Catalytic cracking diesel oil hydro-upgrading catalyst and application thereof

A technology for catalytic cracking diesel oil and hydro-upgrading, which is applied to catalysts containing molecular sieves and application fields, can solve the problems of high operation and investment costs, high initial boiling point of diesel raw materials, harsh operating conditions, etc., and achieves equipment investment and operating costs. Low, enhance the ability of macromolecule conversion, improve the effect of yield

Inactive Publication Date: 2013-10-30
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] US6241876B1 and US6500329B2 disclose a catalytic cracking diesel hydro-upgrading technology. Their common feature is to use a two-stage countercurrent process to treat catalytic diesel oil, one stage for hydrodesulfurization, nitrogen and other impurities, and the second stage for the use of precious metal catalysts containing Y molecular sieves. Hydrodearomatization can greatly increase the cetane number of diesel products. Their disadvantages are harsh operating conditions, the need to use countercurrent technology and the use of precious metal catalysts, so the operation and investment costs are high, and it is difficult for industrial application
[0009] CN1407066A discloses a method for hydrogenation and upgrading of catalytic cracking diesel oil. The method uses a hydrogenation catalyst containing molecular sieves to carry out dearomatization, desulfurization and improvement of sixteen alkane number, but the initial boiling point of the diesel feedstock involved in this method is relatively high

Method used

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  • Catalytic cracking diesel oil hydro-upgrading catalyst and application thereof

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Experimental program
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Effect test

Embodiment 1

[0032] Get 100 grams of nanometers (average grain size 87nm) NaY molecular sieve (crystallinity is 97%, SiO 2 / Al 2 o 3 The molar ratio is 5.6, Beijing Bowen Kefeng Technology Development Co., Ltd.), added to the 70g NH 4 In the 1000ml aqueous solution of Cl, exchange at 80°C for 1 hour. During this process, the pH value is controlled to 3.4. After the exchange, filter, wash, and dry, and then treat it in a muffle furnace at a temperature of 600°C for 2 hours; then follow the same procedure conditions for the second ammonium exchange, after the exchange, filter, wash, and dry, and then treat for 2 hours in a 100% water vapor atmosphere at a temperature of 610°C and a water vapor pressure of 0.2 MPa; the finally obtained modified Y Molecular sieve SiO 2 / Al 2 o 3 The molar ratio is 15, the relative crystallinity is 79%, the average grain size is 80nm, and the specific surface area is 713m2 / g.

Embodiment 2

[0034] Get 100 grams of nanometers (average grain size 87nm) NaY molecular sieve (crystallinity is 97%, SiO 2 / Al 2 o 3 The molar ratio is 5.6, Beijing Bowen Kefeng Technology Development Co., Ltd.), added to the 70g NH 4 NO 3 In 1000ml of aqueous solution, exchange at 80°C for 1 hour. During this process, the pH value is controlled to 3.1. After the exchange, filter, wash, and dry, and then treat it in a muffle furnace at a temperature of 600°C for 2.5 hours; then follow the same conditions Carry out the second ammonium exchange, filter after the exchange, wash with water, dry, and then treat for 2 hours in a 100% water vapor atmosphere at a temperature of 600°C and a water vapor pressure of 0.15 MPa; the finally obtained modified Y molecular sieve SiO 2 / Al 2 o 3 The molar ratio is 18, the relative crystallinity is 81%, the average grain size is 84nm, and the specific surface area is 693m2 / g.

Embodiment 3

[0036] Get modified Y molecular sieve 25.5g in embodiment 1, and 82.9g alumina (for example, the pseudo-boehmite produced by SASOL company, wherein the gibbsite content is 70wt%), 27.2g amorphous silicon aluminum, 4.7g scallop powder, after mixing, add dropwise a mixed solution of 6.5g concentrated nitric acid (96wt%), 4.3g citric acid and 108g water, extrude into a clover shape of about 1.3mm, dry at 110°C, and air atmosphere at 500°C Roast for 4 hours. Then immerse in a solution of 33g of nickel nitrate and 50g of ammonium metatungstate dissolved in 50ml of water for 2 hours, dry at 110°C, and roast at 480°C for 4 hours in an air atmosphere to obtain catalyst A. According to specific requirements, it can be crushed or cut into the required particle size or length, and hydrogenation reaction can be carried out after vulcanization.

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Abstract

The invention relates to a catalytic cracking diesel oil hydro-upgrading catalyst and applications thereof. The catalyst is composed of VIII-group and VIB-group hydrogenation active metal components and a carrier containing a modified Y molecular sieve, amorphous silicon aluminum and alumina; the modified Y molecular sieve is prepared from a NaY molecular sieve by the steps of carrying out ammonium exchange twice, carrying out roasting one time and carrying out hydro-thermal treatment one time. The catalyst is used for carrying out hydro-upgrading on distillate or catalytic cracking diesel oil at a temperature of 160-380 DEG C. After inferior diesel distillate of which the sulfur content is higher than 1000 mu g/g, the nitrogen content is higher than 1000 mu g/g, the aromatics content is higher than 55v% is treated by using the catalyst, the desulfurization rate and the denitrification rate are both higher than 98%, the cetane number is increased by more than 10 units, and the yield of the diesel distillate is over 98wt%.

Description

technical field [0001] The invention relates to a catalytic cracking diesel oil hydrogenation upgrading catalyst and its application, in particular to a molecular sieve-containing catalyst and its application. Background technique [0002] For a long time, my country's heavy oil processing technology has been mainly based on catalytic cracking, and the processing capacity of catalytic cracking accounts for more than 30% of the secondary processing capacity, resulting in more than 30% of the finished diesel oil produced by catalytic cracking. Moreover, the catalytic cracking unit is a device that mainly produces gasoline, and the ratio of diesel to gasoline cannot be increased, so it is difficult to meet the large demand for diesel in my country's market. Moreover, catalytic cracking diesel oil contains more heteroatom compounds, olefins and aromatics, and its stability is poor, especially the cetane number is very low. With the increase of slagging in heavy oil catalytic cr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/16C10G49/08
Inventor 王甫村郭巧霞张志华申宝剑田然孙发民王亮郭金涛朱金玲王艳丹赵野方磊王丹杨庶丛丽茹李凤铉熊玉平马守涛温广明关旭徐伟池
Owner PETROCHINA CO LTD
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