WO2020236707A1 - Catalyseur d'oxyde métallique mixte amélioré utile pour la déshydrogénation de paraffine - Google Patents

Catalyseur d'oxyde métallique mixte amélioré utile pour la déshydrogénation de paraffine Download PDF

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WO2020236707A1
WO2020236707A1 PCT/US2020/033391 US2020033391W WO2020236707A1 WO 2020236707 A1 WO2020236707 A1 WO 2020236707A1 US 2020033391 W US2020033391 W US 2020033391W WO 2020236707 A1 WO2020236707 A1 WO 2020236707A1
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catalyst
metal oxide
support
salts
mixed metal
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PCT/US2020/033391
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English (en)
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Mitrajit Mukherjee
Vamsi M. VADHRI
Narendra Joshi
Grace BROCK
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Exelus, Inc.
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Priority claimed from US16/586,980 external-priority patent/US11033880B2/en
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Publication of WO2020236707A1 publication Critical patent/WO2020236707A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • 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
    • B01J23/90—Regeneration or reactivation
    • B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • Chromium-based catalysts are comparatively cheaper.
  • chromium is a known carcinogen.
  • the object of the present invention is to provide an improved mixed-metal oxide catalyst for the dehydrogenation of paraffins which is preferably essentially free of either Platinum or Chromium.
  • zinc oxide is an inexpensive and low-toxic alternative for dehydrogenation of propane.
  • Zinc has been shown to activate propane through dissociative adsorption over zinc oxide species.
  • US Patent #2,279,198 describes an active, stable and regenerable catalytic system consisting of zinc oxide along with other metal oxides and promoters for the dehydrogenation of alkanes and other organic compounds. Isobutane conversion as high as 26.4% has been reported at 510°C.
  • Zn-based catalysts Numerous other Zn-based catalysts have been explored for dehydrogenation of hydrocarbons. For example, it is reported that when Zn is introduced into acidic zeolites like H- ZSM5, the reaction rate for dehydrogenation of paraffins increases 2 13 . The Zn 2+ species are reported to reside in the cation exchange sites of the zeolite and have a tetrahedral orientation. The main products are aromatic compounds and the selectivity to olefins is usually low ( ⁇ 40%).
  • Zn carries out the two-fold function of promoting the dehydrogenation of the hydrocarbon as well as depleting the surface hydrogen pool by the catalytic recombinative desorption of H-atoms and H2 14 .
  • Zinc has also been used as a promoter for alkane dehydrogenation catalysts 15 20 .
  • studies in literature have shown that the addition of Zn to Pt or Cr containing catalysts resulted in increasing the alkene selectivity during alkane dehydrogenation.
  • Zinc modifies the geometric and electronic properties of the metallic phase of Pt and studies showed that the addition of zinc to Pt-A Os, PtSn-A Os, 15 and PtSn-MgAhC formulations significantly improved their overall performance for propane dehydrogenation 17 .
  • Zinc is known to alloy with platinum and the formation of the alloy is believed to increase the electronic density on the metallic Pt which weakens the alkene adsorption 15 resulting in reduced coke formation and lower associated by-product gases such as methane and ethane.
  • Zinc was also shown to be effective in increasing the activity of hematite towards ethylbenzene dehydrogenation 21 .
  • Zinc based catalysts have been shown to be active in the oxidative dehydrogenation of hydrocarbons. While it was known that simple iron oxide, a-Fe2C>3 catalyzes a rather selective production of butadiene via the oxidative dehydrogenation of butenes and in some cases n- butane, Rennard and Kehl showed that addition of zinc oxide to iron oxide leads to the formation of ZnFe2C>4 which further increases the selectivity to butadiene under identical conditions 22 .
  • the selectivities for butadiene on Fe2C>3 were 83% at 325 °C and 43% at 375 °C, while on ZnFe2C>4 they were 89% at 325 °C and 88% at 375 °C.
  • Comparison of these results with those on iron oxide suggests that zinc ferrite is a more selective oxidation catalyst because it has a higher density of selective oxidation sites and a lower density of combustion sites, and because its combustion sites are less active than those on iron oxide 22 24 .
  • Numerous methods of synthesis with and without the presence of promoters have been described in literature (U.S. Pat. No. 3,743,683, U.S. Pat. No. 3,951,869). For example, it is reported that when a zinc ferrite catalyst doped with chromium or aluminum was used, catalytic activity towards dehydrogenation was increased 25 .
  • Zinc has been used as a support for the dehydrogenation of lower alkanes.
  • Zinc aluminate has been used as a catalyst support due to its low specific surface area and high hydrothermal stability 26 28 .
  • U.S. Pat. No. 5,344,805; U.S. Pat. No. 5,430,220; and EP 0557982A2 describe a process for dehydrogenating at least one alkane comprising 2 to 8 carbon atoms to an alkene in the presence of steam and a catalyst composition comprising zinc aluminate and platinum.
  • Pt and Cr free catalysts have been synthesized via a coprecipitation method using nitrates of various metals and were shown to be active and selective for the dehydrogenation of isobutane to isobutene (US9713804B2, WO2013091822A1).
  • the most active, selective and stable composition consisted of mixed Zn, Mn and Al oxides.
  • Numerous promoters, selected from alkali metals (K, Cs), non-metals (Si) and transition metals (Fe, Cr, Cu, Zr, Ce, etc.) were used to promote these catalysts with varying degrees of success.
  • the catalyst was usually prepared by intimately mixing suitable proportions of zinc oxide and titanium dioxide wherein the atomic ratio of zinc to titanium was usually close to 2:1 and calcining the resulting mixture in air at a temperature in the range of 675° to 975° C.
  • a slurry of powdered zinc titanate was combined with alumina and nitric acid to form a hydrosol that was treated with ammonium hydroxide (aqueous ammonia) to produce a hydrogel.
  • Lysova et al. studied the effect of the chemical composition of the ZnO-TiC>2 catalytic system on its phase composition and catalytic properties in the oxidative and nonoxidative dehydrogenation of isobutane 30 . It was found that samples with an atomic ratio of zinc to titanium > 2 exhibited the highest selectivity with high specific activity. It was reported that ZnO-TiC>2 system was active and selective in ODH of isobutane at 570°C, the maximum yield of isobutene being 54%.
  • the isobutane conversion was 2% at 823 K and 8 mol% at 923 K, with a selectivity of 90% to isobutene.
  • Schweitzer et al. tested a Zn/SiC>2 catalyst for the dehydrogenation of propane 32 . The reaction was run under differential conditions (target conversion of less than 10%). Propylene selectivity was reported to be > 95% at 550 C and the catalyst lost only 50% of its activity in 12 hours. In this catalyst, the Zn 2+ center is coordinated with three O centers of the Si02 surface and is believed to be the active species.
  • US Patent No. 7,087,802 US Published Patent Application No. 2016/0074838 and US Patent No. 6,518,476 describe catalyst systems for the oxidative and/or non-oxidative dehydrogenation of light alkanes where the catalyst consists of a support and an active component.
  • the support is generally a heat-resistant oxide and could be selected from zirconium dioxide, zinc oxide, aluminum oxide, silicon dioxide, titanium dioxide, magnesium oxide, lanthanum oxide, cerium oxide and mixtures thereof.
  • the active component could be a precious metal like Pt or Pd or can be from the other transition, alkali or alkaline earth metal or a mixture of the above components.
  • dehydrogenation catalyst described in these patents can be used in the form of a fixed bed in the reactor or in the form of a fluidized bed with an appropriate shape.
  • the invention provides a mixed-metal oxide catalyst suitable for the dehydrogenation of paraffins having 2-8 carbon atoms comprising oxides of zinc (Zn) as the active catalytic species wherein Zn makes up at least 20 wt% of the total weight of the catalyst, oxides of aluminum (Al), silicon (Si), and titanium (Ti), or mixtures thereof as the catalyst support wherein the catalyst support makes up 10 to 75 wt% of the total weight of the catalyst, preferably 20 to 70 wt% and oxides of metals as catalyst stabilizers selected from the group of cerium (Ce), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), lanthanum (La), neodymium (Nd), praseodymium (Pr), samarium (Sm), terbium (Tb), ytterbium (Yb), yttrium (Y), tungsten (W
  • the catalyst can be further characterized by one or any combination of the following features: an activity parameter of at least 95,000 or an activity in the range of 90,000 to 125,000; wherein the catalyst comprises at least 30 wt% or 20 to 70 or 25 to 70 or 30 to 70 or no more than 60 or no more than 50 wt% of the catalyst; or wherein the catalyst support comprises 20 to 70 or 25 to 70 or 30 to 70 or no more than 60 or no more than 50 wt% of the catalyst; wherein the support stabilizer comprises 0.1 to 20 or 0.2 to 15 or 0.3 to 10 wt% of the catalyst; less than 0.5 wt% S, less than 0.5 wt% of S, N and halides, preferably less than 0.2 wt% S; a Brunauer-Emmet-Teller (BET) surface area of at least 5 or at least 10 m 2 /g; wherein the number average particle diameter of the mixed-metal oxide catalyst is in the range of 30-3000 microns (pm).
  • BET Brunauer-E
  • the catalyst cannot be completely distinguished from the prior art based solely on its elemental composition, the measurement described above is needed for a unique characterization of the catalyst.
  • the catalyst may be further characterized by any of the compositions or physical characteristics described herein.
  • the invention provides a method for preparing a catalyst comprising the steps of: a) dissolving salts of active material, catalyst support and support stabilizer in a solvent; b) coprecipitating the salts using a precipitating agent; c) washing the precipitate, preferably with an aqueous solution; and d) drying and calcining the resultant precipitate to produce the mixed metal oxide catalyst.
  • the wash solution comprises ammonium hydroxide (aqueous ammonia) to remove sulfate, nitrate, and/or chloride.
  • the salts are anions, preferably sulfate, nitrate, or chloride.
  • the solubility of various chemical compounds in selected solvents is known or can be determined by routine experimentation.
  • Preferred salts are nitrates and sulfates.
  • the solvent comprises aqueous ammonia.
  • the precipitating agent comprises aqueous ammonia.
  • the invention provides a method for preparing a catalyst comprising the steps of:
  • a salt solution comprising salts of active catalyst, catalyst support, and support stabilizer dissolved in a solvent
  • the porous spheres are washed with an aqueous solution.
  • the volume average pore diameter of the porous bead is in the range of 3 to 3000 nm. In some embodiments, the volume average pore diameter of the mesoporous bead is in the range of 3-500 nm or 3-25 nm.
  • the invention provides a method for preparing a catalyst comprising the steps of: a) mixing oxides of active catalyst, catalyst support, and support stabilizer in a solvent; b) spray drying and calcining the oxides to produce the mixed metal oxide catalyst suitable for use in a fluidized bed reactor.
  • the invention provides a method for preparing a catalyst comprising the steps of: a) mixing oxides of active catalyst, catalyst support, and support stabilizer in a solvent; b) drying and calcining the oxides to produce the mixed metal oxide catalyst suitable for use in a fixed bed reactor.
  • Binders can be added to the mixed-metal oxide catalysts to provide sufficient mechanical strength for use in commercial reactors.
  • oxides of zinc, oxides of catalyst support and oxides of a catalyst stabilizer are combined with an hydrated alumina (such as boehmite alumina powders sold under the tradename Dispal ® ) that is modified with one or more alkaline earth elements (typically Ca and/or Mg) which moderate Lewis acid sites.
  • a slurry comprising oxides of zinc, titanium and zirconium are combined with an alkaline earth- modified hydrated alumina.
  • the amounts of each component are selected so that the final catalyst composition comprises at least 20 mass% Zn and preferably the final catalyst comprises comprises 20 to 70 or 25 to 70 or 30 to 70 catalyst support (CS) and the support stabilizer (ST) comprises 0.1 to 20 or 0.2 to 15 or 0.3 to 10 wt% of the final catalyst.
  • the catalyst support or the mixed metal oxide catalyst can, in some embodiments, be calcined at 500-1, 100°C, preferably at 600-900°C and most preferably at 700-850°C for 2-6 hrs in an oxygen containing atmosphere, preferably air.
  • the invention also includes processes of dehydrogenating a paraffin (preferably propane or isobutane), comprising contacting the paraffin with any of catalysts described herein in a reaction chamber under conditions sufficient to dehydrogenate the paraffin and resulting in an olefin.
  • a paraffin preferably propane or isobutane
  • the sufficient conditions are conventional conditions for dehydrogenation or identified with no more than routine experimentation.
  • the invention provides a process for continuous dehydrogenation of paraffins having 2-8 carbon atoms, preferably propane or isobutane, comprising:
  • the contacting step is carried out in a fluidized bed reactor or a fixed-bed swing reactor.
  • Another aspect of the invention provides a continuous method for dehydrogenating paraffins having 2-8 carbon atoms wherein the process is performed at a reaction temperature of 500-800 °C, a space velocity of 0.1-25 hr 1 (or, in some embodiments, 0.1 to 1 h -1 ) and a pressure of 0.01-0.2 MPa.
  • the fluidized bed version of the method is shown in Figure 1.
  • the paraffin feedstock 1 is contacted with the catalyst under dehydrogenation conditions for a reaction period in the range of about 0.05 second to 10 minutes in
  • Reactor/Riser A Following the reaction period, the Reactor outlet stream 2 containing catalyst and product gas flows to the Cyclone/Disengager B in which the catalyst is separated from the Product Stream 3.
  • the Separated Catalyst stream 4 is thereafter regenerated in Regenerator C by contacting said catalyst with Combustion Air 5.
  • the catalyst regeneration is performed at a temperature of 500-800 °C, a pressure of 0.01-0.2 MPa and a regeneration period ranging from about 0.05 seconds to 10 minutes and producing Flue Gas stream 6 and Regenerated Catalyst stream 7, which is routed again to the Reactor/Riser A.
  • the process can be carried out using a Reactor/Riser A configured as a fluidized bed reactor or as a fixed-bed swing reactor.
  • the invention provides advantages such as: the product of the catalyst activity and catalyst selectivity exceeding 0.1 ton of product per hour per ton of catalyst; and the overall catalyst consumption does not exceed 1 kg of catalyst per ton of product. None of the prior art catalysts (substantially without Pt or Cr) listed in the prior art meet these two characteristics simultaneously.
  • the invention is further elucidated in the examples below.
  • the invention may be further characterized by any selected descriptions from the examples, for example, within ⁇ 20% (or within ⁇ 10%) of any of the values in any of the examples, tables or figures; however, the scope of the present invention, in its broader aspects, is not intended to be limited by these examples.
  • Figure 1 shows illustrates a reaction scheme for a dehydrogenation.
  • Paraffins 1 enter reactor A.
  • the products 2 pass into separator B wherein olefins 3 are separated and catalyst 4 is regenerated in Regenerator C and regenerated catalyst 7 is returned to the reactor.
  • Oxygen- containing gas 5 passes into the Regenerator and stream 6 exits the Regenerator.
  • k is the rate constant (units 1/sec) of a reaction at temperature T
  • ko is pre-exponential factor
  • E activation energy for the reaction
  • R the universal gas constant
  • T the reaction temperature (in Kelvin)
  • Activity Parameter - The catalyst activity is quantified by the activity parameter which is the pre-exponential factor in the Arrhenius equation ko for the dehydrogenation reaction, an empirical relationship between temperature and rate coefficient using a value of 81.7 kJ/mole for E the Activation Energy for the dehydrogenation reaction using for Titania based catalyst.
  • a catalyst producing propylene with a high selectivity will have a selectivity parameter ⁇ 0.2.
  • Stability Parameter - The loss of catalyst activity with time is quantified by the stability parameter which measures the rate of change of catalyst activity with time.
  • a catalyst with high stability will have a low stability parameter value ⁇ 0.005.
  • kp t is the rate constant of dehydrogenation of propane at time t
  • kpo is the rate constant of dehydrogenation of propane at time 0
  • t is the time on stream (in hours)
  • Characterization of the catalyst is conducted in the absence of a diluent gas such as nitrogen, hydrogen, steam or helium.
  • Attrition Index The attrition resistance of catalysts used in fluidized reactor systems are characterized by the Attrition Index determined by ASTM tests such as AJI - Air Jet Index which is the percent attrition loss at 5 hours (ASTM D5757 - Standard Test Method for Determination of Attrition of FCC Catalysts by Air Jets).
  • Calcination Temperature The term "calcination temperature" refers to the maximum temperature utilized as an intermediate step in the catalyst synthesis procedure intended to convert the metal salts to their oxide form.
  • Conversion of a reactant refers to the reactant mole or mass change between a material flowing into a reactor and a material flowing out of the reactor divided by the moles or mass of reactant in the material flowing into the reactor.
  • conversion is the mass of propane reacted divided by the mass of propane fed.
  • Catalyst particles can be characterized by four so-called "Geldart Groups".
  • the groups are defined by their locations on a diagram of solid-fluid density difference and particle size.
  • For Group A the particle size is between 20 and 100 pm, and the particle density is typically less than 1.4 g/cm 3 .
  • For Group B the particle size lies between 40 and 500 pm and the particle density between 1.4-4 g/cm 3 .
  • Most particles used in fluidized beds are Geldart Group A powders.
  • catalysts of the present invention have the characteristics of Group A; in some embodiments, catalysts of the present invention have the characteristics of Group B.
  • Particle size is number-average particle size, and, for non-spherical particles, is based on the largest dimension.
  • Pore size - Pore size relates to the size of a molecule or atom that can penetrate into the pores of a material.
  • pore size for zeolites and similar catalyst compositions refers to the Norman radii adjusted pore size well known to those skilled in the art. Determination of Norman radii adjusted pore size is described, for example, in Cook, M.; Conner, W. C, "How big are the pores of zeolites?" Proceedings of the International Zeolite Conference, 12th, Baltimore, July 5-10, 1998; (1999), 1, pp 409-414.
  • pore size e.g., minimum pore size, average of minimum pore sizes
  • XRD x-ray diffraction
  • Other techniques that may be useful in determining pore sizes include, for example, helium pycnometry or low- pressure argon adsorption techniques. These and other techniques are described in Magee, J.S. et at, “Fluid Catalytic Cracking: Science and Technology,” Elsevier Publishing Company, July 1, 1993, pp. 185-195.
  • Pore sizes of mesoporous catalysts may be determined using, for example, nitrogen adsorption techniques, as described in Gregg, S. J. at a I, "Adsorption, Surface Area and Porosity,” 2nd Ed., Academic Press Inc., New York, 1982 and Rouquerol, F. et al, "Adsorption by powders and porous materials. Principles, Methodology and Applications,” Academic Press Inc., New York, 1998.
  • Regeneration Temperature The catalyst may be regenerated under flowing air gas at elevated temperatures in order to remove heavier hydrocarbons (coke) from the active catalyst structure.
  • the maximum temperature used in this step is referred to as the "regeneration temperature.”
  • yield is used herein to refer to the amount of a product flowing out of a reactor divided by the amount of reactant flowing into the reactor, usually expressed as a percentage or fraction. Mass yield is the mass of a particular product divided by the mass of feed used to prepare that product. When unspecified, “%” refers to mass% which is
  • mass yield is the mass of propylene produced divided by the mass of propane fed. Mass yield of the inventive processes are preferably at least 50% in a single pass, preferably at least 70 %.
  • the term “comprising” means “including” and does not exclude additional components. Any of the inventive aspects described in conjunction with the term “comprising” also include narrower embodiments in which the term “comprising” is replaced by the narrower terms “consisting essentially of” or “consisting of.” As used in this specification, the terms “includes” or “including” should not be read as limiting the invention but, rather, listing exemplary components. As is standard terminology, “systems” include to apparatus and materials (such as reactants and products) and conditions within the apparatus.
  • the precipitate was subsequently isolated by filtration and stirred in an aqueous solution of 0.25 M ammonium nitrate for 30 minutes at room temperature, filtered and dried overnight and then calcined to a temperature of 815 °C for 4 hours to produce the mixed-metal oxide catalyst.
  • This catalyst is designated as Catalyst A.
  • the catalyst was prepared as in Example 1 with the difference being that the amount of Zinc Nitrate Hexahydrate dissolved was 18 gm. This catalyst is designated as Catalyst B
  • the catalyst was prepared as in Example 1 with the difference being that the amount of Zinc Nitrate Hexahydrate dissolved was 27.45 gm. This catalyst is designated as Catalyst C.
  • the catalyst was prepared as in Example 1 with the difference being that the amount of Zinc Nitrate Hexahydrate dissolved was 33.6 gm. This catalyst is designated as Catalyst D.
  • the catalyst was prepared as in Example 1 with the difference being that the amount of Zinc Nitrate Hexahydrate dissolved was 42 gm. This catalyst is designated as Catalyst E.
  • the catalyst was prepared as in Example 2 with the difference being that after the calcination at 815 °C, 4 gm of alkaline earth metals modified Dispal binder (T25N4-80) dispersed in 10 gm of deionized water for 30 minutes, was mixed with the mixed-metal oxide catalyst followed by drying and calcining at 650 °C to improve the mechanical strength of the catalyst.
  • This catalyst is designated as Catalyst G.
  • Propane dehydrogenation experiments were performed using a fixed-bed reactor such that the d-r/dp > 10 (ratio of diameter of reactor tube to diameter of catalyst particles) and L/dp > 50 (ratio of length of catalyst bed to diameter of catalyst particles) to ensure plug-flow behavior.
  • the catalyst of interest was first loaded into a quartz glass lined reactor. The catalyst was activated in dry air at atmospheric pressure at a temperature of 600°C for 4 hours. Following activation, the reactor was allowed to heat up to reaction temperature of 650°C, then purged with dry nitrogen for 0.5 hours. Propane was fed to the reactor at a WHSV equal to 10 hr 1 . The flow rate was controlled by a Brooks mass flow controller.
  • Catalyst G Physical properties of Catalyst G were measured to characterize its surface area, bulk density, average particle diameter and attrition strength. The results are shown in Table 2. Table 3. Physical properties of mixed-metal oxide Sample G.

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Abstract

L'invention concerne un catalyseur, des procédés de fabrication et un procédé de déshydrogénation de paraffines utilisant le catalyseur. Le catalyseur comprend au moins 20 % en masse de Zn, un support de catalyseur et un stabilisateur de catalyseur. Le catalyseur est en outre caractérisé par des propriétés physiques telles qu'un paramètre d'activité mesuré dans des conditions spécifiées. Le catalyseur peut également être disposé sur un support poreux sous une forme résistant à l'attrition et utilisé dans un réacteur à lit fluidisé.
PCT/US2020/033391 2019-05-17 2020-05-18 Catalyseur d'oxyde métallique mixte amélioré utile pour la déshydrogénation de paraffine WO2020236707A1 (fr)

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US201962849721P 2019-05-17 2019-05-17
US62/849,721 2019-05-17
US16/586,980 US11033880B2 (en) 2018-09-28 2019-09-28 Mixed metal oxide catalyst useful for paraffin dehydrogenation
PCT/US2019/053710 WO2020069480A1 (fr) 2018-09-28 2019-09-28 Catalyseur d'oxyde métallique mixte amélioré utile pour la déshydrogénation de paraffine
US16/586,980 2019-09-28
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115608405A (zh) * 2021-07-16 2023-01-17 中国石油化工股份有限公司 毫米级球形复合载体和脱氢催化剂及其制备方法以及应用
CN115805097A (zh) * 2022-12-01 2023-03-17 中触媒新材料股份有限公司 一种大晶粒Zn@Silicalite-1低碳烷烃脱氢催化剂及其制备方法
WO2023141089A1 (fr) * 2022-01-18 2023-07-27 Basf Se Articles polymères artificiels façonnés avec des particules d'oxyde métallique hybride

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CN115608405A (zh) * 2021-07-16 2023-01-17 中国石油化工股份有限公司 毫米级球形复合载体和脱氢催化剂及其制备方法以及应用
CN115608405B (zh) * 2021-07-16 2024-02-20 中国石油化工股份有限公司 毫米级球形复合载体和脱氢催化剂及其制备方法以及应用
WO2023141089A1 (fr) * 2022-01-18 2023-07-27 Basf Se Articles polymères artificiels façonnés avec des particules d'oxyde métallique hybride
CN115805097A (zh) * 2022-12-01 2023-03-17 中触媒新材料股份有限公司 一种大晶粒Zn@Silicalite-1低碳烷烃脱氢催化剂及其制备方法
CN115805097B (zh) * 2022-12-01 2024-03-01 中触媒新材料股份有限公司 一种大晶粒Zn@Silicalite-1低碳烷烃脱氢催化剂及其制备方法

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