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Element modified ZSM-12 molecular sieve catalyst and preparation method thereof

A technology of ZSM-12 and molecular sieve, which is applied in the field of element-modified ZSM-12 molecular sieve catalyst and its preparation, can solve the problems of being unable to provide Group VIII element-modified ZSM-12 molecular sieve, etc., to improve the conversion rate and overcome the cumbersome process Effect

Active Publication Date: 2016-01-06
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Solve the technical problem that the existing technology cannot provide Group VIII element modified ZSM-12 molecular sieves

Method used

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  • Element modified ZSM-12 molecular sieve catalyst and preparation method thereof
  • Element modified ZSM-12 molecular sieve catalyst and preparation method thereof
  • Element modified ZSM-12 molecular sieve catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] 1. Put ZSM-12 into 0.5mol / L citric acid solution, stir at 80°C for 0.5h, then suction filter, and dry at 80°C for 4h;

[0025] 2. Put the molecular sieve obtained above into 1mol / L ammonium nitrate solution, conduct ammonium ion exchange at 80°C for 4 hours, then wash, filter, and dry at 80°C, repeat the above operation three times, and dry the dried molecular sieve at 550°C Calcined for 4 hours to obtain H-type ZSM-12 molecular sieve;

[0026] 3. Put the above-mentioned molecular sieve into 0.6mol / L ferric nitrate solution for ion exchange at 80°C for 4h, then wash, filter, dry at 80°C, and roast at 550°C for 4h.

[0027] The obtained ZSM-12 molecular sieve catalyst modified by group VIII elements is a ZSM-12 molecular sieve, and the ZSM-12 molecular sieve contains 85% of ZSM-12 molecular sieve, 0.06% of sodium element, and the catalyst contains 1.2% of iron element by mass fraction ; The specific surface area of ​​the catalyst is 330m 2 / g, the pore volume is 0.25cm...

Embodiment 2

[0029] 1. Put ZSM-12 into 0.3mol / L hydrochloric acid solution, stir at 80°C for 1 hour, then suction filter, and dry at 80°C for 4 hours;

[0030] 2. Put the molecular sieve obtained above into 1.5mol / L ammonium sulfate solution, heat ammonium at 80°C for 2 hours, then wash, filter, dry at 80°C, repeat the above operation three times, and roast the dried molecular sieve at 550°C 4h, made H type ZSM-12 molecular sieve;

[0031] 3. Put the above-mentioned molecular sieve into 0.15mol / L cobalt nitrate solution for ion exchange at 85°C for 4h, then wash, filter, dry at 80°C, and roast at 550°C for 4h.

[0032] The obtained ZSM-12 molecular sieve catalyst modified by group VIII elements is a ZSM-12 molecular sieve, and the ZSM-12 molecular sieve contains 96% of ZSM-12 molecular sieve, 0.03% of sodium element, and the catalyst contains 1.4% of cobalt element by mass fraction ; The specific surface area of ​​the catalyst is 230m 2 / g, the pore volume is 0.17cm 3 / g.

Embodiment 3

[0034] 1. Put ZSM-12 into 1mol / L citric acid solution, stir at 80°C for 0.2h, then suction filter, and dry at 80°C for 4h;

[0035] 2. Put the molecular sieve obtained above into 0.6mol / L ammonium chloride solution, heat ammonium at 80°C for 6 hours, then wash, filter, and dry at 80°C. Repeat the above operation three times, and dry the dried molecular sieve at 550°C Calcined for 4 hours to obtain H-type ZSM-12 molecular sieve;

[0036] 3. Put the above-mentioned molecular sieve into 1mol / L nickel chloride solution for ion exchange at 80°C for 4h, then wash, filter, dry at 80°C, and roast at 550°C for 4h.

[0037] The obtained ZSM-12 molecular sieve catalyst modified by Group VIII elements is a ZSM-12 molecular sieve, and the ZSM-12 molecular sieve contains 63% of ZSM-12 molecular sieve, 0.13% of sodium element, and the catalyst contains 1.1% of nickel element by mass fraction ; The specific surface area of ​​the catalyst is 260m 2 / g, the pore volume is 0.19cm 3 / g.

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Abstract

The invention relates to an element modified ZSM-12 molecular sieve catalyst and a preparation method thereof to mainly solve the technical problem of preparation of VIII group element modified ZSM-12 molecular sieve through previous technologies. ZSM-12 molecular sieve is modified by a VIII group element. The preparation method of the element modified ZSM-12 molecular sieve comprises the following steps: pickling the ZSM-12 molecular sieve, filtering, washing, drying, carrying out ammonium ion exchange on the processed ZSM-12 molecular sieve, filtering, washing, and drying; and exchanging the above obtained ZSM-12 molecular sieve by adopting a VIII group element-containing substance, filtering, washing, drying, and roasting to obtain the element modified ZSM-12 molecular sieve catalyst. The catalyst adopting the above scheme well solves the problem, and can be used in xylene production.

Description

technical field [0001] The invention relates to an element-modified ZSM-12 molecular sieve catalyst and a preparation method thereof. Background technique [0002] ZSM-12 molecular sieve is a kind of high silica zeolite, which has one-dimensional linear non-intersecting channels composed of twelve-membered rings. Its channel size between medium-pore and large-pore molecular sieves can effectively realize the selection of most organic molecules. Shape catalytic conversion, ZSM-12 molecular sieve has good geothermal stability, unique pore structure and adjustable acidity, in petroleum refining and chemical industry, alkane cracking, isomerization, reforming and alkylation of aromatics It shows good catalytic activity, product selectivity and catalytic stability in many acid-catalyzed reactions. [0003] At present, the research on the catalytic alkylation of ZSM-12 molecular sieves mainly focuses on the synthesis of 2,6-dimethylnaphthalene. Patent US6232517 discloses the syn...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/76B01J29/74B01J37/30C07C2/86C07C6/12C07C15/08
CPCY02P20/52
Inventor 孔德金冯刚连迎迎
Owner CHINA PETROLEUM & CHEM CORP
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