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C10+ heavy aromatic hydrocarbon hydrodealkylation catalyst and preparation method thereof

A technology for hydroalkyl and heavy aromatics, which is applied in the field of C10+ heavy aromatic hydroalkylation transalkylation catalyst and preparation field, can solve the problems of easy carbon deposition and deactivation of the catalyst, reduced BTX selectivity, large loss of alkyl group, etc. Renewable, high catalyst stability, high conversion effect

Active Publication Date: 2015-02-18
CHINA NAT OFFSHORE OIL CORP +3
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] CN102746093A uses hydrogen-type binderless ten-membered ring zeolite loaded with platinum or palladium as a catalyst, the reaction temperature is 320-450°C, the reaction pressure is 2-4MPa, and the weight hourly space velocity of hydrocarbon raw materials is 1-4h -1 , Under the reaction conditions of 3-10:1 molar ratio of hydrogen hydrocarbon raw materials, heavy aromatics are subjected to hydrocracking reaction, and the BTX content in the product is greater than 57%, C 9 About 20% aromatics, but at least 11-15% low-carbon non-aromatics, with large loss of alkyl groups
If molecular sieves with smaller pores such as ZSM-5 are used to treat C with larger molecules 10 + Aromatics, catalysts are prone to carbon deposition and deactivation, and the use of molecular sieves with larger pore sizes (such as Y-type molecular sieves) will definitely reduce the selectivity of BTX. This is a problem that needs to be solved in the lightening technology of heavy aromatics
In addition, the loss of alkyl groups in the above method is large, a large amount of low-carbon non-aromatic hydrocarbons are generated, and the liquid yield is low, which is also a major defect of the current heavy aromatics lightening technology

Method used

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  • C10+ heavy aromatic hydrocarbon hydrodealkylation catalyst and preparation method thereof
  • C10+ heavy aromatic hydrocarbon hydrodealkylation catalyst and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0041] (1) Dissolve 80 grams of molecular sieves (dry basis, 56g HY and 24g HZSM-5) in 750ml deionized water, heat up to 80°C under stirring, add 5 grams of CeCl 3 ·7H 2 O, continue to stir for 2 hours, and filter and dry with 16gAl 2 o 3 (dry basis) mix evenly, add dilute nitric acid solution with a mass concentration of 3%, extrude the product into the form of a φ1.6 extrudate, dry at 110°C for 8 hours, and roast at 500°C for 4 hours in an air atmosphere to obtain a Ce-loaded Molecular sieve.

[0042] (2) 4 g of polyethylene glycol and 4 g of ammonium paramolybdate were dissolved in 155 ml of deionized water, while 1 mL of phosphoric acid was added dropwise, and stirred for 1 hour to obtain a highly dispersed solution.

[0043] (3) The molecular sieve obtained in step (1) was immersed in the solution obtained in step (2) for 12 hours, the product was dried at 110°C for 8 hours, and calcined at 500°C for 4 hours in an air atmosphere to obtain the finished catalyst 1.

Embodiment 2

[0045] (1) Dissolve 80 grams of molecular sieves (dry basis, 64g HY and 16g HZSM-5) in 750ml deionized water, heat up to 80°C under stirring, add 8.8 grams of Ce(NO 3 ) 3 ·6H 2 O, continue to stir for 2 hours, and filter and dry with 16gAl 2 o 3 (dry basis) mix evenly, add dilute nitric acid solution with a mass concentration of 3%, extrude the product into the form of a φ1.6 extrudate, dry at 110°C for 8 hours, and roast at 500°C for 4 hours in an air atmosphere to obtain a Ce-loaded Molecular sieve.

[0046] (2) Mix 4g of polyethylene glycol and 16g of Ni(NO 3 ) 2 ·6H 2 O was dissolved in 160ml of deionized water, and at the same time, 1mL of phosphoric acid was added dropwise, and stirred for 1 hour to obtain a highly dispersed solution.

[0047] (3) The molecular sieve obtained in step (1) was immersed in the solution obtained in step (2) for 12 hours, the product was dried at 110° C. for 8 hours, and calcined at 500° C. for 4 hours in an air atmosphere to obtain th...

Embodiment 3

[0049] (1) Dissolve 80 grams of molecular sieves (dry basis, 56g USY and 24g HZSM-5) in 750ml deionized water, heat up to 80°C under stirring, add 5 grams of CeCl 3 ·7H 2 O, continue to stir for 2 hours, and filter and dry with 16gAl 2 o 3 (dry basis) mix evenly, add dilute nitric acid solution with a mass concentration of 3%, extrude the product into the form of a φ1.6 extrudate, dry at 110°C for 8 hours, and roast at 500°C for 4 hours in an air atmosphere to obtain a Ce-loaded Molecular sieve.

[0050] (2) 4 g of polyethylene glycol, 4 g of ammonium paramolybdate and 4 g of Ni(NO 3 ) 2 ·6H 2 O was dissolved in 155ml of deionized water, and at the same time, 1mL of phosphoric acid was added dropwise, and stirred for 1 hour to obtain a highly dispersed solution.

[0051] (3) The molecular sieve obtained in step (1) was immersed in the solution obtained in step (2) for 12 hours, the product was dried at 110° C. for 8 hours, and calcined at 500° C. for 4 hours in an air at...

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Abstract

The invention relates to a C10+ heavy aromatic hydrocarbon hydrodealkylation catalyst and a preparation method thereof. The C10+ heavy aromatic hydrocarbon indicates monocyclic / polycyclic aromatic hydrocarbon with a carbon number more than or equal to 10 and a final boiling point not more than 300 DEG C. The C10+ heavy aromatic hydrocarbon hydrodealkylation catalyst provided by the invention is capable of treating the C10+ heavy aromatic hydrocarbon under the condition of hydrogenation and has the advantages of high C10+ heavy aromatic hydrocarbon transformation rate and high mixed xylene selectivity and C9 aromatic hydrocarbon selectivity and can be used for realizing the conversion to light fraction of the C10+ heavy aromatic hydrocarbon. The preparation method disclosed by the invention can be used for increasing the yield of BTX aromatic hydrocarbon and high-quality disproportionate raw materials by carrying out hydrodealkylation reaction by adopting a rare earth metal and transition metal modified mixed molecular sieve catalyst and taking the C10+ heavy aromatic hydrocarbon and light aromatic hydrocarbon which includes benzene and / or methylbenzene as raw materials.

Description

technical field [0001] The invention relates to the technical field of catalysts, specifically a C 10 + Heavy aromatics hydrogenation transalkylation catalyst and preparation method; the C 10 + Heavy aromatics refer to mono / polycyclic aromatics with carbon number greater than or equal to 10 and final boiling point not greater than 300°C. technical background [0002] Heavy aromatics refer to C 9 Aromatic hydrocarbons above 100% mainly come from: C by-product of catalytic reforming unit in refinery 9 Heavy aromatics, C by-product of ethylene plant 9 and C 10 Heavy aromatics, aromatics disproportionation and isomerization to produce oil, heavy aromatics by-product of high-temperature coking of coal, etc. [0003] In recent years, with the continuous improvement of my country's oil refining capacity and the successive commissioning of continuous reforming units in large petrochemical enterprises, the output of heavy aromatics has increased significantly. Due to the refi...

Claims

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Application Information

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IPC IPC(8): B01J29/80C07C6/12C07C15/08C07C15/02
CPCY02P20/52
Inventor 于海斌冯书辉臧甲忠范景新杨卫东王海强张永惠李佳周立坤李响
Owner CHINA NAT OFFSHORE OIL CORP
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