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Method for Propylene Selective Oxidation to Produce Acrolein

A selective, acrolein technology, applied in chemical instruments and methods, preparation of organic compounds, preparation of oxygen-containing compounds by hydrocarbon oxidation, etc., can solve the problems of decreased catalyst activity, unable to improve the activity, and complicated catalyst preparation and loading. Achieve the effect of suppressing hot spots, avoiding the rapid drop of bed temperature, improving the yield of the target product and high selectivity

Active Publication Date: 2015-10-28
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
CN1672790A provides a kind of catalyst that catalyzes the gas-phase oxidation of acrolein to produce acrylic acid. The catalyst contains molybdenum and vanadium, and also contains at least one volatile catalyst poisoning component. Reduce the temperature of the superheated part, and suppress the reduction of the reaction efficiency of thermal degradation
The catalyst bed of the above-mentioned method of oxidizing propylene to acrolein and acrylic acid needs to be filled with different catalysts. The preparation and loading of the catalysts are cumbersome, and once the activity of the catalyst decreases, the activity cannot be improved.

Method used

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  • Method for Propylene Selective Oxidation to Produce Acrolein
  • Method for Propylene Selective Oxidation to Produce Acrolein
  • Method for Propylene Selective Oxidation to Produce Acrolein

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Preparation of Catalyst 1

[0044] Step 1: Prepare catalyst inner layer matrix

[0045] (1) Preparation of active ingredient slurry (a)

[0046] Under stirring conditions, take 197 grams of ammonium molybdate and dissolve in 1000 ml of pure water (water temperature above 65°C) to obtain slurry (1), then take 73 grams of cobalt nitrate, 1.88 grams of potassium nitrate, 112.7 grams of iron nitrate, and 15.1 grams of lanthanum nitrate Dissolve in 500ml of purified water (water temperature above 65°C), stir and mix well to obtain slurry (2). Another 45.1 g of bismuth nitrate was taken and dissolved in dilute nitric acid with stirring to obtain a slurry (3). Then, the slurry (1) is mixed with the slurry (2) to obtain the slurry (4), and then the slurry (3) is added to the slurry (4) to obtain the active ingredient slurry (a).

[0047] (2) Preparation of catalyst inner layer matrix

[0048] Add 61.4 grams of silica powder and 2.5 grams of alumina to the active component s...

Embodiment 2

[0064] Same as the preparation steps and main raw materials of catalyst 1 in Example 1, add 83.7 grams of silicon dioxide to the inner layer, then extrude and roll granulate into a spherical shape with a diameter of 2 mm through an extruder, and add 8.9 grams of silicon dioxide to the outer layer. silicon. The thickness of the coating is 0.5-2.0mm, and the catalyst 2 is obtained by roasting at 560° C. for 3 hours. The main composition of catalyst 2 inner layer matrix is: Mo 12 Bi 2.2 Fe 2.3 co 1.2 W 5 K 1.4 Si 15.0 La 1.2 Ba 0.3 o x , the main composition of the outer layer is: Mo 12 Bi 2.2 Fe 2.3 co 1.2 W 5 K 1.4 Si 1.6 La 1.2 Ba 0.3 o x .

[0065] Propylene Selective Oxidation Process

[0066] The internal diameter of the fixed-bed single-tube reactor is 25mm, and a thermocouple is arranged inside, and the catalyst (F 1 section), 20ml of the above catalyst (F 2 section), the salt bath heating temperature is 306°C. From the entrance of the above reacti...

Embodiment 3

[0070] Same as the preparation steps and main raw materials of the catalyst 1 in Example 1, 57.5 grams of silicon dioxide and 2.3 grams of silicon carbide were added to the inner layer, which were extruded into hollow columnar particles of φ 5 × 5 mm through an extruder, and 28.5 grams of SiO2 were added to the outer layer. silicon oxide. The thickness of the coating is 0.1-1.5 mm, and the catalyst 3 is obtained by calcining at 400° C. for 6 hours. The main composition of the catalyst 3 inner layer matrix is: Mo 12 Bi 7 Fe 1 co 8 W 0.3 K 3.2 Si 10.3 mn 1.8 o x , the main composition of the outer layer is: Mo 12 Bi 7 Fe 1 co 8 W 0.3 K 3.2 Si 5.1 mn 1.8 o x

[0071] Propylene Selective Oxidation Process

[0072] The internal diameter of the fixed-bed single-tube reactor is 25mm, and a thermocouple is arranged inside, and the catalyst (F 1 section), 20ml of the above catalyst (F 2 section), the salt bath heating temperature is 325°C. From the entrance of the...

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Abstract

The invention relates to a method for producing acrolein by propylene selective oxidation. The method utilizes a fixed bed reactor. The fixed bed reactor is divided into a section F1 and a section F2 from a reaction raw material inlet to an outlet. An Mo-Bi double-layer catalyst of which an inner layer concentration is higher than an outer layer concentration is arranged in the section F1. An Mo-Bi double-layer structure catalyst of which an inner layer concentration is lower than an outer layer concentration is arranged in the section F2 of the fixed bed reactor. The method is conducive to target product yield and selectivity improvement and can realize long-period stable production of acrolein and acrylic acid.

Description

technical field [0001] The invention relates to a method for producing acrolein by selective oxidation of propylene. More specifically, it relates to a method for improving the selectivity and yield of acrolein from propylene oxidation. Background technique [0002] The gas-phase catalytic oxidation reaction of propylene to prepare acrolein and acrylic acid is a strong exothermic reaction, and a large amount of reaction heat is accumulated in the reactor instantaneously, forming local hot spots. If the reaction heat cannot be removed in time and effectively, the instantaneously accumulated heat will continue to accumulate, which will lead to catalyst The loss and detachment of active components lead to a decrease in catalyst activity and shortened life, and lead to the formation of by-products due to excessive oxidation reactions, thereby reducing the yield of acrolein and acrylic acid. It even causes a runaway reaction and sinters the catalyst. [0003] "Research Progress...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C27/14C07C45/35C07C47/22C07C57/05C07C51/25
CPCB01J23/002B01J23/8885B01J23/8898B01J2523/00C07C45/35C07C51/252C07C47/22C07C57/04B01J2523/68B01J2523/54B01J2523/842B01J2523/845B01J2523/69B01J2523/13B01J2523/41B01J2523/3706B01J2523/25B01J2523/72B01J2523/47B01J2523/22
Inventor 王学丽张忠东张茵赵玉中谢元李洁常晓昕王玲玲高阳光刘晓兰李耀朱博史蓉高杜娟
Owner PETROCHINA CO LTD
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