CN1058909C - Catalyst for dehydrogenating aromatization of methane under non-oxydation condition - Google Patents
Catalyst for dehydrogenating aromatization of methane under non-oxydation condition Download PDFInfo
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- CN1058909C CN1058909C CN97100978A CN97100978A CN1058909C CN 1058909 C CN1058909 C CN 1058909C CN 97100978 A CN97100978 A CN 97100978A CN 97100978 A CN97100978 A CN 97100978A CN 1058909 C CN1058909 C CN 1058909C
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Abstract
A catalyst for dehydrogenating aromatization of methane under the non-oxydation condition relates to a supported catalyst for preparing aromatic hydrocarbons by catalytically dehydrogenating aromatization of methane. The catalyst has a general formula: SO4<2->-MoO4<2->-AOx/HZSM-5, an HZSM-5 molecular sieve is used as a carrier and AOx is the oxide of transition metals including Zn, Co, Ni, Cu, and the like, and the catalyst comprises the components by weight percentage: 0.5 to 10% of AOx, 0.5 to 8% of SO4<2->, 1.5 to 12% of MoO4<2-> and HZSM-5 as the balance. The catalyst has high activity and high selectivity in catalytically dehydrogenating aromatization of methane under the non-oxydation condition. The conversion rate of methane reaches 21 to 22%, the selectivity of benzene reaches 92%, and the selectivity of toluene reaches 5%. Therefore, the catalyst has perfect prospects of industrial application.
Description
The present invention relates to a kind of methyl hydride catalyzed dehydroaromatizationof system aromatic hydrocarbons loaded catalyst.
In recent years, the research of catalytic dehydrogenation aromatization aspect was reported to some extent under the relevant non-oxide condition of methane both at home and abroad, but quantity is few.Some scholar's handle has supported Pd, Pt, and Re, Mo even load type catalyst is used for methane catalytic cracking aromatic hydrocarbons under the nonoxidizing atmosphere, obtained some significative results, but aromatics yield is lower.U.S. Pat 4507517 (1985) discloses and has adopted the BN catalyst to carry out the reaction of the synthetic aromatic hydrocarbons of catalysis under the non-oxide condition of methane, obtains the aromatic product of low yield.(IZV, Aked, Nauks SSR such as Soviet Union scholar Bragin, Ser Khim, 1989,750) reported and used pulse type reactor, supporting noble metal and Zn, respectively under the reaction temperature of 873K and 1023K, realizing that methane under non-oxydation condition is converted into benzene on the silica-rich zeolite type catalyst of Ga; They are at Pt-CrO
3On/the HZSM-5, reaction temperature is 1023K, and the pulse reaction methane conversion reaches 18%, and the yield of benzene is 14%.The Wang Lin of China Dalian Chemistry and Physics Institute victory waits (Catal.Lette.21 (1993) 35-41) to report methane non-oxide dehydroaromatizationof on the MoHZSM-5 catalyst, being reflected at continuous fixed bed reactor carries out, catalyst amount is 2g, granularity 10～30 orders, reaction pressure is for 200KPa, and reaction temperature is 973K, feed gas methane air speed 144ml/g-h, methane conversion is 7.2%, and the selectivity of benzene reaches 100%.
Purpose of the present invention aims to provide the catalyst of the methane under non-oxydation condition catalytic dehydrogenation aromatization system aromatic hydrocarbons of a kind of high activity, high selectivity.
The said catalyst of the present invention is SO
4 2--MoO
4 2--AOx/HZSM-5 loaded catalyst, catalyst are that the Si/Al ratio is 10～50 among the carrier HZSM-5 with the HZSM-5 molecular sieve, are preferably 18～38, AO
xBe metal oxide, A is transition metal such as Zn, Co, Ni, Cu, and the content of each component is (percentage by weight): AO in the catalyst
xBe 0.5～10%, best 1～6%, SO
4 2-Be 0.5～8%, best 1～5%, MoO
4 2-With MoO
3Reduced quantity counts 1.5～12%, and is best 2～9%, and surplus is HZSM-5.
The HZSM-5 molecular sieve can directly use commercially available product, also can pass through NaZSM-5 or NH
4The ZSM-5 molecular sieve prepares via ion-exchange.
Catalyst adopts immersion process for preparing: the proportioning of pressing each component in the catalyst at first the HZSM-5 molecular sieve carrier in the 383K preliminary treatment after 2 hours, with MoO
4 2-Solution impregnation is on the HZSM-5 molecular sieve carrier, and this material is dried by the fire in 2 hours at 383K, 673～1073K roasting 4～12 hours, the sulfate or the nitrate solution that continue A flood thereon again, in 383K oven dry 2 hours, 673～1073K roasting 4～12 hours, at last, with H
2SO
4Or the ammonium sulfate dipping, or with after the oven dry of sulfate liquor dipping, again with excessive 14N NH
4OH floods it, and then successively 383K oven dry 2 hours, 673K～1073K roasting 4～12 hours promptly gets SO
4 2--MoO
4 2--AO
x/ HZSM-5 loaded catalyst.
The non-oxide dehydroaromatizationof system aromatic hydrocarbons test of methane is carried out on atmosphere gas continuous fixed bed reactor-gas chromatograph combined system, and each test catalyst consumption is 0.6g, unstripped gas CH
4Purity 99.9%, air speed 1500ml/h-g, reaction system pressure are 120kPa, reaction temperature 973K.Methane conversion is calculated by working curve method by chromatogram analysis data and reaches 22%.Benzene selective is 92% in carbonaceous products, methylbenzene selective～5%.
Catalyst provided by the invention, can make methane be converted into aromatic hydrocarbons by non-oxide dehydroaromatizationof, this process has some original advantages, as technical less complexity, does not exist to resemble oxidizing process and be subjected to CO or N with air oxidant thereby the product brought
2The problem of dilution, primary product aromatic hydrocarbons and the CH that transforms
4And accessory substance H
2Be easy to separate, and accessory substance H
2Can be used as the required a large amount of H of oil refinery industry again
2The source.Because catalyst provided by the present invention demonstrates high methane conversion and arenes selectivity in the non-oxide conversion for preparing arene reaction of methane, have better industrial application prospect.
Further specify the present invention by embodiment below.
Embodiment 1:
To close 0.18g MoO through conversion
3Ammonium molybdate solution impregnated in 6g on 2 hours HZSM-5 molecular sieve of 383K preliminary treatment, in 383K oven dry 2 hours, 673K roasting 4 hours obtained the complex catalyst precursor thing, places drier standby.
To contain the solution of zinc sulfate of 0.04g ZnO through conversion, and impregnated in 3g on the pretreated above-mentioned complex catalyst precursor thing of 383K, in 383K oven dry 2 hours, with excessive 14N ammoniacal liquor dipping thereon, in 383K oven dry 2 hours, 673K roasting 4 hours promptly obtained SO subsequently
4 2--MoO
4 2--ZnO/HZSM-5 loaded catalyst.
The non-oxide dehydroaromatizationof system aromatic hydrocarbons test of methane is carried out on atmosphere gas continuous fixed bed reactor-gas chromatograph combined system, each test catalyst consumption is 0.6g, granularity 40～60 orders, reaction system pressure is 120KPa, air speed 1500ml/h-g, in the reaction temperature-rise period, catalyst is in N
2Under the atmosphere protection, when reaching 973K, temperature directly imports the unstripped gas CH of purity 99.9%
4, reactant and product are united by on-line gas chromatography (102GD type) thermal conductivity detector (TCD) and hydrogen flame detector and are made field assay; Chromatographic column filler is D.N.P., and 2 meters of column lengths are with N
2Be the chromatogram carrier gas.Experimental data is taken from reaction beginning 45min system and is reached after the stable state.Methane conversion is pressed working curve method by chromatogram analysis data and is calculated X
CH4Reach 21.5%.Benzene selective is 93% in carbonaceous products, methylbenzene selective～4%.
Embodiment 2:
Improve levels of transition metals in the dipping solution, make in the ammonium molybdate solution and closed MoO through conversion
3Amount is 0.36g, and containing ZnO content through conversion in the solution of zinc sulfate is 0.05g, makes SO according to example 1 preparation procedure
4 2--MoO
4 2--ZnO/HZSM-5 loaded catalyst.
The non-oxide dehydroaromatizationof system aromatic hydrocarbons test of methane the results are shown in Table 1 with example 1.
Table 1 reaction time, (h) 123456789 10 11 12 methane conversions, (%) 20.8 22.4 22.5 22.2 21.1 20.0 19.8 20.2 19.3 18.2 18.4 18.0 benzene selectives, (C%) 93 92 91 91 90 90 89 89 89 89 88 88 methylbenzene selectives, (C%) 4.1 4.9 5.4 5.9 7.2 7.2 8.0 8.0 8.2 8.6 8.6 9.0
Embodiment 3:
Contain the molybdenum predecessor according to example 1 preparation catalyst; To contain the zinc nitrate solution of 0.03g ZnO through conversion, impregnated in 3g on 2 hours above-mentioned complex catalyst precursor thing of 383K preliminary treatment, with the material behind the dipping in 383K oven dry 2 hours, 673K roasting 4 hours, after cool to 383K, dipping contains 0.04g SO through conversion
4 2-Ammonium sulfate, the back was in 383K oven dry 2 hours, 673K roasting 4 hours obtains SO
4 2--MoO
4 2--ZnO/HZSM-5 loaded catalyst.
The non-oxide dehydroaromatizationof system aromatic hydrocarbons test of methane is with example 1, and methane conversion is 12%, and benzene selective is 87%, and methylbenzene selective is 10%.
Embodiment 4:
Contain the molybdenum predecessor according to example 1 preparation catalyst; To contain the zinc nitrate solution of 0.03g ZnO through conversion, impregnated in 3g on 2 hours above-mentioned complex catalyst precursor thing of 383K preliminary treatment, with the material behind the dipping in 383K oven dry 2 hours, 673K roasting 4 hours, after cool to 383K, dipping is to contain 0.04g SO through conversion
4 2-2N H
2SO
4Solution, the back gets SO in 383K oven dry 2 hours
4 2--MoO
4 2--ZnO/HZSM-5 loaded catalyst.
The non-oxide dehydroaromatizationof system aromatic hydrocarbons test of methane was reacted 1 hour with example 1, and corresponding methane conversion reaches 22%, and benzene selective is 94%, and methylbenzene selective is～5%.Reacted 2 hours, corresponding methane conversion reduces to 16%, benzene selective 89%, methylbenzene selective 10%.
Embodiment 5～8:
Method for preparing catalyst is with example 1.
Change the different AO that form
x, investigate the corresponding SO that makes
4 2--MoO
4 2--Ni
2O
3/ HZSM-5, SO
4 2--MoO
4 2--Co
2O
3/ HZSM-5, SO
4 2--MoO
4 2--CuO/HZSM-5, SO
4 2--MoO
4 2-The reactivity of the non-oxide dehydroaromatizationof of methane on four kinds of loaded catalysts such as-ZnO/HZSM-5.
The non-oxide dehydroaromatizationof system aromatic hydrocarbons test of methane is with example 1, and it the results are shown in table 2.
Table 2
Catalyst methane conversion ratio (%) selectivity (C%) embodiment
Benzene toluene 5 SO
4 2--MoO
4 2--Ni
2O
3/ HZSM-5 5.2～99 traces 6 SO
4 2--MoO
4 2--Co
2O
3/ HZSM-5 15.8 91 67 SO
4 2--MoO
4 2--CuO/HZSM-5 21.7 84 68 SO
4 2--MoO
4 2--ZnO/HZSM-5 22.3 93 4
Claims (3)
1. a catalyst for dehydrogenating aromatization of methane under non-oxydation condition is SO
4 2--MoO
4 2--AO
x/ HZSM-5 loaded catalyst, catalyst is a carrier with the HZSM-5 molecular sieve, the Si/Al ratio is 10～50 among the HZSM-5, AO
xTransition metal oxide for Zn, Co, Ni or Cu; The percentage by weight of the content of each component is in the catalyst: AO
xBe 0.5%～10%, SO
4 2-Be 0.5%～8%, MoO
4 2-With MoO
3Reduced quantity counts 1.5%～10%, and surplus is HZSM-5.
2. catalyst for dehydrogenating aromatization of methane under non-oxydation condition as claimed in claim 1 is characterized in that the Si/Al ratio is 18～38 in the HZSM-5 molecular sieve.
3. catalyst for dehydrogenating aromatization of methane under non-oxydation condition as claimed in claim 1 is characterized in that AO in the catalyst
xThe content weight ratio be 1%～6%, SO
4 2-Be 1%～5%, MoO
4 2-With MoO
3Reduced quantity counts 2%～9%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN97100978A CN1058909C (en) | 1997-01-16 | 1997-01-16 | Catalyst for dehydrogenating aromatization of methane under non-oxydation condition |
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| CN97100978A CN1058909C (en) | 1997-01-16 | 1997-01-16 | Catalyst for dehydrogenating aromatization of methane under non-oxydation condition |
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| CN1058909C true CN1058909C (en) | 2000-11-29 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767031B (en) * | 2009-01-07 | 2012-03-14 | 中国石油化工股份有限公司 | Low temperature conversion catalyst for partial oxidation of methane to syngas |
| CN105832896B (en) * | 2016-05-12 | 2019-06-21 | 江苏康缘药业股份有限公司 | A kind of Chinese medicine for treating cervicitis and preparation method thereof, application |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110160508A1 (en) * | 2008-05-21 | 2011-06-30 | Ding Ma | Production of aromatics from methane |
| ATE551313T1 (en) * | 2008-05-21 | 2012-04-15 | Basf Se | METHOD FOR PRODUCING BENZENE, TOLUENE (AND NAPHTHALINE) FROM C1-C4 ALKANES WITH SITELY SEPARATE CO-DOSAGE OF HYDROGEN |
| 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 |
| CN105669343B (en) * | 2016-03-08 | 2018-10-26 | 安徽理工大学 | A kind of method that methane plasma activation anaerobic aromatization prepares aromatic hydrocarbons |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4507517A (en) * | 1983-10-31 | 1985-03-26 | Chevron Research Company | Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a boron compound containing catalyst |
| EP0228267A1 (en) * | 1985-12-23 | 1987-07-08 | The British Petroleum Company p.l.c. | Production of aromatics from hydrocarbon feedstock |
| US4975402A (en) * | 1989-02-21 | 1990-12-04 | Concordia University | Catalyst for aromatization of olefins and paraffins |
| CN1102359A (en) * | 1993-11-04 | 1995-05-10 | 中科院大连化学物理研究所 | Catalyzer for direct synthesis of aromatic hydrocarbon from methane and its application of in building-up reaction |
-
1997
- 1997-01-16 CN CN97100978A patent/CN1058909C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4507517A (en) * | 1983-10-31 | 1985-03-26 | Chevron Research Company | Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a boron compound containing catalyst |
| EP0228267A1 (en) * | 1985-12-23 | 1987-07-08 | The British Petroleum Company p.l.c. | Production of aromatics from hydrocarbon feedstock |
| US4975402A (en) * | 1989-02-21 | 1990-12-04 | Concordia University | Catalyst for aromatization of olefins and paraffins |
| CN1102359A (en) * | 1993-11-04 | 1995-05-10 | 中科院大连化学物理研究所 | Catalyzer for direct synthesis of aromatic hydrocarbon from methane and its application of in building-up reaction |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767031B (en) * | 2009-01-07 | 2012-03-14 | 中国石油化工股份有限公司 | Low temperature conversion catalyst for partial oxidation of methane to syngas |
| CN105832896B (en) * | 2016-05-12 | 2019-06-21 | 江苏康缘药业股份有限公司 | A kind of Chinese medicine for treating cervicitis and preparation method thereof, application |
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|---|---|
| CN1163797A (en) | 1997-11-05 |
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