CN1093431C - Catalyst for aromatizing low-carbon paraffin and its preparing process - Google Patents
Catalyst for aromatizing low-carbon paraffin and its preparing process Download PDFInfo
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- CN1093431C CN1093431C CN98121013A CN98121013A CN1093431C CN 1093431 C CN1093431 C CN 1093431C CN 98121013 A CN98121013 A CN 98121013A CN 98121013 A CN98121013 A CN 98121013A CN 1093431 C CN1093431 C CN 1093431C
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Abstract
The present invention relates to a catalyst for dehydrogenating and aromatizing low-carbon paraffin, which comprises 0.2 to 15 wt% of a transition metal in the sixth subgroup as a main active component, zeolite molecular sieve as a carrier and 0.1 to 10 wt% of halogen-group element as a modifying agent. A preparation process comprises the following procedures: 1) drying and calcining the initial powder of the molecular sieve; 2) carrying out ion exchanging on the carrier with a solution containing ammonium ions, drying and calcining; 3) immersing the carrier obtained by procedure 2) with a solution containing the transition element in the sixth subgroup, drying and calcining; 4) immersing the carrier obtained by procedure 3) with a solution containing the halogen-family element, drying and calcining. The catalyst has strong carbon deposit resistance, high benzene selectivity, and high activity for aromatizing propane.
Description
The present invention relates to low-carbon alkanes (C
1-C
3) catalyst for dehydroaromatizationof and preparation method.
Aromatizing low-carbon paraffin is the effective ways that improve the low-carbon alkanes value, is one of effective way of carbon resource optimization comprehensive utilization.Its aromatisation product such as benzene, toluene, naphthalene etc. are the important source material that organic chemical industry and meticulous organic chemical industry produce, and can distinguish the production of directly or indirectly using flux, rubber, unsaturated polyester (UP) and pharmaceutical intermediate etc., and purposes is very extensive.For its most important class of methane non oxidative aromatization catalyst is that to include the group vib transition elements be main active constituent, adds the high performance catalyst that all kinds co-catalyst makes.Is that catalyst is used for the methane dehydrogenation aromatisation as: Chinese patent 96115372.5 with Mo/HZSM-5; Chinese patent 96115555.8 is used for the methane dehydrogenation aromatisation with the Mo/HZRP-1 catalyst.Because be reflected under 700 ℃ of high temperature and carry out, the carbon deposit of catalyst is more serious, influences the high-temperature stability of catalyst, is unfavorable for the regeneration of catalyst, causes the waste of carbon resource simultaneously.
The purpose of this invention is to provide a kind of preparation method who is used for catalyst for aromatizing low-carbon paraffin.The catalyst of preparing by this method has stronger anti-carbon deposition ability and the benzene selective of Geng Gao to methane aromatizing, and this catalyst also has active preferably to propane aromatization simultaneously.
Catalyst provided by the invention is a catalyst master active constituent with the group vib transition metal, and adding halogen is the modification component, and the carrier of catalyst is a zeolite molecular sieve, surface area 100～500m
2/ g is the best with the HSZM-5 molecular sieve wherein.The kind component weight content of catalyst is (weight with carrier is that benchmark calculates): group vib master active constituent: 0.2～15%; Halogen: 0.1～10%.
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%.Nonmetalloid modifier halogen is F, Cl, Br or I in the catalyst, wherein is best with Cl.
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 dipping process strictness carries out in the following order:
2) 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 cation exchange, the dry and roasting in exchange back, exchange, drying and roasting can be carried out according to a conventional method;
3) will be as the solution impregnating carrier that contains the group vib transition metal 2 of active constituent), drying and roasting make the carrier that contains the group vib transition metal, and dry and roasting can be carried out according to a conventional method;
4) with containing the solution impregnation 3 of halogen family element) carrier that makes, make catalyst after drying and the roasting, dry and roasting can be carried out routinely;
5) under certain atmosphere to 4) the gained catalyst reduces.
The dipping solution that contains active component in the said process, the available oxysalt of metal component, the aqueous solution of nitrate or the ammonia spirit of oxide of containing.Halogen can be with its corresponding salt and acid, but best halogen maceration extract is a hydrochloric acid.Common give-and-take conditions are that 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 back drying and roasting are once.Drying was carried out under 50～150 ℃ 1～10 hour usually among the present invention.Roasting process carried out under 300～800 ℃ 1～10 hour.
In the method for preparing catalyst of the present invention, after its characteristics are to flood the group vib active component,, improve benzene selective, need to flood with hydrochloric acid solution for suppressing the carbon deposit of catalyst surface.The weight content of chlorine element is 0.1～10%.Dry then and roasting makes catalyst.
Catalyst of the present invention is used for the methane dehydrogenation aromatization, and reaction condition is: 400～900 ℃ of reaction temperatures, reaction pressure normal pressure～1MPa, methane air speed 1h
-1
Another characteristics of catalyst of the present invention are, this catalyst is carried out prereduction with the gas that contains lower carbon number hydrocarbons after, have better activity for the dehydrogenating propane aromatization.Reducing gas can be in methane, ethane, propane, butane, the hydrogen one or more.Common reducing condition is: 400～900 ℃ of reduction temperatures, the recovery time is 0.5～6 hour.Promptly can be used for the propane aromatization reaction after the reduction, its reaction condition is: 400～700 ℃ of reaction temperatures, reaction pressure normal pressure～1MPa, propane air speed WHSV=3h
-1
Below by example technology of the present invention is described further.
Example 1
Catalyst " A " consists of 4%Mo and 1.5%Cl is supported on the HZSM-5 molecular sieve.The preparation method is as follows:
(1) processing of the former powder of ZSM-5
With the former powder of ZSM-5 in 110 ℃ of dryings 4 hours, 550 ℃ of roastings 6 hours under the air atmosphere in Muffle 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) preparation of 4%Mo/HZSM-5
A certain amount of carrier (2) places the dipping bottle, will prepare (the NH that is equivalent to 0.4%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.
(4) preparation of 4%Mo-1.5% Cl/HZSM-5
4%Mo/HZSM-5 is placed dipping bottle, with prepare the hydrochloric acid solution that is equivalent to 1.5% content (with the volume ratio of carrier be 1.4: 1) put into 4%Mo/HZSM-5 fast, stirs and made dipping even in 0.5 hour.110 ℃ of dryings 4 hours, 550 ℃ of roastings are 6 hours in the air atmosphere.
The reactivity worth such as the table 1 of catalyst A.
The table 1 Methane dehydro aromatization reactivity worth reaction time selective benzene yield of methane conversion benzene selective carbon deposit (min) is (mol%) (mol%) (mol%) 60 9.78 59.75 15.74 5.84120 9.59 63.71 13.33 6.11180 9.18 67.17 13.26 6.17240 8.97 66.89 13.32 6.00300 8.78 66.32 13.27 5.82360 8.77 65.04 13.49 5.70 (mol%)
Reaction condition: 700 ℃ of reaction pressure normal pressures of reaction temperature WHSV=1h
-1Example 2 catalyst " B " consist of 3%Mo-1.1% Cl/HZSM-5, and its preparation process is identical with " A ".The methane aromatization performance such as the table 2 of catalyst " B ".
(mol%) (mol%) (mol%) for table 2 methane dehydrogenation aromatization performance reaction time methane conversion carbon deposit selectivity benzene yield (min)
60 9.58 12.03 5.37
120 8.84 10.43 5.44
180 8.85 10.02 5.91
240 8.61 10.33 5.81
300 8.35 10.57 5.64
360 7.48 11.01 5.09
Reaction condition: 700 ℃ of reaction pressure normal pressures of reaction temperature WHSV=1h
-1
Comparative example 1
The main active constituent of catalyst " C " is identical with catalyst " A ", but does not flood the chlorine element, and other composition and preparation process are identical with " A ", and its methane dehydrogenation aromatization performance is relatively as table 3.
The methane dehydrogenation aromatization performance of table 3 catalyst " A " and " C "
The catalyst reaction time (min)
60 120 180 240 300 360
Catalytic methane conversion ratio (mol%) 9.78 9.59 9.18 8.97 8.78 8.77
Agent A benzene selective (mol%) 59.75 63.71 67.17 66.89 66.32 65.04
Carbon deposit selectivity (mol%) 15.74 13.33 13.26 13.32 13.27 13.49
Benzene yield (mol%) 5.84 6.11 6.17 6.00 5.82 5.70
Catalytic methane conversion ratio (mol%) 11.09 11.08 10.30 9.77 9.60 9.47
Agent C benzene selective (mol%) 48.20 48.33 52.87 54.90 54.84 53.42
Carbon deposit selectivity (mol%) 16.47 19.04 17.35 17.98 18.00 20.03
Benzene yield (mol%) 5.36 5.35 5.45 5.36 5.26 5.06
Reaction condition: 700 ℃ of reaction pressure normal pressures of reaction temperature WHSV=1h
-1
Comparative example 2
The main active constituent of catalyst " D " is identical with catalyst " B ", but does not flood the chlorine element, and its methane dehydrogenation aromatization performance is relatively if any 4.
Methane dehydrogenation aromatization performance catalyst reaction time (min) of table 4 catalyst " B " and " D "
60 120 180 240 300
Catalytic methane conversion ratio (mol%) 9.58 8.84 8.85 8.61 8.35
Agent B benzene selective (mol%) 12.03 10.43 10.02 10.33 10.57
Carbon deposit selectivity (mol%) 56.05 61.49 66.73 67.47 67.50
Benzene yield (mol%) 5.37 5.44 5.91 5.81 5.64
Catalytic methane conversion ratio (mol%) 11.26 10.21 9.41 9.39 8.90
Agent D benzene selective (mol%) 18.47 19.20 19.04 18.39 19.95
Carbon deposit selectivity (mol%) 48.03 55.19 57.20 55.81 56.97
Benzene yield (mol%) 5.41 5.64 5.38 5.24 5.07
Reaction condition: 700 ℃ of reaction pressure normal pressures of reaction temperature WHSV=1h
-1
Comparative example 1 shows that with the result of comparative example 2 dipping chlorine element can obviously suppress carbon deposit, improves the selectivity of benzene.
Comparative example 3
Catalyst " E " is formed identical with catalyst " C ", is to make in 1 hour through methane reduction in 700 ℃ on the basis of catalyst " C ".Catalyst " E " compares as table 5 with the propane aromatization performance of catalyst " C ".
Methane dehydrogenation aromatization performance catalyst reaction time (min) of table 5 catalyst " C " and " E "
15 80 140 200 260 12.82 13.92 13.13 12.31 10.40 doses of C arenes selectivities of catalysis conversion of propane (mol%) (mol%) 26.14 27.88 27.51 27.24 28.08
The yield of aromatic hydrocarbons (mol%) 3.35 3.88 3.61 3.35 2.92
Catalysis conversion of propane (mol%) 38.46 29.77 25.83 23.63 22.63
Agent E arenes selectivity (mol%) 35.93 37.36 36.78 37.16 37.16
The yield of aromatic hydrocarbons (mol%) 13.82 11.12 9.50 8.78 8.41
Reaction condition: 500 ℃ of reaction pressure normal pressures of reaction temperature WHSV=3h
-1
Comparative example 4
Catalyst " F " is identical with catalyst " A " composition, is to make in 1 hour through methane reduction in 700 ℃ on the basis of catalyst " A ".Catalyst " F " compares as table 6 with the propane aromatization reactivity worth of catalyst " A ".
The methane dehydrogenation aromatization performance of table 6 catalyst " F " and " A "
The catalyst reaction time (min)
15 80 140 200 260
Catalysis conversion of propane (mol%) 14.71 13.46 13.97 12.49 10.98
Agent A arenes selectivity (mol%) 25.09 28.94 29.74 28.35 29.61
The yield of aromatic hydrocarbons (mol%) 3.69 3.90 4.15 3.54 3.25
Catalysis conversion of propane (mol%) 36.31 28.16 26.73 24.78 22.45
Agent F arenes selectivity (mol%) 37.79 38.91 37.40 36.76 37.53
The yield of aromatic hydrocarbons (mol%) 13.72 10.96 10.00 9.12 8.43
Reaction condition: 500 ℃ of reaction pressure normal pressures of reaction temperature WHSV=3h
-1
By the explanation of above-mentioned sample result, adopt catalyst that the inventive method provides that the methane dehydrogenation aromatisation is had advantages such as benzene selective height, carbon deposit are few, can effectively prevent the waste of carbon resource.This catalyst arenes selectivity and activity to the dehydrogenating propane aromatization after reducing all obviously improves simultaneously.
Claims (9)
1. a dehydrogenating low-carbon alkane aromatized catalyst is made up of carrier and active component, and main active component is selected from chromium, molybdenum, the tungsten one or more for the group vib filtering metal, and carrier is a zeolite molecular sieve, and surface area is 100～500m
2/ g is characterized in that with the halogen being modifier, is benchmark with the weight of carrier, and each active component weight percentage is:
Group vib master active ingredient 0.2-15%
Halogen 0.1-10%.
2. by the described dehydrogenating low-carbon alkane aromatized catalyst of claim 1, it is characterized in that main active ingredient is Mo, content is 1～15%.
3. by the described dehydrogenating low-carbon alkane aromatized catalyst of claim 1, it is characterized in that halogen is Cl.
4. by the described dehydrogenating low-carbon alkane aromatized catalyst of claim 1, it is characterized in that carrier is the HZSM-5 molecular sieve.
5. the preparation method of the described dehydrogenating low-carbon alkane aromatized catalyst of claim 1 is characterized in that preparation process 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) with containing the solution impregnation 2 of group vib transition elements) carrier of gained, drying and roasting;
4) with the solution impregnation 3 that contains the halogen family element) gained carrier, drying and roasting.
6. by the preparation method of the described dehydrogenating low-carbon alkane aromatized catalyst of claim 5, it is characterized in that 5-3) described in the solution that contains the group vib transition elements be the ammonia spirit that contains the oxysalt aqueous solution of this family's element or contain the oxide of this family's element.
7. by the preparation method of the described dehydrogenating low-carbon alkane aromatized catalyst of claim 5, it is characterized in that described 4) in the maceration extract of halogen with its corresponding acid or salt.
8. by the preparation method of the described dehydrogenating low-carbon alkane aromatized catalyst of claim 7, it is characterized in that maceration extract hydrochloric acid.
9. press the preparation method of the described dehydrogenating low-carbon alkane aromatized catalyst of claim 5, it is characterized in that described 2) at every turn with the aqueous solution of the inorganic ammonium salt of 0.1～3N to molecular sieve carrier exchange 0.5～8 hour, 30～100 ℃ of exchange temperature, Gu liquid/than being 2～20ml/g; After each exchange after filtration and clean; The exchange number of times is 1～8 time, and per 1～4 exchange back drying and roasting are once.
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| Application Number | Priority Date | Filing Date | Title |
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| CN98121013A CN1093431C (en) | 1998-11-25 | 1998-11-25 | Catalyst for aromatizing low-carbon paraffin and its preparing process |
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|---|---|---|---|
| CN98121013A CN1093431C (en) | 1998-11-25 | 1998-11-25 | Catalyst for aromatizing low-carbon paraffin and its preparing process |
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| CN1093431C true CN1093431C (en) | 2002-10-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100446840C (en) * | 2003-06-26 | 2008-12-31 | 3M创新有限公司 | Broad spectrum filter system including tungsten-based impregnant and being useful for filtering contaminants from air or other gases |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921453B (en) * | 2012-10-25 | 2014-10-29 | 浙江工业大学 | Method for preparing methane non-oxidative aromatization catalyst at low temperature |
| CN103182318A (en) * | 2013-03-06 | 2013-07-03 | 新疆大学 | Activation method of catalyst for oxygen-free aromatization of low-carbon hydrocarbons |
| CN109833903A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of low-carbon alkanes anaerobic dehydrogenation alkene catalyst and its preparation and application |
| CN109569719B (en) * | 2018-12-29 | 2021-08-13 | 中国科学院上海高等研究院 | Carbon-based catalyst for light alkane aromatization and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4814543A (en) * | 1987-12-28 | 1989-03-21 | Mobil Oil Corporation | Nitrogen resistant paraffin hydroisomerization catalysts |
| CN1073198A (en) * | 1991-12-12 | 1993-06-16 | 中国石油化工总公司石油化工科学研究院 | Catalyst for dehydroaromatizationof of alkane and preparation method |
| US5264648A (en) * | 1989-07-19 | 1993-11-23 | Compania Espanola De Petroleos, S.A.--CEPSA | Process for the obtainment of a light paraffin isomerization catalyst |
| CN1167653A (en) * | 1996-06-12 | 1997-12-17 | 中国科学院大连化学物理研究所 | Molybdenum zeolite catalyst for preparation of ethene and aromatic hydrocarbon by oxygen-free dehydrogenation of methane and its use |
-
1998
- 1998-11-25 CN CN98121013A patent/CN1093431C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4814543A (en) * | 1987-12-28 | 1989-03-21 | Mobil Oil Corporation | Nitrogen resistant paraffin hydroisomerization catalysts |
| US5264648A (en) * | 1989-07-19 | 1993-11-23 | Compania Espanola De Petroleos, S.A.--CEPSA | Process for the obtainment of a light paraffin isomerization catalyst |
| CN1073198A (en) * | 1991-12-12 | 1993-06-16 | 中国石油化工总公司石油化工科学研究院 | Catalyst for dehydroaromatizationof of alkane and preparation method |
| CN1167653A (en) * | 1996-06-12 | 1997-12-17 | 中国科学院大连化学物理研究所 | Molybdenum zeolite catalyst for preparation of ethene and aromatic hydrocarbon by oxygen-free dehydrogenation of methane and its use |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100446840C (en) * | 2003-06-26 | 2008-12-31 | 3M创新有限公司 | Broad spectrum filter system including tungsten-based impregnant and being useful for filtering contaminants from air or other gases |
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