Preparation method and use of Cu-SSZ-13 molecular sieve based catalyst

A cu-ssz-13, molecular sieve technology, applied in molecular sieve catalysts, separation methods, chemical instruments and methods, etc., can solve the problems of inability to effectively control the content of active components, consumption of large purified water, high cost, and achieve excellent catalytic activity. , The effect of strong controllability and high crystallinity

Inactive Publication Date: 2016-12-07
HUAZHONG UNIV OF SCI & TECH
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  • Summary
  • Abstract
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  • Claims
  • Application Information

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Problems solved by technology

In this route, expensive templating agents are generally used, such as N,N,N-trimethyl-1-adamantylamine cation (US NO.4,544,538), benzyl quaternary ammonium ion (US NO.60/826 , 882) and benzyl trimethyl quaternary ammonium ions (US NO.60/882, 882), resulting in high cost of synthetic SSZ-13 carrier, while the introduction of copper ions in the synthesis route of Cu-SSZ-13 molecular sieve requires ion exchange method, that is, the SSZ-13 carrier and a certain concentration of copper salt precursor solution are exchanged at a certain temperature, filtered, washed, dried and calcined at a high temperature, and due to the limitation of the SSZ-13 carrier pore size and exchange capacity, in order to ensure the active component The loading capacity and high dispersion of copper require multiple ion exchange processes, which not only affect the stability of the molecular sieve carrier skeleton, but also have a low utilization rate of the copper salt precursor solution during the exchange process, and consume a large amount of pure water during the washing process , the high-temperature calcination process needs to consume energy; another method is to use in-situ synthesis, and use ion exchange to reduce the content of active components to obtain Cu-SSZ-13. Cu-SSZ-13 molecular sieve catalyst (Ren L.M.et al.Designed copper-amine complex as efficient template for one-pot synthesis of Cu-SSZ-13zeolite with excellent activity for selective catalytic reduction of NO x by NH 3 , Chem.Commun.2011,47:9783; Ren Lim

Method used

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  • Preparation method and use of Cu-SSZ-13 molecular sieve based catalyst
  • Preparation method and use of Cu-SSZ-13 molecular sieve based catalyst
  • Preparation method and use of Cu-SSZ-13 molecular sieve based catalyst

Examples

Experimental program
Comparison scheme
Effect test

Example Embodiment

[0026] Example 1 Preparation of Cu-SSZ-13 catalyst with benzyl quaternary ammonium ion as template

[0027] Copper sulfate was added to deionized water and stirred at room temperature for 30 minutes, and then tetraethylenepentamine of the same mass as copper sulfate and a certain amount of organic template were added to it, and stirring was continued for 3 hours to form a copperamine complex solution. The sodium metaaluminate, sodium hydroxide and deionized water were mixed and stirred for 1 hour, and then mixed with the copper amine complex solution, and stirring was continued for 4 hours. Finally, silica sol is added to the mixed solution, mixed and stirred for 4 hours to obtain an initial gel. The system Na 2 O, Al 2 O 3 , SiO 2 , H 2 O. The molar quantities of copper sulfate-tetraethylenepentamine and organic template are shown in Table 1.

[0028] Place the fully stirred gel in a hydrothermal reaction kettle and react at 180°C for 6 days. After the reaction is complete, cool ...

Example Embodiment

[0033] Example 2 Preparation of Cu-SSZ-13 catalyst with N, N, N-trimethyl-1-adamantamine cation as template

[0034] The feeding sequence and stirring time, hydrothermal reaction conditions and post-treatment process of gel preparation are all as in Example 1. The system is Na 2 O, Al 2 O 3 , SiO 2 , H 2 O. The molar quantities of copper sulfate-tetraethylenepentamine and template agent are shown in Table 2.

[0035] The Cu-SSZ-13 molecular sieve catalysts obtained in the five sets of experiments in Example 2 were tested by ICP and XRF respectively, and the loading amounts of the active components measured were 2.64wt.%, 3.91wt.%, 5.98wt.%, 7.05wt.%, 10.13wt.%. It shows that using this template, a catalyst with a lower Cu content can still be obtained without any post-treatment, and the Cu content and the silicon-to-aluminum ratio of the catalyst can be adjusted within a certain range.

[0036] Table 2

[0037]

[0038]

Example Embodiment

[0039] Example 3 Preparation of Cu-SSZ-13 catalyst with choline chloride as template

[0040] The feeding sequence and stirring time, hydrothermal reaction conditions and post-treatment process of gel preparation are all as in Example 1. The system is Na 2 O, Al 2 O 3 , SiO 2 , H 2 O. The molar quantities of copper sulfate-tetraethylenepentamine and organic template are shown in Table 3.

[0041] The Cu-SSZ-13 molecular sieve catalyst obtained from the five experiments of Example 3 was tested by ICP and XRF respectively, and the loading amount of the active components was 2.85wt.%, 2.91wt.%, 2.98wt.%, 3.05 wt.%, 3.13wt.%, and the ratio of silicon to aluminum is 15.8, 16.2, 16.8, 17.2, 17.9. It shows that using the template, a catalyst with lower Cu content can be obtained without post-treatment, and the Cu content and the silicon-to-aluminum ratio of the catalyst can be adjusted within a certain range.

[0042] table 3

[0043]

[0044] Figure 5~6 It is the catalytic performance gr...

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Abstract

The invention provides a preparation method of a Cu-SSZ-13 molecular sieve based catalyst. The preparation method comprises the following steps of adding sodium aluminate, sodium hydroxide, a silica solution, copper sulfate, tetraethylenepentamine and an organic template agent to deionized water, and performing stirring so as to obtain gel; and performing a reaction in a reaction kettle, then performing cooling, performing centrifugal filtration, performing washing, performing drying, and performing calcining so as to obtain the Cu-SSZ-13 molecular sieve based catalyst. The method disclosed by the invention is simple in technology, low in cost, energy-saving, and environmentally-friendly. Use of a copper salt solution ion exchange and calcining technology many times is avoided, and the defect that a conventional technology needs performing later-period ion exchange so as to reduce content of active components is overcome. The silica alumina ratio of the Cu-SSZ-13 molecular sieve based catalyst prepared by the method disclosed by the invention is adjustable within the range of 7.9- 26.7, and the percentage by mass of copper is in the range of 0.47 -8.6wt%, excellent NH3-SCR catalytic activity, water thermal stability, alkali metal poisoning resistance and noble metal poisoning resistance can be kept in a wide-temperature window.

Description

technical field [0001] The present invention relates to a method for preparing Cu-SSZ-13 catalyst in situ with a double-template one-step method, and the catalyst prepared by the method and the catalyst application thereof. The Cu-SSZ-13 catalyst is used for post-treatment of diesel vehicles ( Purification process of nitrogen oxides in the catalytic converter of Urea-SCR) system. Background technique [0002] Chabazite (CHA) structure molecular sieve, also known as chabazite, belongs to the rhombohedral crystal system and has a three-dimensional eight-membered ring channel system. The structure contains cage columns composed of six-membered rings and CHA cages alternately. It is 0.38nm×0.38nm, which belongs to the small-pore molecular sieve. The Cu-SSZ-13 catalyst prepared with SSZ-13 as the carrier has high activity and high hydrothermal stability in the process of purifying nitrogen oxides in diesel vehicle exhaust Urea-SCR system Resistance, anti-alkali metal poisoning, ...

Claims

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Application Information

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IPC IPC(8): B01J29/76B01D53/94B01D53/56
CPCY02T10/12
Inventor 李涛庞磊范驰董才月
Owner HUAZHONG UNIV OF SCI & TECH
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