CN102247887A - Preparation method of high-efficiency and low-load methane aromatization catalyst - Google Patents
Preparation method of high-efficiency and low-load methane aromatization catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of a high-efficiency and low-load methane aromatization catalyst. The method is characterized by containing the steps of: placing an HMCM-49 molecular sieve carrier, a molybdenum species and an alkaline ammonia solution together in a hydrothermal condition, and while conducting a hydro-thermal treatment for optimizing the carrier pore structure, skeleton stability and acidity, changing the aggregation state of the molybdenum species in an aqueous solution by adjusting the pH value, and dispersing the low-load molybdenum species inside a molecular sieve pore path, thus obtaining a high dispersed low-load Mo/HMCM-49 catalyst. The method of the invention is characterized by simple operation, low-load of molybdenum and low cost. In the reaction of aromatic hydrocarbon and hydrogen preparation through methane aromatization, the catalyst prepared by the method of the invention presents a better catalytic property than routine catalysts.
Description
Technical field
The invention belongs to methyl hydride catalyzed transformation technology field in the heterogeneous catalysis, relate to a kind of preparation method who efficiently hangs down the carrying capacity methane aromatization catalyst, thereby be specifically related to molecular sieve carrier of optimization process simultaneously and the method for improving active molybdenum species dispersion acquisition high-performance methane aromatizing system aromatic hydrocarbons and hydrogen catalyst under hydrothermal condition.
Background technology
Natural gas is as important chemical material, and along with the scarcity day by day of petroleum resources, its development and use more and more come into one's own.The main component of natural gas is a methane.Except that the natural mineral reserve such as methane hydrate that natural gas, coal bed gas and benthos are contained, methane also is present in petroleum refinery's gas, the oven gas in a large number, and it is very abundant to originate, and its trans-utilization has broad application prospects.
The dehydrogenation and aromatization of methane under oxygen free condition provides a new way for the direct catalytic conversion of methane and effective utilization of natural gas, has important scientific meaning and potential practical value [J. Lunsford.
Catal. Today, 2000 63:165].From reported first [L. Wang, L. Tao, M. Xie, G. Xu, J. Huang, Y. Xu. in 1993
Catal. Lett., 1993 21:35] since, this research that is reflected on the molybdenum based molecular sieve catalyst has obtained tremendous development [Y. Xu, L. Lin.
Appl. Catal. A, 1999 188:53], [Y. Xu, X. Bao, L. Lin.
J. Catal., 2003 216:386], [Z. Ismagilov, E. Matus, L. Tsikoza.
Energy ﹠amp; Environmental Science, 2008,1:526], but still exist problem demanding prompt solution, for example catalyst activity is not high and carbon distribution causes the catalyst rapid deactivation.The researcher generally acknowledges that molybdenum is effective active metal component, and HZSM-5, HMCM-22, HMCM-49 etc. are effective carriers.Conventional molybdenum based molecular sieve Preparation of Catalyst generally adopts aqueous solution infusion process, and this moment, the molybdenum species were with the bigger poly molybdenum anion (Mo of volume
7O
24 6-Or H
2Mo
7O
24 4-) form exists, and is difficult to enter the duct of molecular sieve, the thermophoresis the when dispersion of molybdenum species can only merely rely on high-temperature roasting on the catalyst.Therefore can only adopt higher molybdenum load capacity, be generally 4-6%, though certain molybdenum active specy has been arranged in the molecular sieve pore passage after the roasting, also there is the gathering of a large amount of molybdenum species in molecular sieve outer surface simultaneously, causes carbon distribution to take place.The pore passage structure defective of molecular sieve carrier and the heterogeneity of acid matter are also limiting the dispersion of molybdenum species greatly.Also the someone adopts chemical vapour deposition (CVD) to add method such as noble metal simultaneously to improve the dispersion of molybdenum species on molecular sieve, but method is too loaded down with trivial details, is difficult to operation.
Summary of the invention
The purpose of this invention is to provide a kind of molecular sieve carrier of optimization process simultaneously and active molybdenum species dispersion of improvement under hydrothermal condition, make that the molybdenum species mainly are distributed in the molecular sieve pore passage under low carrying capacity condition, thereby obtain the method for high-performance methane aromatizing system aromatic hydrocarbons and hydrogen catalyst.
Technical scheme of the present invention is by Hydrothermal Preparation molybdenum based molecular sieve catalyst, when hydrothermal treatment consists is optimized carrier pore passage structure, skeleton stability and acid matter, change the coherent condition of molybdenum species in the aqueous solution by regulating the pH value, the molybdenum species of low carrying capacity are scattered in the molecular sieve pore passage, obtain the low carrying capacity Mo/HMCM-49 catalyst of high degree of dispersion.Specifically, under the hydrothermal condition, be present in the microporous molecular sieve or near the amorphous Si the opening of duct or Al species be removed, increased the accessibility of micropore.Utilize the dynamic exchange of Si in the Si of stripping in the solution or Al species and the molecular sieve or Al species, the skeleton defective of repairing molecular sieve, the pore passage structure of reconstruct molecular sieve improves skeleton stability.This all helps the dispersion of molybdenum species.And in this process, the acid matter of molecular sieve is also by modulation, and acid position the strongest on the molecular sieve is removed.The modulation of acid matter not only helps the dispersion of molybdenum species, the carbon distribution in the methane aromatization that has also suppressed to be caused by strong acidic site.The change of pH value makes the molybdenum species be dissociated into the poly-molybdenum anion (MoO of less list
4 2-) form, can diffuse into effectively in the duct of molecular sieve.
To achieve these goals, the present invention is illustrated by the low carrying capacity Mo/HMCM-49 catalyst of preparation high degree of dispersion.The preparation method may further comprise the steps:
(1) HMCM-49 molecular sieve 2 K/min in air atmosphere with silica alumina ratio 17-21 are warming up to 623 K roastings, 2 h, and 10 K/min are warming up to 823 K roastings, 6 h again, and reducing to room temperature, to put into drier standby.
(2) HMCM-49 molecular sieve carrier and molybdenum species, deionized water, the alkaline ammonia solution with step (1) gained places the hydro-thermal synthesis reactor by a certain percentage together, and wherein HMCM-49 molecular sieve addition is 3-15 g; The molybdenum species be ammonium molybdate or acetic acid molybdenum one of them, addition is counted the 0.8-1.2% of HMCM-49 molecular sieve with the molybdenum quality; The deionized water addition is 2 times of HMCM-49 molecular sieve in mass; The alkalescence ammonia solution is 25% ammoniacal liquor and hexamethylene imine, and the two mass ratio 5:1 controls alkaline ammonia solution addition to final mixture pH value and is 9-12.The hydrothermal treatment consists temperature is controlled at 373-393 K, and pressure is self-generated pressure, time 8-24 h.
(3) mixture of step (2) gained is dried with being lower than under the 1 kPa pressure in 383 K temperature.
(4) oven dry afterproduct 2 K/min in air atmosphere with step (3) gained are warming up to 623-643 K roasting 4 h, and 10 K/min are warming up to 813 K roastings, 2 h again, promptly get catalyst.Grinding, compressing tablet, to be crushed to the 40-60 order standby.
In the presence of catalyst of the present invention, the reaction condition of methane aromatizing system aromatic hydrocarbons and hydrogen is: carry out under the normal pressure in the fixed bed quartz tube reactor of internal diameter 8 mm.0.2-1.0 the g catalyst, 10 K/min are warming up to reaction temperature 873-1073 K in He atmosphere, introduce consisting of 90% CH again
4-10% N
2Reacting gas, total air speed 1000-3000 ml g
-1h
-1
Effect of the present invention and benefit are molecular sieve carrier of optimization process simultaneously and the active molybdenum species dispersions of improvement under hydrothermal condition, make that the molybdenum species mainly are distributed in the molecular sieve pore passage under low carrying capacity condition, thereby obtain high-performance methane aromatizing system aromatic hydrocarbons and hydrogen catalyst.The present invention is simple to operate, and the molybdenum carrying capacity is low, and is with low cost.In methane aromatizing system aromatic hydrocarbons and H-H reaction, utilize the catalyst of the inventive method preparation to show than the better catalytic performance of conventional catalyst.Further specify with example below.
Description of drawings
The invention will be further described below in conjunction with accompanying drawing.
The XRD figure of the low carrying capacity high dispersive Mo/HMCM-49 catalyst of Fig. 1.
The nitrogen adsorption desorption isotherm figure of the low carrying capacity high dispersive Mo/HMCM-49 catalyst of Fig. 2.
Low carrying capacity high dispersive Mo/HMCM-49 catalyst of Fig. 3 and conventional high carrying capacity catalyst be benzene generating rate variation diagram in time in methane aromatization.
Low carrying capacity high dispersive Mo/HMCM-49 catalyst of Fig. 4 and conventional high carrying capacity catalyst be hydrogen generating rate variation diagram in time in methane aromatization.
Wherein: Fig. 3 and Fig. 4 hollow core square are represented low carrying capacity high dispersive Mo/HMCM-49 catalyst of the present invention, and closed square is represented conventional high carrying capacity catalyst.
The specific embodiment
Embodiment 1: low carrying capacity high dispersive Mo/HMCM-49 Preparation of Catalyst: HMCM-49 molecular sieve 2 K/min in air atmosphere of silica alumina ratio 20 are warming up to 623 K roastings, 2 h, and 10 K/min are warming up to 823 K roastings, 6 h again, and reducing to room temperature, to put into drier standby.The baked HMCM-49 molecular sieve carrier of weighing 5 g places the hydro-thermal synthesis reactor by a certain percentage with molybdenum species, deionized water, alkaline ammonia solution, and wherein the molybdenum species are ammonium molybdate, and addition is counted 1.0% of HMCM-49 molecular sieve with the molybdenum quality; The deionized water addition is 2 times of HMCM-49 molecular sieve in mass; The alkalescence ammonia solution is 25% ammoniacal liquor and hexamethylene imine, the two mass ratio 5:1, and controlling alkaline ammonia solution addition to final mixture pH value is 10.The hydrothermal treatment consists temperature is controlled at 373 K, and pressure is self-generated pressure, times 12 h.The mixture of gained is in 383 K temperature with after being lower than under the 1 kPa pressure oven dry, and 2 K/min are warming up to 623 K roastings, 4 h in air atmosphere, and 10 K/min are warming up to 813 K roastings, 2 h again, promptly get catalyst.Utilize means such as XRD, nitrogen adsorption desorption, ICP-AES and XPS that catalyst is characterized.XRD, nitrogen adsorption desorption characterization result are listed among Fig. 1 and Fig. 2.The HMCM-49 molecular sieve still had high degree of crystallinity after XRD result showed the load molybdenum, and this repairs the skeleton defective of molecular sieve to a certain extent owing to hydrothermal treatment consists, and the pore passage structure of reconstruct molecular sieve improves skeleton stability.The specific surface area of catalyst that is calculated by the nitrogen adsorption desorption isotherm is still up to 590 m
2/ g, micropore volume are 0.20 cm
3/ g, specific area and micropore volume do not reduce a lot of situations when high carrying capacity occurring.The result of ICP-AES and XPS shows that caltalyst is consistent with the molybdenum content on nearly surface mutually, shows the high degree of dispersion of molybdenum species, at the molecular sieve surface enrichment, mainly is not distributed in the duct.
Embodiment 2: the reaction evaluating of low carrying capacity high dispersive Mo/HMCM-49 catalyst: methane aromatization carries out under the normal pressure in the fixed bed quartz tube reactor of internal diameter 8 mm.0.2 catalyst g Mo/HMCM-49(40-60 order), 10 K/min are warming up to reaction temperature 973 K in He atmosphere, introduce consisting of 90% CH again
4-10% N
2Reacting gas, total air speed 1500 ml g
-1h
-1, N wherein
2As interior mark.The flow of gas is controlled by mass flowmenter in the experiment.The tail gas of methane aromatization is incubated in 493 K, utilizes the on-line automatic sample introduction gas chromatograph that is equipped with dual detector that it is analyzed.Carry out data according to the carbon number balance principle of reaction and internal standard method and handle, obtain comprising all analysis results of products such as carbon distribution.Reaction result is listed in Fig. 3 and Fig. 4.The result shows that the low carrying capacity catalyst of the inventive method preparation has higher performance than conventional catalyst, and benzene generating rate and hydrogen generating rate all are significantly higher than conventional catalyst.
Comparative Examples 1: conventional high carrying capacity Mo/HMCM-49 Preparation of catalysts and reaction evaluating: the ammonium molybdate aqueous solution that the HMCM-49 molecular sieve is flooded certain Mo content, after the 393 K dryings, 773 K roastings, 6 h make the Mo/ HMCM-49 catalyst of 6 wt. % load capacity of conventional dipping.Reaction evaluating and embodiment 2 are roughly the same.Reaction result is listed in Fig. 3 and Fig. 4.
Embodiment 3: controlling alkaline ammonia solution addition is 9 to final mixture pH value, and the hydrothermal treatment consists temperature is controlled at 393 K, and pressure is self-generated pressure, times 8 h, and other preparation process is identical with embodiment 1.Reaction evaluating and embodiment 2 are roughly the same.This catalyst after 2000 min reaction the benzene generating rate still up to 0.105 μ molg
-1s
-1, be significantly higher than conventional catalyst.
Embodiment 4: molybdenum species addition is counted 1.2% of HMCM-49 molecular sieve with the molybdenum quality, controlling alkaline ammonia solution addition is 11 to final mixture pH value, and the hydrothermal treatment consists temperature is controlled at 373 K, and pressure is self-generated pressure, times 24 h, other preparation process is identical with embodiment 1.Reaction evaluating and embodiment 2 are roughly the same.The highest benzene yield of this catalyst can reach 0.142 μ molg
-1s
-1, the benzene generating rate is still up to 0.097 μ molg after 2000 min reaction
-1s
-1, be significantly higher than conventional catalyst.
Claims (5)
1. the preparation method of an efficient low carrying capacity methane aromatization catalyst, comprise the steps: (1) molecular sieve preliminary treatment: HMCM-49 molecular sieve 2K/min in air atmosphere of silica alumina ratio 17-21 is warming up to 623 K roasting 2h, and 10 K/min are warming up to 823 K roastings, 6 h again; (2) hydrothermal condition prepares catalyst: will place the hydro-thermal synthesis reactor by a certain percentage together by pretreated HMCM-49 molecular sieve carrier, molybdenum species, deionized water and alkaline ammonia solution in step (1), control certain hydrothermal treatment consists temperature and time, after driving still mixture is dried, roasting promptly gets catalyst under the certain condition.
2. the preparation method of efficient low carrying capacity methane aromatization catalyst according to claim 1, it is characterized in that: in step (2), HMCM-49 molecular sieve addition is 3-15 g; The molybdenum species be ammonium molybdate or acetic acid molybdenum one of them, addition is counted the 0.8-1.2% of HMCM-49 molecular sieve with the molybdenum quality; The deionized water addition is 2 times of HMCM-49 molecular sieve in mass; The alkalescence ammonia solution is 25% ammoniacal liquor and hexamethylene imine, and the two mass ratio 5:1 controls alkaline ammonia solution addition to final mixture pH value and is 9-12.
3. the preparation method of efficient low carrying capacity methane aromatization catalyst according to claim 2, it is characterized in that: in step (2), the hydrothermal treatment consists temperature is controlled at 373-393 K, time 8-24h.
4. the preparation method of efficient low carrying capacity methane aromatization catalyst according to claim 3, it is characterized in that: in step (2), directly dry after driving still, do not filter and washing step, drying course carries out with being lower than under the 1 kPa pressure in 383 K temperature.
5. the preparation method of efficient low carrying capacity methane aromatization catalyst according to claim 4, it is characterized in that: in step (2), oven dry afterproduct 2 K/min in air atmosphere are warming up to 623-643 K roasting 4 h, and 10 K/min are warming up to 813 K roastings, 2 h again.
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