CA1076547A - Catalyst treatment - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
In the production of maleic anhydride from benzene employing a molybdenum-vanadium-oxygen oxidation catalyst, addition of a volatilizable compound of a phosphorus halide or an organo phosphorus compound is added to the catalyst to deactivate a portion of the catalyst whereby progressive non-selectivity of a portion of the catalyst resulting in a de-crease in anhydride yield is overcome and high yields of anhydride are maintained.

Description

76~47 This inven-tion relates to improvements in the pre-paration of dicarboxylic acid anhydrides by the vapor phase oxidation of hydrocarbons and more particularly relates to improvements in the process for the catalytic oxidation of hydro-carbons to dicarboxylic anhydrides in the presence of a vanadium-molybdenum-oxygen catalyst.
It has recently been discovered that high yields of dicarboxylic anhydrides may be obtained by Oxidizing hydrocarbons in the vapor phase in contact with a vanadium-molybdenum-oxygen catalyst. Although high yields of dicarboxylic anhydrides have been obtained by such processes, it has been found that the yield of product diminishes with time. It is an advantage of this invention to provide a method whereby the useful life of the catalyst bed may be extended by ln situ treatment and whereby the high yields may be maintained. It has been found as part of the present invention that one reason for the decrease in yield is the progressive non-selectivity o~ a portion of the catalyst particles with use and a decrease in the anhydride yield of the process. ~t is also a feàture of this invention to selectively deactivate catalyst particles without impairing the activity of the remaining catalyst particles. This type of phosphorus treatment is readily distinguished from processes such as those disclosed in U.S. Patent Noq. 3,296,282 and 3,474,041 and British specification 1,291,354 wherein phosphorus is added to replenish phosphorus which is lost during the use of the catalyst and phosphorus added there to actually regenerate the catalyst by replacing lost phosphorus.
Briefly stated, the present invention is the discovery that vanadium-molybdenum-oxygen catalysts may be treated ln situ and stabilized by adding to the catalyst a compound of phosphorus or mixtures thereof. More particularly, volatile or voLatilizable phosphorus compounds or mixtures, are preferably employed.

6SgL7 According to the invention there is provided in a pro-cess for the vapor phase oxidation of benzene to a dicarboxylic acid anhydride wherein a stream comprising benzene and oxygen is contacted with a fixed bed vanadium-molybdenum-oxygen catalyst, ;
having an atomic ratio of molybdenum to vanadium in the range of 0.05 to 0,95:1 and containing less than 25 perc~nt by weight of other components based on the total weight of molybdenum and vanadium there being an exotherm of reaction in said catalyst bed and wherein said catalyst gradually decreases in activity, the improvement wherein a volatilizable compound of a phosphorus halide or an organo-phosphorus compound selected from the group consisting of O O O
Il 11 11 :
R-P-X, R-P-R, R-P-OX, R-P-R
X R OX QX

R-P-QX, RO-P-OX, and RO-P-O-P-OR
bx bR oP~ :
wherein R is phenyl or an alkyl radical of one to 6 carbon atoms and X i9 H or R, is added to said catalyst in an amount to deactivate the portion of said catalyst bed containing the exotherm of reaction present prior to the addition of said :
volatilizable compound, thereby moving said exotherm downstream into said catalyst bed.
The invention is particularly concerned with the pro-cess in which maleic anhydride is produced from the benzene.
In another aspect of the invention there is provided an _ situ method for extending the useful life of a fixed bed catalyst containing vanadium, molybdenum and oxygen, as defined above, in which the volatilizabl.e compound of phosphorus is passed into the fixed bed catalyst in the same direction o~ flow as a reaction stream of benzene in an amount to deactivate the portion of the catalyst bed containing the exotherm of reaction present prior to the addition of said volatilizable compound, thereby moving said exotherm downstream into said catalyst bed.

- la -, ., ~ 1 ~7~S47 Figures 1-4 are graphs showing the deactivation of the original reaction exotherm and relocation thereof deeper in the catalyst bed by the phosphorus treatment o~ the present invention.
Suitable phosphorus compounds are phosphorus halides of the structure PXn wherein X' is Cl, Br, I or F and n is 3 to 5 or an organophosphorus compound selected from the group con-sisting of O O O
R-P-X, R P R, R-P-OX, R-P-R, R-P-QX RO-P-OX and X R OX QX oX QX

RO-P-O-P-OR wherein R is phenyl or an alkyl ~adical of one to 6 OR OR
carbon atoms and X is H or R. Sulphur may be substituted for oxygen in any of these formulas~ Suitable compounds are such as the primary, RPH2, secondary, R2PH, and tertiary, R3P,-phosphines such as ethyl phosphine; the tertiary phosphine oxides, R3PO,such as tripropyl phosphine oxide, and primary, RP(O) (OX)2, and secondary, R2P(O~OX, phosphonic acids such as benzene phosphonic acid, the esters of the phosphonic acids such as diethyl methane-phosphonate, the phosphonous acids, RPO2X2, such as benzene phosphonous acid and the esters thereof such as the monoethyl ester; the phosphonous acids, R2POX, such as diethyl phosphonous acid and the esters thereof such as the monoethyl ester; the pri-mary, ROP(OX)2, secondary, (RO)2POX, and tertiary, (RO3)P, phos-phites such as diethyl phosphite, trimethyl phosphite, triethyl phosphite, triisopropyl phosphite, tripropyl phosphite and tri-butyl phosphite, and the pyrophosphites such as tetraethyl pyro-phosphite. Suitable phosphorous compounds are such as phosphorus trichloride, phosphorus trifluoride, phosphorus dichloride mono-fluoride, phosphorus tribromide, phosphorus dibromide trichloride, phosphorus dibromide trifluoride, phosphorus triiodide, phos-phorus pentachloride, the diphosphorus halides, e.g., phosphorus dichloride (P2C14), - 2 -1~376~47 the primary, RPH2, secondary, R2PH, and tertiary, R3P, phos-phines such as ethyl phosphine, the tertiary phosphine oxides, R3P0, such as tripropyl phosphine oxide, the primary, RP(0) (QX)2 - and secondary R2P(O)OX, phosphonic acids such as benzene phos-phonic acid; the esters of the phosphonic acids such as di-ethyl methanephosphonate, the phosphonous acids, RP02X2, such as benzenephosphonous acidand the esters thereof such as the mono-ethyl ester, the primary, ROP(OX)2, secondary, (R0)2POX, and tertiary, (R03)P, phosphites such as diethyl phosphite, tri-methyl thiophosphite, triethylphosphite, triisopropyl phosphite, tripropyl phosphite and tributyl phosphite, and the pyrophos-phites such as tetraethyl pyrophosphite. Preferred phosphorus compounds are those wherein the phosphorus has a valence of less than plus five. The phosphorus compounds will suitably have a boiling point of no greater than 250C and preferably will have a boiling point of no greater than 200C.
The phosphorus compound may be added up to 0.0012 gram mole per gram mole of vanadium in the vanadium - molyb-denum - oxygen catalyst and generally in the range of 0.00004 to 0.0008 gram mole per gram mole of vanadium.
In a preferred embodiment, the phosphorus compound ` used is preferably one which is volatile or will volatilize under the conditions of addition to the hydrocarbon flow, such as trimethyl phosphite, p~losphorus trichloride, triethyl thio-phosphate, phosphorus pentafluoride and phosphorus dichloride monofluoride.
The regeneration process of the present invention may ~, be initiated at any time a decline in the activity of the catalyst is noted, usually by a decline in the yield from the process or an increase in the temperature of the hot spot in the catalyst bed. An increase in the temperature of the hot spot may require reduction in the hydrocarbon throughput, thereby also .

LC97659~7 reducing the unit yield.
The vanadium - molybdenum - oxygen catalysts are well known and have been described and used for the preparation of maleic anhydride in numerous patents, for example, U.S. Patents 1,636,857, 2,294,130, 2,674,582; 2,885,409; 2,967,185;
3,074,969; 3,163,613 and 3,211,671.
The vanadium - molybdenum - oxygen catalysts to be reactivated according to the present invention, appear to com- -prise vanadium, molybdenum and oxygen combined in a complex, Suitable catalysts may have overall atomic ratios of molybdenum to vanadium in the range of 0.05 to 0.95:1. The vanadium -molybdenum ~ oxygen catalyst may contain various stabilizers and modifiers such as nickel, cobalt, iron, manganese, phosphorus, and alkali and alkaline earth metals, generally in the percents ~-of l~ss than 25 weiyht percent based on the total weight of vanadium and molybdenum~ For example, the vanadium - molybdenum -, oxygen catalyst may be modified with 0.002 to 0.1 atom of nickel, 0~0053 to 1.106 atom of cobalt, 0.0072 to 0.30 atom of iron, 0.0003 to 0.12 atom o phosphorus and/or 0.011 to 0.76 atom of lithium, sodium, potassium, calcium or strontium per atom of - vanadium. The atomic ratio of oxygen to the remaining ~omponents of the catalyst, when the catalyst is in the process of being used to catalyze the oxidation is difficult to determine and is probably not constant due to the competing reactions of oxidation . .
and reduction taking place during the reaction at high temper-atures. The overall ratio of oxygen to the combined atoms of i.`~
vanadium and molybdenum at room temperature would be such as about 4 to 10 atoms of oxygen per the combined atoms of vanadium and molybdenum. At any rate the catalyst is present during the reaction as an oxide of vanadium and molybdenum.
The vanadium - molybdenum - oxygen catalyst may be prepared in a number of ways, as shown in the art. The catalyst .
_ a~_ ~ .

6~ 7 may be prepared by precipitating the vanadium and molybdenum compound, either with or without a carrier, from a colloidal dis-persion of the ingredients in an inert liquid. The catalyst may also be prepared by dissolving vanadium and molybdenum compounds in a common solvent, such as hot oxalic acid and -thereafter de-positing the solution on a carrier. In some instances, the catalyst may be deposited as molten metal compounds on a carrier however, care must be taken not to vaporize off any of the ingredients. The catalyst may also be prepared by heating and mixing anhydrous forms of molybdenum acids with vanadium com-pounds.
In one particular method of catalyst preparation the desired amount of molybdenum oxide is introduced by dissolving ammonium molybdate in concentrated hydrochloric acid. Then, the desired amount of ammonium vanadate was dissolved in the solution. The other components, if any, are dissolved in the acid solution, for example, cobalt nitrate, nickel nitrate, sodium chloride, trisodium phosphate and the like. The result-ing solution of the mixture of compounds is mixed with granules - 20 of ceramically bonded, fused porous alumina, and subjected to evaporation, resulting in the deposition of the catalytic materials on the surface in the pores of the support or carrier. The catalyst - carrier is then calcined in the pre-- sence of air in a kiln held at a constant temperature of 650 -800F.
The process of oxidation described herein is applicable generally to processes for the o~idation of hydrocarbons, e.g., - having four to eight carbon atoms, to dicarboxylic acids in the presence of vanadium - molybdenum - oxygen catalysts. However, the process is particularly applicable to processes for the preparation of maleic anhydride, from C4 hydrocarbons and benzene, and especially the preparation of maleic anhydride from , 76~L7 benzene, terephthalic anhydride from ortho xylene and para-phthalic anhydride from paraxylene. The oxidation of the hydro-carbon to aliphatic dicarboxylic anhydrides may be accomplished by contacting low concentrations of hydrocarbon in oxygen in contact with the vanadium - molybdenum - oxygen catalyst. Air is the most economical source of oxygen, but mixtures of oxygen and diluent gases, such as nitrogen, may also be employed. Air streams enriched with oxygen may also be used. The gaseous feed stream to the reactor normally will contain about 1.1 to about 1.6 mol percent hydrocarbons based on the total gaseous stream.
About 1025 to about 1.5 mol percent of the hydrocarbon generally gives optimum output of product, although higher and lower con-centrations may be utilized. The flow rates of the gaseous stream to the reactor may be varied within fairly wide limits, but a preferred range is at the rate of about 50 to 200 grams of hydrocarbon per liter of catalyst per hour, and generally will be within the range of about 75 to 150 grams of hydro-carbon per liter of catalyst per hour. Residence time of the gas stream will normally be less than about 5 seconds, such as from about 0.01 to less than 2 seconds. The best results have been obtained at residence times of less than 1 second. The flow rates and residence times are calculated at standard con-ditions of 760 mm. of mercury and at 25C. I'he preferred hydro-carbon feed is benzene.
The temperature of reaction for the oxidation of the hydrocarbon to dicarboxylic anhydrides may be varied. The temperature of reaction will depend to some extent upon the size of the reactor, the 'nydrocarbon concentration and the parti-cular vanadium - molybdenum - oxygen catalyst being employed, A suitable temperature of reaction is from about 340C to about 500C, as measured at the maximum temperature in the reactor.

' setter results have been obtained at temperatures from 360 to 475~C, The pressure on the reactor is not generally critical, and the reaction may be conducted at atmosphexic, superatmospheric or below atmospheric pressure, The oxidation of the hydrocarbons to dicarboxylic anhydrides in the presence of a vanadium - molybdenum - oxygen catalyst may be conducted in a variety of reactors, Fixed bed reactors used for the production of maleic anhydride are quite satisfactory, Multiple tube heat exchanger type reactors have been successfully used, Because the reaction is exothermic, the ^- heat generated must be conducted away from the reactor. Normally, ;~ the reactors contain a preheat zone of an inert material, Catalyst support may be used to give the catalyst physical strength and stability, The carrier may vary in size -but generally is from about 2-1/2 m~sh to about 10 mesh in the Tyler Standard Screen Size, Useful carriers are such as the inert alumina carriers or the silicon carbides, The amount of the vanadium - molybdenum - oxygen catalysts on the carrier is usually in the range of about 10 to about 35 weight percent of ~0 the total weight of complex plus carrier. The final particle size of the catalyst particles will also yreferably be about , 2-1/2 to about 10 mesh size, The final catalyst particles may be of a variety of shapes, with the preferred shape being the shape of cylinders or spheres or irregular spheres, Inert ' diluents such as silica may be present in the catalytic surface, but the combined weight of the vanadium, molybdenum and oxygen will preferably be at least 50 weight percent of the catalytic surface, The phosphorus compounds can be added to the vanadium -molybdenum - oxygen catalysts in a number of different ways, The vanadium - molybdenum - oxygen catalyst will first be used for the oxidation of hydrocarbons to dicarboxylic anhydride for a ' . - :,, ' . .

1~7~;~47 period of time until khe yield of dicarboxylic anhydride diminishes, The phosphorus compound may then be added to re-activate the catalyst. The reactivation step may be accomplished either with or without the flows of hydrocarbon and/or oxygen continued.
A preferred method for the reactivation of the vanadium - molybdenum - oxyyen catalyst is by the continuous or ~ intermittent addition of volatile inorganic phosphorus compound ;~ to the gaseous stream of hydrocarbons and oxygen ~ containing gases entering the reactor. By such a technique, the activity ~ of the vanadium - molybdenum - oxygen catalyst is maintained; through continuous reactivation or stabilization. An advantage of this procedure is that the production of dicarboxylic anhydride does not have to be interrupted.
Still another method for the addition of the phos-phorus compound to the vanadium - mo:Lybdenum - oxygen catalyst is by the addition of the phosphorus compound in liquid phase by pouring the phosphorus compound over the catalyst to be re-activated. Reactivation by this technique may suitably be performed at a~out room temperature if desired.
Thus, the phosphorus compound may be added to the vanadium - molybdenum - oxygen catalyst by a variety of methods such as adding the phosphorus compound as a liquid or gas.
Other techniques such as the use of an aerosol to convey the phosphorus compound are also satisfactory. Suspensions or colloidal solutions of the phosphorus compounds may be employed.
Solvents for the phosphorus compound may be included. The phosphorus compound may be added such as the hydrocarbon, the oxygen containing gas or via a diluent gas such as nitrogen.
The overall temperature range for the addition of the phosphorus compound suitably will be from about 0C to 600C, depending upon the particular compound selected. However, the preferred 3L~765~7 temperature of the vanadium - molybdenum - oxygen catalyst at -the time of addition of the phosphorus compound will be at least -325C with still better results being obtained at a catalyst temperature of at least 350C. The upper limits of the tempera-ture of the catalyst during reactivation will suitably be about 450C or 500C, or perhaps higher for momentary periods of time.
The pressure during the addition may be atmospheric, sub-atmospheric or super-atmospheric. The conditions of concent-ration, temperature and pressure should be adjusted to permit ~ - . .
optimum contact of the phosphorus compound with the vanadium -molybdenum - oxygen catalyst.
As pointed out above, the addition may be either inter-mittent or continuous. Of course, even if the phosphorus compound ` is added continuously, it is not necessary that it be added at a constant rate.
-~ It has been found that by utilizing the process of this invention, the, non-selective, catalyst particles are selectively treated. The phosphorus compound selectively deactivates some portions of the catalyst, more speciflcally, the phosphorus .. ~
deactivates the non-selective reaction exotherm and causes the reaction exotherm to migrate deeper into the catalyst bed in a .
beneficial manner. The reaction exotherm of an oxidation is -shown in Fig. 1. Note that the major portion of the catalyst bed is substantially unused, however, over a period of time that portion of the catalyst bed (fixed bed) wherein the reaction exotherm is located, becomes less selective with a corresponding drop in the yield of the anhydride product, increase in C0 and .. : .
C02, and increase in the hot spot temperature. Thus, according to the present invention the phosphorus compound is added to de-activate the non-selective reaction exotherm and to allow a new exotherm to occur in the relatively unused portion of the bed, more specifically, that portion of the bed may be characterized 9 _ ~C~765~7 as less used. ~ence, there will be an improvement obtained over the relatively non-selective reaction exotherm, however, the yield of the process may not again achieve the peak obtained with fresh catalyst. This process may be repeated as long as there is sufficient catalyst bed into which the exotherm may migrate.
It should be appreciated that too much of the phosphorus com-pound passed into the catalyst bed can deactivate the entire bed, thus an appropriate method of obtaining the benefits of the present invention is to add small amounts of phosphorus com-pound, allow the reaction to stabilize, then to add another small ~~
incremental amount and so forth until the original exotherm is deactivated and the relocated exotherm is at an acceptable location.
; Another advantage of the invention is that a fixed catalyst bed containing a preheat zone of inert particles may be activated without removing the pxeheat zone or the catalyst particles from the reactor. The reactivatiOn procedure does not cause the catalyst bed to be plugged.

Benzene was oxidized to maleic anhydride in a 1.06 inch carbon steel, twelve foot long reactor. The reactor was cooled by a salt bath. A mixture of 1.3~ mole percent benzene in air was fed to the reactor. The flow rate was 92.4 grams of benzene per liter of catalyst per hour. The catalyst com-prised an oxide of vanadium and molybdenum. The actives were supported on an inert carrierO The catalyst gave a maximum yield of 88.2 weight percent maleic anhydride after 1400 hours at a throughput of 9.06 pounds of benzene per tube per day.
- The reactor temperature at this time was maintained in the range of 360 to 410C. After 9200 hours of operation the yield had dropped to 72.9 weight percent maleic anhydride, together with an increased amount of C0 and C02. After 9300 hours of ~0~1 ji547 - operation, the catalyst was reactivated. To the benzene - air feed stream was added 0.05 liters per minute of trimethyl phos-phite and then phosphorus trichloride. A total 2000 ml. each of ; (CH3033P and PC13 was added in this manner over a 2 hour period.
After a 2 hour period during which the reaction continued 2 lb.
of MoF6 was added over a 0.5 hour period. After 9600 total hours of operation the yield of maleic anhydride was 80~4 wt. percent, and the percent C0 and C02 had dropped significantly. After 9900 totaL hours of operation, an additional 2000 ml. of phosphorus trichloride was added in the same manner as the original addition followed by 1 lb. of MoF6 to reactivate the catalyst. After ` 10200 total hours of operation an additional 1000 ml. of PC13 was added in the same manner ~ollowed by lb. MoF6 to again re-activate the catalyst. After 10600 hours of operation the -catalyst was producing a yield of 810 7 weight percent maleic anhydride.

This example establishes that the phosphorus selective-ly deactivates a portion of the catalyst bed, which has become - 20 non-selective in the reaction and there is no regeneration of ' :
~; the non-selective portion by the phosphorus.
The following data was collected in a laboratory reactor. The reactor employed 300 milliliters o~ catalyst pack-ed in a 3 foot carbon steel tube, 3/4 inch inside diameter, with inert 1/4 inch Alundum pellets on top of the catalyst material to a height of 1/3 of the height o~ the catalyst. The reactor was encased in a 7 percent sodium nitrate-40 percent nitrite-53 percent potassium nitrate eutec-tic mixture constant temperatures salt bath.
The catalyst employed was a vanadium-molybdenum catalyst of the following composition V205 - MoO3 - Co203 - NaCl of the same general type as that used in Example 1. A mixture * trademark ' . ' .

~L~76S4~7 of benzene and air was fed to the reactor from the top of the bed in vapor phase.
The flow rate varied between 30 and about 100 g ben-zene per liter of catalyst per hour (C6H6g/1/hr), with the major portion of the run being between flow rates of 50 and 80 g C6H6g/1/hr. The benzene concentration varied from a low of .36 percent at start up to a high of 1.12 percent, with the major portion of the run being operated at approximately a 1.0 percent benzene concentration.
After the reactor had been on stream for 200 hours a peak in the mole product of maleic anhydride was obtained, i.e., approximately 72 mole percent MA, at a salt bath temper-- ature of 386C, hot spot of 401, and air flow of 8.0 l/min and benzene concentration of 1.04. The mole percent of maleic anhydride decreased from that point over the next 400 hours at which point the mole percent of MA in the product stream was about 60 percent. This is represented by FigO 1. What is shown in the Figures is a representation of the temperature profile in the catalyst bed. The vertical portion of the four graphs of the Figures represents the depth of the catalyst in centimeters. It can be seen that the exotherm of the reaction in Fig. 1 is at apporximately 72 centimeters, with the exotherm - beginning at approximately 50 centimeters. The salt bath was at 385C. flow rate o~ 13.6 1 air/min, theconcentration of ben-zene was .93 percent, and the conversion was 92 percent.
~t around 630 hours PC13 addition was initiated by bubbling one bubble per minute of nitrogen through PC13 into ., the feedstream to the reactor. The effect of this is demon-strated in Fig. 2. The immediate and initial e~fect was a dramatic drop in the yield of maleic anhydride from 60 percent to 52 mole percent. ~ence, this clearly demonstrates that :~ .

' : . . ' .. ~. . .

~6547 there is a deactivation, however, the full effect of the phos-phorus addition is not appreciated at his point since the exotherm of the reaction remains at about the same spot in the catalyst bed. However, after the addition of 7 ml's of PCl3 at approximately 688 hours, which is shown in Fig. 3 it is clearly demonstrated that the initial portion of the bed where the prior reaction, i.e., the exotherm of reaction occurred between 50 and 90 centimeters of catalyst with the peak of the reaction -being at approximately 72 cm (Fig. 1) has been almost com-pletely deactivated with the exotherm o~ reaction now beginning at 75 centimeters o~ catalyst and extending principally through 105 centimeters with the peak being at 96 centimeters.
The yield of maleic anhydride at this time is 51 mole percent.
Fig. 4 represents 860 hours on stream after the addition of a total of 9 ml's of PCl3. The exotherm of re-action now is totally moved so that it is initiated at approxi-mately 80 centimeters of catalyst depth through about llO with the peak being about 92 centimeters. The exotherm has now been deactivated at the point where it initially occurred, and is in ~act moved along in the bed, in this case down in th~ bed so that catalyst which has not been extensively used is now exposed to the reactants and the yield at this point is 65 mole percent.
Hence, the data clearly shows and establishes that there is no reactivation only deactivation.
The Table provides a summary of the conditions and results corresponding to figures 1-4 and the peak MA yield operation.

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Claims (30)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-

1. In a process for the vapor phase oxidation of benzene to a dicarboxylic acid anhydride wherein a stream comprising benzene and oxygen is contacted with a fixed bed vanadium-molybdenum-oxygen catalyst, having an atomic ratio of molybdenum to vanadium in the range of 0.05 to 0.95:1 and containing less than 25 percent by weight of other components based on the total weight of molybdenum and vanadium there being an exotherm of reaction in said catalyst bed and wherein said catalyst gradually decreases in activity, the improvement wherein a volatilizable compound of a phosphorus halide or an organo-phosphorus compound selected from the group consisting of , , , , and wherein R is phenyl or an alkyl radical of one to 6 carbon atoms and X is H or R, is added to said catalyst in an amount to deactivate the portion of said catalyst bed containing the exotherm of reaction present prior to the addition of said volatilizable compound, thereby moving said exotherm downstream into said catalyst bed.

2. The process according to claim 1, wherein said phosphorus compound has a volatilization temperature of 250°C
or less.

3. The process according to claim 1, wherein said compound is a phosphorus halide.

4. The process according to claim 1, wherein said compound is an organo-phosphorus compound.

5. The process according to claim 1, wherein up to 0.0012 gram mole of phosphorus compound per gram mole of vanadium in the vanadium-molybdenum-oxygen catalyst is added to the catalyst.

6. The process according to claim 5, wherein from 0.00004 to 0.0008 gram mole of phosphorus compound per gram mole of vanadium is added.

7. The process according to claim 1, 5 or 6, wherein said phosphorus compound is added to said catalyst during the vapor phase oxidation of benzene to produce a dicarboxylic acid.

8. The process according to claim 1, wherein maleic anhydride is the principal product.

9. The process according to claim 8, wherein said stream contains about 1.25 to about 1.5 mol percent of benzene.

10. The process according to claim 1, 5 or 6, wherein the portion of said catalyst deactivated is that portion containing the exotherm of reaction prior to the addition of said phosphorus compound.

11. The process according to claim 1, 5 or 6, wherein the phosphorus compound is a phosphorus halide of the structure PX? wherein X' is Cl, Br, I or F and n is 3 to 5.

12. The process according to claim 1, 5 or 6, wherein said catalyst contains 0.0003 to 0.12 atom of phosphorus.

13. The process according to claim 1, wherein said phosphorous compound is added to a vaporous stream of benzene.

14. An in situ method for extending the useful life of a fixed bed catalyst containing vanadium, molybdenum and oxygen, having an atomic ratio of molybdenum to vanadium in the range of 0.05 to 0.95:1 and containing less than 25 weight percent of other components, based on the total weight of molybdenum and vanadium, said catalyst having been used for the vapor phase oxidation of a stream of benzene to produce dicarbox-ylic acid anhydrides, said production of dicarboxylic acid having declined as a result of the non-selectivity of said catalyst comprising: passing a volatilizable compound of a phosphorus halide or an organo-phosphorus compound selected from the group consisting of , , , , , and wherein R is phenyl or an alkyl radical of one to 6 carbon atoms and X is H or R, into said fixed bed catalyst in the same direction of flow as said stream of benzene in an amount to deactivate the portion of said catalyst bed containing the exotherm of reaction present prior to the addition of said volatilizable compound, thereby moving said exotherm downstream with said catalyst bed.

15. The method according to claim 14, wherein said com-pound is organo-phosphorus compound.

16. The method according to claim 14, wherein said volatilizable phosphorus compound is volatilized and added to the stream of benzene.

17. The method according to claim 16, wherein up to 0.0012 gram mole per mole of vanadium is passed into said fixed bed catalyst.

18. In a process for the vapor phase oxidation of benzene to maleic anhydride wherein a stream consisting essentially of said benzene, at about 1.1 to 1.6 mol % of benzene based on the total gaseous stream and a flow rate of 50 to 200 grams of benzene per hour and oxygen, is contacted at a temperature in the range of 340°-500°C with a fixed bed vanadium-molybdenum-oxygen catalyst, having an atomic ratio of molybdenum to vanadium in the range of 0.05 to 0.95:1 and containing less than 25% by weight of other components based on the total weight of molybdenum and vanadium, there being an exotherm of reaction in said catalyst bed and wherein said catalyst gradually decreases in activity, the improvement comprising adding to a stream of at least one of said benzene and oxygen a volatilizable compound of a phosphorus halide or an organo-phosphorus compound selected from the group consisting of , , , , , , and wherein R is phenyl or an alkyl radical of one to 6 carbon atoms and X is H or R, to contact said catalyst in an amount to deactivate only the portion of said catalyst bed containing the exotherm of reaction which was present in said catalyst bed prior to the addition of said phosphorus compound, thereby moving said exotherm down stream into said catalyst bed.

19. The process according to claim 18, wherein said phosphorus compound has a volatilization temperature of 250°C
or less.

20. The process according to claim 18, wherein said compound is a phosphorus halide.

21. The process according to claim 18, wherein said compound is an organo-phosphorus compound.

22. The process according to claim 18, wherein up to 0.0012 gram mole of phosphorus compound per gram mole of vanadium in the vanadium-molybdenum-oxygen catalyst is added to the catalyst.

23. The process according to claim 22, wherein from 0.00004 to 0.0008 gram mole of phosphorus compound per gram mole of vanadium is added.

24. The process according to claim 18, wherein said phosphorus compound is added to said catalyst during the vapor phase oxidation of said benzene to produce said maleic acid anhydride,

25. The process according to claim 18, 19 or 23, wherein the phosphorus compound is a phosphorus halide of the structure PX? wherein xi is Cl, Br, I or F and n is 3 to 5.

26. The process according to claim 18, 19 or 20, wherein said catalyst contains 0.00 03 to 0.12 atom of phosphorus.

27. The process according to claim 18, wherein benzene or oxygen are discontinued from said feed during phosphorus compound addition.

28. The process according to claim 27, wherein benzene is discontinued.

29. The process according to claim 27, wherein oxygen is discontinued.

30. The process according to claim 18, 19 or 23, wherein benzene and oxygen are discontinued from said feed during the phosphorus compound addition.