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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
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Some of these patents have been applied industrially in China, but due to the limitation of butadiene demand and technology level at that time, the production was forced to stop

Method used

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

Examples

Experimental program
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Effect test

Embodiment 1

[0038] (1) First, grind the used metal precursor A chromium nitrate 1200g, B cobalt nitrate 29g, C calcium chloride 44g, D tungsten trioxide 7g into 50 mesh microspheres; secondly, metal precursor A chromium nitrate by 60 % and 40% are divided into two parts of 720g and 480g, and cobalt nitrate, magnesium chloride, nickel nitrate are mixed evenly;

[0039] (2) configure 20L0.45mol / L ferric nitrate solution, under stirring condition, earlier 163g copper nitrate is added in the ferric nitrate solution gradually, react for 40 minutes, then slowly add the mixture of cobalt nitrate, magnesium chloride, nickel nitrate, react After 90 minutes, slowly add 109g of zinc nitrate, and add 100g of methylcellulose after 40 minutes of reaction;

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

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

[0042] (5) Wash t...

Embodiment 2

[0045] Catalyst preparation process is according to embodiment 1, configures 20L0.6mol / L ferric nitrate solution, the metal precursor is ground into 100 mesh microspheres, precursor A is divided into two parts of 60% and 40%, add the metal precursor two intervals The reaction time was 70 minutes and 60 minutes respectively, and the dosage of each metal precursor was: 1190 g of zinc nitrate, 45 g of nickel nitrate, 80.8 g of magnesium chloride, and 10 g of tungsten trioxide. After reacting for 40 minutes, 94 g of scallop powder was added. After stirring for 30 minutes, 15% ammonia water was added dropwise to the slurry to adjust the pH of the slurry to 8.0, and the slurry was thermally modified at a constant temperature of 80° C. for 90 minutes. The slurry was washed with tap water to bring the pH of the slurry to 7.5. Filter the slurry, and bake the filter cake at 160° C. for 10 hours for modification. Calcination modification was carried out at 280°C for 6 hours, at 370°C f...

Embodiment 3

[0047] Catalyst preparation process is according to embodiment 1, configures 20L0.3mol / L ferric nitrate solution, the metal precursor is ground into 80 mesh microspheres, precursor A is divided into two parts of 65% and 35%, add the metal precursor two intervals The reaction time is 50 minutes and 70 minutes respectively, and the dosage of each metal precursor is: copper sulfate 622g, manganese sulfate 34g, barium oxide 104g, tungsten trioxide 2.5g. After reacting for 40 minutes, 70 g of polyacrylamide was added. After stirring for 30 minutes, 25% ammonia water was added dropwise to the slurry to adjust the pH value of the slurry to 8.5, and the slurry was thermally modified at a constant temperature of 90° C. for 90 minutes. Wash the slurry with desalinated water to make the pH of the slurry reach 7.2. Filter the slurry, and bake the filter cake at 140° C. for 12 hours for modification. Calcination modification at 220°C for 12 hours, calcining modification at 340°C for 2 ho...

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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.

Description

technical field [0001] The invention relates to a preparation method of a butadiene oxidative dehydrogenation catalyst applied in a fluidized bed reactor, belonging to the technical field of catalysis. Background technique [0002] 1,3-Butadiene is the basic raw material of petrochemical industry and an important monomer for the production of polymer synthetic materials. Its position in petrochemical olefin raw materials is second only to ethylene and propylene. It has a wide range of uses in synthetic rubber and organic synthesis, and can synthesize butadiene rubber (BR), styrene-butadiene rubber (SBR), nitrile rubber, styrene-butadiene-styrene elastomer (SBS), acrylonitrile -Butadiene-styrene (ABS) resin and other rubber products, in addition, it can also be used in the production of adiponitrile, hexamethylenediamine, nylon 66, 1,4-butanediol and other organic chemical products and as adhesives , gasoline additives, etc., are widely used. [0003] There are two main sou...

Claims

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Application Information

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IPC IPC(8): B01J23/888B01J23/889C07C11/167C07C5/48
Inventor 李长明刘飞田亮孔祥冰孙世林马应海杨德胜韩雪松程亮亮李秋颖许江王小强景丽李世龙程琳
Owner PETROCHINA CO LTD
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