Butylene oxy-dehydrogenation catalyst for fluidized bed and preparation method therefor

A technology for oxidative dehydrogenation and catalyst, applied in the field of catalysis

Active Publication Date: 2016-07-20

PETROCHINA CO LTD

14 Cites 2 Cited by

AI-Extracted Technical Summary

Problems solved by technology

Some of these patents have been applied industrially in China, but due to the limitation...

Method used

As can be seen from Table 1, the catalyst prepared in Examples 1 to 8 can still reach 77 to 81% in the productive rate of butadiene after reacting for 500h, and the selectivity of butadiene is at 92 to 95%. The catalyst prepared in Comparative Example 1 had poor stability, and the yield of butadiene was only 25.4% after 500 hours. The activity of the catalyst prepared in Comparative Example 2 was poor, and the yield of butadiene in the initial stage of the reaction was only 54.6%. In the present invention, the used metal precursor is ground, and the metal precursor A is divided into two parts of 55-70% and 30-45% by weight, and added step by...

Abstract

The invention relates to a butylene oxy-dehydrogenation catalyst for a fluidized bed and a preparation method therefor. The method comprises the steps: dividing a metal precursor A with the particle size of 40 to 100 meshes into two parts, i.e., 55% to 70% and 30% to 45% by weight, and uniformly mixing a metal precursor B, a metal precursor C and a metal precursor D, wherein A is Cu, Zn or Cr, B is Co, Mn, Ni or Mo, C is Ca, Sr, Ba or Mg, and D is W; and gradually adding the 55% to 70% of metal precursor A into a ferric nitrate solution, then, adding the mixture of the metal precursor B, the metal precursor C and the metal precursor D, finally, adding the remaining 30% to 45% of metal precursor A, then, adding a binder, and carrying out filtrating, roasting and the like, thereby obtaining catalyst microspheres with the grain size of 60 to 100 meshes. The catalyst prepared by adopting the method disclosed by the invention is high in catalytic activity and good in stability.

Application Domain

HydrocarbonsMetal/metal-oxides/metal-hydroxide catalysts +1

Technology Topic

Fluidized bedMetal +3

Image

Examples

Experimental program(13)
Comparison scheme(2)
Effect test(1)

Example Embodiment

[0037] Example 1

[0038] (1) First, 1200g of the metal precursor A chromium nitrate, 29g of B cobalt nitrate, 44g of C calcium chloride, and 7g of D tungsten trioxide were ground into 50 mesh microspheres; secondly, the metal precursor A of chromium nitrate was pressed 60 The ratio of% and 40% is divided into two parts of 720g and 480g, and the cobalt nitrate, magnesium chloride, and nickel nitrate are mixed uniformly;

[0039] (2) Configure 20L 0.45mol/L ferric nitrate solution, under stirring conditions, first gradually add 163g copper nitrate to the ferric nitrate solution, react for 40 minutes, then slowly add a mixture of cobalt nitrate, magnesium chloride, and nickel nitrate to react After 90 minutes, slowly add 109g of zinc nitrate. After 40 minutes of reaction, add 100g of methyl cellulose;

[0040] (3) After stirring for 30 minutes, add 20% ammonia water dropwise to the slurry to adjust the pH of the slurry to 9.0;

[0041] (4) Thermally modify the slurry at a constant temperature of 85°C for 90 minutes;

[0042] (5) Wash the slurry with distilled water to make the pH of the slurry reach 7.0;

[0043] (6) The filter cake was roasted and modified at 120°C for 12 hours. It is calcined at 240°C for 6 hours, at 360°C for 4 hours, and at 450°C for 4 hours. After cooling, grinding, sieving out 80-100 mesh catalyst microspheres. The main composition is Cr 3 Co 0.1 Ca 0.2 W 0.03 ·Fe 9 O 16.9 The finished catalyst.

Example Embodiment

[0044] Example 2

[0045] The catalyst preparation process is according to Example 1, with 20L 0.6mol/L ferric nitrate solution, the metal precursor is ground into 100 mesh microspheres, the precursor A is divided into 60% and 40%, and the metal precursor is added twice at intervals The reaction time is 70 minutes and 60 minutes, and the amount of each metal precursor is: 1190 g of zinc nitrate, 45 g of nickel nitrate, 80.8 g of magnesium chloride, and 10 g of tungsten trioxide. After 40 minutes of reaction, 94 g of Sesbania powder was added. After stirring for 30 minutes, 15% ammonia water was added dropwise to the slurry, the pH of the slurry was adjusted to 8.0, and the slurry was thermally modified at a constant temperature of 80° C. for 90 minutes. Wash the slurry with tap water to make the pH of the slurry reach 7.5. The slurry was filtered, and the filter cake was calcined and modified at 160°C for 10 hours. It is calcined at 280°C for 6 hours, at 370°C for 3 hours, and at 440°C for 2 hours. After cooling, grind, sieving out 80-100 mesh catalyst microspheres, and obtain the main composition of Zn 4 W 0.15 Mg 0.4 W 0.04 ·Fe 12 O 22.6 The finished catalyst.

Example Embodiment

[0046] Example 3

[0047] The catalyst preparation process is according to Example 1, with 20L 0.3mol/L ferric nitrate solution, the metal precursor is ground into 80 mesh microspheres, the precursor A is divided into 65% and 35%, and the metal precursor is added twice at intervals The reaction time is 50 minutes and 70 minutes, respectively. The amount of each metal precursor is: 622 g of copper sulfate, 34 g of manganese sulfate, 104 g of barium oxide, and 2.5 g of tungsten trioxide. After 40 minutes of reaction, 70 g of polyacrylamide was added. After stirring for 30 minutes, 25% ammonia water was added dropwise to the slurry, the pH of the slurry was adjusted to 8.5, and the slurry was thermally modified at a constant temperature of 90° C. for 90 minutes. The slurry was washed with desalinated water to bring the pH of the slurry to 7.2. The slurry was filtered, and the filter cake was calcined and modified at 140°C for 12 hours. It was calcined at 220°C for 12 hours, at 340°C for 2 hours, and at 460°C for 3 hours. After cooling, grinding, sieving out 80-100 mesh catalyst microspheres, the main composition is Cu 2.5 Mn 0.2 Ba 0.5 W 0.01 ·Fe 6 O 12.2 The finished catalyst.

PUM

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