ZnO modified all-silicon zeolite molecular sieve supported Pt catalyst, preparation method and application

A zeolite molecular sieve and catalyst technology, which is applied to molecular sieve catalysts, including molecular sieve catalysts, catalysts and other directions, can solve the problems of poor aromatics selectivity, easy formation of carbon deposits, poor catalyst sulfur resistance, etc., and achieves good aromatics selectivity and less cracked dry gas. , The effect of strong sulfur resistance

Active Publication Date: 2018-11-16
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although Pt-based reforming catalysts are mature and widely used, there are still the following problems: (1) Pt/Al 2 o 3 -Cl and reforming catalysts with added metal components such as Re, Sn, Ir, etc. During the use process, the chlorine on the catalyst is continuously lost, resulting in the decline of the acid catalytic function
ZSM-5 and L-type molecular sieve reforming catalysts that do not require chlorine supplementation have been extensively studied, and some have even been applied in industry, but they still have poor product aromatics selectivity, catalysts are prone to carbon deposition and deactivation, and catalysts are resistant to sulfur Poor performance and other issues
For example, the combination of ZSM-5 molecular sieves and traditional reforming catalytic devices has brought considerable benefits to refineries. For example, Exxon Mobil has developed a multi-stage naphtha reforming process and filled rhenium in the last reforming reactor. Content is

Method used

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  • ZnO modified all-silicon zeolite molecular sieve supported Pt catalyst, preparation method and application
  • ZnO modified all-silicon zeolite molecular sieve supported Pt catalyst, preparation method and application
  • ZnO modified all-silicon zeolite molecular sieve supported Pt catalyst, preparation method and application

Examples

Experimental program
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Effect test

Embodiment 1

[0046] Preparation of Pt 0.1 -ZnO 1.0 / Silicalite-1 paraffin reforming catalyst (ZnO / Silicalite-1 carrier, ZnO loading is 1.0wt%; Pt-ZnO / Silicalite-1 paraffin reforming catalyst, Pt loading is 0.1wt%)

[0047] (1) Preparation of Synthetic Silicalite-1 Zeolite Molecular Sieve:

[0048] Reference is made to the publication Chin. J. Catal., 2001, 22, 513-514. Tetraethyl orthosilicate (TEOS) and tetrapropylammonium hydroxide (TPAOH) and deionized water in the following molar ratio SiO 2 :0.3TPAOH:30H 2 O mixed, stirred at 60°C for 3h; then placed in a stainless steel hydrothermal kettle for crystallization at 170°C for 24h to obtain the all-silicon S-1 zeolite precursor; further filtered, washed, and then dried in air at 110°C for 12h, 550°C Calcined in air atmosphere for 6h to obtain Silicalite-1 zeolite molecular sieve.

[0049] (2) Preparation of ZnO 1.0 / Silicalite-1 carrier

[0050] First prepare 0.0123mol / L zinc nitrate aqueous solution; then take the dried and roaste...

Embodiment 2

[0054] Preparation of Pt 0.1 -ZnO 3.0 / Silicalite-1 paraffin reforming catalyst (ZnO / Silicalite-1 carrier, ZnO loading is 3.0wt%; Pt-ZnO / Silicalite-1 paraffin reforming catalyst, Pt loading is 0.1wt%)

[0055] Repeat Example 1, but in step (2), zinc nitrate concentration is configured as 0.0369mol / L, obtains the Pt that ZnO content is 3.0Wt%. 0.1 -ZnO 3.0 / Silicalite.

Embodiment 3

[0057] Preparation of Pt 0.1 -ZnO 6.0Silicalite-1 paraffin reforming catalyst (ZnO / Silicalite-1 carrier, ZnO loading is 6.0wt%; Pt-ZnO / Silicalite-1 paraffin reforming catalyst, Pt loading is 0.1wt%)

[0058] Repeat Example 1, but in step (2), zinc nitrate concentration is configured as 0.0738mol / L in the zinc nitrate aqueous solution, obtains the Pt that ZnO content is 6.0Wt%. 0.1 -ZnO 6.0 / Silicalite-1.

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Abstract

The invention discloses a preparation method of a ZnO modified Silicalite-1 zeolite molecular sieve supported Pt catalyst. The preparation method comprises the following steps: immersing a Silicalite-1 Zeolite molecular sieve in a zinc salt aqueous solution, and performing drying and roasting to obtain a ZnO/Silicalite-1 support; immersing the ZnO/Silicalite-1 support in a chloroplatinic acid or ammonium chloroplatinate aqueous solution, and performing drying and roasting to obtain the ZnO modified Silicalite-1zeolite molecular sieve supported Pt catalyst. The reforming catalyst prepared withthe method has an acid center and a metal active center required for aromatization of paraffins, and paraffin can be subjected to dehydrogenation, isomerization, cyclization and other processes for generation of arene under dual-function synergistic action of metal and acid. Pt particles have better sulfur resistance due to strong interaction between the Pt particles and ZnO clusters.

Description

technical field [0001] The invention belongs to the technical field of zeolite molecular sieves, in particular to a ZnO-modified Silicalite-1 zeolite molecular sieve loaded Pt catalyst and a preparation method thereof, which is used to convert paraffins, especially C 6 ~C 8 The reforming reaction of paraffins into aromatics. Background technique [0002] Aromatics are an important basic raw material for the petrochemical industry. Among the total of about eight million known organic compounds, aromatics account for about 30%, among which BTX aromatics (benzene, toluene and xylene) are called primary Basic organic chemical raw material. Aromatics are widely used in the synthetic resin, synthetic fiber and synthetic rubber industries. For example, aromatic hydrocarbons are used as raw materials in the production of important synthetic materials such as polystyrene, phenolic resin, alkyd resin, polyurethane, polyester, polyether, polyamide and styrene-butadiene rubber. In a...

Claims

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Application Information

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IPC IPC(8): B01J29/035C07C5/31C07C15/06C07C15/04
CPCB01J29/0354B01J2229/18C07C5/31C07C2529/035C07C15/06C07C15/04Y02P20/52
Inventor 郭洪臣刘国东刘家旭贺宁周薇易颜辉
Owner DALIAN UNIV OF TECH
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