Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Metal – metal oxide or metal hydroxide
Patent
1997-07-09
2000-10-10
Knode, Marian C.
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Metal, metal oxide or metal hydroxide
502224, 502226, 502227, 502302, 502303, 502304, 502340, 502344, 502350, 502352, 502353, 585658, 585661, B01J 2706, B01J 27138, B01J 2300, B01J 2316, B01J 2306, C07C 5373, C07C 5333
Patent
active
061301833
DESCRIPTION:
BRIEF SUMMARY
FIELD OF INVENTION
The invention relates to a process for the oxidative dehydrogenation (and cracking as secondary reaction) of C.sub.2 to C.sub.5 paraffinic hydrocarbons (pure hydrocarbons or mixtures, such as liquified petroleum gas-LPG) to C.sub.2 to C.sub.5 olefins, wherein a novel catalyst, which is distinguished by high paraffin conversion and high olefin selectivity, is used.
BACKGROUND OF INVENTION
U.S. Pat. No. 4,524,236 discloses a process for the oxidative dehydrogenation (oxydehydrogenation) of ethane, in which a calcined composition of the elements Mo, V, Nb, Sb as the catalyst [sic] and X=Li, Sc, Na, Be, Mg, Ca, Sr, Ba, Ti, Zr, Hf, Y, Ta, Cr, Fe, Co, Ni, Ce, Zn, Cd, Hg, Al, Tl, Pb, As, Bi, U, W, Te is used. This catalyst provides a conversion of up to 73% at a selectivity of 69% for ethylene at 400.degree. C. and a weight-related space velocity (WHSV) of 1.5 h.sup.-1. The abovementioned patent states that the catalyst, because it does not efficiently oxydehydrogenate propane, n-butane or i-butane, but instead combusts these gases to carbon dioxide and other oxidized carbon products, is essentially limited to the oxydehydrogenation of ethane to ethylene.
The article "Selective Oxidation of Methane and Ethane of Li.sup.- --MgO-Cl.sup.- Catalysis Promoted with Metal Oxides" by S. J. Conway, D. J. Wang and J. H. Lunsford in Applied Catalysis A79, pp. L1 to L5 (1991) discloses catalysts for the oxydehydrogenation of ethane to ethylene that include magnesium oxide and lithium oxide, chlorine and other metals from the La, Nd and Dy group. This catalyst [sic] provides a conversion rate of 83.8% for ethane with a selectivity for ethylene of 63.8% at a temperature of 585.degree. C. and a WHSV of 0.18 h.sup.-1. No further information is available about the performance of this catalyst in the oxydehydrogenation of LPG components.
U.S. Pat. No. 1,777,319 discloses a vanadium-based catalyst for the oxydehydrogenation of C.sub.2 to C.sub.8 paraffins at temperatures of 300 to 700.degree. C. The formula of the catalyst is M.sub.3 (VO.sub.4).sub.2 and/or MV.sub.2 O.sub.6, where M is one of the elements Mg, Zn, Ca, Pb or Cd. The inventors of this catalyst disclose detailed information in later articles.
In these articles, "Selective Oxidative Dehydrogenation of Butane over V--MG--O Catalysts" by M. A. Chaar, D. Partel, M. C. Kung and H. H. Kung journal of Catalysis 105, pp. 483-498, 1987), "Selective Oxidative Dehydrogenation of Propane over V--MG--O Catalysts" by M. A. Chaar, D. Partel and H. H. Kung journal of Catalysis 109, pp. 463 to 467, 1988) and "Selectivity Patterns in Alkane Oxidation over Mg.sub.3 (VO.sub.4).sub.2 to MgO, Mg.sub.2 V.sub.2 O.sub.7 and (VO).sub.2 P.sub.2 O.sub.7 " by P. M. Michalakos, M. C. Kung, I. Jahan and H. H. Kung journal of Catalysis 140, pp. 226 to 242, 1993), the authors disclose mixed oxide catalysts that contain vanadium and magnesium. The catalysts are active at temperatures in the range of 475 to 540.degree. C. for the oxydehydrogenation of propane, butane and isobutane. At 540.degree. C. and WHSV=2 h.sup.-1, conversion is achieved for butane at a level of up to 58.9% and for propane of 35.8%. At 500.degree. C. and WHSV=6.5 h.sup.-1, conversion of 12% is achieved for isobutane with a selectivity for corresponding olefins and butadiene of 48.8% and 42.4% and 53.0%. No information is available about the conversion of LPG over V--MgO catalysts. Based on the data for the pure components, it can be concluded that for LPG containing roughly 50% propane, a conversion of 40% and a selectivity of 50% can be achieved with an olefin yield of roughly 20% per passage at WHSV=2 h.sup.-1. This was confirmed by tests carried out in the framework of studies for the present invention.
An important feature of these V--Mg catalysts is the high selectivity of the oxydehydrogenation path. No cracking reactions were observed. Another feature of these catalysts is that the main product of the dehydrogenation of n-butane is butadiene, whereby the selectivity for C.sub.4 H.sub.6 is 37.7%, with a
REFERENCES:
patent: 3743683 (1973-07-01), Croce et al.
patent: 4774216 (1988-09-01), Kolts et al.
patent: 5118899 (1992-06-01), Kimble et al.
Herskowitz Mordechay
Kaliya Mark
Landau Miron
Dang Thuan D.
K.T.I. Group B.V.
Knode Marian C.
Mannesmann Aktiengesellschaft
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