Hydrodewaxing catalyst as well as preparation method and application thereof

A hydrodewaxing and catalyst technology, applied in catalyst activation/preparation, catalyst carrier, molecular sieve catalyst, etc., can solve the problems of paraffin selectivity reduction, molecular sieve frame collapse, catalyst reduction, etc., to achieve low cracking capacity and reduce side effects. Reaction, effect of high catalytic activity

Active Publication Date: 2011-05-11
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This method adopts the method of high-temperature roasting catalyst support to reduce the acidity of the catalyst, and its main disadvantage is that the aluminum atoms on the outer surface of the molecular sieve cannot be selectively removed during the high-temperature roasting dealumination process, thereby affecting the improvement of the selectivity of the catalyst, and dealumination When the degree is deep, it will also cause the collapse of the molecular sieve framework, which will reduce the selectivity of paraffins.

Method used

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  • Hydrodewaxing catalyst as well as preparation method and application thereof
  • Hydrodewaxing catalyst as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Will be made of small hole alumina (specific surface 238m 2 g -1 , pore volume 0.48mL·g -1 ) is added to HZSM-5 molecular sieve (97wt% on a dry basis, manufacturer: Tianjin Nankai University Catalyst Factory, SiO 2 / Al 2 o 3 molar ratio 38), mixed evenly, extruded, dried at 130°C for 4 hours, and calcined at 580°C for 4 hours to obtain a carrier.

[0029] The above-mentioned carrier is added to an aqueous solution of magnesium nitrate with a weight content of 5% magnesium oxide and impregnated by equal volume for 5 hours. After filtering, the obtained solid phase is dried at 120° C. for 4 hours to obtain a magnesium-modified carrier.

[0030] Add cyclohexane to dimethyl silicone oil to obtain a silicone oil-organic mixed solution with a silicon oxide weight concentration of 15%, and then add the magnesium-modified carrier to the above-mentioned silicone oil-organic mixed solution to impregnate in equal volume, and the immersion time is 3 hours . After filtration, ...

Embodiment 2

[0033] Will be made of small hole alumina (specific surface 238m 2 g -1 , pore volume 0.48mL·g -1 ) was added to HZSM-5 molecular sieve (same as Example 1), mixed evenly, extruded, dried at 130°C for 4 hours, and calcined at 580°C for 4 hours to obtain a carrier.

[0034] Add the above-mentioned carrier to an aqueous solution with a calcium oxide content of 6% calcium nitrate and impregnate it at a volume ratio of 1:1.5 for 4 hours. After filtering, the obtained solid phase is dried at 100°C for 5 hours to obtain calcium-modified carrier.

[0035] Add solvent gasoline to ethyl silicone oil to obtain a silicone oil-organic mixed solution with a silicon oxide weight concentration of 20%, then add the calcium-modified carrier to the above-mentioned silicone oil-organic mixed solution for immersion in a volume ratio of 1:1.5, and the immersion time for 3 hours. After filtration, it was dried at 110° C. for 4 hours and calcined at 560° C. for 4 hours to obtain calcium and silic...

Embodiment 3

[0038] The preparation of the support and the magnesium-modified support is the same as in Example 1.

[0039] Xylene is added to phenylmethyl silicone oil to obtain a silicone oil-organic mixed solution with a silicon oxide weight concentration of 18%, and then the magnesium-modified carrier is added to the above-mentioned silicone oil-organic mixed solution and impregnated at a volume ratio of 1:2. The time is 3 hours. After filtering, it was dried at 120° C. for 4 hours and calcined at 550° C. for 6 hours to obtain a carrier S3 modified by magnesium and silicon, wherein the weight content of magnesium oxide was 3.0%, and the content of silicon oxide surface coating was 5.0%.

[0040] The obtained carrier S3 was immersed in an aqueous solution containing nickel and tungsten, then dried at 120° C. for 5 hours, and calcined at 600° C. for 3 hours to obtain hydrodewaxing catalyst N3.

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Abstract

The invention discloses a hydrodewaxing catalyst as well as a preparation method and application thereof. The hydrodewaxing catalyst is prepared by using a carrier modified with alkaline-earth metals and silicon. The carrier is modified through the following steps: firstly loading the alkaline-earth metals onto the carrier by a traditional carrier immersion method; and then modifying the carrier with silicon oil to form a silica coating on the surface of the carrier. By utilizing the method, the acidity of internal and external surfaces of a molecule sieve and the shape of holes can be effectively adjusted, thereby being beneficial for wax molecules to diffuse into the hole paths of the molecule sieve and be subjected to a shape-selective cracking reaction. Thus the catalyst provided by the invention has the advantages of higher catalyst activity and better target product selectivity. Moreover, due to the weak acidity of the external surface of the molecule sieve and low cracking capacity, the side reaction in the preparation of the target products are reduced. The catalyst is suitable for the hydrodewaxing process of wax-containing raw materials, especially for a hydrodewaxing process of diesel oil or lubricating oil.

Description

technical field [0001] The invention relates to a hydrogenation dewaxing catalyst and a preparation method thereof. The catalyst is used in the hydrodewaxing process of waxy hydrocarbon raw materials, especially in the hydrodewaxing process of diesel oil or lubricating oil. Background technique [0002] Hydrodewaxing refers to the reduction of the waxy molecular content of a waxy hydrocarbon feedstock on the surface of a suitable catalyst in the presence of hydrogen. The principle of dewaxing is that under certain operating conditions, the raw material is mixed with hydrogen and contacted with a hydrodewaxing catalyst. High freezing point components such as aromatics are selectively cracked into small molecules, while other components are basically unchanged, and the purpose of lowering the freezing point of the oil is finally achieved. See US3,894,438, US3,894,439, US 4,173,148 for the specific catalytic dewaxing process. Diesel hydrodewaxing is generally called diesel h...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/48B01J32/00B01J37/00B01J37/02B01J35/10C10G73/02C10G45/64
Inventor 李永泰孟祥兰高鹏
Owner CHINA PETROLEUM & CHEM CORP
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