WO2019055220A1 - Modified trilobe and quadrilobe shaped catalyst extrudates - Google Patents

Modified trilobe and quadrilobe shaped catalyst extrudates Download PDF

Info

Publication number
WO2019055220A1
WO2019055220A1 PCT/US2018/048685 US2018048685W WO2019055220A1 WO 2019055220 A1 WO2019055220 A1 WO 2019055220A1 US 2018048685 W US2018048685 W US 2018048685W WO 2019055220 A1 WO2019055220 A1 WO 2019055220A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst material
mcm
zsm
particle
cross
Prior art date
Application number
PCT/US2018/048685
Other languages
French (fr)
Inventor
Wenyih Frank Lai
Paul Podsiadlo
Nicholas S. ROLLMAN
Kiara M. BENITEZ
Original Assignee
Exxonmobil Research And Engineering Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxonmobil Research And Engineering Company filed Critical Exxonmobil Research And Engineering Company
Publication of WO2019055220A1 publication Critical patent/WO2019055220A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/043—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/302—Basic shape of the elements
    • B01J2219/30296—Other shapes

Definitions

  • the application relates to shaped catalyst extrudates and methods of producing the same.
  • Fixed bed catalysts are usually formulated as extrudates having particular shapes, diameters, and lengths intended to optimize the catalyst performance for a given application. Extruded catalysts need to be further optimized for mechanical strength, active material loading, reactor packing density, and diffusional characteristics. Typical extrudates used commercially are shaped as cylinders, trilobes, twisted trilobes, or quadralobes (tetralobes). Catalysts with multilobal cross-sections have a higher surface-to-volume (or specific volume (S/V)) ratio than cylindrical extrudates of the same diameter. When used in a fixed bed unit, these multilobe- shaped catalyst particles help reduce diffusional resistance, create a more open bed, and reduce pressure drop. Maximizing S/V can be beneficial to diffusion-limited reactions.
  • a catalyst material comprising elongated particles having a novel shape having an expanded trilobe or expanded quadralobe cross-section.
  • the shapes of the catalyst particles are such that the surface to volume ratio of the particles exceeds the surface to volume ratio of a cylindrical particle of the same length and the same effective diameter by at least 10%.
  • each particle has a cross-section comprising a central triangular or rectangular portion having a part-circular lobe at each vertex, wherein the center of the part circle of each lobe and diameter of each lobe are such that adjacent lobes do not intersect.
  • An extrusion die having a plurality of openings through which a catalyst material paste can be extruded, each opening independently having a cross-section as described above is also disclosed, as well as methods for making particles or pieces of a catalyst material by extruding a catalyst material paste through such an extrusion die.
  • a method for making a catalyst material is also provided.
  • the method includes
  • Figures 1 A and IB show a first expanded trilobe design;
  • Figure 1 A shows the geometric elements from which the cross-section is constructed.
  • Figure IB shows the outline and resulting cross-section of the first expanded trilobe design.
  • Figures 2A and 2B show a second expanded trilobe design;
  • Figure 2A shows the geometric elements from which the cross-section is constructed.
  • Figure 2B shows the outline and resulting cross-section of the second expanded trilobe design.
  • Figures 3A and 3B show a traditional trilobe design;
  • Figure 3A shows the geometric elements from which the cross-section is constructed.
  • Figure 3B shows the outline and resulting cross-section of the traditional trilobe design.
  • Figures 4A and 4B show a traditional quadralobe design;
  • Figure 4A shows the geometric elements from which the cross-section is constructed.
  • Figure 4B shows the outline and resulting cross-section of the traditional quadralobe design.
  • Figure 5 shows both of the geometric elements from which the cross-section is constructed and resulting cross-section of the traditional cylindrical design.
  • Figure 6 is a photograph of an extrusion die having a plurality openings with an expanded trilobe cross-section.
  • Figures 7 A and 7B show an expanded quadralobe design;
  • Figure 7 A shows the geometric elements from which the cross-section is constructed.
  • Figure 7B shows the outline and resulting cross-section of the expanded quadralobe design.
  • Figure 8 shows a photograph of extruded MCM-41/V300 catalyst pieces prepared in Example 6.
  • a new design of extrusion die insert which enables production of mechanically strong extruded catalysts with at least 10% or at least 20% higher surface area to volume ratio (S/V) compared to traditional trilobes is disclosed.
  • Application of this new design to making catalyst materials can significantly enhance activity of fixed bed catalysts in variety of refining applications, e.g. hydrocracking, lubes aromatics saturation, and others.
  • Presently disclosed are "expanded trilobe" and "expanded quadralobe" extrudates which provide step-up S/V, e.g. at least 10% increase or at least a 20% increase, when compared to conventional trilobe extrusions (by e.g.
  • the expanded trilobe design was also optimized to not only provide increased specific volume but also good mechanical strength of the finished catalyst material.
  • Exemplary extrusions were performed with a range of active materials: MCM-41, or MCM-22, USY or ZSM-48 zeolite crystals, and different binders, e.g. VersalTM-300 or Pural NGTM.
  • MCM- 41 extrusions showed similar side crush strength as cylinders, but have about 50% higher surface/volume ratio.
  • FIG. 3A and 3B show cross-sectional diagrams of traditional trilobes
  • Figs. 4A and 4B traditional quadralobes
  • Fig. 5 cylinders
  • the specific surface areas can be calculated for different length-to-diameter ratios as well as different effective diameters of the extrudates.
  • the external surface area is the sum of the area of the two ends of the extrudate and the area of the side.
  • Tables 1-3 show summary results of calculations for 3 typical catalyst diameters. The calculations show the effect of changing the ratio of lobe diameter to the
  • the data in Tables 1-3 show that the first expanded trilobe design (“expanded trilobe 1") provides at least a 10% increase, or at least a 20% increase in S/V when compared to a traditional trilobe design, and even greater increase when compared to other geometries.
  • the expanded trilobe 1 design has been further demonstrated using a die insert based on the geometric design from Figure 1.
  • Figure 6 shows a photo of the die insert.
  • the expanded quadralobe is based on similar design principle as the expanded trilobes. Each apex of a square is located in the mid point between center of the circle and its periphery.
  • Figure 7 shows a representation of one such design and Table 4 shows summary results calculations for 1/16 inch effective diameter extrudates with a ratio of lobe diameter to effective diameter of 0.3.
  • the present disclosure describes a catalyst material (extrudate) comprising elongated shaped particles or pieces having an expanded trilobe or expanded quadralobe cross-sectional shape such that the surface to volume ratio of the particles exceeds the surface to volume ratio of a cylindrical particle or piece of the same length and the same effective diameter (i.e. diameter of the cylinder) by at least 10% or by at least 20%.
  • the increase can be as much as 30%, or 40% or even as much as 2-fold or 2.5-fold.
  • Tables 1-4 illustrate the range of improvement obtained by a variety of cross-section geometries disclosed herein and include comparison to a cylindrical, traditional trilobe and traditional quadralobe cross-sections.
  • the catalyst material can be one in which each particle or piece of the extrudate has a cross-section that comprises a central triangular or rectangular portion having a part-circular lobe at each vertex, and wherein the center of the part circle of each lobe and diameter of each lobe are such that adjacent lobes do not intersect.
  • the central rectangular portion can be a square portion.
  • the particle or piece of extruded catalyst material can be one in which the cross-section of each particle occupies the space of an expanded trilobe of a first design that is encompassed by the outer edges of three equidiameter outer circles each centered on a vertex of a equilateral triangle centered on the longitudinal axis of the particle and wherein the length of each side of the equilateral triangle is greater than the diameter of each circle, the cross-sectional area of the particle being composed of the area of the equilateral triangle and the area of each of the circles not including the sector overlapping the central triangle.
  • such a particle or piece of catalyst material can be one in which the effective diameter (D in Fig. 2A) of the elongated shaped particle is equal to the length of a side of the equilateral triangle plus the diameter of an outer circle and in which the lobe diameter (d in Fig. 2A) is equal to the diameter of the equidiameter outer circles and having a ratio of the lobe diameter to the effective diameter of from 0.1 to 0.4 or from 0.2 to 0.3.
  • the extruded particle or piece of catalyst material can be one having an expanded quadralobe cross-section comprising four protrusions each extending from and attached to a central position, wherein the central position is aligned along the longitudinal axis of the particle, the cross-section of the particle occupying the space encompassed by the outer edges of four equidiameter outer circles around a central square, each of the four outer circles being centered at a point (c in Fig. 7A) equidistant along the bisector of the central square (b in Fig.
  • Such a particle or piece of catalyst material (extrudate) having an expanded quadralobe cross-section can be one which the effective diameter (D in Fig. 7A) of the elongated shaped particle is equal to the diameter of a circle circumscribing the cross-section of the particle and in which the lobe diameter (d in Fig. 7A) is equal to the diameter of the equidiameter outer circles, the catalyst material having a ratio of the lobe diameter to the effective diameter of fromO. l to 0.4 or from 0.2 to 0.3.
  • the particle or piece of catalyst material can be one having a second of an expanded trilobe cross-section (“expanded trilobe 2") comprising three protrusions, extending from and attached to a central position, wherein the central position is aligned along the longitudinal axis of the particle, the cross- section of the particle occupying the space encompassed by the outer edges of three equidiameter outer circles, an effective circumference of the particle being the circumference of a circle (C in Fig.
  • a particle or piece of catalyst material having such a second expanded trilobe design can be one in which the effective diameter of the elongated shaped particle is equal to the length of a line (D in Fig. 1 A) drawn from the circumference of an outer circle, through the center of the outer circle and through the center of an adjacent outer circle to the circumference of the outer circle, such that the effective diameter of the elongated shaped particle is greater than the length of a side of the equilateral triangle, and in which the lobe diameter (d in Fig. 1 A) is equal to the diameter of the equidiameter outer circles, the catalyst material having a ratio of the lobe diameter to the effective diameter of from 0.1 to 0.4 or from 0.2 to 0.3.
  • the length of the elongated shaped particle can be from 1 to 10 times the effective diameter of the elongated shaped particle.
  • the catalyst material can be one in which an active catalyst material is a zeolite or MCM-41, or a mixture of any two or more of these (e.g. MCM-41 and a zeolite, or a mixture of any two or more zeolites).
  • the catalyst material can be one in which the amount of zeolite or MCM-41 is from 1-99% by weight of the catalyst material.
  • the proportions of each zeolite (and of MCM-41, if applicable) can be in any ratio.
  • the catalyst material can be one that further comprises at least one noble metal, at least one Group 6 metal, at least one Group 8-10 base metal, or a combination of any two or three of these metals.
  • Platinum and palladium, in group 10 are examples of noble metals.
  • Molybdenum and tungsten are examples of Group 6 metals.
  • Cobalt and Nickel are examples of Group 8-10 base metals.
  • the amount of the metal(s) can be from 1 - 10% by weight of the catalyst material.
  • the active material can be a zeolite ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, Beta, Mordenite, MCM-68, or a MCM-22 family material, or a mixture of two or more thereof.
  • a MCM-22 family material can be selected from the group consisting of MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ERB-1, EMM-10, EMM-10-P, EMM-12, EMM-13, UZM-8, UZM-8HS, ITQ-1, ITQ-2, ITQ-30, or a mixture of two or more thereof.
  • Any catalyst material presently described can further comprise a binder that is alumina, zirconia, titania, silica, ceria or a mixture of any two or more these binders.
  • Any catalyst material presently described can further comprise a dopant.
  • the dopant can be, for example, magnesia, phosphorous, lanthanum or a mixture of any two or more of these.
  • the amount of the dopant is that typically used in the art.
  • a catalyst material according to the present disclosure can be formed by a method comprising:
  • Calcining can be performed in an inert atmosphere, such as nitrogen, or in air.
  • Further processing can include additional steps, e.g. ion exchange, another calcination step, another incipient wetness metals impregnation, reduction steps.
  • the calcining step in making the catalyst material can be followed by one or more steam treatment and/or ion exchange steps and/or washing steps performed as is typical in the art.
  • Ammonium nitrate is an exemplary exchange salt.
  • the extrudate paste can be one comprising active catalyst material that is a zeolite or MCM-41.
  • the amount of zeolite or MCM-41 can be from 1-99% by weight of the catalyst material.
  • the extrudate paste can further comprise a binder that is alumina, zirconia, titania, silica, ceria or a mixture of any two or more of these binders.
  • the extrudate paste can further comprise a dopant, that can be magnesia or phosphorous.
  • the extrudate paste used in any of these methods can be one including one or more elemental precursors.
  • Such an elemental metal precursor can be an organic or inorganic salt of at least one noble metal, an organic or inorganic salt of at least one Group 6 metal, an organic or inorganic salt of at least one Group 8 to Group 10 metal, an organic or inorganic salt of at least one Group 8 to Group 10 non-noble metal, or a mixture of any two or three of these.
  • Platinum and palladium, in group 10 are examples of noble metals.
  • Molybdenum and tungsten are examples of Group 6 metals.
  • Cobalt and Nickel are examples of Group 8-10 base metals.
  • the elemental metal precursor can be added to extrudate paste in an amount that provides from 0.1-10% or 0.5 to 10%, or 0.2% to 5%, or 0.2 to 2%, 0.5-5%, or 0.2-2% by weight of each of the elemental metals desired in the calcined catalyst material.
  • the amount of each metal in the calcined catalyst material can be determined independently.
  • the total amount of metal in the calcined catalyst material can be in the range 0.01 - 25%, 0.1-20%, 0.1-10%, 0.1- 5%, 0.5-20%, 0.5-10%, 1-10%, 2-10%, 2-6% or 5-10%.
  • the extrudate paste used in any of these methods can be one in which the elemental metal precursor is an organic or inorganic salt of nickel,
  • molybdenum molybdenum, cobalt, tungsten, platinum or palladium, or a mixture of two or more of these.
  • the elemental metal precursor can added in an amount that provides an amount by weight of the elemental metal in the calcined catalyst material as described above.
  • the present disclosure also provides an extrusion die comprising a plurality of openings configured for forcing through a material to be extruded, each opening having an expanded trilobe cross-section encompassed by the outer edges of three equidiameter outer circles each centered on a vertex of a equilateral triangle centered on the longitudinal axis of the particle and wherein the length of each side of the equilateral triangle is greater than the diameter of each circle, the cross-sectional area of the particle being composed of the area of the equilateral triangle and the area of each of the circles not including the sector overlapping the central triangle;
  • the plurality of openings in the extrusion die can have an expanded trilobe cross-section comprising three protrusions, extending from and attached to a central position, wherein the central position is aligned along the longitudinal axis of the particle, the cross-section of the particle occupying the space encompassed by the outer edges of three equidiameter outer circles, an effective circumference of the particle being the circumference of a circle encompassing all three of the equidiameter outer circles and being centered on the longitudinal axis of the particle, the equidiameter outer circles being disposed all of the outer circles lie within the effective circumference of the particle and such that the vertices of an equilateral triangle are located at the point where the circumference of each outer circle meets the circle defining the effective circumference of the particle, twice the diameter of the equidiameter outer circles being less than the length of a side of the equilateral triangle, the cross-sectional area of the particle being composed of the area of the equilateral triangle and the
  • the plurality of openings in the extrusion die can have an expanded quadralobe cross-section comprising four protrusions each extending from and attached to a central position, wherein the central position is aligned along the longitudinal axis of the particle, the cross-section of the particle occupying the space encompassed by the outer edges of four equidiameter outer circles around a central square, each of the four outer circles being centered at a point equidistant along the bisector of the central square from the edge of the circle to the vertex of the square and the length of one side of the central square being greater than 1.5x the diameter of one of the outer circles, the cross-sectional area of the particle being composed of the area of the central square and the area of each of the circles not including the sector overlapping the central square.
  • the plurality of openings of the extrusion die can be independently any cross-section shape, in any ratio among them, so long as at least one has a cross-section shape as described above. In some instances all of the openings of the extrusion die will have a cross-section shape as described above.
  • the plurality of cross-section shapes can be all the same, or every cross- section shape can be different.
  • the extrusion die will be of a size typically used in the art of making extruded catalyst materials and will be made of materials usually used in the art to form such extrusion dies.
  • a catalyst material according to the present disclosure can be made by a method comprising mixing a binder, a crystal of an active catalyst material, and water to form an extrudable paste, and extruding the paste through a die as described above.
  • the mixing step can further include one or more elemental metal precursors as described above.
  • Example 1 Preparation of MCM-41/VersalTM-300 extrudates with 1/16" cylinder insert (Comparative 1) [0054] 65 parts (basis: calcined 538 °C) of small pore MCM-41 crystal were mixed with 35 parts of pseudoboehmite alumina of VersalTM-300 (basis: calcined 538 °C) in a muller. Sufficient water was added to produce an extrudable paste on a 1" extruder. The mix of calcined MCM-41, pseudoboehmite alumina, and water containing paste was extruded with 1/16" cylinder and dried in a hotpack oven at 121 °C overnight. The dried extrudate was calcined in air @ 500 °C to decompose and remove the organic template. Calcined extrudates show surface area of about 700 m 2 /g and crush strength of - 45 lbs/in.
  • the extrudate was washed with deionized water to remove residual nitrate ions prior to drying.
  • the ammonium exchanged extrudate was dried at 121 °C overnight and calcined in air at 538 °C.
  • H-formed catalyst showed surface area of - 500 m 2 /g and Alpha of 860.
  • the reaction started as soon as propylene was added and a constant pressure of 2170 KPa-a nitrogen blanketed the autoclave. The reaction was allowed to run for four hours and propylene was completely consumed during this period. Small samples of liquid were withdrawn from the autoclave at regular interval for analysis of propylene, benzene, cumene (IPB), diisopropylbenzene(s) (DIPB), and triisopropylbenzene(s) (TIPB), using gas chromatography. Catalyst performance was assessed by a kinetic activity rate parameter base on propylene and benzene conversion. Cumene selectivity was calculated from the weight ratio of DIPB/cumene (expressed as percentage). The calculation method was as referenced in WO 03/006160.
  • Example 9 Preparation of Pt/Pd (0.1/0.3 wt%) coated MCM-41/VersalTM-300 catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Catalysts (AREA)

Abstract

A catalyst material that is in the form of particles having an expanded trilobe or expanded quadralobe cross-sectional shape having a larger surface to volume ratio than previously known catalyst forms. Also disclosed are a die having a plurality of openings of expanded trilobe or expanded quadralobe cross-sectional shape and methods for making catalyst pieces by extruding a mixture of catalyst material through such a die.

Description

MODIFIED TRILOBE AND QUADRILOBE SHAPED CATALYST EXTRUDATES
FIELD
[0001] The application relates to shaped catalyst extrudates and methods of producing the same.
BACKGROUND
[0002] Fixed bed catalysts are usually formulated as extrudates having particular shapes, diameters, and lengths intended to optimize the catalyst performance for a given application. Extruded catalysts need to be further optimized for mechanical strength, active material loading, reactor packing density, and diffusional characteristics. Typical extrudates used commercially are shaped as cylinders, trilobes, twisted trilobes, or quadralobes (tetralobes). Catalysts with multilobal cross-sections have a higher surface-to-volume (or specific volume (S/V)) ratio than cylindrical extrudates of the same diameter. When used in a fixed bed unit, these multilobe- shaped catalyst particles help reduce diffusional resistance, create a more open bed, and reduce pressure drop. Maximizing S/V can be beneficial to diffusion-limited reactions.
SUMMARY
[0003] A catalyst material comprising elongated particles having a novel shape having an expanded trilobe or expanded quadralobe cross-section is disclosed. The shapes of the catalyst particles are such that the surface to volume ratio of the particles exceeds the surface to volume ratio of a cylindrical particle of the same length and the same effective diameter by at least 10%. Generally, each particle has a cross-section comprising a central triangular or rectangular portion having a part-circular lobe at each vertex, wherein the center of the part circle of each lobe and diameter of each lobe are such that adjacent lobes do not intersect.
[0004] An extrusion die having a plurality of openings through which a catalyst material paste can be extruded, each opening independently having a cross-section as described above is also disclosed, as well as methods for making particles or pieces of a catalyst material by extruding a catalyst material paste through such an extrusion die.
[0005] A method for making a catalyst material is also provided. The method includes
i) mixing a binder, a crystal of an active material that is a zeolite or MCM-41 or a mixture of any two of them, water and optionally one or more elemental metal precursors to form an extrudable paste;
iia) extruding the paste through a die having an expanded trilobe-shaped cross-section to form a green catalyst extrudate having an expanded trilobe-shaped cross-section, for example of a first expanded trilobe design disclosed above or a second expanded trilobe design as disclosed above, to form a green catalyst extrudate having an expanded trilobe cross-section; or iib) extruding the paste through a die having an expanded quadralobe-shaped cross- section to form a green catalyst extrudate having an expanded quadralobe-shaped cross-section; and
iii) calcining the extrudate to form a calcined extrudate catalyst material having an elongated shape and an expanded expanded trilobe-shaped cross-section or an expanded quadralobe-shaped cross-section.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] Figures 1 A and IB show a first expanded trilobe design; Figure 1 A shows the geometric elements from which the cross-section is constructed. Figure IB shows the outline and resulting cross-section of the first expanded trilobe design.
[0007] Figures 2A and 2B show a second expanded trilobe design; Figure 2A shows the geometric elements from which the cross-section is constructed. Figure 2B shows the outline and resulting cross-section of the second expanded trilobe design.
[0008] Figures 3A and 3B show a traditional trilobe design; Figure 3A shows the geometric elements from which the cross-section is constructed. Figure 3B shows the outline and resulting cross-section of the traditional trilobe design.
[0009] Figures 4A and 4B show a traditional quadralobe design; Figure 4A shows the geometric elements from which the cross-section is constructed. Figure 4B shows the outline and resulting cross-section of the traditional quadralobe design.
[0010] Figure 5 shows both of the geometric elements from which the cross-section is constructed and resulting cross-section of the traditional cylindrical design.
[0011] Figure 6 is a photograph of an extrusion die having a plurality openings with an expanded trilobe cross-section.
[0012] Figures 7 A and 7B show an expanded quadralobe design; Figure 7 A shows the geometric elements from which the cross-section is constructed. Figure 7B shows the outline and resulting cross-section of the expanded quadralobe design.
[0013] Figure 8 shows a photograph of extruded MCM-41/V300 catalyst pieces prepared in Example 6.
DETAILED DESCRIPTION OF THE INVENTION
[0014] A new design of extrusion die insert which enables production of mechanically strong extruded catalysts with at least 10% or at least 20% higher surface area to volume ratio (S/V) compared to traditional trilobes is disclosed. Application of this new design to making catalyst materials can significantly enhance activity of fixed bed catalysts in variety of refining applications, e.g. hydrocracking, lubes aromatics saturation, and others. [0015] Presently disclosed are "expanded trilobe" and "expanded quadralobe" extrudates which provide step-up S/V, e.g. at least 10% increase or at least a 20% increase, when compared to conventional trilobe extrusions (by e.g. at least 10% or 20%), cylinders (e.g. at least 10%, 20%, or at least 40% or at least 50%) or quadralobes (e.g. at least 10%, at least 20% or at least -25 or at least -30%). The expanded trilobe design was also optimized to not only provide increased specific volume but also good mechanical strength of the finished catalyst material.
Exemplary extrusions were performed with a range of active materials: MCM-41, or MCM-22, USY or ZSM-48 zeolite crystals, and different binders, e.g. Versal™-300 or Pural NG™. MCM- 41 extrusions showed similar side crush strength as cylinders, but have about 50% higher surface/volume ratio.
[0016] The design of the expanded trilobe is based on the cross-sectional depictions shown in Figures 1A and IB and Figures 2A and 2B. For comparison, Figures 3-5 also show cross- sectional diagrams of traditional trilobes (Figs. 3A and 3B), traditional quadralobes (Figs. 4A and 4B) and cylinders (Fig. 5). "D" in Fig. 3A, Fig. 4A and Fig. 5 is the effective diameter of the traditional trilobe cross-section, the traditional quadralobe cross-section and the cylinder cross- section, respectively.
[0017] Based on the geometric designs depicted in Figures 1-5, the specific surface areas can be calculated for different length-to-diameter ratios as well as different effective diameters of the extrudates. The external surface area is the sum of the area of the two ends of the extrudate and the area of the side. Tables 1-3 show summary results of calculations for 3 typical catalyst diameters. The calculations show the effect of changing the ratio of lobe diameter to the
extrudate diameter. Typical pieces of catalyst material have L/D = 2.0 or L/D = 2.5. The data in Tables 1-3 show that the first expanded trilobe design ("expanded trilobe 1") provides at least a 10% increase, or at least a 20% increase in S/V when compared to a traditional trilobe design, and even greater increase when compared to other geometries.
Table 1. Specific volumes comparison for 1/8 inch diameter extrudates.
S/V
D=
/8 in Cylinder Quadralobe Trilobe Expanded Trilobe 1 Expanded Trilobe 2
Lobe Lobe Lobe Lobe D/Extrudate D D/Extrudate D D/Extrudate D D/Extrudate D
L/D d/D = 0.3 d/D = 0.2 d/D = 0.3 d/D = 0.2
8 34 41 44 55 58 75 78
4 36 43 46 57 60 77 80 2.5 38 46 49 60 63 80 82
2 40 47 50 61 64 81 84
1 48 55 58 69 72 89 92
Table 2. Specific volumes comparison for 1/16 inch diameter extrudates.
S/V
D=
/16 in Cylinder Quadralobe Trilobe Expanded Trilobe 1 Expanded Trilobe 2
Lobe Lobe Lobe Lobe D/Extrudate D D/Extrudate D D/Extrudate D D/Extrudate D
L/D d/D = 0.3 d/D = 0.2 d/D = 0.3 d/D = 0.2
8 68 82 86 110 116 150 156
4 72 86 93 114 120 154 160
2.5 77 91 97 119 125 159 164
2 80 94 101 122 128 162 168
1 96 110 117 138 144 178 184
Table 3. Specific volumes comparison for 1/20 inch diameter extrudates.
S/V
D=
/20 in Cylinder Quadralobe Trilobe Expanded Trilobe 1 Expanded Trilobe 2
Lobe Lobe Lobe Lobe D/Extrudate D D/Extrudate D D/Extrudate D D/Extrudate D
L/D d/D = 0.3 d/D = 0.2 d/D = 0.3 d/D = 0.2
8 85 103 111 138 145 188 195
4 90 108 116 143 150 193 200
2.5 96 114 122 149 156 199 206
2 100 118 126 153 160 203 210
1 120 138 146 173 180 223 230
[0018] The expanded trilobe 1 design has been further demonstrated using a die insert based on the geometric design from Figure 1. Figure 6 shows a photo of the die insert. [0019] The expanded quadralobe is based on similar design principle as the expanded trilobes. Each apex of a square is located in the mid point between center of the circle and its periphery. Figure 7 shows a representation of one such design and Table 4 shows summary results calculations for 1/16 inch effective diameter extrudates with a ratio of lobe diameter to effective diameter of 0.3.
Table 4. Specific volumes comparison for 1/16 inch diameter extrudates with expanded quadralobe design.
Figure imgf000006_0001
[0020] The present disclosure describes a catalyst material (extrudate) comprising elongated shaped particles or pieces having an expanded trilobe or expanded quadralobe cross-sectional shape such that the surface to volume ratio of the particles exceeds the surface to volume ratio of a cylindrical particle or piece of the same length and the same effective diameter (i.e. diameter of the cylinder) by at least 10% or by at least 20%. The increase can be as much as 30%, or 40% or even as much as 2-fold or 2.5-fold. The data in Tables 1-4 illustrate the range of improvement obtained by a variety of cross-section geometries disclosed herein and include comparison to a cylindrical, traditional trilobe and traditional quadralobe cross-sections.
[0021] The catalyst material can be one in which each particle or piece of the extrudate has a cross-section that comprises a central triangular or rectangular portion having a part-circular lobe at each vertex, and wherein the center of the part circle of each lobe and diameter of each lobe are such that adjacent lobes do not intersect. The central rectangular portion can be a square portion.
[0022] Referring to Figs. 2A and 2B, the particle or piece of extruded catalyst material can be one in which the cross-section of each particle occupies the space of an expanded trilobe of a first design that is encompassed by the outer edges of three equidiameter outer circles each centered on a vertex of a equilateral triangle centered on the longitudinal axis of the particle and wherein the length of each side of the equilateral triangle is greater than the diameter of each circle, the cross-sectional area of the particle being composed of the area of the equilateral triangle and the area of each of the circles not including the sector overlapping the central triangle.
[0023] In these instances, such a particle or piece of catalyst material (extrudate) can be one in which the effective diameter (D in Fig. 2A) of the elongated shaped particle is equal to the length of a side of the equilateral triangle plus the diameter of an outer circle and in which the lobe diameter (d in Fig. 2A) is equal to the diameter of the equidiameter outer circles and having a ratio of the lobe diameter to the effective diameter of from 0.1 to 0.4 or from 0.2 to 0.3.
[0024] Alternatively, referring to Figs. 7A and 7B, the extruded particle or piece of catalyst material can be one having an expanded quadralobe cross-section comprising four protrusions each extending from and attached to a central position, wherein the central position is aligned along the longitudinal axis of the particle, the cross-section of the particle occupying the space encompassed by the outer edges of four equidiameter outer circles around a central square, each of the four outer circles being centered at a point (c in Fig. 7A) equidistant along the bisector of the central square (b in Fig. 7A) from the edge of the outer circle to the vertex of the square and the length of one side of the central square being greater than 1.5x the diameter of one of the outer circles (d in Fig. 7A), the cross-sectional area of the particle being composed of the area of the central square and the area of each of the circles not including the sector overlapping the central square.
[0025] Such a particle or piece of catalyst material (extrudate) having an expanded quadralobe cross-section can be one which the effective diameter (D in Fig. 7A) of the elongated shaped particle is equal to the diameter of a circle circumscribing the cross-section of the particle and in which the lobe diameter (d in Fig. 7A) is equal to the diameter of the equidiameter outer circles, the catalyst material having a ratio of the lobe diameter to the effective diameter of fromO. l to 0.4 or from 0.2 to 0.3.
[0026] In a third alternative, referring to Figs. 1 A and IB, the particle or piece of catalyst material (extrudate) can be one having a second of an expanded trilobe cross-section ("expanded trilobe 2") comprising three protrusions, extending from and attached to a central position, wherein the central position is aligned along the longitudinal axis of the particle, the cross- section of the particle occupying the space encompassed by the outer edges of three equidiameter outer circles, an effective circumference of the particle being the circumference of a circle (C in Fig. 1 A) encompassing all three of the equidiameter outer circles and being centered on the longitudinal axis of the particle, the equidiameter outer circles being disposed so that all of the outer circles lie within the effective circumference of the particle and such that the vertices of an equilateral triangle are located at the point where the circumference of each outer circle meets the circle defining the effective circumference of the particle, twice the diameter of the equidiameter outer circles being less than the length of a side of the equilateral triangle, the cross-sectional area of the particle being composed of the area of the equilateral triangle and the area of each of the circles not including the sector overlapping the central triangle.
[0027] A particle or piece of catalyst material having such a second expanded trilobe design can be one in which the effective diameter of the elongated shaped particle is equal to the length of a line (D in Fig. 1 A) drawn from the circumference of an outer circle, through the center of the outer circle and through the center of an adjacent outer circle to the circumference of the outer circle, such that the effective diameter of the elongated shaped particle is greater than the length of a side of the equilateral triangle, and in which the lobe diameter (d in Fig. 1 A) is equal to the diameter of the equidiameter outer circles, the catalyst material having a ratio of the lobe diameter to the effective diameter of from 0.1 to 0.4 or from 0.2 to 0.3.
[0028] In any of the above alternatives, the length of the elongated shaped particle can be from 1 to 10 times the effective diameter of the elongated shaped particle.
[0029] In any of the above alternatives, additionally or alternately, the catalyst material can be one in which an active catalyst material is a zeolite or MCM-41, or a mixture of any two or more of these (e.g. MCM-41 and a zeolite, or a mixture of any two or more zeolites).
[0030] Additionally or alternately, the catalyst material can be one in which the amount of zeolite or MCM-41 is from 1-99% by weight of the catalyst material. In the case of mixed catalysts, the proportions of each zeolite (and of MCM-41, if applicable) can be in any ratio.
[0031] Additionally or alternately, the catalyst material can be one that further comprises at least one noble metal, at least one Group 6 metal, at least one Group 8-10 base metal, or a combination of any two or three of these metals. Platinum and palladium, in group 10, are examples of noble metals. Molybdenum and tungsten are examples of Group 6 metals. Cobalt and Nickel are examples of Group 8-10 base metals.
[0032] In any of the catalyst materials disclosed, the amount of the metal(s) can be from 1 - 10% by weight of the catalyst material.
[0033] In any of the catalyst materials disclosed the active material can be a zeolite ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, Beta, Mordenite, MCM-68, or a MCM-22 family material, or a mixture of two or more thereof. A MCM-22 family material can be selected from the group consisting of MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ERB-1, EMM-10, EMM-10-P, EMM-12, EMM-13, UZM-8, UZM-8HS, ITQ-1, ITQ-2, ITQ-30, or a mixture of two or more thereof. [0034] Any catalyst material presently described can further comprise a binder that is alumina, zirconia, titania, silica, ceria or a mixture of any two or more these binders.
[0035] Any catalyst material presently described can further comprise a dopant. The dopant can be, for example, magnesia, phosphorous, lanthanum or a mixture of any two or more of these. The amount of the dopant is that typically used in the art.
[0036] A catalyst material according to the present disclosure can be formed by a method comprising:
i) mixing a binder, a crystal of an active material that is a zeolite or MCM-41 or a mixture of any two of them, water and optionally one or more elemental metal precursors to form an extrudable paste;
iia) extruding the paste through a die having an expanded trilobe-shaped cross-section to form a green catalyst extrudate having an expanded trilobe-shaped cross-section, for example of a first expanded trilobe design disclosed above or a second expanded trilobe design as disclosed above, to form a green catalyst extrudate having an expanded trilobe cross-section; or iib) extruding the paste through a die having an expanded quadralobe-shaped cross- section to form a green catalyst extrudate having an expanded quadralobe-shaped cross-section; and
[0037] calcining the extrudate to form a calcined extrudate catalyst material having an elongated shape and an expanded expanded trilobe-shaped cross-section or an expanded quadralobe-shaped cross-section.
[0038] Calcining can be performed in an inert atmosphere, such as nitrogen, or in air.
[0039] Further processing can include additional steps, e.g. ion exchange, another calcination step, another incipient wetness metals impregnation, reduction steps. For example, the calcining step in making the catalyst material can be followed by one or more steam treatment and/or ion exchange steps and/or washing steps performed as is typical in the art. Ammonium nitrate is an exemplary exchange salt.
[0040] In such methods for making an elongated particle or piece of catalyst material the extrudate paste can be one comprising active catalyst material that is a zeolite or MCM-41. In these methods, the amount of zeolite or MCM-41 can be from 1-99% by weight of the catalyst material.
[0041] In any of these methods, the extrudate paste can further comprise a binder that is alumina, zirconia, titania, silica, ceria or a mixture of any two or more of these binders.
[0042] In addition, the extrudate paste can further comprise a dopant, that can be magnesia or phosphorous. [0043] Additionally or alternatively, the extrudate paste used in any of these methods can be one including one or more elemental precursors. Such an elemental metal precursor can be an organic or inorganic salt of at least one noble metal, an organic or inorganic salt of at least one Group 6 metal, an organic or inorganic salt of at least one Group 8 to Group 10 metal, an organic or inorganic salt of at least one Group 8 to Group 10 non-noble metal, or a mixture of any two or three of these. Platinum and palladium, in group 10, are examples of noble metals. Molybdenum and tungsten are examples of Group 6 metals. Cobalt and Nickel are examples of Group 8-10 base metals.
[0044] The elemental metal precursor can be added to extrudate paste in an amount that provides from 0.1-10% or 0.5 to 10%, or 0.2% to 5%, or 0.2 to 2%, 0.5-5%, or 0.2-2% by weight of each of the elemental metals desired in the calcined catalyst material. The amount of each metal in the calcined catalyst material can be determined independently. The total amount of metal in the calcined catalyst material can be in the range 0.01 - 25%, 0.1-20%, 0.1-10%, 0.1- 5%, 0.5-20%, 0.5-10%, 1-10%, 2-10%, 2-6% or 5-10%.
[0045] Additionally or alternatively, the extrudate paste used in any of these methods can be one in which the elemental metal precursor is an organic or inorganic salt of nickel,
molybdenum, cobalt, tungsten, platinum or palladium, or a mixture of two or more of these.
[0046] In any of these instances, the elemental metal precursor can added in an amount that provides an amount by weight of the elemental metal in the calcined catalyst material as described above.
[0047] The present disclosure also provides an extrusion die comprising a plurality of openings configured for forcing through a material to be extruded, each opening having an expanded trilobe cross-section encompassed by the outer edges of three equidiameter outer circles each centered on a vertex of a equilateral triangle centered on the longitudinal axis of the particle and wherein the length of each side of the equilateral triangle is greater than the diameter of each circle, the cross-sectional area of the particle being composed of the area of the equilateral triangle and the area of each of the circles not including the sector overlapping the central triangle;
[0048] Alternatively the plurality of openings in the extrusion die can have an expanded trilobe cross-section comprising three protrusions, extending from and attached to a central position, wherein the central position is aligned along the longitudinal axis of the particle, the cross-section of the particle occupying the space encompassed by the outer edges of three equidiameter outer circles, an effective circumference of the particle being the circumference of a circle encompassing all three of the equidiameter outer circles and being centered on the longitudinal axis of the particle, the equidiameter outer circles being disposed all of the outer circles lie within the effective circumference of the particle and such that the vertices of an equilateral triangle are located at the point where the circumference of each outer circle meets the circle defining the effective circumference of the particle, twice the diameter of the equidiameter outer circles being less than the length of a side of the equilateral triangle, the cross-sectional area of the particle being composed of the area of the equilateral triangle and the area of each of the circles not including the sector overlapping the central triangle.
[0049] In a third alternative, the plurality of openings in the extrusion die can have an expanded quadralobe cross-section comprising four protrusions each extending from and attached to a central position, wherein the central position is aligned along the longitudinal axis of the particle, the cross-section of the particle occupying the space encompassed by the outer edges of four equidiameter outer circles around a central square, each of the four outer circles being centered at a point equidistant along the bisector of the central square from the edge of the circle to the vertex of the square and the length of one side of the central square being greater than 1.5x the diameter of one of the outer circles, the cross-sectional area of the particle being composed of the area of the central square and the area of each of the circles not including the sector overlapping the central square.
[0050] The plurality of openings of the extrusion die can be independently any cross-section shape, in any ratio among them, so long as at least one has a cross-section shape as described above. In some instances all of the openings of the extrusion die will have a cross-section shape as described above. The plurality of cross-section shapes can be all the same, or every cross- section shape can be different.
[0051] The extrusion die will be of a size typically used in the art of making extruded catalyst materials and will be made of materials usually used in the art to form such extrusion dies.
[0052] A catalyst material according to the present disclosure can be made by a method comprising mixing a binder, a crystal of an active catalyst material, and water to form an extrudable paste, and extruding the paste through a die as described above.
[0053] The mixing step can further include one or more elemental metal precursors as described above.
Examples
Example 1: Preparation of MCM-41/Versal™-300 extrudates with 1/16" cylinder insert (Comparative 1) [0054] 65 parts (basis: calcined 538 °C) of small pore MCM-41 crystal were mixed with 35 parts of pseudoboehmite alumina of Versal™-300 (basis: calcined 538 °C) in a muller. Sufficient water was added to produce an extrudable paste on a 1" extruder. The mix of calcined MCM-41, pseudoboehmite alumina, and water containing paste was extruded with 1/16" cylinder and dried in a hotpack oven at 121 °C overnight. The dried extrudate was calcined in air @ 500 °C to decompose and remove the organic template. Calcined extrudates show surface area of about 700 m2/g and crush strength of - 45 lbs/in.
Example 2: Preparation of MCM-41 /Vers al™-300 extrudates with 1/16" expanded trilobe insert
[0055] 65 parts (basis: calcined 538 °C) of small pore MCM-41 crystal were mixed with 35 parts of pseudoboehmite alumina of Versal™-300 (basis: calcined 538 °C) in a muller. Sufficient water was added to produce an extrudable paste on a 1" extruder. The mix of calcined MCM-41, pseudoboehmite alumina, and water-containing paste was extruded with 1/16" expanded trilobe inserts and dried in a hotpack oven at 121 °C overnight. The dried extrudate was calcined in air @ 500 °C to decompose and remove the organic template. Calcined extrudates have a surface area of ~ 750 m2/g and crush strength of 44 lbs/in. These are similar to the properties of the cylindrical catalyst pieces of Example 1 and with much higher specific surface area (S/V).
Example 3: Preparation of MCM-49/V-300(80/20) extrudates with 1/20" traditional quadralobe insert (Comparative 2)
[0056] 80 parts (basis: calcined 538 °C) of MCM-49 crystal with Si/A12 of - 19/1 synthesized from US Patent No. 4,954,325 were mixed with 20 parts alumina (basis: calcined 538 °C) in a muller. The mixture of 49, alumina, and water was extruded into 1/20" traditional quadrulobe pieces and then dried at 121 °C overnight. The dried extrudate was calcined in nitrogen @ 538 °C to decompose and remove the organic template. The N2 calcined extrudate was humidified with saturated air and exchanged with 1 N ammonium nitrate to remove sodium (spec: < 500 ppm Na). After ammonium nitrate exchange, the extrudate was washed with deionized water to remove residual nitrate ions prior to drying. The ammonium exchanged extrudate was dried at 121 °C overnight and calcined in air at 538 °C. H-formed catalyst showed typical surface area of - 500 m2/g and Alpha of > 600.
Example 4: Preparation of MCM-49/V-300(80/20) with 1/16" expanded trilobe insert
[0057] 80 parts (basis: calcined 538 °C) of MCM-49 crystal with Si/A12 of - 19/1 synthesized from US Patent No. 4,954,325 were mixed with 20 parts alumina (basis: calcined 538 °C) in a muller. The mixture of MCM-49, alumina, and water was extruded into a 1/16" expanded trilobe insert and then dried at 121 °C overnight. The dried extrudate was calcined in nitrogen @ 538 °C to decompose and remove the organic template. The N2 calcined extrudate was humidified with saturated air and exchanged with 1 N ammonium nitrate to remove sodium (spec: < 500 ppm Na). After ammonium nitrate exchange, the extrudate was washed with deionized water to remove residual nitrate ions prior to drying. The ammonium exchanged extrudate was dried at 121 °C overnight and calcined in air at 538 °C. H-formed catalyst showed surface area of - 500 m2/g and Alpha of 860.
Example 5: Preparation of MCM-49/V-300(80/20) with 1/20" expanded trilobe insert
[0058] 80 parts (basis: calcined 538 °C) of MCM-49 crystal with Si/A12 of - 19/1 synthesized from US Patent No. 4,954,325 were mixed with 20 parts alumina (basis: calcined 538 °C) in a muller. The mixture of MCM-49, alumina, and water was extruded into a 1/20" expanded trilobe insert and then dried at 121 °C overnight. The dried extrudate was calcined in nitrogen @ 538 °C to decompose and remove the organic template. The N2 calcined extrudate was humidified with saturated air and exchanged with 1 N ammonium nitrate to remove sodium (spec: < 500 ppm Na). After ammonium nitrate exchange, the extrudate was washed with deionized water to remove residual nitrate ions prior to drying. The ammonium exchanged extrudate was dried at 121 °C overnight and calcined in air at 538 °C. H-formed catalyst showed surface area of - 490 m2/g and Alpha of 850.
Examples 6, 7, and 8: CAP testing
[0059] Those catalysts prepared in Examples 3, 4, and 5 were tested for benzene alkylation with propylene in a 300 ml autoclave. The finished catalyst was transferred into a catalyst basket and then dried in an oven at 260° C. for about 16 hours. This catalyst basket was then transferred into a 300 ml autoclave quickly with minimum exposure to ambient atmosphere. The catalyst was then purged with dry nitrogen for 2 hours at 181° C inside the reactor to remove air and moisture from the reactor. One hundred fifty six grams of benzene was transferred to the reactor under nitrogen and equilibrated with the catalyst for 1 hour at 130° C. Twenty eight grams of propylene was transferred into reactor under 2170 KPa-a of nitrogen pressure. The reaction started as soon as propylene was added and a constant pressure of 2170 KPa-a nitrogen blanketed the autoclave. The reaction was allowed to run for four hours and propylene was completely consumed during this period. Small samples of liquid were withdrawn from the autoclave at regular interval for analysis of propylene, benzene, cumene (IPB), diisopropylbenzene(s) (DIPB), and triisopropylbenzene(s) (TIPB), using gas chromatography. Catalyst performance was assessed by a kinetic activity rate parameter base on propylene and benzene conversion. Cumene selectivity was calculated from the weight ratio of DIPB/cumene (expressed as percentage). The calculation method was as referenced in WO 03/006160.
[0060] The results are shown in the following Table 5. Catalysts having an expanded trilobe cross-section show higher CAP, than those having a traditional quadralobe cross-section consistent with their higher S/V ratio.
Table 5. CAP activity of exemplary catalysts
Catalyst Activity Selectivity DIPB/Cumene (%)
Example 3 - 280 17.5
Example 4 293/338 17.8
Example 5 364 17.0
Example 9: Preparation of Pt/Pd (0.1/0.3 wt%) coated MCM-41/Versal™-300 catalysts
[0061] 65 parts (basis: calcined 538 °C) of small pore MCM-41 crystal were mixed with 35 parts of pseudoboehmite alumina of Versal™-300 (basis: calcined 538 °C) and novel metal precursors (Platinum tetraamine nitrate and Palladium tetraamine nitrate solutions) in a muller. Sufficient water was added to produce an extrudable paste on a 1" extruder. The mix of calcined MCM-41, pseudoboehmite alumina, metal precursor, and water containing paste was extruded with 1/16" cylinder (3A) and Trilobe inserts(3B, Figure 9) and dried in a hotpack oven at 121 °C overnight. The dried extrudate was calcined in air @ 450 and 500 °C to decompose and remove the organic template.

Claims

CLAIMS;
1. A catalyst material comprising elongated shaped extrudates having an expanded trilobe or expanded quadralobe cross-sectional shape such that the external surface area to volume ratio of the extrudates exceeds the surface area to volume ratio of respectively, a traditional trilobe or a traditional quadralobe of the same length and the same effective diameter by at least 10%.
2. The catalyst material of claim 1, wherein each extrudate in cross-section comprises a central triangular or rectangular portion having a part-circular lobe at each vertex, and wherein the center of the part circle of each lobe and diameter of each lobe are such that adjacent lobes do not intersect.
3. The catalyst material of claim 1, wherein the cross-section of each extrudate occupies the space encompassed by the outer edges of three equidiameter outer circles each centered on a vertex of a equilateral triangle centered on the longitudinal axis of the particle and wherein the length of each side of the equilateral triangle is greater than the diameter of each circle, the cross- sectional area of the particle being composed of the area of the equilateral triangle and the area of each of the circles not including the sector overlapping the central triangle.
4. The catalyst material of claim 3, in which the effective diameter of the elongated shaped particle is equal to the length of a side of the equilateral triangle plus the diameter of an outer circle and in which the lobe diameter is equal to the diameter of the equidiameter outer circles and having a ratio of the lobe diameter to the effective diameter of from 0.1 to 0.4.
5. The catalyst material of claim 4, in which the length of the elongated shaped particle is from 1 to 10 times the effective diameter of the elongated shaped particle.
6. The catalyst material of claim 3, in which the catalyst material is formed by a method comprising:
mixing a binder, a crystal of an active material that is a zeolite or MCM-41 or a mixture of any two of them, water and one or more elemental metal precursors to form an extrudable paste;
extruding the paste through a die having an expanded trilobe-shaped cross-section to form a green catalyst extrudate having an expanded trilobe-shaped cross-section; and
calcining the extrudate to form a calcined extrudate catalyst material having an elongated shape and an expanded trilobe-shaped cross-section.
7. The catalyst material of claim 2, in which an active catalyst material is a zeolite or MCM- 41 or a mixture of any two of these.
8. The catalyst material of claim 7, in which the amount of zeolite or MCM-41 is from 1- 99% by weight of the catalyst material.
9. The catalyst material of claim 7, which further comprises at least one noble metal, at least one Group 6 metal, at least one Group 8-10 base metal, or a combination of any two or three of these metals.
10. The catalyst material of claim 9, in which the amount of the metal(s) is from 0.01 - 25% by weight of the catalyst material.
11. The catalyst material of claim 8, in which the active material is a zeolite ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, Beta, Mordenite, MCM-68, or a MCM-22 family material, or a mixture of two or more thereof.
12. The catalyst material of claim 11, in which the active material is a crystal of MCM-22 family material selected from the group consisting of MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ERB-1, EMM-10, EMM-10-P, EMM-12, EMM-13, UZM-8, UZM-8HS, ITQ-1, ITQ-2, ITQ-30, or a mixture of two or more thereof.
13. The catalyst material of claim 2, that further comprises a binder that is alumina, zirconia, titania, silica, ceria or a mixture of any two or more these binders.
14. The catalyst material of claim 13, in which the catalyst material further comprises a dopant.
15. The catalyst material of claim 14, in which the dopant is magnesia or phosphorous or lanthanum.
16. The catalyst material of claim 3, in which an active catalyst material is a zeolite or MCM- 41.
17. The catalyst material of claim 16, in which the amount of zeolite or MCM-41 is from 1- 99% by weight of the catalyst material.
18. The catalyst material of claim 17, which further comprises at least one noble metal, at least one Group 6 metal, at least one Group 8-10 base metal, or a combination of any two or three of these metals.
19. The catalyst material of claim 18, in which the amount of the metal(s) is from 0.01 - 25% by weight of the catalyst material.
20. The catalyst material of claim 17, in which the active material is a zeolite ZSM-5, ZSM- 11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, Beta, Mordenite, MCM-68, or a MCM-22 family material, or a mixture of two or more thereof.
21. The catalyst material of claim 10, in which the active material is a crystal of MCM-22 family material selected from the group consisting of MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ERB-1, EMM-10, EMM-10-P, EMM-12, EMM-13, UZM-8, UZM-8HS, ITQ-1, ITQ-2, ITQ-30, or a mixture of two or more thereof.
22. The catalyst material of claim 4, in which an active catalyst material is a zeolite or MCM- 41.
23. The catalyst material of claim 22, in which the amount of of zeolite or MCM-41 is from 1-99% by weight of the catalyst material.
24. The catalyst material of claim 23, which further comprises at least one noble metal, at least one Group 6 metal, at least one Group 8-10 base metal, or a combination of any two or three of these metals.
25. The catalyst material of claim 24, in which the amount of the metal(s) is from 0.01 - 25% by weight of the catalyst material.
26. The catalyst material of claim 23, in which the active material is a zeolite ZSM-5, ZSM- 11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, Beta, Mordenite, MCM-68, or a MCM-22 family material, or a mixture of two or more thereof.
27. The catalyst material of claim 26, in which the active material is a crystal of MCM-22 family material selected from the group consisting of MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ERB-1, EMM-10, EMM-10-P, EMM-12, EMM-13, UZM-8, UZM-8HS, ITQ-1, ITQ-2, ITQ-30, or a mixture of two or more thereof.
28. The catalyst material of claim 4, that further comprises a binder that is alumina, zirconia, titania, silica, ceria or a mixture of any two or more of these binders.
29. The catalyst material of claim 28, in which the catalyst material further comprises a dopant.
30. The catalyst material of claim 29, in which the dopant is magnesia or phosphorous or lanthanum.
31. The catalyst material of claim 6, in which the zeolite or MCM-41 is added to provide an amount from 1.0-99% by weight in the calcined catalyst material.
32. The catalyst material of claim 25, in which the active material is a zeolite ZSM-5, ZSM- 11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, Beta,
Mordenite, MCM-68, or a MCM-22 family material, or a mixture of two or more thereof.
33. The catalyst material of claim 32, in which the active material is a crystal of MCM-22 family material selected from the group consisting of MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ERB-1, EMM-10, EMM-10-P, EMM-12, EMM-13, UZM-8, UZM-8HS, ITQ-1, ITQ-2, ITQ-30, or a mixture of two or more thereof.
34. The catalyst material of claim 6, in which the binder is alumina, zirconia, titania, silica, ceria or a mixture of any two or more of these binders.
35. The catalyst material of claim 34, in which the extrudable paste further comprises a dopant.
36. The catalyst material of claim 35, in which the dopant is magnesia or phosphorous or lanthanum.
37. The catalyst material of claim 6, in which the elemental metal precursor is an organic or inorganic salt of at least one noble metal, an organic or inorganic salt of at least one Group 6 metal, an organic or inorganic salt of at least one Group 8 to Group 10 metal, an organic or inorganic salt of at least one Group 8 to Group 10 non-noble metal, or a mixture of any two or three of these.
38. The catalyst material of claim 37, in which the elemental metal precursor is added in an amount that provides from 0.01 -25% by weight of the elemental metal in the calcined catalyst material.
39. The catalyst material of claim 6, in which the elemental metal precursor is an organic or inorganic salt of nickel, molybdenum, cobalt, tungsten, platinum or palladium, or a mixture of two or more of these.
40. The catalyst material of claim 39, in which the elemental metal precursor is added in an amount that provides from 0.01 -25% by weight of the elemental metal in the calcined catalyst material.
41. The catalyst material of claim 1 , having an expanded quadralobe cross-section comprising four protrusions each extending from and attached to a central position, wherein the central position is aligned along the longitudinal axis of the particle, the cross-section of the particle occupying the space encompassed by the outer edges of four equidiameter outer circles around a central square, each of the four outer circles being centered at a point equidistant along the bisector of the central square from the edge of the circle to the vertex of the square and the length of one side of the central square being greater than 1.5x the diameter of one of the outer circles, the cross-sectional area of the particle being composed of the area of the central square and the area of each of the circles not including the sector overlapping the central square.
42. The catalyst material of claim 41, in which the effective diameter of the elongated shaped particle is equal to the diameter of a circle circumscribing the cross-section of the particle and in which the lobe diameter is equal to the diameter of the equidiameter outer circles, the catalyst material having a ratio of the lobe diameter to the effective diameter of fromO.1 to 0.4.
43. The catalyst material of claim 41 , in which the catalyst material is formed by a method comprising:
mixing a binder, a crystal of an active catalyst material that is a zeolite or MCM-41 or a mixture of any two of them, water and one or more elemental metals or elemental metal precursors to form an extrudable paste; extruding the paste through a die having an expanded quadralobe-shaped cross-section to form a green catalyst extrudate having an expanded quadralobe-shaped cross-section; and
calcining the extrudate to form a calcined extrudate catalyst material having an elongated shape and an expanded quadralobe-shaped cross-section.
44. The catalyst material of claim 43, in which the elemental metal precursor is an organic or inorganic salt of at least one noble metal, an organic or inorganic salt of at least one Group 6 metal, an organic or inorganic salt of at least one Group 8 to Group 10 metal, an organic or inorganic salt of at least one Group 8 to Group 10 non-noble metal, or a mixture of any two or three of these.
45. The catalyst material of claim 44, in which the elemental metal precursor is an organic or inorganic salt of nickel, molybdenum, cobalt, tungsten, platinum or palladium, or a mixture of two or more of these.
46. The catalyst material of claim 1 , having an expanded trilobe cross-section comprising three protrusions, extending from and attached to a central position, wherein the central position is aligned along the longitudinal axis of the particle, the cross-section of the particle occupying the space encompassed by the outer edges of three equidiameter outer circles, an effective circumference of the particle being the circumference of a circle encompassing all three of the equidiameter outer circles and being centered on the longitudinal axis of the particle, the equidiameter outer circles being disposed all of the outer circles lie within the effective circumference of the particle and such that the vertices of an equilateral triangle are located at the point where the circumference of each outer circle meets the circle defining the effective circumference of the particle, twice the diameter of the equidiameter outer circles being less than the length of a side of the equilateral triangle, the cross-sectional area of the particle being composed of the area of the equilateral triangle and the area of each of the circles not including the sector overlapping the central triangle.
47. The catalyst material of claim 46, in which the effective diameter of the elongated shaped particle is equal to the length of a line drawn from the circumference of an outer circle, through the center of the outer circle and through the center of an adjacent outer circle to the
circumference of the outer circle, such that the effective diameter of the elongated shaped particle is greater than the length of a side of the equilateral triangle, and in which the lobe diameter is equal to the diameter of the equidiameter outer circles, the catalyst material having a ratio of the lobe diameter to the effective diameter of fromO.1 to 0.4.
48. The catalyst material of claim 46, in which the catalyst material is formed by a method comprising: mixing a binder, a crystal of an active catalyst material that is a zeolite or MCM-41 or a mixture of them, water and one or more elemental metals or elemental metal precursors to form an extrudable paste;
extruding the paste through a die having an expanded trilobe-shaped cross-section to form a green catalyst extrudate having an expanded trilobe-shaped cross-section; and
calcining the extrudate to form a calcined extrudate catalyst material having an elongated shape and an expanded trilobe-shaped cross-section.
49. An extrusion die comprising a plurality of openings configured for forcing through a material to be extruded, each opening having
an expanded trilobe cross-section encompassed by the outer edges of three equidiameter outer circles each centered on a vertex of a equilateral triangle centered on the longitudinal axis of the particle and wherein the length of each side of the equilateral triangle is greater than the diameter of each circle, the cross-sectional area of the particle being composed of the area of the equilateral triangle and the area of each of the circles not including the sector overlapping the central triangle;
an expanded trilobe cross-section comprising three protrusions, extending from and attached to a central position, wherein the central position is aligned along the longitudinal axis of the particle, the cross-section of the particle occupying the space encompassed by the outer edges of three equidiameter outer circles, an effective circumference of the particle being the circumference of a circle encompassing all three of the equidiameter outer circles and being centered on the longitudinal axis of the particle, the equidiameter outer circles being disposed all of the outer circles lie within the effective circumference of the particle and such that the vertices of an equilateral triangle are located at the point where the circumference of each outer circle meets the circle defining the effective circumference of the particle, twice the diameter of the equidiameter outer circles being less than the length of a side of the equilateral triangle, the cross-sectional area of the particle being composed of the area of the equilateral triangle and the area of each of the circles not including the sector overlapping the central triangle; or
an expanded quadralobe cross-section comprising four protrusions each extending from and attached to a central position, wherein the central position is aligned along the longitudinal axis of the particle, the cross-section of the particle occupying the space encompassed by the outer edges of four equidiameter outer circles around a central square, each of the four outer circles being centered at a point equidistant along the bisector of the central square from the edge of the circle to the vertex of the square and the length of one side of the central square being greater than 1.5x the diameter of one of the outer circles, the cross-sectional area of the particle being composed of the area of the central square and the area of each of the circles not including the sector overlapping the central square.
PCT/US2018/048685 2017-09-15 2018-08-30 Modified trilobe and quadrilobe shaped catalyst extrudates WO2019055220A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762558898P 2017-09-15 2017-09-15
US62/558,898 2017-09-15

Publications (1)

Publication Number Publication Date
WO2019055220A1 true WO2019055220A1 (en) 2019-03-21

Family

ID=63684454

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2018/048685 WO2019055220A1 (en) 2017-09-15 2018-08-30 Modified trilobe and quadrilobe shaped catalyst extrudates

Country Status (1)

Country Link
WO (1) WO2019055220A1 (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10787400B2 (en) 2015-03-17 2020-09-29 Lummus Technology Llc Efficient oxidative coupling of methane processes and systems
US10787398B2 (en) 2012-12-07 2020-09-29 Lummus Technology Llc Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products
US10793490B2 (en) 2015-03-17 2020-10-06 Lummus Technology Llc Oxidative coupling of methane methods and systems
US10829424B2 (en) 2014-01-09 2020-11-10 Lummus Technology Llc Oxidative coupling of methane implementations for olefin production
US10836689B2 (en) 2017-07-07 2020-11-17 Lummus Technology Llc Systems and methods for the oxidative coupling of methane
US10865165B2 (en) 2015-06-16 2020-12-15 Lummus Technology Llc Ethylene-to-liquids systems and methods
US10870611B2 (en) 2016-04-13 2020-12-22 Lummus Technology Llc Oxidative coupling of methane for olefin production
US10894751B2 (en) 2014-01-08 2021-01-19 Lummus Technology Llc Ethylene-to-liquids systems and methods
US10927056B2 (en) 2013-11-27 2021-02-23 Lummus Technology Llc Reactors and systems for oxidative coupling of methane
US10960343B2 (en) 2016-12-19 2021-03-30 Lummus Technology Llc Methods and systems for performing chemical separations
US11001542B2 (en) 2017-05-23 2021-05-11 Lummus Technology Llc Integration of oxidative coupling of methane processes
US11001543B2 (en) 2015-10-16 2021-05-11 Lummus Technology Llc Separation methods and systems for oxidative coupling of methane
US11008265B2 (en) 2014-01-09 2021-05-18 Lummus Technology Llc Reactors and systems for oxidative coupling of methane
WO2021156351A1 (en) 2020-02-07 2021-08-12 Basf Se Star-shaped ceramic body for use as catalyst
US11186529B2 (en) 2015-04-01 2021-11-30 Lummus Technology Llc Advanced oxidative coupling of methane
US11242298B2 (en) 2012-07-09 2022-02-08 Lummus Technology Llc Natural gas processing and systems
US11254626B2 (en) 2012-01-13 2022-02-22 Lummus Technology Llc Process for separating hydrocarbon compounds
WO2023088940A1 (en) * 2021-11-17 2023-05-25 Basf Se Catalyst having a trilobal geometry for preparing polytetrahydrofuran

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3764565A (en) * 1970-03-09 1973-10-09 Standard Oil Co Catalyst for hydrocracking a resid hydrocarbon
US3966644A (en) * 1973-08-03 1976-06-29 American Cyanamid Company Shaped catalyst particles
US4441990A (en) * 1982-05-28 1984-04-10 Mobil Oil Corporation Hollow shaped catalytic extrudates
EP0220933A1 (en) * 1985-10-25 1987-05-06 Mobil Oil Corporation Quadrulobe-type shaped catalytic extrudates
US4954325A (en) 1986-07-29 1990-09-04 Mobil Oil Corp. Composition of synthetic porous crystalline material, its synthesis and use
WO2003006160A1 (en) 2001-07-11 2003-01-23 Exxonmobil Chemical Patents, Inc. Reactivation of aromatics alkylation catalysts
US20050130837A1 (en) * 2002-06-07 2005-06-16 Shell Oil Company Shaped catalyst particles for hydrocarbon synthesis
US20080262115A1 (en) * 2007-01-18 2008-10-23 Hans Peter Alexander Calis Catalyst, catalyst precursor, and catalyst carrier
US20110166403A1 (en) * 2007-02-09 2011-07-07 Clark Michael C Alkylaromatic Production Process
US20140162866A1 (en) * 2012-12-07 2014-06-12 Exxonmobil Research And Engineering Company Fiber reinforced zeolite extrudates with enhanced physical properties
CN106272906A (en) * 2016-09-13 2017-01-04 姚光纯 A kind of miniature catalyst carrier mould, the processing technology of this mould and the method utilizing this mould to prepare carrier

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3764565A (en) * 1970-03-09 1973-10-09 Standard Oil Co Catalyst for hydrocracking a resid hydrocarbon
US3966644A (en) * 1973-08-03 1976-06-29 American Cyanamid Company Shaped catalyst particles
US4441990A (en) * 1982-05-28 1984-04-10 Mobil Oil Corporation Hollow shaped catalytic extrudates
EP0220933A1 (en) * 1985-10-25 1987-05-06 Mobil Oil Corporation Quadrulobe-type shaped catalytic extrudates
US4954325A (en) 1986-07-29 1990-09-04 Mobil Oil Corp. Composition of synthetic porous crystalline material, its synthesis and use
WO2003006160A1 (en) 2001-07-11 2003-01-23 Exxonmobil Chemical Patents, Inc. Reactivation of aromatics alkylation catalysts
US20050130837A1 (en) * 2002-06-07 2005-06-16 Shell Oil Company Shaped catalyst particles for hydrocarbon synthesis
US20080262115A1 (en) * 2007-01-18 2008-10-23 Hans Peter Alexander Calis Catalyst, catalyst precursor, and catalyst carrier
US20110166403A1 (en) * 2007-02-09 2011-07-07 Clark Michael C Alkylaromatic Production Process
US20140162866A1 (en) * 2012-12-07 2014-06-12 Exxonmobil Research And Engineering Company Fiber reinforced zeolite extrudates with enhanced physical properties
CN106272906A (en) * 2016-09-13 2017-01-04 姚光纯 A kind of miniature catalyst carrier mould, the processing technology of this mould and the method utilizing this mould to prepare carrier

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11254626B2 (en) 2012-01-13 2022-02-22 Lummus Technology Llc Process for separating hydrocarbon compounds
US11242298B2 (en) 2012-07-09 2022-02-08 Lummus Technology Llc Natural gas processing and systems
US10787398B2 (en) 2012-12-07 2020-09-29 Lummus Technology Llc Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products
US11168038B2 (en) 2012-12-07 2021-11-09 Lummus Technology Llc Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products
US10927056B2 (en) 2013-11-27 2021-02-23 Lummus Technology Llc Reactors and systems for oxidative coupling of methane
US11407695B2 (en) 2013-11-27 2022-08-09 Lummus Technology Llc Reactors and systems for oxidative coupling of methane
US11254627B2 (en) 2014-01-08 2022-02-22 Lummus Technology Llc Ethylene-to-liquids systems and methods
US10894751B2 (en) 2014-01-08 2021-01-19 Lummus Technology Llc Ethylene-to-liquids systems and methods
US11008265B2 (en) 2014-01-09 2021-05-18 Lummus Technology Llc Reactors and systems for oxidative coupling of methane
US11208364B2 (en) 2014-01-09 2021-12-28 Lummus Technology Llc Oxidative coupling of methane implementations for olefin production
US10829424B2 (en) 2014-01-09 2020-11-10 Lummus Technology Llc Oxidative coupling of methane implementations for olefin production
US11542214B2 (en) 2015-03-17 2023-01-03 Lummus Technology Llc Oxidative coupling of methane methods and systems
US10793490B2 (en) 2015-03-17 2020-10-06 Lummus Technology Llc Oxidative coupling of methane methods and systems
US10787400B2 (en) 2015-03-17 2020-09-29 Lummus Technology Llc Efficient oxidative coupling of methane processes and systems
US11186529B2 (en) 2015-04-01 2021-11-30 Lummus Technology Llc Advanced oxidative coupling of methane
US10865165B2 (en) 2015-06-16 2020-12-15 Lummus Technology Llc Ethylene-to-liquids systems and methods
US11001543B2 (en) 2015-10-16 2021-05-11 Lummus Technology Llc Separation methods and systems for oxidative coupling of methane
US10870611B2 (en) 2016-04-13 2020-12-22 Lummus Technology Llc Oxidative coupling of methane for olefin production
US11505514B2 (en) 2016-04-13 2022-11-22 Lummus Technology Llc Oxidative coupling of methane for olefin production
US10960343B2 (en) 2016-12-19 2021-03-30 Lummus Technology Llc Methods and systems for performing chemical separations
US11001542B2 (en) 2017-05-23 2021-05-11 Lummus Technology Llc Integration of oxidative coupling of methane processes
US10836689B2 (en) 2017-07-07 2020-11-17 Lummus Technology Llc Systems and methods for the oxidative coupling of methane
WO2021156351A1 (en) 2020-02-07 2021-08-12 Basf Se Star-shaped ceramic body for use as catalyst
WO2023088940A1 (en) * 2021-11-17 2023-05-25 Basf Se Catalyst having a trilobal geometry for preparing polytetrahydrofuran

Similar Documents

Publication Publication Date Title
WO2019055220A1 (en) Modified trilobe and quadrilobe shaped catalyst extrudates
EP0220933A1 (en) Quadrulobe-type shaped catalytic extrudates
KR20020040821A (en) Method for preparing a low acidity refractory oxide-bound zeolite catalyst
CA2531079C (en) A process and catalyst for the selective hydrogenation of diolefins contained in an olefin containing stream and for the removal of arsenic therefrom and a method of making such catalyst
US9724680B2 (en) Fiber reinforced zeolite extrudates with enhanced physical properties
CN106715654B (en) Use the alkylation process for the catalyst for including the cerium-rich rare earth containing zeolite and hydrogenation metal
WO2009006087A2 (en) Solid phosphoric acid with controlled macroporosity
WO2015009409A2 (en) Process and catalyst for c9+ aromatics conversion
US9314779B2 (en) Method of making a catalyst and catalyst made thereby
CN101945704A (en) Production of shaped silica-rich bodies
CN103801388A (en) Aromatization catalyst and preparation method and application thereof
CN101293662A (en) Method for preparing gamma-aluminum oxide
CN112570016B (en) Anti-nitrogen aromatic hydrocarbon type hydrocracking catalyst and preparation method and application thereof
CN1353168A (en) Hydrorefining catalyst and its preparing process
KR20220091584A (en) Supported catalyst, manufacturing method thereof, and use thereof
CN114130420B (en) Benzene hydroalkylation catalyst and preparation method and application thereof
CN111094519A (en) Process for producing metal-containing catalyst
EP3898559B1 (en) Isomerisation process
CN1443737A (en) Catslyst for benzene and C9 and more than that arene transalkylation
CN1443736A (en) Benzene and C9 and more than that arene transalkylation method
WO2019055222A1 (en) Method for manufacturing higher performance catalysts, catalysts et method of hydrogenation of aromatic hydrocarbons
CN113546671B (en) Light gasoline cracking yield-increasing propylene catalyst containing ultra-macroporous silica gel, and preparation method and application thereof
CN111375450A (en) Alumina carrier and preparation method and application thereof
CN112742392B (en) Fischer-Tropsch synthesis catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method
RU2772462C1 (en) Catalyst for transalkylation of diisopropylbenzenes with benzene into isopropylbenzene and method for its preparation

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18778621

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18778621

Country of ref document: EP

Kind code of ref document: A1