Molybdenum-vanadium double-metal oxide catalyst and application of same to chemical-chain dehydrogenation of light alkanes
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A double metal oxide and catalyst technology, applied in the field of oxidative dehydrogenation of low-carbon alkanes to olefins, supported molybdenum vanadium double metal oxides, to achieve the effect of increased conversion rate, high single-pass conversion rate, and high selectivity
Active Publication Date: 2019-02-26
TIANJIN UNIV
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While maintaining high catalytic activity, the selec
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Embodiment 1
[0045] Step 1, get the ammonium metavanadate (NH 4 VO 3 ) and 2.9 mass parts of oxalic acid (C 2 h 2 o 4 ) was dissolved in 3mL deionized water, after the reaction was complete, a certain mass of ammonium molybdate ((MH 4 ) 6 Mo 7 o 24 ﹒ 4H 2 O), the Al of 2.0 mass parts 2 o 3 Immerse in the above solution.
[0046] Step 2, drying the material obtained in step 1 at a room temperature of 25 degrees Celsius for 12 hours, then drying at 70 degrees Celsius for 12 hours, and finally roasting at 600 degrees Celsius for 4 hours in an air atmosphere to obtain a molybdenum-vanadium bimetallic composite oxide supported on alumina, Its molecular formula is Mo 1 V y . Wherein, y represents the amount of V relative to 1 mol of Mo, and y=4, 6, 9, 12, 18, 30, that is, the molar ratio of metal V to metal Mo.
[0047] Step 3, the Mo 1 V y The solid powder is compressed into tablets to make a granular catalyst with a size of 20-40 mesh.
Embodiment 2
[0049] Adopt embodiment 1 method to react, its difference is only that the quality of the ammonium molybdate of step (1) is 0, obtains VO x catalyst.
Embodiment 3
[0051] Step 1, get the ammonium molybdate ((MH 4 ) 6 Mo 7 o 24 ﹒ 4H 2 O), be dissolved in 3mL deionized water, with 2.0 parts by mass of Al 2 o 3 Soak in the above solution, dry at room temperature for 12 hours, and dry at 80°C for 2 hours;
[0052] Step 2, drying the material obtained in step 1 at room temperature 25 degrees Celsius for 12 hours, then drying at 70 degrees Celsius for 12 hours, and finally roasting at 600 degrees Celsius for 4 hours in an air atmosphere to obtain molybdenum oxide supported on alumina, and its molecular formula is MoO x .
[0053] Step 3, the MoO x The solid powder is compressed into tablets to make a granular catalyst with a size of 20-40 mesh.
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Abstract
The invention discloses a molybdenum-vanadium double-metal oxide catalyst and application of the same to chemical-chain dehydrogenation of light alkanes. The molybdenum-vanadium double-metal oxide catalyst has a molecular formula of Mo1Vy, wherein y represents a molar ratio of vanadium atoms to molybdenum atoms; the molybdenum-vanadium double-metal oxide catalyst is prepared by using a dipping method; and the Mo1Vy oxygen carrier is prepared through dipping, drying, calcining and tableting. When the loaded molybdenum-vanadium double-metal oxide is applied to the dehydrogenation reaction of light alkanes for preparation of olefins and a reaction temperature is kept at 450-550 DEG C, high-activity high-selectivity oxidative dehydrogenation of propane into propylene can be achieved, the conversion rate of propane is maintained at 30 -40%, and the selectivity of propylene is 80-90%. After the fresh oxygen carrier reacts with propane, the fresh oxygen carrier turns from a high valence stateto a low valence state; a low-valence-state oxygen carrier reacts with air or oxygen and is oxidized into a high valence state, and lattice oxygen is regained and is circulated again; and after repeated regeneration, the oxygen carrier still has stable reaction performance. The catalyst provided by the invention can be used in reaction units such as fixed-bed reactors, moving-bed reactors or circulating fluidized beds.
Description
technical field [0001] The invention relates to a technology for dehydrogenating low-carbon alkanes by using metal oxides, and more specifically, to a method and application of supported molybdenum-vanadium double metal oxides for oxidative dehydrogenation of low-carbon alkanes to olefins. Background technique [0002] As an important unconventional natural gas resource, shale gas is rich in low-carbon alkanes. Converting low-carbon alkanes in shale gas into higher-value chemical products has important energy and environmental significance. In recent years, the preparation of corresponding alkenes by dehydrogenation of alkanes has been fully developed. [0003] Taking the dehydrogenation of propane to produce propylene as an example, the traditional anaerobic dehydrogenation (PDH) technology uses Pt or Cr-based catalysts. The PDH reaction has a high selectivity for propylene under the catalytic conditions of Pt-based catalysts, but due to thermodynamic limitations The singl...
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