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Boron-containing multi-metallic oxide catalyst and preparation method thereof

A multi-metal oxide and catalyst technology, applied in the preparation of organic compounds, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problems of poor thermal stability, inconsistency, deactivation, etc., and achieve high catalyst activity, Good selectivity and stable performance

Inactive Publication Date: 2015-02-25
SHENYANG INSTITUTE OF CHEMICAL TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The catalyst of vanadium phosphorus oxygen system is not ideal for the selective oxidation of propane to prepare acrylic acid, and the yield of acrylic acid is not more than 15%. However, the catalyst system of heteropolyacid and its salt is not calcined at high temperature, so the structure of the catalyst is unstable. At an operating temperature higher than 400 °C, it is easy to be inactivated due to structural collapse. In addition to the disadvantage of poor thermal stability, the effect of heteropolyacids and their salts on the oxidation of propane to acrylic acid is not ideal. The highest yield of acrylic acid Not more than 20%
At present, the hottest research at home and abroad is the composite metal oxide, most of which use the Mo-V-Te-Nb-O system, which is applied to the one-step oxidation of propane to prepare acrylic acid, and the yield of acrylic acid varies. Mitsubishi Kasai company uses Mo-V-Te-Nb-O catalyst, the yield of acrylic acid is as high as 52%, while the research groups in the United States and Europe use Mo-V-Te-Nb-O catalyst, and they have not repeated the data of Mitsubishi Kasai Company, which is very big Due to its complex multi-component elements, multi-step preparation process and sensitivity to preparation parameters

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] 1. Preparation of catalyst

[0023] Weigh 3.54 g of ammonium molybdate and 0.82 g of ammonium metavanadate and add them into 50 ml of deionized water to dissolve them to obtain solution A, weigh 0.72 g of tellurium dioxide and add them to 15 ml of 30% hydrogen peroxide solution to obtain solution B Take by weighing 1.23 g niobium hydroxide and dissolve in the oxalic acid solution, make solution C, take by weighing 0.23 g boric acid and dissolve in 10ml deionized water, get solution D, solution A and solution B are mixed, in constant temperature magnetic stirrer 70 Stir for 30 min at °C. Then, add solution C and solution D into the mixed solution, and after mixing evenly, use dilute nitric acid with a mass fraction of 6% to control the pH=2 of the solution, and then further stir at a temperature of 90 °C for 2 h to obtain a catalyst mother liquor, which is passed through Freeze-drying at -25 °C, thawing at 3-7 °C, and then in a drying oven at 80 °C for 24 h to obtain th...

Embodiment 2

[0029] According to the ratio of the first four active components in Example 1, the molybdenum vanadium tellurium niobium compound precursor was prepared, and then it was immersed in an aqueous solution containing 0.23 g of boric acid for 8 h, and then vacuum-dried at a temperature of 80 ℃, and the drying time was 12 h to obtain the catalyst precursor. The catalyst precursor was roasted, and the temperature was first raised to 300 °C at a rate of 10 °C / min in a nitrogen atmosphere, and kept for 2 h; then the temperature was raised to 600 °C at a rate of 10 °C / min. Insulate for 2 h, and obtain the finished catalyst after roasting.

[0030] The catalyst activity test is the same as in Example 1, and the reaction results are shown in Table 1.

Embodiment 3

[0032] The tellurium source in Example 1 was prepared by using 0.90 g of telluric acid to prepare solution B, and the active components were mixed to obtain a catalyst mother liquor. The catalyst mother liquor was vacuum-dried and kept in a vacuum oven at a temperature of 90 °C for 12 h to obtain a catalyst Precursors and catalyst precursors were roasted, and in an argon atmosphere, the temperature was first raised to 300°C at a rate of 15°C / min, and kept at a temperature of 1 to 4 hours; The finished catalyst is obtained after roasting.

[0033] The catalyst activity test is the same as in Example 1, and the reaction results are shown in Table 1.

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PUM

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Abstract

The invention provides a boron-containing multi-metallic oxide catalyst and a preparation method thereof, which relate to a catalyst and a preparation method thereof. The boron-containing multi-metallic oxide catalyst comprises the raw materials such as ammonium molybdate, ammonium metavanadate, tellurium dioxide or telluric acid, niobium oxalate, boric acid and the like. The preparation method comprises the following steps of: drying catalyst mother liquid containing active components such as molybdenum, vanadium, tellurium, niobium and boron to obtain a catalyst precursor, or soaking a composite oxide precursor containing molybdenum, vanadium, tellurium and niobium into a boron (B)-containing solution for certain time, and then drying the soaked composite oxide precursor to obtain a catalyst precursor, and baking the catalyst precursor to obtain the catalyst. The catalyst is applied to acrylic acid preparation through single-step oxidation of propylene or propane, the propylene conversion rate is 85-92 percent, the acrylic acid yield is 64-78 percent, the propane conversion rate is 62-74 percent, and the acrylic acid yield is 50-58 percent. The catalyst has the advantages of high catalytic activity, good selectivity and stable performance, and is suitable for industrial popularization and application.

Description

technical field [0001] The invention relates to a catalyst and a preparation method, in particular to a boron-containing multi-metal oxide catalyst and a preparation method thereof. Background technique [0002] Acrylic acid (AA for short) is the most attractive monomer for synthetic polymers. It is mainly used for the synthesis of acrylate and polyacrylic acid. Polyacrylic acid is used for the production of sanitary materials, detergents, dispersants, flocculants and thickeners, etc. Acrylates are used in synthetic coatings, adhesives, textile, paper, leather and plastic additives. Now the industrial production of acrylic acid is mainly based on the two-step method of propylene, that is, propylene is first partially oxidized on the oxide catalyst containing molybdenum and bismuth to form acrolein, and the generated acrolein is further oxidized on the molybdenum and vanadium oxide catalyst to form acrylic acid. [0003] At present, the two-step process of producing acrylic ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J27/057C07C57/05C07C51/25C07C51/215
Inventor 李双明邵慧陈灿于三三李文秀
Owner SHENYANG INSTITUTE OF CHEMICAL TECHNOLOGY