WO2020254184A1 - Ferromagnetic catalyst support for induction heated catalysis - Google Patents

Ferromagnetic catalyst support for induction heated catalysis Download PDF

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Publication number
WO2020254184A1
WO2020254184A1 PCT/EP2020/066197 EP2020066197W WO2020254184A1 WO 2020254184 A1 WO2020254184 A1 WO 2020254184A1 EP 2020066197 W EP2020066197 W EP 2020066197W WO 2020254184 A1 WO2020254184 A1 WO 2020254184A1
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WIPO (PCT)
Prior art keywords
catalyst support
support material
core
catalyst
ferromagnetic
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PCT/EP2020/066197
Other languages
French (fr)
Inventor
Ib Chorkendorff
Sebastian Thor WISMANN
Nikolaj Ørbæk LANGEMARK
Cathrine FRANDSEN
Peter Mølgaard Mortensen
Original Assignee
Haldor Topsøe A/S
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Publication of WO2020254184A1 publication Critical patent/WO2020254184A1/en

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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
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Definitions

  • Embodiments of the invention generally relate to a catalyst support material arranged for supporting a catalytically active phase, a catalyst material comprising the catalyst support material as well as a catalytically active phase, a method of preparing particles for the catalyst support material and a method of preparing the catalyst material.
  • the catalyst support material and the catalyst material are ferromagnetic and are suited for inductive heating of endothermic reactions.
  • Endothermic processes incl. catalytic chemical reactions, require heat to proceed. Per forming endothermic reactions will often be challenged by how efficient heat can be transferred to the reactive zone of the catalyst material within a reactor unit. Conven tional heat transfer by convection, conduction and/or radiation can be slow and will often meet large resistance in many configurations, due to i.a. inefficient heat transport to central parts of the reactor unit.
  • This challenge can be illustrated with a tubular reformer in a steam reforming plant, which practically can be considered as a large heat exchanger with heat transfer as the rate limiting step.
  • the tempera ture is often above optimal at the wall of tubes of the tubular reformer, and below op timal in the center of the tubes.
  • Induction heating by eddy current heating or magnetic hysteresis heating, is a poten tial means to circumvent this challenge, as magnetic fields are able to permeate many materials and therefore may induce magnetic heating directly within the active zone inside a reactor unit.
  • heat may be supplied more directly and hence overcome the traditional problems associated with transferring heat.
  • a catalyst material suitable for a given endothermic reaction is not inherently ferromagnetic, and inductively heated reactors may need to be combined with other heating means. Only few experimental evidences has been given and these have typi cally been confined to having ferromagnetic active phases, as described e.g. by P. M. Mortensen, J.
  • ferromagnetic catalyst material should not change, e.g. it should not dissolve or oxidize, nor should it affect the chemistry of the reactor, e.g. it should not cause metal dusting or alloying.
  • a first aspect of the invention generally relate to a catalyst support material compris- ing a plurality of phase-segregated particles.
  • the segregated particles comprises a core and a boundary layer surrounding the core, where the core comprises one or more fer romagnetic elements and has a diameter of up to 500 pm, and the boundary layer is an oxidic material.
  • the catalyst support material moreover comprises a ceramic material and the segregated particles are at least partly embedded within the ceramic material.
  • a catalyst support material is provided, where one or more ferromagnetic ele ments is/are embedded within or incorporated in a catalytic carrier in the form of the ceramic material.
  • the segregated particles When the segregated particles are incorporated within or integrated in the catalyst support material, which is impregnated with a catalytically active phase, it is possible to establish efficient heat transfer between the ferromagnetic element(s) of the segregated particles and a catalytically active phase, whilst avoiding alloying be tween the ferromagnetic core and the catalytically active phase due to the presence of the boundary layer.
  • the boundary layer of oxidic material increases corrosion re sistance and functions as a boundary layer, making the segregated particles partially inert to the environment in reactors for endothermal reactions.
  • an unpro- tected metal particle might oxidize, cause metal dusting and/or alloy with other metal lic particles present in the reactor.
  • the core with ferro magnetic element(s) has a diameter of up to 50 pm, such as between 10 and 50 pm.
  • the term "segregated particles” are meant to denote particles wherein different domains exist, where different domains have different composition of ele ments. Such segregated particles are thus multi-domain particles where one domain is one domain is the core and another domain is the boundary layer surrounding the core.
  • the core itself may additionally have areas of one composition and other areas of other compositions.
  • the oxidic material may be a ceramic material or a ceramic-type material.
  • boundary layer is meant to denote a layer of different composition than the core.
  • the boundary layer surrounds the core and covers at least the majority of the core, so that the core is not directly exposed to the surroundings.
  • the boundary layer could also be denoted a shell.
  • core is correspondingly meant to denote the part of a segregated particle that lies within the boundary layer.
  • the boundary layer of the segregated particles can be similar to existing catalytic car rier materials and is thus compatible with such. Thereby, the boundary layer of the segregated particles form an integrated part of the catalyst support material, on to which a catalytically active phase may be impregnated.
  • the core is preferably made of a ferro magnetic material with a high, well-defined Curie temperature in order to provide for induction heating up to the Curie temperature.
  • the boundary layer of oxidic material is corrosion resistant and acts as a boundary layer. This makes the segregated particles at least substantially inert to the environment in reactors. In contrast, unprotected metal particles, viz. metal particles without a boundary layer, may oxidize, cause metal dust ing and/or alloy with other metallic particles present in a reactor unit. Such processes would destroy the catalytic performance, the induction performance and/or the reac tor unit.
  • the material of the core comprising one or more ferro- magnetic elements is also denoted "ferromagnetic material”.
  • the term "fer romagnetic sites" are meant to denote the ferromagnetic elements or material of the core.
  • the core itself can have domains with higher ferromagnetism than other areas within the core.
  • the composition of the oxidic material and the ceramic material is substantially equal.
  • the catalytically active phase can be distributed both within the oxidic material and within the ceramic material.
  • the one or more ferromagnetic ele ments of the core has a Curie temperature of between 320°C and 1130°C. Advanta geously, the Curie temperature is above 650°C, more preferably above 800°C, such as at or above 900°C or even higher.
  • the first ceramic material is com- posed of a material that is chemically inert, at least at temperatures up to about
  • inert means that the material is not chemically reactive, viz. it does not react or only reacts very little with gasses flowing over the material.
  • the core comprises one or more of the following elements: Co, Fe, Ni, or alloys thereof. These are all ferromagnetic above room temperature. Other ele ments, which might be present in the core, could be Cr, Al, Ti, Cu, among others.
  • the oxidic material comprises one or more of the following elements: Al, Y, Zr, Hf, La, Si, Ce, Mg, Cr, Co, Fe, Ni, O or combinations thereof. These elements oxi dize relatively easily, and in their oxidized form, they have significant resistance to dif- ferent reactor conditions.
  • the oxidic element comprises Al and O. Depend ing on the exact application of the catalyst support material, the choice of starting ma terials for preparing the catalyst support material should be tuned to match the struc ture and composition of the desired catalyst support material as well as the required heating performance and chemical stability.
  • the ceramic material comprises one or more of the following ele ments: Al, Y, Zr, Hf, La, Si, Ce, Mg, O, or combinations thereof.
  • the ceramic material e.g. comprises MgA C , AI2O3, CaA O ⁇ ZrC>2, CeC>2, MgO, or SiC>2.
  • the oxidic material, and the ceramic material, respectively has a first and second porosity, respectively, wherein the first porosity is smaller than the second porosity.
  • the porosity of the catalyst support material ensures its suitability to be impregnated with catalytically active particles or elements, whilst the ferromag- netic properties provide the catalyst support material the ability to being inductively heated.
  • the porosity of the catalyst support material is intrinsically connected to the surface area thereof.
  • the porosity of the ceramic material is in the range from about 15% to about 60%; a preferred subinterval is porosity between about 20% to about 45%, for example between 30% and 40%.
  • the porosity of the oxidic material is in the range from about 5% to about 50%.
  • An overall surface area of the catalyst support material of above about 1 m 2 /g is pref erable, e.g. between 5 m 2 /g and 50 m 2 /g or between 5 m 2 /g and 20 m 2 /g.
  • a ferromagnetic and porous material with these parameters is suitable as catalyst sup port material for supporting a catalytically active phase so that a catalyst material com prising the ferromagnetic and porous catalyst support material impregnated with cata lytically active phase will be both ferromagnetic and catalytically active.
  • the porosity of the catalyst support material ensures that an appropriate amount of a catalytically ac- tive phase may be impregnated onto the catalyst support material.
  • such a ferromagnetic and catalytically active material is suitable for inductive heating and for catalyzing endothermic reactions.
  • the segregated particles have a diameter of less than 10 pm.
  • the largest dimension of the catalyst support material is between 1 and 10 cm, preferably between 3 and 5 cm.
  • the catalyst material comprises a catalyst support material according to the invention and further comprises a catalytically active phase supported by the oxidic material and/or the ceramic material.
  • the catalytically active phase comprises Ni, Co, Ru, Rh, Pt, Pd, Fe,
  • the invention relates to a method of preparing a catalyst support material according to the invention.
  • the method comprises the following steps:
  • the high temperature, under which the alloy is annealed is preferably between 800°C and 1000°C, such as about 800°C, about 850°C, about 900°C, about 950°C or about 1000°C.
  • the boundary layer is of the non-ferromagnetic material, whilst a core of ferromagnetic material is formed beneath the boundary layer.
  • the oxidizing condi tions may be any appropriate oxidizing conditions where the one or more ferromag- netic element is unlikely to oxidize compared to the one or more non-ferromagnetic element, thus allowing the boundary layer to form.
  • the oxidizing conditions may be mildly oxidating.
  • Non limiting examples of oxidizing atmospheres may be:
  • O2 lean air e.g. 1% O2 in N2 •
  • Steam and hydrogen mixtures e.g. 5% H2O in H2 or 50% H2O in H2
  • the size of the core of the segregated particles which is particularly relevant for the induction heating properties, as well as the thickness of the boundary layer, which is relevant for the protection of the core of the segregated particles, can be tuned by the choice of the initial size of the particles of an alloy of one or more non-ferromagnetic elements and one or more ferromagnetic elements and by the initial composition of the alloy.
  • the heating power transferred to the material by hysteresis heating is the area of the hysteresis curve times the frequency of the alternating magnetic field.
  • the Curie temperature of the segregated particle is considerably higher than the Curie temperature of the particles of the untreated alloy of non-ferromagnetic and ferro- magnetic elements.
  • the area of the hysteresis curve of the segregated parti cle is considerably larger than the area of the hysteresis curve of the particles of the al loy of one or more non-ferromagnetic and one or more ferromagnetic elements used as starting material for the segregated particles.
  • the alloy and annealing conditions are chosen so as to ensure that the one or more ferromagnetic elements is unlikely to oxidize compared to the one or more non-ferromagnetic elements.
  • the segregated particle formed has a core comprising the one or more ferromagnetic elements and a boundary layer comprising the one or more non ferromagnetic elements, where the size of the core and of the boundary layer is deter mined by the choice of particle size of the particles of the alloy and/or by the initial composition of the alloy.
  • the boundary layer is of an oxidic material.
  • the ceramic material is impregnated with a catalytically active phase before mixing with the segregated particles
  • the method comprises the step of impregnating the catalyst sup- port material with a catalytically active phase.
  • the method comprises the step of reducing the catalyst support material or catalyst material in a reducing atmosphere at elevated temperatures.
  • the close proximity between the catalytically active phase and the ferromagnetic ma- terial within the catalyst material enables efficient heating of the catalytically active phase by close proximity heat conduction from the ferromagnetic material.
  • An im portant feature of the inductive heating process is thus that the energy is supplied in side the object itself, instead of being supplied from an external heat source via heat conduction, convection and radiation.
  • the hottest part of the reactor sys- tern will be within the housing or shell of the reactor system.
  • the electrical power supply and the catalyst material are dimensioned so that at least part of the cat alyst material reaches a temperature of 850-1100°C when the endothermic reaction is the steam reforming reaction, a temperature of 700-1200°C when the endothermic re action is the hydrogen cyanide synthesis, a temperature of 500-700°C when the endo- thermic reaction is dehydrogenation, a temperature of 200-300°C when the endother mic reaction is the methanol cracking, and a temperature of ca. 500°C when the endo thermic reaction is the ammonia cracking reaction.
  • the surface area of the catalyst ma terial, the size of the segregated particles, the type, and structure of the ceramic mate rial, and the amount and composition of the catalytically active phase may be tailored to the specific endothermic reaction at the given operating conditions.
  • feed gas is meant to denote a gas having a suitable composi tion for the given endothermic reaction.
  • the endothermic reaction is steam me thane reforming this may be typically be hydrocarbons, methane, hydrogen, carbon monoxide, carbon dioxide, steam, and inerts as nitrogen and argon.
  • the endo thermic reaction is dehydrogenation it may be a hydrocarbon as propane or styrene together with inert and potentially hydrogen.
  • the endothermic reaction is hy drogen cyanide synthesis or a synthesis process for organic nitriles it may be higher hy drocarbons, ammonia, methane, nitrogen, hydrogen, oxygen, and/or inert.
  • the endothermic reaction When the endothermic reaction is methanol cracking it may be methanol, steam, carbon monox ide, carbon dioxide, hydrogen, and inert.
  • the endothermic reaction When the endothermic reaction is ammonia cracking it may be ammonia, hydrogen, nitrogen, and inert.
  • the catalyst material of the invention is useful for any endothermic reaction.
  • the catalyst material is suitable for the steam reforming reaction, the prereforming reaction, or the water gas shift reaction, the dehydrogenation reac tion, the methanol cracking reaction, the ammonia cracking reaction, or the hydrogen cyanide synthesis reaction.
  • steam reforming is meant to denote a reforming reaction according to one or more of the following reactions:
  • Reactions (i) and (ii) are steam methane reforming reactions, whilst reaction (iii) is the dry methane reforming reaction.
  • reaction (i) is generalized as:
  • steam methane reforming is meant to cover the reactions (i) and (ii)
  • steam reforming is meant to cover the reactions (i), (ii) and (iv)
  • methanation covers the reverse reaction of reaction (i). In most cases, all of these re- actions (i)-(v) are at, or close to, equilibrium at the outlet from the reactor system.
  • prereforming is often used to cover the catalytic conversion of higher hy drocarbons according to reaction (iv). Prereforming is typically accompanied by steam reforming and/or methanation (depending upon the gas composition and operating conditions) and the water gas shift reaction. Prereforming is often carried out in adia- batic reactors but may also take place in heated reactors.
  • R1-CH2-CH2-R2 ⁇ - RI-CH CH-R 2 (viii)
  • Ri and R 2 may be any appropriate group in a hydrocarbon molecule, such as -H, -CHs, -CH 2 , or -CH.
  • methanol cracking reaction is accompanied by the water gas shift reaction (v).
  • ammonia cracking is meant to denote the following reactions:
  • the endothermic reaction is dehydrogenation of hydrocarbons.
  • the catalyst material for the reac tion may be composed of a core with high content of Fe, an oxidic material with high content of Al, a ceramic material with high content of AI 2 0 3 , and catalytically active phase of Pt.
  • the maximum temperature of the reactor may be between 500-700°C.
  • the pressure of the feed gas may be 2-5 bar.
  • the endothermic reaction is cracking of methanol. This reaction takes place according to reaction (v), (ix), and (x).
  • the catalyst material for the reaction may be composed of a core with high content of Ni, an oxidic material with high con tent of Al, a ceramic material with high content of AI 2 0 3 , and catalytically active phase of Cu.
  • the maximum temperature of the reactor may be between 200-300°C.
  • the pres sure of the feed gas may be 2-30 bar, preferably about 25 bar.
  • the endothermic reaction is steam reforming of hydrocarbons.
  • This reaction takes place according to reaction (i)-(v).
  • the catalyst material for the reaction may be composed of a core with high content of Co, an oxidic material with high con tent of Al, a ceramic material with high content of MgA ⁇ Os, and catalytically active phase of Ni.
  • the ceramic material may have high content of ZrC>2 or CaAhOs.
  • the catalytically active phase may also be Ru, Rh, Ir, or combina- tions thereof.
  • the maximum temperature of the reactor may be between 850-1300°C.
  • the pressure of the feed gas may be 15-180 bar, preferably about 25 bar.
  • the endothermic reaction is ammonia cracking. This reaction takes place according to reaction (xi).
  • the catalyst material for the reaction may be com- posed of a core with high content of Fe, an oxidic material with high content of Al, a ceramic material with high content of AI 2 O 3 , and catalytically active phase of Fe or Ru.
  • the maximum temperature of the reactor may be between 400-700°C.
  • the pressure of the feed gas may be 2-30 bar, preferably about 25 bar.
  • the endothermic reaction is the hydrogen cyanide synthesis or a synthesis process for organic nitriles. This reaction takes place according to reaction (vi) and (vii).
  • the catalyst material for the reaction may be composed of a core with high content of Co, an oxidic material with high content of Al, a ceramic material with high content of AI 2 O 3 , and catalytically active phase of Pt.
  • the catalyti- cally active phase may be Co, or SnCo.
  • the maximum temperature of the reactor may be between 700-1200°C.
  • the pressure of the feed gas may be 2-30 bar, preferably about 5 bar.
  • the endothermic reaction is aromatization of hydrocarbons. This is advantageously aromatization of higher hydrocarbons.
  • Figure 1 is a schematic drawing of a catalyst support material
  • Figures 2 and 3 are SEM images of catalyst support material
  • Figure 4 is a graph of methane conversion rates for different power values.
  • FIG. 1 is a schematic drawing of a catalyst support material 100.
  • the catalyst support material comprises a number of segregated particles 10.
  • Each of the segregated parti- cles 10 has a core 12 and a boundary layer 14.
  • the core 12 is of ferromagnetic mate rial, i.e. comprises one or more ferromagnetic elements, whilst the boundary layer is of an oxidic material.
  • the segregated particles 10 are embedded or partly embedded within a ceramic material 20.
  • Figures 2 and 3 are SEM images of catalyst support material having a core of Co with traces of Al, a boundary layer of oxidic material, in the form of AI 2 O 3 , and a ceramic material of MgAhO ⁇
  • the magnification of the SEM picture of figure 3 is about 50 times the magnification of the SEM picture of figure 2.
  • a piece of catalyst support material is shown with a plurality of segregated particles.
  • the segregated particles are the lightest part of the SEM image. Since the oxidic material of the boundary layer and the ceramic material are similar materials and due to the magnification in figure 2 only being about 80, the boundary layer of the segregated particles are not easily discerni ble in figure 2.
  • a single segregated particle has been enlarged and it can be seen that the segregated particle is embedded within a ceramic material, viz. the material surrounding the segregated particle, and that the segregated particle has a boundary layer and a core.
  • the boundary layer of the segregated particle is almost black and of the same color as the ceramic material.
  • the core comprises two different colors: a white and a light grey color.
  • the white parts of the core correspond to areas of Co, whilst the light grey parts corresponds to areas containing both Co and Al.
  • the given catalyst support material was produced from an initial alloy of CoAI.
  • Figure 4 is a graph of methane conversion rates for different power values.
  • the meas urements are made on a catalyst material comprising a catalyst support material with a plurality of segregated particles and a ceramic material.
  • the segregated particles have a core of Co79-AI21 and the ceramic material of MgAhO ⁇
  • This catalyst material have been impregnated with Ni as the catalytically active phase. Tests have been made with this catalyst material and with three different flow rates of methane, viz. at 100 Nml/min, 150 Nml/min and 200 Nml/min methane, respectively, at a H2O/CH4 ratio of 2 with 5% cofeed of H2 and figure 4 shows the graphs from these tests.

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Abstract

The invention relates to a catalyst support material comprising a plurality of segregated particles. The segregated particles comprises a core and a boundary layer surrounding the core. The core is comprises one or more ferromagnetic elements and has a diameter of up to 500 µm, and the boundary layer is of an oxidic material. The catalyst support material moreover comprises a ceramic material and the segregated particles are at least partly embedded within the ceramic material. The invention moreover relates to a catalyst material comprising the catalyst support material of the invention as well as a catalytically active phase.

Description

Ferromagnetic catalyst support for induction heated catalysis
FIELD OF THE INVENTION
Embodiments of the invention generally relate to a catalyst support material arranged for supporting a catalytically active phase, a catalyst material comprising the catalyst support material as well as a catalytically active phase, a method of preparing particles for the catalyst support material and a method of preparing the catalyst material. The catalyst support material and the catalyst material are ferromagnetic and are suited for inductive heating of endothermic reactions.
BACKGROUND
Endothermic processes, incl. catalytic chemical reactions, require heat to proceed. Per forming endothermic reactions will often be challenged by how efficient heat can be transferred to the reactive zone of the catalyst material within a reactor unit. Conven tional heat transfer by convection, conduction and/or radiation can be slow and will often meet large resistance in many configurations, due to i.a. inefficient heat transport to central parts of the reactor unit. This challenge can be illustrated with a tubular reformer in a steam reforming plant, which practically can be considered as a large heat exchanger with heat transfer as the rate limiting step. Here, the tempera ture is often above optimal at the wall of tubes of the tubular reformer, and below op timal in the center of the tubes.
Induction heating, by eddy current heating or magnetic hysteresis heating, is a poten tial means to circumvent this challenge, as magnetic fields are able to permeate many materials and therefore may induce magnetic heating directly within the active zone inside a reactor unit. Thus, by incorporating magnetic materials susceptible to induc tion heating inside the reactor unit, heat may be supplied more directly and hence overcome the traditional problems associated with transferring heat. Typically, a catalyst material suitable for a given endothermic reaction is not inherently ferromagnetic, and inductively heated reactors may need to be combined with other heating means. Only few experimental evidences has been given and these have typi cally been confined to having ferromagnetic active phases, as described e.g. by P. M. Mortensen, J. S. Engbaek, S. B. Vendelbo, M. F. Hansen, M. 0stberg, Ind. Eng. Chem. Res., 56, 14006, 2017, doi:10.1021/acs.iecr.7b02331.
It is desirable to provide a catalyst support material and a catalyst material which ren der induction heating of a catalytically active phase possible, independently of whether the catalytically active phase itself is ferromagnetic or not. Thereby, induction heating of a broad variety of types of catalytically active phases is possible, and the catalyst material may be arranged for catalyzing a broad variety of different endothermic reac tions. It is also desirable to provide a catalyst material which in itself is ferromagnetic and thus suitable for being inductively heated. Thereby, inductive heating of the catalyst material is independent of the presence of further units of ferromagnetic material. Moreover, energy efficiency is enhanced and high heating rates are obtainable by a ferromagnetic catalyst material.
Moreover, it is desirable to provide a catalyst support material and a catalyst material which are ferromagnetic at sufficiently high temperatures, and which are also able to remain chemically inert, even over long times, in the often harsh conditions of a heated reactor. This implies that the ferromagnetic catalyst material should not change, e.g. it should not dissolve or oxidize, nor should it affect the chemistry of the reactor, e.g. it should not cause metal dusting or alloying.
SUMMARY OF THE INVENTION
A first aspect of the invention generally relate to a catalyst support material compris- ing a plurality of phase-segregated particles. The segregated particles comprises a core and a boundary layer surrounding the core, where the core comprises one or more fer romagnetic elements and has a diameter of up to 500 pm, and the boundary layer is an oxidic material. The catalyst support material moreover comprises a ceramic material and the segregated particles are at least partly embedded within the ceramic material. Hereby a catalyst support material is provided, where one or more ferromagnetic ele ments is/are embedded within or incorporated in a catalytic carrier in the form of the ceramic material. When the segregated particles are incorporated within or integrated in the catalyst support material, which is impregnated with a catalytically active phase, it is possible to establish efficient heat transfer between the ferromagnetic element(s) of the segregated particles and a catalytically active phase, whilst avoiding alloying be tween the ferromagnetic core and the catalytically active phase due to the presence of the boundary layer. The boundary layer of oxidic material increases corrosion re sistance and functions as a boundary layer, making the segregated particles partially inert to the environment in reactors for endothermal reactions. In contrast, an unpro- tected metal particle might oxidize, cause metal dusting and/or alloy with other metal lic particles present in the reactor. Such processes would be detrimental to the reactor and the catalytic and inductive performance thereof. Preferably, the core with ferro magnetic element(s) has a diameter of up to 50 pm, such as between 10 and 50 pm. As used herein, the term "segregated particles" are meant to denote particles wherein different domains exist, where different domains have different composition of ele ments. Such segregated particles are thus multi-domain particles where one domain is one domain is the core and another domain is the boundary layer surrounding the core. The core itself may additionally have areas of one composition and other areas of other compositions.
The oxidic material may be a ceramic material or a ceramic-type material.
The term "boundary layer" is meant to denote a layer of different composition than the core. The boundary layer surrounds the core and covers at least the majority of the core, so that the core is not directly exposed to the surroundings. The boundary layer could also be denoted a shell. The term "core" is correspondingly meant to denote the part of a segregated particle that lies within the boundary layer. The boundary layer of the segregated particles can be similar to existing catalytic car rier materials and is thus compatible with such. Thereby, the boundary layer of the segregated particles form an integrated part of the catalyst support material, on to which a catalytically active phase may be impregnated. Close contact and thereby effi cient heat transport is achievable between the core comprising ferromagnetic material and a catalytically active phase impregnated onto the catalyst support material, whilst the risk of alloying between the catalytically active phase and the ferromagnetic mate rial, is reduced considerably due to the boundary layer around the core protecting the ferromagnetic material. An advantage of the catalyst support material of the invention is that close contact between heating sites and catalyst sites is achieved by having high distribution of small ferromagnetic sites in the pm scale placed around catalytic sites in the nm scale with distances of few pm or less. The core is preferably made of a ferro magnetic material with a high, well-defined Curie temperature in order to provide for induction heating up to the Curie temperature. The boundary layer of oxidic material is corrosion resistant and acts as a boundary layer. This makes the segregated particles at least substantially inert to the environment in reactors. In contrast, unprotected metal particles, viz. metal particles without a boundary layer, may oxidize, cause metal dust ing and/or alloy with other metallic particles present in a reactor unit. Such processes would destroy the catalytic performance, the induction performance and/or the reac tor unit. It should be noted that the material of the core comprising one or more ferro- magnetic elements is also denoted "ferromagnetic material". Moreover, the term "fer romagnetic sites" are meant to denote the ferromagnetic elements or material of the core. The core itself can have domains with higher ferromagnetism than other areas within the core. In an embodiment, the composition of the oxidic material and the ceramic material is substantially equal. Hereby, when the catalyst support material is impregnated with a catalytically active phase, the catalytically active phase can be distributed both within the oxidic material and within the ceramic material.
In an embodiment of the catalyst support material, the one or more ferromagnetic ele ments of the core has a Curie temperature of between 320°C and 1130°C. Advanta geously, the Curie temperature is above 650°C, more preferably above 800°C, such as at or above 900°C or even higher. In an embodiment, the first ceramic material is com- posed of a material that is chemically inert, at least at temperatures up to about
1100°C. Here, the term "inert" means that the material is not chemically reactive, viz. it does not react or only reacts very little with gasses flowing over the material.
In an embodiment, the core comprises one or more of the following elements: Co, Fe, Ni, or alloys thereof. These are all ferromagnetic above room temperature. Other ele ments, which might be present in the core, could be Cr, Al, Ti, Cu, among others. In an embodiment, the oxidic material comprises one or more of the following elements: Al, Y, Zr, Hf, La, Si, Ce, Mg, Cr, Co, Fe, Ni, O or combinations thereof. These elements oxi dize relatively easily, and in their oxidized form, they have significant resistance to dif- ferent reactor conditions. Preferably, the oxidic element comprises Al and O. Depend ing on the exact application of the catalyst support material, the choice of starting ma terials for preparing the catalyst support material should be tuned to match the struc ture and composition of the desired catalyst support material as well as the required heating performance and chemical stability.
In an embodiment, the ceramic material comprises one or more of the following ele ments: Al, Y, Zr, Hf, La, Si, Ce, Mg, O, or combinations thereof. The ceramic material e.g. comprises MgA C , AI2O3, CaA O^ ZrC>2, CeC>2, MgO, or SiC>2. In an embodiment, the oxidic material, and the ceramic material, respectively, has a first and second porosity, respectively, wherein the first porosity is smaller than the second porosity. The porosity of the catalyst support material ensures its suitability to be impregnated with catalytically active particles or elements, whilst the ferromag- netic properties provide the catalyst support material the ability to being inductively heated. The porosity of the catalyst support material is intrinsically connected to the surface area thereof. The porosity of the ceramic material is in the range from about 15% to about 60%; a preferred subinterval is porosity between about 20% to about 45%, for example between 30% and 40%. The porosity of the oxidic material is in the range from about 5% to about 50%.
An overall surface area of the catalyst support material of above about 1 m2/g is pref erable, e.g. between 5 m2/g and 50 m2/g or between 5 m2/g and 20 m2/g. A ferromagnetic and porous material with these parameters is suitable as catalyst sup port material for supporting a catalytically active phase so that a catalyst material com prising the ferromagnetic and porous catalyst support material impregnated with cata lytically active phase will be both ferromagnetic and catalytically active. The porosity of the catalyst support material ensures that an appropriate amount of a catalytically ac- tive phase may be impregnated onto the catalyst support material. Thereby, such a ferromagnetic and catalytically active material is suitable for inductive heating and for catalyzing endothermic reactions.
In an embodiment, the segregated particles have a diameter of less than 10 pm.
In an embodiment, the largest dimension of the catalyst support material is between 1 and 10 cm, preferably between 3 and 5 cm.
Typically, the surface area is between about 1 m2/g and 100 m2/g. According to another aspect of the invention, the catalyst material comprises a catalyst support material according to the invention and further comprises a catalytically active phase supported by the oxidic material and/or the ceramic material. In an embodiment, the catalytically active phase comprises Ni, Co, Ru, Rh, Pt, Pd, Fe,
Cu, Sn, Ir, or Ga, or a combination thereof.
According to another aspect, the invention relates to a method of preparing a catalyst support material according to the invention. The method comprises the following steps:
- providing particles of an alloy of one or more non-ferromagnetic elements and one or more ferromagnetic elements,
- annealing the alloy under oxidizing conditions at a high temperature for a time suffi cient for a boundary layer to form, thereby forming segregated particles,
- mixing the segregated particles with ceramic material,
- sintering the mixture of segregated particles and ceramic material together in an oxi dizing atmosphere.
The high temperature, under which the alloy is annealed, is preferably between 800°C and 1000°C, such as about 800°C, about 850°C, about 900°C, about 950°C or about 1000°C.
As noted above, the boundary layer is of the non-ferromagnetic material, whilst a core of ferromagnetic material is formed beneath the boundary layer. The oxidizing condi tions may be any appropriate oxidizing conditions where the one or more ferromag- netic element is unlikely to oxidize compared to the one or more non-ferromagnetic element, thus allowing the boundary layer to form. The oxidizing conditions may be mildly oxidating.
Non limiting examples of oxidizing atmospheres may be:
• Air
O2 lean air, e.g. 1% O2 in N2 • Steam and hydrogen mixtures, e.g. 5% H2O in H2 or 50% H2O in H2
• Reduced partial pressure steam and hydrogen mixtures, e.g. 0.1% H2O and 1% H2 in Ar
• C02 in inert gas, e.g. 5% CO2 in He.
The size of the core of the segregated particles, which is particularly relevant for the induction heating properties, as well as the thickness of the boundary layer, which is relevant for the protection of the core of the segregated particles, can be tuned by the choice of the initial size of the particles of an alloy of one or more non-ferromagnetic elements and one or more ferromagnetic elements and by the initial composition of the alloy.
An estimation of the hysteresis heating is given by the formula: P=f §BdH, where P denotes the heating power transferred to the material, B the magnetic flux density, dH the change in the magnetic field strength, and / the frequency of the alternating mag netic field. Thus, the heating power transferred to the material by hysteresis heating is the area of the hysteresis curve times the frequency of the alternating magnetic field. An estimation of the ohmic/eddy current heating is given by P=n/20-Bm 2-\2-o-f2, where P denotes the heating power transferred to the material, Bm is the magnetic flux den- sity induced in the material, 1 is a characteristic length of the material, s is the conduc tivity of the material and / is the frequency of the alternating magnetic field. Thus, the heating power transferred to the material by eddy current heating is proportional to the magnetic flux density squared as well as the frequency of the alternating magnetic field squared.
It has been determined that when the alloy has annealed to form segregated particles, the Curie temperature of the segregated particle is considerably higher than the Curie temperature of the particles of the untreated alloy of non-ferromagnetic and ferro- magnetic elements. Moreover, the area of the hysteresis curve of the segregated parti cle is considerably larger than the area of the hysteresis curve of the particles of the al loy of one or more non-ferromagnetic and one or more ferromagnetic elements used as starting material for the segregated particles.
In an embodiment, the alloy and annealing conditions are chosen so as to ensure that the one or more ferromagnetic elements is unlikely to oxidize compared to the one or more non-ferromagnetic elements. In an embodiment, the segregated particle formed has a core comprising the one or more ferromagnetic elements and a boundary layer comprising the one or more non ferromagnetic elements, where the size of the core and of the boundary layer is deter mined by the choice of particle size of the particles of the alloy and/or by the initial composition of the alloy. Preferably, the boundary layer is of an oxidic material.
In an embodiment, the ceramic material is impregnated with a catalytically active phase before mixing with the segregated particles,
In an embodiment, the method comprises the step of impregnating the catalyst sup- port material with a catalytically active phase.
In an embodiment, the method comprises the step of reducing the catalyst support material or catalyst material in a reducing atmosphere at elevated temperatures.
The close proximity between the catalytically active phase and the ferromagnetic ma- terial within the catalyst material enables efficient heating of the catalytically active phase by close proximity heat conduction from the ferromagnetic material. An im portant feature of the inductive heating process is thus that the energy is supplied in side the object itself, instead of being supplied from an external heat source via heat conduction, convection and radiation. Moreover, the hottest part of the reactor sys- tern will be within the housing or shell of the reactor system. Preferably, the electrical power supply and the catalyst material are dimensioned so that at least part of the cat alyst material reaches a temperature of 850-1100°C when the endothermic reaction is the steam reforming reaction, a temperature of 700-1200°C when the endothermic re action is the hydrogen cyanide synthesis, a temperature of 500-700°C when the endo- thermic reaction is dehydrogenation, a temperature of 200-300°C when the endother mic reaction is the methanol cracking, and a temperature of ca. 500°C when the endo thermic reaction is the ammonia cracking reaction. The surface area of the catalyst ma terial, the size of the segregated particles, the type, and structure of the ceramic mate rial, and the amount and composition of the catalytically active phase may be tailored to the specific endothermic reaction at the given operating conditions.
In this context, the term feed gas is meant to denote a gas having a suitable composi tion for the given endothermic reaction. When the endothermic reaction is steam me thane reforming this may be typically be hydrocarbons, methane, hydrogen, carbon monoxide, carbon dioxide, steam, and inerts as nitrogen and argon. When the endo thermic reaction is dehydrogenation it may be a hydrocarbon as propane or styrene together with inert and potentially hydrogen. When the endothermic reaction is hy drogen cyanide synthesis or a synthesis process for organic nitriles it may be higher hy drocarbons, ammonia, methane, nitrogen, hydrogen, oxygen, and/or inert. When the endothermic reaction is methanol cracking it may be methanol, steam, carbon monox ide, carbon dioxide, hydrogen, and inert. When the endothermic reaction is ammonia cracking it may be ammonia, hydrogen, nitrogen, and inert.
The catalyst material of the invention is useful for any endothermic reaction. In differ- ent embodiments, the catalyst material is suitable for the steam reforming reaction, the prereforming reaction, or the water gas shift reaction, the dehydrogenation reac tion, the methanol cracking reaction, the ammonia cracking reaction, or the hydrogen cyanide synthesis reaction. Herein, the term "steam reforming" is meant to denote a reforming reaction according to one or more of the following reactions:
CH4 + H2O CO + BH2 (i)
CH4 + 2H2O CO2 + 4H2 (ii)
CH4 + CO2 2CO + 2H2 (iii)
Reactions (i) and (ii) are steam methane reforming reactions, whilst reaction (iii) is the dry methane reforming reaction. For higher hydrocarbons, viz. CnHm, where n>2, m > 4, equation (i) is generalized as:
CnHm + n H2O <-> nCO + (n + m/2)H2 (iv)
where n>2, m > 4.
Typically, steam reforming is accompanied by the water gas shift reaction (v):
Figure imgf000013_0001
The term "steam methane reforming" is meant to cover the reactions (i) and (ii), the term "steam reforming" is meant to cover the reactions (i), (ii) and (iv), whilst the term "methanation" covers the reverse reaction of reaction (i). In most cases, all of these re- actions (i)-(v) are at, or close to, equilibrium at the outlet from the reactor system.
The term "prereforming" is often used to cover the catalytic conversion of higher hy drocarbons according to reaction (iv). Prereforming is typically accompanied by steam reforming and/or methanation (depending upon the gas composition and operating conditions) and the water gas shift reaction. Prereforming is often carried out in adia- batic reactors but may also take place in heated reactors.
The term "hydrogen cyanide synthesis" is meant to denote the following reactions:
2 CH4 + 2 NH3 + 3 02 <-> 2 HCN + 6 H20 (vi)
CH4 + NH3 HCN + 3H2 (vii)
The term "dehydrogenation" is meant to denote the following reactions:
R1-CH2-CH2-R2 <- RI-CH=CH-R2 (viii) Where Ri and R2 may be any appropriate group in a hydrocarbon molecule, such as -H, -CHs, -CH2, or -CH.
The term "methanol cracking" is meant to denote the following reactions:
CH3OH <-> CO + 2H2 (ix)
CH3OH + H20 CO2 + BH2 (X)
Typically, methanol cracking reaction is accompanied by the water gas shift reaction (v).
The term "ammonia cracking" is meant to denote the following reactions:
2NH3 N2 + 3H2 (xi)
In an embodiment, the endothermic reaction is dehydrogenation of hydrocarbons.
This reaction takes place according to reaction (viii). The catalyst material for the reac tion may be composed of a core with high content of Fe, an oxidic material with high content of Al, a ceramic material with high content of AI203, and catalytically active phase of Pt. The maximum temperature of the reactor may be between 500-700°C.
The pressure of the feed gas may be 2-5 bar.
In an embodiment, the endothermic reaction is cracking of methanol. This reaction takes place according to reaction (v), (ix), and (x). The catalyst material for the reaction may be composed of a core with high content of Ni, an oxidic material with high con tent of Al, a ceramic material with high content of AI203, and catalytically active phase of Cu. The maximum temperature of the reactor may be between 200-300°C. The pres sure of the feed gas may be 2-30 bar, preferably about 25 bar.
In an embodiment, the endothermic reaction is steam reforming of hydrocarbons. This reaction takes place according to reaction (i)-(v). The catalyst material for the reaction may be composed of a core with high content of Co, an oxidic material with high con tent of Al, a ceramic material with high content of MgA^Os, and catalytically active phase of Ni. Alternatively, the ceramic material may have high content of ZrC>2 or CaAhOs. In addition, the catalytically active phase may also be Ru, Rh, Ir, or combina- tions thereof. The maximum temperature of the reactor may be between 850-1300°C. The pressure of the feed gas may be 15-180 bar, preferably about 25 bar.
In an embodiment, the endothermic reaction is ammonia cracking. This reaction takes place according to reaction (xi). The catalyst material for the reaction may be com- posed of a core with high content of Fe, an oxidic material with high content of Al, a ceramic material with high content of AI2O3, and catalytically active phase of Fe or Ru. The maximum temperature of the reactor may be between 400-700°C. The pressure of the feed gas may be 2-30 bar, preferably about 25 bar. In an embodiment, the endothermic reaction is the hydrogen cyanide synthesis or a synthesis process for organic nitriles. This reaction takes place according to reaction (vi) and (vii). The catalyst material for the reaction may be composed of a core with high content of Co, an oxidic material with high content of Al, a ceramic material with high content of AI2O3, and catalytically active phase of Pt. Alternatively, the catalyti- cally active phase may be Co, or SnCo. The maximum temperature of the reactor may be between 700-1200°C. The pressure of the feed gas may be 2-30 bar, preferably about 5 bar.
In an embodiment, the endothermic reaction is aromatization of hydrocarbons. This is advantageously aromatization of higher hydrocarbons.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic drawing of a catalyst support material;
Figures 2 and 3 are SEM images of catalyst support material, and
Figure 4 is a graph of methane conversion rates for different power values. DETAILED DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic drawing of a catalyst support material 100. The catalyst support material comprises a number of segregated particles 10. Each of the segregated parti- cles 10 has a core 12 and a boundary layer 14. The core 12 is of ferromagnetic mate rial, i.e. comprises one or more ferromagnetic elements, whilst the boundary layer is of an oxidic material. The segregated particles 10 are embedded or partly embedded within a ceramic material 20. Figures 2 and 3 are SEM images of catalyst support material having a core of Co with traces of Al, a boundary layer of oxidic material, in the form of AI2O3, and a ceramic material of MgAhO^ The magnification of the SEM picture of figure 3 is about 50 times the magnification of the SEM picture of figure 2. In Figure 2, a piece of catalyst support material is shown with a plurality of segregated particles. The segregated particles are the lightest part of the SEM image. Since the oxidic material of the boundary layer and the ceramic material are similar materials and due to the magnification in figure 2 only being about 80, the boundary layer of the segregated particles are not easily discerni ble in figure 2. However, in figure 2 a single segregated particle has been enlarged and it can be seen that the segregated particle is embedded within a ceramic material, viz. the material surrounding the segregated particle, and that the segregated particle has a boundary layer and a core. In figure 2, the boundary layer of the segregated particle is almost black and of the same color as the ceramic material. The core comprises two different colors: a white and a light grey color. The white parts of the core correspond to areas of Co, whilst the light grey parts corresponds to areas containing both Co and Al. The given catalyst support material was produced from an initial alloy of CoAI.
Figure 4 is a graph of methane conversion rates for different power values. The meas urements are made on a catalyst material comprising a catalyst support material with a plurality of segregated particles and a ceramic material. The segregated particles have a core of Co79-AI21 and the ceramic material of MgAhO^ This catalyst material have been impregnated with Ni as the catalytically active phase. Tests have been made with this catalyst material and with three different flow rates of methane, viz. at 100 Nml/min, 150 Nml/min and 200 Nml/min methane, respectively, at a H2O/CH4 ratio of 2 with 5% cofeed of H2 and figure 4 shows the graphs from these tests. It is seen from figure 4, that the catalyst material is heated up to temperatures sufficient to carry out steam methane reforming, up to conversion rates of almost 95%. Figure 4 therefore shows that it is possible to carry out induction heated steam methane reforming when using the catalyst material of the invention with Co-AI as the ferromagnetic material of the cores of segregated particles.
While the invention has been illustrated by a description of various embodiments and while these embodiments have been described in detail, it is not the intention of the applicant to restrict or in any way limit the scope of the appended claims to such de tail. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative methods, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the spirit or scope of applicant's general inventive concept.

Claims

CLAIMS:
1. A catalyst support material comprising a plurality of segregated particles, wherein said segregated particles comprising a core and a boundary layer surrounding the core, said core comprising a ferromagnetic material and having a diameter of up to 500 pm, and said boundary layer being an oxidic material, wherein said catalyst support mate rial moreover comprises a ceramic material and wherein said segregated particles are at least partly embedded within said ceramic material.
2. The catalyst support material according to claim 1, wherein the ferromagnetic mate rial of said core has a Curie temperature of between 320 and 1130°C.
3. The catalyst support material according to claim 1 or 2, wherein said oxidic material is composed of a material that is chemically inert, at least at temperatures up to about 1100°C.
4. The catalyst support material according to any of the preceding claims, wherein the core comprises one or more of the following elements: Co, Fe, Ni, or alloys thereof.
5. The catalyst support material according to any of the preceding claims, wherein the oxidic material comprises one or more of the following elements: Al, Y, Zr, Hf, La, Si, Ce, Mg, Cr, Co, Fe, Ni, O, or combinations thereof.
6. The catalyst support material according to any of the preceding claims, wherein the ceramic material comprises one or more of the following elements: Al, Y, Zr, Hf, La, Si,
Ce, Mg, O, or combinations thereof.
7. The catalyst support material according to any of the preceding claims, wherein the ceramic material comprises MgA O^ AI2O3, CaA O^ ZrC>2, CeC>2, MgO, or SiC>2.
8. The catalyst support material according to any of the preceding claims, wherein the oxidic material and the ceramic material, respectively, has a first and second porosity, respectively, and wherein the first porosity is smaller than the second porosity.
9. The catalyst support material according to any of the preceding claims, wherein the segregated particles have a diameter of less than 10 pm.
10. The catalyst support material according to any of the preceding claims, wherein the largest dimension of the catalyst support material is between 1 and 10 cm, preferably between 3 and 5 cm.
11. The catalyst material comprising a catalyst support material according to claims 1 to 10, further comprising a catalytically active phase supported by said oxidic material and/or said ceramic material.
12. The catalyst material according to claim 11, wherein the catalytically active phase comprises Ni, Co, Ru, Rh, Pt, Pd, Fe, Cu, Sn, Ir, Ga, or a combination thereof.
13. A method of preparing a catalyst support material, said method comprising the fol- lowing steps:
- providing particles of an alloy of one or more non-ferromagnetic elements and one or more ferromagnetic elements,
- annealing said alloy under oxidizing conditions at a high temperature for a time suffi cient for a boundary layer to form, thereby forming segregated particles,
- mixing said segregated particles with ceramic material,
- sintering the mixture of segregated particles and ceramic material together in an oxi dizing atmosphere.
14. The method according to claim IB, wherein the alloy and annealing conditions are chosen so as to ensure that the one or more ferromagnetic elements is unlikely to oxi dize compared to the one or more non-ferromagnetic elements.
15. The method according to claim 13 or 14, wherein said segregated particle formed has a core comprising said one or more ferromagnetic elements and a boundary layer comprising said one or more non-ferromagnetic elements, where the size of the core and of the boundary layer is determined by the choice of particle size of the alloy parti cle and/or by the initial composition of said alloy.
16. The method according to any of the claims 13 to 15, wherein the boundary layer is of an oxidic material.
17. The method of preparing a catalyst support material according to any of the claims 13 to 16, wherein said ceramic material is impregnated with a catalytically active phase before mixing with said segregated particles.
18. The method of preparing a catalyst material according to any of the claims 13 to
17, said method comprising the step of impregnating said catalyst support material with a catalytically active phase.
19. The method of preparing a catalyst material according to any of the claims 13 to
18, said method comprising the step of reducing said catalyst support material or cata lyst material in a reducing atmosphere at elevated temperatures.
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