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Zinc ferrite catalysts, method of preparing thereof and method of preparing 1,3-butadiene using thereof

一种丁二烯、催化剂的技术,应用在制备1,制备该铁酸锌催化剂领域,能够解决催化剂难商业化、改变催化剂活性、产率降低等问题,达到简单结构和合成过程、提高经济效益、高度可重现性的效果

Active Publication Date: 2010-03-17
SK INNOVATION CO LTD +1
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  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Among them, 90% of the butadiene is supplied by the naphtha cracking process, but the problem is: in order to meet the increasing demand for butadiene, new naphtha cracking centers (NCCs) must be established; and the problem is also: due to The naphtha cracking process is not a butadiene-only process, so excess other base fractions as well as butadiene will be produced
[0011] In the oxidative dehydrogenation of n-butene, when zinc ferrite catalysts or mixed phase catalysts substituted with other metals are used, compared with conventional zinc ferrite catalysts, the process of producing 1,3-butadiene High activity can be obtained in , but there is a problem that the above-mentioned catalyst is difficult to synthesize, and the above-mentioned catalyst is also difficult to reproduce, so the above-mentioned catalyst is difficult to commercialize
In addition, because the C4 mixture used as a reactant in the present invention contains various components as well as n-butene, when the above-mentioned catalyst is used, there is a problem that the activity of the catalyst and the catalyst pair 1 are greatly changed due to side reactions, 3-butadiene selectivity
[0012] Another problem with the oxidative dehydrogenation of n-butene is that the yield of 1,3-butadiene decreases when the reactants include a predetermined amount or more of n-butane [L.M. Welch, L.J. Croce, H.F. Christmann , Hydrocarbon Processing (processing of hydrocarbons), p. 131 (1978)]
However, 1,3-butadiene was produced over pure single-phase zinc ferrite catalysts using C4-raffinate-3 mixtures or C4 mixtures containing multiple components and high concentrations of n-butane without additional Examples of pretreatment or posttreatment and metal substitution steps have not been reported

Method used

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  • Zinc ferrite catalysts, method of preparing thereof and method of preparing 1,3-butadiene using thereof
  • Zinc ferrite catalysts, method of preparing thereof and method of preparing 1,3-butadiene using thereof
  • Zinc ferrite catalysts, method of preparing thereof and method of preparing 1,3-butadiene using thereof

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preparation example Construction

[0034] According to Preparation Example 1 of the present invention, the phase characteristics of the co-precipitated catalysts at different pHs were compared by X-ray diffraction analysis, and it was found that the characteristics of the catalyst lattice changed with the pH of the co-precipitated solution. Specifically, it was found that the catalysts coprecipitated at pH 3–5, mainly formed α-iron(III) oxide (α-Fe 2 o 3 )(III), instead of zinc ferrite, this α-iron(III) oxide is known to have low selectivity to 1,3-butadiene due to complete oxidation in the oxidative dehydrogenation of n-butene, so This catalyst is not suitable as a catalyst for the present invention. In contrast, it was found that the catalyst coprecipitated at pH 6, mainly formed zinc ferrite, and the catalyst coprecipitated at pH 7-12, formed single-phase zinc ferrite (see Figure 1 to Figure 3 ).

[0035] Therefore, preferably, the catalyst for preparing 1,3-butadiene of the present invention is a single...

preparation Embodiment 1

[0045] Identification of precursors and solvents for the production of zinc ferrite catalysts

[0046] Zinc chloride (ZnCl 2 ) as the zinc precursor, ferric chloride hexahydrate (FeCl 3 ·6H 2 O) as an iron precursor. Both the zinc precursor and the iron precursor are easily soluble in distilled water, the zinc precursor and the iron precursor are respectively dissolved in distilled water, and then mixed with each other to form a precursor aqueous solution. A predetermined amount of distilled water is provided as a co-precipitation medium, and then the precursor aqueous solution is added to the distilled water, and at the same time, a predetermined amount of sodium hydroxide aqueous solution is added to adjust the pH, thereby forming a mixed solution. At this time, in order to precisely adjust the pH, the aqueous precursor solution and the aqueous sodium hydroxide solution were slowly added dropwise to the distilled water. In order to obtain a sample with a uniform compos...

Embodiment 1

[0051] Oxidative Dehydrogenation of C4-Raffinate-3 Mixture or C4 Mixture over Zinc Ferrite Catalyst

[0052] Using the zinc ferrite catalyst produced in Preparation Example 1, the oxidative dehydrogenation reaction of n-butene was carried out under the following experimental conditions.

[0053] In the present invention, a C4 mixture whose composition is shown in Table 1 was used as a reactant in the oxidative dehydrogenation reaction of n-butene. The C4 mixture as a reactant was introduced into a reactor in the form of a mixed gas together with air and steam, and a straight-type Pyrex glass fixed-bed reactor was used as the reactor. The composition ratio of the reactants was set based on the amount of n-butene in the C4 mixture, and the ratio was set so that the mixing ratio of n-butene:air:steam was 1:3.75:15. The steam formed by the vaporization of liquid phase water is mixed with other reactants (for example: C4 mixture and air) and then introduced into the reactor. Th...

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Abstract

The present invention relates to a zinc ferrite catalyst, a method of producing the same, and a method of preparing 1,3 -butadiene using the same. Specifically, the present invention relates to a zinc ferrite catalyst which is produced in a pH-adjusted solution using a coprecipitation method, a method of producing the same, and a method of preparing 1,3- butadiene using the same, in which the 1,3-butadiene can be prepared directly using a C4 mixture including n-butene and n-butane through an oxidative dehydrogenation reaction. The present invention is advantageous in that 1,3-butadiene can be obtained at a high yield directly using a C4 fraction without performing an additional process for separating n-butene, as a reactant, from a C4 fraction containing impurities.

Description

technical field [0001] The invention relates to a zinc ferrite catalyst, a method for preparing the zinc ferrite catalyst, and a method for preparing 1,3-butadiene by using the zinc ferrite catalyst. Specifically, the present invention relates to a zinc ferrite catalyst, which is produced in a pH-adjusted solution by coprecipitation. alkanes, n-butenes, etc.) as reactants to produce high value-added 1,3-butadiene without additional n-butane separation process or n-butene extraction Process; The present invention also relates to a method for preparing the zinc ferrite catalyst, and a method for preparing 1,3-butadiene using the zinc ferrite catalyst. Background technique [0002] The demand for 1,3-butadiene in the petrochemical market is gradually increasing. 1,3-butadiene is produced through the process of naphtha cracking, direct dehydrogenation of n-butene or oxidative dehydrogenation of n-butene produced by the reaction of hydrogen and subsequently supplied to the petr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/80
CPCB01J37/031C07C5/3332B01J23/80C07C2523/80B01J35/002B01J23/002B01J2523/00B01J35/30C07C11/167B01J2523/27B01J2523/842B01J23/06B01J23/74C07C5/333
Inventor 郑英敏李成俊金泰禛吴承勋金容昇宋仁奎金希洙郑智撤李镐元
Owner SK INNOVATION CO LTD
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