US20150314274A1 - Metal oxide-stabilized zirconium oxide ceramic materials - Google Patents

Metal oxide-stabilized zirconium oxide ceramic materials Download PDF

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Publication number
US20150314274A1
US20150314274A1 US14/267,948 US201414267948A US2015314274A1 US 20150314274 A1 US20150314274 A1 US 20150314274A1 US 201414267948 A US201414267948 A US 201414267948A US 2015314274 A1 US2015314274 A1 US 2015314274A1
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Prior art keywords
oxide
ceramic material
zirconium oxide
metal oxide
range
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US14/267,948
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English (en)
Inventor
Wenqin Shen
Franz PETZOLD
Karen Libby
Wayne Turbeville
Matthew Purcell
Marc K. BORN
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Clariant Corp
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Clariant Corp
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Priority to US14/267,948 priority Critical patent/US20150314274A1/en
Assigned to CLARIANT CORPORATION reassignment CLARIANT CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BORN, MARC K., PURCELL, MATTHEW, TURBEVILLE, WAYNE, LIBBY, Karen, PETZOLD, Franz, SHEN, Wenqin
Priority to PCT/US2015/027701 priority patent/WO2015167978A1/en
Priority to CN201580023264.1A priority patent/CN106458768A/zh
Priority to EP15720888.5A priority patent/EP3137434A1/en
Publication of US20150314274A1 publication Critical patent/US20150314274A1/en
Priority to US15/463,911 priority patent/US10065910B2/en
Abandoned legal-status Critical Current

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Definitions

  • the present disclosure relates generally to ceramic materials, catalysts and methods for using them, such as methods for converting sugars, sugar alcohols, and glycerol to commercially-valuable chemicals and intermediates.
  • Zirconium oxide has been used as a support material in the field of chemical catalysis because of its high physical and chemical stability and moderately acidic surface properties. Nonetheless, the use of zirconium oxide as a supporting material for heterogeneous catalysts has limited application due to its relatively high cost and difficulties in forming certain shapes from. Furthermore, the zirconium oxide is especially susceptible to undergoing a phase transition that results in loss of surface area and pore volume. This reduces the strength and durability of the zirconium oxide. To counteract these phase transformation effects, stabilizing agents are used to inhibit phase transformation from the preferable tetragonal phase to the less desirable monoclinic phase. Previously used stabilizing agents include, for example, silicon oxide, yttrium oxide, lanthanum oxide, tungsten oxide, magnesium oxide, calcium oxide, cerium oxide, chromium oxide and manganese oxide.
  • chromium-containing materials especially chromium(VI) containing materials
  • chromium(VI) containing materials are less desirable because of their toxic, corrosive, and carcinogenic properties.
  • Manganese-containing materials are a viable alternative to chromium-containing materials, but their use as catalyst materials can often be limited to aqueous phase reactions with a product pH above 6. There remains a need environmentally nonhazardous materials that are also stable for aqueous phase applications at a wide range of pH values.
  • the present invention addresses the need for a chromium-free catalyst or catalyst support suitable for aqueous phase applications.
  • the disclosure provides a zirconium oxide-metal oxide material that is hydrothermally stable, suitable for use in aqueous phase reduction reactions, stable to low pH, and can be easily forming.
  • the metal oxides in the material can in certain aspects serve as a textural promoter to stabilize zirconium oxide in aqueous phase, and serve as a promoter to improve the catalytic performance, and even themselves serve as a catalytic active component.
  • the materials are especially useful in aqueous phase hydrogenation and hydrogenolysis processes.
  • the disclosure provides a ceramic material comprising zirconium oxide and metal oxide, wherein the zirconium oxide is present within the range of about 50 wt. % to about 99 wt. % of the material; the metal oxide is one or more of nickel oxide, copper oxide, cobalt oxide, iron oxide and zinc oxide; and the metal oxide is present within the range of about 1 wt. % to about 50 wt. % of the material.
  • the catalyst material can also be substantially free of any binder, extrusion aid or additional stabilizing agent.
  • the disclosure provides catalysts that include a ceramic material as described herein (e.g., as a catalyst support material), in combination with a catalytically active material.
  • the catalytically active material can be a catalytic metal, e.g., Ni, Cu, Co, Fe, Ru, Rh, Pd, Ag, Re, Os, Ir, Pt, Au, Sb, La, Bi or any combination thereof, such as NiCu, NiBi or NiSb.
  • a method for performing a catalytic reaction includes contacting one or more reactants with a ceramic material or catalyst as described herein, wherein at least one of the reactants is in the aqueous phase.
  • the reaction is conducted at a temperature within the range of 50° C. to 325° C., and a pressure within the range of about 10 bar to about 250 bar.
  • the disclosure provides methods for reduction reactions, such as the hydrogenation or hydrogenolysis of sugars, sugar alcohols and glycerol.
  • reduction reactions include contacting the sugar, sugar alcohol or glycerol with hydrogen and a ceramic material or catalyst as described herein.
  • certain such methods include a process for converting a sugar, sugar alcohol or glycerol into a polyol or an alcohol comprising a shorter carbon-chain backbone by contacting the sugar, sugar alcohol or glycerol with hydrogen and a ceramic material or catalyst as described herein.
  • the disclosure also provides methods to use the ceramic materials or catalysts for the hydrogenation of an organic acid, e.g., in an aqueous phase.
  • certain such methods include a process for reducing an organic acid (e.g., lactic acid, succinic acid, adipic acid, 3-hydroxypropionic acid, and/or a sugar acid) by contacting the organic acid with hydrogen and a ceramic material or catalyst as described herein.
  • an organic acid e.g., lactic acid, succinic acid, adipic acid, 3-hydroxypropionic acid, and/or a sugar acid
  • a ceramic material is made by extruding a zirconium oxide-metal oxide precursor in the absence of any binder, extrusion aid or additional stabilizing agent.
  • a ceramic material is made by extruding a catalytically active material-zirconium oxide-metal oxide precursor in the absence of any binder, extrusion aid, or additional stabilizing agent.
  • a catalyst is made by depositing one or more catalytically active materials on to a zirconium oxide-metal oxide support material. Depositing may include, but is not limited to, impregnation, incipient wetness methods, precipitation, and physical mixing.
  • FIG. 1 provides the XRD patterns of nickel oxide-stabilized zirconium oxide ceramic materials containing 6.6 wt. %, 15 wt. % and 18 wt. % nickel (wt. % calculated as metallic Ni).
  • XRD was performed after calcination at 450° C. for 3 h.
  • the XRD patterns demonstrate that the crystalline content of the zirconium oxide is predominantly in a tetragonal phase. Peaks corresponding to NiO are marked with asterisks.
  • FIG. 2 provides the XRD patterns of copper oxide-stabilized zirconium oxide materials containing 16 wt. %, 23 wt. %, 28 wt. % and 32 wt. % copper (wt. % calculated as metallic Cu).
  • XRD was performed after calcination at 450° C. for 3 h.
  • the XRD patterns demonstrate that the crystalline content of the zirconium oxide is predominantly in an amorphous phase. Peaks corresponding to CuO are marked with asterisks.
  • FIG. 3 provides the XRD patterns of copper oxide-stabilized zirconium oxide materials containing 6.5 wt. % and 7.5 wt. % copper (wt. % calculated as metallic Cu). XRD was performed after calcination at 550° C. for 3 h. The XRD patterns demonstrate that the crystalline content of the zirconium oxide is predominantly in a stabilized tetragonal phase. No CuO is observed.
  • FIG. 4 provides XRD patterns of cobalt oxide-stabilized zirconium oxide materials containing 9.9 wt. % cobalt (wt. % calculated as metallic Co).
  • XRD was performed after calcination at 450 and 600° C. for 3 h.
  • the XRD patterns demonstrate that the crystalline content of the zirconium oxide is predominantly in a fully stabilized tetragonal phase. Peaks corresponding to Co 3 O 4 are marked with asterisks.
  • FIG. 5 provides the XRD pattern of an iron oxide-stabilized zirconium oxide material containing 9.9 wt. % iron (wt. % calculated as metallic Fe). XRD was performed after calcination at 600° C. for 3 h. The XRD patterns demonstrate that the crystalline content of the zirconium oxide is predominantly in a fully stabilized tetragonal phase.
  • FIG. 6 provides the XRD patterns of zinc oxide-stabilized zirconium oxide materials containing 6 wt. % and 11 wt. % zinc (wt. % calculated as metallic Zn). XRD was performed after calcination at 450° C. and 550° C. for 3 h. All materials show a fully stabilized tetragonal phase as the crystalline content of the zirconium oxide. Zinc oxide was not observed.
  • FIG. 7 provides the XRD pattern of a ternary phase zirconium oxide material containing 10 wt. % nickel and 10 wt. % lanthanum (wt. % calculated as metallic Ni and La, respectively).
  • XRD was performed after calcination at 600° C. for 3 h.
  • the XRD patterns demonstrate that the crystalline content of the zirconium oxide is predominantly in a fully stabilized tetragonal phase.
  • FIG. 8 provides the XRD patterns of a conventional zirconium oxide material.
  • XRD was performed after calcination at 450° C. and 550° C. for 3 h.
  • the XRD patterns demonstrate that the zirconium oxide is predominantly in a tetragonal phase when calcined at 450° C. and a monoclinic mixture when calcined at 550° C.
  • Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
  • contacting includes the physical contact of at least one substance to another substance.
  • weight percent (weight %, also as wt %) of a component is based on the total weight of the formulation or composition in which the component is included (e.g., on the total amount of the active material). All mol % values are based on the moles of metal atoms.
  • the methods and materials described herein can be configured by the person of ordinary skill in the art to meet the desired need.
  • the disclosed materials, methods, and apparati provide improvements in supports or carriers utilized in catalysis, particularly in aqueous phase hydrogenolysis and hydrogenation.
  • the materials are less environmentally hazardous than Cr-based materials, hydrothermally stable, suitable for use in continuous aqueous phase hydrogenolysis and hydrogenation, and can be easily extruded in the absence of any binder and/or extrusion aid.
  • One embodiment of the invention is a ceramic material including zirconium oxide (e.g., ZrO 2 ) and one or more metal oxides.
  • the zirconium oxide is present in the ceramic material in an amount within the range of about 50 wt. % to about 99 wt. %.
  • the metal oxide in the ceramic material is present in an amount within the range of about 1 wt. % to about 50 wt. %.
  • the metal oxide is one or more of nickel oxide (wt. % calculated as metallic Ni); copper oxide (wt. % calculated as metallic Cu); cobalt oxide (wt. % calculated as metallic Co); iron oxide (wt. % calculated as metallic Fe); and zinc oxide (wt. % calculated as metallic Zn).
  • the zirconium oxide and the metal oxide are desirably substantially present together in the same phase of the material (e.g., as a mixed oxide MZrO x ).
  • the metal oxide is present together in the same phase of the material as the zirconium oxide.
  • the ceramic materials described herein can be useful in the field of catalysis.
  • the ceramic materials described herein can be used as catalyst support materials, on which catalyst metals or metal compounds can be disposed.
  • the ceramic materials described herein can be used themselves as catalysts, either in their oxide form, or upon activation by reduction of part of the metal oxide to the corresponding metal.
  • the metal oxide is present in an amount (i.e., calculated on the metallic basis) within the range from about 1 wt. % to about 20 wt. %, or about 1 wt. % to about 15 wt. %, or about 1 wt. % to about 10 wt. %, or about 1 wt. % to about 8 wt. %, or about 1 wt. % to about 7 wt. %, or about 3 wt. % to about 15 wt. %, or about 3 wt. % to about 10 wt. %, or about 3 wt. % to about 7 wt. %, or about 5 wt.
  • the zirconium oxide is present in an amount on the zirconium oxide basis within the range from about 80 wt. % to about 99 wt. %; from about 85 wt. % to about 99 wt. %; from about 90 wt. % to about 99 wt. %; from about 92 wt. % to about 99 wt. %; from about 93 wt. % to about 99 wt. %; from about 85 wt. % to about 97 wt. %; from about 90 wt. % to about 97 wt. %; from about 93 wt. % to about 97 wt. %.
  • the metal oxide can include oxides of iron, cobalt, nickel, copper or zinc.
  • the oxidation state of metal can be variable, and the metal can be present in one or more of a variety of oxidation states within the material.
  • the metal oxide is iron oxide.
  • the iron oxide can be present as iron(II), iron (III) or a mixture thereof.
  • the iron oxide is present as iron (II) oxide.
  • the iron oxide is present as iron (III) oxide.
  • the iron oxide is present as a mixed iron (II, III) oxide.
  • the iron oxide is present in an amount on the Fe metallic basis within the range from about 1 wt. % to about 30 wt. %, about 1 wt. % to about 20 wt. %, or about 1 wt. % to about 15 wt. %, or about 1 wt. % to about 12 wt. %, or about 1 wt. % to about 10 wt. %, or about 1 wt. % to about 8 wt. %, or about 1 wt. % to about 7 wt. %, or about 1 wt. % to about 3 wt. %, or about 3 wt.
  • the iron oxide is present in an amount within the range from about 5 wt. % to about 30 wt. % of the ceramic material.
  • the metal oxide is cobalt oxide.
  • the cobalt oxide can be present as cobalt(II), cobalt (III) or a mixture thereof.
  • the cobalt oxide is present as cobalt (II) oxide.
  • the cobalt oxide is present as cobalt (III) oxide.
  • the cobalt oxide is present as a mixed cobalt (II, III) oxide.
  • the cobalt oxide is present in an amount on the Co metallic basis within the range from about 1 wt. % to about 25 wt. %, or about 1 wt. % to about 15 wt. %, or about 1 wt. % to about 12 wt. %, or about 1 wt. % to about 10 wt. %, or about 1 wt. % to about 8 wt. %, or about 1 wt. % to about 7 wt. %, or about 1 wt. % to about 3 wt. %, or about 3 wt. % to about 15 wt.
  • the cobalt oxide is present in an amount within the range from about 5 wt. % to about 25 wt. % of the catalytic material.
  • the metal oxide is nickel oxide.
  • the nickel oxide is present as nickel (II) oxide.
  • the nickel oxide is present in an amount on the Ni metallic basis within the range from about 1 wt. % to about 40 wt. %, or about 1 wt. % to about 30 wt. %, or about 1 wt. % to about 20 wt. %, or about 1 wt. % to about 15 wt. %, or about 1 wt. % to about 12 wt. %, or about 1 wt. % to about 10 wt. %, or about 1 wt. % to about 8 wt. %, or about 1 wt. % to about 7 wt. %, or about 1 wt.
  • the nickel oxide is present in an amount within the range from about 5 wt. % to about 20 wt. % of the catalytic material.
  • the metal oxide is copper oxide.
  • the copper oxide can be present as copper(I), copper(II) or a mixture thereof.
  • the copper oxide is present as copper (I) oxide.
  • the copper oxide is present as copper (II) oxide.
  • the copper oxide is present as a mixed copper (I, II) oxide.
  • the copper oxide is present in an amount on the Cu metallic basis within the range from about 1 wt. % to about 40 wt. %, or about 1 wt. % to about 35 wt. %, or about 1 wt. % to about 30 wt. %, or about 1 wt. % to about 25 wt. %, or about 1 wt. % to about 20 wt. %, or about 1 wt. % to about 15% or about 1 wt. % to about 10 wt. %, or about 1 wt. % to about 8 wt. %, or about 1 wt.
  • % to about 7 wt. % or about 1 wt. % to about 3 wt. %, or about 3 wt. % to about 15 wt. %, or about 3 wt. % to about 10 wt. %, or about 3 wt. % to about 7 wt. %, or about 5 wt. % to about 7 wt. %, or about 5 wt. % to about 8 wt. %, or about 5 wt. % to about 10 wt. %, or about 15 wt. % to about 35 wt. %, or about 20 wt. % to about 35 wt. %, or about 25 wt.
  • the copper oxide is present in an amount within the range from about 5 wt. % to about 35 wt. % of the catalytic material.
  • the metal oxide is zinc oxide.
  • the zinc oxide is present as zinc (II) oxide.
  • the zinc oxide is present in an amount on the Zn metallic basis within the range from about 1 wt. % to about 25 wt. %, or about 1 wt. % to about 20 wt. %, or about 1 wt. % to about 15 wt. %, or about 1 wt. % to about 12 wt. %, or about 1 wt. % to about 10 wt. %, or about 1 wt. % to about 8 wt. %, or about 1 wt. % to about 7 wt. %, or about 1 wt. % to about 3 wt. %, or about 3 wt.
  • the zinc oxide is present in an amount within the range from about 5 wt. % to about 25 wt. % of the catalytic material.
  • the metal oxide acts to stabilize the zirconium oxide from undergoing the undesirable phase transition from the preferable tetragonal phase or amorphous phase to the less desirable monoclinic phase. Accordingly, the ratio of zirconium oxide to the metal oxide can be important for the performance of the ceramic material.
  • At least about 70 wt. % of the ceramic material is the zirconium oxide and the one or more metal oxides.
  • at least about 80 wt. %, at least about 90 wt. %, at least about 95 wt. %, at least about 99 wt. %, at least about 99.5 wt. % or even at least about 99.9 wt. % of the ceramic material is the zirconium oxide and the one or more metal oxides.
  • the ceramic materials described herein can be made without chromium but still provide zirconium oxide stabilized in a tetragonal phase or a amorphous phase, thus providing more environmentally benign materials. Accordingly, in some embodiments of the materials and methods as described herein, the material is substantially free of chromium.
  • the materials are substantially free of manganese and oxides thereof.
  • other metal oxides i.e., other than oxides of nickel, copper, cobalt, iron and zinc
  • Additional non-reducible metal oxides can include, for example, oxides of yttrium, lanthanum, cerium, niobium, tungsten, molybdenum, titanium, calcium, magnesium, boron, tin, anitmony and mixtures thereof.
  • such other metal oxides may be used to provide additional desirable properties to the ceramic material, for example tuning the acidity/basicity of the catalytic materials, or improving the metal oxides used herein dispersion, or improving the reducibility, improving the texture properties.
  • the other reducible metal oxides can also be used as precursors for a catalytic metal, described in more detail below.
  • Reducible metal oxides suitable for use as catalytic metal precursors include, e.g., palladium, platnium, iridinium, rhenium, silver and ruthenium.
  • the additional metal oxide can be present in an amount on metal basis up to about 15 wt. %, for example, up to about 12 wt. %, up to about 10 wt. %, up to about 8 wt. %, up to about 7 wt. %, up to about 3 wt. %, up to about 1 wt.
  • the additional metal is present in an amount within the range from about 0.05 wt. % to about 12 wt. %, or about 0.05 wt. % to about 10 wt. %, or about 0.05 wt. % to about 8 wt. %, or about 0.05 wt. % to about 7 wt. %, or about 3 wt. % to about 15 wt. %, or about 3 wt. % to about 10 wt. %, or about 3 wt. % to about 7 wt. %, or about 5 wt. % to about 7 wt. %, or about 5 wt. % to about 8 wt. %, or about 5 wt. % to about 10 wt. %, or about 10 wt. % to about 15 wt. %.
  • At least about 70 wt. % of the ceramic material is the zirconium oxide and the one or more metal oxides (i.e., including the one or more additional metal oxides).
  • at least about 80 wt. %, at least about 90 wt. %, at least about 95 wt. %, at least about 99 wt. %, at least about 99.5 wt. % or even at least about 99.9 wt. % of the ceramic material is the zirconium oxide and the one or more metal oxides (i.e., including the one or more additional metal oxides).
  • a ceramic material as described herein includes (or, in one embodiment, consists essentially of) zirconium oxide in an amount (calculated on the basis of ZrO 2 ) within the range of about 50 to about 99 wt. %; one or more of nickel oxide, copper oxide, cobalt oxide, iron oxide and zinc oxide, in an amount on the metallic basis within the range of about 1 wt. % to about 50 wt. %; and optionally one or more additional metal oxides in an amount up to about 15 wt. %.
  • a ceramic material as described herein includes (or, in one embodiment, consists essentially of) zirconium oxide in an amount within the range of about 70 to about 99 wt.
  • a ceramic material as described herein includes (or, in one embodiment, consists essentially of) zirconium oxide in an amount on the basis of zirconium oxide within the range of about 75 to about 99 wt. %; one or more of nickel oxide, copper oxide, cobalt oxide, iron oxide and zinc oxide, in an amount on the metallic basis within the range of about 1 wt. % to about 25 wt.
  • a ceramic material as described herein includes (or, in one embodiment, consists essentially of) zirconium oxide in an amount on the basis of zirconium oxide within the range of about 80 to about 99 wt. %; one or more of nickel oxide, copper oxide, cobalt oxide, iron oxide and zinc oxide, in an amount on the metallic basis within the range of about 1 wt. % to about 20 wt. %; and optionally one or more additional metal oxides in an amount on the metal basis up to about 15 wt. %.
  • a ceramic material as described herein includes (or, in one embodiment, consists essentially of) zirconium oxide in an amount on the basis of zirconium oxide within the range of about 85 to about 99 wt. %; one or more of nickel oxide, copper oxide, cobalt oxide, iron oxide and zinc oxide, in an amount on the metallic within the range of about 1 wt. % to about 12 wt. %; and optionally one or more additional metal oxides in an amount on metallic basis up to about 10 wt. %.
  • the ceramic material includes (or, in one embodiment, consists essentially of) zirconium oxide in an amount on the basis of zirconium oxide within the range of about 90 wt.
  • % to about 99 wt. % a metal oxide in an amount on metallic basis within the range of about 1 wt. % to about 8 wt. %; optionally one or more additional metal oxides in an amount on metallic basis up to about 5 wt. %.
  • the ceramic material may be made via a number of different techniques familiar to the person of ordinary skill in the art.
  • the ceramic material can be made with a variety of crystalline forms, such as one or more of monoclinic, tetragonal, cubic and/or amorphous phases as determined by well-known powder x-ray diffraction (XRD) techniques and devices (e.g., see “Introduction to X-ray Powder Diffraction,” R. Jenkins and R. L Snyder, Chemical Analysis, Vol. 138, John Wiley & Sons, New York, 1996).
  • XRD powder x-ray diffraction
  • the zirconium oxide in the ceramic material as described herein is predominantly (e.g., greater than about 50%, greater than about 70%, greater than about 80%, greater than about 90%, or even greater than about 95%) in a phase having either tetragonal geometry or amorphous phase, or a combination thereof, and has a relatively minor amount (e.g., less than about 50%, less than about 30%, less than about 20%, less than about 10%, or even less than about 5%) of zirconium oxide in the monoclinic phase, in order to maintain the desired mechanical strength and physical properties to be used as a catalytic material.
  • a relatively minor amount e.g., less than about 50%, less than about 30%, less than about 20%, less than about 10%, or even less than about 5%
  • a ceramic material as described herein may be provided in any suitable form.
  • a ceramic material as described herein can be formed as spheres, pellets, cylinders (hollow or otherwise), symmetrical or asymmetrical tri-quadrulobes, for example, using extrusion methods as described below.
  • the person of ordinary skill in the art will appreciate that the ceramic materials can be provided in a variety of other forms.
  • a ceramic material as described herein can be provided with a variety of different pore volumes, depending, e.g., on the methods used for making them and the desired end use.
  • a ceramic material as described herein has a pore volume within the range of about 0.1 to about 0.6 cm 3 /g, or about 0.2 to about 0.5 cm 3 /g, or about 0.3 to about 0.5 cm 3 /g, or about 0.4 to about 0.6 cm 3 /g, or about 0.1 to about 1 cm 3 /g.
  • a ceramic material as described herein has a pore volume of about 0.1 cm 3 /g, or about 0.2 cm 3 /g, or about 0.3 cm 3 /g, or about 0.4 cm 3 /g, or about 0.5 cm 3 /g, or about 0.6 cm 3 /g.
  • the ceramic material has a pore volume within the range of about 0.2 to about 0.5 cm 3 /g. In other particular embodiments, the ceramic material has a pore volume within the range of about 0.2 to about 0.4 cm 3 /g.
  • the ceramic materials described herein can be provided with a variety of different surface areas, depending, e.g., on the methods used for making them and the desired end use.
  • the surface area of a ceramic material as described herein within the range of about 10 to about 400 m 2 /g.
  • the surface areas are measured using the Brunauer-Emmett-Teller (BET) Surface Area method.
  • a ceramic material as described herein has a surface area within the range of from about 10 to about 400 m 2 /g, or about 50 to about 400 m 2 /g, or about 70 to about 400 m 2 /g, or about 100 to about 400 m 2 /g, or about 200 to about 400 m 2 /g, or about 300 to about 400 m 2 /g, or about 10 to about 300 m 2 /g, or about 50 to about 300 m 2 /g, or about 70 to about 300 m 2 /g, or about 100 to about 300 m 2 /g, or about 200 to about 300 m 2 /g, or about 10 to about 200 m 2 /g, or about 50 to about 200 m 2 /g, or about 70 to about 200 m 2 /g, or about 100 to about 200 m 2 /g.
  • a ceramic material as described herein has a surface area of about 25 to about 250 m 2 /g. In another embodiment, a ceramic material as described herein has a surface area of about 50 to about 150 m 2 /g. In another embodiment, a ceramic material as described herein has a surface area of about 30 to about 120 m2/g.
  • a ceramic material as described herein has a crush strength within the range of about 45 N/cm (i.e., ⁇ 1 lb/mm) to about 450 N/cm (i.e., ⁇ 10.0 lb/mm.)
  • a ceramic material as described herein has a crush strength of at least 45 N/cm (i.e., ⁇ 1 lb/mm), or at least 67 N/cm (i.e., ⁇ 1.5 lb/mm), or at least 90 N/cm (i.e., ⁇ 2 lb/mm), or at least 134 N/cm (i.e., ⁇ 3 lb/mm), or at least 178 N/cm (i.e., ⁇ 4 lb/mm), depending on its use.
  • a ceramic material as described herein has a crush strength within the range of about 45 N/cm to about 178 N/cm, or about 45 N/cm to about 134 N/cm, or about 45 N/cm to about 90 N/cm, or about 45 N/cm to about 67 N/cm, or about 67 N/cm to about 178 N/cm, or about 67 N/cm to about 134 N/cm, or about 67 N/cm to about 90 N/cm, about 90 N/cm to about 178 N/cm, or about 90 N/cm to about 134 N/cm.
  • the crush strength of a material is measured using ASTM D6175-03 (2008), Standard Test Method for Radial Crush Strength of Extruded Catalyst and Catalyst Carrier Particles.
  • a ceramic material as described herein can be prepared, for example, using extrusion methods without the use of any binder, extrusion aid or additional stabilizing agent. Accordingly, in certain embodiments, a ceramic material as described herein is substantially free of any binder. In other embodiments, a ceramic material as described herein is substantially free of any extrusion aid. For example, in one particular embodiment, a ceramic material as described herein is substantially free of any binder and any extrusion aid. Moreover, as the metal oxide can stabilize the zirconium oxide, in certain embodiments, a ceramic material as described herein can be substantially free of an additional stabilizing agent.
  • a ceramic material as described herein is substantially free of any binder, extrusion aid or additional stabilizing agent.
  • a ceramic material as described herein is substantially free of silicon dioxide, aluminum compounds, silica-alumina compounds, graphite and carbon black. In all such embodiments, the ceramic material can be provided as an extrudate.
  • the ceramic materials described herein can be made using a variety of techniques.
  • a co-precipitation technique is used to make a ceramic material as described herein.
  • a zirconium compound and one or more metal oxide precursor compounds can be combined in aqueous solution and co-precipitated with base to co-precipitate a zirconium oxide-metal oxide precursor.
  • the zirconium compound may be precipitated first and then the metal oxide precursor compound may be mixed with the precipitated zirconium oxide precursor to form the zirconium oxide-metal oxide precursor.
  • Metal oxide precursors can also be added (for example, at relatively low levels, e.g., when they are to be used as a catalyst metal precursor) via well-known impregnation techniques.
  • the zirconium oxide-metal oxide precursor can then be dried, shaped and calcined in accordance with well-known processes to form a finished ceramic material.
  • zirconium-containing compounds can be used as starting materials.
  • the zirconium compound may be selected from the group consisting of zirconium or zirconyl halides, zirconium or zirconyl nitrates, zirconium or zirconyl organic acids, and combinations thereof.
  • Specific compounds include, for example, ZrCl 4 , ZrOCl 2 , Zr(NO 3 ) 2 5H 2 O, ZrO(NO 3 ) 2 and ZrO(CH 3 COO) 2 .
  • zirconium compounds can be used; the processes described herein are not limited to the compounds specifically identified herein.
  • zirconium can be in a form of zirconyl (ZrO 2+ ) or zirconium ion (Zr 4+ or Zr 2+ ) that may be obtained by dissolving corresponding salts in water.
  • metal-containing compounds can be used as the metal oxide precursor.
  • Metal compounds can be, for example, in the form of halides, nitrates or organic acid salts similar to those described above with respect to the zirconium compound.
  • the metal oxide precursor compound for iron can be Fe(NO 3 ) 3 .
  • Other metal oxide precursors are described below with respect to the Examples, and would be evident to the person of ordinary skill in the art.
  • the metal oxide precursor compound can be provided as the metal oxide itself.
  • the optional additional metal oxides e.g., of yttrium, lanthanum, cerium, niobium, tungsten, molybdenum, titanium, calcium, magnesium, boron, tin, anitmony silver, rhenium, ruthenium, palladium, rhodium, and iridium
  • the optional additional metal oxides can be incorporated into the zirconium oxide-metal oxide precursor by including corresponding salts in the solution to be precipitated, by impregnation, or by mixing of metal oxide precursor (e.g., the metal oxide itself) with the precipitated material.
  • the salts can be, for example, in the form of halides, nitrates or organic acid salts similar to those described above with respect to the zirconium starting material and metal oxide precursor compound.
  • lanthanum can be introduced as lanthanum nitrate hexahydrate.
  • Other metal oxide precursors are described below with respect to the Examples, and would be evident to the person of ordinary skill in the art.
  • the zirconium compound and the metal oxide precursor compound are dissolved, together with any other additional metal oxide precursors in aqueous solution.
  • a base e.g., ammonia, ammonium hydroxide, sodium carbonate or sodium hydroxide
  • the base is 25 wt. % NaOH and the pH of final precipitation is between about 7 and about 10.
  • the pH of final precipitation is between about 8 and about 9.
  • the zirconium oxide-metal oxide precursor precipitate may be filtered or otherwise separated from the liquid.
  • a variety of methods and/or apparatuses may be utilized, including the use of filter paper and vacuum pump, as well as centrifugal separation, other vacuum mechanisms and/or positive pressure arrangements.
  • the zirconium oxide-metal oxide precursor may be washed if any of the feed materials used in the process contain undesirable elements or compounds, such as chloride or sodium. Typically, one to ten washings, or even more washings may be desirable if undesired elements or other contaminants are present in the feed materials.
  • the zirconium oxide-metal oxide precursor can then be dried, using a variety of techniques and conditions as would be apparent to the person of ordinary skill in the art.
  • the drying of the zirconium oxide-metal oxide precursor may be aided by dividing (e.g., breaking) it into smaller quantities.
  • the division (e.g. breaking) of the filter-cake may be manual or automated.
  • the zirconium oxide-metal oxide precursor may be dried at ambient conditions (e.g., room temperature and ambient pressure) or under moderate temperatures ranging up to about 120° C. In one embodiment, the zirconium-metal oxide precursor is dried at a temperature ranging between 40° C. and 90° C.
  • the zirconium oxide-metal oxide precursor is dried until a loss of ignition (LOI) is achieved in a range between about 60 wt. % to about 70 wt. %.
  • LOI loss of ignition
  • the zirconium oxide-metal oxide precursor or the precipitated zirconium precursor is dried until a LOI of about 64 wt. % to about 68 wt. %, or about 65wt. % to 68 wt. % is achieved.
  • the zirconium oxide-metal oxide precursor can be dried to a level that is desirable for a subsequent forming step. In some embodiments, it may be desirable to leave the zirconium oxide-metal oxide precursor a little wet to aid in forming.
  • the zirconium oxide-metal oxide precursor can be formed into any shape suitable for a catalyst support/carrier, using any of the forming methods familiar to the person of ordinary skill in the art.
  • the dried zirconium oxide-metal oxide precursor is formed by being extruded through a suitable die. Extrusion methods are well-known in the art. For example, a screw extruder, a press extruder, or any other extrusion devices and/or methods known in the art may be used.
  • the zirconium oxide-metal oxide precursor may be formed by pressing, tableting, pelleting, granulating, or even spray drying; the person of ordinary skill in the art will adjust the wetness of the zirconium oxide-metal oxide precursor to be suitable for the particular forming process used.
  • the extruded or otherwise formed zirconium oxide-metal oxide precursor may be further dried (for example, at moderate temperatures, e.g., up to about 120° C., for example, for a moderate period of time, e.g., typically about 1 to 5 hours) after being formed.
  • the zirconium oxide-metal oxide precursor can be calcined.
  • the extruded or otherwise formed zirconium oxide-metal oxide precursor is ceramic at a temperatures within the range of about 300° C. to about 1000° C., or in another embodiment, of about 400° C. to about 700° C.
  • the extruded or otherwise formed zirconium oxide-metal oxide precursor is calcined at a temperature within the range of about 300° C. to about 1000° C., or of about 400° C.
  • an extruded or otherwise formed zirconium oxide-metal oxide precursor is ceramic at about 600° C.
  • a variety of heating programs can be used in calcining.
  • a slow temperature ramp may be used to avoid thermal shock of the material.
  • an extruded or otherwise formed zirconium oxide-metal oxide precursor as described herein may be calcined with heating at a rate of 1° C. per minute to 600° C. at which temperature the calcining continues for about 3 hours. Based on the Examples described herein, the person of ordinary skill in the art can identify appropriate calcination conditions to provide the desired ceramic material.
  • the ceramic materials as described herein may be provided in combination with one or more catalytically active materials to form a catalyst.
  • another aspect of the invention is the ceramic material described herein used as a catalyst support material, with a catalytically active material disposed thereon.
  • the catalytically active material can be, for example, a catalytic metal.
  • a catalyst includes the ceramic material as described herein, and one or more catalytic metals selected from the group consisting of Ni, Cu, Co, Fe, Ru, Rh, Pd, Ag, Re, Os, Ir, Pt, Au, Sb, La, Bi or any combination thereof.
  • the catalytic metal is one or more of nickel, copper and antimony.
  • the catalytic metal can be NiCu, NiBi or NiSb.
  • the catalyst support materials can be useful with other catalysts, for example, palladium, platinum, rhodium and ruthenium.
  • Catalytic metals can be provided via impregnation, plating or deposition, or via reduction (e.g., in situ) of part of the metal oxide of the ceramic material.
  • the ceramic materials and catalysts described herein can, in certain embodiments, exhibit high hydrothermal and mechanical stability, and thus can be suitably durable for advantageous use in reduction reactions, such as aqueous phase hydrogenation or hydrogenolysis reactions, which include the reduction of sugars, sugar alcohols or glycerol. Accordingly, additional aspects of the invention relate to various uses of the ceramic materials and catalysts described herein.
  • one embodiment of the invention is a method of conducting a catalytic reaction including contacting one or more reactants with a catalyst as described herein, wherein at least one of the reactants is in the aqueous phase. Such reactions can, in certain embodiments, be conducted at relatively high temperatures (e.g., in the range of 50° C.
  • At least one reactant is a gas (e.g., hydrogen), provided at partial pressure that is at least about 20%, at least about 50%, or even at least about 90% of the overall pressure.
  • a gas e.g., hydrogen
  • the ceramic materials and catalysts described herein can, in certain embodiments, be stable at a wide variety of pH values. Accordingly, the methods described herein can be performed at a variety of pH values, including acidic pH values.
  • a reaction as described herein is conducted such that the pH of the reaction mixture is (at some point during the process) in the range of about 2 to about 10, for example, in the range of about 2 to about 6, or about 2.5 to about 5.
  • the process can be performed such that the ceramic material or catalyst is in contact with the reaction mixture at such pH values for at least about 1 minute, at least about 2 minutes, at least about 10 minutes, or even at least about 30 minutes.
  • the ceramic materials and catalysts described herein can be especially useful in catalytic hydrogenation or hydrogenolysis of a sugar, a sugar alcohol, or glycerol, for example, into commercially-valuable chemical products and intermediates, including, but not limited to, polyols or an alcohol comprising a shorter carbon-chain backbone such as propylene glycol (1,2-propanediol), ethylene glycol (1,2-ethanediol), glycerin, trimethylene glycol (1,3-propanediol), methanol, ethanol, propanol and butandiols.
  • polyol(s) refers to any polyhydric alcohol containing more than one hydroxyl group.
  • the term polyol may encompass both the reactants and/or the products described above.
  • a sugar, a sugar alcohol or glycerol is contacted with a source of hydrogen and a ceramic material or catalyst as described herein.
  • the source of hydrogen can be hydrogen gas.
  • the ceramic materials and catalysts described herein can also be useful in catalytic hydrogenation of organic acids into commercially-valuable chemical products and intermediates.
  • organic acids include, but are not limited to, acetic acid, formic acid, propionic acid, butyric acid, caproic acid, glycolic acid, lactic acid, 3-hydroxypropionic acid, hydroxylbutyric acid, hydroxycyclopentanoic acid, salicylic acid, mandelic acid, benzoic acid, fatty acids, and sugar acids.
  • sugar acid(s) refers to any monosaccharide containing one or more carboxylic acid moieties.
  • Examples include, but are not limited to glyceric acid, xylonic acid, gluconic acid, ascorbic acid, tartaric acid , mucic acid, saccharic acid, glucuronic acid, and galacturonic acid.
  • the organic acids may also include polycarboxylic acid compounds, such as tartaric acid, citric acid, malic acid, oxalic acid, succinic acid, adipic acid, malonic acid, galactaric acid, 1,2-cyclopentane dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, terephthalic acid, phenylmalonic acid, hydroxyphthalic acid, dihydroxyfumaric acid, tricarballylic acid, benzene-1,3,5-tricarboxylic acid, isocitric acid, mucic acid and glucaric acid.
  • polycarboxylic acid compounds such as tartaric acid, citric acid, malic acid, oxalic acid, succin
  • the organic acid is selected from lactic acid, succinic acid, adipic acid, and various sugar acids.
  • a catalytic method as described herein includes contacting an organic acid and hydrogen gas with a catalyst as described herein (e.g., with Ni, Cu, Co, Fe, Ru, Rh, Pd, Ag, Re, Os, Ir, Pt, Au, Sb, La, Bi or any combination thereof as the catalytic metal).
  • the contacting can be performed at a relatively high temperature and/or pressure as described above.
  • the catalysts described herein can be made by any suitable method.
  • a catalytically active material e.g., a catalytic metal
  • a catalyst support material as described herein using conventional methods, for example, by depositing the catalytically active material thereon. Depositing may include, but is not limited to, impregnation, incipient wetness, precipitation, and physical mixing.
  • the catalytically active material can be provided at any stage in the formation of the catalyst (e.g., as the catalytically active material or as some precursor for the catalytically active material that gets converted to catalytically active material in a later step).
  • Nickel-stabilized zirconium oxide materials were prepared by co-precipitation of a nickel nitrate (Ni(NO 3 ) 2 ) and zirconyl nitrate (ZrO(NO 3 ) 2 ) precursor solution using a sodium hydroxide solution.
  • Ni(NO 3 ) 2 nickel nitrate
  • ZrO(NO 3 ) 2 zirconyl nitrate
  • Sample 6 of Table 1 below as an example 550 g nickel nitrate solution (13.8 wt. % nickel on metal basis) was premixed with 1665 g zirconyl nitrate solution (equivalent to 20 wt. % zirconium oxide) and precipitated with a 25 wt. % NaOH solution. The precipitation was conducted at a constant pH ranging from 6-10, typically, 8-9 at room temperature with vigorous stirring.
  • the precipitate was aged overnight (about 16 h) and washed with excess de-ionized water until the conductivity of the final filtered water was less than 0.4 mS/cm.
  • the precipitate was dried accordingly and the resulting material was extruded using an auger extruder.
  • the extrudates were dried at 110° C. for 3 h, followed by calcination at a temperature ranging from 400-650° C. for 2-5 h.
  • Table 1 lists the physical properties of six preparations, Samples 1-6.
  • Nickel content on metal basis varied from 6.6 wt. % to approximately 18 wt. % as analyzed by XRF bulk analysis. All extrudates exhibited good crush strength (above 1.9 lb/mm) and a pore volume of 0.15 to 0.22 mL/g.
  • the Brunauer-Emmett-Teller surface area (BET S.A.) varied from about 50 m 2 /g to about 120 m 2 /g with the variation of calcination temperature, precipitation pH and aging time.
  • FIG. 1 shows the XRD pattern of the selected nickel-stabilized zirconium oxide materials (Samples 1, 4 and 6). After calcination at 450° C. for 3 h, the nickel-stabilized zirconium oxide materials exhibit predominantly tetragonal phase zirconium oxide patterns as well as NiO peaks (marked with asterisks) in the higher nickel content materials.
  • Copper-stabilized zirconium oxide materials were prepared by co-precipitation of a copper nitrate and zirconyl nitrate precursor solution using a sodium hydroxide solution.
  • Sample 10 as an example, 467 g copper nitrate (Cu(NO 3 ) 2 ) solution (15.5 wt. % Cu on metal basis) was premixed with 1169 g zirconyl nitrate solution (equivalent to 20 wt. % ZrO 2 ) and precipitated with a 25 wt. % NaOH solution. The precipitation was conducted at a constant pH ranging from 6-10, typically, 8-9 at room temperature with vigorous stirring.
  • the precipitate was aged overnight (about 16 h) and washed with excess de-ionized water until the conductivity of the final filtered water was less than 0.4 mS/cm.
  • the cake was dried, and the resulting dried material was extruded using an auger extruder.
  • the extrudates were dried at 110° C. for 3 h, followed by calcination at a temperature ranging from 400-600° C. for 2-5 h.
  • Table 2 lists six of the preparations and the related physical properties.
  • Cu content on metal basis varied from 6.5 wt. % to approximately 32 wt. % as analyzed by XRF bulk analysis. All extrudates showed good crush strength above 2.3 lb/mm and a pore volume of 0.2 mL/g to 0.5 mL/g.
  • the Brunauer-Emmett-Teller surface area (BET S.A.) varied from about 50 to approximately 200 m 2 /g for the resulting materials due to the variation in calcination temperature and precipitation pH.
  • FIG. 2 provides the XRD patterns of the copper-stabilized zirconium oxide materials calcined at 450° C. (Samples 9-12). Zirconium oxide is in the form of an amorphous phase. With higher copper loadings of 28% and 32%, CuO peaks (marked with asterisks) are also observed.
  • FIG. 3 provides the XRD patterns of copper-stabilized zirconium oxide materials calcined at 550° C. (Samples 7 and 8). A fully stabilized tetragonal phase of zirconium oxide was evident in the copper-stabilized zirconium oxide having 6.5% and 7.5% Cu content (calculated as metallic Cu).
  • Cobalt-stabilized zirconium oxide materials were prepared by precipitation of a cobalt nitrate hexahydrate and zirconyl nitrate mixed precursor solution using a sodium hydroxide solution.
  • a typical preparation i.e., the preparation of Samples 13 and 14
  • 120 g Co(NO 3 ) 2 .6H 2 O was premixed with 1040 g zirconyl nitrate solution (20 wt. % ZrO 2 ) and precipitated with a 25 wt. % NaOH solution.
  • the precipitation was conducted at a constant pH ranging from 6-10, typically, 8-9 at room temperature with vigorous stirring.
  • the precipitate was aged overnight (about 16 h) and washed with excess de-ionized water until the conductivity of the final filtered water was less than 0.4 mS/cm. Then, the cake was dried appropriately. The resulting dried material was extruded using an auger extruder. The extrudates so-formed were dried at 110° C. for 3 h, followed by calcination at a temperature ranging from 400-600° C. for 2-5 h.
  • Table 3 lists two such preparations (Samples 13 and 14) and their physical properties.
  • Cobalt content was about 10 wt. % on metal basis as analyzed by XRF bulk analysis.
  • the extrudates exhibited good crush strength above 1.2 lb/mm and a pore volume of about 0.4 g/mL.
  • the Brunauer-Emmett-Teller surface area (BET S.A.) varied from about 32 to approximately 90 m 2 /g, depending significantly on calcination temperature, precipitation pH and aging time.
  • FIG. 4 provides the XRD patterns of the cobalt-stabilized zirconium oxide materials calcined at 450° C. and 600° C.
  • Zirconium oxide is in the form of fully or partially stabilized tetragonal phase.
  • cobalt oxide Co 3 O 4
  • the amount of cobalt oxide particles grew with calcination temperature from 450° C. to 600° C. Due to the decreased concentration of cobalt oxide in the zirconium oxide lattice, part of the stabilized tetragonal zirconium oxide phase reverted to monoclinic zirconium oxide in the material calcined at 600° C. (Sample 13).
  • Iron-stabilized zirconium oxide materials were prepared by precipitation of an iron nitrate nonahydrate and zirconyl nitrate mixed precursor solution using a 25 wt. % sodium hydroxide solution.
  • a typical preparation i.e., the preparation of Sample 15
  • 147 g Fe(NO 3 ) 3 .9H 2 O was premixed with 885 g zirconyl nitrate solution (20 wt. % ZrO 2 ) and precipitated with a 25 wt. % NaOH solution.
  • the precipitation was conducted at a constant pH ranging from 6-10, typically, 8-9 at room temperature with vigorous stirring.
  • the precipitate was aged overnight (about 16 h) and washed with excess de-ionized water until the conductivity of the final filtered water was less than 0.4 mS/cm. Then, the cake was dried appropriately. The resulting dried material was extruded using an auger extruder. The extrudates so-formed were dried at 110° C. for 3 h, followed by calcination at a temperature ranging from 400-600° C. for 2-5 h.
  • Table 4 lists one of the preparations for iron-stabilized zirconium oxide and its physical properties.
  • Fe content was about 9.9 wt. % on metal basis as analyzed by XRF bulk analysis.
  • the extrudates are relatively weak with a crush strength around 0.6 lb/mm.
  • the Brunauer-Emmett-Teller surface area (BET S.A.) was 148 m 2 /g and the pore volume is about 0.5 g/mL.
  • FIG. 5 shows the XRD patterns of the iron stabilized zirconium oxide materials calcined at 600° C.
  • Zirconium oxide is in the form of a fully stabilized tetragonal phase.
  • Zinc-stabilized zirconium oxide materials were prepared by precipitation of a zinc nitrate hexahydrate and zirconyl nitrate mixed precursor solution using a sodium hydroxide solution.
  • a zinc nitrate hexahydrate and zirconyl nitrate mixed precursor solution using a sodium hydroxide solution.
  • 60.5 g Zn(NO 3 ) 2 .6H 2 O was premixed with 1052 g zirconyl nitrate solution (20 wt. % ZrO 2 ) and precipitated with a 25 wt. % NaOH solution.
  • the precipitation was conducted at a constant pH ranging from 6-10, typically, 8-9 at room temperature with vigorous stirring.
  • the precipitate was aged overnight (about 16 h) and washed with excess de-ionized water until the conductivity of the final filtered water was less than 0.4 mS/cm. Then, the cake was dried appropriately.
  • the resulting drying material was extruded using an auger extruder. The extrudates so-formed were dried at 110° C. for 3 h, followed by calcination at temperature ranging from 400-600° C. for 2-5 h.
  • Table 5 lists three of the preparations for zinc-stabilized zirconium oxide and their physical properties. Zn content was varied from 6% to 11% on metal basis as analyzed by XRF bulk analysis. The extrudates are strong with crush strength above 2 lb/mm for samples calcined at 550° C. By lowering the calcination temperature to 450° C., the surface area was significantly increased from 40 to 110 m 2 /g. The pore volume of the resulting materials was about 0.2-0.4 g/mL depending on composition,calcination profile, precipitation pH and aging time.
  • FIG. 6 provides the XRD patterns of the Zn-stabilized zirconium oxide materials of Table 5.
  • the materials were calcined at 450° C. and 550° C. for 3 h, respectively. A stabilized tetragonal phase was seen over all the materials. No isolated zinc oxide was observed.
  • a nickel/lanthanum-stabilized zirconium oxide material was prepared by precipitation of nickel nitrate solution(13.8 wt. % nickel on metal basis), lanthanum nitrate hexahydrate and zirconyl nitrate mixed precursor solution using a sodium hydroxide solution.
  • nickel nitrate solution (13.8 wt. % nickel on metal basis)
  • lanthanum nitrate hexahydrate lanthanum nitrate hexahydrate
  • zirconyl nitrate mixed precursor solution using a sodium hydroxide solution.
  • 85 g La(NO 3 ) 3 .6H 2 O and 205 g nickel nitrate solution was premixed with 1031 g zirconyl nitrate solution (20 wt. % ZrO 2 ) and precipitated with a 25 wt. % NaOH solution.
  • the precipitation was conducted at a constant pH range from 6-10, typically, 8-9 at room temperature with vigorous stirring.
  • the precipitate was aged overnight (about 16 h) and washed with excess de-ionized water until the conductivity of the final filtered water was less than 0.4 mS/cm. Then, the cake was dried appropriately.
  • the resulting dried material was extruded using an auger extruder.
  • the extrudates so-formed were dried at 110° C. for 3 h, followed by calcination at a temperature ranging from 400-600° C. for 2-5 h.
  • Table 6 lists two of the preparations for ternary zirconium oxide materials and the related physical properties.
  • the extrudates are strong with good crush strength above 2.0 lb/mm and a pronounced surface area.
  • FIG. 7 provides XRD patterns of a ternary zirconium oxide ceramic (Sample 19) in a stabilized tetragonal phase. This material was calcined at 600° C. for 3 h.
  • Pure zirconium oxide was prepared by using the same precipitation approach in order to compare to the metal oxide stabilized zirconium oxide.
  • the properties of the ZrO 2 extrudates calcined at 450° C. and 550° C. are shown in Table 7.
  • the materials showed a very weak crush strength and became powder after finger pressing.
  • the attrition is more than 40%. As used herein, attrition is defined as loss of fines through abrasion, which is wearing, grinding, or rubbing of the particles with each other or with container walls.
  • test is performed as described in ASTM D4058, which is hereby incorporated herein by reference, or alternately by manually shaking 5-10 grams of material vigorously/evenly in a closed 30 mL plastic container for 5 min and measure the loss of fines by sieving through a 16 mesh sieve, e.g. as described in Pure & Appl. Chem., Vol. 63, No. 9, 1227-1246 (1991) which is hereby incorporated herein by reference.
  • the pure ZrO 2 extrudate prepared by the method above in the absence of any binder and extrusion aid is not suitable for use as a shaped carrier.
  • FIG. 8 provides XRD patterns of zirconium oxide prepared in the same approach with varied calcination temperatures.
  • the XRD patterns in FIG. 8 shows the phase transition from tetragonal zirconium oxide to a mixture of tetragonal and monoclinic mixture with the increased calcination temperature on a pure zirconium oxide material.
  • the feed (100 mL) contained about 40 wt. % glycerin with initial pH of 6.8.
  • Catalyst was first sized to 10-14 mesh size.
  • About 6.5-7.0 g catalyst was loaded into the reactor basket and reduced in-situ at 220° C. for 2 h with a slow heating ramp rate of 0.5 K/min and a hydrogen GHSV of 2000 h ⁇ 1 .
  • the test was conducted at 220° C. under 100 bar hydrogen pressure for 6 h.
  • the product was sampled every one to 2 h during the test.
  • T4466 a commercial CuCr catalyst, was also studied for glycerin hydrogenolysis at the same testing condition. This catalyst was reduced at 185° C. for 2 h with a slow heating ramp rate of 0.5 K/min and a hydrogen GHSV of 2000 h ⁇ 1 .
  • Cobalt-stabilized zirconium oxide Sample 14 was also studied for glycerin hydrogenloysis under the exactly same conditions.
  • the cobalt-stabilized zirconium oxide sample was reduced at 480° C. for 2 h with a heating ramp rate of 5 K/min and a hydrogen GHSV of 1000 h ⁇ 1 .
  • the ICP analysis for the aqueous product after 6 h reaction demonstrated no leaching of Cu into the solution for the copper-stabilized zirconium oxide samples even though the product pH was as low as 2.8. In contrast, 20 ppm Co was detected and 2 ppm Cu was detected over a cobalt-stabilized zirconium oxide sample and T4466.
  • T4466 a commercial CuCr catalyst, is also listed for comparison.
  • T4466 are tablet and was size to 10-14 mesh in irregular shape.
  • Sugar hydrogenation to sugar alcohol is an industrial important process. This process is carried out in the aqueous phase. Accordingly, catalyst stability in aqueous phase under elevated temperature and pressure is highly desirable, especially for a fixed bed continuous process.
  • Nickel-stabilized zirconium oxide (Sample 4) and nickel/lanthanum-stabilized zirconium oxide (Sample 19) were studied for xylose hydrogenation.
  • a palladium promoted nickel-stabilized zirconium oxide (No.4) was also studied for xylose hydrogenation in order to boost the catalytic activity.
  • Pd promoted NiZrO x -No.4 was prepared by conventional incipient wetness method. The desired amount of palladium nitrate hydrate (Pd: 39 wt. %) was first dissolved in water and dropped into NiZrO x -No.4, followed by drying at 110° for 2 h and calcination at 450° C. for 2 h.
  • the test was conducted in a fixed bed reactor with an O.D. of 1 inch. 30 mL of each catalyst was loaded into the reactor with a 1:1 volumetric dilution of SiC (40-60 mesh). All the catalysts were activated at 450° C. for 4 hours with a heating ramp rate of 3 K/min under a flow of pure hydrogen with GHSV of 1000 h ⁇ 1 .
  • the feed contained food grade xylose (Danisco USA Inc) and the pH was adjusted by diluted sodium carbonate before being pumped into the reactor.
  • the spent catalysts were unloaded easily from the reactor and maintained good physical integrity. All of the spent catalysts demonstrated XRD peaks characteristic of FCC nickel metal and fully-stabilized tetragonal zirconium oxide. The crush strength, surface area, and the pore volume of the spent catalysts decreased slightly with no major inverse impact.
  • a NiSb catalyst was developed on a nickel-stabilized zirconium oxide material (Sample 1), which originally contained about 6.6 wt. % nickel on metal basis.
  • the catalyst was made by a conventional impregnation method.
  • the nickel-stabilized zirconium oxide (Sample 1, 50 g) was immersed in a mixed solution of nickel nitrate, antimony acetate and citric acid for 1 h and the leftover solution was decanted.
  • the resulting material was then dried at 110° C. for 2 h and calcined at 450° C. for 2 h.
  • the solution was then mixed with a nickel nitrate solution (13.8 wt. % on metal basis).
  • the xylitol hydrogenolysis test was conducted in a fixed bed reactor with an O.D. of 0.5 inch. 15 mL of the catalyst was loaded into reactor with a 1:1 volumetric dilution with SiC (60-80 mesh). The catalysts were activated at 450° C. for 4 hours with a heating ramp rate of 3 K/min under a flow of pure hydrogen with GHSV of 1000 h ⁇ 1 .
  • the feed contained food grade xylitol (Danisco USA Inc) and the pH was adjusted proprietly by a diluted NaOH solution before being pumped into the reactor.
  • the detailed testing conditions are listed in Table 11. The tests were conducted at 210° C.

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200270190A1 (en) * 2015-12-17 2020-08-27 Shell Oil Company Hydrogenation or hydrogenolysis of an oxygenate
US11219889B2 (en) * 2016-08-31 2022-01-11 Shell Oil Company Methane oxidation catalyst, process to prepare the same and method of using the same
US20220250043A1 (en) * 2019-05-03 2022-08-11 Golu Hydrogen Technologies Inc. Catalysts for hydrogen production
US11420190B2 (en) * 2018-08-22 2022-08-23 Sogang University Research Foundation Process for preparing porous iron oxide-zirconia composite catalyst, porous iron oxide-zirconia composite catalyst prepared thereby, and method for producing alcohol using the catalyst

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107754813B (zh) * 2016-08-18 2019-09-20 万华化学集团股份有限公司 一种用于聚醚胺合成的负载型催化剂及其制备方法
CN110255614B (zh) * 2019-06-26 2022-03-08 西安建筑科技大学 一种稳定氧化锆粉体及其制备方法与应用
CN111875377A (zh) * 2020-08-03 2020-11-03 湖南省新化县林海陶瓷有限公司 一种绝缘定位陶瓷套件材料及其制备工艺

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060216227A1 (en) * 2005-03-24 2006-09-28 University Of Regina Catalysts for hydrogen production

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2279198A (en) * 1938-01-18 1942-04-07 Union Oil Co Catalytic conversion of hydrocarbons
DE3903367A1 (de) * 1989-02-04 1990-08-16 Basf Ag Katalysator und verfahren zur hydrierenden aminierung von alkoholen
GB9221976D0 (en) 1992-10-20 1992-12-02 Alcan Int Ltd Shaped articles of zirconia
US5447898A (en) * 1993-09-21 1995-09-05 Shell Oil Company Process for the preparation of zirconia
CA2213777A1 (en) * 1995-04-17 1996-10-24 James F. White Formed compositions
US20040179994A1 (en) 2003-01-21 2004-09-16 Fenouil Laurent Alain Zirconia extrudates
US7056853B2 (en) * 2003-02-05 2006-06-06 Matsushita Electric Industrial Co., Ltd. Oxide ceramic material, ceramic substrate employing the same, ceramic laminate device, and power amplifier module
US7297321B2 (en) 2004-01-12 2007-11-20 The Texas A&M University System Supermicroporous metal oxides
JP4660135B2 (ja) * 2004-07-26 2011-03-30 第一稀元素化学工業株式会社 ジルコニア系多孔質体及びその製造方法
EP1979082A2 (en) 2006-02-03 2008-10-15 Saint-Gobain Ceramics & Plastics, Inc. Articles comprising tetragonal zirconia and methods of making the same
CN101462057A (zh) 2007-12-21 2009-06-24 中国石油化工股份有限公司 一种脱除微量一氧化碳的铜锆基催化剂、其制备方法及其应用
WO2010101636A2 (en) 2009-03-02 2010-09-10 Sud-Chemie Inc. Promoted zirconium oxide catalyst support
BRPI1009218A2 (pt) 2009-03-02 2016-03-15 Süd Chemie Inc conversão de açúcar, álcool de açúcar ou glicerina em produtos químicos valiosos usando um catalisador sobre suporte de óxido de zircônio promovido
US20110009614A1 (en) * 2009-06-30 2011-01-13 Paul George Blommel Processes and reactor systems for converting sugars and sugar alcohols
WO2011057196A1 (en) 2009-11-09 2011-05-12 Wayne State University Metaloxide-zr02 catalysts for the esterification and transesterification of free fatty acids and triglycerides to obtain bio -diesel
US8778833B2 (en) 2010-11-11 2014-07-15 Basf Corporation Copper-zirconia catalyst and method of use and manufacture
US9387464B2 (en) * 2012-04-27 2016-07-12 Toyota Jidosha Kabushiki Kaisha Iron oxide-zirconia composite oxide and method for producing same, and exhaust gas purification catalyst
CN102757219B (zh) * 2012-07-31 2014-04-16 嘉兴佳利电子股份有限公司 一种两相复合微波介质陶瓷材料及其制备方法
US9132418B2 (en) 2013-06-27 2015-09-15 Clariant Corporation Manganese oxide-stabilized zirconia catalyst support materials

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060216227A1 (en) * 2005-03-24 2006-09-28 University Of Regina Catalysts for hydrogen production

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200270190A1 (en) * 2015-12-17 2020-08-27 Shell Oil Company Hydrogenation or hydrogenolysis of an oxygenate
US11219889B2 (en) * 2016-08-31 2022-01-11 Shell Oil Company Methane oxidation catalyst, process to prepare the same and method of using the same
US11420190B2 (en) * 2018-08-22 2022-08-23 Sogang University Research Foundation Process for preparing porous iron oxide-zirconia composite catalyst, porous iron oxide-zirconia composite catalyst prepared thereby, and method for producing alcohol using the catalyst
US20220250043A1 (en) * 2019-05-03 2022-08-11 Golu Hydrogen Technologies Inc. Catalysts for hydrogen production

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