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Loaded double-metal hydrogenation catalyst, and preparation method and application thereof

A hydrogenation catalyst and bimetallic technology, which is applied in the field of supported bimetallic hydrogenation catalyst and its preparation and application, can solve the problems of complex preparation process, difficulty in industrial application, poor controllability and repeatability, etc., and achieve improvement Hydrodesulfurization performance, good industrial application prospects, guaranteed full utilization effect

Active Publication Date: 2016-04-27
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the ammonia precipitation method has poor controllability and repeatability in the process of in-situ synthesis of hydrotalcite. At the same time, the ion exchange process not only complicates the preparation process, but also makes it difficult to ensure a high exchange rate, resulting in low raw material utilization.
In short, the preparation route of this technology is relatively complicated, the controllability and repeatability are poor, and the cost is high, so it is not suitable for large-scale application
[0009] In summary, the existing technical routes for preparing supported catalysts from hydrotalcite precursors are often difficult to achieve industrial application due to the complexity of the process, poor controllability of the operation process, and high production costs.

Method used

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  • Loaded double-metal hydrogenation catalyst, and preparation method and application thereof
  • Loaded double-metal hydrogenation catalyst, and preparation method and application thereof
  • Loaded double-metal hydrogenation catalyst, and preparation method and application thereof

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preparation example Construction

[0036] The invention provides a preparation method of a supported bimetallic hydrogenation catalyst, the preparation method comprising the following steps:

[0037] (1) Under the conditions of crystallization, will contain water-soluble Group VIII metal salt, urea, water and γ-Al 2 o 3 The mixture of base carriers is placed in a closed container for crystallization, and the Al contained in it 2 o 3 , the weight ratio of water to alumina in the mixture is ≥1;

[0038] (2) Using the solution containing the VIB group metal salt as the impregnating liquid, impregnating the solid obtained from the crystallization in step (1), followed by drying and roasting in sequence.

[0039] The essence of the method of the present invention is to first support Group VIII metals through simple, controllable, and low-cost in-situ synthetic hydrotalcite technology, and then introduce Group VIB metals by conventional impregnation methods to obtain a supported bimetallic hydrogenation catalyst ...

Embodiment 1

[0061] (1) Prepare 50 mL of a solution containing 0.2 mol / L nickel nitrate and 0.6 mol / L urea; weigh 10 g of γ-Al with a diameter of 2-5 mm 2 o 3 The particles were poured into the above solution to obtain a mixture, the pH of which was 7.5; the mixture was transferred to an autoclave, and placed in an oven for crystallization at 80° C. for 12 hours;

[0062] (2) Filter the material obtained after the crystallization in step (1), wash the solid with water, put it in an oven and dry it at 100°C for 5 hours to obtain NiAl-CO 3 2- -LDHs / γ-Al 2 o 3 Composite material; the NiAl-CO 3 2- -LDHs / γ-Al 2 o 3 SEM images of composite materials figure 1 shown;

[0063] (3) Prepare a sodium molybdate solution containing 6.0 g of sodium molybdate and about 10 mL, and add it dropwise to the NiAl-CO obtained in step (1). 3 2- -LDHs / γ-Al 2 o 3 Soak it in water, dry it at room temperature, then dry it at 100°C for 5h, and bake it at 500°C for 4 hours to get NiMo / γ-Al 2 o 3 Catalyst...

Embodiment 2

[0075] (1) Prepare 50 mL of a solution containing 0.2 mol / L cobalt nitrate and 1.0 mol / L urea, and weigh 15 g of γ-Al with a diameter of 2-5 mm 2 o 3 The particles were poured into the above solution to obtain a mixture, the pH of which was 7.5; the mixture was transferred to an autoclave, and placed in an oven for crystallization at 80°C for 24 hours;

[0076] (2) Filter the material obtained after the crystallization in step (1), wash the solid with water, and dry it in an oven at 100°C for 6 hours to obtain CoAl-CO 3 2--LDHs / γ-Al 2 o 3 Composite material; the CoAl-CO 3 2- -LDHs / γ-Al 2 o 3 The SEM image of the composite material and figure 1 resemblance;

[0077] (3) Prepare an ammonium molybdate solution containing 4.4g of ammonium molybdate and about 15mL, and add it dropwise to the above-mentioned CoAl-CO 3 2- -LDHs / γ-Al 2 o 3 Soak it in water, dry it at room temperature, then dry it at 100°C for 5 hours, and bake it at 400°C for 5 hours to get CoMo / γ-Al 2 o...

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Abstract

The invention provides a loaded double-metal hydrogenation catalyst, and a preparation method and application thereof. The catalyst comprises a gamma-Al2O3-contained carrier and active metal components loaded on the gamma-Al2O3-contained carrier, wherein the active metal components comprise a group-VIB metal component and a group-VIII metal component which have the following characteristics: through the analysis of an X-ray photoelectron spectroscopy, the mol ratio of the group-VIB metal atom to the Al atom on the surface of the catalyst is measured to be 0.11 to 0.25, and the mol ratio of the group-VIII metal atom to the Al atom on the surface of the catalyst is measured to be 0.01 to 0.10; and through the analysis of an X-ray fluorescence spectroscopy, the mol ratio of the group-VIII metal atom to the group-VIB metal atom in the catalyst is measured to be 0.2 to 1. The loaded double-metal hydrogenation catalyst prepared by using the method provided by the invention has good dispersibility, active-centre accessibility and structural stability, significantly improves hydrodesulphurization property of the catalyst, and has good industrial application prospects.

Description

technical field [0001] The invention relates to a preparation method of a supported bimetallic hydrogenation catalyst, the supported bimetallic hydrogenation catalyst prepared by the method and its application in hydrodesulfurization. Background technique [0002] Hydrogenation technology is the most important means of producing clean oil products, among which efficient hydrogenation catalyst is the core technology of hydrogenation technology. The main active component is VIB group metal W or Mo, the VIII group metal Ni or Co is the auxiliary active component, and γ-A1 2 o 3 or modified γ-A1 2 o 3 The supported catalyst is a hydrogenation catalyst widely used in industry at present. γ-A1 2 o 3 Because of its suitable mechanical strength, acidity and pore structure, using it as a carrier or modifying it has been widely used in the preparation of hydrorefining and hydrocracking catalysts. [0003] The traditional preparation technology mainly uses impregnation to introd...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/883B01J23/888B01J37/03B01J35/10C10G45/08
Inventor 韩伟龙湘云张乐刘学芬李明丰杨清河聂红李大东
Owner CHINA PETROLEUM & CHEM CORP
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