CN1132697C - Catalyst for methane dehydrogenation to prepare aromatic hydrocarbon and hydrogen and preparation process thereof - Google Patents
Catalyst for methane dehydrogenation to prepare aromatic hydrocarbon and hydrogen and preparation process thereof Download PDFInfo
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- CN1132697C CN1132697C CN 02115329 CN02115329A CN1132697C CN 1132697 C CN1132697 C CN 1132697C CN 02115329 CN02115329 CN 02115329 CN 02115329 A CN02115329 A CN 02115329A CN 1132697 C CN1132697 C CN 1132697C
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Abstract
The present invention provides a catalyst for methane dehydrogenation to prepare aromatic hydrocarbons and hydrogen by using HZSM-5 as a carrier. The catalyst of the present invention has 4 to 8% of Mo as an active component. The present invention adopts temperature programming technique to precisely pre-treat HZSM-5 as a carrier under the condition of air or inert atmosphere so that the prepared catalyst has high reaction activity and excellent high temperature stability and the service life is greatly prolonged to 30 hours. The present invention provides a feasible path of industrialization of preparation of aromatic hydrocarbons and hydrogen through methane dehydrogenation. The present invention also provides a preparation method of the catalyst for methane dehydrogenation to prepare aromatic hydrocarbons and hydrogen by using HZSM-5 as a carrier.
Description
Technical field
The present invention relates to a kind of methane dehydrogenation to prepare aromatic hydrocarbon and hydrogen catalyst and preparation method thereof.
Background technology
Methane dehydrogenation to prepare aromatic hydrocarbon is one of effective way of natural gas comprehensive utilization, methane is as the main component of natural gas and coal bed gas, resource is very abundant, and along with petroleum resources are deficient day by day, methane is expected to become 21 century the most considerable alternative energy source and one of industrial chemicals.Methane dehydrogenation to prepare aromatic hydrocarbon and hydrogen have been avoided causing the low shortcoming of selectivity of product because of deep oxidation, it is big and be convenient to separate to have the product demand simultaneously, characteristics such as equipment investment is few, and the reaction process path is simple become the research focus that methane optimization in recent years utilizes.For the methane dehydrogenation to prepare aromatic hydrocarbon catalyst, its most important class is to be carrier with molecular sieve HZSM-5, is the effective catalyst of active component with the Mo element, can add all kinds auxiliary agent in addition to improve reactive activity and stability.Is that catalyst is used for the methane dehydrogenation aromatisation as Chinese patent 96115372.5 with Mo/HZSM-5, and Chinese patent 97100978.3 is with SO
4 2--MoO
4 2--Ao
x/ HZSM-5 is that loaded catalyst is used for methyl hydride catalyzed dehydroaromatizationof, and Chinese patent application 98121011.2 has proposed a kind of catalyst for oxygen-free aromatization of methane without carbon deposition and preparation method.Because methane dehydrogenation to prepare aromatic hydrocarbon and H-H reaction need to carry out under 700 ℃, so require catalyst to have anti-carbon deposit and pyroreaction stability, to prolong the service life of catalyst, but it is at present this by changing the activity of such catalysts component or adding auxiliary agent or change the catalyst that carrier obtains, scarcely surpass 6 hours its service life, makes this reaction of methane dehydrogenation to prepare aromatic hydrocarbon and hydrogen be difficult to industrialization.How prolonging the service life of catalyst significantly, is subject matter anxious to be solved at present.
Summary of the invention
The purpose of this invention is to provide a kind of methane dehydrogenation to prepare aromatic hydrocarbon and hydrogen catalyst that has high reaction activity and are prolonged greatly in high-temperature stability, service life, for methane dehydrogenation to prepare aromatic hydrocarbon and H-H reaction industrialization provide a feasible approach.
Another object of the present invention provides the preparation method of a kind of methane dehydrogenation to prepare aromatic hydrocarbon of the present invention and hydrogen catalyst.
For achieving the above object, catalyst provided by the invention is to be carrier with HZSM-5, is active component with Mo, is benchmark with the catalyst weight, and Mo content is 4-8%, and this catalyst is to flood above-mentioned carrier with molybdate solution, and drying and roasting form; The Si/Al of above-mentioned carrier is 24-26, and in advance under air or inert atmosphere, carry out double roasting: it is 200-400 ℃ of following constant temperature calcining 3-5 hour that roasting for the first time earlier is warming up to temperature from room temperature for 1-3 ℃ by the heating rate per minute, be warming up to temperature 450-600 ℃ of following constant temperature calcining 5-7 hour by 1-5 ℃ of heating rate per minute again, carry out the roasting second time after being cooled to room temperature, being warming up to temperature by 5-10 ℃ of heating rate per minute is 400-600 ℃ of following constant temperature calcining 3-5 hour.
The content of above-mentioned active component Mo is 6%, and the Si/Al of carrier is 25.
Above-mentioned catalyst also contains auxiliary agent Fe, and the content of auxiliary agent Fe is 0.01-0.1% (weight).
The present invention also provides a kind of method for preparing catalyst of the present invention, and this method in turn includes the following steps:
(1) the former dried bean noodles of molecular sieve HZSM-5 is dry;
(2) to the former powder of (1) prepared HZSM-5, under air or inert atmosphere, carry out double roasting, it is 200-400 ℃ of following constant temperature calcining 3-5 hour that roasting for the first time earlier is warming up to temperature from room temperature for 1-3 ℃ by the heating rate per minute, being warming up to temperature by 1-5 ℃ of heating rate per minute again is 450-600 ℃ of following constant temperature calcining 5-7 hour, carry out the roasting second time after being cooled to room temperature, being warming up to temperature by 5-10 ℃ of heating rate per minute is 400-600 ℃ of following constant temperature calcining 3-5 hour;
(3) with molybdate solution dipping (2) prepared carrier HZSM-5, drying and roasting, baking temperature is 80-150 ℃, the time is 6-8 hour; Sintering temperature is 400-600 ℃, and the time is 3-8 hour, 10-15 ℃ of heating rate per minute.
The former powder of above-mentioned HZSM-5 can directly use commercially available product, also can get via ion-exchange by the NaZSM-5 molecular sieve.
The activity of methane dehydrogenation to prepare aromatic hydrocarbon of the present invention and hydrogen catalyst and study on the stability carry out in fixed bed continuous-flow reaction system, and reaction unit is made with quartz ampoule (diameter 12mm), and reaction bed temperature is controlled by thermocouple.But reacted product is via making field assay in the chromatograph that enters two temperature programmings after the six-way valve sampling, band hydrogen flame detector wherein, and packed column is 2.5 meters long Porapak-p; Another is a thermal conductivity cell detector, and packed column is 2 a meters long 5A molecular sieve.
Reaction condition: 650～800 ℃ of temperature, pressure 0.2Mpa, air speed 700～2000ml/ (g.h), catalyst is 20～60 orders, loading amount is 0.1～1g, and unstripped gas is the gaseous mixture of methane and argon gas, obtains methane conversion, product selectivity and yield by internal standard method with the carbon number balance.Logical inert gas is protected in the temperature-rise period before reaction, and logical inert gas carried out activation processing 0.5～3 hour to catalyst under reaction temperature, feeds reaction mixture gas then and begins reaction.
Catalyst of the present invention by precision control, carries out pre-treatment to carrier, is 15 hours when the reaction time, and methane conversion can reach more than 10%, and aromatics yield is greater than 6%; Reacted 30 hours, methane conversion still can reach more than 8.5%, and aromatics yield is also greater than 5.3%; Show that catalyst of the present invention has high reaction activity and fabulous pyroreaction stability, obtain greatly service life prolonging.
Specific embodiment example 1
Get a certain amount of Si/Al and be 25 NaZSM-5 molecular sieve, with the 1NN of 50ml
4NO
3The aqueous solution at room temperature stirs exchange 1 hour, exchanges continuously 2 times after the filtration again.The molecular sieve that obtains after ion-exchange is following dry 4 hours at 110 ℃, in air atmosphere, heat up from room temperature, heating rate is 2 ℃ of per minutes, in temperature is 300 ℃ of following constant temperature calcinings 4 hours, temperature is controlled at ± 0.5 ℃ (down together) during constant temperature, again 500 ℃ of following constant temperature calcinings 4 hours, 4 ℃ of heating rate per minutes; Carry out the roasting second time after reducing to room temperature in nitrogen atmosphere, 6 ℃ of heating rate per minutes 500 ℃ of following constant temperature calcinings 4 hours, obtain the former powder of HZSM-5.
Flood and spend the night with configuring the ammonium molybdate solution that is equivalent to 6%Mo content, in 110 ℃ dry 8 hours down, under air atmosphere, 500 ℃ of following roastings 6 hours, 12 ℃ of heating rate per minutes can make catalyst of the present invention.Example 2
Utilize the 6%Mo/HZSM-5 catalyst of example 1 method preparation, 700 ℃ of temperature, pressure 0.2Mpa, air speed 1400ml/ (g.h) reacts under the catalyst loading amount 0.2g.Heat up under helium atmosphere before the reaction, programming rate is 10 ℃ of per minutes, and with helium catalyst is carried out activation processing 0.5 hour under reaction temperature, then switches unstripped gas and reacts.By the yield of internal standard method, and reacting acquisition stabilization result such as table one in 30 hours with carbon number EQUILIBRIUM CALCULATION FOR PROCESS methane conversion and product.
The oxygen-free aromatization reaction result of table 1 methane on the 6%Mo/HZSM-5 catalyst
| Reaction time (hour) | Methane conversion (%) | Benzene yield (%) | Carbon distribution yield (%) |
| 2 | 15.75 | 6.50 | 2.73 |
| 5 | 11.41 | 6.23 | 2.40 |
| 15 | 10.05 | 6.00 | 1.81 |
| 20 | 9.28 | 5.99 | 1.22 |
| 30 | 8.81 | 5.88 | 0.99 |
| 35 | 7.43 | 4.44 | 0.86 |
As can be seen from Table 1: react in 5 hours, with above-mentioned 6%Mo/HZSM-5 catalyst, the methane conversion of methane dehydrogenation to prepare aromatic hydrocarbon and H-H reaction is more than 11%, react that methane conversion can reach more than 10% after 15 hours, react that methane conversion can reach more than 8% after 30 hours, and the productive rate of benzene maintains more than 5.80% at this moment, and the carbon deposit yield also maintains about 1.2%, demonstrates fabulous high-temperature stability.Example 3
Press example 1 ion-exchange, dried molecular sieve, in air atmosphere, in temperature is 400 ℃ of following constant temperature calcinings 4 hours, 2 ℃ of heating rate per minutes, and temperature is controlled at ± 0.5 ℃ (down together) during constant temperature, again 500 ℃ of following constant temperature calcinings 4 hours, 4 ℃ of heating rate per minutes carried out the roasting second time after reducing to room temperature in argon gas atmosphere, 500 ℃ of following constant temperature calcinings 4 hours, 6 ℃ of programming rate per minutes make the HZSM-5 molecular screen primary powder; Immersion process for preparing 6%Mo/HZSM-5 catalyst obtains the 6%Mo/HZSM-5 catalyst under another roasting condition with example 1.
Methane dehydrogenation to prepare aromatic hydrocarbon and H-H reaction are reacted after 30 hours with example 2, and methane conversion is more than 9.0%, and the benzene yield is greater than 5.5%, and average carbon deposit yield is 1.6%.Example 4
Press the HZSM-5 molecular screen primary powder of example 1 preparation, with behind the infusion process dipping Mo 110 ℃ of dryings 8 hours, in nitrogen atmosphere, 500 ℃ of roastings 6 hours, 12 ℃ of heating rate per minutes, during constant temperature temperature be controlled at ± 0.5 ℃, obtain the 6%Mo/HZSM-5 catalyst under another roasting condition.
Methane dehydrogenation to prepare aromatic hydrocarbon and H-H reaction are reacted after 30 hours with example 2, and methane conversion is more than 8.5%, and the benzene yield is greater than 5.8%, and average carbon deposit yield is 1.4%.Example 5
Press the HZSM-5 molecular screen primary powder of example 1 preparation, flood with the iron nitrate solution that contains 0.05wt%Fe, 110 ℃ dry 8 hours down, in the nitrogen atmosphere in 300 ℃ of following roastings 5 hours, press the molecular sieve dipping Mo of 4 couples of load Fe of example again, can obtain the Fe-Mo/HZSM-5 catalyst.Methane dehydrogenation to prepare aromatic hydrocarbon and H-H reaction are with example 2, reaction result such as table 2.The oxygen-free aromatization reaction result of table 2 methane on the Fe-Mo/HZSM-5 catalyst
| Reaction time (hour) | Methane conversion (%) | Benzene yield (%) | Carbon distribution yield (% |
| 2 | 19.16 | 10.28 | 3.83 |
| 5 | 15.44 | 11.05 | 0.68 |
| 15 | 11.89 | 9.04 | 0.36 |
| 20 | 11.71 | 8.19 | 1.24 |
| 25 | 10.22 | 6.18 | 2.45 |
| 30 | 8.82 | 5.35 | 1.65 |
As can be seen from Table 2, reaction last stage methane conversion is higher, reacted 20 hours, methane conversion is more than 11.71%, react that methane conversion still can reach more than 8.82% after 30 hours, this moment, the productive rate of benzene also maintained more than 5.35%, this shows that auxiliary agent Fe can make catalyst that the methane dehydrogenation to prepare aromatic hydrocarbon reactive activity is improved.
The regeneration of catalyst can feed O
2, H
2Or air kept 0.5～5 hour at 400～700 ℃, can recover activity of such catalysts, reused.
Claims (11)
1, a kind of methane dehydrogenation to prepare aromatic hydrocarbon and hydrogen catalyst comprise carrier HZSM-5, and active component Mo element is a benchmark with the catalyst weight, and Mo content is 4-8%, and described catalyst is to flood described carrier with molybdate solution, and drying and roasting form; It is characterized in that: the Si/Al of described carrier is 24-26, and in advance under air or inert atmosphere, carry out double roasting: it is 200-400 ℃ of following constant temperature calcining 3-5 hour that roasting for the first time earlier is warming up to temperature from room temperature for 1-3 ℃ by the heating rate per minute, being warming up to temperature by 1-5 ℃ of heating rate per minute again is 450-600 ℃ of following constant temperature calcining 5-7 hour, carry out the roasting second time after being cooled to room temperature, being warming up to temperature by 5-10 ℃ of heating rate per minute is 400-600 ℃ of following constant temperature calcining 3-5 hour.
2, catalyst according to claim 1, it is characterized in that: described first time of roasting earlier by heating rate be per minute to be warming up to temperature from room temperature for 2 ℃ be 300 ± 0.5 ℃ of following roastings 4 hours, being warming up to temperature by 4 ℃ of heating rate per minutes again is 500 ± 0.5 ℃ of following roastings 4 hours.
3, catalyst according to claim 1 and 2 is characterized in that: it is 500 ± 0.5 ℃ of following roastings 4 hours that the described roasting second time is warming up to temperature by 6 ℃ of heating rate per minutes.
4, catalyst according to claim 1 and 2 is characterized in that: the content of described active component Mo is 6%, and the Si/Al of carrier is 25.
5, catalyst according to claim 3 is characterized in that: the content of described active component Mo is 6%, and the Si/Al of carrier is 25.
6, catalyst according to claim 1 is characterized in that: described catalyst also contains auxiliary agent Fe, and the content of auxiliary agent Fe is 0.01-0.1% (weight).
7, catalyst according to claim 6 is characterized in that: described auxiliary agent Fe content is 0.05% (weight).
8, catalyst according to claim 1 is characterized in that: described molybdate solution is an ammonium molybdate solution.
9, the described Preparation of catalysts method of a kind of claim 1 in turn includes the following steps:
(1) the former dried bean noodles of molecular sieve HZSM-5 is dry;
(2) to the former powder of (1) prepared HZSM-5, under air or inert atmosphere, carry out double roasting, it is 200-400 ℃ of following constant temperature calcining 3-5 hour that roasting for the first time earlier is warming up to temperature from room temperature for 1-3 ℃ by the heating rate per minute, being warming up to temperature by 1-5 ℃ of heating rate per minute again is 450-600 ℃ of following constant temperature calcining 5-7 hour, carry out the roasting second time after being cooled to room temperature, being warming up to temperature by 5-10 ℃ of heating rate per minute is 400-600 ℃ of following constant temperature calcining 3-5 hour;
(3) with molybdate solution dipping (2) prepared carrier HZSM-5, drying and roasting, baking temperature is 80-150 ℃, the time is 6-8 hour; Sintering temperature is 400-600 ℃, and the time is 3-8 hour, 10-15 ℃ of heating rate per minute.
10, preparation method according to claim 9 is characterized in that: the former powder of described HZSM-5 is to get by ion-exchange with the NaZSM-5 molecular sieve.
11, preparation method according to claim 9 is characterized in that described step (3) baking temperature is 110 ℃, and the time is 8 hours; Sintering temperature is 500 ℃, and the time is 6 hours, 12 ℃ of heating rate per minutes.
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| US7728186B2 (en) * | 2006-04-21 | 2010-06-01 | Exxonmobil Chemical Patents Inc. | Production of aromatics from methane |
| CN112058302B (en) * | 2020-10-26 | 2023-02-28 | 陕西延长石油（集团）有限责任公司 | Preparation method and application of ZSM-5 molecular sieve catalyst |
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