Oxidation of 1-butene and butadiene to maleic anhydride. 1. Role of oxygen partial pressure

Abstract

Ind. Eng. Chem. Prod. Res. Dev. 1983, 22, 565-570 565 Oil Company for aging the catalyst on an engine dynamometer.Registry NO. Pd, 7440-05-3; Pt, 7440-06-4; Rh, CO, 630-08-0; NO,, 11104-93-1. Literature CitedEngh, 0. T.; Wallman, S. SA€ (Society of Automotive Engineers) 1977, Falk, C. D.; Mooney. J. J. SA€ 1980, 800462. Fed. Regist. 1977, 42(124), 32906. Gandhl, H. S.; Steplen, H. K.; Shelef, M. Meter. Res. Bull. 1975, IO, 837. Gandhl, H. S.; Plken, A. G.; Shelef, M.; Delosh, R. G. SA€ Trans. 1978, 85, 770295. 901; SA€ 1978, 760201. Gandhi, H. S.; Plken, A. G.; Shelef, M.; Delosh, R. G.; Steplen, H. K.; Heyde, M. E. SA€ 1977, 770196. Patent 4 172047, 1979. Gandhi, H. S.; Shelef, M.; Yao, H. C.; Kummer, J. T.; Steplen, H. K. US. Gandhl, H. S.; Yao, H. C.; Steplen, H. K. ACS Symp. Ser. 1982, 178. 143. Hammerle, R. H.; Wu, C. H. Submitted to SAE International Congress, 1984. Hammerle, R. H.; Wu, C. H. SA€ 1981, 810275. Hegedus, L. L. Am. Chem. SOC. Div. fat. Chem. frepr. 1973, 18, 487. Jones, J. H.; Kummer, J. T.; Otto, K.; Shelef, M.; Weaver, E. E. Envfron. Sci. Technol. 1971, 5 , 790. Kummer, J. T.; Yao, Y.. McKee, D. SA€ 1978, 760143. Lachman, I. M.; McNelly. R. N. Preprints of Papers, 83rd Annual Meeting of American Ceramic Society, Washington, DC, 1981. Lester, G. R.; Marlnangell, R. E. SA€ 1980, 800844. Mooney. J. J.; Thompson, C. E.; Dettllng, J. C. SA€ 1977, 770365. National Fuel Survey, Motor Vehlcle Manufacturers Assoc., Detroit, 1982. Oda, I.; Matsuhlsa. T. Preprints of Papers, 83rd Annual Meeting of American Ceramic Society, Washington, DC, 1981. Oser, P. SA€ 1979, 790306. Seler, R. E.; Clark. R. J. SA€ 1978, 780203. Shelef, M.; Koester, D. W.; Mlchel, M. M., Jr., Adv. Chem. Ser. 1975, No. Steplen, H. K.; Wllllamson, W. B.; Gandhi. H. S. SA€ 1980, 800843. Weaver, E. E.; Shlller, J.; Plken. A. 0. AIChE Symp. Ser. 1976, 72(156), Yao, H. C.; Shelef, M. J . Catal. 1978, 43, 393. Yao, H. C.; Japar, S.; Shelef, M. J . M a l . 1977, 5 0 , 407. Yao, H. C.; Wynblatt, P.; Sleg, M.; Plummer, B. K., Jr. In "Sintering Processes"; Kuczynskl, G. C., Ed.; Plenum: New York, 1980; p 561.The oxidation of 1-butene and butadiene to maleic anhydride was tested with an integral reactor with vanadiumphosphorus mixed oxides prepared by different methods and presenting different activities and selectivities. The data were analyzed by utilizing a Langmuir-Hinshelwood type rate expression derived under differential conditions. At high partial pressure, competition between 1-butene and butadiene for the same active centers leads to a decrease in the rate of formatlon of maleic anhydride. This competitlon does not affect the rates of formation of methyl vinyl ketone, acetaldehyde, and carbon oxides. Emphasis is made on the necessity of operating with oxygen-nriched air in order to avoid the negative effect of the reactant on the rate of maleic anhydride formation.

Structure and reactivity of vanadium-phosphorus oxides

“…In fact, the specific rates of both n-butane depletion and maleic anhydryde formation per m 2 of surface area of the catalyst are higher on (VO)2P207 prepared according to method (ii) than on (VO)2P20 7 prepared in aqueous medium [14]. In contrast, no great differences in the specific rate of but-1-ene oxidation are found on (VO)2P20 7 phases prepared by the two methods [2,14]. This considerable influence of the micro-structure of the catalyst on the rate of n-butane, but not on the rate ofbut-l-ene selective oxidation, suggests that the nature of the structure of the active phase mainly influences the first step of selective paraffin oxidation, that is the dehydrogenation of n-butane to butenes.…”

“…89 prepared in different ways, on the redox properties of oxidation and reduction of vanadium for catalysts prepared with different P : V atomic ratios in the range 0.9-1.3, and on the surface properties determined by TPD of catalysts with different P : V ratios. The relationship between these properties and the catalytic properties in the selective oxidation of n-butane and but-l-ene is discussed.Vanadium-phosphorus mixed oxides comprise a very interesting catalytic system for selective oxidation and ammoxidation reactions; these catalysts not only give high yields, but are also able to promote the selective oxidation of different reactants, such as paraffins (n-butane), olefins (but-l-ene and butadiene) and alkylaromatics (toluene derivatives) [1,2]. In all cases the active phase is a pyrophosphate of vanadium(IV) [3-811 (VO)2P207 is formed by dehydration of VOHPO4 " 89 that can be prepared in different ways [3,6,8,[9][10][11][12].…”

Oxidación selectiva de hidrocarburos ligeros sobre catalizadores basados en óxidos metálicos mixtos

“…Estos rendimientos, aunque no sean muy superiores a los que se alcanzan a partir de butenos [106,107], se Por tanto, parece lógico pensar que, con la elección del catalizador adecuado, las tecnologías y condiciones de reacción, pueda ser posible y competitiva la sustitución de olefinas por alcanos en otros procesos de oxidación selectiva, disminuyendo además el número de subproductos (compuestos oxigenados parcialmente oxidados que deberían eliminarse al final del proceso encareciendo el mismo). Sin embargo, por el momento, todavía existe una diferencia considerable entre los rendimientos que exige la demanda industrial y los que se obtienen en la mayoría de los procesos de oxidación selectiva de alcanos bajo investigación.…”

“…Estos rendimientos, aunque no sean muy superiores a los que se alcanzan a partir de butenos [106,107], se obtienen con una menor presencia de subproductos (compuestos parcialmente oxidados). En efecto, a partir de n-buteno se observa la formación de pequeñas cantidades de furano, acetaldehído, crotonaldehído o metil-vinil-cetona, lo que encarece el proceso, ya que es necesario una etapa de purificación [103].…”

“…En efecto, a partir de n-buteno se observa la formación de pequeñas cantidades de furano, acetaldehído, crotonaldehído o metil-vinil-cetona, lo que encarece el proceso, ya que es necesario una etapa de purificación [103]. Sin embargo, estos subproductos no se observan durante la oxidación selectiva de nbutano [104,106,107].…”