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Modified composite oxide catalyst and modification method

A catalyst and mixture technology, which is applied in the field of improving the activity of composite oxide catalysts, can solve the problems of low catalyst activity, low catalyst selectivity, inability to propylene and high acrylic acid yield, etc.

Active Publication Date: 2015-05-27
SHANGHAI HUAYI NEW MATERIAL
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] The activity of the catalyst mentioned in the above-mentioned patent is not very high, or the activity is high, but the selectivity of the catalyst decreases with the increase of the activity, which cannot make propylene maintain a high acrylic acid yield stably for a long time at a high space velocity

Method used

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  • Modified composite oxide catalyst and modification method

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preparation example Construction

[0056] The catalyst precursor of the present invention can be prepared by common methods known in the art. In an example of the present invention, the preparation method of described catalyst precursor comprises:

[0057] (i) Dissolve Mo, V and W sources in water at 70-100°C to obtain A solution, and dissolve Cu, X and Y sources in water at 60-80°C to obtain B solution;

[0058] (ii) Pour solution B into solution A at 40-80°C to obtain solution C, directly add component Z to the solution and stir and mix evenly to obtain solution D, and dry solution D to obtain catalyst powder; or dry solution C first The powder is obtained, and then the powder is mixed with the Z component uniformly to obtain the catalyst powder.

[0059] Drying is static drying at 90-200°C or spray drying at an inlet temperature of 270-350°C and an outlet temperature of 120-160°C.

[0060] The catalyst carrier of the present invention can also be purchased from the market, for example, it can be purchased ...

Embodiment 1

[0086] Preparation of catalyst precursor

[0087] Add 65.1g ammonium molybdate, 11.8g ammonium metatungstate and 16.6g ammonium metavanadate to 300g water at 90°C, stir and dissolve to obtain A solution;

[0088] Add 5g of antimony trioxide, 2g of strontium nitrate and 12g of copper nitrate into 50g of water at 60°C, stir and dissolve to obtain solution B;

[0089] Pour B solution into A solution at 60°C to obtain C solution, and spray C solution at an inlet temperature of 270°C and an outlet temperature of 120°C to obtain a dry powder;

[0090] Take 30g of dry powder and 30g of silicon powder and mix evenly to obtain catalyst powder.

[0091] Improve the activity of catalyst precursors

[0092] Add 15g of sulfolane to 60g of the catalyst precursor powder prepared above and mix well; dry at 150°C in air for 12 hours; ) in an atmosphere of 380 ° C for 5 hours to obtain the catalyst.

[0093] The performance of the obtained catalyst was evaluated by the above method, and...

Embodiment 2～4

[0095] The same experimental method as in Example 1 was adopted, except that the amount of sulfolane shown in Table 1 was used in the method for improving the activity of the composite oxide catalyst.

[0096] The performance of the obtained catalyst was evaluated by the above method, and the results are shown in Table 1.

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PUM

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Abstract

The invention discloses a modified composite oxide catalyst and a modification method. The catalyst comprises a catalyst precursor shown in a following general formula, wherein X is at least one of Nb, Sb, Te, Ce, La, Nd, Sm, Cs and Ge; Y is at least one of Mg, Ca, Sr and Ba; a is 1-10; b is 0-6; c is 0-7; d is 0-4; e is 0-5; f is a value determined by n oxidation state of the composition elements; Z is simple substance silicon; wherein the catalyst precursor is activated by the following steps: 1)according to weight of the catalyst precursor, adding 5-100wt% of hexamethyl phosphoric triamide, dimethyl sulfoxide, N,N-dimethyl formamide, carbonic acid-1,2-propylene, sulfolane, N-methyl 2 pyrrolidone, 1,1,3,3-tetramethylurea and lactic acid; 2)drying for 2-28 hours at 60-250 DEG C in oxygen containing gas; 3)forming; and 4)calcinating for 1-24 hours under 350-410 DEG C in oxygen containing gas. Mo12VaCubWcXdYeOf / Z (1).

Description

technical field [0001] The invention provides a method for improving the activity of a composite oxide catalyst. The method is especially suitable for the improvement of catalytic activity of propylene (or isobutylene) to oxidize acrolein (or isobutyraldehyde) or further oxidize to acrylic acid (or methacrylic acid). Background technique [0002] Since the 1980s, the world's acrylic acid production equipment mainly adopts the two-step oxidation method of propylene, which has mature technology and good economy. Up to now, it is still the mainstream process in the acrylic acid industry. [0003] Catalysts for the two-step oxidation of propylene to acrylic acid have undergone a process of continuous improvement and performance improvement. At present, the space velocity of propylene in almost all industrial production units has changed from 60h in the initial stage of industrialization to -1 increase to 90h -1 Above, some even reach 120h -1 above. The increase of propylene...

Claims

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Application Information

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IPC IPC(8): B01J23/888C07C57/055C07C51/25
Inventor 冯世强李雪梅蔡敏庄岩吴通好马建学褚小东季金华
Owner SHANGHAI HUAYI NEW MATERIAL
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