Preparation method of acrolein

A technology for acrolein and propylene, applied in the field of selective oxidation of propylene to acrolein, can solve the problems of loss of catalyst active components, huge energy consumption, huge economic losses, etc. heat buildup effect

Active Publication Date: 2013-03-27
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

There are more than 50,000 reaction tubes, and it is difficult to ensure that the catalyst is not filled empty. If the catalyst is sintered quickly because the hot spot is too high, and the catalyst is replaced in a short period of time, it can be expected that the economic loss will be huge; in addition, for propylene The production of aldehyde and acrylic acid should be carried out under low temperature conditions as much as possible, because the reaction needs to be heated in a salt bath, and the energy consumption for maintaining production is also a huge expense; due to the generation of hot spots, high temperature resistance is required for the reaction tube, and for tens of thousands For the reaction tube, the cost of the tube is a very large cost
The scouring of the mixed flow of propylene, air and water vapor will also cause the loss of active components in the catalyst

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Preparation of Catalyst 1

[0036] Step 1: Prepare catalyst inner layer matrix

[0037] (1) Preparation of active component slurry (a)

[0038] Under stirring conditions, 183.6 grams of ammonium molybdate, 27.97 grams of copper nitrate, and 23.4 grams of cesium nitrate were dissolved in 1000 ml of pure water (water temperature above 65°C) to obtain a slurry (1), and then 217 grams of bismuth nitrate was dissolved in dilute nitric acid , to obtain solution (2). Take 77.6 grams of ferric nitrate and 55.9 grams of cobalt nitrate, and dissolve them in 1000 ml of pure water (water temperature above 65° C.) under stirring conditions to obtain slurry (3). Then, mix the slurry (1) with the slurry (2), and then add ammonia water to adjust the pH value to alkaline to obtain the slurry (4). After 20 minutes, slowly add the slurry (3) to the slurry (4), and simultaneously add 12 g of silica, stirred vigorously at 80°C for 2 hours.

[0039] (2) Preparation of auxiliary material ...

Embodiment 2

[0058] Preparation of Catalyst 2

[0059] Step 1: Prepare catalyst inner layer matrix

[0060] (1) Preparation of active component slurry (a)

[0061] Under stirring conditions, 169.5 grams of ammonium molybdate, 37.2 grams of copper nitrate, and 20.2 grams of cesium nitrate were dissolved in 1000 ml of pure water (water temperature above 65°C) to obtain a slurry (1), and then 310.5 grams of bismuth nitrate was dissolved in dilute nitric acid , to obtain solution (2). Take 97 grams of ferric nitrate and 93.1 grams of cobalt nitrate, and dissolve them in 1000 ml of pure water (water temperature above 65° C.) under stirring to obtain slurry (3). Then, mix the slurry (1) with the slurry (2), and then add ammonia water to adjust the pH value to alkaline to obtain the slurry (4). After 20 minutes, slowly add the slurry (3) to the slurry (4), and simultaneously add 8 g of silica, stirred vigorously at 80°C for 2 hours.

[0062] (2) Preparation of auxiliary material slurry (b)

...

Embodiment 3

[0083] Step 1: Prepare catalyst inner layer matrix

[0084] (1) Preparation of active component slurry (a)

[0085] Under stirring conditions, 198 grams of ammonium molybdate, 37.2 grams of copper nitrate, and 15.6 grams of cesium nitrate were dissolved in 1000 ml of pure water (water temperature above 65°C) to obtain a slurry (1), and then 116.4 grams of bismuth nitrate was dissolved in dilute nitric acid , to obtain solution (2). Then take 48.5 grams of ferric nitrate and 104.8 grams of cobalt nitrate, and dissolve them in 1000 ml of pure water (water temperature above 65° C.) under stirring conditions to obtain slurry (3). Then, mix the slurry (1) with the slurry (2), and then add ammonia water to adjust the pH value to alkaline to obtain the slurry (4). After 20 minutes, slowly add the slurry (3) to the slurry (4), and simultaneously add 14 g of silicon dioxide was vigorously stirred at 80° C. for 2 hours.

[0086] (2) Preparation of auxiliary material slurry (b)

[00...

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Abstract

The invention relates to a preparation method of acrolein. According to the invention, a fixed-bed single-pipe reactor is adopted. A reaction raw material is preheated, and is delivered into a reactor. A Mo-Bi series multi-metal oxide catalyst is loaded in the reactor. The composition of the catalyst can be represented by the general formula (I): MoaBibFecCodCseCufSigAhBiOj (I). With the production method provided by the invention, single-pipe reactor local heat accumulation can be effectively reduced, hot spot formation can be inhibited, and catalyst sintering is prevented. The method has the characteristics of high reaction activity, high selectivity, and long service life. With the method, device long-period stable operation can be satisfied.

Description

technical field [0001] The invention relates to a preparation method for selectively oxidizing propylene or isobutene to generate corresponding unsaturated aldehydes, especially suitable for selectively oxidizing propylene to acrolein. Background technique [0002] At present, acrylic acid is mainly produced in the industry by two-step oxidation of propylene, that is, a fixed bed reactor is usually used, propylene is first oxidized to acrolein, and acrolein is oxidized to acrylic acid. The gas-phase catalytic oxidation reaction of propylene is a strong exothermic reaction. Hot spots will be generated in the catalyst bed, and the heat accumulated instantaneously will continue to accumulate, which will lead to the loss and shedding of the active components of the catalyst, so that the activity of the catalyst will decrease and its life will be shortened. Excessive oxidation reaction aggravates the formation of by-products, and even causes runaway reactions, causing catalyst si...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C47/22C07C45/35B01J23/887B01J23/888B01J23/889
Inventor 王学丽常晓昕颉伟龚光碧王玲玲陈红白竞冰李耀刘肖飞高冬梅景志刚葛汉青王书峰李燕
Owner PETROCHINA CO LTD
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