Hydro-upgrading catalyst for diesel oil with high content of aromatic hydrocarbons, and preparation method and application thereof

A hydrogenation upgrading and catalyst technology, applied in molecular sieve catalysts, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems of low octane number and high sulfur content of products

Inactive Publication Date: 2017-06-16
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] The main purpose of the present invention is to provide a high-aromatic diesel hydrogenation upgrading catalyst and its preparation method and application to overcome the low octane number and high sulfur content of the product when the existing hydrogenation catalyst is used for high-aromatic diesel upgrading Defects

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] The small grain high silicon aluminum ratio NaY type molecular sieve (skeleton SiO 2 / Al 2 o 3 Molar ratio 6.2, grain diameter 200nm ~ 300nm) add NH 4 An ammonium exchange was carried out in aqueous Cl solution. The mass ratio of each material NaY:NH 4 Cl:H 2 O is 1:0.5:10, the temperature of the exchange system is 70°C, the exchange time is 0.5 hours, and the pH value of the exchange solution is 4.6-4.8. After the exchange, filter, wash, and dry to obtain NH 4 NaY, put the above NH 4 The NaY molecular sieve is subjected to a hydrothermal treatment, the condition is 100% water vapor atmosphere, at a temperature of 500 ° C, and the treatment is performed for 1 hour to obtain USY Ⅰ -1 sample; will USY Ⅰ -1 sample is subjected to the second ammonium exchange and the second hydrothermal treatment, the method is the same as the first ammonium exchange and the first hydrothermal treatment, and the USY Ⅱ -1 sample; will USY Ⅱ -1 sample was treated with citric acid, th...

Embodiment 2

[0048] The NaY type molecular sieve (specification is the same as embodiment 1) with small grain high silicon aluminum ratio is added NH 4 An ammonium exchange was carried out in aqueous Cl solution. The mass ratio of each material NaY:NH 4 Cl:H 2 O is 1:0.8:10, the temperature of the exchange system is 85°C, the exchange time is 2 hours, and the pH value of the exchange solution is 3.8-4.0. After the exchange, suction filtration, washing, and drying give NH 4 NaY, put the above NH 4 NaY molecular sieves were subjected to a hydrothermal treatment under the condition of 100% water vapor atmosphere at a temperature of 580°C for 2 hours to obtain USY Ⅰ -2 samples; will USY Ⅰ -2 The sample is subjected to the second ammonium exchange and the second hydrothermal treatment, and the method is the same as the first ammonium exchange and the first hydrothermal treatment to obtain USY Ⅱ -2 samples; will USY Ⅱ -2 The sample was treated with oxalic acid, the reaction temperature was...

Embodiment 3

[0050] The NaY type molecular sieve (specification is the same as embodiment 1) with small grain high silicon aluminum ratio is added NH 4 An ammonium exchange was carried out in aqueous Cl solution. The mass ratio of each material NaY:NH 4 Cl:H 2 O is 1:1.2:10, the temperature of the exchange system is 95°C, the exchange time is 4 hours, the pH value of the exchange solution is 3.0-3.2, after the exchange, suction filtration, washing, drying, to obtain NH 4 NaY, put the above NH 4 NaY molecular sieves were subjected to a hydrothermal treatment under the condition of 100% water vapor atmosphere at a temperature of 680°C for 4 hours to obtain USY Ⅰ -3 samples; will USY Ⅰ -3 samples were subjected to the second ammonium exchange and the second hydrothermal treatment, and the method was the same as the first ammonium exchange and the first hydrothermal treatment to obtain USY Ⅱ -3 samples; will USY Ⅱ -3 Sample was treated with citric acid, the reaction temperature was 95°C,...

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Abstract

The invention relates to a hydro-upgrading catalyst for diesel oil with high content of aromatic hydrocarbons, and a preparation method and application thereof. The catalyst comprises, by weight, 20 to 65% of a composite molecular sieve, 10 to 50% of alumina, 10 to 30% of VIB-group metal (in terms of oxide) and 3 to 8% of VIII-group metal (in terms of oxide), wherein the composite molecular sieve is composed of a small-grain modified Y molecular sieve and a SAPO-11 molecular sieve in a weight ratio of 2: 1 to 10: 1. The invention also discloses a preparation method for the small-grain modified Y molecular sieve. The preparation method comprises the following step: successively subjecting a raw material, i.e., a small-grain high-silica-alumina-ratio NaY molecular sieve with a SiO2/Al2O3 mol ratio of 6.0 to 7.0, to primary ammonium exchanging, primary hydro-thermal treatment, secondary ammonium exchanging, secondary hydro-thermal treatment and primary acid treatment. With the catalyst prepared in the invention, high liquid product yield is obtained, and diesel oil with high content of aromatic hydrocarbons can be used for production of low-sulfur olefin-free high-octane-number gasoline and ultra-low-sulfur clean diesel oil.

Description

technical field [0001] The invention relates to a catalyst for hydrogenation and upgrading of high-aromatic diesel oil, in particular to a catalyst for hydrogenation and upgrading of high-aromatic diesel oil in the field of petroleum refining, especially for producing high-octane gasoline and ultra-low sulfur diesel from high-aromatic diesel catalyst. Background technique [0002] Catalytic cracking is one of the main means of heavy oil processing. In my country, the processing capacity of catalytic cracking accounts for about one-third of the primary processing capacity of crude oil. As a result, in the composition of gasoline and diesel products, catalytic cracking gasoline accounts for more than 75%, and catalytic diesel oil accounts for 30%. %above. Catalyzed diesel oil contains more heteroatom compounds, aromatics and olefins, with poor stability and low cetane number. With the increasingly poor quality of crude oil, and in order to improve the quality of gasoline or i...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/85B01J35/10C10G47/20
CPCB01J29/005B01J29/166B01J29/85B01J35/1019B01J35/1038C10G47/20C10G2300/70
Inventor 夏恩冬孙发民吕倩秦丽红郭金涛徐铁刚谢方明张铁珍李海岩王甫村王亮王燕谢彬郭立艳张全国孙生波赵晶莹李圣平张云桐唐成孙庆
Owner PETROCHINA CO LTD
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