth) to form spherical balls which were dried in a fluid bed dryer (Smooth).
  • the result was spherical granules with a diameter of 800 ⁇ m (D50).
  • This granulate was preheated in the same manner as in Example 2 with exclusion of oxygen for 1 h at 250 0 C and then thermally treated at 450 0 C for 2 h.
  • the friction value here was 1.4 wt .-% and the compressive strength was here 11 wt .-%.
  • Example 1 The carbon granules obtained in Example 1 were placed in an oven and preheated in the absence of oxygen.
  • the exclusion of oxygen was achieved by combustion of propane with stoichiometric amounts of oxygen, so that all of the oxygen was converted to CO 2 .
  • the temperature was 1100 0 C and the duration of the thermal treatment was 3 h.
  • the carbon granules produced in Example 2 were placed in a rotor agglomerator. 1 kg of a suspension of 15% by weight of MCC and 20% by weight of iron (III) citrate were sprayed onto the carbon granules per kg of carbon granules. The sprayed carbon granules were heated with the exclusion of oxygen as described in Example 2, and the activated catalyst was placed under a nitrogen atmosphere directly in a cylinder of molten candle wax. The lower part of the cylinder, containing more than 80% of the activated catalyst, was placed in a granulator (Glatt VG) to produce a free-flowing granule of the activated catalyst in the wax-encapsulated catalyst.
  • Glatt VG granulator
  • the carbon granules prepared in Example 2 were placed in a rotor agglomerator, with 1 kg of a suspension of 5 wt.% MCC (Avicel PH 102, FMC Corp.) and 15 wt.% NiNO 3 per kg of carbon granules and 10 wt% ground coconut carbon powder (Pica G202X). This suspension was sprayed in a rotor (smooth) on the carbon granules, whereby a grain size D50 of about 200 microns was obtained. As in Example 2, the carbon granules were thermally treated in the absence of oxygen and the activated catalyst was transferred immediately under a nitrogen atmosphere in a cylinder of molten candle wax and pressed down with a sieve plate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne un granulé carboné, formé par pyrolyse à partir de cellulose microcristalline. L'invention concerne également un procédé de fabrication de ce granulé. Le granulé selon l'invention trouve une utilisation, notamment en tant que structure support pour catalyseurs solides.
EP07725308A 2006-05-16 2007-05-16 Granulé carboné, son procédé de fabrication et son utilisation Withdrawn EP2032251A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006022866A DE102006022866A1 (de) 2006-05-16 2006-05-16 Kohlenstoff-Granulat, Verfahren zu dessen Herstellung und dessen Verwendung
PCT/EP2007/004393 WO2007131795A2 (fr) 2006-05-16 2007-05-16 Granulé carboné, son procédé de fabrication et son utilisation

Publications (1)

Publication Number Publication Date
EP2032251A2 true EP2032251A2 (fr) 2009-03-11

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EP07725308A Withdrawn EP2032251A2 (fr) 2006-05-16 2007-05-16 Granulé carboné, son procédé de fabrication et son utilisation

Country Status (3)

Country Link
EP (1) EP2032251A2 (fr)
DE (1) DE102006022866A1 (fr)
WO (1) WO2007131795A2 (fr)

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US8555896B2 (en) 2007-12-19 2013-10-15 Philip Morris Usa Inc. Activated carbon from microcrystalline cellulose
EP2233207A1 (fr) * 2009-02-27 2010-09-29 Basf Se Procédé pour la préparation de corps contenant du carbone et du métal
US10010867B2 (en) 2009-02-27 2018-07-03 Basf Corporation Process for producing carbon nanofibers and/or carbon nanotubes
EP2224045A1 (fr) * 2009-02-27 2010-09-01 Basf Se Procédé de production de nanofibres de carbone et/ou nanotubes de carbone
US10279328B2 (en) 2009-02-27 2019-05-07 Basf Corporation Process for the preparation of metal-carbon containing bodies
BR112012014697A2 (pt) * 2009-12-16 2016-04-12 Lyondell Chemical Tech Lp extrudado contendo titânia
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