Zeolite catalyst, method of preparation thereof, and non-oxidative methane conversion process

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides high-silica zeolite catalyst comprising molybdenum and a second modifying element, namely nickel, content of the former in catalyst being no higher than 4.0 wt % and that of the latter from 0.1 to 0.5 wt %. Preparation of the catalyst involves modifying zeolite with molybdenum and second promoting element, the two being introduced into zeolite in the form of nano-size metal powders in above-indicated amounts.

EFFECT: enhanced efficiency of non-oxidative methane conversion process due to increased activity and stability of catalyst.

3 cl, 1 tbl, 7 ex

 

The invention relates to the petrochemical and chemical industries, in particular to a method for producing catalysts for the conversion of methane to aromatic hydrocarbons in a non-oxidizing conditions.

It is known that to improve time stable high action of zeolites of type ZSM-5 containing molybdenum, during non-oxidative methane conversion using additives such promoters as Fe, Cr, Ga [Dong Qun, Ichkawa M. Catalytic features of systems of Mo/HZSM-5 promoted additives of the second metal in the aromatization of methane // Fenzi cuihua=J.Mol.Catal. (China) - 2001. - Vol.15. No. 1.-33-36] and Co [Tian Bing-lun Lui Hong-mei, Shu Yu-ying, Wang Lin-sheng, Xu Yi-de Dehydroaromatization methane in the absence of oxygen in the presence of the modified cobalt catalysts of Mo/HZSM-5 // Fenzi cuihua=J.Mol.Catal. (China) - 2000. - vol.14 No. 3-200-204].

Closest to the proposed catalyst is a catalyst containing 4.0 wt.% molybdenum [Jun-Zhong Zhang, Mervyn A. Long, Russell F. Howe Molybdenum ZSM-5 zeolite catalysts for the conversion of methane to benzene // Catalysis Today 44(1998)293-300].

Closest to the proposed method is a method for Mo-Cu/HZSM-5 catalyst by introducing Cu in zeolite H-ZSM-5 by an ion exchange method from an aqueous solution of copper acetate, drying, calcination and subsequent addition of a mechanical mixture of the required number of Moo3. Prepared Mo-Cu/HZSM-5 catalyst thoroughly ismelda the camping and hot air at 500° C for 4 hours [S. Li, S. Zhang, Q. Kan, D. Wang, T. Wu, L. The function of Cu(II) ions in the Mo/Cu-HZSM-5 catalyst for methane conversion under non-oxidative condition // Applied Catalysis A: General 187(1999) 199-206].

The disadvantage of this method is the high time for preparation of the catalyst, due to the multi-stage process, as well as relatively low catalytic activity during non-oxidative conversion of methane at a temperature of 750°and a space velocity of 800 h-1.

Closest to the proposed method is a method of non-oxidative methane conversion in the presence of zeolite catalyst modified Mo [Jun-Zhong Zhang, Mervyn A. Long, Russell F. Howe Molybdenum ZSM-5 zeolite catalysts for the conversion of methane to benzene // Catalysis Today 44(1998) 293-300].

Object of the present invention to provide a catalyst for raising the degree of conversion of methane and yield of aromatic hydrocarbons, and increasing the period of stable action of Mo/ZSM-5 catalyst by adding Ni as a second promoting element.

The technical result is achieved by the fact that Ni-Mo/HZSM-5 catalysts obtained by dry mechanical mixing of zeolite HZSM-5 with a molar ratio of SiO2/Al2O3=40 (M=40) and nanosized powders (APCS) Mo and Ni obtained by electrical explosion of wire metals in an argon atmosphere, followed by annealing the p is vigotovlennya mixtures at a temperature of T=500° C for 4 hours. The result of Ni-Mo/HZSM-5 catalysts containing not more than 4.0 wt.% PPR Mo and not less than 0.1 wt.% APC Ni. Catalytic activity and stability prepared contacts higher than that of catalysts prepared by modification of zeolite HZSM-5 copper by the method of ion exchange from aqueous solution of its salts with subsequent mixing with the Moo3and catalyst obtained by mechanical mixing of zeolite HZSM-5 with nanopowder Mo without the addition of APC Ni, under the same process conditions.

Examples of specific performance.

Example 1. To 4.0 g decationizing zeolite H-ZSM-5 (M=40) added 0.16 g PPR Mo (4.0 wt%) and 0.004 g APCS Ni (0.1 wt.%), obtained by the method of electrical explosion of wires of metal in argon. The resulting mixture was stirred in a vibratory mill for 0.5 h and calcined at 500°C for 4 hours and Then the catalyst was pressed into tablets, cut up and taken away for research fraction of 0.5-1.0 mm

Catalytic testing of the samples is carried out in flow-through installation at the reaction temperature of 750°C, the volumetric flow rates of methane 800-1000 h-1and atmospheric pressure. The catalyst in the amount of 1 ml was placed in a quartz tubular reactor with a diameter of 12 mm Before the beginning of the reaction the catalyst is heated in a current of 750°C and maintained at this temperature for 20 min, then in eactor serves methane, the degree of purity is 99.9%. The reaction products and not converted methane come in castigados tap for sampling for analysis.

To prevent condensation or solid adsorption forming higher hydrocarbons tube at the exit of the reactor and castigados crane are at temperatures above 200°C. Analysis of the products of the methane conversion is performed after 60 min of operation of the catalyst by gas chromatography. Conversion of methane flow rate 800 h-1after 60 min of operation the catalyst is 14.2%. Study of the effect of reaction time on the activity of the catalyst shows that conversion remains almost constant (13-14%) for 300 min of operation catalyst, then there is a gradual reduction, and reaction time 480 min, it decreased to 10.9%.

Example 2. In the same way as in example 1, but the content APC Ni is 0.25% by weight of the zeolite. The conversion of methane at 800 h-113.8% after 60 min of operation of the catalyst and reduced to 10.0% for a reaction time of 480 minutes

Example 3. In the same way as in example 1, but the content APC Ni is 0.5% by weight of the zeolite. The conversion of methane at 800 h-112.5% after 60 min of operation of the catalyst and decreases to 7.8% for a reaction time of 480 minutes

Example 4. In the same way as in example 1, but the content APC Ni is 1.0% by weight of the zeolite. The conversion of methane is at 800 h -1is 11.1% after 60 min of operation of the catalyst and reduced to 3.5% for a reaction time of 480 minutes

Example 5. In the same way as in example 1, but Mo/HZSM-5 catalyst does not contain Ni. The conversion of methane 13.8% after 60 min of operation of the catalyst and reduced to 8.4% for a reaction time of 480 minutes

Example 6. In the same way as in example 1, but the volumetric flow rate of methane is equal to 1000 h-1while methane conversion after 60 min of operation the catalyst is 13.6% and decreased to 8.4% for a reaction time of 480 minutes

Example 7. In the same way as in example 6, but Mo/HZSM-5 catalyst does not contain Ni. The conversion of methane is 12.1% after 60 min of operation of the catalyst and decreases to 5.4% for a reaction time of 480 minutes

The table shows the comparative characteristics of catalytic activity and stability samples of Ni-Mo/HZSM-5 and Mo/ZSM-5 obtained by modification of zeolite PPR Mo and Ni, and Mo-Cu/ZSM-5 catalyst obtained by modifying the zeolite with copper by an ion exchange method from an aqueous solution of copper acetate and subsequent mechanical mixing of sample Cu/ZSM-5 with molybdenum oxide (prototype).

As can be seen from the table, the proposed method allows to obtain a catalyst that is different from the prototype of the higher activity and stability in the process of conversion of methane into aromatic hydrocarbons.

Table
Comparative characteristic activity of modified zeolite catalysts
IndicatorsThe proposed methodPrototype
1234567
Temperature, °750750750750750750750750
Space velocity, h-180080080080080010001000800
Conversion for a reaction time of 60 min, %14,213,812,511,113,813,612,110,0
Selectivity for arenas, %81,781,279,279,379,078,778,585,0
Output arenes %the 11.611,29,98,810,910,79,58,5
Conversion for reaction time 480 min, %10,910,0 7,83,58,48,4of 5.47,2 (300 min)
The ratio of the Ni(Cu)/Mo in the catalyst0,040,10,20,4-0,04-0,13

1. High-silica zeolite catalyst process for non-oxidative methane conversion, incorporating molybdenum and the second modifying element, characterized in that the content of molybdenum in the catalyst is not more than 4.0 wt.%, second modifying element - Nickel from 0.1 to 0.5 wt.%.

2. The method of preparation of the zeolite catalyst process for non-oxidative methane conversion, including the modification of the zeolite with molybdenum and the second modifying element with subsequent annealing, characterized in that the molybdenum and the second the promoting element Nickel is introduced into the zeolite in the form of nanosized powders of metals, while the molybdenum content in the resulting catalyst is not more than 4.0 wt.%, and Nickel, from 0.1 to 0.5 wt.%.

3. The way non-oxidative methane conversion in the presence of high zeolite catalyst, characterized in that the use of the catalyst according to claim 1.



 

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