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Multi-layer catalyst, preparation method thereof, and method for preparing unsaturated aldehyde (acid) by using multi-layer catalyst

A multi-layer catalyst and catalyst technology, applied in the field of propylene oxidation to acrolein or isobutylene oxidation to methacrolein, to achieve the effects of long life, high thermal conductivity and extended service life

Active Publication Date: 2016-03-23
WANHUA CHEM GRP CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The service life of the multi-layer catalyst is more than 20% longer than that of existing commercial catalysts

Method used

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  • Multi-layer catalyst, preparation method thereof, and method for preparing unsaturated aldehyde (acid) by using multi-layer catalyst

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Experimental program
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Effect test

Embodiment 1

[0045] Multilayer Catalyst Preparation

[0046] Preparation of outer layer catalyst powder: under 50 DEG C, 4kg ammonium heptamolybdate (chemical formula is (NH 4 ) 6 Mo 7 o 24 4H 2 O) be dissolved in 5L pure water, obtain solution A after dissolving completely. With 1.4kg bismuth nitrate (chemical formula is Bi(NO 3 ) 3 ·5H 2 O), 4.5kg cobalt nitrate (chemical formula is Co(NO 3 ) 2 ·6H 2 O), 1.4kg iron nitrate (chemical formula is Fe(NO 3 ) 3 9H 2 O), 19g potassium nitrate (chemical formula is KNO 3 ), 550g nickel nitrate (chemical formula is Ni(NO 3 ) 2 ·6H 2 O) be dissolved in 4.25kg dilute nitric acid aqueous solution (15wt%), obtain solution B after dissolving completely. Keep the solution temperature at 65°C, add B dropwise to A while stirring, adjust the pH to 3 with ammonia water during the addition process, stir and mature for 6 hours, dry at 250°C, and roast at 350°C for 4 hours to obtain outer layer catalyst powder body, the thermal conductivity i...

Embodiment 2

[0053] Multilayer Catalyst Preparation

[0054] Preparation of outer layer catalyst powder: Dissolve 4 kg of ammonium heptamolybdate in 5 L of pure water at 50° C. to obtain solution A after complete dissolution. 460g of bismuth nitrate, 2.2kg of cobalt nitrate, 1.9kg of iron nitrate, 1.4kg of nickel nitrate, and 38g of potassium nitrate were dissolved in 4.25kg of dilute nitric acid aqueous solution (15wt%) to obtain solution B after completely dissolving. Keep the solution temperature at 65°C, add B to A while stirring, and then adjust the pH to 0.8 with ammonia water. After adjustment, it was stirred and matured for 6 hours, dried at 80°C, and calcined at 350°C for 4 hours to obtain outer layer catalyst powder with a thermal conductivity of 140W / (m·K) and a porosity of the outer layer catalyst of 0.12%.

[0055] Preparation of intermediate layer catalyst powder: 3.1kg ammonium heptamolybdate, 1.1kg molybdenum trioxide, 25g niobium pentoxide (chemical formula Nb 2 o 5 ) w...

Embodiment 3

[0061] Multilayer Catalyst Preparation

[0062] Preparation of outer layer catalyst powder: Dissolve 4 kg of ammonium heptamolybdate in 5 L of pure water at 60° C. to obtain solution A after complete dissolution. With 3.6kg bismuth nitrate, 2.8kg cobalt nitrate, 760g iron nitrate, 440g nickel nitrate, 62g cesium carbonate (chemical formula is Cs 2 CO 3 ) into 5kg dilute nitric acid aqueous solution (15wt%), and obtain solution B after dissolving completely. Keep the solution temperature at 80°C, add B to A while stirring, and then adjust the pH to 6.5 with ammonia water. After adjustment, it was stirred and matured for 6 hours, dried at 160°C, and calcined at 350°C for 4 hours to obtain outer layer catalyst powder with a thermal conductivity of 120W / (m·K) and a porosity of the outer layer catalyst of 0.13%.

[0063] Preparation of intermediate layer catalyst powder: 4kg ammonium heptamolybdate, 1.1kg ammonium metavanadate, 523.2g silicotungstic acid (chemical formula H 4 [...

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Abstract

The present invention relates to a multi-layer catalyst and a preparation method thereof. The multi-layer catalyst can be represented by the following formula from an outer layer, an intermediate layer to an inner layer: (Mo12BibFecCodNieAfOx):m(Moa1NbgVhWiBjOy):n(Moa2PbkAllSipCqOz). The multi-layer catalyst has the characteristics of high activity, high thermal conductivity and long service life; the conversion rate can be higher than 99% in a reaction process for preparing unsaturated aldehyde (acid) from gas-phase oxidation unsaturated olefin, particularly unsaturated olefin smaller than C5; when C3 unsaturated olefin is used, the effective selectivity of the unsaturated aldehyde (acid) smaller than C3 is higher than 96%, and the yield of the unsaturated aldehyde (acid) is more than 95%; and when C4 or C5 unsaturated olefin is used, the effective selectivity of C4 or C5 unsaturated aldehyde (acid) is higher than 84%, and the yield of the unsaturated aldehyde (acid) is more than 82%. Compared with the existing commercial catalyst, the service life of the multi-layer catalyst is prolonged by more than 20%.

Description

technical field [0001] The invention relates to a multilayer catalyst and a preparation method thereof, which are used to catalyze the gas-phase selective oxidation of unsaturated olefins to prepare corresponding unsaturated aldehydes (acids), especially for the preparation of acrolein (acid) by the oxidation of propylene or the preparation of methyl by the oxidation of isobutene. Acrolein (acid). Background technique [0002] Unsaturated aldehydes (acids) are used in a wide range of fields, and one of the representative products is acrylic acid and esters. Its application fields cover coatings, adhesives, chemical fibers, papermaking, leather, building materials, plastic modification, synthetic rubber, radiation curing water treatment agents and other industries. The methods for the production of acrylic acid on an industrial scale generally include the chlorohydrin method, the high-pressure Reppe method, the propiolactone method, the Dorr-Badishe method (that is, the impr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/887B01J23/888C07C27/12C07C45/35C07C47/22C07C51/25C07C57/05
CPCB01J23/002B01J23/8877B01J23/8885B01J2523/00C07C45/35C07C51/25B01J2523/68B01J2523/54B01J2523/842B01J2523/845B01J2523/847B01J2523/13B01J2523/55B01J2523/22B01J2523/44B01J2523/31B01J2523/41B01J2523/56B01J2523/15B01J2523/69B01J2523/17C07C47/22C07C57/04
Inventor 万毅易光铨曹传宗于海彬孙康初乃波黎源华卫琦
Owner WANHUA CHEM GRP CO LTD