Patent Application
20180185822
The following is directed generally to catalyst carriers, and more particularly to aluminate based catalyst carriers and methods of making the same.
Porous ceramic particles may be used in a wide variety of applications and, in particular, are uniquely suited to serve, for example, in the catalytic field as a catalysts, catalyst carriers or component of catalyst carriers. The production and use of thermally stable catalysts, catalyst carriers and components of catalyst carriers is desirable for their use in environmental applications as well as the chemical industry, often in fixed bed catalytic reactors. Aluminate based materials containing elements with various redox levels (i.e., Mn, Fe, etc.) are generally desirable for such catalyst based applications due to the material's thermal and reactivity characteristics. Accordingly, the industry continues to demand improved aluminate based porous ceramic particles having various desired chemical qualities, such as, known reactivity and high stability, in combination with desired physical qualities, such as, a set porosity and surface area and desired mechanical properties.
According to a first aspect, a catalyst carrier may include an aluminate based body and may have a specific surface area of not greater than about 20 m2/g. The aluminate based body may include a hexaaluminate phase.
According to yet another aspect, a method of forming a catalyst carrier may include providing an aluminate precursor mixture, forming the aluminate precursor mixture into a green carrier and heating the aluminate precursor mixture to form the catalyst carrier. The catalyst carrier may include a hexaaluminate phase and formation of the hexaaluminate phase may occur in-situ during heating of the aluminate precursor mixture.
According to still another aspect, a method of forming a catalyst carrier may include providing a porous alumina body, impregnating the porous alumina body with a solution or suspension of at least one aluminate forming component to form an impregnated porous alumina body and heating the impregnated porous alumina body to form the catalyst carrier. The catalyst carrier may include a hexaaluminate phase and formation of the hexaaluminate phase may occur in-situ during heating of the impregnated porous alumina body.
The present disclosure can be better understood, and its numerous features and advantages made apparent to those skilled in the art by referencing the accompanying drawings.
Skilled artisans appreciate that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help to improve understanding of embodiments of the invention.
The use of the same reference symbols in different drawings indicates similar or identical items.
The following description, in combination with the figures, is provided to assist in understanding the teachings disclosed herein. The following discussion will focus on specific implementations and embodiments of the teachings. This discussion is provided to assist in describing the teachings and should not be interpreted as a limitation on the scope or applicability of the teachings.
The term “averaged,” when referring to a value, is intended to mean an average, a geometric mean, or a median value. As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of features is not necessarily limited only to those features but can include other features not expressly listed or inherent to such process, method, article, or apparatus. As used herein, the phrase “consists essentially of” or “consisting essentially of” means that the subject that the phrase describes does not include any other components that substantially affect the property of the subject.
Further, unless expressly stated to the contrary, “or” refers to an inclusive-or and not to an exclusive-or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
The use of “a” or “an” is employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural, or vice versa, unless it is clear that it is meant otherwise.
Further, references to values stated in ranges include each and every value within that range. When the terms “about” or “approximately” precede a numerical value, such as when describing a numerical range, it is intended that the exact numerical value is also included. For example, a numerical range beginning at “about 25” is intended to also include a range that begins at exactly 25. Moreover, it will be appreciated that references to values stated as “at least about,” “greater than,” “less than,” or “not greater than” can include a range of any minimum or maximum value noted therein.
Referring initially to a first method of forming a catalyst carrier,
According to particular embodiments, the aluminate precursor mixture provided in step 102 may include particular materials. For example, the precursor mixture provided in step 102 may include boehmite, gamma alumina, or combinations thereof and at least one aluminate forming component. According to still other embodiments, the aluminate forming component may include a soluble salt or fine powder. According to still other embodiments, the aluminate forming component may include soluble salts or fine powders of calcium, strontium, a rare earth, or combinations thereof. According to yet other embodiments, the aluminate forming component may further include another dopant selected from the group of Mg, Ba, Mn, Fe, Co, Cu, Ni and Zn.
Referring to step 104, according to certain embodiments, forming the aluminate precursor mixture into a green carrier may include using any extrusion technique that is well known in the art. Moreover, according to yet other embodiments, the green carrier can be formed using any pressing technique that is well known in the art.
According to yet other embodiments, forming the aluminate precursor mixture into a green carrier may further include adding pore forming agents, such as, for example, known organic pore forming agents to the aluminate precursor mixture.
Referring to step 106, heating the aluminate precursor mixture, e.g., the green carrier formed from the aluminate precursor mixture, to form a catalyst carrier may include heating the green carrier at a sufficient temperature and for a sufficient amount of time to form a catalyst carrier that may include a hexaaluminate phase. According to still other embodiments, heating the aluminate precursor mixture, e.g., the green carrier formed from the aluminate precursor mixture, to form a catalyst carrier may include heating the green carrier such that formation of the hexaaluminate phase occurs in-situ during heating of the green carrier.
According to still other embodiments, heating the aluminate precursor mixture, e.g., the green carrier formed from the aluminate precursor mixture, to form a catalyst carrier may include any known heating technique.
According to certain embodiments, heating the green carrier to form a catalyst carrier may include heating the green carrier at a particular temperature. For example, the green carrier formed from the aluminate precursor mixture can be heated to a temperature of at least about 500° C., such as, at least about 750° C. or at least about 1000° C. or at least about 1250° C. or at least about 1350° C. or at least about 1400° C. According to still other embodiments, the green carrier formed from the aluminate precursor mixture can be heated to a temperature of not greater than about 1800° C., such as, not greater than about 1700° C. or not greater than about 1600° C. It will be appreciated that the green carrier formed from the aluminate precursor mixture can be heated to a temperature of any value between, and including, any of the minimum and maximum values noted above. It will be further appreciated that the green carrier formed from the aluminate precursor mixture can be heated to a temperature within a range between, and including, any of the minimum and maximum values noted above.
According to other embodiments, heating the green carrier to form a catalyst carrier may include holding the green carrier at a particular temperature as noted above for a particular number of minutes. For example, the green carrier formed from the aluminate precursor mixture may be held at any of the temperatures noted above for at least about 5 minutes, such as, at least about 10 minutes or at least about 20 minutes or at least about 30 minutes or at least about 60 minutes. According to still other embodiments, the green carrier formed from the aluminate precursor mixture may be held at any of the temperatures noted above for a time not greater than 600 minutes, such as, not greater than about 540 minutes or not greater than about 480 minutes or not greater than about 420 minutes or not greater than about 360 minutes or not greater than about 300 or not greater than about 300 minutes or not greater than about 240. It will be appreciated that the green carrier formed from the aluminate precursor mixture may be held at any of the temperatures noted above for a time of any value between, and including, any of the minimum and maximum values noted above. It will be further appreciated that the green carrier formed from the aluminate precursor mixture may be held at any of the temperatures noted above for a time within a range between, and including, any of the minimum and maximum values noted above.
Referring now to a second method of forming a catalyst carrier,
According to particular embodiments, the porous alumina body provided in step 202 may include a particular content of gamma alumina. For example, the porous alumina body may include a content of gamma alumina of at least about 70 vol. % of a total volume of the porous alumina body, such as, at least about 75 vol. % or at least about 80 vol. % or at least about 85 vol. % or at least about 90 vol. % or at least about 91 vol. % or at least about 92 vol. % or at least about 93 vol. % or at least about 94 vol. % or at least about 95 vol. % or at least about 96 vol. % or at least about 97 vol. % or at least about 98 vol. % or at least about 99 vol. %. It will be appreciated that the content of gamma alumina in the porous alumina body may be any value between, and including, any of values noted above. It will be further appreciated that content of gamma alumina in the porous alumina body may be within a range between, and including, any of the values noted above.
According to still other embodiments, the porous alumina body provided in step 202 may include a particular pore volume as measured by mercury porosimetry. For example, the porous alumina body may have a pore volume of at least 0.1 about milliliters per gram (ml/g), such as, at least about 0.2 ml/g or at least about 0.3 ml/g or at least about 0.4 mug or at least about 0.5 ml/g. According to still other embodiments, the porous alumina boy may have a pore volume of not greater than about 1.0 ml/g, such as, not greater than about 0.9 ml/g or not greater than about 0.8 ml/g or not greater than about 0.7 ml/g or not greater than about 0.6 ml/g. It will be appreciated that the porous alumina body may have a pore volume of any value between, and including, any of the minimum and maximum values noted above. It will be further appreciated that the porous alumina body may have a pore volume within a range between, and including, any of the minimum and maximum values noted above.
Referring now to step 204 and according to still other embodiments, impregnating the porous alumina body with a solution or suspension of at least one aluminate forming compound may include using a particular aluminate forming compound. For example, and as also noted in regards to the aluminate forming compound described above in conjunction with the catalyst forming process 100 of
According to still other embodiments, the porous alumina body may be impregnated with the solution or suspension of at least one aluminate forming compound by spraying the porous alumina body with the solution or suspension. According to yet other embodiments, the porous alumina body can be impregnated with the solution or suspension by immersing the porous alumina body in the solution or suspension for a predetermined amount of time. According to still alternative embodiments, the porous alumina body can be impregnated using any other known technique.
Referring now to step 206, heating the impregnated porous alumina body to form a catalyst carrier may include heating the impregnated porous alumina body at a sufficient temperature and for a sufficient amount of time to form a catalyst carrier may include a hexaaluminate phase. According to still other embodiments, heating the impregnated porous alumina body to form a catalyst carrier may include heating the impregnated porous alumina body at a sufficient temperature and for a sufficient amount of time such that formation of the hexaaluminate phase in the impregnated porous alumina body occurs in-situ during heating of the impregnated porous alumina body.
According to still other embodiments, heating the impregnated porous alumina body to form a catalyst carrier may include any heating technique that is well known in the art.
According to certain embodiments, heating the impregnated porous alumina body to form a catalyst carrier may include heating the impregnated porous alumina body at a particular temperature. For example, the impregnated porous alumina body can be heated to a temperature of at least about 500° C., such as, at least about 750° C. or at least about 1000° C. or at least about 1250° C. or at least about 1350° C. or at least about 1400° C. According to still other embodiments, the impregnated porous alumina body can be heated to a temperature of not greater than about 1800° C., such as, not greater than about 1700° C. or not greater than about 1600° C. It will be appreciated that the impregnated porous alumina body can be heated to a temperature of any value between, and including, any of the minimum and maximum values noted above. It will be further appreciated that the impregnated porous alumina body can be heated to a temperature within a range between, and including, any of the minimum and maximum values noted above.
According to certain embodiments, heating the impregnated porous alumina body to form a catalyst carrier may include heating the impregnated porous alumina body at a particular temperature as noted above for a particular number of minutes. For example, the impregnated porous alumina body may be held at any of temperatures noted above for at least about 5 minutes, such as, at least about 10 minutes or at least about 20 minutes or at least about 30 minutes or at least about 60 minutes. According to still other embodiments, the impregnated porous alumina body may be held at any of the temperatures noted above for a time not greater than 600 minutes, such as, not greater than about 540 minutes or not greater than about 480 minutes or not greater than about 420 minutes or not greater than about 360 minutes or not greater than about 300 or not greater than about 300 minutes or not greater than about 240. It will be appreciated that impregnated porous alumina body may be held at any of the temperatures noted above for a time of any value between, and including, any of the minimum and maximum values noted above. It will be further appreciated that impregnated porous alumina body may be held at any of the temperatures noted above for a time within a range between, and including, any of the minimum and maximum values noted above.
Referring now to a third method of forming a catalyst carrier,
Referring now to step 308, according to particular embodiments, drying the impregnated porous alumina body may occur before heating of the impregnated porous alumina body as shown in
According to certain embodiments, drying the impregnated porous alumina body, or the catalyst carrier formed from heating the impregnated porous alumina body may include drying the impregnated porous alumina body at a particular temperature as noted above for a particular number of minutes. For example, the impregnated porous alumina body may be dried at any of the temperatures noted above for at least about 5 minutes, such as, at least about 30 minutes or at least about 60 minutes or at least about 120 minutes or at least about 240 minutes. According to still other embodiments, the impregnated porous alumina body may be dried at any of the temperatures noted above for a time not greater than 600 minutes, such as, not greater than about 480 minutes or not greater than about 360 minutes. It will be appreciated that impregnated porous alumina body may be dried at any of the temperatures noted above for a time of any value between, and including, any of the minimum and maximum values noted above. It will be further appreciated that impregnated porous alumina body may be dried at any of the temperatures noted above for a time within a range between, and including, any of the minimum and maximum values noted above.
Referring now to the catalyst carrier formed according to embodiments described herein in regards to catalyst carrier forming processes 100, 200 or 300,
As shown in
As shown in
According to certain embodiments, the catalyst carrier 400 may includes an aluminate based body and the aluminate may include a hexaaluminate phase.
According to other embodiments, a catalyst carrier 400 may include a particular hexaaluminate phase content. For example, a catalyst carrier 400 may include a hexaaluminate phase content of at least about 70 vol. % of a total volume of the catalyst carrier, such as, at least about 75 vol. % or at least 80 vol. % or at least about 85 vol. % or at least about 90 vol. % or at least about 95 vol. %. It will be appreciated that a catalyst carrier 400 may include a hexaaluminate phase content of any value between, and including, any of the values noted above. It will be further appreciated that a catalyst carrier 400 may include a hexaaluminate phase content within a range between, and including, any of the values noted above.
According to yet other embodiments, a catalyst carrier 400 may include a particular content of spinel. For example, a catalyst carrier 400 may include a spinel content of not greater than about 30 vol. % of a total volume of the catalyst carrier, such as, not greater than about 25 vol. % or not greater than about 20 vol. % or not greater than about 15 vol. % or not greater than about 10 vol. % or not greater than about 5 vol. % or not greater than about 1 vol. %. It will be appreciated that the spinel content may be any value between, and including, any of values noted above. It will be further appreciated that the spinel content may be within a range between, and including, any of the values noted above.
According to still other embodiments, a catalyst carrier 400 may include a particular content of perovskite phase. For example, a catalyst carrier 400 may include a perovskite phase content of not greater than about 30 vol. % of a total volume of the catalyst carrier, such as, not greater than about 25 vol. % or not greater than about 20 vol. % or not greater than about 15 vol. % or not greater than about 10 vol. % or not greater than about 5 vol. % or not greater than about 1 vol. %. It will be appreciated that the perovskite phase content may be any value between, and including, any of values noted above. It will be further appreciated that the perovskite phase content may be within a range between, and including, any of the values noted above.
According to other embodiments, a catalyst carrier 400 may include a particular content of α-alumina phase. For example, a catalyst carrier 400 may include a α-alumina phase content of not greater than about 30 vol. % of a total volume of the catalyst carrier, such as, not greater than about 25 vol. % or not greater than about 20 vol. % or not greater than about 15 vol. % or not greater than about 10 vol. % or not greater than about 5 vol. % or not greater than about 1 vol. %. It will be appreciated that the α-alumina phase content may be any value between, and including, any of values noted above. It will be further appreciated that the α-alumina phase content may be within a range between, and including, any of the values noted above.
According to yet other embodiments, the hexaaluminate phase of the body 402 of the catalyst carrier 400 may include a magnetoplumbite phase, a ß-aluminate phase or combinations thereof.
According to still other embodiments, the hexaaluminate phase may include a particular content of magnetoplumbite phase. For example, the hexaaluminate phase may include a magnetoplumbite phase content of at least about 50 vol. % of a total volume of the hexaaluminate phase, such as, at least about 60 vol. % or at least about 70 vol. % or at least about 75 vol. % or at least about 80 vol. % or at least about 85 vol. % or at least about 90 vol. % or at least 95 vol. % or at least 99 vol. %. It will be appreciated that the hexaaluminate phase may include a magnetoplumbite phase content of any value between, and including, any of the values noted above. It will be further appreciated that the hexaaluminate phase may include a magnetoplumbite phase content within a range between, and including, any of the values noted above.
According to yet other embodiments, the hexaaluminate phase of the body 402 of the catalyst carrier 400 may have a particular formula. For example, the hexaaluminate phase of the body 402 of the catalyst carrier 400 may have a formula M1-xDyLnxAl12-xO19-x+y, MDyLnxAl12-xO19+y or MxDyLnAl11O18+x+y, where M is selected from the group consisting of Ca and Sr, where D is selected from the group consisting of Mg, Ba, Mn, Fe, Co, Cu, Ni, Zn, where Ln is selected from the group consisting of praseodymium, samarium, europium, holmium, lanthanum, gadolinium, dysprosium, neodymium, erbium, and mixtures thereof, where 1≥x≥0, and where 1≥y≥0.
According to still other embodiments, the hexaaluminate phase of the body 402 of the catalyst carrier 400 may have a formula of LaAl11O18, LaZnAl11O19, LaMgAl11O19, LaSrAl11O19, LaMnAl11O19, LaFeAl11O19, LaCuAl11O19, LaCoAl11O19, LaNiAl11O19, SrAl12O19, Sr0.5Mn0.5Al12O19, Sr0.5Fe0.5Al12O19, CaAl12O19, Ca0.5Mn0.5Al12O19, Ca0.5Fe0.5Al12O19 or any combination thereof.
According to yet other embodiments, the catalyst carrier 400 may have a particular combined content of any oxides of M elements and any oxides of Ln compounds Further, the catalyst carrier 400 can include a combined content of any oxides of M elements, any oxides of D elements and any oxides of Ln compounds, where M is selected from the group consisting of Ca and Sr, where D is selected from the group consisting of Mg, Ba, Mn, Fe, Co, Cu, Ni, Zn, and where Ln is selected from the group consisting of praseodymium, samarium, europium, holmium, lanthanum, gadolinium, dysprosium, neodymium, erbium, and mixtures thereof. For example, the combined content of any oxides of M elements, any oxides of D elements and any oxides of Ln compounds may be at least about 10 vol. % of a total volume of the catalyst carrier, such as, at least about 20 vol. % or at least about 30 vol. % or at least about 40 vol. % or at least about 50 vol. % According to still other embodiments, the combined content of any oxides of M elements, any oxides of D elements and any oxides of Ln compounds may be not greater than about 60 vol. % or not greater than about 58 vol. % or not greater than about 55 vol. % or not greater than about 53 vol. %. It will be appreciated the combined content of any oxides of M elements, any oxides of D elements and any oxides of Ln compounds may be any value between, and including, any of the minimum and maximum values noted above. It will be further appreciated that the combined content of any oxides of M elements and any oxides of Ln compounds may be within a range between, and including, any of the minimum and maximum values noted above.
According to yet other embodiments, the catalyst carrier 400 may include a particular Al2O3 content. For example, the catalyst carrier 400 may include a Al2O3 content of at least about 60 vol. % of a total volume of the catalyst carrier, such as, at least about 65 vol. % or at least about 70 vol. % or at least about 75 vol. % or at least about 80 vol. % or at least about 85 vol. %. According to still other embodiments, the catalyst carrier 400 may include a Al2O3 content of not greater than about 90 vol. % of a total volume of the catalyst carrier, such as, not greater than about 89 vol. % or not greater than about 88 vol. % or not greater than about 87 vol. % or not greater than about 86 vol. %. It will be appreciated the Al2O3 content may be any value between, and including, any of the minimum and maximum values noted above. It will be further appreciated that the Al2O3 content may be within a range between, and including, any of the minimum and maximum values noted above.
According to yet other embodiments, the catalyst carrier 400 may include a particular SiO2 content. For example, the SiO2 content may be not greater than about 5 vol. % of a total volume of the catalyst carrier, such as, not greater than about 4 vol. % or not greater than about 3 vol. % or not greater than about 2 vol. % or not greater than about 1 vol. % or not greater than about 0.5 vol. % or not grater than about 0.1 vol. %. It will be appreciated the SiO2 content may be any value between, and including, any of the values noted above. It will be further appreciated that the SiO2 content may be within a range between, and including, any of the values noted above.
According to yet other embodiments, the catalyst carrier 400 may include a particular alkali oxides content. For example, the alkali oxides content may be not greater than about 5 vol. % of a total volume of the catalyst carrier, such as, not greater than about 4 vol. % or not greater than about 3 vol. % or not greater than about 2 vol. % or not greater than about 1 vol. % or not greater than about 0.5 vol. % or not grater than about 0.1 vol. %. It will be appreciated the alkali oxides content may be any value between, and including, any of the values noted above. It will be further appreciated that the alkali oxides content may be within a range between, and including, any of the values noted above.
As further illustrated in
According to certain embodiments, the platelets may include a particular hexaaluminate phase content. For example, the platelets may include a hexaaluminate phase content of at least about 70 vol. % of a total volume of the catalyst carrier, such as, at least about 75 vol. % or at least 80 vol. % or at least about 85 vol. % or at least about 90 vol. % or at least about 95 vol. %. It will be appreciated that the platelets may include a hexaaluminate phase content of any value between, and including, any of the values noted above. It will be further appreciated that the platelets may include a hexaaluminate phase content within a range between, and including, any of the values noted above.
According to still other embodiments, the catalyst carrier 400 may include a particular platelet content. For example, the catalyst carrier 400 may include a platelet content of at least about 70 vol. % of a total volume of the catalyst carrier, such as, at least about 85 vol. % or at least about 90 vol. % or at least about 95 vol. % or at least about 99 vol. %. It will be appreciated that the platelet content may be any value between, and including, any of the values noted above. It will be further appreciated that the platelet content may be within a range between, and including, any of the values noted above.
According to yet other embodiments, the platelets may have a particular average diameter. For example, the average diameter of the platelets may be at least about 0.1 microns, such as, at least about 0.2 microns or at least about 0.3 microns or at least about 0.4 microns or at least about 0.5 microns or at least about 1 micron. According to still other embodiments, the platelets may have a diameter of not greater than about 10 microns, such as, not greater than about 9 microns or not greater than about 8 microns or not greater than about 7 microns or not greater than about 6 microns or not greater than about 5 microns. It will be appreciated that the platelets may have an average diameter of any value between, and including, any of the minimum and maximum values noted above. It will be further appreciated that the platelets may have an average diameter within a range between, and including, any of the minimum and maximum values noted above.
According to yet other embodiments, the platelets may have a particular average aspect ratio, where the aspect ratio is equal to the ratio between the diameter of the platelet and the thickness of the platelet. For example, the average aspect ratio of the platelets may be at least about 2, such as, at least about 3 or at least about 4 or at least about 5. According to still other embodiments, the platelets may have an average aspect ratio of not greater than about 20, such as, not greater than about 15 or not greater than about 14 or not greater than about 13 or not greater than about 12 or not greater than about 11 or not greater than about 10. It will be appreciated that the platelets may have an average aspect ratio of any value between, and including, any of the minimum and maximum values noted above. It will be further appreciated that the platelets may have an average aspect ratio within a range between, and including, any of the minimum and maximum values noted above.
According to yet other embodiments, the platelets may have a hexagonal shape.
According to still other embodiments, the catalyst carrier 400 may have a plurality of pores 422. According to still other embodiments, the catalyst carrier 400 may include a particular porosity content. For example, the catalyst carrier 400 may have a porosity content of at least about 20 vol. % of a total volume of the catalyst carrier, such as, at least about 30 vol. % or at least about 40 vol. % or at least about 50 vol. %. According to still other embodiments, the catalyst carrier 400 may have a porosity content of not greater than about 85 vol. %, such as, not greater than about 80 vol. % or not greater than about 70 vol. %. It will be appreciated that the catalyst carrier 400 may have a porosity content of any value between, and including, any of the minimum and maximum values noted above. It will be further appreciated that the catalyst carrier 400 may have a porosity content within a range between, and including, any of the minimum and maximum values noted above.
According to yet other embodiments, the catalyst carrier 400 may include a particular specific surface area as measured by Brunauer-Emmett-Teller (BET) N2 adsorption method. For example, the catalyst carrier 400 may have a specific surface area of not greater than about 20 meters squared per gram (m2/g), such as, not greater than about 18 m2/g or not greater than about 15 m2/g or not greater than about 13 or not greater than about 10 m2/g or not greater than about 8 or not greater than about 5 m2/g. According to still other embodiments, the catalyst carrier 400 may have a specific surface area of at least about 0.5 m2/g, such as, at least about 1 m2/g or at least about 2 m2/g or at least about 3 m2/g or at least about 4 m2/g or at least about 5 m2/g. It will be appreciated that the catalyst carrier 400 may have a specific surface area of any value between, and including, any of the minimum and maximum values noted above. It will be further appreciated that the catalyst carrier 400 may have a specific surface area within a range between, and including, any of the minimum and maximum values noted above.
According to still other embodiments, the catalyst carrier 400 may include a particular porosity volume as measured by mercury porosimetry according to ASTM D4284-12. For example, the catalyst carrier 400 may have a porosity volume of at least about 0.05 milliliters per gram (ml/g), such as, at least about 0.1 ml/g or as at least about 0.2 ml/g or at least about 0.3 ml/g or at least about 0.4 ml/g or at least about 0.5 ml/g. According to still other embodiments, the catalyst carrier 400 may have a pore volume of not greater than about 1.0 ml/g, such as, not greater than about 0.9 ml/g or not greater than about 0.8 ml/g or not greater than about 0.7 ml/g or not greater than about 0.6 ml/g. It will be appreciated that the catalyst carrier 400 may have a porosity volume of any value between, and including, any of the minimum and maximum values noted above. It will be further appreciated that the catalyst carrier 400 may have a porosity volume within a range between, and including, any of the minimum and maximum values noted above.
According to still other embodiments, the catalyst carrier 400 may include a particular crush strength as measured according to ASTM D4179-11 for single pellet crush strength. For example, the catalyst carrier 400 may have a crush strength of at least about 10 MPa, such as, at least about 20 MPa or as at least about 30 MPa or at least about 40 MPa or at least about 50 MPa or at least about 100 MPa. According to still other embodiments, the catalyst carrier 400 may have a crush strength of not greater than about 500 MPa, such as, not greater than about 400 MPa or not greater than about 300 MPa or not greater than about 200 MPa. It will be appreciated that the catalyst carrier 400 may have a crush strength of any value between, and including, any of the minimum and maximum values noted above. It will be further appreciated that the catalyst carrier 400 may have a crush strength within a range between, and including, any of the minimum and maximum values noted above.
Many different aspects and embodiments are possible. Some of those aspects and embodiments are described herein. After reading this specification, skilled artisans will appreciate that those aspects and embodiments are only illustrative and do not limit the scope of the present invention. Embodiments may be in accordance with any one or more of the embodiments as listed below.
A catalyst carrier comprising an aluminate based body, wherein the aluminate comprises a hexaaluminate phase and wherein the catalyst carrier has a specific surface area of not greater than about 20 m2/g.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises a hexaaluminate phase content of at least about 70 vol. % of a total volume of the catalyst carrier.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises a spinel content of not greater than about 30 vol. % of a total volume of the catalyst carrier or not greater than about 5 vol. % or not greater than about 1 vol. %.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises a perovskite phase content of not greater than about 30 vol. % of a total volume of the catalyst carrier or not greater than about 5 vol. % or not greater than about 1 vol. %.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises a α-alumina phase content of not greater than about 30 vol. % of a total volume of the catalyst carrier or not greater than about 5 vol. % or not greater than about 1 vol. %.
The catalyst carrier of embodiment 1, wherein the hexaaluminate phase comprises a magnetoplumbite phase, a ß-aluminate phase or combinations thereof.
The catalyst carrier of embodiment 1, wherein at least about 50 vol. % of the hexaaluminate phase is a magnetoplumbite phase.
The catalyst carrier of embodiment 1, wherein the hexaaluminate phase has a formula M1-xDyLnxAl12-xO19-x+y, MDyLnxAl12-xO19+y or MxDyLnAl11O18+x+y, where M is selected from the group consisting of Ca and Sr, where D is selected from the group consisting of Mg, Ba, Mn, Fe, Co, Cu, Ni, Zn, where Ln is selected from the group consisting of praseodymium, samarium, europium, holmium, lanthanum, gadolinium, dysprosium, neodymium, erbium, and mixtures thereof, where 1≥x≥0, and where 1≥y≥0.
The catalyst carrier of embodiment 1, wherein the hexaaluminate phase has a formula of LaAl11O18, LaZnAl11O19, LaMgAl11O19, LaSrAl11O19, LaMnAl11O19, LaFeAl11O19, LaCuAl11O19, LaCoAl11O19, LaNiAl11O19, SrAl12O19, Sr0.5Mn0.5Al12O19, Sr0.5Fe0.5Al12O19, CaAl2O19, Ca0.5Mn0.5Al12O19, Ca0.5Fe0.5Al12O19 and any combination thereof.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises a combined content of any oxides of M elements and any oxides of Ln compounds of at least about 10 vol. % of a total volume of the catalyst carrier, where M is selected from the group consisting of CA and Sr, where D is selected from the group consisting of Mg, Ba, Mn, Fe, Co, Cu, Ni, Zn, and where Ln is selected from the group consisting of praseodymium, samarium, europium, holmium, lanthanum, gadolinium, dysprosium, neodymium, erbium, and mixtures thereof.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises a combined content of any oxides of M elements and any oxides of Ln compounds of not greater than about 50 vol. % of a total volume of the catalyst carrier, where M is selected from the group consisting of CA and Sr, where D is selected from the group consisting of Mg, Ba, Mn, Fe, Co, Cu, Ni, Zn, and where Ln is selected from the group consisting of praseodymium, samarium, europium, holmium, lanthanum, gadolinium, dysprosium, neodymium, erbium, and mixtures thereof.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises an Al2O3 content of at least about 60 vol. % of a total volume of the catalyst carrier.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises an Al2O3 content of not greater than about 90 vol. % of a total volume of the catalyst carrier.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises a SiO2 content of not greater than about 5 vol. % of a total volume of the catalyst carrier or not greater than about 0.1 vol. % of a total volume of the catalyst carrier.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises a total content of alkali oxides of not greater than about 5 vol. % of a total volume of the catalyst carrier or not greater than about 0.1 vol. % of a total volume of the catalyst carrier.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises particles in the shape of platelets.
The catalyst carrier of embodiment 16, wherein the platelets comprise a hexaaluminate phase.
The catalyst carrier of embodiment 16, wherein catalyst carrier comprises a platelet content of at least about 70 vol. % of a total volume of the catalyst carrier or at least about 95 vol. % or at least about 99 vol. %.
The catalyst carrier of embodiment 16, wherein the platelets comprise an average diameter of at least about 0.1 microns and not greater than about 10 microns, preferably at least about 0.5 microns and not greater than about 5 microns.
The catalyst carrier of embodiment 16, wherein the platelets comprise an average aspect ratio of at least about 2 and not greater than about 20, preferably at least about 5 and not greater than about 10, where the aspect ratio is equal to the ratio between the diameter of the platelet and the thickness of the platelet.
The catalyst carrier of embodiment 16, wherein the platelets have a hexagonal shape.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises a porosity content of at least about 20 vol. % of a total volume of the catalyst carrier.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises an open porosity content of not greater than about 85 vol. % of a total volume of the catalyst carrier.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises a specific surface area of not greater than about 20 m2/g.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises a specific surface area of at least about 0.5 m2/g.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises a pore volume of at least about 0.05 ml/g.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises a pore volume of not greater than about 1 ml/g.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises a crush strength of at least about 10 MPa.
The catalyst carrier of embodiment 1, wherein the catalyst carrier comprises a crush strength of not greater than about 500 MPa.
The catalyst carrier of embodiment 1, wherein the catalyst carrier has an extruded pentaring shape, a spheronized ball shape, an extruded ring shape, a pressed ring shape, an extruded trilobes shape, an extruded pellets shape, an extruded quadrilobes shape.
A method of forming a catalyst carrier, wherein the method comprises: providing an aluminate precursor mixture; forming the aluminate precursor mixture into a green carrier; and heating the aluminate precursor mixture to form the catalyst carrier, wherein the catalyst carrier comprises a hexaaluminate phase, and wherein formation of the hexaaluminate phase occurs in-situ during heating of the aluminate precursor mixture.
The method of embodiment 31, wherein the aluminate precursor mixture comprises: boehmite, gamma alumina or combinations thereof; and at least one aluminate forming component.
A method of forming a catalyst carrier, wherein the method comprises: providing a porous alumina body; impregnating the porous alumina body with a solution or suspension of at least one aluminate forming component to form an impregnated porous alumina body; heating the impregnated porous alumina body to form the catalyst carrier, wherein the catalyst carrier comprises a hexaaluminate phase, and wherein formation of the hexaaluminate phase occurs in-situ during heating of the impregnated porous alumina body.
The method of embodiment 33, wherein the method further comprises drying the impregnated porous alumina body.
The method of embodiment 33, wherein the porous alumina body comprises gamma alumina.
The method of embodiment 33, wherein the porous alumina body comprises a pore volume of at least about 0.5 ml/g.
The method of embodiment 33, wherein the porous alumina body comprises a pore volume of not greater than about 1 ml/g.
The method of any one of embodiments 32 and 33, wherein the aluminate forming component comprises a soluble salt or fine powder.
The method of any one of embodiments 32 and 33, wherein the aluminate forming component comprises soluble salts or fine powders of calcium, strontium a rare earth or combinations thereof and, optionally, a dopant selected from the group of Mg, Ba, Mn, Fe, Co, Cu, Ni and Zn.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises a hexaaluminate phase content of at least about 70 vol. % of a total volume of the catalyst carrier.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises a spinel content of not greater than about 30 vol. % of a total volume of the catalyst carrier or not greater than about 5 vol. % or not greater than about 1 vol. %.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises a perovskite phase content of not greater than about 30 vol. % of a total volume of the catalyst carrier or not greater than about 5 vol. % or not greater than about 1 vol. %.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises a α-alumina phase content of not greater than about 30 vol. % of a total volume of the catalyst carrier or not greater than about 5 vol. % or not greater than about 1 vol. %.
The method of any one of embodiments 32 and 33, wherein the hexaaluminate phase comprises a magnetoplumbite phase, a 8-aluminate phase or combinations thereof.
The method of any one of embodiments 32 and 33, wherein at least about 50 vol. % of the hexaaluminate phase is a magnetoplumbite phase.
The method of any one of embodiments 32 and 33, wherein the hexaaluminate phase has a formula M1-xDyLnxAl12-xO19-x+y, MDyLnxAl12-xO19+y or MxDyLnAl11O18+x+y, where M is selected from the group consisting of Ca and Sr, where D is selected from the group consisting of Mg, Ba, Mn, Fe, Co, Cu, Ni, Zn, where Ln is selected from the group consisting of praseodymium, samarium, europium, holmium, lanthanum, gadolinium, dysprosium, neodymium, erbium, and mixtures thereof, where 1≥x≥0, and where 1≥y≥0.
The method of any one of embodiments 32 and 33, wherein the hexaaluminate phase has a formula of LaAl11O18, LaZnAl11O19, LaMgAl11O19, LaSrAl11O19, LaMnAl1O19, LaFeAl11O19, LaCuAl11O19, LaCoAl11O19, LaNiAl11O19, SrAl12O19, Sr0.5Mn0.5Al12O19, Sr0.5Fe0.5Al12O19, CaAl12O19, Ca0.5Mn0.5Al12O19, Ca0.5Fe0.5Al12O19 and any combination thereof.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises a combined content of any oxides of M elements and any oxides of Ln compounds of at least about 10 vol. % of a total volume of the catalyst carrier, where M is selected from the group consisting of CA and Sr, where D is selected from the group consisting of Mg, Ba, Mn, Fe, Co, Cu, Ni, Zn, and where Ln is selected from the group consisting of praseodymium, samarium, europium, holmium, lanthanum, gadolinium, dysprosium, neodymium, erbium, and mixtures thereof.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises a combined content of any oxides of M elements and any oxides of Ln compounds of not greater than about 50 vol. % of a total volume of the catalyst carrier, where M is selected from the group consisting of Ca and Sr, where D is selected from the group consisting of Mg, Ba, Mn, Fe, Co, Cu, Ni, Zn, and where Ln is selected from the group consisting of praseodymium, samarium, europium, holmium, lanthanum, gadolinium, dysprosium, neodymium, erbium, and mixtures thereof.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises an Al2O3 content of at least about 60 vol. % of a total volume of the catalyst carrier.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises an Al2O3 content of not greater than about 90 vol. % of a total volume of the catalyst carrier.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises a SiO2 content of not greater than about 5 vol. % of a total volume of the catalyst carrier or not greater than about 0.1 vol. % of a total volume of the catalyst carrier.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises a total content of alkali oxides of not greater than about 5 vol. % of a total volume of the catalyst carrier or not greater than about 0.1 vol. % of a total volume of the catalyst carrier.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises particles in the shape of platelets.
The method of embodiment 54, wherein the platelets comprise a hexaaluminate phase.
The method of embodiment 54, wherein catalyst carrier comprises a platelet content of at least about 70 vol. % of a total volume of the catalyst carrier or at least about 95 vol. % or at least about 99 vol. %.
The method of embodiment 54, wherein the platelets comprise an average diameter of at least about 0.1 microns and not greater than about 10 microns, preferably at least about 0.5 microns and not greater than about 5 microns.
The method of embodiment 54, wherein the platelets comprise an average aspect ratio of at least about 2 and not greater than about 20, preferably at least about 5 and not greater than about 10, where the aspect ratio is equal to the ratio between the diameter of the platelet and the thickness of the platelet.
The method of embodiment 54, wherein the platelets have a hexagonal shape.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises a porosity content of at least about 20 vol. % of a total volume of the catalyst carrier.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises an open porosity content of not greater than about 85 vol. % of a total volume of the catalyst carrier.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises a specific surface area of not greater than about 20 m2/g.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises a specific surface area of at least about 0.5 m2/g.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises a pore volume of at least about 0.05 ml/g.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises a pore volume of not greater than about 1 ml/g.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises a crush strength of at least about 10 MPa.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier comprises a crush strength of not greater than about 500 MPa.
The method of any one of embodiments 32 and 33, wherein the catalyst carrier has an extruded pentaring shape, a speronized ball shape, an extruded ring shape, a pressed ring shape, an extruded trilobes shape, an extruded pellets shape, an extruded quadrilobes shape.
Twelve sample aluminate materials S1-S12 were formed according to embodiments described herein. Each sample aluminate material S1-S12 was formed through impregnation of a porous alumina body with a solution or suspension of an aluminate forming component. The porous alumina body used to form each sample aluminate material S1-S12 was a gamma alumina porous body (i.e., an alumina body that includes at least 95 vol. % gamma alumina of a total volume of the porous body) and had a mass of 20 grams.
Table 1 below summarizes the impregnation solution or suspension composition, and heating hold time for each sample aluminate material S1-S12. Each sample was heated up at a heating pace of 500° C. per hour until they reached a temperature of 1500° C.
Physical properties for each sample aluminate material S1-S12 were observed, measured and recorded. Table 2 below summarizes the observed and measured physical properties for each sample, including specific surface area, pore volume, median pore diameter and phase presence within the sample.
As shown in Table 2 above, each sample aluminate material included a hexaaluminate phase formed in-situ during sintering of the sample.
In the foregoing, reference to specific embodiments and the connections of certain components is illustrative. It will be appreciated that reference to components as being coupled or connected is intended to disclose either direct connection between said components or indirect connection through one or more intervening components as will be appreciated to carry out the methods as discussed herein. As such, the above-disclosed subject matter is to be considered illustrative, and not restrictive, and the appended claims are intended to cover all such modifications, enhancements, and other embodiments, which fall within the true scope of the present invention. Moreover, not all of the activities described above in the general description or the examples are required, that a portion of a specific activity cannot be required, and that one or more further activities can be performed in addition to those described. Still further, the order in which activities are listed is not necessarily the order in which they are performed.
The disclosure is submitted with the understanding that it will not be used to limit the scope or meaning of the claims. In addition, in the foregoing disclosure, certain features that are, for clarity, described herein in the context of separate embodiments, can also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, can also be provided separately or in any subcombination. Still, inventive subject matter can be directed to less than all features of any of the disclosed embodiments.
Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that can cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.
Thus, to the maximum extent allowed by law, the scope of the present invention is to be determined by the broadest permissible interpretation of the following claims and their equivalents, and shall not be restricted or limited by the foregoing detailed description.
This application claims the benefit of U.S. Provisional Application No. 62/439,988 filed Dec. 29, 2016.
| Number | Date | Country | |
|---|---|---|---|
| 62439988 | Dec 2016 | US |
