A kind of composite modified sapo-34 molecular sieve and preparation method thereof

A SAPO-34, composite modification technology, applied in molecular sieve catalyst, molecular sieve and alkali exchange phosphate, chemical instruments and methods, etc., can solve the problem of high reaction temperature, achieve high methanol low temperature conversion rate, and enhance methanol low temperature conversion process. , high-quality selective effects

Active Publication Date: 2019-11-08
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0011] The main purpose of the present invention is to provide a kind of composite modified SAPO-34 molecular sieve and preparation method thereof, to overcome the high shortcoming of SAPO-34 molecular sieve or metal modified SAPO-34 molecular sieve reaction temperature in the prior art

Method used

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Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0027] The invention provides a kind of preparation method of the SAPO-34 molecular sieve of composite modification, and this method comprises the steps:

[0028] (1) Preparation of SAPO-34 molecular sieve;

[0029] Mix and stir template agent, silicon source, aluminum source, phosphorus source, and deionized water to form a gel, age at room temperature for 2-6 hours, put it in a closed pressure-resistant container, and crystallize at 180-210°C for 48-72 hours , centrifuged and washed, dried at 80°C to 110°C to constant weight, and finally calcined at 550°C to 600°C for 4h to 6h to obtain SAPO-34 molecular sieve.

[0030] Wherein, the aluminum source is pseudo-boehmite, aluminum phosphate, aluminum isopropoxide, aluminum chloride, activated alumina, aluminum sulfate, aluminum nitrate or aluminum hydroxide or any mixture thereof, preferably pseudo-boehmite.

[0031] Wherein, the phosphorus source is phosphoric acid, phosphorous acid, phosphate or phosphite or any mixture thereof...

Embodiment 1

[0055] Using equal volume immersion method, press S 2 o 8 2- Loading capacity 0.8wt% ammonium persulfate solution and the ZrO that comparative example 2 obtains 2 / SAPO-34 molecular sieves were mixed evenly at room temperature, stirred for 1 hour, then evaporated to dryness at 80°C, and finally calcined at 500°C for 1 hour to obtain S 2 o 8 2- / ZrO 2 / SAPO-34 molecular sieve.

[0056]A fixed-bed microreactor with a loading capacity of 1 g was used to evaluate the MTO reaction, and the gas-phase product composition was analyzed with an Agilent 6890N chromatographic analyzer after gas-liquid separation. to S 2 o 8 2- / ZrO 2 / SAPO-34 molecular sieve evaluation conditions are temperature 350°C, normal pressure, methanol weight space velocity 2.5h -1 (methanol concentration 95%). This S 2 o 8 2- / ZrO 2 / SAPO-34 molecular sieve has the highest mass selectivity to ethylene and propylene of 83.42%, and the conversion rate of methanol is 99%.

Embodiment 2

[0058] Using equal volume immersion method, press S 2 o 8 2- Loading capacity 1.0wt% Ammonium persulfate solution and Zn-SAPO-34 molecular sieve obtained in Comparative Example 4 were mixed uniformly at room temperature, stirred for 1 h, then evaporated to dryness at 80 ° C, and finally roasted at 400 ° C for 2 h to obtain S 2 o 8 2- / Zn-SAPO-34 molecular sieve.

[0059] A fixed-bed microreactor with a loading capacity of 1 g was used to evaluate the MTO reaction, and the gas-phase product composition was analyzed with an Agilent 6890N chromatographic analyzer after gas-liquid separation. to S 2 o 8 2- The evaluation conditions of / Zn-SAPO-34 molecular sieve are temperature 350°C, normal pressure, methanol weight space velocity 2.5h -1 (methanol concentration 95%). This S 2 o 8 2- / Zn-SAPO-34 molecular sieve has the highest mass selectivity to ethylene and propylene of 84.92%, and the conversion rate of methanol is 98%.

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Abstract

The invention discloses a composite modified SAPO-34 molecular sieve and a preparation method thereof. The preparation method comprises: (1) preparing a SAPO-34 molecular sieve; (2) modifying the SAPO-34 molecular sieve by using a metal; and (3) modifying the SAPO-34 molecular sieve by using a persulfate, wherein the metal modified SAPO-34 molecular sieve is impregnated into a persulfate solutionaccording to a volume ratio of 1:1 to prepare the composite modified SAPO-34 molecular sieve. According to the present invention, the catalyst can promote and achieve the conversion process of low-temperature methanol-to-low-carbon-olefin through the SAPO-34 molecular sieve, improve the selectivity of the SAPO-34 molecular sieve to the low-carbon olefin at the low reaction temperature, and enhancethe low-temperature activity stability of the molecular sieve catalyst.

Description

technical field [0001] The invention relates to the technical field of methanol-to-light olefin chemical industry, in particular to a modified SAPO-34 molecular sieve catalyst and a preparation method thereof. Background technique [0002] Low-carbon olefins represented by ethylene and propylene are important basic raw materials in the petrochemical industry. The existing low-carbon olefin production technology relies heavily on petroleum resources, and the main method for preparing ethylene and propylene is the cracking process with naphtha and light diesel oil as raw materials. Due to the increasing shortage of petroleum resources and the advent of the post-petroleum era, the contradiction between supply and demand brought about by the traditional petroleum route to produce ethylene and propylene tends to be tense, and the development of non-petroleum production of low-carbon olefins has become the focus of major research institutions and enterprises focus. Among them, c...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C01B39/54B01J29/85
CPCB01J29/85B01J2229/18C01B39/54
Inventor 代跃利汲永钢刘剑孙淑坤万书宝褚洪岭张永军王斯晗杜海徐显明王桂芝王淑兰李影辉赵铁凯王磊于静李瑞峰邴淑秋
Owner PETROCHINA CO LTD
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