Hydro-dewaxing catalyst and preparation method and application thereof

A hydrogenation dewaxing and catalyst technology, which is applied in the direction of catalyst activation/preparation, catalyst carrier, molecular sieve catalyst, etc., can solve the problems of inability to selectively remove paraffins, selectivity reduction of paraffins, collapse of molecular sieve skeleton, etc., and achieve high Target product selectivity, low cracking ability, and the effect of reducing side reactions

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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  • Hydro-dewaxing catalyst and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] 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.

[0030] The above-mentioned support is added to an aqueous zinc nitrate solution with a weight content of 6% zinc 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 zinc-modified support.

[0031]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 zinc-modified carrier to the above-mentioned silicone oil-organic mixed solution to impregnate in equal volume for 3 hours . After filtration, it was dried at 100° C. for 4 hours and calcine...

Embodiment 2

[0034] 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.

[0035] The above-mentioned carrier is added to the aqueous solution of 3% copper nitrate and 3% magnesium nitrate with the content of copper oxide and immersion in the aqueous solution of magnesium nitrate with a volume ratio of 1: 1.5. The immersion time is 4 hours. After filtering, the solid phase obtained is subjected to 120 °C for 5 hours to obtain a copper- and magnesium-modified support.

[0036] Add solvent gasoline to ethyl silicone oil to obtain a silicone oil-organic mixed solution with a silicon oxide weight concentration of 20%, and then add the copper and magnesium-modified carrier to the above-mentioned silicone oil-organic mixed solution at a volume ratio of 1:1.5 for impregnation, The soaking time...

Embodiment 3

[0039] 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.

[0040] Add the above carrier to an aqueous solution with a lanthanum oxide content of 9% lanthanum nitrate and impregnate it at a volume ratio of 1:1.5 for 4 hours. After filtering, the obtained solid phase is dried at 120°C for 5 hours to obtain lanthanum-modified carrier.

[0041] 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 lanthanum-modified carrier to the above-mentioned silicone oil-organic mixed solution for immersion at a volume ratio of 1:1.5, and the immersion time for 3 hours. After filtration, it was dried at 120° C. for 4 hours and calcined at 500° C. for 8 hours to obtain a carrier S3 modifi...

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Abstract

The invention discloses a hydro-dewaxing catalyst and a preparation method and application thereof. The hydro-dewaxing catalyst comprises a carrier modified by a metal aid and silicon, and is prepared by the following steps of: supporting the metal aid by using a conventional carrier impregnation method, modifying by using silicon oil, and forming a silica coating on the surface of the carrier. The method can effectively regulate the acidity and pore shapes of the inner surface and the outer surface of a molecular sieve to contribute to diffusing wax molecules into the pores of the molecular sieve for shape-selective cracking reaction, and ensures higher catalytic activity and higher selectivity for target products; in addition, the acidity of the outer surface of the molecular sieve is lower, the cracking capacity is low, and the side reaction of the target products is reduced. The hydro-dewaxing catalyst is suitable for the hydro-dewaxing process for wax-containing raw materials, particularly the diesel hydro-dewaxing or lubricating oil hydro-dewaxing process.

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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