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ZSM-12 molecular sieve supported high-dispersion Pt catalyst and preparation method thereof

A molecular sieve and catalyst technology, applied in the field of catalytic materials, can solve problems such as poor isomeric selectivity, and achieve the effects of small particle size, easy operation, and excellent anti-coking performance.

Inactive Publication Date: 2019-05-21
CHINA CATALYST HLDG CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, when molecular sieves with larger pore size and three-dimensional structure, such as USY and Beta molecular sieves, are used as catalysts, the proportion of multi-branched isomers in long-chain alkane isomerization products will increase, but the isomer selectivity is poor.

Method used

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  • ZSM-12 molecular sieve supported high-dispersion Pt catalyst and preparation method thereof
  • ZSM-12 molecular sieve supported high-dispersion Pt catalyst and preparation method thereof
  • ZSM-12 molecular sieve supported high-dispersion Pt catalyst and preparation method thereof

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Experimental program
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Effect test

Embodiment 1

[0031] This embodiment illustrates the method for preparing Pt-HZSM-12 molecular sieve catalyst:

[0032] 1) Add 0.5g Pt(NH 3 ) 4 ](NO 3 ) 2 , 1.0141g of 3-mercaptopropyltrimethoxysilane, 9.92g of 6.3% NaOH solution were mixed and dissolved, coordinate exchanged, filtered and washed to obtain a water-soluble Pt-S coordination compound;

[0033] 2) 100.0g silica sol (SiO 2 Content: 30wt%), 1.3054g pseudo-boehmite (Al 2 o 3 Content: 65wt%), 2.0174g NaOH, 64.8955g concentration of 20% N,N-dimethyl-N'-ethylcyclohexyl ammonium hydroxide (DMECHAOH) and 102.3110g deionized water obtained in 1) A mixed gel formed by a Pt-S coordination compound, in which n(Pt-S):nSiO 2 :nAl 2 o 3 :nNaOH:n(DMECHAOH):nH 2 The molar ratio of O=0.0026:1:0.0167:0.15:0.05:25; then the gel mixture was transferred to a hydrothermal crystallization kettle, and crystallized at 180° C. with a stirring speed of 80 rpm for 72 hours. After the crystallization reaction, the sample was taken out for quench...

Embodiment 2

[0036] This embodiment illustrates the method for preparing Pt-HZSM-12 molecular sieve catalyst:

[0037] 1) 0.75g[Pt(NH2CH2CH2NH2)2]Cl2, 2.3152g 3-mercaptopropyltriethoxysilane, 8.08g concentration of 13.5% NaOH solution are mixed and dissolved, coordinate exchanged, filtered and washed to obtain Water-soluble Pt-S coordination compounds;

[0038] 2) Mix 100.0g ethyl silicate, 1.2255g aluminum isopropoxide, 2.0174g NaOH, 9.5699g N,N-ethyl-N'-dimethylcyclohexylammonium bromide (DMECHABr) and 255.5042g deionized water A mixed gel formed with the Pt-S coordination compound obtained in 1), in which n(Pt-S):nSiO 2 :nAl 2 o 3 :nNaOH:n(DMECHABr):nH 2 The molar ratio of O=0.0041:1:0.0125:0.08:0.08:30; then the gel mixture was transferred to a hydrothermal crystallization tank, and crystallized at 170° C. with a stirring speed of 60 rpm for 96 hours. After the crystallization reaction, the sample was taken out for quenching, filtered, washed, and dried at 105° C. for 12 hours to ...

Embodiment 3

[0041] This embodiment illustrates the method for preparing Pt-HZSM-12 molecular sieve catalyst:

[0042] 1) Add 0.85g [Pt(NH 2 CH 2 CH 2 NH 2 ) 2 ](NO 3 ) 2 , 1.2671g 2-ammonium mercaptoacetate, 11.61g concentration is that 10.0% NaOH solution carries out mixing and dissolving, coordination exchange, obtains the Pt-S coordination compound soluble in water through filtering, washing;

[0043] 2) 100.0g water glass (SiO 2 Content: 25.0wt%, Na 2 O content: 7.5wt%), 1.3054g sodium aluminate (Al 2 o 3 Content: 37.38wt%, Na 2 O content: 29.22wt%), 1.0351g NaOH, 11.6069g benzyltrimethylammonium bromide (BTMABr) and 36.6338g deionized water and the mixed gel formed by the Pt-S coordination compound obtained in 1), the n(Pt-S) in gel: nSiO 2 :nAl 2 o 3 :nNaOH:n(BTMABr):nH 2 The molar ratio of O=0.0047:1:0.0083:0.12:0.18:15; then the gel mixture was transferred to a hydrothermal crystallization tank, and crystallized at 160° C. with a stirring speed of 90 rpm for 144 hou...

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Abstract

The invention provides a ZSM-12 molecular sieve supported high-dispersion Pt catalyst and a preparation method thereof, and is characterized in that active component metal Pt nanoparticles of the catalyst are highly dispersed and supported in H-type ZSM-12 molecular sieve channels, the Pt content in the catalyst is 0.1-3.0wt%, the silicon-aluminum ratio of the H-type ZSM-12 molecular sieve is 50-200, and the catalyst presents needle-like microcrystals. According to the preparation method of the ZSM-12 molecular sieve supported high-dispersion Pt catalyst, a one-pot crystallization synthesis reaction is applied, wherein the preparation method comprises the following steps of: mixing and reacting an organic sulfhydryl ligand, a Pt metal precursor and a NaOH solution to form a Pt-S coordination compound, adding the Pt-S coordination compound into silicon-aluminum mixed gel, carrying out crystallization reaction to obtain raw powder of a ZSM-12 molecular sieve containing Pt, and carrying out ammonium ion exchange and reduction reaction to prepare a catalyst finished product. The preparation method is simple and convenient to operate and has universality. The catalyst of the invention shows better catalytic activity in long-chain normal alkane isomerization, alkene hydrogenation, alkane dehydrogenation or Fischer-Tropsch synthesis reaction, shows excellent anti-coking performance, and has good industrial application prospect.

Description

technical field [0001] The invention relates to a supported molecular sieve noble metal catalyst and a preparation method thereof, in particular to a ZSM-12 molecular sieve supported highly dispersed metal Pt nanoparticle catalyst and a preparation method thereof, belonging to the technical field of catalytic materials. Background technique [0002] Highly dispersed nanoscale metal-supported catalysts have attracted much attention due to their unique properties (small particle size, large specific surface area, high catalytic activity, etc.). Among them, the highly dispersed metal molecular sieve carrier catalyst has the characteristics of high dispersion of the metal center of the highly dispersed metal catalyst and the excellent structure of the molecular sieve catalyst, and is an ideal high-performance catalyst material. The preparation methods of such catalysts mainly include co-precipitation method, impregnation method, in-situ synthesis method, ion exchange method and ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/74B01J37/30C07C5/27C07C9/22
Inventor 王志光王建青王炳春李进
Owner CHINA CATALYST HLDG CO LTD
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