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Supported type catalyst, preparation method thereof, application thereof and Fischer-Tropsch synthesis method thereof

A supported catalyst and Fischer-Tropsch synthesis technology, applied in chemical instruments and methods, physical/chemical process catalysts, metal/metal oxide/metal hydroxide catalysts, etc., can solve the problems that the catalyst activity needs to be further improved, and achieve Effects of improved Fischer-Tropsch synthesis performance, high C5+ selectivity, and high CO conversion

Active Publication Date: 2017-04-05
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although this method can improve the activity of the catalyst under the condition of low metal content to a certain extent, the activity of the catalyst still needs to be further improved.

Method used

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  • Supported type catalyst, preparation method thereof, application thereof and Fischer-Tropsch synthesis method thereof
  • Supported type catalyst, preparation method thereof, application thereof and Fischer-Tropsch synthesis method thereof
  • Supported type catalyst, preparation method thereof, application thereof and Fischer-Tropsch synthesis method thereof

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preparation example Construction

[0029] The present invention also provides a preparation method of a supported catalyst, the preparation method comprising the following steps:

[0030]1) impregnating the support with a solution of a compound containing a cobalt metal component;

[0031] 2) reducing and activating the impregnated carrier obtained in step 1);

[0032] 3) impregnating the reductively activated product in step 2) with a solution of a compound containing a precious metal active component in a reducing or inert atmosphere;

[0033] 4) impregnating the carrier with a solution of a compound containing a non-precious metal auxiliary component;

[0034] Wherein, the step 4) is performed in any period before, during, and after step 1), and before, during, and after step 3).

[0035] Preferably, the solution containing the compound of the cobalt metal component in step 1) also contains the compound of the noble metal active component, and the weight ratio of the compound of the noble metal active comp...

Embodiment 1

[0062] (1) Catalyst preparation and characterization

[0063] According to the metal salt content required by the equal volume impregnation method, it is formulated into 42.5 ml of cobalt nitrate containing 176 g / L of cobalt, 0.24 g / L of platinum, 10.2 g / L of zirconium, dichlorotetraammine platinum and zirconium oxynitrate dihydrate. dipping solution. Decant the impregnation liquid to 50 g SiO 2 The carrier (Fuji Silicon Co., Japan, with an average particle size of 40-80 microns) was stirred at 20°C for 4 hours, dried at 120°C, calcined at 400°C for 4 hours, reduced by hydrogen at 400°C for 4 hours, and the hydrogen pressure was 0.1 MPa. After reduction, the temperature was lowered to room temperature, and 63.8 ml of a dichlorotetraammine platinum aqueous solution containing 0.63 g / L of platinum was added under a hydrogen atmosphere, allowed to stand for 1 hour, and then dried with hydrogen. Then by O 2 / N 2The mixed gas with a volume ratio of 0.5% was passivated for 0.5 ...

Embodiment 2

[0067] (1) Catalyst preparation and characterization

[0068] According to the metal salt content required by the equal volume impregnation method, 42.5 ml of the impregnation solution containing cobalt 176 g / L, iridium 0.48 g / L, zirconium 10.2 g / L, iridium chloride and zirconium oxynitrate dihydrate was prepared. Decant the impregnation liquid to 50 g SiO 2 The carrier (Qingdao Ocean Chemical Plant, average particle size is 40-80 microns), stirred evenly at 15°C, allowed to stand for 6 hours, dried at 100°C, calcined at 450°C for 2 hours, reduced with hydrogen at 450°C for 2 hours, and the hydrogen pressure was 1 MPa. After reduction, the temperature was lowered to room temperature, and 63.8 ml of an iridium chloride aqueous solution containing 1.26 g / L of iridium was added under a hydrogen atmosphere, allowed to stand for 1 hour, and then blown dry with hydrogen. Then by O 2 / N 2 The mixed gas with a volume ratio of 0.8% was passivated for 2 hours and stored in a desicca...

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Abstract

The invention discloses a supported type catalyst which comprises a carrier as well as an active ingredient Co element, a noble metal MNoble element and a non-noble metal auxiliary element supported on the carrier. The supported type catalyst is characterized in that a weight ratio of Co to the noble metal (in terms of a metal element) meets a relationship (MNoble / MCo)XPS / (MNoble / MCo)XRF=2.0-20.0, wherein MNoble / MCo)XPS is a weight ratio of a catalyst noble metal component represented by X-ray photoelectron spectroscopy to Co in terms of metal elements; and (MNoble / MCo)XRF is a weight ratio of the catalyst noble metal component represented by X-ray fluorescence spectrum to Co in terms of metal elements. The noble metal component is at least one of Pt, Pd, Ru, Rh and Ir. The invention also provides a preparation method for the catalyst and the Fischer-Tropsch synthesis method for the catalyst. Compared with a catalyst with the same metal content prepared in the prior art, the supported type catalyst has the advantages that a Fischer-Tropsch synthesis catalyst containing noble metal has relatively high C<5+> selectivity and relatively low methane selectivity while relatively high reaction activity is kept.

Description

technical field [0001] The present invention relates to a supported catalyst, a preparation method of the supported catalyst, the supported catalyst prepared by the method, its application and a Fischer-Tropsch synthesis method. Background technique [0002] In today's turbulent international energy situation and fierce competition between energy supply and demand, further efficient and clean utilization of coal and natural gas resources is of great strategic significance. Hydrocarbons manufactured based on Fischer-Tropsch synthesis and other technologies have excellent performance and can be used directly or mixed with fuels produced from low-quality crude oil to meet increasingly stringent requirements for environmental protection and oil performance indicators. At present, Sasol Company of South Africa and Shell Company of England / Netherlands have the world's leading Fischer-Tropsch industrial synthetic oil technology. The reactors they use include tubular fixed bed and s...

Claims

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Application Information

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IPC IPC(8): B01J23/89C10G2/00
Inventor 郑仁垟李明丰李会峰夏国富晋超吴玉张荣俊侯朝鹏褚阳刘锋
Owner CHINA PETROLEUM & CHEM CORP
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