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Catalyst and process method for butene oxidative dehydrogenation to butadiene

An oxidative dehydrogenation and catalyst technology, which is applied in metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, chemical instruments and methods, etc. It can improve the utilization rate of resources, inhibit carbon deposition and reduce by-products.

Active Publication Date: 2018-05-11
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The technical problem to be solved by the present invention is that the existing catalysts for butadiene oxidative dehydrogenation to butadiene are not high in selectivity to butadiene, and produce deep oxidation products CO and CO 2 More problems, provide a new catalyst for the oxidative dehydrogenation of butene to butadiene, the preparation method of the catalyst is simple, in the oxidative dehydrogenation of butene, the deep oxidation products CO and CO are reduced 2 The generation of butadiene has the advantages of high selectivity of butadiene, less by-products, especially deep oxides, and high stability of catalyst performance

Method used

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  • Catalyst and process method for butene oxidative dehydrogenation to butadiene

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Experimental program
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Effect test

Embodiment 1

[0024] Weigh 808.0g ferric nitrate (Fe(NO 3 ) 3 9H 2 O), 128.0g magnesium nitrate (Mg(NO 3 ) 2 ·6H 2 O), 74.0g zinc nitrate (Zn(NO 3 ) 2 ·6H 2 O), 62.7g manganese nitrate (Mn(NO 3 ) 2 4H 2 O), 30.2g gold chloride (AuCl 3 ), 60.2g indium nitrate (In(NO 3 ) 3 ), 20.1g manganese nitrate (Mn(NO 3 ) 2 4H 2 O) and 86.8g cerium nitrate (Ce(NO 3 ) 3 ·6H 2 O) Dissolve in 4L of deionized water and stir evenly to form a solution. Then the above solution is co-precipitated with 20% ammonia solution, the precipitation pH value is kept at 9.5, and the precipitation temperature is room temperature, then the solid sample in the precipitated product is separated with a centrifuge, washed with 4L deionized water, and the obtained solid Dry in an oven at 110°C for 4 hours. The dried sample was calcined in a muffle furnace at 600°C for 4 hours to obtain catalyst A, which was ground into 40-60 mesh particles for catalyst evaluation. The molar ratio of the elemental composition...

Embodiment 2

[0026] Weigh 808.0g ferric nitrate (Fe(NO 3 ) 3 9H2 O), 204.8g magnesium nitrate (Mg(NO 3 ) 2 ·6H 2 O), 29.6g zinc nitrate (Zn(NO 3 ) 2 ·6H 2 O), 25.6g manganese nitrate (Mn(NO 3 ) 2 4H 2 O), 3.0g gold chloride (AuCl 3 ), 3.0g indium nitrate (In(NO 3 ) 3 ), 2.5g manganese nitrate (Mn(NO 3 ) 2 4H 2 O) and 4.3g cerium nitrate (Ce(NO 3 ) 3 ·6H 2 O) Dissolve in 4L of deionized water and stir evenly to form a solution. Then the above solution is co-precipitated with 10% ammonia solution, the precipitation pH value is maintained at 6.0, and the precipitation temperature is 10 ° C. Then, the solid sample in the precipitated product is separated with a centrifuge, washed with 4L deionized water, and the resulting The solid was dried in an oven at 90°C for 24 hours. The dried sample was calcined in a muffle furnace at 400°C for 24 hours to obtain catalyst B, which was ground into 40-60 mesh particles for catalyst evaluation. The molar ratio of the elemental composit...

Embodiment 3

[0028] Weigh 808.0g ferric nitrate (Fe(NO 3 ) 3 9H 2 O), 25.6g magnesium nitrate (Mg(NO 3 ) 2 ·6H 2 O), 236.8g zinc nitrate (Zn(NO 3 ) 2 ·6H 2 O), 25.6g manganese nitrate (Mn(NO 3 ) 2 4H 2 O), 186.9g gold chloride (AuCl 3 ), 300.9g indium nitrate (In(NO 3 ) 3 ), 251.0g manganese nitrate (Mn(NO 3 ) 2 4H 2 O) and 434.0g cerium nitrate (Ce(NO 3 ) 3 ·6H 2 O) Dissolve in 4L of deionized water and stir evenly to form a solution. Then the above solution is co-precipitated with 30% ammonia solution, the precipitation pH value is maintained at 12, and the precipitation temperature is 80 ° C. Then, the solid sample in the precipitated product is separated with a centrifuge, washed with 4L deionized water, and the resulting The solid was dried in an oven at 150°C for 1 hour. The dried sample was calcined in a muffle furnace at 650°C for 1 hour to obtain catalyst C, which was ground into 40-60 mesh particles for catalyst evaluation. The molar ratio of the elemental co...

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Abstract

The invention relates to a catalyst for butadiene oxidative dehydrogenation to butadiene and a process method thereof, which mainly solves the problem that the existing catalysts for butene oxidative dehydrogenation to butadiene have low selectivity to butadiene and deep production The problem of more oxidation products CO and CO2. The present invention adopts a catalyst for oxidative dehydrogenation of butene to prepare butadiene and its process method. The catalyst uses divalent metal ferrite MeIIFe2O4 as the main active component, wherein the divalent metal MeII is selected from Zn and Mg , at least one of Mn, Ni, Co and Cu, and the technical scheme of using oxides of IB group elements, IIIA group elements, VIIB group elements and lanthanide elements as additives can better solve this problem, and is efficient, The butadiene product is produced stably, the production of deep oxidation products CO and CO2 is reduced, and it can be used in the industrial production of butadiene by oxidative dehydrogenation of butene.

Description

technical field [0001] The invention relates to a catalyst and a process for preparing butadiene by oxidative dehydrogenation of butene. Background technique [0002] 1,3-Butadiene is an important monomer for synthetic rubber and resin, and plays an important role in petrochemical olefin raw materials. In recent years, with the rapid development of the synthetic rubber and resin industry and the increasing use of butadiene, the market demand for butadiene continues to grow, and the raw materials of butadiene are in short supply. At present, butadiene is mainly obtained through the extraction of naphtha cracking products, which is far from meeting the market demand, and the development of coal chemical industry and large-scale shale gas in the emerging energy field cannot provide butadiene products, so people begin to pay attention to other Butadiene production methods, among which the research on butene oxidative dehydrogenation technology is relatively extensive. The C4 f...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/89B01J23/889C07C5/48C07C11/167
Inventor 曾铁强缪长喜吴文海樊志贵姜冬宇
Owner CHINA PETROLEUM & CHEM CORP