Catalyst for preparing butadiene from mixed C4 and preparation method thereof

A technology for mixing C4 and catalysts, which is applied in chemical instruments and methods, physical/chemical process catalysts, metal/metal oxide/metal hydroxide catalysts, etc., can solve the problem of high energy consumption and production costs, and the selectivity of target products It is not high, the catalyst reactivity is not high, etc., to achieve the effect of strong anti-coking ability, good technical effect, good activity and stability

Inactive Publication Date: 2013-09-25
王伟跃
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0011] The problem to be solved by the present invention is that the catalytic activity of butadiene is not high in the oxidative dehydrogenation of butene in the prior ar

Method used

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  • Catalyst for preparing butadiene from mixed C4 and preparation method thereof

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Experimental program
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Effect test

Embodiment 1

[0038] Ferric nitrate, zinc nitrate, manganese nitrate, and calcium nitrate solution are mixed according to the ratio of 1: 0.3: 0.2: 0.3 (molar ratio), while stirring while dripping ammonia water, stop dripping ammonia water after the pH value of the mixed solution is 9.0; Then the temperature of the mixed solution was raised to 80°C, stirred for 30 minutes and left to stand to obtain a coprecipitated mixed solution; the coprecipitated mixed solution was washed with deionized water until the pH value of the filtrate was 7.5 to obtain a catalyst sol; the catalyst The sol was directly extruded into a cylindrical bar-shaped catalyst, then dried at 100°C for 18 hours, and then calcined at 550°C for 8 hours to obtain fixed-bed catalyst sample 1.

[0039] Apply this catalyst sample to a 2-stage axial fixed-bed reactor with a volumetric space velocity of butene of 400 hours -1 The inlet temperature of the first stage reactor is 340°C, the inlet pressure of the first stage reactor is...

Embodiment 2

[0041] Mix ferric chloride, zinc chloride, manganese chloride, and calcium chloride solutions in a ratio of 1:0.8:0.3:0.5 (molar ratio), and stir while dripping ammonia water until the pH value of the mixed solution is 9.5, then stop Add ammonia water dropwise; then raise the temperature of the mixed solution to 80°C, stir for 23 minutes and let it stand to obtain a co-precipitation mixed solution; wash the coprecipitated mixed solution with deionized water until the pH value of the filtrate is 7.8 to obtain a catalyst sol The catalyst sol was directly extruded into a clover-shaped catalyst, then dried at 120°C for 13 hours, and then calcined at 650°C for 6 hours to obtain fixed bed catalyst sample 2.

[0042] Apply this catalyst sample to a 3-stage axial fixed-bed reactor with a volumetric space velocity of butene of 350 hours -1 , the inlet temperature of the first-stage reactor is 340° C., the inlet pressure of the first-stage reactor is 0.28 MPaG, and the ratio (molar rati...

Embodiment 3

[0044] Mix ferric chloride, zinc chloride, manganese chloride, and calcium chloride solutions in a ratio of 1:0.5:0.1:0.1 (molar ratio), and stir while dripping ammonia water until the pH value of the mixed solution is 8.3, then stop Add ammonia water dropwise; then raise the temperature of the mixed solution to 86°C, stir for 31 minutes and let it stand to obtain the co-precipitation mixed solution; wash the coprecipitated mixed solution with deionized water until the pH value of the filtrate is 7.1 to obtain the catalyst sol ; The catalyst sol was directly extruded into a cylindrical bar-shaped catalyst, then dried at 120°C for 15 hours, and then calcined at 600°C for 8 hours to obtain a fixed-bed catalyst sample 3.

[0045] The catalyst sample is applied to a first-stage tubular isothermal fixed-bed reactor. The catalyst is packed in the tubular, and desalinated water is used outside the tubular to exchange heat and generate low-pressure steam; the volume space velocity of b...

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Abstract

The invention discloses a catalyst for preparing butadiene from mixed C4 and a preparation method thereof. According to the catalyst, zinc ferrite serves as an active main body, and manganese ferrite and calcium ferrite serve as auxiliary active ingredients. The method comprises the following steps: mixing an iron salt solution, a zinc salt solution, a manganese salt solution and a calcium salt solution according to a certain ratio, so as to obtain a coprecipitation solution under the action of an alkaline solution; filtering and washing to obtain a catalyst sol, molding, drying and roasting the sol to obtain an axial fixed bed or constant-temperature fixed bed catalyst used for a fixed bed reaction process; preparing slurry from the sol and an adhesive with a certain ratio, and performing spray drying forming, drying and roasting to obtain a fluidized bed catalyst used for a fluidized bed reaction process. The catalyst has high activity and stability on dehydrogenation production of butadiene through the mixed C4 under the condition of the presence of oxygen, the conversion per pass of the butane in the mixed C4 is 88-93 percent, the selectivity on the butadiene is over 95 percent, and the catalyst can be applied to the field of industrial production of the butadiene.

Description

technical field [0001] The invention relates to a catalyst for preparing butadiene by mixing carbon four and a preparation method thereof. Background technique [0002] Butadiene plays an important role in the national economy and is the main raw material for synthetic rubber such as butadiene rubber, nitrile rubber, styrene-butadiene rubber, ABS engineering plastics, nylon, adiponitrile, 1,4-butanediol, etc. In recent years, the market has been in short supply. With the rise of crude oil prices and more and more oilfield gas and shale gas being used as raw materials for steam cracking, the shortage of butadiene will be difficult to change in the next few years. At present, butadiene mainly comes from the by-product mixed carbon four of the steam cracking unit. [0003] Mixed carbon four is one of the main by-products of steam cracking units and refinery catalytic cracking units. According to the difference of raw material, reaction depth and catalyst, the composition diff...

Claims

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Application Information

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IPC IPC(8): B01J23/889C07C11/167C07C5/48
Inventor 王伟跃
Owner 王伟跃
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