Multistage structure ZSM-5 molecular sieve containing molybdenum and nickel or/and zinc and preparation method and application thereof

A technology of ZSM-5 and molecular sieve, which is applied in the field of catalytic materials and catalytic chemistry, can solve the problems of reduced catalyst reaction performance, inability to enter zeolite micropores, and reduced pore size, and achieve high desulfurization and selective conversion of olefins into isoparaffins and aromatic performance, excellent mass transfer and diffusion performance, and the effect of increasing carbon storage capacity

Inactive Publication Date: 2020-11-10
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Secondly, it is necessary to solve the problem that transition metal precursors cannot enter the micropores of zeolite due to rapid precipitation in the strong base system of zeolite synthesis.
Finally, solve the problem of pore blocking or pore volume and pore size reduction caused by a large number of metal oxides or metal ions in the zeolite channel, resulting in a decrease in catalyst reaction performance
[0007] Therefore, how to develop and utilize the traditional hydrothermal synthesis method to introduce transition metal ions (Zn, Ni, Mo, W, etc.) The preparation of metal or metal oxide catalysts is a huge challenge, and there have been no relevant patent reports so far

Method used

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  • Multistage structure ZSM-5 molecular sieve containing molybdenum and nickel or/and zinc and preparation method and application thereof
  • Multistage structure ZSM-5 molecular sieve containing molybdenum and nickel or/and zinc and preparation method and application thereof
  • Multistage structure ZSM-5 molecular sieve containing molybdenum and nickel or/and zinc and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] Embodiment 1: the preparation of the hierarchical structure ZSM-5 molecular sieve containing molybdenum

[0047] (1) Treatment of silicon source:

[0048] Take 2g of tetrapropylammonium bromide (0.0075mol, equivalent to 0.06 times that of coarse-pored silica gel) at 25°C, add it to 10g of water (0.556mol, equivalent to 4.444 times that of coarse-pored silica gel), stir evenly, and then add 7.5g Coarse-porous silica gel (0.125mol) was stirred for about 30 minutes to obtain a silicon source solution.

[0049] (2) Treatment of aluminum source and molybdenum source:

[0050]At 25°C, add 0.82g of sodium metaaluminate (0.0036mol, equivalent to 0.04 times that of coarse-pored silica gel) into 8.75g of water (0.486mol, equivalent to 3.889 times that of coarse-pored silica gel), stir for 5 minutes and then add 0.14g Molybdenum oxide (0.0007mol, equivalent to 0.0055 times that of coarse-pore silica gel) and 0.8g sodium hydroxide (0.02mol, equivalent to 0.16 times that of coarse...

Embodiment 2

[0055] Embodiment 2: Preparation of molybdenum-containing and nickel-containing multi-level structure ZSM-5 molecular sieves

[0056] (1) Treatment of silicon source and nickel source:

[0057] At 25°C, take 3g of tetrapropylammonium bromide (0.0113mol, equivalent to 0.09 times that of coarse-pore silica gel) and add it to 10g of water (0.556mol, equivalent to 4.444 times that of coarse-pore silica gel), stir evenly, and then add 7.5g Coarse-porous silica gel (0.125mol) and 0.80g nickel acetate (0.0032mol, equivalent to 0.026 times of coarse-porous silica gel), continue to stir for about 30 minutes to obtain silicon source and nickel source solutions, and then aged at 90°C for 2 hours to obtain a uniform solution.

[0058] (2) Treatment of aluminum source and molybdenum source:

[0059] At 25°C, add 1.02g of aluminum isopropoxide (0.005mol, equivalent to 0.04 times that of coarse-pored silica gel) into 8.75g of water (0.486mol, equivalent to 3.889 times that of coarse-pored s...

Embodiment 3

[0064] Embodiment 3: Preparation of molybdenum-containing and zinc-containing low-silicon multi-level structure ZSM-5 zeolite molecular sieves

[0065] (1) Treatment of silicon source:

[0066] Take 3g of tetrapropylammonium bromide (0.0188mol, equivalent to 0.15 times of coarse-pore silica gel) at 30°C and add them to 10g of water (0.556mol, equivalent to 4.444 times of coarse-pore silica gel) and stir evenly, then add 7.5g Coarse-porous silica gel (0.125mol) was continuously stirred for about 30 minutes to obtain silicon source and nickel source solutions, and then aged at 50° C. for 6 hours to obtain a uniform solution.

[0067] (2) Treatment of aluminum source, zinc source and molybdenum source:

[0068] Add 0.77g of pseudoboehmite (0.005mol, equivalent to 0.04 times that of coarse-pored silica gel) at 30°C into 8.75g of water (0.486mol, equivalent to 3.889 times that of coarse-pored silica gel), stir for 5 minutes, and then add 0.52g zinc sulfate (0.0032mol, equivalent ...

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Abstract

The invention relates to a multilevel structure ZSM-5 molecular sieve containing molybdenum and nickel or / and zinc, a preparation method of the multilevel structure ZSM-5 molecular sieve, and application of the multilevel structure ZSM-5 molecular sieve as a catalyst in gasoline desulfurization and olefin reduction. The multilevel structure ZSM-5 molecular sieve has a low silica-alumina ratio, high molybdenum and zinc or nickel loading capacity and many mesopores, wherein the primary particle size of the molecular sieve is 300 nm-2 [mu]m, and the secondary accumulated particle size of the molecular sieve is 2 [mu]m-8 [mu]m. The whole preparation process of the multilevel structure ZSM-5 molecular sieve containing molybdenum and nickel or / and zinc is simple to operate. The multilevel structure ZSM-5 molecular sieve containing molybdenum and nickel or / and zinc has higher acid content and L acid / B acid ratio, and more mesopores improve the diffusion rate of macromolecular reactants or products, so the carbon capacity of the catalyst is enhanced; the catalyst has high desulfurization and olefin reduction octane number recovery activity and long-period stability in the catalytic gasoline desulfurization and olefin reduction reaction.

Description

technical field [0001] The invention belongs to the technical field of catalytic materials and catalytic chemistry, and specifically relates to a molybdenum-containing and nickel-containing or / and zinc-containing multi-level structure ZSM-5 molecular sieve and its preparation method, and its application as a catalyst in gasoline desulfurization-reduction of olefins . Background technique [0002] ZSM-5 molecular sieve is a zeolite molecular sieve with a unique pore structure and acid properties. It has high hydrothermal stability and lipophilic and hydrophobic properties. It is a good catalyst in itself and is often used as a solid acid catalyst. Widely used in Alkylation, catalytic cracking, alcohol dehydration and other reactions. At the same time, because of its high specific surface area and excellent ion exchange performance, it is also an excellent carrier for catalytically active metal ions or metal compounds. The catalysts such as iron, silver, and copper supported ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/46B01J37/10B01J35/10C01B39/38C10G45/12
CPCB01J29/46B01J37/10B01J35/1014B01J35/1019B01J35/1038B01J37/0018C01B39/38C10G45/12C01P2006/12C01P2006/14C01P2004/62C01P2004/61C01P2004/24C01P2004/50B01J2229/18C10G2300/202C10G2300/305
Inventor 吴志杰鞠雅娜李天舒葛少辉张然胡亚琼宋绍彤潘涛张城纲徐可
Owner PETROCHINA CO LTD
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