WO2016050906A1 - Catalyst stabilization by wax - Google Patents

Catalyst stabilization by wax Download PDF

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Publication number
WO2016050906A1
WO2016050906A1 PCT/EP2015/072677 EP2015072677W WO2016050906A1 WO 2016050906 A1 WO2016050906 A1 WO 2016050906A1 EP 2015072677 W EP2015072677 W EP 2015072677W WO 2016050906 A1 WO2016050906 A1 WO 2016050906A1
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WO
WIPO (PCT)
Prior art keywords
substance
catalyst particles
carbon atoms
boiling point
wax
Prior art date
Application number
PCT/EP2015/072677
Other languages
French (fr)
Inventor
Peter John Van Den Brink
Hans Michiel Huisman
Fouad MOUSSATEN
Thomas Joris Remans
Anna Maria KAMANS-SCHUITEMA
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Oil Company
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 Shell Internationale Research Maatschappij B.V., Shell Oil Company filed Critical Shell Internationale Research Maatschappij B.V.
Publication of WO2016050906A1 publication Critical patent/WO2016050906A1/en

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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
    • 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
    • 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
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds

Definitions

  • the present invention relates to a method for applying organic compounds to catalyst particles.
  • the present invention is especially suitable for particulate catalysts containing at least one pyrophoric metal in reduced form and a metal oxide carrier.
  • pyrophoric metals are Ni, Co, Cu and Mo and mixtures thereof.
  • metal oxide carriers are the oxides of aluminium, silicon, titanium, zirconium, magnesium, and mixtures thereof.
  • Such reduced metal catalysts are widely used, for example in hydrogenation reactions.
  • the metals in their catalytically active, i.e. finely divided and reduced, form are pyrophoric - i.e. when exposed to atmospheric air they tend to oxidize very rapidly, thereby producing considerable heat.
  • safety measures are required in the production, storage and handling of these catalysts.
  • DD-B 155390 there is disclosed a method for preparing pyrophoric metal catalysts in powder form, wherein the powder is suspended in an excess of molten fatty material such as solid paraffin, and the suspension is simultaneously sprayed and cooled.
  • DE-A 2850719 there is disclosed a method for preparing nickel catalysts in powder form, wherein the powder is impregnated with a solution of fatty material, followed by removing the solvent.
  • catalysts prepared according to SA 961848 while indeed being sufficiently protected from spontaneous oxidation by air, tend to cake and clog together, especially during transport. Their bad flowing property which apparently is due to the particles being encapsulated with a continuous paraffin coating, is obviously detrimental to the uniform filling of fixed-bed reactors with these particles.
  • the method of the present invention does not require a rotary reactor for the mixing of particles with oil and/or wax. Therefore, the present invention provides a less complex method as compared to EP 1607465.
  • the present invention provides a method for applying organic compounds to catalyst particles which comprises: (a) combining catalyst particles, a substance A and a substance B
  • substance A consists of organic compounds having 15 to 1000 carbon atoms
  • substance B consists of organic compounds having 4 to 14 carbon atoms; whereby the final boiling point (T95) of substance B is at least 10 degrees lower than the initial boiling point (T5) of substance A, and;
  • weight ratio of substance A to substance B is in the range between 60:40 to 95:5;
  • step (b) in case in step (a) the volume of substance A is larger than the total pore volume of the catalyst particles, separating a part of substance A until the amount of substance A is 20-99.9 vol%, preferably 50-99.9 vol%, of the total pore volume of the catalyst particles at a temperature above the melting point of the combination of substance A and substance B, preferably at a temperature above the melting point of substance A, and below the initial boiling point (T5) of substance B;
  • the present invention provides a method for applying organic compounds to catalyst particles.
  • the present invention is especially suitable for particulate catalysts containing at least one pyrophoric metal in reduced form and a metal oxide carrier.
  • pyrophoric metals are Ni, Co, Cu and Mo and mixtures thereof.
  • the catalyst particles comprise cobalt.
  • metal oxide carriers are the oxides of aluminium, silicon, titanium, zirconium, magnesium, and mixtures thereof.
  • the catalyst particles comprise silica or titania, most preferably titania.
  • At least 90% of the catalyst particles has a size in the range of between 0.05 and 0.5 mm, or has a size of at least 1 mm, or at least 1 mm and at most 50 mm, or consists of structured catalyst particles.
  • the present invention can be used for powdered catalysts.
  • Preferably at least 90% of these catalyst particles has a size in the range of between 0.05 and
  • the present invention is especially suitable for catalyst particles that can be used in a packed-bed, or fixed bed, reactor.
  • a fixed bed preferably at least 90% of the catalyst particles has a size of at least
  • At least 90% of the catalyst particles has a size of at most 50 mm, more preferably at most 30 mm.
  • These catalyst particles can have different shapes and sizes. Beads, spheres, saddles are suitable. Also extrudates, for example with a trilobe shape, can be used in a packed-bed reactor.
  • the present invention can also be used for structured catalyst particles.
  • these catalyst particles comprise a porous body having a longest internal length of at least 1 mm.
  • These catalyst particles further comprise a catalyst material having pores with a size of more than 10 micro-meter.
  • the structured catalyst particles, i.e. porous body along with catalyst material preferably has an internal voidage of at least 50% and at most 95%.
  • the structured catalyst particles, i.e. porous body along with catalyst material preferably has an external voidage in situ in a reactor between 5 and 60% by volume.
  • at least 90% of these catalyst particles comprise a porous body having a longest internal length of at most 10 meter, more preferably at most 2 meter.
  • the catalyst material on the porous body preferably comprises a pyrophoric metal, such as Ni, Co, Cu or Mo or mixtures thereof, and a metal oxide carrier such as the oxides of aluminium, silicon, titanium, zirconium, magnesium, or mixtures thereof.
  • a pyrophoric metal such as Ni, Co, Cu or Mo or mixtures thereof
  • a metal oxide carrier such as the oxides of aluminium, silicon, titanium, zirconium, magnesium, or mixtures thereof.
  • the catalyst material comprises cobalt.
  • the catalyst material comprises silica or titania, most preferably titania.
  • the initial boiling point (T5) is the 5% boiling temperature at atmospheric pressure.
  • the final boiling point (T95) is the 95% boiling temperature at atmospheric pressure .
  • Substance A may be a wax.
  • the combination of substance A and substance B may be a waxy solid at room temperature.
  • the melting point of a wax or waxy solid can be determined by determining its slip melting point.
  • a slip melting point is determined by casting a 10 mm column of the solid in a glass tube with an internal diameter of about 1 mm and a length of about 80 mm, and then immersing it in a temperature-controlled water bath. The slip point is the temperature at which the column of the solid begins to rise in the tube due to buoyancy, and because the outside surface of the solid is molten.
  • a detailed description of a suitable method for determining a slip melting point can be found in European
  • step (a) catalyst particles, a substance A and a substance B are combined.
  • the temperature at which these are combined is above the melting point of the
  • step (a) the sum of the volume of substance A plus the volume of substance B is equal to or larger than the total pore volume of the catalyst particles.
  • the catalyst particles may be totally immersed in the combination of substance A and substance B.
  • More than 90 wt% of substance A consists of organic compounds having 15 to 1000 carbon atoms.
  • more than 90 wt% of substance A more preferably more than 95 wt%, even more preferably more than 99 wt%, still more preferably more than 99.9 wt%, of substance A consists of wax having 15 to 1000 carbon atoms or oil having 15 to 40 carbon atoms, more
  • paraffinic wax having 15 to 1000 carbon atoms or paraffinic oil having 15 to 40 carbon atoms preferably paraffinic wax having 15 to 1000 carbon atoms.
  • compound A is a compounds having up at least 15 and up to 200 carbon atoms. Preferably at least 80% of the C atoms in the molecules are part of an alkyl-group. Preferably Compound A is a Fischer-Tropsch wax or a wax derived thereof.
  • substance B consists of one or more organic compounds having 9 to 12 carbon atoms,
  • substance B consists of one or more hydrocarbons having 9 to 12 carbon atoms, preferably consists of one or more
  • hydrocarbons comprising 9 carbon atoms, one or more hydrocarbons comprising 10 carbon atoms, or one or more hydrocarbons comprising 12 carbon atoms, or a combination thereof, more preferably consists of dodecane.
  • the final boiling point (T95) of substance B is at least 10 degrees lower than the initial boiling
  • step (a) the weight ratio of substance A to substance B is in the range between 60:40 to 95:5.
  • the weight ratio of A to B is in the range between 70:30 to 95:5 in step (a) .
  • the catalyst particles used in step a) were subjected to activation before step a) .
  • Activation preferably is performed by subjecting the particles to hydrogen or to hydrogen sulfide.
  • the catalyst particles used in step a) were subjected to activation, followed by passivation before step a) .
  • Activation preferably is performed by subjecting the particles to a hydrogen and/or hydrogen sulfide comprising gas
  • Passivation preferably is performed by subjecting the particles to an oxygen comprising gas. During passivation a part of the pyrophoric metal is oxidised.
  • Activation may take place in a container, for example a reactor, while step (a) is performed in another container, for example another reactor. Activation and step (a) may also take place in the same container, for example the same reactor.
  • the catalyst particles, substance A and substance B may, for example, be combined by adding the particles to a mixture of substance A and substance B.
  • the catalyst particles, substance A and substance B may, for example, be combined by adding substance A and substance B, or a mixture of substance A and substance B, to the catalyst particles.
  • substance A and substance B, or a mixture of substance A and substance B may be introduced at the bottom of a container which comprises the catalyst particles.
  • the catalyst particles, substance A and substance B may, for example, be combined in a rotating drum, on a conveyor belt. Additionally or alternatively, the catalyst particles may be dipped into a mixture of substance A and substance B.
  • a mixture of substance A and substance B may be combined with the catalyst particles.
  • a mixture of substance A and substance B may be prepared by mixing substance A and substance B, or by distilling at least one fraction away from organic compounds having 4 to 1000 carbon atoms .
  • Step (b) is not performed in case the volume of substance A used in step (a) is equal to or smaller than the total pore volume of the catalyst particles. In case in step (a) the volume of substance A is larger than the total pore volume of the catalyst particles, a part of substance A is separated in
  • step (b) This is performed until the amount of
  • substance A is 20-99.9 vol%, preferably 50-99.9 vol%, of the total pore volume of the catalyst particles.
  • step (b) is performed at a
  • a part of substance B may be
  • the ratio of substance A to substance B in the presence of the catalyst particles remains the same or almost the same during step (b) .
  • This can be achieved by simultaneously separating substance A and substance B.
  • Substance A and substance B may, for example, be
  • draining of the combination of substance A and substance B is performed until the amount of substance A is 20-99.9 vol%, preferably 50-99.9 vol%, of the total pore volume of the catalyst particles. This is performed at a temperature above the melting point of the
  • step (b) The ratio of substance A to substance B in the presence of the catalyst particles may change during step (b) . Therefore also the melting point of the combination of substance A and substance B in the presence of the catalyst particles may change during step (b) .
  • step (b) may be performed at a temperature above the melting point of any of the ratios of substance A and substance B that may exist during step (b) .
  • step (b) is performed at a
  • the temperature is adjusted during step (b) and is kept above the changing melting point of the combination of substance A and substance B in the presence of the catalyst particles.
  • step (c) the catalyst particles are subjected to a temperature above 0.65 times the final boiling
  • T95 point (T95) of substance B is: 0.7 x 216 °C, which corresponds to 151 °C.
  • step (c) all or most of substance B is evaporated. All or a part, preferably all or most, of substance A remains in the presence of the catalyst particles .
  • step (c) the combination of substance A and substance B in the presence of the particles decreases in volume and has an increasing content of substance A.
  • Step (c) may be performed under vacuum.
  • an inert gas for example nitrogen, may be passed along the catalyst particles.
  • step (c) can be adjusted by adjusting the temperature at which step (c) is performed.
  • substance A After evaporation of substance B, substance A is mainly or completely present in the pores of the
  • catalyst particles with organic compounds in the pores which have an angle of repose that differs at most 2 or 3 degrees with the angle of repose before applying the organic compounds are especially the case for powdered catalyst particles having a size in the range of between 0.05 and 0.5 mm, and for fixed bed catalyst particles having a size of at least 1 mm and at most 50 mm. It is especially advantageous for fixed bed catalyst particles having a size of at least 1 mm and at most 50 mm as the preparation of a fixed bed of catalyst particles is preferably performed with particles that are protected by organic compounds, such as oil and/or wax, but do not stick together.
  • organic compounds such as oil and/or wax
  • Catalyst samples (extrudates) were impregnated as follows .
  • a static soaking method was used. With this method instead of impregnating with pure wax, the catalyst is soaked in a wax/volatile mixture. After draining the excess of wax mixture the volatile in the wet catalyst is evaporated. The wax/volatile ratio determines the amount of wax present in the pores after impregnation and drying .
  • Catalyst was loaded into a vessel. After loading the catalyst, N 2 was passed through the catalyst bed. The vessel is heated at the desired temperature (usually 80
  • the wax vessel When catalyst and wax are at the desired temperature (standard approximately 80 °C) , the wax vessel was connected to the impregnation vessel. Subsequently, the wax mixture was pumped into the impregnation vessel for example (depending on the set up used) via the bottom of this vessel. N 2 that is present in and between the extrudates will bubble upwards through the wax. Typically it takes a few minutes before the bubbling stops . To keep the wax mixture liquefied in the tubes and speed up N 2 rising the pump direction was reversed three times moving the wax mixture in and out of the vessel.
  • the nitrogen flow was stopped. After cooling to room temperature the catalyst was unloaded.
  • the amount of wax in the sample can be calculated by subtracting the weight of the dried starting sample from the weight of the final waxed product, if determined directly after the impregnation. However after incomplete stripping, besides wax, the sample may still contain dodecane and when the impregnated catalyst has been left open to the air it can also contains traces of water.
  • the amount of water and/or dodecane present in waxed samples and in the pre-reduced catalyst cannot be determined by measuring the LOI, because this will also burn of the wax in the sample and/or oxidize the sample. Therefore the amount of water is determined after drying of the catalyst at 110 °C in an inert atmosphere.
  • the method was used to prepare a batch of catalysts using an 80/20% wax/dodecane mixture at 80 °C and repeated at 90 °C. At both temperatures a pore fill of up to 74% was reached . The experiment was repeated for a mixture of 85/15% wax/dodecane at temperatures of 80 °C and 95°C resulting in a pore fill of 80 and 78 % respectively.
  • the inventors repeated the above experiment for mixtures based on nonane and/or base wax with similar results.
  • the obtained catalyst particles with organic compounds in the pores have an angle of repose (determined on sight) that differs at most 2 or 3 degrees with the angle of repose before applying the organic compounds .
  • the pore fill is calculated according to the following formula wherein PV stands for pore volume prior to filling :
  • Wt% wax is determined by the weight increase due to filling of the particles by measuring the catalyst particles prior to and after filling.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The present invention provides a method for applying organic compounds to catalyst particles. Catalyst particles, a substance A and a substance B are combined. The weight ratio of substance A to substance B is in the range between 60:40 to 95:5. More than 90 wt% of substance A consists of organic compounds having 15 to 1000 carbon atoms, and more than 90 wt% of substance B consists of organic compounds having 4 to 14 carbon atoms. The final boiling point (T95) of substance B is at least 10 degrees lower than the initial boiling point (T5) of substance A. A part of substance A may be separated until the amount of substance A is 20-99.9 vol% of the total pore volume of the catalyst particles. Then substance B is evaporated.

Description

CATALYST STABILIZATION BY WAX
Field of the invention
The present invention relates to a method for applying organic compounds to catalyst particles.
Background of the invention
The present invention is especially suitable for particulate catalysts containing at least one pyrophoric metal in reduced form and a metal oxide carrier. Examples of pyrophoric metals are Ni, Co, Cu and Mo and mixtures thereof. Examples of metal oxide carriers are the oxides of aluminium, silicon, titanium, zirconium, magnesium, and mixtures thereof.
Such reduced metal catalysts are widely used, for example in hydrogenation reactions. However the metals in their catalytically active, i.e. finely divided and reduced, form are pyrophoric - i.e. when exposed to atmospheric air they tend to oxidize very rapidly, thereby producing considerable heat. Hence, safety measures are required in the production, storage and handling of these catalysts.
The stabilization of such catalysts by partial oxidation of the finely divided reduced metal is known (US-A 4,090,980; DD-B 156169). However it is not
sufficiently protective.
It is also known to protect such catalysts by coating the catalysts with fatty material.
In DD-B 155390 there is disclosed a method for preparing pyrophoric metal catalysts in powder form, wherein the powder is suspended in an excess of molten fatty material such as solid paraffin, and the suspension is simultaneously sprayed and cooled. In DE-A 2850719 there is disclosed a method for preparing nickel catalysts in powder form, wherein the powder is impregnated with a solution of fatty material, followed by removing the solvent.
In South African Patent 961848 there is disclosed a method for preparing a wax encapsulated particulate pyrophoric catalyst comprising (a) placing a porous container containing particulate pyrophoric catalyst into a vat of melted paraffin wax for a sufficient time to allow said wax to coat said particulate catalyst; (b) removing said container from said vat and (c) allowing said paraffin to cool and harden whereby a continuous oxygen excluding coating is formed over each particle of catalyst. The resulting particulate pyrophoric catalyst encapsulated in a paraffin wax is also claimed. This document also does not mention stabilization by partial oxidation .
The present inventors found that catalysts prepared according to SA 961848, while indeed being sufficiently protected from spontaneous oxidation by air, tend to cake and clog together, especially during transport. Their bad flowing property which apparently is due to the particles being encapsulated with a continuous paraffin coating, is obviously detrimental to the uniform filling of fixed-bed reactors with these particles.
In EP 1607465 a method is described in which paraffin wax is adsorbed into the pores of catalyst particles rather than being coated on their outside, and that the thus prepared porous catalyst particles have excellent flow properties along with being protected from undue oxidation. This effect is reached by mixing the particles gently with an amount of molten paraffin wax not exceeding the total pore volume of the particulate catalyst material used.
Summary of the invention
An improved method has been found in which oil and/or wax is adsorbed into the pores of catalyst particles rather than being coated on their outside. The thus prepared porous catalyst particles have excellent flow properties along with being protected from undue
oxidation .
The method of the present invention does not require a rotary reactor for the mixing of particles with oil and/or wax. Therefore, the present invention provides a less complex method as compared to EP 1607465.
Additionally, with the method of the present invention there is a smaller risk of breakage and fines formation as compared to EP 1607465.
The present invention provides a method for applying organic compounds to catalyst particles which comprises: (a) combining catalyst particles, a substance A and a substance B
at a temperature above the melting point of the combination of substance A and substance B, preferably at a temperature above the melting point of substance A, and below the initial boiling point (T5) of substance B;
whereby the sum of the volume of substance A plus the volume of substance B is equal to or larger than the total pore volume of the catalyst particles;
whereby more than 90 wt% of substance A consists of organic compounds having 15 to 1000 carbon atoms;
whereby more than 90 wt% of substance B consists of organic compounds having 4 to 14 carbon atoms; whereby the final boiling point (T95) of substance B is at least 10 degrees lower than the initial boiling point (T5) of substance A, and;
whereby the weight ratio of substance A to substance B is in the range between 60:40 to 95:5;
(b) in case in step (a) the volume of substance A is larger than the total pore volume of the catalyst particles, separating a part of substance A until the amount of substance A is 20-99.9 vol%, preferably 50-99.9 vol%, of the total pore volume of the catalyst particles at a temperature above the melting point of the combination of substance A and substance B, preferably at a temperature above the melting point of substance A, and below the initial boiling point (T5) of substance B;
whereby optionally a part of substance B is separated as well;
(c) subjecting the catalyst particles to a temperature above 0.65 times the final boiling point (T95) of substance B, preferably above 0.7 times the final boiling point (T95) of substance B, and below the final boiling point (T95) of substance A, preferably below the initial boiling point (T5) of substance A.
Detailed description of the invention
The present invention provides a method for applying organic compounds to catalyst particles.
The present invention is especially suitable for particulate catalysts containing at least one pyrophoric metal in reduced form and a metal oxide carrier. Examples of pyrophoric metals are Ni, Co, Cu and Mo and mixtures thereof. Preferably the catalyst particles comprise cobalt. Examples of metal oxide carriers are the oxides of aluminium, silicon, titanium, zirconium, magnesium, and mixtures thereof. Preferably the catalyst particles comprise silica or titania, most preferably titania.
Preferably at least 90% of the catalyst particles has a size in the range of between 0.05 and 0.5 mm, or has a size of at least 1 mm, or at least 1 mm and at most 50 mm, or consists of structured catalyst particles.
The present invention can be used for powdered catalysts. Preferably at least 90% of these catalyst particles has a size in the range of between 0.05 and
0.5 mm .
The present invention is especially suitable for catalyst particles that can be used in a packed-bed, or fixed bed, reactor. For a fixed bed, preferably at least 90% of the catalyst particles has a size of at least
1 mm, i.e. a longest internal straight length of at least 1 mm. Preferably at least 90% of the catalyst particles has a size of at most 50 mm, more preferably at most 30 mm. These catalyst particles can have different shapes and sizes. Beads, spheres, saddles are suitable. Also extrudates, for example with a trilobe shape, can be used in a packed-bed reactor.
The present invention can also be used for structured catalyst particles. Preferably at least 90% of these catalyst particles comprise a porous body having a longest internal length of at least 1 mm. These catalyst particles further comprise a catalyst material having pores with a size of more than 10 micro-meter. The structured catalyst particles, i.e. porous body along with catalyst material, preferably has an internal voidage of at least 50% and at most 95%. The structured catalyst particles, i.e. porous body along with catalyst material, preferably has an external voidage in situ in a reactor between 5 and 60% by volume. Preferably at least 90% of these catalyst particles comprise a porous body having a longest internal length of at most 10 meter, more preferably at most 2 meter. The catalyst material on the porous body preferably comprises a pyrophoric metal, such as Ni, Co, Cu or Mo or mixtures thereof, and a metal oxide carrier such as the oxides of aluminium, silicon, titanium, zirconium, magnesium, or mixtures thereof.
Preferably the catalyst material comprises cobalt.
Preferably the catalyst material comprises silica or titania, most preferably titania.
The initial boiling point (T5) is the 5% boiling temperature at atmospheric pressure. The final boiling point (T95) is the 95% boiling temperature at atmospheric pressure .
Substance A may be a wax. Also the combination of substance A and substance B may be a waxy solid at room temperature. The melting point of a wax or waxy solid can be determined by determining its slip melting point. A slip melting point is determined by casting a 10 mm column of the solid in a glass tube with an internal diameter of about 1 mm and a length of about 80 mm, and then immersing it in a temperature-controlled water bath. The slip point is the temperature at which the column of the solid begins to rise in the tube due to buoyancy, and because the outside surface of the solid is molten. A detailed description of a suitable method for determining a slip melting point can be found in European
Pharmacopoeia method 2.2.15.
In step (a) catalyst particles, a substance A and a substance B are combined. The temperature at which these are combined is above the melting point of the
combination of substance A and substance B, preferably at a temperature above the melting point of substance A, and below the initial boiling point (T5) of substance B.
In step (a) the sum of the volume of substance A plus the volume of substance B is equal to or larger than the total pore volume of the catalyst particles. The catalyst particles may be totally immersed in the combination of substance A and substance B.
More than 90 wt% of substance A consists of organic compounds having 15 to 1000 carbon atoms. Preferably more than 95 wt%, more preferably more than 99 wt%, even more preferably more than 99.9 wt%, of substance A consists of organic compounds having 15 to 1000 carbon atoms.
Preferably more than 90 wt% of substance A, more preferably more than 95 wt%, even more preferably more than 99 wt%, still more preferably more than 99.9 wt%, of substance A consists of wax having 15 to 1000 carbon atoms or oil having 15 to 40 carbon atoms, more
preferably paraffinic wax having 15 to 1000 carbon atoms or paraffinic oil having 15 to 40 carbon atoms, most preferably paraffinic wax having 15 to 1000 carbon atoms.
More than 90 wt%, preferably more than 95 wt%, more preferably more than 99 wt%, even more preferably more than 99.9 wt%,of substance B consists of organic
compounds having 4 to 14 carbon atoms.
The inventors have found that particular good results are obtained in case compound A is a compounds having up at least 15 and up to 200 carbon atoms. Preferably at least 80% of the C atoms in the molecules are part of an alkyl-group. Preferably Compound A is a Fischer-Tropsch wax or a wax derived thereof.
Preferably more than 90 wt%, more preferably more than 95 wt%, even more preferably more than 99 wt%, still more preferably more than 99.9 wt%, of substance B consists of one or more organic compounds having 9 to 12 carbon atoms,
More preferably more than 90 wt%, more preferably more than 95 wt%, even more preferably more than 99 wt%, still more preferably more than 99.9 wt%, of substance B consists of one or more hydrocarbons having 9 to 12 carbon atoms, preferably consists of one or more
hydrocarbons comprising 9 carbon atoms, one or more hydrocarbons comprising 10 carbon atoms, or one or more hydrocarbons comprising 12 carbon atoms, or a combination thereof, more preferably consists of dodecane.
The final boiling point (T95) of substance B is at least 10 degrees lower than the initial boiling
point (T5) of substance A. Preferably there is a
difference of at most 50 degrees, preferably at most 30 degrees, between the initial boiling point (T5) of substance B and the final boiling point (T95) of
substance B.
In step (a) the weight ratio of substance A to substance B is in the range between 60:40 to 95:5.
Preferably the weight ratio of A to B is in the range between 70:30 to 95:5 in step (a) .
In a preferred embodiment, the catalyst particles used in step a) were subjected to activation before step a) . Activation preferably is performed by subjecting the particles to hydrogen or to hydrogen sulfide.
In another preferred embodiment, the catalyst particles used in step a) were subjected to activation, followed by passivation before step a) . Activation preferably is performed by subjecting the particles to a hydrogen and/or hydrogen sulfide comprising gas
Passivation preferably is performed by subjecting the particles to an oxygen comprising gas. During passivation a part of the pyrophoric metal is oxidised.
Activation may take place in a container, for example a reactor, while step (a) is performed in another container, for example another reactor. Activation and step (a) may also take place in the same container, for example the same reactor.
The catalyst particles, substance A and substance B may, for example, be combined by adding the particles to a mixture of substance A and substance B. The catalyst particles, substance A and substance B may, for example, be combined by adding substance A and substance B, or a mixture of substance A and substance B, to the catalyst particles. For example, substance A and substance B, or a mixture of substance A and substance B, may be introduced at the bottom of a container which comprises the catalyst particles. The catalyst particles, substance A and substance B may, for example, be combined in a rotating drum, on a conveyor belt. Additionally or alternatively, the catalyst particles may be dipped into a mixture of substance A and substance B.
Substance A and substance B may be combined
separately with the catalyst particles. Additionally or alternatively, a mixture of substance A and substance B may be combined with the catalyst particles. A mixture of substance A and substance B may be prepared by mixing substance A and substance B, or by distilling at least one fraction away from organic compounds having 4 to 1000 carbon atoms .
Step (b) is not performed in case the volume of substance A used in step (a) is equal to or smaller than the total pore volume of the catalyst particles. In case in step (a) the volume of substance A is larger than the total pore volume of the catalyst particles, a part of substance A is separated in
step (b) . This is performed until the amount of
substance A is 20-99.9 vol%, preferably 50-99.9 vol%, of the total pore volume of the catalyst particles.
When performed, step (b) is performed at a
temperature above the melting point of the combination of substance A and substance B, preferably at a temperature above the melting point of substance A, and below the initial boiling point (T5) of substance B.
During step (b) a part of substance B may be
separated as well.
Preferably the ratio of substance A to substance B in the presence of the catalyst particles remains the same or almost the same during step (b) . This can be achieved by simultaneously separating substance A and substance B. Substance A and substance B may, for example, be
separated simultaneously by means of draining. In that case draining of the combination of substance A and substance B is performed until the amount of substance A is 20-99.9 vol%, preferably 50-99.9 vol%, of the total pore volume of the catalyst particles. This is performed at a temperature above the melting point of the
combination of substance A and substance B, and
preferably at a temperature above the melting point of substance A, and below the initial boiling point (T5) of substance B.
The ratio of substance A to substance B in the presence of the catalyst particles may change during step (b) . Therefore also the melting point of the combination of substance A and substance B in the presence of the catalyst particles may change during step (b) . In that case step (b) may be performed at a temperature above the melting point of any of the ratios of substance A and substance B that may exist during step (b) . Preferably step (b) is performed at a
temperature above the melting point of substance A.
Alternatively; the temperature is adjusted during step (b) and is kept above the changing melting point of the combination of substance A and substance B in the presence of the catalyst particles.
In step (c) the catalyst particles are subjected to a temperature above 0.65 times the final boiling
point (T95) of substance B, preferably above 0.7 times the final boiling point (T95) of substance B, and below the final boiling point (T95) of substance A, preferably below the initial boiling point (T5) of substance A.
In case the final boiling point (T95) of substance B is 216 °C, then 0.65 times the final boiling point (T95) of substance B is: 0.65 x 216 °C. This corresponds to 140 °C. In that case 0.7 times the final boiling
point (T95) of substance B is: 0.7 x 216 °C, which corresponds to 151 °C.
During step (c) all or most of substance B is evaporated. All or a part, preferably all or most, of substance A remains in the presence of the catalyst particles .
During step (c) the combination of substance A and substance B in the presence of the particles decreases in volume and has an increasing content of substance A.
Without wising to be bound to any theories, it is believed that the liquid that resides between the particles retracts into the pores of the catalyst particles . Step (c) may be performed under vacuum.
During step (c) an inert gas, for example nitrogen, may be passed along the catalyst particles.
The duration of step (c) can be adjusted by adjusting the temperature at which step (c) is performed.
After evaporation of substance B, substance A is mainly or completely present in the pores of the
catalyst. After cooling of the catalyst particles, the particles do not stick together.
With the method of the present invention oil and/or wax is adsorbed into the pores of catalyst particles rather than being coated on their outside. The thus prepared porous catalyst particles have excellent flow properties along with being protected from undue
oxidation .
With the method of the present invention it is possible to obtain catalyst particles with organic compounds in the pores which have an angle of repose that differs at most 2 or 3 degrees with the angle of repose before applying the organic compounds. This is especially the case for powdered catalyst particles having a size in the range of between 0.05 and 0.5 mm, and for fixed bed catalyst particles having a size of at least 1 mm and at most 50 mm. It is especially advantageous for fixed bed catalyst particles having a size of at least 1 mm and at most 50 mm as the preparation of a fixed bed of catalyst particles is preferably performed with particles that are protected by organic compounds, such as oil and/or wax, but do not stick together. Example
Catalyst samples (extrudates) were impregnated as follows .
A static soaking method was used. With this method instead of impregnating with pure wax, the catalyst is soaked in a wax/volatile mixture. After draining the excess of wax mixture the volatile in the wet catalyst is evaporated. The wax/volatile ratio determines the amount of wax present in the pores after impregnation and drying .
Catalyst was loaded into a vessel. After loading the catalyst, N2 was passed through the catalyst bed. The vessel is heated at the desired temperature (usually 80
°C) .
In a wax preparation vessel the wax (Shell Sarawax SX 70)/dodecane mixture is heated up to the desired
temperature, which should be above 70 °C for the wax to melt .
When catalyst and wax are at the desired temperature (standard approximately 80 °C) , the wax vessel was connected to the impregnation vessel. Subsequently, the wax mixture was pumped into the impregnation vessel for example (depending on the set up used) via the bottom of this vessel. N2 that is present in and between the extrudates will bubble upwards through the wax. Typically it takes a few minutes before the bubbling stops . To keep the wax mixture liquefied in the tubes and speed up N2 rising the pump direction was reversed three times moving the wax mixture in and out of the vessel.
After pumping the mixture out of the vessel for the final time, the bottom of the vessel was connected to a cold trap and the top of the vessel was closed (Figure 4) . The N2 flow (standard around 850 ml/minute) was lead over the wet catalyst bed to evaporate the dodecane, which condensed in the cold trap.
When all the dodecane had evaporated, the nitrogen flow was stopped. After cooling to room temperature the catalyst was unloaded. The amount of wax in the sample can be calculated by subtracting the weight of the dried starting sample from the weight of the final waxed product, if determined directly after the impregnation. However after incomplete stripping, besides wax, the sample may still contain dodecane and when the impregnated catalyst has been left open to the air it can also contains traces of water.
The amount of water and/or dodecane present in waxed samples and in the pre-reduced catalyst cannot be determined by measuring the LOI, because this will also burn of the wax in the sample and/or oxidize the sample. Therefore the amount of water is determined after drying of the catalyst at 110 °C in an inert atmosphere. The method was used to prepare a batch of catalysts using an 80/20% wax/dodecane mixture at 80 °C and repeated at 90 °C. At both temperatures a pore fill of up to 74% was reached . The experiment was repeated for a mixture of 85/15% wax/dodecane at temperatures of 80 °C and 95°C resulting in a pore fill of 80 and 78 % respectively.
The inventors repeated the above experiment for mixtures based on nonane and/or base wax with similar results.
The obtained catalyst particles with organic compounds in the pores have an angle of repose (determined on sight) that differs at most 2 or 3 degrees with the angle of repose before applying the organic compounds .
The pore fill is calculated according to the following formula wherein PV stands for pore volume prior to filling :
Wt% wax is determined by the weight increase due to filling of the particles by measuring the catalyst particles prior to and after filling.

Claims

C L A I M S
1. A method for applying organic compounds to catalyst particles which comprises:
(a) combining catalyst particles, a substance A and a substance B
at a temperature above the melting point of the combination of substance A and substance B, preferably at a temperature above the melting point of substance A, and below the initial boiling point (T5) of substance B;
whereby the sum of the volume of substance A plus the volume of substance B is equal to or larger than the total pore volume of the catalyst particles;
whereby more than 90 wt% of substance A consists of organic compounds having 15 to 1000 carbon atoms;
whereby more than 90 wt% of substance B consists of organic compounds having 4 to 14 carbon atoms;
whereby the final boiling point (T95) of substance B is at least 10 degrees lower than the initial boiling point (T5) of substance A, and;
whereby the weight ratio of substance A to substance B is in the range between 60:40 to 95:5;
(b) in case in step (a) the volume of substance A is larger than the total pore volume of the catalyst particles, separating a part of substance A until the amount of substance A is 20-99.9 vol%, preferably 50-99.9 vol%, of the total pore volume of the catalyst particles at a temperature above the melting point of the combination of substance A and substance B, preferably at a temperature above the melting point of substance A, and below the initial boiling point (T5) of substance B;
whereby optionally a part of substance B is separated as well;
(c) subjecting the catalyst particles to a temperature above 0.65 times the final boiling point (T95) of substance B, preferably above 0.7 times the final boiling point (T95) of substance B, and below the final boiling point (T95) of substance A, preferably below the initial boiling point (T5) of substance A.
2. The method according to claim 1, wherein there is difference of at most 50 degrees, preferably at most degrees, between the initial boiling point (T5) of substance B and the final boiling point (T95) of
substance B.
3. The method according to claim 1 or 2 wherein more than 90 wt%, preferably more than 95 wt%, more preferably more than 99 wt%, even more preferably more than
99.9 wt%, of substance B consists of one or more organic compounds having 9 to 12 carbon atoms, preferably one or more hydrocarbons having 9 to 12 carbon atoms, more preferably dodecane.
4. The method according to claim 3 wherein compound A is a compounds having up at least 15 and up to 200 carbon atoms, preferably at least 80% of the C atoms in the molecules are part of an alkyl-group, more preferably Compound A is a Fischer-Tropsch wax or a wax derived thereof .
5. The method of any one of the above claims wherein more than 95 wt%, preferably more than 99 wt%, more preferably more than 99.9 wt%, of substance A consists of organic compounds having 15 to 1000 carbon atoms, preferably consists of wax having 15 to 1000 carbon atoms or oil having 15 to 40 carbon atoms, more preferably paraffinic wax having 15 to 1000 carbon atoms or
paraffinic oil having 15 to 40 carbon atoms, most preferably paraffinic wax having 15 to 1000 carbon atoms.
6. The method according to any one of the above claims wherein at least 90% of the catalyst particles has a size in the range of between 0.05 and 0.5 mm, or has a size of at least 1 mm, or consists of structured catalyst particles .
7. The method according to any one of the above claims wherein the catalyst particles used in step a) were sub ected to activation before step a) , preferably by subjecting the particles to hydrogen or to hydrogen sulfide, or
were subjected to activation, preferably by subjecting the particles to a hydrogen and/or hydrogen sulfide comprising gas, followed by passivation, preferably by subjecting the particles to an oxygen comprising gas, before step a) .
8. The method according to any one of the above claims wherein in step (a) the weight ratio of A to B is in the range between 70:30 to 95:5.
9. The method according to any one of the above claims wherein in step (c) an inert gas, preferably nitrogen, is passed along the catalyst particles.
PCT/EP2015/072677 2014-10-01 2015-10-01 Catalyst stabilization by wax WO2016050906A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3453217A (en) * 1966-12-16 1969-07-01 Chevron Res Protection of sulfided hydrotreating catalysts against reaction with oxygen
US20050085378A1 (en) * 2003-09-11 2005-04-21 Peter Birke Particulate catalyst comprising pyrophoric metal and stabilized by wax
EP1607465A1 (en) * 2003-09-11 2005-12-21 Shell Internationale Researchmaatschappij B.V. Particulate catalyst comprising pyrophoric metal and stabilized by wax

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3453217A (en) * 1966-12-16 1969-07-01 Chevron Res Protection of sulfided hydrotreating catalysts against reaction with oxygen
US20050085378A1 (en) * 2003-09-11 2005-04-21 Peter Birke Particulate catalyst comprising pyrophoric metal and stabilized by wax
EP1607465A1 (en) * 2003-09-11 2005-12-21 Shell Internationale Researchmaatschappij B.V. Particulate catalyst comprising pyrophoric metal and stabilized by wax

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