EP1899436A1 - Utilisation d'une argile anionique dans un procede fcc - Google Patents

Utilisation d'une argile anionique dans un procede fcc

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Publication number
EP1899436A1
EP1899436A1 EP06786182A EP06786182A EP1899436A1 EP 1899436 A1 EP1899436 A1 EP 1899436A1 EP 06786182 A EP06786182 A EP 06786182A EP 06786182 A EP06786182 A EP 06786182A EP 1899436 A1 EP1899436 A1 EP 1899436A1
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EP
European Patent Office
Prior art keywords
anionic clay
catalyst
potassium
anionic
clay
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06786182A
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German (de)
English (en)
Inventor
Dennis Stamires
Paul O'connor
Erik Jeroen Laheij
Michael F. Brady
Julie A. Francis
Maria M. Ludvig
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Albemarle Netherlands BV
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Albemarle Netherlands BV
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Publication date
Application filed by Albemarle Netherlands BV filed Critical Albemarle Netherlands BV
Publication of EP1899436A1 publication Critical patent/EP1899436A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J23/007—Mixed salts
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C10G11/182—Regeneration
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil
    • C10G25/09—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil according to the "fluidised bed" technique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • 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
    • B01J35/19—Catalysts containing parts with different compositions

Definitions

  • the present invention relates to the use in a fluid catalytic cracking (FCC) process of a catalyst or catalyst additive comprising a specific type of anionic clay.
  • FCC fluid catalytic cracking
  • Anionic clays are layered structures corresponding to the general formula
  • M 2+ is a divalent metal
  • M 3+ is a trivalent metal
  • X is an anion with valance z, such as CO 3 2" , OH " , or any other anion normally present in the interlayers of anionic clays.
  • the crystal structure of anionic clays consists of positively charged layers built up of specific combinations of metal hydroxides between which there are additional anions and water molecules.
  • Hydrotalcite is an example of a naturally occurring anionic clay in which Al is the trivalent metal, Mg is the divalent metal, and X is carbonate.
  • Meixnerite is an anionic clay in which Al is the trivalent metal, Mg is the divalent metal, and X is hydroxyl.
  • anionic clay encompasses the frequently used terms “hydrotalcite-like material” and "layered double hydroxide", which are synonymous. It further includes the various polytypes of anionic clays, such as the common 3Ri-polytype and the 3R 2 -polytype disclosed in WO 01/012550. For more information on the various polytypes of anionic clays, reference may be had to Clay and Clay Minerals, Vol. 41 , No. 5, pages 551-557 and 558-564.
  • anionic clays Upon mild calcination, i.e. at about 200-800 0 C, anionic clays are transformed into a rehydratable mixed oxide, which in this specification is referred to as a solid solution.
  • a solid solution contains a well-known memory effect whereby the exposure to water of such calcined materials results in the reformation of the anionic clay structure.
  • a spinel structure is formed, which is not rehydratable to anionic clay anymore.
  • thermally treated form of anionic clay includes both solid solutions and spinel structures.
  • anionic clays are made by (i) preparing a solution of the nitrate salts of the divalent and the trivalent metal, (ii) co-precipitating the divalent and trivalent metals using sodium hydroxide, followed by (iii) aging the resulting mixture for one hour at 65 0 C and (iv) filtering and washing the precipitate with demineralized water to remove unwanted ions, such as sodium.
  • anionic clays Another method of preparing anionic clays is disclosed in WO 99/41195 and WO 00/44671 , in which (thermally treated) aluminum trihydrate or (pseudo)boehmite is slurried with magnesium oxide or hydroxide and subsequently aged to form an anionic clay.
  • the advantage of this process is that these aluminum and magnesium sources do not introduce unwanted anions.
  • no acids, bases, or metal salts need to be added during the process, which also avoids the introduction of unwanted ions, such as Na + . Consequently, the resulting anionic clay does not need to be washed or filtered and can be dried, shaped, or added to other catalyst (additive) ingredients directly.
  • the present invention relates to the use in an FCC process of a catalyst or catalyst additive containing an anionic clay or its thermally treated form, said anionic clay comprising at least 0.5 wt% of potassium, calculated as K 2 O and based on the weight of potassium-containing anionic clay.
  • the anionic clay preferably contains 1 to 30 wt% of K, more preferably 3 to 15 wt% of K (as K 2 O).
  • Catalysts and catalyst additives comprising this (thermally treated) K-containing anionic clay show increased performance in SO x removal compared to K-free anionic clays. Furthermore, K is less detrimental to the catalytic properties of zeolites than is Na.
  • K-containing anionic clays are easier to prepare by precipitation than K- free or Na-free anionic clays, because a K compound can be used as the base, and no washing step is required to remove undesired cations introduced by the base.
  • the anionic clay structure of the K-containing anionic clays suitable for use according to the present invention may be built up from various trivalent and divalent metals.
  • suitable trivalent metals (M 3+ ) include Al 3+ , Ga 3+ , In 3+ , Bi 3+ , Fe 3+ , Cr 3+ , Co 3+ , Sc 3+ , La 3+ , Ce 3+ , and combinations thereof.
  • Suitable divalent metals (M 2+ ) include Mg 2+ , Ca 2+ , Ba 2+ , Zn 2+ , Mn 2+ , Co 2+ , Mo 2+ , Ni 2+ , Fe 2+ , Sr 2+ , Cu 2+ , and combinations thereof.
  • Preferred metal combinations are Mg-Al, Zn-Al, Ca-Al, Ba-Al, Fe-Al, Mn-Al, and Co-Al anionic clays.
  • the K-containing anionic clay suitable for use according to the present invention can be prepared by various methods, some of which are exemplified here. Method 1 involves the co-precipitation of a divalent and a trivalent metal salt using a K-containing base - such as KOH, K 2 CO 3 , or KHCO 3 - to form a suspension comprising a precipitate. This suspension is then aged, resulting in a suspension of anionic clay.
  • This aging may be conducted at a temperature in the range of 25- 250 0 C, preferably 50-180 0 C, for 10 minutes to 48 hours, more preferably 30 minutes to 24 hours, and most preferably 1 to 6 hours. If hydrothermal aging conditions are used (i.e. above 100°C), autogenous pressure is preferably applied.
  • the anionic clay is then dried, for instance by spray-drying, without first being separated from the remaining solution. The latter is important, because such a separation step (e.g. filtration) would remove K ions.
  • the anionic clay also is not washed prior to drying.
  • Suitable salts of the divalent and trivalent metals include their nitrate, chloride, sulphate, acetate, formiate, carbonate, and hydroxycarbonate salts.
  • Method 2 involves the aging of a suspension comprising a divalent and a trivalent metal compound, at least one of them being water-insoluble, in the presence of a potassium salt or potassium base.
  • Suitable potassium salts include KCI, and KNO 3 .
  • Suitable potassium bases include KOH, K 2 CO 3 , and KHCO 3 . This aging may be conducted at a temperature in the range 25-250°C, preferably 50-18O 0 C, for 10 minutes to 48 hours, more preferably 30 minutes to 24 hours, and most preferably 1 to 6 hours. If hydrothermal aging conditions are used (i.e. above 100 0 C), autogenous pressure is preferably applied.
  • the potassium salt may be introduced into the suspension as a separate compound from the slurry of divalent and trivalent metal compounds, it may be added to the divalent or the trivalent metal compound prior to combining said di- and trivalent metal compounds in the slurry, or it may already be present in the di- or the trivalent metal compound. In the latter case, a K-doped divalent or trivalent metal compound is used.
  • the resulting anionic clay is not separated from the liquid prior to drying, e.g. spray-drying.
  • Suitable trivalent metal compounds to be used in method 2 are water-insoluble compounds of the trivalent metals aluminium, gallium, indium, iron, chromium, vanadium, cobalt, vanadium, manganese, and combinations thereof.
  • Suitable divalent metal compounds are water-insoluble compounds of the divalent metals magnesium, zinc, nickel, copper, iron, cobalt, manganese, calcium, barium, and combinations thereof.
  • the divalent and trivalent metal compounds are preferably used in the form of oxides, hydroxides, carbonates, and hydroxycarbonates.
  • suitable aluminium compounds are aluminium trihydrate (including gibbsite, bayerite, and bauxite ore concentrate, BOC) and its thermally treated forms (including flash- calcined alumina), sols, amorphous alumina, and (pseudo)boehmite. Flash- calcined aluminium trihydrate may be obtained by treating aluminum trihydrate at temperatures between 800-1 ,000 0 C for very short periods of time in special industrial equipment, as is described in US 4,051 ,072 and US 3,222,129.
  • suitable magnesium compounds are MgO, Mg(OH) 2 , hydromagnesite, magnesium carbonate, magnesium hydroxy carbonate, and magnesium bicarbonate.
  • Method 3 involves calcining an existing anionic clay at a temperature of 200- 800 0 C, thereby forming a so-called solid solution, which can then be re-hydrated to a K-containing anionic clay by contacting this calcined anionic clay with an aqueous solution containing a potassium salt or a potassium base.
  • This rehydration may be conducted at a temperature in the range of 25-250 0 C, preferably 50-18O 0 C, for 10 minutes to 48 hours, more preferably 30 minutes to 24 hours, and most preferably 1 to 6 hours.
  • hydrothermal aging conditions are used (i.e. above 100 0 C), autogenous pressure is preferably applied.
  • Suitable potassium salts include KCI and KNO 3 .
  • Suitable potassium bases include KOH, K 2 CO 3 , and KHCO 3 .
  • Method 4 involves the impregnation of an existing anionic clay with a potassium salt or base.
  • Suitable potassium salts include KCI and KNO 3 .
  • Suitable potassium bases include KOH, K 2 CO 3 , and KHCO 3 .
  • one or more additional metal compounds may be incorporated into the K-containing anionic clay by having these metal compound(s) present during the preparation of the K-containing anionic clay, or by impregnating the K-containing anionic clay with the metal compound(s).
  • Preferred metal compounds are Ce and/or V salts, but also other metal compounds can be introduced, such as La, Si, P, B, Ca, Ba, Fe, Cr, Ni, Mn, Ti, Zr, Cu, Zn, Mo, Sn, W, Pd, Pt, Rh, and/or Ru salts.
  • the anion present in the interiayers of the K-containing anionic day may be exchanged with another anion, e.g. NO 3 " , OH, Cl “ , Br “ , I “ , SO 4 2” , SiO 3 2” , CrO 4 2” , BO 3 2' , MnO 4 ' , HGaO 3 2” , HVO 4 2” , CIO 4 " , BO 3 2” , tungstates, pillaring anions such as VioO 28 6" and Mo 7 O 24 6” , monocarboxylates such as acetate, dicarboxylates such as oxalate, or alkyl sulphonates such as lauryl sulphonate.
  • another anion e.g. NO 3 " , OH, Cl “ , Br “ , I “ , SO 4 2” , SiO 3 2” , CrO 4 2” , BO 3 2' , MnO 4 ' , HG
  • the K-containing anionic clay may be calcined in order to obtain a thermally treated anionic clay.
  • Mild calcination 200-800 0 C is preferred, because the use of solid solutions is preferred over the use of spinel-type structures.
  • the catalyst additive that can be used according to the present invention preferably comprises 1-99 wt%, more preferably 20-80 wt%, and most preferably 40 to 70 wt% of (thermally treated) K-containing anionic clay, calculated as oxide and based on the total weight of additive.
  • This additive further comprises a binder, preferably alumina, silica, or silica- alumina, in a preferred amount of 1-99 wt%, more preferably 5-60 wt%, and most preferably 8-20 wt%, calculated as AI 2 O 3 and based on the total weight of additive.
  • the additive may also comprise zeolites (such as ZSM-5 or zeolite beta) in a preferred amount of 5-30 wt% and balance kaolin.
  • the catalyst additive is used in the FCC process in physical admixture with an FCC catalyst.
  • This FCC catalyst can be any conventional FCC catalyst.
  • the FCC catalyst and the additive can be introduced into the FCC unit separately or in physical admixture.
  • the K-containing anionic clay-containing catalyst that can be used according to the present invention preferably comprises 0.1-50 wt%, more preferably 1-30 wt%, and most preferably 3 -15 wt% of (thermally treated) K-containing anionic clay, calculated as oxide and based on the total weight of the catalyst.
  • This catalyst further comprises conventional FCC catalyst ingredients.
  • a binder or matrix material preferably alumina, silica, and/or silica- alumina, in a preferred amount of less than 50 wt%, more preferably 5 to 40 wt%, and most preferably 20 - 30 wt%, calculated as oxide and based on the total weight of the catalyst.
  • It further contains a faujasite zeolite, e.g. zeolite Y, zeolite USY, or rare-earth metal exchanged zeolite Y or USY (RE-Y, RE-USY), in a preferred amount of 5-50 wt%, more preferably 10-30 wt%, and balance kaolin.
  • the catalyst and the catalyst additive to be used according to the present invention can be prepared by slurrying the (thermally treated) K-containing anionic clay and the other ingredients of the catalyst or the additive, followed by shaping, e.g., spray-drying, the slurry to form particles. This spray-drying may optionally be followed by a calcination step.
  • the (thermally treated) K-containing anionic clay Before addition to the slurry, the (thermally treated) K-containing anionic clay may be milled in order to decrease its particle size.
  • the slurry containing the (thermally treated) K-containing anionic clay and other ingredients of the catalyst or the additive is milled.
  • “Milling” is defined as any method that results in a reduction of the particle size. Such a particle size reduction can at the same time result in the formation of reactive surfaces and/or heating of the particles.
  • Instruments that can be used for milling include ball mills, high-shear mixers, colloid mixers, and electrical transducers that can introduce ultrasound waves into a slurry. Low-shear mixing, i.e. stirring that is performed essentially to keep the ingredients in suspension, is not regarded as "milling".
  • Example 1 A K-containing anionic clay was prepared by slurrying precipitated boehmite alumina and MgO in a molar ratio Mg/AI of 2, resulting in a slurry with a solids content of 10 wt%. The slurry was aged at 85 0 C for 4 hours and subsequently spray-dried to form microspheres. These microspheres were calcined at 600 0 C for 1 hour and then rehydrated by slurrying in a 0.1 molar potassium hydroxide solution for 1 hour at 80°C. The resulting K-containing anionic clay contained 3.6 wt% K (as K 2 O), measured by X-Ray Fluorescence Spectroscopy (XRF).
  • XRF X-Ray Fluorescence Spectroscopy
  • Example 2 was repeated, except that the calcined anionic clay was rehydrated in the absence of potassium.
  • the resulting product was an Mg-Al anionic clay substantially free of K.
  • Example 1 and Comparative Example 2 were tested for their SO x reducing ability in FCC processes using the thermographimetric test described in Ind. Eng. Chem. Res. Vol. 27 (1988) pp. 1356-1360.
  • 30 mg of the product sample was heated under nitrogen at 700 0 C for 30 minutes.
  • the nitrogen was replaced by a gas containing 0.32% SO 2 , 2.0% O 2 , and balance N 2 with a flow rate of 200 ml/min.
  • the SOz-containing gas was replaced by nitrogen and the temperature was reduced to 650°C.
  • 15 minutes nitrogen was replaced by pure H 2 and this condition was maintained for 20 minutes. This cycle was repeated 3 times.
  • the sample's SO x uptake during hydrogen treatment was measured as the sample's weight change (in %). The SO x uptake of these cycles is shown in Table I.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne l'utilisation, dans un procédé de craquage catalytique fluide, d'un catalyseur ou d'un additif catalytique comprenant une argile anionique ou cette argile sous forme traitée thermiquement, ladite argile anionique comprenant au moins 0,5 % en poids de potassium, calculé en tant que K2O et par rapport au poids de l'argile anionique contenant du potassium. L'utilisation d'un tel catalyseur ou additif permet de réduire les émissions de SOx du régénérateur d'une unité FCC.
EP06786182A 2005-07-01 2006-06-30 Utilisation d'une argile anionique dans un procede fcc Withdrawn EP1899436A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US69632205P 2005-07-01 2005-07-01
PCT/US2006/025921 WO2007005795A1 (fr) 2005-07-01 2006-06-30 Utilisation d'une argile anionique dans un procede fcc

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EP1899436A1 true EP1899436A1 (fr) 2008-03-19

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EP (1) EP1899436A1 (fr)
JP (1) JP2008544850A (fr)
CN (1) CN101208410A (fr)
CA (1) CA2613470A1 (fr)
WO (1) WO2007005795A1 (fr)

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JP4818156B2 (ja) * 2007-02-19 2011-11-16 一般財団法人石油エネルギー技術センター 炭化水素油の接触分解触媒及び該触媒を用いる炭化水素油の接触分解方法
US20100111797A1 (en) * 2007-03-20 2010-05-06 Albemarle Netherlands B.V. Additive-containing anionic clays for reducing sox emissions from an fcc regenerator and process for making them
EP2153894A1 (fr) * 2008-08-05 2010-02-17 Sued-Chemie AG Catalyseur pour la réduction d'oxydes d'azote dans des gaz d'échappement
CN107841306A (zh) * 2017-10-24 2018-03-27 上海理工大学 一种二价铕离子激活玻璃态荧光材料及其制备方法和应用

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WO2007005795A1 (fr) 2007-01-11
JP2008544850A (ja) 2008-12-11
CA2613470A1 (fr) 2007-12-24
CN101208410A (zh) 2008-06-25

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