Catalyst containing rare earth for ammoxidation of alkane

An oxidation reaction and catalyst technology, which is applied in the preparation of hydrocarbon ammoxidation, physical/chemical process catalysts, organic chemistry, etc., can solve the problems of poor catalyst stability, complicated preparation process, and low yield, and achieve improved oxidation-reduction The effect of speed, good repeatability, and easy availability of raw materials

Inactive Publication Date: 2010-08-11
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0016] The technical problem to be solved by the present invention is to overcome problems such as complex preparation process and low yield caused by reflux of Sb in the

Method used

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  • Catalyst containing rare earth for ammoxidation of alkane
  • Catalyst containing rare earth for ammoxidation of alkane

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] 13.7 grams of ammonium heptamolybdate and 4.43 grams of telluric acid are dissolved in 40.0 grams of hot water to make solution (I); 3.07 grams of ammonium metavanadate are dissolved in 70.0 grams of hot water to make solution (II); 5.77 grams of niobium oxalate are dissolved in 17.0 grams of hot water to make solution (III); 1.7 grams of cerium nitrate and 1.8 grams of calcium nitrate are dissolved in 5.0 grams of water to make (IV); 2.32 grams of oxalic acid are dissolved in 5 grams of water to make into a solution (V); 1ml of 98% concentrated sulfuric acid was dissolved in 9 grams of water to make a solution (VI). Add solution (II) to solution (I) under stirring, then add solution (III), solution (IV), solution (V) and solution (VI) in sequence, and finally add 50 grams of silicon with a weight concentration of 40%. Sol, prepare catalyst slurry, stir and evaporate the slurry at 90°C to obtain a viscous slurry, then dry, grind, and roast in a nitrogen atmosphere at 60...

Embodiment 2～7 and comparative example 2～4

[0049] Catalysts with different compositions in the following table were prepared by the same method as in Example 1, and the ammoxidation of propane to acrylonitrile was carried out under the following reaction conditions with the prepared catalyst. See Table 1 for specific changes and results.

[0050] The reaction conditions of above-mentioned embodiment and comparative example are:

[0051] Fixed bed reactor with an inner diameter of 8 mm

[0052] Reaction temperature 400°C

[0053] Reaction pressure Atmospheric pressure

[0054] Catalyst loading 2.0 grams

[0055] Catalyst contact time 1.2 g·s / ml

[0056] Raw material ratio (mole) propane / ammonia / air=1 / 1.2 / 10

Embodiment 7

[0057] The stability evaluation results of Example 7 and Comparative Example 1 are shown in Table 2.

[0058] Table 1

[0059]

Example

Catalyst composition

Preparation key steps

Acrylonitrile Yield

(%)

Example 1

Mo 1 V 0.34 Nb 0.24 Te 0.25 Ce 0.05 Ca 0.1 o x +50% SiO2 2

The reducing agent is oxalic acid, acid

for sulfuric acid

51.6

Example 2

Mo 1 V 0.31 Nb 0.22 Te 0.96 Nd 0.05 Fe 0.08 o x +40% SiO2 2

The reducing agent is acetol

48.8

Example 3

Mo 1 V 0.37 Nb 0.26 Te 0.25 PR 0.6 W 0.01 o x +70% SiO2 2

Roasting in nitrogen at 500°C 2

Hour

45.3

Example 4

Mo 1 V 0.11 Nb 0.95 Te 0.25 Nd 0.1 PR 0.01 Bi 0.01 o x +60% SiO2 2

The reducing agent is oxalic acid, acid

for nitric acid

50.3

Example 5

...

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PUM

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Abstract

The invention relates to a catalyst containing rare earth for the ammoxidation of alkane, which contains a silicon dioxide carrier and a composition comprising the following general formula in atomic ratio: MoVaNbbTecDdEeOx, wherein D is selected from at least one of rare earth elements; and E is selected from one and a mixture of Ca, Sn, Ti, Fe, Bi, Sb or W. The invention mainly solves the problems of easily volatile Te, complex preparation process, instable preparation environment and poor catalyst stability caused by easily volatile active components of the catalyst existing in the prior art. In the invention, Mo-V-Nb-Te base is used as a main component of the catalyst, and a reducing agent and acid are added during preparation to change the preparation environment, i.e. the preparation process comprises the following steps of: firstly, dissolving corresponding salts or oxides of Mo and Te; then, respectively adding solutions of the corresponding salts or oxides of V, Nb and rare earth elements; subsequently, adding a certain amount of reducing agent and acid to regulate the pH value; and finally, adding a certain amount of silica sol. The catalyst has excellent oxidation reduction stability, low reaction temperature and high product yield, and can be applied to the industrial production of preparing unsaturated nitriles by the ammoxidation of the alkane.

Description

technical field [0001] The invention relates to a rare earth-containing alkane ammoxidation catalyst. Especially the catalyst for the ammoxidation of propane to acrylonitrile and the ammoxidation of isobutane to methacrylonitrile. Background technique [0002] Although most of the production of acrylonitrile currently adopts the propylene ammoxidation process of BP / Sohio, with the changes in the petrochemical market and the in-depth research on the selective oxidation of alkanes, due to the price difference between propane and propylene or the price of isobutane and isobutene The process route of producing acrylonitrile by propane ammoxidation or isobutane ammoxidation to methacrylonitrile has been paid more and more attention. [0003] In order to obtain a catalyst with high activity and high selectivity for the ammoxidation of propane to acrylonitrile, people have made a series of improvements through continuous exploration. Early attempts to develop an efficient process...

Claims

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Application Information

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IPC IPC(8): B01J27/057C07C255/08C07C253/24
CPCY02P20/52
Inventor 汪国军卢冠忠郭耘
Owner EAST CHINA UNIV OF SCI & TECH
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