WO1999046039A1 - Materiau support de catalyseur ameliore - Google Patents

Materiau support de catalyseur ameliore Download PDF

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Publication number
WO1999046039A1
WO1999046039A1 PCT/NO1999/000085 NO9900085W WO9946039A1 WO 1999046039 A1 WO1999046039 A1 WO 1999046039A1 NO 9900085 W NO9900085 W NO 9900085W WO 9946039 A1 WO9946039 A1 WO 9946039A1
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WO
WIPO (PCT)
Prior art keywords
metal
catalyst
support material
catalyst support
calcinated
Prior art date
Application number
PCT/NO1999/000085
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English (en)
Inventor
Erling Rytter
Duncan Akporiaye
Unni Olsbye
Original Assignee
Den Norske Stats Oljeselskap A.S
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Den Norske Stats Oljeselskap A.S filed Critical Den Norske Stats Oljeselskap A.S
Priority to AU34465/99A priority Critical patent/AU3446599A/en
Priority to EP99916091A priority patent/EP1073516A1/fr
Publication of WO1999046039A1 publication Critical patent/WO1999046039A1/fr

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Classifications

    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • C07C5/324—Catalytic processes with metals
    • C07C5/325—Catalytic processes with metals of the platinum group
    • 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
    • B01J21/10—Magnesium; 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
    • B01J23/007—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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • C07C5/324—Catalytic processes with 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • 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
    • C07C2521/10—Magnesium; 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
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • 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
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/26—Chromium
    • 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
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum

Definitions

  • the present invention relates to the preparation of highly stable, high surface area catalyst carrier materials derived from hydrotalcite-type materials by calcination at an elevated temperature.
  • Hydrotalcite is a layered mineral of formula: Mg 6 AI 2 (OH) 16 CO 3 4H 2 O.
  • These compounds are characterised by a sheet-like structure, in which the anions are located in the interlayer between two brucite-like sheets containing the metal ions.
  • M M 1 " metal ions having an ionic radius which is not too different from Mg 2+ can form hydrotalcite-like compounds (1).
  • a catalyst comprising a Group VIII noble metal, a Group IVA metal, optionally a Group IA metal and a carrier substantially consisiting of a mixed Magnesium/Aluminium Oxide Mg(AI)O is disclosed in Den norske stats oljeselskap's International Patent Application WO 94/29021.
  • the catalyst is particularly suitable for the dehydrogenation of C 2 . 5 alkanes to C 2 . 5 alkenes with or without simultaneous oxidation of the hydrogen formed. 2
  • One major use for the materials described in the present application is as support materials for catalysts (1), for instance for the catalytic dehydrogenation of lower alkanes (5).
  • the International Patent Application WO94/29021 discloses a new catalyst and processes for dehydrogenating saturated hydrocarbons.
  • the catalyst disclosed therein contains 0.1 to 1.0 percent by weight of a Group VIII noble metal, 0.1 to 3.0 percent by weight of a Group IVA metal, 0-0.7 percent by weight of a Group IA metal, calculated on the total weight of the catalyst.
  • Said catalyst is prepared by incorporating a Group VIII noble metal, a Group IVA metal and optionally Group IA alkali metal onto a carrier consisting essentially of a mixed oxide of magnesium and aluminum, Mg(AI)O, and subjecting the thereby obtained material to a pretreatment (ROR pretreatment) comprising a reduction, preferably in hydrogen, subsequent oxidation, preferably in air optionally mixed with nitrogen, and finally a second reduction, preferably in hydrogen.
  • ROR pretreatment comprising a reduction, preferably in hydrogen, subsequent oxidation, preferably in air optionally mixed with nitrogen, and finally a second reduction, preferably in hydrogen.
  • the catalyst is described to be used in a process for dehydrogenating dehydrogenatable C 2 . 30 hydrocarbons, preferably C 2 . 5 paraffins, wherein the hydrocarbons under suitable dehydrogenation conditions are contacted in one or more reaction zones with a solid catalyst of the abovementioned composition.
  • the carrier for the catalyst may be prepared by adding a solution of sodium hydroxide and sodium carbonate to a solution of magnesium nitrate and aluminum nitrate according to the method described in Journal of Catalysis 94 (1985), the pages 547-557.
  • sodium hydroxide and sodium carbonate potassium hydroxide and potassium carbonate can be used, see Applied Catalysis 55 3
  • a hydrotalcite-like compound Mg 6 AI 2 (OH) 16 CO 3 .4H 2 O is formed by evaporation (drying) of the abovementioned mixtures. The hydrotalcite is then calcinated at a temperature 500-800°C to give Mg(AI)O.
  • the molar ratio of Mg to Al typically ranges from 1 :1 to 10:1 , and the surface area is typically ranging from 100 to 300 m 2 per gram, preferably from 140 to 210 m 2 per gram, and the particle size can be in the range of 100 ⁇ m to 20 mm.
  • calcination temperature in the examples is consistently 700°C for about 15 hours.
  • the aim of the present invention was therefore to develop a catalyst having the same catalytic performance as this prior art catalyst with regard to catalyst activity, but at the same time increasing the catalyst life time by preventing irreversible deactivation like sintering of the support.
  • the present invention provides for a catalyst support material comprising a mixed oxide consisting essentially of a divalent metal and a trivalent metal in a substantially homogeneous phase, which is a calcination product of a hydrotalcite- like phase calcinated at a temperature of about 700 - 1200 °C, wherein the divalent metal/trivalent metal molar ratio is equal to, or higher than 2.
  • the present invention thus relates to a catalyst support material comprising a mixed oxide consisting essentially of Mg and Al in a substantially homogenous phase, which is a calcination product of a hydrotalcite phase, preferably calcinated at a temperature of 750 to 950°C, wherein the Mg/AI molar ratio is equal 2 or higher than 2.
  • a catalyst support material comprising a mixed oxide consisting essentially of Mg and Al in a substantially homogenous phase, which is a calcination product of a hydrotalcite phase, preferably calcinated at a temperature of 750 to 950°C, wherein the Mg/AI molar ratio is equal 2 or higher than 2.
  • the calcination has been effected at 770 to 850 °C and preferred at about 800 °C .
  • the Mg/AI molar ratio is in the range of about 2.5 to 6.0, and particularly the Mg/AI molar ratio is in the range about 3 to about 5.
  • a method for preparing said catalyst support material wherein a solution comprising a divalent metal salt and trivalent metal salt is mixed with a basic aqueous solution, the reaction product recovered from said reaction mixture, said product being washed and dried, and the dried product is calcinated at a temperature ranging from about 700 - 1200 °C.
  • the preferred divalent metal therein is Mg and the preferred trivalent metal therein is AI.
  • Calcination temperatures in the range of 750 - 950 °C have been found particularly suitable.
  • the calcination takes place at a temperature ranging from about 770 to about 850°C.
  • the calcination may be effected for f.i. about 1 to about 20 hours, and preferably the calcination is effected for about 2-15 hours.
  • the basic aqueous solution used in this process is preferably a composition of aqueous ammonium or alkali metal hydroxides and carbonates. 5
  • the molar ratio of hydroxide to carbonate may f.i. be within the range of 1 :1 to 3:1.
  • the present invention relates to a dehydrogenation catalyst comprising a 1. Transition row metal of the Periodic System and/or a Group VIII metal impregnated on to the catalyst support described above.
  • Transition row metal of the Periodic System is Cr.
  • this catalyst comprises both a Group IVA metal and a Group VIII metal impregnated on to the catalyst support material mentioned above.
  • a Group IA metal may be used together with the Group VIII metal and the Group IVA metal.
  • the Group VIII is Pt , the Group IV metal is Sn and the Group IA metal is Cs.
  • the Group VIII metal catalyst is in the range of 0.05 to 5.0 percent by weight and the amount of the Group IVA metal is 0.05 to 7.0 percent by weight, optionally Group IA 0,05 to 5 percent by weight.
  • the present invention also relates to a process for the catalytic dehydrogenation of light alkanes wherein a stream of such light alkanes is passed through a layer of the catalytic active compositions described above in the presence or absence of steam.
  • this process is performed in the presence of steam.
  • the process is performed in the absence of steam.
  • the present invention relates to the use of the catalytic composition as described above for the dehydrogenation of light alkanes.
  • Figure 1 shows steam stabilisation tests at 650 °C , materials prepared by Mg/AI ratio 3 and 5 and calcination temperature 700 and 800 °C . 6
  • Figure 2 shows steam stabilisation tests at 650 °C , materials prepared by Mg/AI ratio 3 and 5 and calcination temperature 800 °C .
  • Calcination was performed under flowing air (100 ml/min). The sample (5-50 g) was heated with a heating rate of 3°C/min to the final calcination temperature.
  • the sample was cooled with a cooling rate of appx. 2°C/min.
  • a Mg(AI)O material having an atomic ratio of Mg to Al of 3:1 was prepared according to the following procedure: An aqueous solution of NaOH and Na 2 CO 3 was treated with a solution of MgCI 2 -6H 2 O and AICI 3 -6H 2 O in a similar way as in example 1 resulting in the above mentioned Mg(AI)O material. After filtration, washing and drying also in a similar way as in example 1 a hydrotalcite Mg 6 AI 2 (OH) 16 CO 3 4H 2 O was formed. The structure was confirmed by X-ray diffraction analysis. a) The material thus obtained was calcined at about 700°C for about 15 hours, whereby Mg(AI)O was formed.
  • the structure was confirmed by X-ray diffraction analysis, and the surface area was measured to be 187 m 2 /g.
  • the material thus obtained was calcined at about 800°C for about 15 hours, whereby Mg(AI)O was formed.
  • the structure was confirmed by X-ray diffraction analysis, and the surface area was measured to be 162 m 2 /g.
  • the material thus obtained was calcined at about 900°C for about 15 hours, whereby Mg(AI)O was formed, together with traces of inverse MgAI 2 O 4 spinel.
  • the structure was confirmed by X-ray diffraction analysis, and the surface area was measured to be 110 m 2 /g.
  • TheTnaterial thus obtained was calcined at about 1000°C for about 15 hours, whereby Mg(AI)O was formed, together with some inverse MgAI 2 O 4 spinel.
  • the 8 structure was confirmed by X-ray diffraction analysis, and the surface area was measured to be 61 m 2 /g.
  • a Mg(AI)O material having an atomic ratio of Mg to Al of 5:1 was prepared according to the following procedure: An aqueous solution of NaOH and Na 2 CO 3 was treated with a solution of MgCI 2 -6H 2 O and AICI 3 -6H 2 O in a similar way as in example 1 resulting in the above mentioned Mg(AI)O material. After filtration, washing and drying also in a similar way as in example 1 a hydrotalcite MgeAI 2 (OH) 16 CO 3 4H 2 O was formed. The structure was confirmed by X-ray diffraction analysis.
  • the material was loaded into the reactor, which was then heated to 600°C under a N 2 flow. When 600°C was reached, steam was added to the feed. Such conditions (600°C, 50%H 2 O/50%N 2 ) were maintained for 22 hours. A sample of the material was then withdrawn from the reactor, and the temperature increased to 650°C. Such conditions (650°C, 50%H 2 O/50%N 2 ) were maintained for 48 hours. New samples- were withdrawn at 650°C. After completion of the test, the steam feed was turned off, and the reactor cooled to 25°C under a N 2 flow. The remainder of the material was then collected. The sample materials were analysed by BET and XRD.
  • the results for the whole test (314 hours) are shown in Figure 2.
  • the test for the first 72 hours is shown in Figure 1 together with the results from Example 4.
  • the surface area in m 2 /g plotted along the vertical axis is expressed as a function of the duration of the steam stability test in hours (plotted along the horisontal axis).
  • Example 4 To investigate its thermal stability, the support material obtained as described in Example 3b was tested as described in Example 5, except that 100% N 2 was used as feed gas during the whole test. The thermal stability test results are shown in Figure 4.
  • Example 7 To investigate its steam stability, a material prepared as described in Example 7, with Mg/AI ratio of 3, and which had been calcined at 700°C prior to impregnation, was tested as described in Example 4. The steam stability test results are shown in Figure 1.
  • results presented in the Examples show that the initial surface area of the calcined materials decreases with increasing calcination temperature.
  • the results presented in Figure 1 and 2 further show that the materials calcined at a higher temperature maintain a higher specific surface area during subsequent steam testing at 600-650°C. Indeed, for a steam test duration of more than 72 hours, the materials calcined at 800°C have a higher specific surface area than those calcined at 700°C.
  • the initial specific surface area of the materials calcined at a certain temperature decreases with an increasing Mg/AI ratio.
  • the material with a higher Mg/AI ratio maintain a higher specific surface area compared to the material with a lower Mg/AI ratio ( Figure 2).
  • the order of specific surface area is reversed, so that the materials with a higher Mg/AI ratio have a higher specific surface area than those with a lower Mg/AI ratio ( Figure 1).
  • the dehydrogenation can advantageously be performed without steam.

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

Abstract

L'invention porte sur un nouveau matériau support de catalyseur fait d'un mélange d'oxydes essentiellement d'un métal divalent et d'un métal trivalent en phase sensiblement homogène résultant de la calcination d'une phase du genre hydrotalcite calcinée à une température comprise entre 700 °C et 1200 °C, le rapport molaire entre le métal divalent et le métal trivalent étant égal ou supérieur à 2. L'invention porte également sur le procédé de préparation dudit support, sur un catalyseur de déshydrogénation comprenant un métal brut de transition et/ou un métal du groupe VIII imprégnant ledit support, et sur un procédé de déshydrogénation d'alcanes légers à l'aide dudit catalyseur.
PCT/NO1999/000085 1998-03-13 1999-03-11 Materiau support de catalyseur ameliore WO1999046039A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU34465/99A AU3446599A (en) 1998-03-13 1999-03-11 Improved catalyst support material
EP99916091A EP1073516A1 (fr) 1998-03-13 1999-03-11 Materiau support de catalyseur ameliore

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO19981126 1998-03-13
NO19981126A NO307693B1 (no) 1998-03-13 1998-03-13 Forbedret katalysatorbaerermateriale, fremgangsmate for fremstilling derav, dehydrogeneringskatalysator, og katalytisk dehydrogenering av lette alkaner

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WO1999046039A1 true WO1999046039A1 (fr) 1999-09-16

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EP (1) EP1073516A1 (fr)
AU (1) AU3446599A (fr)
NO (1) NO307693B1 (fr)
WO (1) WO1999046039A1 (fr)
ZA (1) ZA992037B (fr)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002102507A1 (fr) * 2001-06-15 2002-12-27 Consejo Superior De Investigaciones Cientificas Catalyseur bimetallique pour le traitement d'eaux qui contiennent des nitrates
WO2004009233A1 (fr) * 2002-07-23 2004-01-29 Beijing University Of Chemical Technology Catalyseur a base solide nanometrique magnetique et son procede de preparation
US7173143B2 (en) 2002-08-30 2007-02-06 Basf Aktiengesellschaft Integrated method for synthesis propylene oxide
US7247598B2 (en) 2002-07-23 2007-07-24 Beijing University Of Chemical Technology Nano-scale magnetic solid base catalyst and its preparation method
US7321058B2 (en) 2000-06-14 2008-01-22 Basf Aktiengesellschaft Method for producing acrolein and/or acrylic acid
WO2008074787A1 (fr) 2006-12-19 2008-06-26 Basf Se Réacteur pour réaliser une déshydrogénation oxydante en continu et procédé associé
DE102007006647A1 (de) 2007-02-06 2008-08-07 Basf Se Verfahren zur Regenerierung eines im Rahmen einer heterogen katalysierten partiellen Dehydrierung eines Kohlenwasserstoffs deaktivierten Katalysatorbetts
US7482500B2 (en) 2003-12-30 2009-01-27 Basf Aktiengesellschaft Preparation of butadiene
US7485761B2 (en) 2003-10-27 2009-02-03 Basf Aktiengesellschaft Method for producing 1-butene
US7488857B2 (en) 2003-12-30 2009-02-10 Basf Aktiengesellschaft Method for the production of butadiene and 1-butene
US7488858B2 (en) 2003-12-30 2009-02-10 Basf Aktiengesellschaft Method for the production of butadiene
CN100464849C (zh) * 2007-07-26 2009-03-04 南京大学 一种用氧化铝改性的中孔分子筛为载体的丙烷脱氢制丙烯的催化剂
US7518024B2 (en) 2003-10-27 2009-04-14 Basf Aktiengesellschaft Process for preparing 1-butene
EP2070900A2 (fr) 2006-07-20 2009-06-17 Basf Se Procédé de fabrication d'isopropanol et de 2-butanol à partir d'alcanes correspondants
DE102008044946A1 (de) 2008-08-29 2010-03-04 Evonik Stockhausen Gmbh Einsatz von Schaumkörpern in Oxidations-Reaktoren zur Herstellung ungesättigter Aldehyde oder Carbonsäuren
US8530717B2 (en) 2008-07-21 2013-09-10 Basf Se Process for the industrial isolation of propene
CN111111654A (zh) * 2019-12-31 2020-05-08 湘潭大学 一种改进型Pt/Mg-Al-O脱氢催化剂的制备方法及其应用
US11760702B2 (en) 2020-03-06 2023-09-19 Exxonmobil Chemical Patents Inc. Processes for upgrading alkanes and alkyl aromatic hydrocarbons
US11760703B2 (en) 2020-03-06 2023-09-19 Exxonmobil Chemical Patents Inc. Processes for upgrading alkanes and alkyl aromatic hydrocarbons

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Publication number Priority date Publication date Assignee Title
EP4347117A1 (fr) 2021-06-02 2024-04-10 ExxonMobil Chemical Patents Inc. Procédés pour la régénération de catalyseurs et pour la revalorisation d'hydrocarbures d'alcanes et/ou aromatiques alkyliques
WO2023107797A1 (fr) 2021-12-06 2023-06-15 Exxonmobil Chemical Patents Inc. Compositions de catalyseur et leurs procédés de fabrication et d'utilisation

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EP0251351A2 (fr) * 1986-05-23 1988-01-07 Shell Internationale Researchmaatschappij B.V. Procédé pour la préparation de magnésie stabilisée et son application dans des procédés catalytiques
WO1994029021A1 (fr) * 1993-06-14 1994-12-22 Den Norske Stats Oljeselskap A.S. Nouveau catalyseur, et procedes pour deshydrogener des hydrocarbures deshydrogenables
US5439861A (en) * 1991-08-16 1995-08-08 Amoco Corporation Catalyzed vapor phase process for making synthesis gas
WO1996023727A1 (fr) * 1995-02-03 1996-08-08 RWE-DEA Aktiengesellschaft für Mineraloel und Chemie Procede de preparation d'hydrotalcites et leurs oxydes de metal

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Publication number Priority date Publication date Assignee Title
EP0251351A2 (fr) * 1986-05-23 1988-01-07 Shell Internationale Researchmaatschappij B.V. Procédé pour la préparation de magnésie stabilisée et son application dans des procédés catalytiques
US5439861A (en) * 1991-08-16 1995-08-08 Amoco Corporation Catalyzed vapor phase process for making synthesis gas
WO1994029021A1 (fr) * 1993-06-14 1994-12-22 Den Norske Stats Oljeselskap A.S. Nouveau catalyseur, et procedes pour deshydrogener des hydrocarbures deshydrogenables
WO1996023727A1 (fr) * 1995-02-03 1996-08-08 RWE-DEA Aktiengesellschaft für Mineraloel und Chemie Procede de preparation d'hydrotalcites et leurs oxydes de metal

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7321058B2 (en) 2000-06-14 2008-01-22 Basf Aktiengesellschaft Method for producing acrolein and/or acrylic acid
WO2002102507A1 (fr) * 2001-06-15 2002-12-27 Consejo Superior De Investigaciones Cientificas Catalyseur bimetallique pour le traitement d'eaux qui contiennent des nitrates
ES2186547A1 (es) * 2001-06-15 2003-05-01 Univ Valencia Politecnica Un catalizador bimetalico para el tratamiento de aguas que contienen nitratos.
WO2004009233A1 (fr) * 2002-07-23 2004-01-29 Beijing University Of Chemical Technology Catalyseur a base solide nanometrique magnetique et son procede de preparation
US7247598B2 (en) 2002-07-23 2007-07-24 Beijing University Of Chemical Technology Nano-scale magnetic solid base catalyst and its preparation method
US7173143B2 (en) 2002-08-30 2007-02-06 Basf Aktiengesellschaft Integrated method for synthesis propylene oxide
US7485761B2 (en) 2003-10-27 2009-02-03 Basf Aktiengesellschaft Method for producing 1-butene
US7518024B2 (en) 2003-10-27 2009-04-14 Basf Aktiengesellschaft Process for preparing 1-butene
US7482500B2 (en) 2003-12-30 2009-01-27 Basf Aktiengesellschaft Preparation of butadiene
US7488857B2 (en) 2003-12-30 2009-02-10 Basf Aktiengesellschaft Method for the production of butadiene and 1-butene
US7488858B2 (en) 2003-12-30 2009-02-10 Basf Aktiengesellschaft Method for the production of butadiene
US7750194B2 (en) 2006-07-20 2010-07-06 Basf Aktiengesellschaft Process for preparing isopropanol and 2-butanol from the corresponding alkanes
EP2070900A2 (fr) 2006-07-20 2009-06-17 Basf Se Procédé de fabrication d'isopropanol et de 2-butanol à partir d'alcanes correspondants
WO2008074787A1 (fr) 2006-12-19 2008-06-26 Basf Se Réacteur pour réaliser une déshydrogénation oxydante en continu et procédé associé
DE102007006647A1 (de) 2007-02-06 2008-08-07 Basf Se Verfahren zur Regenerierung eines im Rahmen einer heterogen katalysierten partiellen Dehydrierung eines Kohlenwasserstoffs deaktivierten Katalysatorbetts
CN100464849C (zh) * 2007-07-26 2009-03-04 南京大学 一种用氧化铝改性的中孔分子筛为载体的丙烷脱氢制丙烯的催化剂
US8530717B2 (en) 2008-07-21 2013-09-10 Basf Se Process for the industrial isolation of propene
WO2010023053A2 (fr) 2008-08-29 2010-03-04 Evonik Stockhausen Gmbh Utilisation de corps en mousse dans des réacteurs à oxydation pour la préparation d'aldéhydes ou d'acides carboxyliques insaturés
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US8841481B2 (en) 2008-08-29 2014-09-23 Evonik Degussa Gmbh Use of foam bodies in oxidation reactors for preparing unsaturated aldehydes or carboxylic acids
DE102008044946B4 (de) 2008-08-29 2022-06-15 Evonik Superabsorber Gmbh Einsatz von Schaumkörpern in Oxidations-Reaktoren zur Herstellung ungesättigter Carbonsäuren
CN111111654A (zh) * 2019-12-31 2020-05-08 湘潭大学 一种改进型Pt/Mg-Al-O脱氢催化剂的制备方法及其应用
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ZA992037B (en) 1999-11-02
NO307693B1 (no) 2000-05-15
NO981126L (no) 1999-09-14
AU3446599A (en) 1999-09-27

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