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Copper-based microporous composite molecular sieve-based catalyst for FCC (fluid catalytic cracking) regenerated flue gas denitration, and preparation method and application thereof

A composite molecular sieve and regeneration flue gas technology, which is applied in the field of FCC regeneration flue gas denitrification, preparation, and copper-based microporous composite molecular sieve-based catalysts for FCC regeneration flue gas denitrification, which can solve the problem of limiting product and reactant diffusion, increasing reaction rate, etc. problems, to achieve high reactivity and selective catalytic reduction rate, low silicon-aluminum ratio, and strong chemical stability

Inactive Publication Date: 2014-09-10
CHINA UNIV OF PETROLEUM (BEIJING) +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in many studies on Cu-based microporous molecular sieve catalysts, NO x It can be seen from the research report on selective catalytic reduction reaction that, on the one hand, there is no practical catalyst with both high activity and selectivity and stability; on the other hand, in the existing research on such catalysts and related Mechanism studies have shown that Cu-based microporous molecular sieves limit the diffusion of products and reactants due to the small pores of the microporous molecular sieves, thus limiting the further improvement of the reaction rate.

Method used

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  • Copper-based microporous composite molecular sieve-based catalyst for FCC (fluid catalytic cracking) regenerated flue gas denitration, and preparation method and application thereof
  • Copper-based microporous composite molecular sieve-based catalyst for FCC (fluid catalytic cracking) regenerated flue gas denitration, and preparation method and application thereof
  • Copper-based microporous composite molecular sieve-based catalyst for FCC (fluid catalytic cracking) regenerated flue gas denitration, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0059] Preparation of Example 1 ZSM-5 sample (Si / Al=15, Cu load=4%wt)

[0060] First, 27.3792g of tetrapropylammonium hydroxide (25%) was added to 10.8198g of deionized water, fully stirred for 30-60min, then 0.3820g of aluminum isopropoxide was added to the solution, after stirring for 30-60min, 20.0332g Add tetraethyl orthosilicate into the solution, stir for 8-16 hours, put it into a crystallization kettle, crystallize at 120°C for 32 hours, then centrifuge the reaction product, and then wash the lower layer of solid with alcohol, repeat twice , dried at 100°C for 12h, and calcined at 550°C for 6h to obtain a nanoscale ZSM-5 carrier. Subsequently, 0.7604g Cu(NO) 3 ·3H 2O Dissolve the salt containing the required heteroatoms in 3g of deionized water, add 5g of nano-sized ZSM-5 molecular sieve after it is completely dissolved, stir evenly, ultrasonically clean for 30-40min, dry at 100°C for 12h, and roast at 550°C for 6h to get the final product.

Embodiment 2

[0061] Preparation of Example 2 Cu / ZSM-5 / SAPO-34 sample (m=SAPO-34 / ZSM-5=1, Cu load=4%w)

[0062] First, add 24.2707g of tetraethylammonium hydroxide into 1.3151g of deionized water, stir for 30-60min, then add 3g of pseudo-boehmite into the solution, stir for 30-60min, then add 4.7479g of phosphorus source into the In the solution, stir for 30-60min, then add 1.8563g of silica sol into the solution, stir for 5-10h, add 4.63g of nano-sized ZSM-5 seeds, put it into a crystallization kettle, and crystallize at 200°C After 72 hours, the reaction product was centrifuged, dried at 100° C. for 12 hours, and calcined at 550° C. for 6 hours to obtain a nanoscale ZSM-5 / SAPO-34 carrier. Subsequently, dissolve 0.7604g of Cu(NO)3 3H2O salt containing the desired heteroatom into 3g of deionized water, add 5g of ZSM-5 / SAPO-34 after complete dissolution, stir evenly, and ultrasonically clean for 30- 40min, drying at 100°C for 12h, and calcination at 550°C for 6h to obtain the final product....

Embodiment 3

[0064] First, tetrapropylammonium hydroxide (25%) was added to deionized water, fully stirred for 30-60min, then aluminum isopropoxide was added to the solution, after stirring for 30-60min, tetraethyl orthosilicate was added to In solution, wherein control reaction raw material add-on, make tetrapropyl ammonium hydroxide: Al 2 o 3 :SiO2 2 :H 2 The molar ratio of O and four is 9:0.25:5:500. After stirring for 8-16 hours, put it into a crystallization tank, crystallize at 90°C for 24 hours, then centrifuge the reaction product, and then wash the lower layer solid with alcohol. After repeating twice, dry at 90°C for 24h, and bake at 500°C for 8h to obtain nanoscale ZSM-5 carrier.

[0065] First, add the template agent tetraethylammonium hydroxide into deionized water, stir for 30-60min, then add pseudoboehmite into the solution, stir for 30-60min, then add the phosphorus source into the solution, stir for 30-60min , then, add silica sol to the solution, control the amount of...

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Abstract

The invention relates to a copper-based microporous composite molecular sieve-based catalyst for FCC (fluid catalytic cracking) regenerated flue gas denitration, and a preparation method and application thereof. A nano-level ZSM-5 molecular sieve is prepared by performing solution stirring mixing, crystallization, washing separation, drying baking and the like on tetraethyl orthosilicate serving as a silicon source, aluminium isopropoxide serving as an aluminum source and organic amino and deionized water which serve as raw materials. A ZSM-5 / SAPO-34 microporous composite molecular sieve is prepared by performing solution stirring mixing, crystallization, washing separation, drying baking and the like on silica sol serving as a silicon source, pseudo-boehmite serving as an aluminum source, phosphoric acid serving as a phosphorous source and the organic amino and the deionized water which serve as the raw materials, and adding nano-level ZSM-5 crystal seeds; then a final product is obtained by loading an active component on the molecular sieve by an isometric steeping method. The catalyst is high in reaction activity, wide in reaction temperature window and good in application prospect in SCR (silicon controlled rectification) reaction for the FCC regenerated flue gas denitration.

Description

technical field [0001] The invention relates to FCC regeneration flue gas denitrification technology. Specifically, the invention relates to a copper-based microporous composite molecular sieve-based catalyst for FCC regeneration flue gas denitrification, a preparation method and an application thereof, which belong to the field of environmental protection technology. Background technique [0002] Catalytic cracking (FCC) unit is an important unit in the deep processing of crude oil, and occupies a pivotal position in the oil refining industry. During the catalytic cracking reaction, when the raw oil cracks, 30% to 50% of the nitrogen-containing compounds enter the oil coke, and then deposit on the surface of the catalyst. The activity of the catalyst is reduced due to the oil coke attached to the surface, so it must be regenerated. During regenerator charring, most of the nitrogenous compounds are converted to N 2 , but 10% to 30% are converted into NO x , discharged wit...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/80B01J35/10B01D53/86B01D53/56
Inventor 刘坚赵震许驰于富红程锴韦岳长段爱军姜桂元
Owner CHINA UNIV OF PETROLEUM (BEIJING)
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