WO2002051539A1 - Compositions a plusieurs oxydes metalliques cristallins et procedes de preparations et d'utilisations de celles-ci - Google Patents

Compositions a plusieurs oxydes metalliques cristallins et procedes de preparations et d'utilisations de celles-ci Download PDF

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WO2002051539A1
WO2002051539A1 PCT/US2000/035011 US0035011W WO02051539A1 WO 2002051539 A1 WO2002051539 A1 WO 2002051539A1 US 0035011 W US0035011 W US 0035011W WO 02051539 A1 WO02051539 A1 WO 02051539A1
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composition
mixtures
ions
niobium
tantalum
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PCT/US2000/035011
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English (en)
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Robert L. Bedard
Paula L. Bogdan
Lisa M. King
Susan C. Koster
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Uop Llc
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Priority to EP00991706A priority Critical patent/EP1349651A4/fr
Priority to PCT/US2000/035011 priority patent/WO2002051539A1/fr
Publication of WO2002051539A1 publication Critical patent/WO2002051539A1/fr

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Definitions

  • This invention relates to a new family of crystalline metal oxide compositions. These compositions contain either niobium, or tantalum (M), a cation (A) such as an alkali metal, at least one M' metal where M' is tungsten or molybdenum, and optionally a M" metal such as antimony or vanadium. This invention also relates to a hydrothermal process for preparing the crystalline compositions and to an ammoxidation process using the compositions.
  • Olefins e.g., propylene or isobutene are used to prepare a number of higher value products such as aldehydes, acids and nitriles. Since the price of the corresponding alkanes, i.e., propane or isobutane is lower than that of the olefins, it would be advantageous to be able to produce the higher value product directly from the alkanes.
  • compositions have spinel or perovskite structures.
  • a catalyst comprising Mo a VbNb c Sb d Xe is disclosed, where X includes Li, Sc, Na, Fr, Ta, etc.
  • US-A-4892856 discloses a catalyst having the composition Mo a VbA c BdC e D f O x where A is tungsten or niobium, B is Fe, Cu, Bi, Cr, Sb or TI, C is an alkali or alkaline earth metal and D is Si, Al or Ti.
  • US-A-5807531 discloses a multimetaloxide having an empirical formula of M ⁇ i 2 - a - -cV a 1 b M 2 c O x . However, these materials have a low surface area of 17m 2 /g or lower.
  • this invention relates to a new family of crystalline compositions, a process for preparing these compositions and a process which uses the compositions. Accordingly, one embodiment of the invention is a crystalline metal oxide composition having an empirical formula of:
  • A is a cation selected from the group consisting of an alkali metal ion, ammonium ion or mixtures thereof
  • M is tantalum or niobium
  • M' is molybdenum, tungsten and mixtures thereof
  • M" is selected from the group consisting of antimony, tellurium, vanadium, tantalum, niobium, titanium, tin, indium, gallium, aluminum, bismuth and mixtures thereof
  • "n” varies from about 0.1 to about 2
  • "x” varies from about 0.01 to about 8
  • "y” varies from zero to about 4
  • "p” has a value such that it balances the valence of the combined elements,
  • A, M, M', M" the composition characterized in that it has at least one x-ray diffraction peak at a d spacing of about 3.9 ⁇ 0.15 ⁇ and when M is Nb and M' is either Mo or a mixture of W and Mo and M" is V and y
  • Another embodiment of the invention is a process for preparing the crystalline compositions described above.
  • the process comprising forming a reaction mixture containing reactive sources of A, M, M' and optionally M" at a temperature and a time sufficient to form the crystalline composition, the mixture having a composition expressed in terms of mole ratios of oxides of: aA 2 0:M0 5/ 2:bMO3:cMO q/2 :dH 2 0
  • a new family of crystalline metal oxide compositions has been synthesized and characterized. These compositions contain either niobium or tantalum, at least one of tungsten and molybdenum, and optionally a third metal such as vanadium antimony or tellurium. A cation such as lithium is also present. These crystalline metal oxides are described by the empirical formula:
  • n MM' x M" y Op where "n” varies from 0.1 to 2.
  • the value of "x” varies from 0.01 to 8, while the value of "y” varies from zero to 4.
  • M is niobium or tungsten
  • M' is molybdenum, tungsten, or mixtures thereof
  • M" is selected from the group consisting of vanadium, tantalum, antimony, tellurium, niobium, titanium, tin, indium, aluminum and mixtures thereof.
  • "p” has a value such that it balances the valence of the combined elements A, M, M', M" and A is an alkali metal cation, an ammonium cation or mixtures thereof.
  • alkali metals examples include: lithium, sodium, potassium, rubidium, cesium and mixtures thereof.
  • M is niobium
  • M' is not niobium and likewise when M is tantalum, M" is not tantalum.
  • novel crystalline metal oxide compositions are hydrothermally prepared. That is, a reaction mixture is prepared from reactive sources of the desired components along with water and heated at a temperature and for a time sufficient to form the desired product.
  • Reactive sources of the alkali metals include the hydroxide, carbonate, halide, acetate, and sulfate compounds.
  • Niobium reactive sources include niobium pentoxide (Nb 2 ⁇ 5), hydrous niobium oxide, niobium ethoxide, and ammonium niobium oxalate.
  • Molybdenum sources include molybdic acid ((NH 4 ) 6 Mo 7 ⁇ 2 4 # 4H 2 0), molybdenum trioxide (M0O 3 ), sodium molybdate and molybdenum (VI) oxychloride.
  • Tungsten sources include ammonium tungstate, tungsten (VI) oxide, tungsten (VI) chloride, sodium tungstate, and tungstic acid.
  • Vanadium sources include vanadium (V) oxide, vanadium (V) oxychloride, vanadium oxide sulfate, and ammonium vanadate.
  • Tantalum sources include tantalum oxide, hydrous tantalum oxide, tantalum butoxide, tantalum bromide, and tantalum chloride.
  • Tellurium sources include ammonium tellurium oxide, telluric acid, and tellurium oxide.
  • Tin, indium, gallium aluminum and bismuth sources include the nitrates and chlorides, while titanium sources include titanium alkoxides, (NH 4 ) 2 Ti(OH) 2 (C 3 H 4 0 3 )2 and TiCI 3 . It should be pointed out that this list is only by way of examples and other reactive sources of individual elements may also be used. Using the above described reactive sources, a reaction mixture is formed which in terms of molar ratios of the oxides is expressed by the formula:
  • reaction mixture it is required that it have a pH of 4 to 10 and preferably from 6 to 9. This can be done by using a basic compound of the A cation. Alternatively, the A cation can be added as a non-basic compound and the pH adjusted by the addition of an appropriate amount of an organic base such as an alkyl amine or a tetraalkylammonium hydroxide.
  • an organic base such as an alkyl amine or a tetraalkylammonium hydroxide.
  • reaction mixture is formed and pH adjusted, it is reacted at a temperature of 100-225°C for a period of time of about 1 hr to 96 hr in a sealed reaction vessel under autogenous pressure.
  • the mixture is filtered to isolate the solid product which is washed with deionized water and dried in air.
  • the product may be isolated and washed by centrifugation techniques.
  • the product may also be washed with aqueous acid rather than deionized water to convert the composition to the proton exchanged form during workup.
  • the crystalline metal oxide compositions of the invention are characterized by their unique x-ray diffraction pattern and their surface area.
  • the x-ray diffraction pattern has at least one peak at a d spacing of 3.9 ⁇ 0.15 ⁇ .
  • a second peak at y ⁇ of the 3.9 ⁇ 0.15A spacing is also often present in these compositions.
  • Another X-ray diffraction peak, which is sometimes distinct but usually broad, is located at 10.7 ⁇ 0.25 A. This peak is always broader than the
  • the crystalline metal oxide compositions of the invention are also characterized by their surface areas. These materials generally have a surface area of at least 15 m 2 /g, and preferably at least 25 m 2 /g.
  • M metal is niobium and M' is either molybdenum or a combination of molybdenum and tungsten and M" metal is vanadium and y>0, then the surface area must be at least 25 m 2 /g.
  • compositions can be ion exchanged so that the A cation is exchanged for another cation.
  • cations which can be exchanged into the metal oxide composition include, without limitation, other alkali metal ions, hydronium ions, alkaline earth ions, lanthanide ions, divalent transition metal ions, trivalent transition metal ions and organic cations such as amphiphilic ammonium ions, quaternary ammonium cations and alkylpyridinium cations.
  • Ion exchange can be carried out by means well known in the art. The process usually involves contacting the composition with a solution containing the desired cation at exchange conditions. Exchange conditions include a temperature of room temperature to 100°C and a time of 20 minutes to 4 days.
  • the crystalline compositions of this invention can be used in various processes in which hydrocarbons are one of the reactants.
  • Hydrocarbon conversion processes are well known in the art and include cracking, hydrocracking, alkylation of both aromatics and isoparaffin, isomerization, polymerization, reforming, aromatization, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanation and syngas shift process.
  • Specific reaction conditions and the types of feeds which can be used in these processes are set forth in U.S. Patent Nos. 4,310,440 and 4,440,871 which are incorporated by reference.
  • Preferred hydrocarbon conversion processes are reforming aromatization, transalkylation, isomerization, dealkylation and dehydrogenation. Generally these processes are carried out at a pressure of about 10 to about 750 psig, a weight hourly space velocity of about 0.1 to about 30 hr "1 with respect to the hydrocarbon, a gas hourly space velocity of about 10 to about 10,000 hr "1 with respect to hydrogen and a temperature of about 100°C to about 650°C.
  • the compositions of this invention can also be used to catalyze transalkylation.
  • transalkylation is meant the process where an alkyl group on one aromatic nucleus is intermolecularly transferred to a second aromatic nucleus.
  • a preferred transalkylation process is one where one or more alkyl groups of a polyalkylated aromatic compound is transferred to a nonalkylated aromatic compound, and is exemplified by reaction of diisopropylbenzene with benzene to give two molecules of cumene.
  • the reaction conditions for transalkylation include temperatures in the range of about 100° to about 250°C, pressures in the range of 100 to about 750 psig, and a molar ratio of unalkylated aromatic to polyalkylated aromatic in the range from about 1 to about 10.
  • alkanes such as propane and isobutane
  • nitriles i.e., acrylonitrile and methacrylonitrile.
  • Conditions for ammoxidation may be found in the art and specifically in US-A- 4788173; 5171876 and 5049692.
  • General conditions include a temperature of 350°C to 700°C, an HSV of 100 to 10,000 hr "1 , an ammonia to alkane mole ratio of 0.5:1 to 3:1 , an oxygen to ammonia mole ratio of 0.5:1 to 10:1 and a pressure of atmospheric to 1034 kPa.
  • the sources of oxygen can be air, pure oxygen or oxygen with a diluent such as nitrogen, etc.
  • a slurry was prepared by mixing in a container 21.8g of Nb 2 ⁇ 5 # 12.2H 2 0 and 91.9g of water followed by the addition of 16.41 g of NH 4 V0 3 , 49.51 g of (NH 4 ) 6 Mo 7 0 24 # 4H 2 0 and 4.39g of NH 4 OH.
  • the resulting yellow suspension was stirred for 1 hour, divided into aliquots which were placed into PTFE lined steel reactors and reacted as follows: 2A - 150°C for 24 hours, 2B - 150°C for 48 hours, 2C - 200°C for 48 hours; 2E - 225° for 24 hours and 2F - 225°C for 48 hours.
  • compositions were prepared as described above and a description of the reaction mixture, synthesis conditions and empirical formulas are presented in Table 1.
  • the major product was one displaying an x-ray powder diffraction pattern with peaks at about 3.91 A, 1.96A and a peak at about 10.8A with varying degrees of broadness and definition.
  • compositions described in examples 1-4 were tested in a continuous flow fixed bed laboratory plant.
  • the reactor consisted of a %" ID stainless steel tube reactor which contained a 10 cc catalyst bed volume.
  • the propane, ammonia, air and nitrogen (diluent) were mixed at the top of the reactor and down flowed over the catalyst.
  • the amount of catalyst in the bed can be varied from 2 cc to 10 cc with the remainder of the volume being taken up with inert quartz sand.
  • the catalyst tests were carried out at the temperatures indicated in Table 2, and the effluent was analyzed by GC. Results of these tests are presented in Table 2.
  • EXAMPLE 7 In a mortar, 1.80 g U 2 CO 3 was ground, followed by the addition of 10.25 g WO 3 and further grinding. Next, 6.90g Nb ⁇ 5 »12.2H 2 0 was added and the mixture was ground to yield a damp yellow-green powder. This powder was then added to a vessel containing 15.2 g of water and stirred for 1 hour after which the pH was 8.31. The resultant mixture was loaded into a PTFE lined stainless steel reactor and reacted for 48 hours at 200°C. After the reaction was completed, the solid reaction products were isolated by high-speed centrifugation. After centrifugation, the supernatant solution appeared to be colloidal and was decanted and retained as fines.
  • Fines product 1.99% Li, 25.6% Nb, 46.1 % W with an LOI of 9.97 mass %, giving the empirical formula Lh. 04 NbWo.g2Op.
  • Amorphous hydrous Ta' 2 0 5 was prepared by adding 34.0 g of
  • a reaction mixture was prepared by suspending 27.04 g Ta 2 0 5 : 13 H 0, prepared above, in 48.3 g of deionized water and adding to it a homogeneous powder of 1.50 g Li 2 C0 3 and 23.03 g M0O 3 .
  • the resultant reaction mixture was stirred for one hour and was found to have a pH of 5.02 and a composition in terms of molar oxide ratios of;
  • the N 2 BET surface area was determined to be 141 m 2 /g. This product was identified as sample A.
  • Nitrogen BET surface area was found to be 87 m 2 /g for Sample D.
  • composition of the reaction mixture in terms of molar oxide ratios was determined to be:
  • the mixture was stirred for an hour, split into several aliquots which were loaded into Teflon lined reactors and the mixtures reacted at either 150°C or 200°C for various times under quiescent autogenous conditions.
  • the solid products were isolated by vacuum filtration, washed and then dried at ambient air.
  • Nitrogen BET surface area was measured to be 145 m2/g. This product was identified as sample J. A 3.5 g portion of the solid product obtained above was slurried in 200 mL of 1 M HN0 3 for 2 hours at room temperature, vacuum filtered to isolate the solid product and then washed with 500 mL 1 M HN0 3 . After drying, elemental analysis showed that this product contained less than 0.002 wt. % Li and gave a composition with the empirical formula of:
  • Nitrogen BET surface area was found to be 125 m 2 /g. This product was identified as product K.
  • Nitrogen BET surface area was measured to be 161 m 2 /g. This product was identified as Sample L. A 3.5 g portion of Sample L was slurried in 200 mL of 1 M HNO 3 for 2 hours at room temperature, vacuum filtered to isolate the solid product and then washed with 500 mL 1 M HN0 3 . This product was identified as sample M.
  • Samples from Examples 1 , 2, 3 and 6 were tested for the dehydrogenation of methylcyclohexane (MCH) to toluene using the following procedure.
  • MCH methylcyclohexane
  • a reactor there were placed 250 mg (40-60 mesh) of the sample to be tested and the sample was pretreated at 565°C for 180 min. in hydrogen.
  • the sample was then cooled to 300°C under hydrogen. Over this sample there was flowed, at a rate of 250 cc/min, methylcyclohexane that was saturated with hydrogen at 0°C.
  • the temperature was then increased and measurements taken at 300°C, 325°C, 350°C, 375°C, 400°C, 450°C and 500°C. Analysis of the effluent was carried out using a GC analyzer. The results of these experiments are shown in Table 1.
  • compositions of this invention have significant acidity, can isomerize paraffins and aromatize n-heptane.

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Abstract

L'invention concerne la synthèse d'une nouvelle famille de compositions d'oxydes métalliques cristallins. Ces compositions sont représentées par la formule empirique suivante : AnMM'xM''yOp, dans laquelle A représente un métal alcalin, un ion d'ammonium et des mélanges de ceux-ci, M représente un niobium, un tantale, M' représente un tungstène, un molybdène, ou des mélanges de ceux-ci. M' représente un vanadium, un tantale, un niobium, un titane, un indium d'étain, un gallium, un aluminium, un bismuth, un antimoine, un tellure et des mélanges de ceux-ci. M' représente un métal facultatif. Ces compositions sont caractérisées en ce qu'elles présentent un diagramme de diffraction des rayons X comportant au moins une crête à un écartement d d'environ 3,9 Å. Par ailleurs, l'invention concerne une procédure de synthèse hydrothermale ainsi que des procédés de conversion d'hydrocarbures faisant intervenir ladite composition.
PCT/US2000/035011 2000-12-22 2000-12-22 Compositions a plusieurs oxydes metalliques cristallins et procedes de preparations et d'utilisations de celles-ci WO2002051539A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004035527A1 (fr) * 2002-10-17 2004-04-29 Basf Aktiengesellschaft Masses d'oxyde multimetallique
CN1313440C (zh) * 2002-10-17 2007-05-02 巴斯福股份公司 多金属氧化物材料
US8623781B2 (en) * 2011-06-28 2014-01-07 King Fahd University of Pretroleum and Minerals Oxidative dehydrogenation of propane

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4524236A (en) * 1984-06-28 1985-06-18 Union Carbide Corporation Process for oxydehydrogenation of ethane to ethylene
US4892856A (en) * 1987-06-05 1990-01-09 Nippon Shokubai Kagaku Kogyo Co., Ltd. Catalyst for oxidation of acrolein and process for preparation thereof
US6037304A (en) * 1999-01-11 2000-03-14 Saudi Basic Industries Corporation Highly active and selective catalysts for the production of unsaturated nitriles, methods of making and using the same
US6043185A (en) * 1999-04-02 2000-03-28 The Standard Oil Company Gallium promoted molybdenum vanadium-antimony-oxide based catalyst for selective paraffin ammoxidation
US6171571B1 (en) * 1999-05-10 2001-01-09 Uop Llc Crystalline multinary metal oxide compositions, process for preparing and processes for using the composition

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000026123A (ja) * 1998-07-08 2000-01-25 Mitsubishi Chemicals Corp 複合酸化物および複合酸化物の製造方法
JP2000143244A (ja) * 1998-07-24 2000-05-23 Mitsubishi Chemicals Corp 複合金属酸化物の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4524236A (en) * 1984-06-28 1985-06-18 Union Carbide Corporation Process for oxydehydrogenation of ethane to ethylene
US4892856A (en) * 1987-06-05 1990-01-09 Nippon Shokubai Kagaku Kogyo Co., Ltd. Catalyst for oxidation of acrolein and process for preparation thereof
US6037304A (en) * 1999-01-11 2000-03-14 Saudi Basic Industries Corporation Highly active and selective catalysts for the production of unsaturated nitriles, methods of making and using the same
US6043185A (en) * 1999-04-02 2000-03-28 The Standard Oil Company Gallium promoted molybdenum vanadium-antimony-oxide based catalyst for selective paraffin ammoxidation
US6171571B1 (en) * 1999-05-10 2001-01-09 Uop Llc Crystalline multinary metal oxide compositions, process for preparing and processes for using the composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1349651A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004035527A1 (fr) * 2002-10-17 2004-04-29 Basf Aktiengesellschaft Masses d'oxyde multimetallique
WO2004035528A1 (fr) * 2002-10-17 2004-04-29 Basf Aktiengesellschaft Procede de production d'une masse constituee d'oxydes polymetalliques
US7038082B2 (en) 2002-10-17 2006-05-02 Basf Aktiengesellschaft Preparation of a multimetal oxide material
US7091377B2 (en) 2002-10-17 2006-08-15 Basf Aktiengesellschaft Multimetal oxide materials
CN1313440C (zh) * 2002-10-17 2007-05-02 巴斯福股份公司 多金属氧化物材料
CN1315791C (zh) * 2002-10-17 2007-05-16 巴斯福股份公司 生产多金属氧化物材料的方法
US8623781B2 (en) * 2011-06-28 2014-01-07 King Fahd University of Pretroleum and Minerals Oxidative dehydrogenation of propane

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