CN1239443C - Method aromatization catalyst and its preparation method and application - Google Patents
Method aromatization catalyst and its preparation method and application Download PDFInfo
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- CN1239443C CN1239443C CNB031556833A CN03155683A CN1239443C CN 1239443 C CN1239443 C CN 1239443C CN B031556833 A CNB031556833 A CN B031556833A CN 03155683 A CN03155683 A CN 03155683A CN 1239443 C CN1239443 C CN 1239443C
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- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
一种甲烷直接合成芳烃的催化剂，其特征在于：该催化剂组成为A-R/D，活性组份A为錸和/或钼的氧化物中的至少一种，其重量担载量为0.01-15%；助剂R为碱土金属元素，其重量担载量为0.01-10%；载体D为可以用于甲烷直接合成芳烃的分子筛，可以包括ZSM-5、ZSM-11、MCM-22、MCM-49、MCM-56等。其甲烷芳构化反应在连续进料的固定床反应器系统中进行，反应原料为纯甲烷或者甲烷、二氧化碳混合气体，反应压力为0.05～2.5MPa，反应温度为650～800℃，反应空速为100～5000ml/g.h。在甲烷芳构化合成芳烃的过程中使用本发明催化剂，催化剂的稳定性得到提高。A catalyst for directly synthesizing aromatics from methane, characterized in that: the catalyst is composed of A-R/D, the active component A is at least one of rhenium and/or molybdenum oxides, and its weight loading is 0.01-15% The auxiliary agent R is an alkaline earth metal element, and its weight loading is 0.01-10%; the carrier D is a molecular sieve that can be used to directly synthesize aromatics from methane, and can include ZSM-5, ZSM-11, MCM-22, MCM-49 , MCM-56, etc. Its methane aromatization reaction is carried out in a fixed-bed reactor system with continuous feeding. The reaction raw material is pure methane or a mixed gas of methane and carbon dioxide. 100~5000ml/g.h. The catalyst of the invention is used in the process of methane aromatization to synthesize aromatics, and the stability of the catalyst is improved.
Description
Technical field
The present invention relates to a kind of catalyzer, specifically, relate to a kind of catalyzer that is used in direct synthesis of arene with methane.
The invention still further relates to above-mentioned Preparation of catalysts method.
The invention still further relates to the application of this catalyzer in methane system aromatic hydrocarbons.
Background technology
Methane can thermal transition generate benzene under greater than 900 ℃ condition, can obtain 6～10% benzene under 1200～1300 ℃ condition.
For the Methane Conversion under the catalytic condition, Science in 1966 have reported the result of methyl hydride catalyzed synthetic aromatic hydrocarbons on silica-gel catalyst, at 1000 ℃ of aromatics yields that obtain 4.2-7.2%.In addition, reported methane the eighties in 20th century in succession at the multi-functional complex metal oxides of boron nitride (BN), supersiliceous zeolite supports the result of the synthetic aromatic hydrocarbons of catalysis on Pt-Cr and Ga catalyzer and the carbon fibre material.
1993, Xie Maosong etc. at first reported the aromatization that methane is fastened at Mo/HZSM-5 and Zn/HZSM-5 catalyst body in Chinese patent (CN1102359A).
Zhang Hongbin etc. have reported that methane is at WO in Chinese patent (CN1170633)
3Generate the process of aromatic hydrocarbons on the/ZSM-5 catalyzer.
Xu Yide etc. report in Chinese patent (CN1266041) through the methane aromatizing process on the Mo/ZSM-5 catalyzer of microwave treatment, find that arenes selectivity is good through methane conversion height on the catalyzer of microwave treatment, and can realize low carbon deposit.
Lv Yuan etc. report the methane aromatizing process on the Mo/ZSM-5 catalyzer of handling through high-temperature vapor in Chinese patent (CN1254618), find to reduce through methane coke content on the catalyzer of steam treatment, and stability improves.
Shu Yuying etc. have reported that in Chinese patent (CN1271622) methane makes the process of aromatic hydrocarbons on the MCM-22 zeolite catalyst that Mo supports.
Xu Yide etc. have reported that in Chinese patent (CN1167653) methane is adding the second component R (R=La, Ce, Pr, the aromatization process on Mo-R/HZSM-5 catalyzer Nd).
Liu Hongmei etc. report that in " catalysis journal " interpolation of Co has improved the stability of Mo/HZSM-5 catalyzer in reaction process.
Dong Qun etc. report the influence of the interpolation of Fe, Cr, Co, Ga to Mo/HZSM-5 catalyst methane aromatization in " Journal of Molecular Catalysis ", find that change has taken place the performance of catalyzer.
Wang Qiying etc. have reported the Effect on Performance of rare-earth additive Y to Mo/HZSM-5 catalyst methane aromatization in " Guangzhou chemical industry ", find that methane conversion improves.
Shu Yuying etc. have reported the interpolation of Ru to Mo/HZSM-5 catalyst methane anaerobic dehydrogenation aromatization Effect on Performance in " catalysis journal ", find that the interpolation of Ru has improved activity of such catalysts.
Tan Ping even waits and has reported that in " oil and gas chemical industry " precious metal and Li, P etc. to the influence of Mo/HZSM-5 catalyzer, find that metal Pt adds component and reduces carbon distribution to a certain extent, but the reactive behavior of catalyzer decrease.
Xiong Zhitao etc. have reported the influence of the interpolation of Mg to the W/HZSM-5 catalyst performance in " Catalysis Letters ".
Summary of the invention
The object of the present invention is to provide a kind of catalyzer of methane aromatizing, improve the stability that methane directly prepares the aromatic hydrocarbons process.
The invention provides a kind of catalyzer of direct synthesis of arene with methane, this catalyzer consists of A-R/D, that is: active constituent-auxiliary agent/carrier.Wherein, at least a in the oxide compound of active constituent A Wei Rhenium and/or molybdenum, its weight loading is 0.01-15%; Auxiliary agent R is an alkali earth metal, and its weight loading is 0.01-10%; Carrier D can comprise ZSM-5, ZSM-11, MCM-22, MCM-49 or MCM-56 etc. for being used for the molecular sieve of direct synthesis of arene with methane.
Be MoO with the active ingredient among the present invention
3Be the best, its content is 2～12% better.
The alkali earth metal that is used as auxiliary agent among the present invention is best with Mg, and its weight loading is better with 0.03～1.5%.
Preparation of catalysts method provided by the present invention is:
A) with molecular sieve with nitric acid ammonia solution (0.8 mol) 80-100 ℃ down exchange for several times, washing, 400-800 ℃ roasting 1-5 hour;
B) molecular sieve powder that obtains with the solution impregnation step a that alkali earth metal is provided, dipping time 1-24 hour, drying, 400-800 ℃ roasting 1-8 hour;
C) powder that obtains with the solution impregnation step b that Re and/or Mo element be provided, dipping time 1-24 hour, drying, 400-800 ℃ roasting 2-8 hour;
D) product that makes of step c is ground into the 16-32 order.
Above-mentioned steps b and step c can repeat arbitrarily, and the order of step b and step c can be changed.
In the presence of catalyzer of the present invention, the condition of the directly synthetic aromatic hydrocarbons of low-carbon alkanes such as methane is: be reflected in the fixed bed reactor system of continuously feeding and carry out, reaction raw materials can be pure methane or methane, carbon dioxide mix gas, reaction pressure is 0.05～2.5MPa, temperature of reaction is 650～800 ℃, and the charging air speed is 100～5000ml/g.h.
In methane aromatization, use catalyzer provided by the invention, can improve stability than the catalyzer that does not add alkali earth metal.
Description of drawings
Fig. 1 represents methane conversion and the selectivity of product on the 6Mo/ZSM-5 catalyzer.
Fig. 2 represents the comparison of methane conversion on the different 6MoxMg/ZSM-5 catalyzer.
Embodiment
With following example method of the present invention is described, and the present invention is not subjected to the restriction of these methods, such as: only enumerate Na type ZSM-5 molecular sieve among the embodiment, and to those skilled in the art, be readily appreciated that for embodiment equally suitable to ZSM-5, ZSM-11, MCM-22, MCM-49, MCM-56 equimolecular sieve.In like manner, in the Preparation of catalysts method, maturing temperature 400-800 ℃ can, be not limited to 500 ℃ among the embodiment, and roasting time is not limited to embodiment too.
Embodiment 1
Na type ZSM-5 molecular sieve is exchanged 3 times under 80～100 ℃ condition with the nitric acid ammonia solution, wash 3 times, roasting 3 hours in 550 ℃ of air atmospheres then, it is standby to obtain H-ZSM-5.Taking by weighing 10 gram H-ZSM-5, to place concentration be the Mg (NO of 0.039g/ml
3)
2In 20 milliliters of the solution, standing over night, evaporate to dryness in 70～80 ℃ of water-baths, oven dry is 4 hours in 120 ℃ of air atmospheres, roasting 6 hours in 500 ℃ of air atmospheres then, it is 20 milliliters of the ammonium molybdate solutions of 0.028g/ml that the gained calcining matter places concentration, standing over night, evaporate to dryness in 70～80 ℃ of water-baths, oven dry is 4 hours in 120 ℃ of air atmospheres, roasting 6 hours in 500 ℃ of air atmospheres then, products therefrom (catalyst A) compression molding, it is stand-by to be ground into 16～32 orders.
Embodiment 2
Na type ZSM5 molecular sieve is exchanged 3 times under 80～100 ℃ condition with the nitric acid ammonia solution, wash 3 times, roasting 3 hours in 550 ℃ of air atmospheres then, it is standby to obtain H-ZSM-5.Taking by weighing 10 gram H-ZSM-5, to place concentration be the Mg (NO of 0.053g/ml
3)
2In 20 milliliters of the solution, standing over night, evaporate to dryness in 70～80 ℃ of water-baths, oven dry is 4 hours in 120 ℃ of air atmospheres, roasting 6 hours in 500 ℃ of air atmospheres then, it is 20 milliliters of the ammonium molybdate solutions of 0.028g/ml that the gained calcining matter places concentration, standing over night, evaporate to dryness in 70～80 ℃ of water-baths, oven dry is 4 hours in 120 ℃ of air atmospheres, roasting 6 hours in 500 ℃ of air atmospheres then, products therefrom (catalyst B) compression molding, it is stand-by to be ground into 16～32 orders.
Embodiment 3
Na type ZSM-5 molecular sieve is exchanged 3 times under 80～100 ℃ condition with the nitric acid ammonia solution, wash 3 times, roasting 3 hours in 550 ℃ of air atmospheres then, it is standby to obtain H-ZSM-5.Taking by weighing 10 gram H-ZSM-5, to place concentration be the Mg (NO of 0.053g/ml
3)
2In 20 milliliters of the solution, standing over night, evaporate to dryness in 70～80 ℃ of water-baths, oven dry is 4 hours in 120 ℃ of air atmospheres, roasting 3 hours in 550 ℃ of air atmospheres then, it is 20 milliliters of the ammonium molybdate solutions of 0.037g/ml that the gained calcining matter places concentration, standing over night, evaporate to dryness in 70～80 ℃ of water-baths, oven dry is 4 hours in 120 ℃ of air atmospheres, roasting 6 hours in 500 ℃ of air atmospheres then, products therefrom (catalyzer C) compression molding, it is stand-by to be ground into 16～32 orders.
Comparative example
Na type ZSM-5 molecular sieve is exchanged 3 times under 80～100 ℃ condition with the nitric acid ammonia solution, wash 3 times, roasting 3 hours in 550 ℃ of air atmospheres then, it is standby to obtain H-ZSM-5.Taking by weighing 10 gram H-ZSM-5, to place concentration be 20 milliliters of the ammonium molybdate solutions of 0.028g/ml, standing over night, evaporate to dryness in 70～80 ℃ of water-baths, oven dry is 4 hours in 120 ℃ of air atmospheres, roasting 6 hours in 500 ℃ of air atmospheres then, products therefrom (catalyzer d) compression molding, it is stand-by to be ground into 16～32 orders.
Embodiment 4
Methane aromatizing system benzene is reflected on the continuous flow fixed bed and carries out, and reactor is the crystal reaction tube of internal diameter 7～8mm, and the each loading amount of catalyzer is 0.4 gram.Reaction pressure is 0.1MPa, and temperature of reaction is 720 ℃, and the methane feed air speed is 1500ml/g.h.Switching to unstripped gas after 30 minutes with the He gas disposal (consists of 9.54%Ar, 1.91%CO down at 720 ℃
2, 88.55%CH
4) carry out catalyzed reaction, adopting Ar is that interior mark calculates carbon distribution in interior carbon number balance result.Its result is referring to Fig. 1 and Fig. 2.
Claims (7)
1, a kind of methane aromatization catalyst, it consists of A-R/D, and wherein, active constituent A is at least a in the oxide compound of Re and/or Mo, and its weight loading is 0.01-15%; Auxiliary agent R is an alkali earth metal, and its weight loading is 0.01-10%; Carrier D is for being used for the molecular sieve of direct synthesis of arene with methane.
2, catalyzer as claimed in claim 1 is characterized in that, described active ingredient is MoO
3
3, catalyzer as claimed in claim 1 or 2 is characterized in that, described active ingredient weight loading is 2～12%.
4, catalyzer as claimed in claim 1 is characterized in that, described auxiliary agent is Mg.
As claim 1 or 4 described catalyzer, it is characterized in that 5, described auxiliary agent weight loading is 0.03～1.5%.
6, catalyzer as claimed in claim 1 is characterized in that, described molecular sieve comprises ZSM-5, ZSM-11, MCM-22, MCM-49 or MCM-56.
7, the application of catalyzer as claimed in claim 1 in direct synthesis of arene with methane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031556833A CN1239443C (en) | 2003-09-03 | 2003-09-03 | Method aromatization catalyst and its preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB031556833A CN1239443C (en) | 2003-09-03 | 2003-09-03 | Method aromatization catalyst and its preparation method and application |
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| CN1590352A CN1590352A (en) | 2005-03-09 |
| CN1239443C true CN1239443C (en) | 2006-02-01 |
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| CNB031556833A Expired - Fee Related CN1239443C (en) | 2003-09-03 | 2003-09-03 | Method aromatization catalyst and its preparation method and application |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101652182B (en) * | 2007-04-04 | 2013-11-06 | 埃克森美孚化学专利公司 | Production of aromatics from methane |
| US20110160508A1 (en) * | 2008-05-21 | 2011-06-30 | Ding Ma | Production of aromatics from methane |
| CN111644197A (en) * | 2020-05-15 | 2020-09-11 | 北京化工大学 | Catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion, preparation method and application |
| CN113578376A (en) * | 2021-08-27 | 2021-11-02 | 西北大学 | Catalyst for improving carbon deposit resistance and stability of oxygen-free aromatization of methane and preparation method thereof |
| CN116120139A (en) * | 2021-11-15 | 2023-05-16 | 中国科学院大连化学物理研究所 | Method for generating aromatic hydrocarbon by coupling alkane and carbon dioxide |
| WO2023082271A1 (en) * | 2021-11-15 | 2023-05-19 | 中国科学院大连化学物理研究所 | Method for generating aromatic hydrocarbon by coupling alkane and carbon dioxide |
| CN117324028A (en) * | 2022-06-24 | 2024-01-02 | 中国石油化工股份有限公司 | Aromatization catalyst and preparation method and application thereof |
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