Preparation of a metal manganese modified silicon-aluminum molecular sieve material Mn-SSZ-13, and applications of the material in alkene preparation from methanol and denitration

A silicon-aluminum molecular sieve and metal manganese technology, applied in the field of methanol to olefins and denitrification, can solve the problem of serious hydrogen transfer side reactions and other problems

Inactive Publication Date: 2017-02-15
TIANJIN POLYTECHNIC UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

SSZ-13 and SAPO-34 have the same topology and similar catalytic properties, but the stronger acidity of SSZ-13 molecular sieves leads to serious side reactions of hydrogen transfer in the early stage of MTO reaction.

Method used

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  • Preparation of a metal manganese modified silicon-aluminum molecular sieve material Mn-SSZ-13, and applications of the material in alkene preparation from methanol and denitration
  • Preparation of a metal manganese modified silicon-aluminum molecular sieve material Mn-SSZ-13, and applications of the material in alkene preparation from methanol and denitration
  • Preparation of a metal manganese modified silicon-aluminum molecular sieve material Mn-SSZ-13, and applications of the material in alkene preparation from methanol and denitration

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Preparation of gel: Dissolve 1.3856g of solid sodium metaaluminate in 17.4872ml of deionized water, add 4.0673g of copper nitrate and 3.6078g of tetraethylenepentamine solution in turn to form a Cu-TEPA complex, and then add 2.7755g of solid hydrogen Sodium oxide and fully stirred, then added dropwise 16.2360g silica sol (SiO 2 The mass fraction is 30.72%), stirred at room temperature for 4 hours to obtain a uniform gel.

[0027] Crystallization: Put the initial gel into a PTFE high-pressure reactor and crystallize at 140°C for 4 days. After the crystallization is completed, the product is washed with deionized water and dried at 100°C for 12 hours to obtain Cu-Na-SSZ -13 molecular sieves.

[0028] Ammonium exchange: Take 3g of the above-mentioned roasted sample, put it into a 100ml beaker, add a solution made of 10.68g of ammonium chloride and 200g of deionized water, heat up to 80°C and keep stirring for 4h, filter with suction, and then add 200g of deionized water f...

Embodiment 2

[0033] Preparation of lye: add 0.83g of sodium hydroxide to 18g of water, stir until the sodium hydroxide dissolves, add 3.43g of N,N,N-trimethyladamantane ammonium hydroxide (template agent), and stir until a homogeneous solution.

[0034] Preparation of gel: Add 13.05g of silica sol to the reaction kettle, stir in a water bath at room temperature, then add lye, stir evenly, add 3.25g of aluminum sulfate, stir evenly, add 0.16g of molecular sieve of chabazite (CHA) crystal phase as crystal species, and stirred at room temperature for 4 hours to obtain a homogeneous gel.

[0035] Crystallization: Put the initial gel into a PTFE autoclave and crystallize at 165°C for 2-4 days. After the crystallization is complete, wash the product with deionized water until the filtrate is neutral, and dry at 100°C for 12 hours .

[0036] Roasting: The dried samples were heated up to 600°C in an air atmosphere for 4 hours, and then baked for 4 hours.

[0037] Manganese nitrate exchange: Add ...

Embodiment 3

[0040] Preparation of gel: Dissolve 1.3856g of solid sodium metaaluminate in 17.4872ml of deionized water, add 4.0673g of copper nitrate and 3.6078g of tetraethylenepentamine solution in turn to form a Cu-TEPA complex, and then add 2.7755g of solid hydrogen Sodium oxide and fully stirred, then added dropwise 16.2360g silica sol (SiO 2 The mass fraction is 30.72%), stirred at room temperature for 4 hours to obtain a uniform gel.

[0041] Crystallization: Put the initial gel into a PTFE high-pressure reactor and crystallize at 140°C for 4 days. After the crystallization is completed, the product is washed with deionized water and dried at 100°C for 12 hours to obtain Cu-Na-SSZ -13 molecular sieves.

[0042] Ammonium exchange: Take 3g of the above-mentioned roasted sample, put it into a 100ml beaker, add a solution made of 10.68g of ammonium chloride and 200g of deionized water, heat up to 80°C and keep stirring for 4h, filter with suction, and then add 200g of deionized water for...

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Abstract

A metal manganese modified silicon-aluminum molecular sieve material Mn-SSZ-13 is provided. The material comprises 0.1-10% of manganese, 0-15% of aluminum, 75-100% of silicon and 0-25% of copper. Two materials have CHA type topological structures, and the specific surface area measured by a BET process after calcination at 600 DEG C for 4 h is not less than 500 m<2>/g. A preparing process includes fully mixing a copper source (may be none), a template, an aluminum source, sodium hydroxide, a silicon source and water according to a certain sequence to obtain an initial gel solution, crystallizing, performing ammonium chloride ion exchange, calcinating and performing manganese ion exchange to obtain a product. The prepared molecular sieve material has advantages of high MTO diolefin selectivity and long catalytic service lifetime, and can be used for nitrogen oxide selective reduction (SCR catalysts).

Description

technical field [0001] The invention relates to a preparation method of a silicon-aluminum molecular sieve material Mn-SSZ-13 modified by metal manganese, and its application in the fields of methanol-to-olefin (MTO) and denitrification. Background technique [0002] With the increasing shortage of petroleum resources and the increasing demand for ethylene propylene, the development of a route to replace petroleum to produce ethylene propylene has been extensively studied. Methanol to olefins (MTO) technology is a new route to produce olefins from non-petroleum resources. The core of the methanol-to-olefins process is the catalyst, widely known as SAPO-34 molecular sieve, SSZ-13 molecular sieve, etc. [0003] Nitrogen oxides (NO x ) is one of the main pollution sources of the atmosphere, mainly from thermal power plants and motor vehicle exhaust emissions, and is an important reason for the formation of acid rain and photochemical smog. At present, the removal technology o...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/78C07C1/20C07C11/04C07C11/06C07C11/12B01D53/86B01D53/56
CPCB01D53/8628B01D2257/404B01J29/78B01J2229/18C07C1/20C07C11/04C07C11/06C07C11/12Y02P20/52Y02P30/20Y02P30/40
Inventor 李渊赵飞张岩
Owner TIANJIN POLYTECHNIC UNIV
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