CN1254618A - Catalyst for oxygen-free aromatization of methane without carbon deposition and its preparing process - Google Patents
Catalyst for oxygen-free aromatization of methane without carbon deposition and its preparing process Download PDFInfo
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- CN1254618A CN1254618A CN 98121011 CN98121011A CN1254618A CN 1254618 A CN1254618 A CN 1254618A CN 98121011 CN98121011 CN 98121011 CN 98121011 A CN98121011 A CN 98121011A CN 1254618 A CN1254618 A CN 1254618A
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Abstract
A carbon deposit resistant catalyst for oxygen-free aromatization of methane is prepared from transition metal element in VI B family as active component (1-15 wt.%), zeolite molecular sieve as carrier and element in VI A family as assitant (0.1-10 wt.%) through drying and calcining raw powder of molecular sieve; ion exchange of carrier in solution containing ammonium ions, drying and calcining; high-temp steam treating to obtained carrier; modifying the carrier with element in VI family; immersing in solution containing transition element in VI B family; and drying and calcining obtained carrier. Its advantages are higher reaction activity and output rate of arene, stronger carbon deposit resistance, and high high-temp reaction stability.
Description
The present invention relates to methane dehydrogenation aromatized catalyst and preparation method thereof.
The methane dehydrogenation aromizing is one of effective way of Sweet natural gas comprehensive utilization.Its aromizing product such as benzene, toluene, naphthalene etc. are the important source material that organic chemical industry and meticulous organic chemical industry produce, and can directly or indirectly be used for the production of solvent, rubber, unsaturated polyester and pharmaceutical intermediate respectively, and purposes is very extensive.For its most important class of methane non oxidative aromatization catalyzer is that to include the group vib transition element be main active constituent, adds the high performance catalyst that all kinds promotor makes.Is that catalyzer is used for the methane dehydrogenation aromizing as: Chinese patent 96115372.5 with Mo/HZSM-5; Chinese patent 96115555.8 is that catalyzer is used for the methane dehydrogenation aromizing with Mo/HZRP-1.Because be reflected under 700 ℃ of high temperature and carry out, carbon deposit is serious.Influence the high-temperature stability of catalyzer, be unfavorable for the regeneration of catalyzer, cause the waste of carbon resource simultaneously.
The purpose of this invention is to provide a kind of preparation method who is used for the methane dehydrogenation aromatized catalyst.Catalyzer of preparing by this method and the described catalyzer of above-mentioned patent compare methane aromatizing higher reactive behavior and aromatics yield, stronger anti-carbon deposition ability is arranged, and have pyroreaction stability preferably.
Catalyzer provided by the invention is a catalyzer master active constituent with the group vib transition metal, and auxiliary agent is a VIA family element, and the carrier of catalyzer is a zeolite molecular sieve, surface-area 100～500m
2/ g is the best with the HZSM-5 molecular sieve wherein.
Above-mentioned group vib transition metal as active constituent is one or more elements in chromium, molybdenum, the tungsten, wherein is best with the molybdenum element.Preferable molybdenum element weight content is 1～15%.VIA family element as auxiliary agent is Si, Ge, Sn, Pb, is the best with the Si element wherein.Preferable Si element wt content is 0.1～10%.
Preparation of catalysts method provided by the present invention is that the soln using dipping technique as the soluble compound of catalyst component is supported on the carrier, it is characterized in that the steeping process strictness carries out in the following order:
1) the dry and roasting with molecular screen primary powder, dry and roasting can be carried out routinely;
2) with 1) carrier and the inorganic ammonium salt solution that make carries out cationic exchange, exchange after drying and roasting, exchange, drying and roasting can be carried out according to a conventional method;
3) to 2) prepared carrier carries out superheated vapor and handles;
4) to 3) the gained carrier carries out modification, method is to contain the solution impregnation 3 of VIA family element) and the gained carrier, dry and roasting, dry and roasting can be carried out routinely;
5) will be as the solution impregnating carrier that contains the group vib transition metal 4 of active constituent), through making the carrier that contains the group vib transition metal in dry and roasting, dry and roasting, dry and roasting can be carried out according to a conventional method.
The dipping solution that contains active ingredient in the said process, the available oxysalt of metal component, the aqueous solution of nitrate or the ammonia soln of oxide compound of containing.Common ion-exchange condition is: at every turn (0.1～3N) to molecular sieve carrier exchange 0.5～8 hour, and the exchange temperature is 30～100 ℃ of (Gu liquid/than being 2～20ml/g) with the aqueous solution of inorganic ammonium salt.After each exchange after filtration and clean.The exchange number of times is 1～8 time.Per 1～4 exchange after drying and roasting are once.Drying of the present invention was carried out under 50～150 ℃ 1～10 hour usually.Roasting process carried out under 300～800 ℃ 1～10 hour.
In the method for preparing catalyst of the present invention, its characteristics are be to improve activity of such catalysts, before the dipping group vib active ingredient, need 2) carrier that makes carries out modification with VIA family element.Wherein be best with the element silicon.
In the method for preparing catalyst of the present invention, its characteristics also are to flood before the group vib active ingredient, be to suppress the carbon deposit of catalyst surface, improve benzene selective, need 2) carrier that makes carries out high-temperature vapor and handles.Treatment time is 0.5～20 hour, and treatment temp is 300～800 ℃, and steam partial pressure is 100～1520mmHg.Oven dry afterwards.
Catalyzer of the present invention is used for the methane dehydrogenation aromatization, and reaction conditions is: 500～900 ℃ of temperature of reaction, reaction pressure normal pressure～1MPa, methane air speed 1h
-1Below by example technology of the present invention is described further.
Example 1
Catalyzer " A " consists of 4%Mo-0.8%Si and is supported on the HZSM-5 molecular sieve, and molecular sieve is the process steam treatment before using.The preparation method is as follows:
(1) processing of the former powder of ZSM-5
With the former powder of ZMS-5 in 100 ℃ of dryings 4 hours, 550 ℃ of roastings 6 hours under the air atmosphere in retort furnace.
(2) preparation of HZSM-5
(1) gained carrier is placed the ion-exchange bottle, pour the 1N ammonium nitrate solution (liquid-solid ratio is 10ml/g) for preparing into the exchange bottle, stir, be warming up to 90 ℃, kept 4 hours, then the elimination mother liquor, with the washed with de-ionized water filter cake, carry out the exchange second time afterwards.For the second time after the exchange after filtration, clean, filter cake in 110 ℃ dry 4 hours down, the following 550 ℃ of roastings of air atmosphere 4 hours.
(3) steam of HZSM-5 is handled
The carrier that (2) make is handled 550 ℃ of treatment temps, treatment time 6hr, steam partial pressure 290mmHg with high-temperature vapor.
(4) preparation of 0.8%Si/HZSM-5
A certain amount of carrier (3) places the dipping bottle, with prepare the tetraethyl silicate resin that is equivalent to 0.8%Si content cyclohexane solution (with the volume ratio of carrier be 1.4: 1) put into carrier fast, stir and made dipping evenly in 0.5 hour, room temperature left standstill 12 hours then, 110 ℃ of dryings 4 hours, 550 ℃ of roastings are 6 hours in the air atmosphere.
(5) preparation of 4%Mo-0.8%Si/HZSM-5
A certain amount of carrier (4) places the dipping bottle, will prepare (the NH that is equivalent to 4%Mo content
4)
6Mo
7O
244H
2O solution (with the volume ratio of carrier be 1.4: 1) put into carrier fast, stir and made dipping in 0.5 hour evenly, room temperature left standstill 12 hours then, 110 ℃ of dryings 4 hours, 550 ℃ of roastings are 6 hours in the air atmosphere.The reactivity worth such as the table 1 of catalyzer " A ".
The reactivity worth reaction time methane conversion carbon deposit selective aromatics yield (min) of table 1 Methane dehydro aromatization is (mol%) (mol%) 60 11.41 11.65 10.08 120 10.67 9.83 9.62 180 10.29 10.26 9.23 240 10.07 9.01 9.16 300 9.74 9.68 8.80 360 9.51 9.49 8.61 (mol%)
Reaction conditions: 700 ℃ of reaction pressure normal pressures of temperature of reaction WHSV=1h
-1
Example 2
Catalyzer " B " consists of 1%Mo-3.2%Si/HZSM-5, and preparation process is identical with " A ", just each component loading difference.
The reactivity worth such as the table 2 of catalyzer " B ".
(mol%) (mol%) (mol%) for the yield (min) of the reactivity worth reaction times methane conversion carbon deposit selectivity benzene of table 2 methane dehydrogenation aromizing
15 9.71 31.08 6.69
60 7.63 21.72 5.97
120 6.49 19.26 5.24
180 5.76 18.34 4.70
240 5.52 19.17 4.46
Reaction conditions: 700 ℃ of reaction pressure normal pressures of temperature of reaction WHSV=1h
-1
Comparative example 1
Catalyzer " C " consist of 4%Mo/HZSM-5, do not carry out the silicon modification, carrier is handled without steam, other preparation process is identical with catalyzer " A ".Catalyzer " D " consist of 4% Mo-0.8% Si/HZSM-5, carrier is handled without steam, other preparation process is identical with catalyzer " A ", catalyzer " C " is compared as follows with the methane dehydrogenation aromatization performance of " D ":
Methane dehydrogenation aromatization performance catalyst reaction time (min) of table 3 catalyzer " C " and " D "
The yield (mol%) 5.66 6.21 6.08 5.86 5.69 5.67 of 11.64 11.73 11.25 10.53 10.12 10.00 doses of D benzene of 60 120 180 240 300 360 catalytic methane transformation efficiencys (mol%)
The yield (mol%) 5.36 5.35 5.45 5.36 5.26 5.06 of 11.09 11.08 10.30 9.77 9.60 9.47 doses of C benzene of aromatics yield (mol%) 8.60 8.69 8.27 7.86 7.46 7.29 catalytic methane transformation efficiencys (mol%)
Aromatics yield (mol%) 8.84 8.59 8.10 7.60 7.44 7.15
Reaction conditions: 700 ℃ of reaction pressure normal pressures of temperature of reaction WHSV=1h
-1
Comparative example 2
Catalyzer " F " consist of 4%Mo/HZSM-5, carrier is handled through steam, does not carry out the silicon modification, other preparation method and treating processes are identical with catalyzer " A ".Catalyzer " A " is compared as follows with the aromatization performance of " F ":
Methane dehydrogenation aromatization performance catalyst reaction time (min) of table 4 catalyzer " A " and " F "
The yield (mol%) 6.29 6.51 6.48 6.58 6.39 of 11.41 10.67 10.29 10.07 9.74 doses of A benzene of 60 120 180 240 300 catalytic methane transformation efficiencys (mol%)
The yield (mol%) 6.19 6.17 6.01 5.99 5.93 of 11.37 10.17 9.50 9.16 9.08 doses of F benzene of aromatics yield (mol%) 10.08 9.62 9.23 9.16 8.80 catalytic methane transformation efficiencys (mol%)
Aromatics yield (mol%) 9.73 8.70 8.16 7.96 7.70
Reaction conditions: 700 ℃ of reaction pressure normal pressures of temperature of reaction WHSV=1h
-1
Comparative example 3
Catalyzer " C " consist of 4%Mo/HZSM-5, carrier does not pass through steam treatment, catalyzer " F " is formed identical with " C ", but carrier is through the steam processing, other preparation process is identical.Catalyzer " C " is compared as follows with the methane dehydrogenation aromatization performance and the carbon deposit performance of " F ":
Methane dehydrogenation aromizing performance catalyst reaction time (min) of table 5 catalyzer " C " and " F "
60 120 180 240 300 360 11.09 11.08 10.30 9.77 9.60 9.47 doses of C aromatics yields of catalytic methane transformation efficiency (mol%) (mol%) 8.84 8.59 8.10 7.60 7.44 7.15
Carbon deposit selectivity (mol%) 16.47 19.04 17.35 17.98 18.00 20.03 11.37 10.14 9.50 9.16 9.08 8.80 doses of F aromatics yields of catalytic methane transformation efficiency (mol%) (mol%) 9.73 8.70 8.16 7.96 7.70 7.42
Carbon deposit selectivity (mol%) 11.32 8.90 9.35 8.60 10.48 9.19
Reaction conditions: 700 ℃ of reaction pressure normal pressures of temperature of reaction WHSV=1h
-1Comparative example 4 catalyzer " D " are compared as follows with the methane dehydrogenation aromizing performance and the carbon deposit performance of " A ":
Methane dehydrogenation aromizing performance catalyst reaction time (min) of table 6 catalyzer " D " and " A "
The yield (mol%) 10.08 9.62 9.23 9.16 8.80 8.61 of 11.41 10.67 10.29 10.07 9.74 9.51 doses of A benzene of 60 120 180 240 300 360 catalytic methane transformation efficiencys (mol%)
The yield (mol%) 8.60 8.69 8.27 7.86 7.49 7.29 of 11.64 11.73 11.25 10.53 10.12 10.00 doses of D benzene of aromatics yield (mol%) 11.65 9.83 10.26 9.01 9.68 9.49 catalytic methane transformation efficiencys (mol%)
Aromatics yield (mol%) 22.66 22.64 22.45 21.96 22.51 23.13
Reaction conditions: 700 ℃ of reaction pressure normal pressures of temperature of reaction WHSV=1h
-1Comparative example 5 catalyzer " C " are compared as follows with " F " methane aromatizing activity and stability under 750 ℃ of high temperature:
Methane dehydrogenation aromatization performance catalyst reaction time (min) of table 7 catalyzer " C " and " F "
The yield (mol%) 12.03 11.01 8.78 7.50 5.95 of 18.92 17.57 14.55 12.66 10.57 doses of C benzene of 60 120 240 360 480 catalytic methane transformation efficiencys (mol%)
Yield (mol%) 11.86 10.78 9.53 8.56 7.86 aromatics yields (mol%) 20.44 18.74 18.36 19.48 19.58 of 15.44 13.99 12.38 11.53 10.77 doses of F benzene of aromatics yield (mol%) 33.73 33.44 34.49 34.10 35.08 catalytic methane transformation efficiencys (mol%)
Reaction conditions: 700 ℃ of reaction pressure normal pressures of temperature of reaction WHSV=1h
-1
By above-mentioned sample result explanation, in this experiment institute investigation scope, catalyzer all is improved to the activity and the selectivity of methane aromatizing: to handle the pyroreaction stability that can obviously suppress carbon deposit and improve catalyzer by steam by the silicon modification.Adopt the catalyzer of the inventive method preparation that the methane dehydrogenation aromizing is had active height, carbon deposit is less, advantages such as pyroreaction good stability.
Claims (10)
1. catalyst for oxygen-free aromatization of methane without carbon deposition, form by carrier and active constituent, carrier is a zeolite molecular sieve, active constituent is selected from chromium, molybdenum, the tungsten one or more for the group vib transition metal, it is characterized in that: with VIA family elements Si, Ge, Sn, a kind of of Pb is auxiliary agent, and the active ingredient weight content is
Main active ingredient 1～15%
Auxiliary agent 0.1～10%.
2. by the described catalyst for oxygen-free aromatization of methane without carbon deposition of claim 1, it is characterized in that: main active ingredient is Mo.
3. by the described catalyst for oxygen-free aromatization of methane without carbon deposition of claim 1, it is characterized in that: auxiliary agent is Si.
4. by the described catalyst for oxygen-free aromatization of methane without carbon deposition of claim 1, it is characterized in that: carrier is the HXSM-5 molecular sieve.
5. the preparation method of the described catalyst for oxygen-free aromatization of methane without carbon deposition of claim 1, it is characterized in that: catalyst preparation process is undertaken by following step
1) the dry and roasting with molecular screen primary powder;
2) carrier is carried out ion-exchange, drying and roasting with the solution that contains ammonium ion;
3) to 2) carrier of gained carries out high-temperature vapor and handles:
4) to 3) to carry out VI family element modified for the carrier of gained;
5) at last with the solution impregnation 4 that contains the group vib transition element) gained carrier, drying and roasting.
6. by the preparation method of the described anti-carbon methane catalyst for dehydroaromatizationof of claim 5, it is characterized in that: water temperature treatment condition described 3) are: 0.5～20 hour treatment time, 300～800 ℃ of treatment temps, steam partial pressure 100～1520mmHg.
7. by the preparation method of the described anti-carbon methane catalyst for dehydroaromatizationof of claim 5, it is characterized in that: steeping fluid described 4) is the oxysalt that contains metal component, the aqueous solution of nitrate or the ammonia soln of oxide compound.
8. press the preparation method of the described anti-carbon methane catalyst for dehydroaromatizationof of claim 5, it is characterized in that: give-and-take conditions described 2) exchange 0.5～8 hour for the each aqueous solution 0.1～3N with inorganic ammonium salt to molecular sieve carrier, the exchange temperature is 30～100 ℃, Gu liquid/than being 2～20ml/g; After filtration and clean, the exchange number of times is 1～8 time after each exchange, and per 1～4 exchange after drying and roasting are once.
9. by the preparation method of claim 5,6,7 or 8 described anti-carbon methane catalyst for dehydroaromatizationof, it is characterized in that: dry under 50～150 ℃, carrying out 1～10 hour.
10. by the preparation method of the described anti-carbon methane catalyst for dehydroaromatizationof of claim 5, it is characterized in that: roasting process carried out under 300～800 ℃ 1～10 hour.
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| CNB981210112A CN1133496C (en) | 1998-11-25 | 1998-11-25 | Catalyst for oxygen-free aromatization of methane without carbon deposition and its preparing process |
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| CN1133496C CN1133496C (en) | 2004-01-07 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104907091A (en) * | 2014-03-13 | 2015-09-16 | 上海碧科清洁能源技术有限公司 | Catalyst used for preparing aromatic hydrocarbons by methanol, preparation method and application thereof |
| CN113710361A (en) * | 2019-05-20 | 2021-11-26 | 庄信万丰股份有限公司 | Catalyst preparation method |
-
1998
- 1998-11-25 CN CNB981210112A patent/CN1133496C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104907091A (en) * | 2014-03-13 | 2015-09-16 | 上海碧科清洁能源技术有限公司 | Catalyst used for preparing aromatic hydrocarbons by methanol, preparation method and application thereof |
| CN113710361A (en) * | 2019-05-20 | 2021-11-26 | 庄信万丰股份有限公司 | Catalyst preparation method |
| CN113710361B (en) * | 2019-05-20 | 2023-09-26 | 庄信万丰股份有限公司 | Catalyst preparation method |
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| CN1133496C (en) | 2004-01-07 |
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