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Copper-containing beta molecular sieve and preparation method thereof

A technology of beta molecular sieve and copper content, applied in the field of beta molecular sieve and its preparation, can solve problems such as variation, limitation of ion exchange species, and structural damage

Active Publication Date: 2012-08-01
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] 3. Since the β molecular sieve needs to remove the organic amine template agent in advance to make the pores unimpeded, but its structure is easily damaged in the process of conventional template release agent, and the skeleton is also easy to dealuminate, which makes the activity and stability become worse
This method proposes for the first time the combination of solvent oxidative deamination and liquid ion exchange to prepare molecular sieves. Low-temperature deamination not only protects the molecular sieve framework from damage, inhibits the framework dealumination, but also simplifies the molecular sieve treatment process; the disadvantage is that ion exchange The process is limited by the deamination process. Insufficient deamination will also lead to insufficient ion exchange, and in order to cooperate with the use of oxidants, other metal ions are often introduced, which limits the types of ion exchange.

Method used

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  • Copper-containing beta molecular sieve and preparation method thereof
  • Copper-containing beta molecular sieve and preparation method thereof
  • Copper-containing beta molecular sieve and preparation method thereof

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preparation example Construction

[0028] In the preparation method provided by the present invention, the copper-containing compound is selected from copper nitrate, copper chloride, cuprous chloride, copper sulfate, copper acetate, copper ammonia solution, copper hydroxide and other compounds containing monovalent or divalent copper One or more of them. Preferred copper-containing compounds are copper chloride and copper hydroxide, and copper hydroxide is more preferred. In the first method, the copper-containing compound and the ammonium-type β molecular sieve are charged with a molar ratio of copper to aluminum of 1:0.1 to 1:10, more preferably 1:0.1 to 1:4. In the second method, the copper-containing compound and the The feed ratio of the ammonium type β molecular sieve is that the molar ratio of copper to aluminum is 1:0.5 to 1:10, more preferably 1:0.5 to 1:4, the ammonium type β molecular sieve is calculated as aluminum, and the copper-containing compound is calculated as copper.

[0029] In the preparati...

Embodiment 1

[0041] Weigh 0.61 g of copper chloride dihydrate, add 500 g of water to form a copper chloride aqueous solution, and add 0.48 g of 25% concentrated ammonia water dropwise to prepare a copper hydroxide gel. Weigh 20g of NH containing template 4 The β molecular sieve was stirred and mixed with it at room temperature, filtered, washed, and the filter cake was dried and placed in a muffle furnace. In an air atmosphere, the temperature was raised from room temperature to 400°C, and the mixture was calcined at 400°C for 4 hours to obtain sample S1.

[0042] The thermogravimetric analysis diagram of sample S1 is attached figure 1 The S1 curve shows that the organic amine template is removed cleanly.

[0043] Sample S1 was analyzed by X-ray fluorescence method, and the copper content was 2.06% by weight based on CuO.

[0044] The X-ray photoelectron spectrum of sample S1 is shown in figure 2 , See the split peak spectrum Figure 7 , Where Cu + / (Cu + +Cu 2+ ) The content is 81.78.

Embodiment 2

[0046] Weigh 2.43 g of copper chloride dihydrate, add 500 g of water to form a copper chloride aqueous solution, and add 1.94 g of 25% concentrated ammonia water dropwise to prepare a copper hydroxide gel. With 20g of NH containing template 4 The β molecular sieve was stirred and mixed at room temperature, filtered, washed, and the filter cake was dried and placed in a muffle furnace. In an air atmosphere, the temperature was raised to 350°C and roasted at 350°C for 4 hours to obtain sample S2a. See the thermogravimetric map Attached figure 1 The S2a curve shows that the organic template is removed cleanly.

[0047] The sample S2a was pulverized into powder in the quartz mill, 100 mL of ammonium acetate aqueous solution with a mass fraction of 10% was added, and the pH was adjusted to about 7.0 with ammonia water. Stir at room temperature for 120-180 minutes, filter, wash, and dry to obtain sample S2.

[0048] Sample S2 was analyzed by X-ray fluorescence method, and the copper con...

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Abstract

Copper-containing beta molecular sieve is characterized in that the beta molecular sieve comprises 0.01-10wt% of Cu (by CuO), the value of Cu<+> / ( Cu<+>+ Cu<2+>) of the surface of the beta molecular sieve is equal to or greater than 50wt%, and there is no deamination weight loss peak in a weight loss curve obtained through thermogravimetric characterization after 450DEG C. The molecular sieve of the invention is obtained by carrying out solid state ion exchange on copper ions and the molecular sieve while removing an organic amine template from the organic template-containing ammonium type beta molecular sieve.

Description

Technical field [0001] The present invention relates to a beta molecular sieve and a preparation method thereof, in particular to a beta molecular sieve modified with transition metal copper and a preparation method thereof. Background technique [0002] β molecular sieve is the only high-silica molecular sieve with a cross twelve-membered ring channel system synthesized for the first time by wadlinger et al. of Mobil company in 1967. Its framework silicon to aluminum ratio can be adjusted between 10-200, and its pores are between large Between the X-type, Y-type and the mesoporous ZSM-5, there are straight channels with a pore diameter of 0.75×0.57nm and a sinusoidal channel with a pore size of 0.65×0.56nm. Due to the specific structure of β molecular sieve, relatively large specific surface area, and the acidity of strong inorganic proton acids, it is currently being widely used in hydrocarbon catalytic cracking, hydrocracking, esterification, etherification, isomerization, alk...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B39/04B01J29/76C07C15/073C07C2/66
CPCY02P20/52
Inventor 张凤美狄伟李黎声王卫东秦凤明舒兴田
Owner CHINA PETROLEUM & CHEM CORP
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