CA1103241A

CA1103241A - Catalyst and method of manufacture and use thereof

Info

Publication number: CA1103241A
Application number: CA271,247A
Authority: CA
Inventors: Walter M. Douglas
Original assignee: UOP LLC
Current assignee: Honeywell UOP LLC
Priority date: 1976-02-24
Filing date: 1977-02-07
Publication date: 1981-06-16
Also published as: MX143626A; IT1075292B; ES456195A1; ZA77718B; AU506689B2; YU50277A; BR7701063A; GB1572614A; PT66162A; JPS596185B2; DE2706515C2; SE7702010L; SE436699B; AU2257477A; SU942576A3; DE2706515A1; YU39382B; US4049572A; FR2342099B1; IN155898B

Abstract

ABSTRACT OF THE DISCLOSURE
A catalytic composition comprising a metal phthalocyanine composition of matter is prepared by reacting a 4-sulfophthalic acid with a metal salt, an ammonium donor and a phthalic anhydride or derivative thereof at 250 to 325°C
for one-half to ten hours. The catalytic composition of the present invention is a powerful oxidizing catalyst, especially suited for the catalyzing oxidation of mercaptan sulfur to di-sulfides. Mereaptan contamination of hydrocarbons is a pre-vailing problem in industry as mercaptans are present in natural gases, gasolines, kerosene and fuel oils. Mercaptans are objectionable because of their strong odors and their corrosive-ness. The catalytic composition of the present invention appears different from the conventional phthalocyanine catalysts and is produced by a simpler and cleaner process.

Description

* * SPECIFICATION * *
The invention relates to a new ca-talyst, its method of preparation and use.
The catalyst is characterized by its method of prepa-ration, i.e., reaction of a 4-sulfophthalic acid, an ammonium dGnorr a metal salt, a phthalic anhydride or one of its deriv-atives and an optional promoter in water at a temperature of 250 to 325 C for one-half to ten hours.
When the metal salt used is a cobalt salt, it is pos-sible to make a cobalt phthalocyanine sulfonate with unique properties. This catalyst is a powerful oxidizing catalyst, especially suited for catalyzing oxidation of mercaptan sul-fur to disulfides.
Many hydrocarbons contain mercaptan sulfur. Mercaptan contamination of hydrocarbons is a prevailing problem in in-dustry. Mercaptans are frequently present in natural gases, such as methane and ethane. They are almost invariably pres-ent in cracked gasolines, straight gasolines, natural gasolines, and heavier hydrocarbon distillates including, e.g., kerosene and fuel oil.
These mercaptan components are objectionable because ." ~

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of their strong odor. These mercaptans al~30 are corrosive.
There have been many attempts to provide processes which would remove or convert mercaptans. Som~ of the earliest processes inclucled treatment of the hydrocarbon fraction with caustic, clays, and hydrotreating. A significant improvement in the treating of hydrocarbon fractions was made when the UOP
Merox Process was announced to the industry in 1959. The Oil & Gas J. 57 (44), 73-8 (1959), cont:ains a discussion of the Merox Process and also of some prior art processes. The Merox Process uses a catalyst which is soluble in caustic, or alter-natively is held on a support, to oxidize mercaptans to disulfides in the presence of oxygen and caustic.
In U.S. Patent 3,108,~81, there is disclosed a catalyst comprising an adsorptive carrier and a phthalocyanine catalyst for the oxidation of mercaptans. This patent taught that a particularly preferred phthalocyanine was the sulfonated derivative, with the monosulfonate being especially preferred.
Metal phthalocyanine monosulfonates are well known compounds and are easily prepared. The most common method used to prepare these is by reaction of the corresponding metal phthalocyanine with oleum or sulfuric acid. Unfortunately, the reaction in oleum is somewhat hard to control in that a very large proportion of the phthalocyanine consists of di- and tri-sulfonated derivatives. The di- and tri- sulfonated derivatives of the metal phthalocyanines, especially ) ~ 2 .
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of cobalt phthalocyanine, are much more soluble in hydrocar-bon and in caustic than -the monosulfonate. This solubility characteristic is of critical importance when this catalyst is u.sed for the fixed bed treat:ing of sour hydrocarbons to sweeten them. This is because the catalyst must have some solubility to permit its incorporation onto a solid carrier.
However, the catalyst once placed on the carrier must remain attached so that catalytic activity will be maintained.
From an economic viewpoint, it is desirable that the catalyst easily be placed on the support from the impreynating solution and not require extensive recycling to support all the cata-lyst. Accordingly, refiners and researchers in petroleum technology have made extensive studies of catalyst which can be used on fixed bed systems.
As applied to the fixed bed sweetening of hydrocar-bons, use of the cobalt phthalocyanine monosulfonate was preferred. The unsulfonated cobalt phthalocyanine was not soluble, and attempts to prepare a fixed bed of cobalt phthalocyanine catalyst were unsuccessful.
Though it is easy to dissolve the more highly sul-fonated materials in the impregnating solution, their very solubility makes it more diEficult to place all the catalyst on the support. It can be accomplished if repeated recycling of the impregnatin~ solutions is performed, but this is unde-sirable from an economic viewpoint. Furthermore, the more highly sulfonated species are susceptible to leaching from the catalyst support when caustic solutions -- an integral part of sweetening process -- are applied. This leaching means the loss of catalyst from the suppor-t.
The monosulfonate was thus considered the best form of the phthalocyanine catalyst for use in ~ixed bed sweetening.
Although it was relatively difficult to dissolve, and required a fairly elaborate impregnation procedure, once attached to the support it was generally held tenaciously by the support.
It was only with careful control of reaction conditions that a reasonably pure monosulfonate could be obtained via the oleum preparation method. Despite careful juggling of amounts of reagents used, a significant amount of the more highly sulfonated derivatives was formed, and these derivatives presented the difficulties mentioned above. rrhe loss of catalyst to the aqueous alkaline solutions encountered in sweetening operations could be tolerated if the multi-sulfonated derivatives of the metal phthalocyanines were kept to a minimum.
Another problem with the monosulfonate prepared~by reacting a metal phthalocyanine ln oleum was the waste dls-posal problem, l.e., getting rid of the spent sulfuric acid and reagents which did not form catalyst. There was also a significant expense involved in isolating the active catalyst, ; i.e., the metal phthalocyanine monosulfonate, from the reaction mass.
To put in proper perspective the magnitude of the~
problem faclng petroleum technologists, it is worthy of note that most of the refineries in the world have a UOP Merox unit in one form or another. It is estimated that over 5 .
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million barrels per day of hydrocarbons pass through Merox units ranging in capacity from 40 to 120,000 barrels per day.
Because of the worldwide interest which was shown in this process, there have been continuing attempts to improved upon it.
I studied the work that prior researchers had done, and in attempting to develop better and cheaper ways of making the catalyst, unexpectedly came upon a new catalyst. The catalyst is difficult to characterize, but appears to differ from conventional phthalocyanine catalysts, in addition to being produced by a simpler and cleaner procedure.
Accordingly the present invention provides a cata-lyst comprising a metal phthalocyanine composition of matter prepared by the method which comprises reacting a 4-sulfophthalic acid compound with a metal salt, an ammonium donor,and a compound selected from the group of benzene-1,2-dicarboxylic acid and derivatives thereof, in aqueous solution by heating to 250 to 325 C for one-half to 10 hours.
In another embodiment, the present invention pro-vides a method of manufacturlng a catalyst which comprisesreacting a 4-sulfophthalic acid compound with a metal salt, an ammonium donor, and a compound selected from the group of benzene-1,2-dicarboxylic acid and derivatives thereof,~in aqueous solution by heating to 250 to 325 C for one-half to 10 hours.
In yet another embodiment, the present invention pro-vides in a process for oxidizing a mercaptan with oxygen in .

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the presence of a catalyst, the improvement comprising, use of the catalyst of Claim 1.
The catalyst of the present invention is especially useful for sweetening of sour hydrocarbon fractions. The catalyst may also be used for electrochemical reactions, bio-chemical reactions, hydroformy]ation, and many other reactions wherein catalysts are used.
The material prepared by the method of the present invention also may be useful as a dye. A cobalt composition of matter prepared by the method of the present invention has a blue-black appearance, as do alcoholic solutions thereof, while a compound prepared by the oleum route has a purple cast.
The novel catalyst o~ the present invention is characterized by its method of preparation. The essential ingredients are a metal salt, an ammonium donor, a 4-sul-fophthalic acid, and a 1,2-dicarboxylic acid or derivative ,,1 thereof. Typical of the 1,2-dicarboxylic acids are benzene-1,2-dicarboxylic acid or a derivative of said acid such as benzene-1,2-dicarboxylic acid anhydride (also known as phthalic anhydride), benzene-1,2-dicarboxylic acid di-amide (phthalic diamide1 and other such derivatives commonly known as phthalamic acid, dicyanobenzene, etc. It is preferred to include a promoter, which seems to act as a catalyst to pro-mote the desired reactions. The promoter may be compoundssuch as boric acids, ammonium chromate, chromic oxide, selenic acid, ammonium chloride, ferric chloride, potassium vanadate, vanadic acid, lead monoxide or dioxide, zinc oxide, arsenous or arsenic o~ide, antomony oxide, molybdic o~ide, phosphomolybdic acid, molybdic oxide, ammonium molybdate and similar compounds.
The 4-sulfophthalic acid compound may be either the acid or an acid salt, e.g., triammonium 4-sulfophthalate. IE
the salt is used, it may possess a cation of e.g., lithium, potassium, rubidium, cesium, barium, strontium, calcium, mag-nesium, beryllium, titanium, scandium, zirconium, manganese, rhenium, etc.
The metal salt which is dissolved in an aqueous medium for reaction with the reactants may be any metal salt from Groups IV-B, V-B, VI-B or preferably Group VIII of the Periodic Table, e.g., cobalt sulfate, cobaltous bromide, nickel nitrate.
Thus, in general, any metal salts such as the sulfatej nitrate or chloride, etc., of a Group VIII metal, or of a metal of Groups IV-B, V-B, VI-B, may be used. It is also possible to start with a metal which forms a metal salt, in situ, during the course of the reaction. For instance cobalt or copper dust may be used in place of the metals salt.
The ammonium donor compound can be anything which will decompose to give ammonia or react with the phthalates to form amides, imides, etc. These compounds are well known in the art and include urea, alum, ammonium borate, biuret,h~drazine, guanidine and similar compounds.
Any derivatives of benzene-1,2-dicarboxylic acid such as phthalic acid itself, phthalimide, phthalonitrile, or phthalic _ 7 _ anhydride, may be used as one of the essential starting materials.
Phthalic anhydride is preferred.
The amount of the various reactants required may be determined by calculating the stoichiometric amount necessary to produce the phthalocyanine monosulfonate. Especially in the presence of a promoter, the reaction proceeds rapidly with mini-mal production of byproducts or undesirable side reactions.
Accordingly, none of the reactants need -to be present in any great excess. ~a-ter is also a necessary part of the reaction mixture, because during the early stages of the reaction, it insures proper mixing of the first reaction mixture. The pre-ferred amount of water required to permit the reaction to properly proceed is 10 wt. percent, or more, based on the o-ther dry ingredients. Optimum results seem to be obtained with 15 to 25 wt. percent water, again based on dry ingredients. In-clusion of more water than this is not harmful, because the excess water eventually evaporates at the high temperatures used, however, there is no particular advantage gained by using excess amounts of water.
The reaction pressure is not critlcal. The reaction may be carried out at any pressure from sub-atmospheric to super-atmospheric though it is generally most economical to carry out the process at atmospheric pressure.
In a specific embodiment the first reaction mass, consisting of a 4-sulfophthalic acid,~ a phth~alic anhydride, a metal salt, urea, and a promoter, lS heated in a di-partite or tri-partite manner or at a single high temperature of between 250 and 325 C. In a tri-partite heatiny manner, -the first reaction tempera-ture is 165 to 210 C, the second reaction tem-perature is 200 to 250 C and the third reaction -temperature is 250 to 325 C. Typically, :if heated less than 185 C the percentage of the desired component will be about 25~. If an initial -temperature of less -than 165 C is used, the poor yields make the process uneconomic. If a single reaction temperature is utilized, it has been found that the desirable component of tne catalytic composition of matter is optimized by heating at a temperature between 250 and 325 C for a period of 1/2-10 hrs.
Although it is not completely understood, it is ~e-lieved that, when using a tri-partite heating cycle, during the first reaction temperature cycle the 4-sulfophthalic acid, phthalic anhydride, and urea react with each other to produce lS an intermediate of the proper composition and configuration for iinal condensation into the product which possesses the internal ring structure characteristic of phthalocyanine compounds.
y wor~ has shown that if the first reaction temperatures are lower than those specified in this invention are used, the amount of the desired component in the final catalytic product is decreased by 50%. A typical catalyst will have more than one component of which one -- the monosulfonated component --is the most desired for fixed bed sweeteniny. If the first reaction te.nperature is in accord with this invention, it is found that the final product can contain over 50~ of the desired component, the remainder being more highly sulfonated species.
If the first reaction temperature is less than that specified 3~

in -this invention, the desired component can drop to less than 25~ of the produc-t with a sorresponding increase in the sum of more highly sulfona-ted components. This is undesirable because the more highly sulfonated components are those components which are susceptible to removal Erom the support upon which this ca-talyst is used. It is felt tha-t the reason why -the higher reaction temperature enriches the final product in the desired component is that the relative reactivit~ of -the 4-sulfophthalic acid and phthalic anhydride become more nearly equal. At lower temperatures, 4-sulfophthalic acid is more reac-tive than phthalic anhydride and preferentially forms with itself the intermediate susceptible to final condensation into the phthalocyanine structure. The result of such preferential first reaction is enrichment of the product in the more highly sulfonated components.
During the time at the second reaction temperature, the intermediate formed during the first period is condensed by ring formation and closure into a product possessing the characteristic phthalocyanine structure. It is believed that the promoter such as ammonium molybdate facilitates -this for-mation and closure by coordination to the intermediate. This coordination brings the parts of the intermediate into the proper spacial arrangement for final formation of the product.
At some point during this process, the metal atom, such as cobalt, nickel, vanadium, etc., which will be contained in the final product is placed in the center oE the phthalocyanine ring to give the final product.

2~

If a single heat'ing temperature of between 250 ~nd 325 C is used, the processes ~hi~h occur in tlle bi- and tri-partite hea-ting methods are accelerated and, with due allowance for requirin the initial reaction ma~s to be dehydrated of its water and raised in temperature, may be envisioned as occurring simul;_aneously.
Based on experimental analysis, the nominally desig-naied cobalt pllthalocyanine monosulfonate prei?ared by the Method of the present invention, though containing predorninantly the monosulfonate, was also found to contain some of the more nighlv sulfonated materials such as the disulfonate, trisul-fonate, and tetrasulfonate. In contradistinction to practical experience in actually using catalysts prepared by suifonation of cobalt phthalocyanine in oleum ~prior art), tne presence of these more highly sulfonated components in the catalytic reaction mass produced by this invention did not lead to loss of catalyst f-om the supporting bed as evidenced by the co7 or of the fluids leaving the reaction zone. This difference is rirst observed when the su?port is irnpregnated with an alco-holic dispersion of the catalyst. The deeply blue catalystso~ution is poured over the top of the bed and the effluent alco'nol cornins out of the bed is colorless, thereby indicating that the catalyst has been fully deposited on tne supporting bed. Furtller, when a caustic solution is applied to the bed, no color is observed in the effluent coming out of the bed.
As a result of these distinctions, it is felt that a catalyst prepared by the method of this inventlon and a catalyst pre--:, :

, 3~

pared by the method of the prior ar-t, are not identical.
Ilighly sulfonated phthalocyanines prepared by the prior art are oEten washed off the suppor-t material when a caustic is applied and can only ~e redeposited on the support by repea-ted 5 recycling of the caustic. The catalyst prepared by the method oi the present invention easily goes onto -the support and is not readily washed off the support when a caus-tic solution is applied. If some material does happen to come off the support, it can be redeposited thereon by a single recycling of the caustic and will not subsequen-tly wash off -the support.
Further sup;oort for the two materials being different comes from a report in J. Chemical Society (1950) 2975. In tnat article, Linstead and Weiss reported that copper tetra-4-sulfophthalocyanine, prepared from 4-sulfophthalic acid, is redder than the product prepared by the direct sulfonation of coppe`r phthalocyanine. They believed that the greenness of the directly sulfonated product is attributable to the presence of one or more sulfonic acid groups in the 3 position. In using 4-sulfophthalic acid, the sulfonic acid groups are restricted to the 4-position in the final product.
By analogy to the above clted work, it is felt that the product of this invention, prepared by reaction with 4-sulfophthalic acid, will likewise restrict the sulfonic acid group to the 4-position in the final product, whereas direct sulfonation of cobalt phthalocyanine will lead to a ma~terial containing some or all of ti~e sulfonic acid group in the 3-position. I'his explanation hel~s to understand why the catalyst ~g; ~

of the present invention, when viewed as a solid, has a dark blue-black appearance whereas catalyst p~epared by oleum or sulfuric acid sulfonation has a strong purple cast.
The exact difference between the catalyst Of the present invention and that of the prior art is not fully understood at this time.
The catalyst OL the present invention may be, and preferably is, incorporated onto a solid support. The solid support may be any porous, high surface area material such as fuller's earth, bentonite, charcoal, alumina, mordenite, fau-jasite, or any other well-known catalyst carrier materials, though all supports do not give equivalent results and cannot always be impregnated in the same fashion. Especially pre-ferred are the charcoals available commercially which are de-rived from vegetable sources, e.g., Nuchar, sold by Westvacoand Norit, sold by the Norit Co.
The catalyst may be incorporated into the carrier material by any methods known in the art. An excellent way to prepare the carrier material is to dissolve the metal phthalo-cyanine monosulfonate in an alcoholic solution and pass thesolution over a fixed bed of carrier materialO The catalyst may comprise from .001 to 10 weight percent of the carrier material. It is preferable that a relatively dilute impregnat-ing solution be used, because if a very concentrated impregnat-ing solution is used there is a tendency to have most of thecatalyst deposited on the point in the catalyst bed nearest the impregnating fluid inlet. Impregnation may occur in upflow, .

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downflow, or radial flow. ~lternatively, impregnat:ion may be accomplished in a batch operation wherein the catalyst, carrier, and alcohol or other catalvst dispersion medium are contacted by mixing in a vessel.
When applied to the sweetening of hydrocarbons, the reaction conditions and methods disclosed in previously mentioned U.S. Patent 3,108,081 may be used. I'his patent relates to a fi~ed bed sweetening process.
In an alternative sweetening process, the catalyst of the present invention may be used, dissolved in caustic, though not necessarily with equivalent results. It is not under-stood why the catalyst of the present invention is so tenaceously held by charcoal; however, it is believed that in the absence of a charcoal or o-ther carrier, and in the presence of caustic, that the presence of the more highly sulfonated derivatives, of the metal phthalocyanine will lead to good results when used as an o~idation catalyst for liquid-liquid sweetening. Details of the liquid-liquid sweetening process are given in U.S. Patent 2,882,224 (Class 208-206). The catalys-t of the present inven-tion should work in, but is not preferred for liquid-liquid sweetening, because its slightly decreased solubility makes use of other sulfonated derivatives more attractive, as they are more soluble.
EXAMPLE
Several catalyst samples were prepared by the method of the present invention and by prior art methods. For comparison , - 14 -~ ~ 3 91~

purposes a commercially available catalyst, which is believed made by the oleum route and a material prepared by the sulfo-nation oE cobalt phthalocyanine in sulfuric acid according to the teaching of ~.S. Patent No. 3,091,618 are also included.
In order to compare the cat~lyst of the present in~
vention with that of the prior art, cobalt ph-thalocyanine was sulfonated in sulfuric acid under an atmosphere of carbon dioxide in a manner similar to that described in ~.S. Patent

3,091,618. In this experiment 52 parts of cobalt phthalocyanine was added to 720 parts of 100~ sulfuric acid over a period of 1.5 hours. The mixture was then stirred at room temperature for 16 hours to insure that the cobalt phthalocyanine had completely dissolved. The reaction mixture was heated to a temperature of 120-~1 C over a period of 2.5-3.0 hours and then maintained at that temperature for a period of 6.0 hours. The reaction was considered complete when, according to U.S. Pat-ent 3,091,618, "...2 drops of the sulfonation when boiled for 30 seconds in 10 cc of 10% sodium carbonate became completely soluble on the addition of 2 cc of pyridine. This required 6 hours of heatin~ at 120C." The product of the sulfonation was isolated according to teachings of U.S~. Patent 3,091,618.
In a typical preparation of a catalyst of the present invention, 15 parts by weight of a 50 wt. % solution of 4-sulfo-phthalic acid, 9.3 parts of CoSO4 7H2O, 0.1 parts of ammonium molybdate and lS parts of water were mixed together by stirring until all the solids had dissolved. To this solution 40 parts of urea were added and the mixture was stirred until most of the .
.

urea had dissolved. This react:Lon mixture was poured into a reactor to which 14 parts of phthalic anhydride had previously been added. The complete reactlon mixture was then placed into a hea-ting vessel which was preheated to 210 C. The temperature was maintained between 190-215 C. ior a period of 3 hours. The tempera-ture was then raised to 260-270 C. and maintained for an additional 3.5 hours. After cooling and grinding the reac-tion product, the material was found by chromatograph to con-tain 54% of the monosulfonated material (Catalyst O, Table II).
The various catalysts were analyzed by a chromatographic separation process to distinguish between the various catalysts produced. The chromatographic separation shows differences between catalyst of the present invention and catalyst of the prior art, however, not all of the catalyst species which are separated are identifiable. Some of the catalyst components are merely listed as Unknowns A and ~, some are listed as two Lorms of a monosulfonate, ~'1 and M2, but it is impossible to draw a picture showing the differences between Ml and il2.
Similarly, the chromatographic process used shows that there are two forms of the disulfonate derivatives, but the exact configuration of the Dl and D2 derivatives is not known. No separation of trisulfonated phthalocyanines occurred, but with highly sulfonated derivatives such as these there vexy well may be varying isomeric dlstributions. The percentage of tetrasulfonated derivatives and non-sulfonated derivatives are lumped together, though the tetrasulfonate derivatives are believed to comprise the majority of this material.

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Tile reaction conditions used to prepare each ca-talyst are also listed, along with the weight ratios of reac-tants used~
Also, reported are tes-ts on some oE the more promising cata-lysts for ac-tivity Eor converting mercaptan sulfur to disul-fides. The -test procedure used was basically that outlined in the solid bed sweetening process of U.S. Patent 3,108,081.
The catalysts were tested for their ability to swee-ten a kero-sene charge stoclc which from prior experience was known to be difficult to sweeten. These experimental tests are only in-tended for comparison purposes. The test procedure used on allcatalysts was uniEorm, i.e., same charcoal support, same reac-tion conditions during the mercaptan oxidation test runs, and same feedstock. Thus, they are believed valid indicators of the relative performances of these catalysts at one particular set of test conditions.
The test results reported are weight ppm mercaptan sulfur remaining in the charge stock after twenty hours of operation through a fixed bed unit. The test results during intermediate hours of operation are also reported for a number of the catalysts which gave the most interesting results. From the test results it appears that the catalysts prepared by the oleum preparation method, and even some of the catalysts of the present invention, actually increase in activity for a few hours and then slowly decline in activity. Some of the catalysts of the present invention exhibited contrary behavior, namely highest activity at the start with a constant decline in activity.
High initial activity followed by a gradual decline in activity ' ~

, .

may be considered the expected r.esult in testing a catalyst, however, it is contrary to expeI~imental results obtained with prior art catalysts. The test method used is, of course, an accelerated test and does not correspond to commercial opera-tion, i.e., commercially, fixed bed sweetening units usuallyoperate for several weeks or months before regeneration is required.
The results are reported under three tables. Table I shows the effect of chanying the concentration of phthalic anhydride on the product, while holding the time and tempera-ture of reaction generally constant. Table II permits some variation in reactants used, but primarily investigates the effect of different temperatures used during catalyst prepara-tion. Table III reports the data obtained at intermediate time intervals in the mercaptan conversion test. ~11 of the catalysts tested in Table III were also included in Table II, however, more extensive data are presented.

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~ rom an inspection OL the above data, it is evident tha-t the catalyst of -the present invention provides excellent activity for the conversion of mercaptans. Especially pre-ferred are catalysts prepared using a single high temperature reaction step, e.g., catalysts S and T. ~hese catalysts had very high activities, and wou:Ld be fairly easy to make commer-cially because of the simplicity of the reaction condi-tions.
Catalysts S and T had higher activity than did Catalyst U, a commercially available mono-sulfonate. It is believed that Ca-talyst U was made by approxiMately the same procedure as Catalyst V, reaction with H2SO4 or oleum, and this belief is further substantiated by an examination of the isomer distribu-tion of these catalysts. The ratio of ~2 -to ~1 is almost iden-tical in each of the oleum route preps, about 2.7 to 1. In contrast the catalyst of the present invention had a signifi-cantly different ra-tio, approximately 0.5:1 for Catalyst S, and 0.8 to 1 for Catalyst T. These ratios refer to different mono-sulfonate isomers, as previously mentioned i~ll and M2 are bo-th isomers of mono-sulfonates. Thus it is believed that catalysts of the present invention are different materials than catalysts prepared by prior art methods. In addition to being a differ-ent material, the catalyst of the present invention is pre-pared by a much simpler method, without the danger both to per-sonnel and the environment, of using a sulfuric acid cr oleum route to prepare sulfonated derivatives.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method of manufacturing a catalytic composition which comprises reacting a 4-sulfophthalic acid compound with a metal salt, an ammonium donor, and a compound selected from the group of benzene-1,2-dicarboxylic acid and derivatives thereof, in aqueous solution by heating to 250 to 325°C for one-half to 10 hours.

2. The method of claim 1 wherein the solution is heated at 250 to 300°C for one to six hours.

3. The method of claim 1 wherein the solution is heated at 165 to 275 C for one to four hours and then heated to 250 to 325°C for one to four hours.

4. The method of claim 1 wherein the solution is heated at 165 to 210°C for one to four hours, 200 to 250°C for one to four hours, and 250 to 325°C for one to four hours.

5. The method of claim 1 wherein the reaction is con-ducted at a pressure sufficient to maintain liquid phase.

6. The method of claim 1, 3 or 4 wherein -the metal salt is selected from the group of a cobalt metal salt, a vanadyl metal salt, a rhodium metal salt, and a manganese metal salt.

7. The method of claim 1, 3 or 4 wherein the ammonium donor is selected from the group consisting of urea, alum, hydrazine, biuret, and guanidine.

8. The method of claim 1 wherein the reaction conditions include the presence of a promoter.

9. The method of claim 1, 3 or 4 wherein the benzene-1, 2-dicarboxylic acid or its derivative is selected from the group of phthalic anhydride, phthalic acid, phthalimide, and 0-dicyano-benzene and phthalamic acid.

10. The method of claim 1, 3 or 4 wherein the 4-sulfo-phthalic acid compound is selected from the group of 4-sulfo-phthalic acid, and salts of said acid.

11. The method of claim 1, 3 or 4 wherein the 4-sulfo-phthalic acid compound is an acid salt of said acid and contains a cation selected from the group of lithium, potassium, rubidium, cesium, barium, strontium, calcium, magnesium, beryllium, titanium, scandium, zirconium, manganese and rhenium.

12. The method of claim 1 wherein 4-sulfophthralic acid.
and phthalic anhydride are reacted in a weight ratio of 1/2:1 to 4:1, respectively.

13. The method of claim 12 wherein the 4-sulfophthalic acid and phthalic anhydride are reacted in a weight ratio of 1:1 to 2:1, respectively.