CN1593760A - Mo based molecular sieve catalyst and preparation method thereof - Google Patents
Mo based molecular sieve catalyst and preparation method thereof Download PDFInfo
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- CN1593760A CN1593760A CN 200410028083 CN200410028083A CN1593760A CN 1593760 A CN1593760 A CN 1593760A CN 200410028083 CN200410028083 CN 200410028083 CN 200410028083 A CN200410028083 A CN 200410028083A CN 1593760 A CN1593760 A CN 1593760A
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Abstract
The invention relates to a kind of Mo basic molecule sieve catalyst for manufacturing aromatic and hydrogen with methane, and its manufacturing method. Make the carrying molecule sieve HZSM-5 have the preliminary treatment, and treat the aluminium salt water-solution with hot pressing in the sealed vessel. Compared with the existing catalyst that isn't with the process mentioned above, the methane conversion rate and the aromatic yield rate of the invention all have the obvious improvement in the aromatic production. The low selectivity and the low yield rate of charcoal, can indicate that the molecule sieve catalyst of the invention has high reacting activity and the high temperature reacting stability, so also can prolong the service life of it.
Description
Technical field
The present invention relates to a kind of molecular sieve catalyst, particularly a kind ofly prepare the Mo based molecular sieve catalyst that uses in aromatic hydrocarbons and the hydrogen at methane.The invention still further relates to above-mentioned Preparation of catalysts method.
Background technology
Methane is the main component of natural gas and coal bed gas, also can produce a large amount of methane in some hydro carbons process.China is the profuse country of natural gas and coal bed gas resource, and the resource base of development of natural gas industry is energetically arranged.Under the situation of current energy resources growing tension, make full use of this resources advantage, with methyl hydride catalyzed more useful chemicals or the liquid fuel of being converted into, be of great practical significance undoubtedly.In addition, along with the raising of countries in the world government and Public Environmental Awareness, hydrogen will occupy the status of dominance in energy consumption structure from now on as clear energy sources.The methane dehydrogenation aromatization is when making aromatic hydrocarbons, and rich product does not contain the high-purity H of CO
2, after separating, can be directly used in fuel cell, therefore be subjected to the extensive concern of catalysis educational circles, become one of focus of Recent study.
Explore through the researchs in nearly ten years, all obtaining important achievement aspect methane activation mechanism and carbochain growth, cyclisation and the aromatisation mechanism, and some main viewpoints have been formed, as Mo/HZSM-5 is a difunctional catalyst, and high price Mo species become MoC for methane reduction in the induction period of aromatization
2Or MoO
xC
y, these Mo species become the real active sites of methane activation after carbon deposit is modified, formed CH behind the methane activation
xOr C
2Further dehydrogenation, cyclisation and aromatization change into aromatic hydrocarbons such as purpose product benzene on intermediate, the intermediate Bronsted acidic site in molecular sieve pore passage.But with regard to the improvement aspect of catalyst reaction performance, big breakthrough is not arranged always but, the coking deactivation of catalyst is still seriously restricting the process of industrialization of this reaction.Nearly 2～3 years, there is the researcher to pass through in reaction system, to add trace amounts of CO or CO
2, the method that improves reaction system pressure is restrained the carbon deposit of catalyst, has improved the reaction stability of catalyst more significantly.Yet CO
2Interpolation increased the complexity of reaction undoubtedly.For this reason, the emphasis of research still is to optimize the Preparation of catalysts condition at present, explores and holds the new catalyst that the carbon amount is big, anti-carbon deposition ability is strong.The researcher is arranged recently by methods such as the steam of catalyst carrier, aqueous slkali, silanization preliminary treatment being restrained the carbon deposit of catalyst, to improve the reaction stability of catalyst.But the service life of the catalyst that the employing said method makes is scarcely above 25 hours.Therefore developing that anti-carbon deposition ability is strong, the new catalyst of long service life, is problem anxious to be solved at present.
Summary of the invention
The object of the present invention is to provide and a kind ofly in methane prepares the process of aromatic hydrocarbons and hydrogen, use Mo based molecular sieve catalyst with high reaction activity and high-temperature stability, anti-carbon deposit, long service life.
Another object of the present invention is to provide aforementioned Mo based molecular sieve Preparation of catalysts method.
For achieving the above object, Mo based molecular sieve catalyst Mo/HZSM-5 provided by the present invention comprises carrier HZSM-5 and active component Mo, described active component Mo accounts for the 4-8% (weight ratio of described catalyst, down together), the Si/Al of described carrier HZSM-5 is 25-50, it is characterized in that described carrier is filling the Al that content is 0.1～1.0mol/l
3+In the airtight container of the aqueous solution with 80-150 ℃ Temperature Treatment 4-24 hour, products obtained therefrom rises to 250-400 ℃ with per minute 1-3 ℃ heating rate by room temperature behind the filtration drying, and kept 4-8 hour in this temperature, then rise to 500-600 ℃ of roasting 4-8 hour with per minute 4-10 ℃ heating rate again; Support the Mo of 4-8% after the described carrier roasting, rise to 300-400 ℃ with per minute 1-2 ℃ heating rate then, and kept 1-4 hour, rise to 500-550 ℃, roasting 2-10 hour with per minute 5-10 ℃ heating rate again in this temperature.
Described carrier was filling the Al that content is 0.5～0.8mol/L before supporting Mo
3+In the airtight container of the aqueous solution with 80-150 ℃ Temperature Treatment 4-24 hour, products obtained therefrom rises to 350 ℃ with the heating rate of 2 ℃ of per minutes by room temperature behind the filtration drying, and kept 6 hours in this temperature, then rise to 530 ℃ of roastings 6 hours with the heating rate of 5 ℃ of per minutes again.
Described aluminum saline solution is a kind of in aluminum nitrate, aluminum acetate, the aluminium oxide aqueous solution.
Described supported carrier Mo adopts a kind of in infusion process, solid reaction process and the mechanical mixing.
The present invention also provides the method for a kind of Mo of preparation based molecular sieve catalyst Mo/HZSM-5, carries out according to the following steps:
(1) carrier HZSM-5 molecular sieve is being filled the Al that content is 0.1～1.0mol/l
3+In the airtight container of the aqueous solution with 80-150 ℃ Temperature Treatment 4-24 hour, products obtained therefrom rises to 250-400 ℃ with per minute 1-3 ℃ heating rate by room temperature behind the dry filter, and kept 4-8 hour in this temperature, then rise to 500-600 ℃ of roasting 4-8 hour with per minute 4-10 ℃ heating rate again;
(2) with the Mo of (1) gained supported carrier 4-8%;
(3) (2) gained carrier is risen to 300-400 ℃ with per minute 1-2 ℃ heating rate, and kept 1-4 hour, rise to 500-550 ℃, roasting 2-10 hour with per minute 5-10 ℃ heating rate again in this temperature.
Filling the Al that content is 0.5～0.8mol/L before described step (1) the supported carrier Mo
3+In the airtight container of the aqueous solution with 80-150 ℃ Temperature Treatment 4-24 hour, products obtained therefrom rises to 350 ℃ with the heating rate of 2 ℃ of per minutes by room temperature behind the filtration drying, and kept 6 hours in this temperature, then rise to 530 ℃ of roastings 6 hours with the heating rate of 5 ℃ of per minutes again.
Mo based molecular sieve method for preparing catalyst of the present invention carries out the aluminum salt solution processing to carrier HZSM-5 molecular sieve before being included in and supporting active component Mo, do not compare with existing through the catalyst of this process, its methane conversion and aromatics yield all are significantly increased when preparation aromatic hydrocarbons, the carbon deposit selectivity is low and yield is low, show that molecular sieve catalyst of the present invention has high reaction activity and pyroreaction stability, prolonged service life greatly.
The specific embodiment
Embodiment 1
Take by weighing 20 grams through 700 ℃, the 0.5 hour pretreated NaZSM-5 molecular sieve of roasting (Si/Al=50), with the NH of 1M
4NO
3The aqueous solution carries out ion-exchange reactions 4 times at 80 ℃.The molecular sieve that obtains after ion-exchange is following dry 4 hours at 110 ℃.The NH that obtains
4The ZSM-5 sample slowly is warming up to 500 ℃ in air atmosphere, and keeps under this temperature 12 hours, treat that it reduces to room temperature after, grind to form powdery, make the HZSM-5 molecular screen primary powder.The former powder of HZSM-5 is warming up to 350 ℃ in air atmosphere, heating rate is 2 ℃/min, keeps under this temperature 6 hours, then rises to 530 ℃ of temperature with the heating rate of 5 ℃/min again, and roasting 6 hours makes required HZSM-5 molecular sieve.
With above-mentioned HZSM-5 molecular sieve at Al
3+Content is to carry out hot-pressing processing in the deionized water solution of 0.5mol/L, treatment conditions are: temperature range is 100 ℃, time is 10 hours, dried product has carried out preliminary treatment by following roasting mode: the heating rate with 2 ℃/min appreciates carrier 350 ℃ by room temperature, and under this temperature, kept 6 hours, then be warming up to 530 ℃ with 5 ℃/min again, roasting 6 hours.Adopt immersion process for preparing Mo/HZSM-5 (Mo wt.%=6%), maceration extract is ammonium molybdate ((NH
4)
6Mo
7O
244H
2O, AR, Shanghai chemical reagents corporation of Chinese Medicine group) aqueous solution, the product behind the dipping is dry 12h under 110 ℃, 350 ℃ of roastings 2 hours, is warming up to 530 ℃ of roastings 4 hours again, can make catalyst of the present invention thus.
The activity of such catalysts evaluation is to carry out on the quartz fixed bed reactor (directly for 8mm) in continuous-flow.Loaded catalyst is 0.2g, and reaction temperature is 973K, and air speed is 1500ml/ (g
Cata/ h).At first in air atmosphere, 773K roasting 30min then switches to He gas (10mL/min) and is warming up to 973K catalyst, and constant temperature is handled 30min.Switch to 10.5%Ar/CH again
4Unstripped gas reacts.Product separates the twin columns method that adopts, and one is the stainless steel column that is filled with TDX-01, is used for H
2, Ar, CH
4, CO, CO
2Separation; Another root is the stainless steel column of Porapak-P, is used for CH
4, product such as C2 species, benzene, toluene, naphthalene separation.The separation species of TDX-01 post enter to be furnished with thermal conductivity cell detector the gas chromatograph of (TCD) is analyzed, and the separation species of Porapak-P post enter to be furnished with hydrogen flame detector another HP-5890 gas chromatograph of (FID) is analyzed.As interior mark, is benchmark with material carbon number balance with Ar, calculates methane conversion, product selectivity (comprising the carbon distribution selectivity) and yield.
Mo/HZSM-5 catalyst with method for preparing carries out catalysis to the reaction of methane non oxidative aromatization system aromatic hydrocarbons and hydrogen, the results are shown in Table shown in 1,2.For Al is described
3+The processing of salting liquid is to the influence of catalyst performance, and table 1 has been listed the product distribution situation of two kinds of catalyst when the different reaction time.Wherein 6Mo/HZSM-5 (P) represents the catalyst that molecular sieve carrier is handled without salting liquid, and 6Mo/HZSM-5 (ST) represents the Al of carrier with 0.5M
3+Salting liquid is handled the catalyst of back preparation.Data show in the table, and when reacting 6 h, two kinds of Mo/HZSM-5 catalyst show similar methane conversion activity (being about 11%), but the distribution of product then exists bigger difference.The carbon deposit selectivity of Mo/HZSM-5 (P) catalyst is up to 32.4%, the result make methane conversion from react 6 hours 10.7% sharply be reduced to 12 hours 6.4%, the yield of aromatic hydrocarbons is reduced to 3.9% from 6.7%; The carbon deposit selectivity of Mo/HZSM-5 (ST) catalyst only is 15.2%, and the Mo/HZSM-5 (P) that handles without aluminium salt has significant reduction, and when reaction proceeds to 12 hours, the methane conversion of this catalyst and the yield of aromatic hydrocarbons maintain original level substantially.This shows Al
3+Salting liquid is handled the formation of carbon deposit on the catalyst in the course of reaction of can drawing up, and improves the reactivity and the stability of catalyst.
Table 1 6Mo/HZSM-5 catalyst is in the primary product distribution situation of differential responses time
*
| Catalyst | Methane conversion/% | Selectivity/% | Aromatics yield/% | ||||
| Benzene | Dimethylbenzene | Naphthalene | Ethane, ethene | Carbon deposit | |||
| Mo/HZSM-5 (P) a | ????10.7 | ????49.2 | ??3.0 | ??10.8 | ????4.0 | ????32.4 | ????6.7 |
| Mo/HZSM-5 (P) b | ????6.4 | ????51.6 | ??3.2 | ??6.7 | ????8.6 | ????29.7 | ????3.9 |
| Mo/HZSM-5 (ST) a | ????10.8 | ????61.7 | ??3.6 | ??14.6 | ????4.7 | ????15.2 | ????8.6 |
| Mo/HZSM-5 (ST) b | ????10.5 | ????62.5 | ??3.7 | ??13.8 | ????4.8 | ????15.1 | ????8.4 |
*Reaction condition: temperature, 973K; Pressure, 1atm; Air speed, 1500mL/g
Cata./h
a. reaction was carried out 6 hours;
b. reaction was carried out 12 hours.
P: the HZSM-5 that does not use the processing of Al salting liquid; ST: with the HZSM-5 after the Al salting liquid processing of 0.5M.
Table 2 methane is at Al
3+Dehydrogenation and aromatization result on the Mo/HZSM-5 catalyst after salting liquid is handled
*
| Reaction time (hour) | Methane conversion (%) | Benzene yield (%) | Carbon deposit yield (%) |
| ??6 | ??10.8 | ??6.66 | ??1.64 |
| ??12 | ??10.5 | ??6.56 | ??15.9 |
| ??18 | ??10.4 | ??6.55 | ??1.69 |
| ??24 | ??9.8 | ??6.23 | ??1.60 |
| ??28 | ??8.0 | ??5.06 | ??1.27 |
*Catalyst filling amount: 0.2g, reaction temperature: 700 ℃, pressure: 1atm, GHSV:1500mL/g
Cata./h
Table 2 is that methane is at Al
3+Methane dehydrogenation aromatisation result on the 6Mo/HZSM-5 catalyst after salting liquid is handled.Data show that reaction was carried out 6 hours, and methane conversion is 10.8% on the catalyst, reacts 24 hours methane conversions and still remains on about 10%, reacts 28 hours methane conversions also up to 8%, and the productive rate of benzene maintains more than 5% at this moment.In addition, it should be noted that: in the time range of The effects, the carbon deposit selectivity is consistent on the catalyst maintains lower level, and the carbon deposit yield is lower than 2%.This catalyst that processing method preparation provided by the invention is described has stronger anti-carbon deposition ability, demonstrates high reactivity and good reaction stability in the methane dehydrogenation aromatization.
Embodiment 2
The preparation method is identical with embodiment 1 Preparation of catalysts method, but catalyst is before supporting active component Mo, and carrier molecule sieve HZSM-5 carries out following processing: carrier is filling Al
3+At content is with 80 ℃ Temperature Treatment 4 hours in the airtight container of the aluminum acetate aqueous solution of 0.1mol/L, dry back gains rise to 250 ℃ with the heating rate of 1 ℃ of per minute by room temperature, and kept 4 hours in this temperature, then rise to 500 ℃ of roastings 4 hours with the heating rate of 4 ℃ of per minutes again.
Embodiment 3
The preparation method is identical with embodiment 1 Preparation of catalysts method, but catalyst carrier molecule sieve HZSM-5 before supporting active component Mo carries out following processing: carrier is filling Al
3+At content is with 150 ℃ temperature drying 24 hours in the aluminium oxide aqueous solution of 1.0mol/L, dry back gains rise to 400 ℃ with the heating rate of 3 ℃ of per minutes by room temperature, and kept 8 hours in this temperature, then rise to 600 ℃ of roastings 8 hours with the heating rate of 10 ℃ of per minutes again.
Claims (6)
1. Mo based molecular sieve catalyst, comprise carrier HZSM-5 and active component Mo, described active component Mo accounts for described catalyst total amount 4-8% (weight ratio, down together), the Si/Al of described carrier HZSM-5 is 25-50, it is characterized in that: described carrier is filling the Al that content is 0.1～1.0mol/l
3+In the airtight container of the aqueous solution with 80-150 ℃ Temperature Treatment 4-24 hour, products therefrom rises to 250-400 ℃ with per minute 1-3 ℃ heating rate by room temperature behind the filtration drying, and kept 4-8 hour in this temperature, then rise to 500-600 ℃ of roasting 4-8 hour with per minute 4-10 ℃ heating rate again; Support the Mo of 4-8% after the described carrier roasting, rise to 300-400 ℃ with per minute 1-2 ℃ heating rate then, and kept 1-4 hour, rise to 500-550 ℃, roasting 2-10 hour with per minute 5-10 ℃ heating rate again in this temperature.
2. catalyst according to claim 1 is characterized in that: described carrier is filling the Al that content is 0.5～0.8mol/l
3+In the airtight container of the aqueous solution with 100 ℃ Temperature Treatment 10 hours, products therefrom rises to 350 ℃ with the heating rate of 2 ℃ of per minutes by room temperature behind the filtration drying, and kept 4-8 hour in this temperature, then rise to 530 ℃ of roastings 4 hours with the heating rate of 5 ℃ of per minutes again; Support the Mo (weight ratio) of 4-8% after the described carrier roasting, the heating rate with 2 ℃ of per minutes rises to 350 ℃ then, and keeps 2 hours in this temperature, and the heating rate with 5 ℃ of per minutes rises to 500 ℃ again, roasting 4 hours.
3. catalyst according to claim 1 is characterized in that described aluminum saline solution is a kind of in aluminum nitrate, aluminum acetate, the aluminium oxide aqueous solution.
4. catalyst according to claim 1 is characterized in that described supported carrier Mo adopts a kind of in infusion process, solid reaction process and the mechanical mixing.
5. method for preparing Mo based molecular sieve catalyst, carry out according to the following steps:
(1) carrier HZSM-5 molecular sieve is being filled the Al that content is 0.1～1.0mol/l
3+In the airtight container of the aqueous solution with 80-150 ℃ Temperature Treatment 4-24 hour, products obtained therefrom rises to 250-400 ℃ with per minute 1-3 ℃ heating rate by room temperature behind the dry filter, and kept 4-8 hour in this temperature, then rise to 500-600 ℃ of roasting 4-8 hour with per minute 4-10 ℃ heating rate again;
(2) with the Mo (weight ratio) of (1) gained supported carrier 4-8%;
(3) (2) gained carrier is risen to 300-400 ℃ with per minute 1-2 ℃ heating rate, and kept 1-4 hour, rise to 500-550 ℃, roasting 2-10 hour with per minute 5-10 ℃ heating rate again in this temperature.
6. preparation method according to claim 5 is characterized in that filling the Al that content is 0.5～0.8mol/L before step (1) the supported carrier Mo
3+In the airtight container of the aqueous solution with 80-150 ℃ Temperature Treatment 4-24 hour, products obtained therefrom rises to 350 ℃ with the heating rate of 2 ℃ of per minutes by room temperature behind the filtration drying, and kept 6 hours in this temperature, then rise to 530 ℃ of roastings 6 hours with the heating rate of 5 ℃ of per minutes again.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111644198A (en) * | 2020-07-06 | 2020-09-11 | 山西大学 | Coal gangue catalytic combustion catalyst, preparation method and application |
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2004
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111644198A (en) * | 2020-07-06 | 2020-09-11 | 山西大学 | Coal gangue catalytic combustion catalyst, preparation method and application |
| CN111644198B (en) * | 2020-07-06 | 2021-07-27 | 山西大学 | Coal gangue catalytic combustion catalyst, preparation method and application |
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| CN1281317C (en) | 2006-10-25 |
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