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Butylene oxidative dehydrogenation used for fixed beds, and preparation method thereof

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

Active Publication Date: 2016-07-13
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 oxidative dehydrogenation used for fixed beds, and preparation method thereof

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Effect test

Embodiment 1

[0049] (1) First, grind 1455g of metal precursor A cobalt nitrate, B tungsten oxide 12g, C magnesium chloride 40g, D zinc oxide 25g into 60 mesh microspheres; secondly, metal precursor A cobalt nitrate by 60% and 40% The ratio is divided into two parts of 873g and 582g, and the zinc oxide, magnesium chloride and nickel nitrate are mixed evenly;

[0050] Configure 20L of 0.65mol / L ferric nitrate solution, under stirring conditions, first gradually add 873g of cobalt nitrate to the ferric nitrate solution, react for 70 minutes, then slowly add the mixture of zinc oxide, magnesium chloride and zinc oxide, react for 90 minutes Then slowly add 582g of cobalt nitrate, and add 170g of fennel powder after reacting for 60 minutes;

[0051] (2) Stir the slurry for 30 minutes and gradually add ammonia water with a concentration of 20% to the slurry to adjust the pH value of the slurry to 9.0;

[0052] (3) Place the slurry in an environment of 85°C for thermal modification, and the modif...

Embodiment 2

[0062] Catalyst preparation process is according to Example 1, configuration 30L0.5mol / L ferric nitrate solution, the metal precursor is ground into 100 mesh microspheres, precursor A is divided into two parts of 65% and 35%, and the metal precursor is added twice at intervals The reaction time is 30 minutes and 40 minutes respectively, and the dosage of each metal precursor is: copper sulfate 1494g, tungsten oxide 14g, calcium chloride 22g, potassium oxide 19g. After reacting for 40 minutes, add 25 g of scallop powder. After stirring for 30 minutes, 15% ammonia water was added dropwise to the slurry to adjust the pH value of the slurry to 9.5, and the slurry was thermally modified at a constant temperature of 85° C. for 90 minutes. Wash the slurry with distilled water to bring the pH of the slurry to 7.0. The slurry was filtered and extruded into strips, and modified by firing at 160°C for 8 hours. Calcination modification at 240°C for 6 hours, calcining modification at 380...

Embodiment 3

[0064] Catalyst preparation process is according to embodiment 1, configures 20L0.6mol / L ferric nitrate solution, the metal precursor is ground into 80 mesh microspheres, precursor A is divided into two parts of 55% and 45%, and the metal precursor is added twice at intervals The reaction time is 50 minutes and 80 minutes respectively, and the dosage of each metal precursor is: chromium nitrate 2088g, tungsten oxide 10g, strontium chloride 80g, vanadium pentoxide 9.5g. After reacting for 60 minutes, add 20 g of scallop powder. After stirring for 30 minutes, 20% ammonia water was added dropwise to the slurry to adjust the pH of the slurry to 9.0, and the slurry was thermally modified at a constant temperature of 85° C. for 120 minutes. Wash the slurry with desalinated water to make the pH of the slurry reach 7.0. The slurry was filtered and extruded into strips, and modified by roasting at 180°C for 6 hours. Calcination modification at 280°C for 4 hours, calcining modificatio...

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PUM

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Abstract

The main composition of a butylene oxidative dehydrogenation used for fixed beds is AaBbCcDd.FexOe, wherein a is 2-10, b is 0.01-0.1, c is 0.01-0.5, d is 0.01-0.5, x is 6-20, e is a value meeting valence requirements, A is Cr, Co or Cu, B is W, C is Ca, Mg, Sr or Ba, and D is K, V or Zn. The invention also provides a preparation method of the catalyst. The method comprises the following steps: processing metal precursors, sequentially adding the processed precursors to a certain concentration of an iron nitrate solution, reacting, and adding a certain amount of a binder to obtain a precursor precipitate slurry; gradually adding ammonia water to the slurry to adjust the pH value of the slurry; carrying out thermal modification on the slurry at a certain temperature; filtering and washing the slurry, filtering the slurry, and carrying out strip extrusion molding; and carrying out roasting modification at 100-500DEG C for 12-28h to obtain the finished catalyst.

Description

technical field [0001] The invention relates to a preparation method of a catalyst for preparing butadiene by oxidative dehydrogenation of butene applied in a fixed-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]...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/888C07C11/16C07C11/167C07C5/333
Inventor 李长明王玫刘飞孙世林孔祥冰李秋颖蔡智军曹泽允孙生莲马应海黄剑锋许江张松显李世龙景丽
Owner PETROCHINA CO LTD
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