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Catalyst for preparing butadiene through butylene oxydehydrogenation and use thereof

An oxidative dehydrogenation and catalyst technology, applied in metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, organic chemistry, etc., can solve the problem of low yield of butadiene, etc., and achieve strong catalytic oxidation Effects of dehydrogenation performance, cost reduction, and stability enhancement

Active Publication Date: 2016-04-27
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The technical problem to be solved by the present invention is that the existing catalysts for the oxidative dehydrogenation of butene to butadiene need to pre-separate the butane in the butene raw material, and the 1-butene and cis-2-butene with different reactivity The three isomers of alkene and trans-2-butene have different conversion rates under the same reaction conditions, which causes the problem that the yield of butadiene is not high, and a new method for preparing butadiene by oxidative dehydrogenation of butene is provided. Catalyst, the preparation method of the catalyst is simple, suitable for the C4 mixture containing n-butane and n-butene including three isomers as butene raw material, it has the advantages of high catalytic activity, high butadiene selectivity, and high stability of catalyst performance

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Weigh 4443.92g iron nitrate (Fe(NO 3 ) 3 9H 2 O), 1183.87g zinc nitrate (Zn(NO 3 ) 2 ·6H 2 O), 1280.12g magnesium nitrate (Mg(NO 3 ) 2 ·6H 2 O), 80g chromium nitrate (Cr(NO 3 ) 3 9H 2 O), 25.1g manganese nitrate (Mn(NO 3 ) 2 4H 2 O), 9.36g ammonium metavanadate (NH 4 VO 3 ), 67.74g antimony chloride (SbCl 3 ), 86.79g cerium nitrate (Ce(NO 3 ) 3 ·6H 2 O), 25.49g gallium nitrate (Ga(NO 3 ) 3 ) and 60.17g indium nitrate (In(NO 3 ) 3) was dissolved in 5L of distilled water and stirred evenly to form a solution. Then the above solution is co-precipitated with 20% ammonia solution, the precipitation pH value is maintained 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 5L distilled water, and the resulting solid is placed in an oven. Dry at 110°C for 4 hours. The dried sample was calcined in a muffle furnace at 600°C for 4 hours to obtain cataly...

Embodiment 2

[0027] Weigh 4443.92g iron nitrate (Fe(NO 3 ) 3 9H 2 O), 384.76g zinc nitrate (Zn(NO 3 ) 2 ·6H 2 O), 281.63g magnesium nitrate (Mg(NO 3 ) 2 ·6H 2 O), 4g chromium nitrate (Cr(NO 3 ) 3 9H 2 O), 2.51g manganese nitrate (Mn(NO 3 ) 2 4H 2 O), 1.16g ammonium metavanadate (NH 4 VO 3 ), 2.26g antimony chloride (SbCl 3 ), 4.34g cerium nitrate (Ce(NO 3 ) 3 ·6H 2 O), 2.55g gallium nitrate (Ga(NO 3 ) 3 ) and 3.01g indium nitrate (In(NO 3 ) 3 ) was dissolved in 4L of distilled water and stirred evenly to form a solution. Then above-mentioned solution and 10% ammonia solution are carried out co-precipitation, precipitation pH value is kept on 6.0, and precipitation temperature is 10 ℃, then the solid sample in the precipitation product is separated with centrifuge, washes with 5L distilled water, and gained solid is in Dry 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 in...

Embodiment 3

[0033] Weigh 4443.92g iron nitrate (Fe(NO 3 ) 3 9H 2 O), 3995.57g zinc nitrate (Zn(NO 3 ) 2 ·6H 2 O), 1066.77g magnesium nitrate (Mg(NO 3 ) 2 ·6H 2 O), 400g chromium nitrate (Cr(NO 3 ) 3 9H 2 O), 250.96g manganese nitrate (Mn(NO 3 ) 2 4H 2 O), 116.96g ammonium metavanadate (NH 4 VO 3 ), 225.81g antimony chloride (SbCl 3 ), 433.93g cerium nitrate (Ce(NO 3 ) 3 ·6H 2 O), 254.89g gallium nitrate (Ga(NO 3 ) 3 ) and 300.87g indium nitrate (In(NO 3 ) 3 ) was dissolved in 5L of distilled water and stirred evenly to form a solution. Then above-mentioned solution and 30% ammonia solution are carried out co-precipitation, precipitation pH value is kept on 12, and precipitation temperature is 80 ℃, then the solid sample in the precipitation product is separated with centrifuge, washes with 5L distilled water, and gained solid is in Dry 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 w...

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PUM

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Abstract

The invention relates to a catalyst for preparing butadiene through butylene oxydehydrogenation and a use thereof. The catalyst mainly solves the problem that the existing catalyst for preparing butadiene through butylene oxydehydrogenation needs separation of butane in butylene raw materials and has different conversion rates of three isomers such as 1-butene, cis-2-butene and trans-2-butene under the same reaction conditions so that a butadiene yield is low. The lattice oxygen catalyst comprises alpha-Fe2O3, ZnFe2O4, MgFe2O4 and one or more M metal oxides and M represents one or more of Cr, Mn, V, Sb, Ce, Ga and In. The catalyst realizes efficient, stable and continuous preparation of a butadiene product and can be used for industrial production for preparing butadiene through butylene oxydehydrogenation.

Description

technical field [0001] The invention relates to a catalyst for producing butadiene by oxidative dehydrogenation of butene and its application. Background technique [0002] 1,3-Butadiene is an important raw material of petrochemical industry, especially an important monomer of synthetic rubber and resin, and plays an important role in petrochemical olefin raw materials. At present, the main production method of butadiene is to extract it from the carbon four fraction of naphtha steam cracking product by extraction method, butadiene is also produced industrially by dehydrogenation of butane or butene. Because alkanes are relatively stable, butane dehydrogenation process has a higher reaction temperature and more by-products, while butene is more active, and the reaction temperature of butene oxidative dehydrogenation is lower and the selectivity is higher, which has the advantage of being easy to industrialize. [0003] In recent years, with the rapid development of the synt...

Claims

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Application Information

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