ACTIVATION PROCESS FOR FLUID BED OXIDATION CATALYSTS USEFUL IN THE PREPARATION OF MALEIC ANHYDRIDE

Abstract: A process for activating fluid bed catalysts useful for producing maleic anhydride from 4-carbon atom hydrocar­ bons consists in contacting the fluidized catalyst containing the mixed oxides of vanadium and phosphorus with oxygen and a reducing gas at least partially combustible with oxy­ gen at elevated temperatures sufficient to cause such com­ bustion, the molar ratio of reducing gas to oxygen being below the stiochiometric ratio required for complete com­ bustion of the reducing gas. The activated catalysts are used to producing maleic anhydride from 4-carbon atom hydro­ carbons.

Description: ACTIVATION PROCESS FOR FLUID BED OXIDATION CATALYSTS USEFUL IN THE PREPARATION OF KBLEIC RUKYDRIDE The present invention relates to the activation of fluid bed oxidation catalysts. More particularly the present invention relates to the activation of fluid bed oxidation catalysts useful in the preparation of maleic anhydride from 4-carbon atom hydrocarbons, including n-butane. Oxidation catalysts containing the mixed oxides of vanadium and phosphorus have been utilized to produce maleic anhydride from 4-carbon atom hydrocarbons, such as n-butane. Methods have been investigated for activating, or increasing the catalytic activity of these catalysts. It is taught in the literature to "condition" vanadium phosphate-containing maleic anhydride catalysts under the flow of a low level of hydrocarbon in air, such as 0.2 volume percent to 2 volume percent hydrocarbon in air at temperaturers of 3000C to 6000C, as in U.S. Patent No. 4,171,316. U.S. Patent No. X,122,096 teaches conditioning of a dehydrated catalyst precursor with CO, H2 or H2S in the absence of oxygen, at a temperature of from 3000C to 6000C. U.S. Patent Nos. 4,178,298 and 4,181,628 discuss activating a mixed vanadium and phosphorus oxide catalyst at temperature of 3000C to 5000C by passing a gaseous hydrocarbon component having 2 to 6 carbon atoms with the exclusion of molecular oxygen over the catalyst. Attempting to "condition" a fluid bed catalyst with low level of hydrocarbon in air under normal operating conditions has been found to have little beneficial effect. Further, it is impractical and nearly impossible to utilize an in-reactor activation method in a fluid bed reactor which comprises contacting the fluidized catalyst with a hydrocarbon at high temperature in the absence of molecular oxygen. Commerical fluid bed reactors do not contain means for heating the catalyst bed and gas streams to the temperatures required to achieve the desired activation utilizing oxygen-free hydrocarbon feeds. The requisite external heating mode of operation is not desired for fluid bed reactions, and indeed fluid bed processes are attractive for the reason that such external heating means are not required for normal operation. There it is desired to activate catalysts containing the mixed oxides of vanadium and phosphorus for the partial oxidation of n-butane to form maleic anhydride, the activation of the catalyst with the hydrocarbon n-butane in the absence of oxygen lfould be extremely expensive, from the point of view of the volume of butane required to "fluidize" the catalyst bed. In addition, stringent safety precaustions would also be required to insure that no explosive mixturers of air/ butane result outside the reactor. Apart from economic and mechanical considerations, it is thought that contacting the vanadium phosphorus mixed oxide catalyst with reducing gases, including hydrocarbons, in the absence of oxygen merely causes reduction of the catalyst components (particularly} vanadium) by extracting lattice oxygen, causing the catalyst crystallite structure to reach a static configuration. Oxygen atoms are thus depleted from the catalystic active sites, and are unavailable for reaction lfith hydrocarbon reactants to yield useful product. While this procedure may enhance the activity of catalysts tiiat were initially ovcr-oxidized, the overall effect upon catalysts having a proper component valence range could be detrimeiital over a period of time by inducing change to the static configuration. We have found that fluid bed maleic anhydride catalysts containing the mixed oxides of vanadium and phosphorus can be activated in situ (in the fluid bed reactor) by contacting the fluidized catalyst with oxygen and a reducing gas at least partially c-ombust- ible with oxygen at an elevated temperature sufficient to cause such combustion. Contacting the catalyst, while fluidized, with both oxygen and a reducing gas at least partially combustible with oxygen at an elevated temperature sufficient to cause such combustion surprisingly provides a more effective, dynamic activation of the catalyst. In contrast to the static extraction of oxygen from the catalyst to provide reduction as in the prior art, when oxygen is present together with thd combustible reducing gas asian the process of the present invention, at elevated temperature, the catalyst is induced to operate catalytically, and a dynamic, interactive catalytic activation process results. The catalyst is permitted to take up oxygen as well as yield oxygen to the reducing feed component, allowing the active site and catalyst microcrystalline structure to undergo dynamic reorientation. This is thought to result in localized crystailine phase changes which optimize the catalyst activity. Because the activation procedure is carried out at temperatures sufficient to cause at least partial combustion of the reducing gas, the required activation temperature is attained by the heat of combustion after initial startup heating by conventional fluid bed preheaters. The fact that partical combustion takes place in the fluidized bed lessens the concentration of heated combustitle reducing gas in the effluent stream, such reducing gas being diluted by the combustion products, although precautions should still be taken to insure that an explosive mixture is not permitted to develop dolçn- stream of the reactor. The presence of the combustion product diluents, such as H20 if H2 is utilized as the reducing gas, Ii2Q and SO2 if H2 S is utilized as the reducing gas, and H20 and C02 if hydrocarbon is utilized as the reducing gas, decreases the concentraction of combustible gas in the effluent. The activating feed of the present invention, utilizing air in addition to reducing gas, is also less costly. In general, the process of the present invention includes activating a fluid bed catalyst by contacting a fluidized catalyst containing the mixed oxides of vanadium and phosphorus with oxygen and a reducing gas at least partially combustible with oxygen at an elevated temperature sufficient to cause combustion, wherein the molar ratio of reducing gas to oxygen its below the stoichiometric ratio required for complete combustion of the reducing gas. The present invention further provides a flu idizable catalyst containing the mixed oxides of vanadium and phosphorus, activated by the above process. The present invention further provides a process for producing maleic anhydride, utilizing the activated catalyst prepared by the above process. Catalysts for the production of maleic anhydride from 4-carbon atom hydrocarbon, such as n-butane, butenes and butadiene, particularly n-butane, generally contain the mixed oxides of vanadium and phosphorus. The -catalysts may additionally contain promoter elements, including but not limited to alkali or alkaline earth metals, titanium, zirconium, hafnium, niobium, molybdenum, iron, cobalt, nickel, copper. zinc, cadium, rare earths, cerium, u7allilml and mixturers thereof. The oar ratio of promoter elements to vanadium is generally 0.001:1 to 1:1, preferably 0.1:1 to 0.5:1. The molar ratio of phosphorus to vanadium is generally 0.5:1 to 2:1, preferably 0.9:1 to 1.6:1. The valence of the vanadium component of the catalyst is generally reduced Trom the pentavalent state, the valence of vanadium generally being between 3.5 to 4.6 and preferably being approximately 4. The maleic anhydride catalyst may additionally contain diluents or supports, suc as titania, alumina, alumina-silica, zirconia, silica, and silicon carbide. The catalysts may be prepared by reacting catalyst component containing compounds in the presence or absence of a corrosive reducing agent in a liquid, including but not limited to water, alcohols, aldehydes, glycols, ketones and halogenated olefins. Suitable corrosive reducing agents to provide vanadium in the proper valence state include but are not limited to HC1, IBr, and oxilic acid. Suitable liquid media capable of reducing vanadium to its proper valence state include but are not limited to isopropanol, isobutanol, crotylalcohol, al lyl alcohol, isopentanol, acetaldehyde, propionaldehyde, butyraldehyde, ethylene glycol, methyl ethyl ketone, perchloropropene and hexachlorobutadiene. Suitable vanadium compounds for use in preparing the maleic anhydride catalysts include vanadium pentoxide or vanaditini salts, such as ammonium metavanadate and vanadium oxytrihalides. Suitable phosphorus containing comp wounds include phosphoric acid, including metaphosphoric acid, orthophosphoric acid, triphosphoric acid and pyrop hospllosplloric acid and phosphorus pentoside, phosphorus oxyiodide, phosphorus oxycliloride and phosphorus petach- lode. Suitable promo tor elements containing compounds include promoter metal oxides, hydroxides, nitrates, halides, or salts of organic acids such as acetates, formates, butyrates and benzylates. The catalyst components are mIxed in the liquid medium, before or after the vanadium component is reduced to its proper valence state. The catalyst precursor formed is recovered and dried. The catalyst is formed into fluid bed form by crushing and screening the catalyst particles to a proper size, such as in the range of 20 to 500 microns, by the oil drop method, wherein an aqueous solution o slurry of the catalyst is dropped into a heated oil bath to form solid particles, or by spray drying to form the desired particles. The catalyst may be calcined before or after forming into the fluidizable particles, depen dent upon the method of preparation chosen. A method of preparing fluidizable catalysts useful for the production of maleic anhydride from 4-carbon atom hydrocarbons such as n-butane is disclosed in EP 0056901 (Application No: 81505882.5). The specific method of preparing the catalysts to be activated is not, however, critical to the process of the present invention. Hydrocarbons reacted to form maleic anhydride include n-butane, n-butenes, 1,5 butadiene, or a mixture thereof. The molecular oxygen used in the reaction is most conveniently added as air, but synthetic streams containing molecular oxygen are also suitable. In addition to the hydrocarbon and molecular oxygen, other gases may be added to the reactant feed, such as steam or nitrogen. Preferably, oxygen/ hydrocarbon ratios in the reactor feed are from 4 to 20 moles of oxygen per mole of hydrocarbon. The reaction temperature may vary widely and is dependent upon the particular hydrocarbon and catalyst employed. Temperatures of 3250C to 5000C are preferred. The reaction may be conducted at atmospheric, super atmospheric or subabuo spheric pressure, although operation at superatmospheric pressure is preferred. As indicated above maleic anhydride catalysts containing the mixed oxides of vanadium and phosphorus can be activated by contacting the catalyst in the absence of molecular oxygen with gaseous hydrocarbons or reducing agents such as hydrogen or hydrogen sulfide. Such activation is only suitable or fised bed catalyst forms, but as explained above, cannot readily be utilized as an in situ activation for fluidizable catalysts in a fluid bed reactor. In the process of the present invention, fluidizable catalysts containing the mixed oxides of vanadium and phosphorus are activated by contacting the catalyst with oxygen and a reducing gas at least partially combustible with oxygen at at elevated temper- ature sufficiellt to cause such combustion, in a molar ratio of reducing gas to oxygen below the stoichiometric ratio required for complete combustion. Suitable reducing gases include the hydrocarbon being utilized as a reactant to provide maleic anhydride, such as n-butane, n-butenes, and butadiene although other hydrocarbons are also suitable. Such other hydrocarbons may have up to 10 carbon atoms any may include methane, ethane, propane, isobutane, isobutylene, pentane, hexane and benzene . Other suitable reducing agents include hydrogen, ammonia, carbon monoxide and hydrogen sulfide. Oxygen may be added as air or synthetic streams containing molecular oxygen may be utilized. Inert gases may be added to the activating leed, examples of such gases being nitrogen, argon, carbon dioxide and steam. The molar ratio of reducing gas to oxygen in the activation feed stream is 10:1 to 1:3, preferably 5:1 to 1:2. If air is used as the source of oxygen, the molar ratio of reducing gas to air is 2:1 to 1:15 preferably 1:1 to 1:10. Inert gases in addition to those provided by air in the activation feed, may be added according to the process of the present invention. The amount of total inert gas to reducing gas may be between 0:1 to 50:1 6r greater, although preferably the amount of inert gas added to the activation feed, in addition to the inerts provided by air, are added in the molar ratio of inerts to reducing gas of 3:1 to 30:1. The activation procedure should be carried out at a temperature high enough to cause and sustain at least partial combustion of the reducing gas. The tempeiature required varies for different catalyst formulations, but can be determined by simple experimentation. Generally, the activation procedure is carried out at temperaturers between 4000C and 5500 C. The time required for activation depends in part upon the degree of activation required and the temperature at which the activation is carried out. In general, higher activation temperatures and longer activation time, independently contribute to a more activated form of the catalyst. Activation may take place at subatmospheric, atmospheric or superatmospheric pressurers. Activating conditions can be reached by various methods. The change to and from activating temperaturers may be accomplished under reaction feeds, activating feeds, or an inert gas. The activation procedure according to the process of the present invention may be carried out in the fluid bed reactor at any tile in the catalysts' life that activity is desired to be increased. It is preferred, however, that the activation procedure be carried out with catalyst that has operated to produce maleic anhydride from hydrocarbon. That is, the activation procedure seems to have a more beneficial effect upon catalyst in which active sites of catalytic activity have been established by working to catalyze the reaction of hydrocarbon, preferably n-butane, to maleic anhydride, in contrast to catalyst which has not yet been subjected to normal maleic anhydride producing conditions. The products of the activation procedure are essentially the combustion products CO and C02, when hydrocarbons are utilized as a reducing gas. Even when n-butane is utilized as the reducing gas, during activation there is little or no maleic anhydride production. There is some hydrocarbon breakthrough, however, and this can be either recycled or disposed of in a catalytic incinerator, without permitting an explosive mixture of oxygen and heated hydrocarbon to form. The following examples illustrate the invention: Example 1 A catalyst containing the mixed oxides of vanadium and phosphorus, having a phosphorus to vanad ila ratio of 1.2:1 were prepared as described EP 0056901 (Application No: 81305882.5). The fluidizable catalyst was used to produce malcic anhydride from n-butane in a 440 cc fluid bed reactor consisting of a 51 cm length of stainless steel tubing having a outer diameter of 5.5 em, having a stainless steel sparger at the bottom of the tube to act as a gas (air) distributor with an axial 0.64 cm outer diameter thermowell and a separate hydrocarbon inlet at the bottom of the tube. The reactor was fitted with internal gas redistributing baffles. Gas preheating and reactor temperature control was accomplished by placement of the reactor unit in a thermostatic fluidized sand bath. Flasks for receiving the product maleic anhydride were air cooled, and tail gases were routed to a gas chromatograph for analysis. Reaction conditions and results of the tests run are described in the Table below. The throughout of hydrocarbon feed in the production of maleic anhydride, or the working rate imposed upon the catalyst can be described as lfWH, or weight of feed/weight of catalyst/hour, being 0.05 FJH, After the catalyst had been run for 200 hours, achieving a molar yield of 51.4%, the activation feed of 1 mole butane to 1 mole air to 3 moles additional nitrogen was used to fluidize the catalyst bed at temperature of 4800C for 19.4 hours. After the activation procedure, reaction feeds of 1 mole of butane to 50 moles of air were resumed resulting in an increase of activity demonstrated by a 55.6% yield to maleic anhydride. Even after the reaction temperature was dropped 600 from the post activation run temperature of 4210C tile activity of the catalyst remained excellent, with a 55.oe,0 yield of maleic anhydride. Reaction and activation conditions and results for example 1 and the following examples are contained in the Table below. Examples 2-5 Catalysts were prepared according to the procedure of Example 1. The catalysts were used to produce maleic anhydride by n-butane oxidation, and were subjected to the activation process of the present invention under varied times, temperaturers, and activation feeds as set out in the Table below After the activation had been carried out in each example, the catalysts exhibited a substantial increase in activity, demonstrated by a sizable increase in the yield of maleic anhydride. In example 5, the catalyst underwent two successive activations, with a substantial increase in activity resulting after both activation procedures. Examples 6-S Vanadium, phosphorus mixed oxide containing catalysts were prepared by methods designed to produce catalytic material having lower activity than the catalysts prepared above, to determine whether the activation procedure of the present invention was useful in increaseing the activity of low conversion catalysts. As reported in the Table below, in each Example, the activation procedure resulted in a substantial increase in catalytic activity. These catalysts were tested according to the run procedure of Example 1. The activation procedure may be carried out while the reactor is on line" or operating, by changing the reaction feed to the activation feed and either maintaining or increasing temperature. It is also within the scope of the present invention that a slip stream be provided from the reactor to permit catalyst to be continuously withdrawn, subjected to the activation procedure in a continuous loop and reintroduced into the main reactor continuously while the reactor continues in operation. Such a procedure would permit the maintenance of a high level of activity in the reactor catalyst bed by continuously introducing freashly activated catalyst to the main catalyst bed. It is also within the scope of the present invention to apply the activation feeds and procedures to fised catalyst beds, although the process of the present invention is particularly suited to the activation of fluidized catalyst beds. Activation/Operation of Vanadium Phosphorus Mixed Oxide Catalysts for N-Butane Oxidation to Maleic Anhydride Run Feed = 30 Air/l HC WWH = 0.05 Activation ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ Example No. Feed Temperature Time Recovery Runs HC/Air/N2 C Hours Before 1. 1/1/3 480 19.4 After Before 2. 1/10/15 / 460-472 19 After Before 3. 1/1/3 420 18 After Before 4. 1/1/3 500 2 After Table (Continued) Example No. Run % Total Maleic Anhydride Recovery Runs, Temperature Conversion % Yield % Selectvity C Before 422 90.4 51.4 56.9 1. After 421 94.2 55.6 59.1 Before 420 87.9 49.2 56.0 2. After 419 92.1 56.2 61 Before 421 86.5 53.2 61.5 3. After 420 90.8 57.7 63.5 Before 420 87.6 50.8 58.0 4. After 400 85.9 57.1 66.5 HC = n-butane Table (continued) Activation Example No. Feed Temperature Time Recovery Runs HC/Air/N2 C Hours Before 1st 5. 1/1/3 460 19.2 After 1st Before 2nd 1/1/3 480 15.5 Before 6. 1/1/3 460 5.2 After Before 7. 1/10/5.7 460 14.6 After Before 8. 1/1/3 500 16.5 Table (continued) Example No. Run total Maleic Anhydride Recovery Runs. Temperature Conversion % Yield % Selectivty C Before 1st 419 86.0 52.1 60.5 5. After 1st Before 2nd 419 89.4 55.7 62.5 After 2nd 420 92.4 58.5 63.3 Before 421 60.3 41.2 70.2 6. After 421 66.9 46.9 70.1 Before 421 61.8 38.7 62.6 7. After 419 68.3 43.7 64.1 Before 421 50.7 29.5 58.2 8. After 420 70.6 47.0 66.6

Claims: Claims 1. A process for activating a fluid bed catalyst by contacting a fluidized catalyst containing the mixed oxides of vanadium and phosphorus with oxygen and a reducing gas at least partially combustible with oxygen at an elevated temperature sufficient to cause combustion, wherein the molar ratio of reducing gas to oxygen is below the stoicjiometric ratio required for complete combustion of the reducing gas. 2. A process as in claim 1 characterized in that the ratio of reducing gas to oxygen is from 10:1 to 1:3, preferably from 5:1 to 1:2. 3. A process as claimed in claim 1 or 2 characterized in that the source, of oxygen, is air. 4. A process as claimed in any of claims 1 to 3 characterized in that the catalyst is additionally contacted with an inert gas, preferably in addition to that in any air feed. 5. A process as claimed in any of claims 1 to 4 characterized in that the temperature is within a range of 4000C to 5500C. 6. A process as claimed in any of claims 1 to 5 characterized in that the reducing gas is selected from 112, H2S, CO, hydrocarbons having from 1 to about 10 carbon atoms, and mixturers thereof. 7. A process as claimed in any of claims 1 to 6 characterized in that the catalyst additionally contains a promotor element selected from at least one of an alkali metal, an alkaline earth metal, titanium, zirconium, hafnium, niobimll, molybdenum, iron, cobalt, nickel, molybdenum, iron, cobalt, copper, zine, cadmium, ceruim, rare earths, uranium and mixturers thereof. 8. A process as claimed in any of claims I to 7 characterized in that phosphonis vanadium ratio in the catalyst is from 0.5:1 to 2:1. 9. A catalyst when activated by a process as claimed in any of claims 1 to 8. 10. A catalyst claimed in claim 9 which is fluidizable 11. A catalyst as claimed in claim 9 or claim 10 characterized in that the average valence state of the vanadium is between +3.5 and +4.6. 12. A process for the production of maleic anhydride by the oxidation of 4-carbon hydrocarbons with molecular oxygen or an oxygen containing gas in a fluid bed reactor at a reaction temperature of 3250C to 5000C in the presence of a catalyst containing the mixed oxides of vanadium and phosphorus, characterized in that the catalyst is a catalyst as claimed in any of claims 9 to 11.

Inventors: BLUM, PATRICIA RAE, MILBERGER, ERNEST CARL, NICHOLAS, MARK LEE, ZOCK, PATRICIA ANN
Applicants: THE STANDARD OIL COMPANY
Application year: 1982
Main classification: B01J27
IPC codes: C07C51, B01J27, B01J38, C07D307, C07B61, B01J37