UNSUPPORTED FIXED-BED CATALYST TABLET AND METHOD FOR MAKING SAME

Abstract: Non-supported, fixed bed catalyst tablets made by spray drying a slurry of the components into microspheres followed by tabletting the microspheres under high pressure in apparatus such as punch and die sets. The catalysts formed according to the process of this invention have better catalytic performance and/or crush strength than do conventionally made pellets such as extrudates.

Description: IMPROVED DEHYDROGENATION CATALYST TABLET AND METHOD FOR MAKING SAME Non-supported, fixed-bed catalyst pellets are used in many chemical processes. Among these are processes for dehydrogenation, hydrogenation, and oxidation of organics. Dehydrogenation processes using such fixed- -bed, non-supported catalysts include the dehydrogenation of ethylbenzene to produce styrene, of ethyl toluene to produce vinyl toluene, and of butane or butene to produce butadiene. Hydrogenation processes which use such fixed -bed, non-supported catalysts include such processes as thau for producing saturated hydrocarbons from olefins. Oxidation processes which use such fixed-bed, non-supported catalyst pellets include such processes as those for making aldehydes and acids from saturated and unsaturated hydrocarbons, e.g., acrylic acid from po- pylene. For the sake of conciseness, the word "pellets" is hereinafter used as a generic term to include those spray dried tablets made by the process of this invention as well as other forms of pellets made by such processes as extrusion, i.e., extrudates. "Tablet" is defined to be any pellet made by the process of this invention. In the past, improvements in the catalytic performance and/or crush strength of non-supported catalyst pellets for the processes referred to above, have generally been obtained by changing the formulation of components. Typically such non-supported catalyst pellets are made by extruding a paste of components through cylindrical dies to form moist cylinders having a diameter of from about 1/16 inch to about 1/2 inch (0.16 -1.27 cm). As these cylinders exit from the extruder the are usually either chopped into predetermined lengths or allowed to break of their own weight, forming cylindrical pellets (extrudates) having a length of from about 1/8 inch (0.32 cm) to about one inch (2.54 cm). Methods other than extrusion have been taught for forming non-supported catalyst pellets. For example U.S. Patent 1,680,807 (August 14, 1928) teaches the formation of catalyst pellets by compression of a multiplic ity of fine particles of catalytic material, which particles are not naturally coherent in the dry state. Spray drying of fluid bed catalysts is known. See U.S. Patents 2,768,145 (Tongue et al. 1956) and 1,680,807 (Scultze 3928). Spray drying catalyst materials on catalyst carriers or supports is known. See U.S. Patent 2,435,379 (Archibald 1948). The present invention is directed to a method for making an unsupported fixed-bed catalyst tablet, said method characterized by (a) spray drying a slurry of catalyst source constituents into microspheres; and (b) forming the catalyst tablet by subjecting a elected amount of the microspheres to compres sive pressure. For some unknown reason this coinbination of steps produces a catalyst tablet having superior catalytic performance and/or crush strength qualities. The present invention is also directed to catalyst tablets made by the process described immedi- ately above. It solid be noted that the phrase "a slurry of catalyst source components" is used above in the spray drying step as opposed to "a slurry of catalyst components". This is done to point out that sometimes the constituents used in making up the slurr for spray drying are not the same components as those found in the final formulation of the catalyst tablets to be used. Often after adding the constituents together! or in sequent steps in making the catalyst pellets, chemical changes occur in these constituents. Thus different constituents other than those started with often appea in the final catalyst pellet formulation. Of course, there are also catalyst slurry formulations which are not changed. This invention is applicable to both. Hence, as used hereinafter the phrase "catalyst source constituents" is defined to mean not only those constituents which appear in one form in the slurry and another form in the finished catalyst tablet, but also to those constituents that appear in the same form in both the slurry and the finished tablet. For example K2CO3 is a source for K20 if the K2C03 is converted to K2O Also K2O itself is a source of K2O by this definition. The tablets made by the claimed process are useful in various organic chemical processes, including dehydrogenation, hydrogenation, and oxidation processes. In many applications the catalyst tablets must be further treated to be useful. For example, dehydrogenation catalyst tablets often must be calcined, while oxidation catalyst tablets often must be heated in the presence of hydrogen or a hydrogen source. The method of making these tablets has found use in making fixed-bed, non-supported, dehydrogenation catalyst tablets for use in the known process of dehydrogenation of alkyl aromatics, e.g., those aromatics having alkyl groups containing from two to eight carbon atoms, and particularly dehydrogenation of ethylbenzene to styrene. This process comprises passing at an elevated temperature, ethylbenzene mixed with steam over catalyst tablets, said catalyst tablets containing at least oxides of iron, potassium and chromium. To specifically illustrate the process by which these new catalyst tablets are made as well as the unexpected improvement in catalytic performance and crush strength of the tablets made by this process, the discussion and examples given below refer to a catalyst tabletting process, and the tablets made by this process, which are used in the dehydrogenation of ethylbenzene to produce styrene. Typically, styrene is made in a dehydrogenation reactor by passing ethylbenzene and steam at an elevated temperature through a bed of catalyst pellets. These pellets are comprised of oxides of iron, potassium and chromium. In the past these pellets have usually been formed by a process comprising: (a) forming a paste comprised of water, lub ricant, binders and catalyst source constituents of the oxides of iron, potassium, and chromium; (b) extruding the paste into cylindrical pel lets having a diameter of fom about 1/8 inch (0.32 cm) to about 3/16 inch (0.4± cm) and a length of from about 1/8 inch (0.32 cm) to about 3/4 inch (1.90 cm); and (c) calcining the pellets at a temperature of from about 500OC to about 1200 C. Producing catalyst tablets utilizing the method of this invention can be accomplished b: (a) forming a slurry capable of being spray dried comprised of water and catalyst source con stituents of oxides of iron, potassium and chromiun (b) spray drying the slurrv to form micro spheres; (c) forming a catalyst tablet from a select amount of the spray dried microspheres by compresse the microspheres; and (d) calcining the tablet at a temperature of at least 5000C. These steps will now be elaborated upon in the following discussion. SLURRY FORMATION In forming a slurry suitable for spray drying, any method can be used which gets the catalyst formation components into an aqueous solution, aqueous suspension, or both. The amount of water present in the slurry is not critical. This amount depends only on the operating capabilities of the particular spray dryer used. A slurry containing from about 20 weight percent to about 70 weight percent water is found satisfactory for nearly al spray dryers. A range of about 4C weight percent to about 60 weight percent water is preferable for most disk type spray dryers. The oxides of iron, chromium, and potassium which are found to be necessary in the final catalyst tablet can be provided jn other chemical forms in the slurry, such as, for example, potassium carbonate, potassium dichromate and ferric oxide. These other chemical forms, however, must be convertible to the oxides during the remainder of the process of making the tablets. The calcining step is usually the step in which these other forms of iron, potassium, and chromium are converted to the oxides, Fe2O3, Cr203, and K2O. It is material in what form the elements of iron, potassium, chromium, and oxygen occur. in the slurry preparation step so long as the can be changed to the oxides themselves in the finished catalyst tablet. In preparing pellets by the old method of extrusion (i.e., preparing evtrtldates), it is known that the water-insoluble constituents of the siurry should be ground or otherwise converted into powdered particles. Usually this powder is available commercially. The same water-insoluble podered ingredients used in the process of producing extrudates are used in the process of this invention. For the comparative runs given below, for each diameter pellet of each formulation, the ingredients used were from the same source. This was done so that there would be no variation in the test results due to variations in the source materials. SPRAY DRYING Spray drying is a process long known as a cess for producing very small, discontimlous, spherical particles from a slurry feed, the particles being micro- spheres usually having a diameter no greater than about 500-1,000 microns for most formulations from most spray dryers. For a general description of spray dryers and their operation, see Perry's Chemical Engineers' Handbook, John H. Perry, editor, Third Edition, McGraw-Hill Book Co., Inc., New York, Toronto, and London, pages 838-545 (1950). Spray dryers are classified into three general categories, cetntifugal disk, pressure nozzles, two-fluid nozzles. Any of these are suitable for use the process of this invention, on, but the disk type is pre- felled foi large-scale commercial operations. Neither the moisture content nor the pti- cle size distribution of the microspheres made by the spray drying step of this invention are critical limitations. However, there are practical limitations that the particular spray dryer being used imposes upon these two parameters, and the microspheres' diameters should not be of the same order of magnitude as the finished non-supported catalyst tablets desired to be produced. Having the diameter of the spray dried microspheres approach the size of the finished tablets poses no problem generally. This is so because the diameter or size of the smallest tablet contemplated by this invention is about 1/16 inch (0.16 cm) while the largest microspheres usually produced by commercial spray dryers are on the order of only about 500-1,000 icrons. This size microsphere is within the operable limits for making the tablets conterlplated by this invention. It was found that better catalytic performance of the catalyst tablets was achieved when the diameter of about 80 percent of the microspheres was greater than about 20 microns. It is preferable to have a particle size distribution of the spray dried microspheres such that about 80 percent of the microspheres have diameters which lie in a range of from about 20 microns to about 200 microns, and more preferable lf this range is from about 20 microns to about 100 microns. Smaller microspheres caused the equipment used in the tabletting step to bind and exhibit extreme ear. The larger sizes caused no perceptible problems. Variaticns in moisture content of the spray dried ijiicrospheres was not critical for the catalytic performance of the finished tablets. moisture content of the microspheres had more of an effect on the operation of the particular spray dryer and auxiliary eguipment used. A moIsture content of ftom about zero weight percent to about 5.0 weight percent produced catalytic tablets which were satisfactory in their catalytic per fcrmance and crush strength as well as for operation of the equipment. Large moisture contents caused poor flow properties. COMPRLSSION INTO TABLETS After spray drying the slurry into microspheres, the next step in the process of this invention is to form relatively large tablets from these microspheres by subjecting predetermined amounts of these microspheres to a compressive pressure. This compressive pressure is not critical, but should be great enough to produce tablets having sufficient crush strength to withstand the physical loads and attrition to which they will ultimately be subjected. Usually such compressive pressures are best achieved in punch and die equiprent As a general rule, the greater the tabletting pressure used, the greater will be the crush strength of the tablets. Tablets with adequate strength were made using a compressive tabletting pressure as low as about 3,000 psi (212 kg/cm2). It is generally preferred to use a compressive pressure of greater than about 15,000 psi (1060 kg/cmê). It is more preferred to use a compressive pressure of from about 22,000 psi (1550 kg/cmê) to about 45,000 psi (3180 kg/cmê) and most preferable to use a compressive pressure of from about 28,000 psi to 38,000 psi (1980-2680 kg/cm2). The higher pressures cf these latter two pressure ranges are chosen as a compromise between acceptable tablet crush strengths and catalytic performance and thc- pressure operating limits of the equipment used. No upper limit was found for the compres- sive pressure, however. Compressive pressure greater than about 130,000 psi (9160 kg/cmê) were used in a laboratory test run which produced very good tablets, but known commercial equipment was not available for larae- -scale manufacture cf tablets made with this large a pressure. Subjection of the spray dried material to compressive pressures greater than from about 3,000-15,000 psi (212-1060 ky/cm2) is herein also referred to as "tab letting". The pellets formed by such tabletting are herein also referred to as "tablets" to distinguish them from those pellets formed by extrusion, herein also referred to as extrudates. In the tabletting step of the process, the molds or dies are chosen with shapes such that the tablets formed will have the desired size and shape. The most preferred shape for fixed-bed, non -supported catalyst pellets produced by any method is spherical. Adequate dies to produce such spherical shapes, however, were not readily available at the time the experiments which follow herein were conducted. Thus no examples are shown for making spherical shaped fixed-bed, self-supporting catalyst tablets. This shape, however, is certainly within the scope of this invention as are other non-cylindrical shaped pellets, such as ellipsoids, cubes, star shapes, frustoconical shapes and hollow cylinders. Generally cylindrically shaped tablets are easier to make and those with convex ends are preferable. There is no critical size limit for these tablets. Catalytic periorma!ice tends to fall off as the diameter of the tablets varies from about 3/16 inch (0.48 cm) in the strene reactors tested. The diameter of these cylindrical tablets can be from about 1/leo inch (0.16 cm) to about one inch (2.54 cm). Preferably the diameter is from about 1/8 inch (0.39 cm) to about 1/2 inch (1.27 cm), with a more preferred diameter being from about 1/8 inch (0.32 cm) to 1/4 inch (0.64 cm). The most preferred diameter is 3/16 inch (0.48 cm). The length of the cyl & - ders can be from about 1/16 inch (0.16 cm) up to about one inch (2.54 cm). It has been found, however, that less attrition and mechanical breakage of the tablets occur if the tab]ets are made so that their length is approximately the same as their diameter. CALCINTIllG Following the compression of the microspheres to form tablets, these tablets are usually calcined. Typically calcining is carried out at a temperature of from about 500 C to about 12000C for a time of from about 1 or 2 to about 20 hours. Calcining can be carried out in a special calcining chamber or in the reactor itself. This calcining step for the tablets formed by the method of this invention is carried out in virtually the same manner as has hereto four been done for the calcining of extrudates. Examples of Making Spray Dried Tablets by the Method of this Invention A scurry was made as follows: To 1411 U.S. gal (5330 1) of water were added the following water -soluble solid constituents in the amounts given: 56GO lb (2540 kg) of K2CO3#3/2H2O, 839.5 lb (381 kg) of K2 Cr207, and 839.5 lb (381 kg) of V205. To this solution was added the following water-insoluble solid components in powdered form in the amounts given aiid in particle size distribution given: 14,573 lb (6610 kg) of Fe203 powdered particles ranging in size from about 3 microns to about 49 microns, 6883 lb (2670 kg) of Fe2O3#H2O powdered particles ranging in size from about 2 microns to about 52 microns, 869 lb (395 kg) of Portland cement ranging in size from about 2 microns to 55 microns, 4278 Ib (1943 kg) of methyl cellulose (a binder) powdered particles ranging in size from about 3 microns to about 250 microns; and 4145 ib (1880 kg) of graphite powdered particles ranging in size from about 1 micron to about 13 microns. Additional water was added to the above slurry so there was a solids to water ratio of 0.94:1 in the resulting slurry. This suspension was then fed as the feed to the feed inlet pu. of a centrifugal rotating disk type spray dryer at a temperature of 300C. The model used had an atomizing disk wheel 5 inches (12.7 cm) in diameter which was located near the top of the drying cham bor of the spray dryer. The drying chamber was conical in shape and supported vertically with the larger portion above the smaller portion. Its largest diameter was 7 feet (2.14 m) and its height was 12 feet (3.66 m). The flow of the drying air was concurrent to the downward falling of the microspheric particles. The rate of the feed to the atomizer disk '7as 0.77 U.S. al/min (2.91 l/m). The disk was rotated at a speed of 21,600 rpm. The inlet temperature of the drying air was 960 C while its outlet temperature was 1490C. The dried microspheres were exhausted from the spray drying chamber of the spra dryer into its bag filter collector. The microspheres were observed to be both of the ruptured surface and smooth surface type. They had a particle s?.ze distribution of from 5 microns to about 27 microns diameter with moisture of less than 1 weight percent. The microspheres were then fed to a tabletting machine having 0.200 inch (0.51 cm) inside diameter dies and ere compressed with punches at a pressure of 36,400 psi (2570 kg/cm2). The tablets produced by the tabletting machine were cylindrical in shape. They were 0.210 inch (0.52 cm) in diameter and 0.180 to 0.290 inch long (0.46-0.74 cm). They had an average crush strength of 29 lb (13.2 kg) as measured by a hardness tester instrument. The tablets were then calcined in a kin at temperatures ranging from 6830C to 7320C with an average temperature of 703 C for 1 to 1.5 hours. Fullowing calcination, the tablets were observed to have an average relative crush strength of 27 1b (12.2 kg) measured by the same instrument used above to measure the uncalcined tablets. The calcined tablets were then analyzed and found to contain Fe203 - 70.2 wt. %; K20 - 4.6 wt. %; K2CO3 - 10.6 . 6 wt. %; Cr2O3 - 2.8 wt. %; V205 - 4.0 wt. %; cement - 3.3 wt. %; carbon - 4.3 wt. %. Examples and Comparative Runs Eighteen experiments were made so that nine pairs of comparisons could be made between the catalvtic performance and crush strength of catalyst tablets made by the method of the present invention and the catalytic performance and crush strength of catalyst extrudates made by conventional extrusion. In each pair of experiments made, the catalyst pellets (tablets and extrudates) were made from the same formulation and had the same diameter. Three different formulations were used and three different di am- eters for the catalyst pellets were used for each formulation. Two different methods of pellet preparation were used for each dieter. The comparisons made are between those pairs of experiments in Table II whose catalyst pellets were made from the same formulation and have the same diameter. In all of these experiments ethyl bezene (EB) was dehydrogenated to form styrene. Data are assembled in Table II. The three different formulations used are well-known, useful dehydrogenation catalysts. The particular constituents of these formulations and their weight ratios (excluding free water) are given in Table T, These specific formulations are herein referred to as F-1, F-2, and F-3. TABLE I Slurry Formulations (wt. Percent) Methyl Catlyst Fe2O3 Fe2O3#H2O K2CO3#3/2 H2O K2Cr2O7 Cr2O3 V2O5 Cement Cellulose Graphite F-1 79.7 - 18.0 - 2.3 - - - F-2 50.6 12.6 17.9 2.7 - 2.7 3.0 8.9 1.6 F-3 9.6 64.4 20.5 2.2 - - 3.3 - - The three different pellet diameters chosen for testing each formulation were 1/8 inch (0.3s cm), 3/16 inch (0.48 cm) and 1/2 inch (1.27 cm). In the past, conventional catalyst pellet diameters have ranged from about 1/8 inch (0.32 cm) to about 1/4 inch (0.64- cm). It is known that smaller diameter pellets are normally more active and have greater crush strength than larger ones. Large diameter pellets have the advantage of producing less pressure drop in the reactor, which allows the use of a lower absolute pressure than would be permitted otherwise. This in tur increases the conversion of the ethylbenzene. Thus a compromise has been utilized in the past between using a smaller catalyst pellet which has greater catalytic activity, and using a larger catalyst pellet which allows a lower operating pressure. With the present invention such a compromise still has to be made, but by this invention, larger catalyst pellets can be used with less loss in catalytic activity and crush strength as was experienced before when using conventionally made extruded pellets. In the examples and comparatJve runs below pellet crush strength was determined on an average value of 20 pellets (tablets and extrudates) from each of the 18 batches of pellets made using a harmless tester instrument. This instrument gives a reading proportional to the total force, in units of pounds force (kg/force), requiredto crush the pellets. The two different methods of catalyst preparation used for each diameter of each formulation were (1) the conventional method of extruding a paste into pellet extrudates and then calcining the extrudates, and (2) spray drying a slurry containing the catalyst constituents, sufficiently compressing the microspheres in a tabletting machine to form tablets of the same diameters and formulations as the extrudates, and then calcining the tablets. A detailed elaboration of these two methods for preparing the catalyst extrudates and tablets is given following Table II. The extrudates and tabletted pellets prepared for each diameter of each formulation were tested for performance in mini-reactors. The reactor used for both the 1/8 inch (0.32 cm) and 3/16 inch (0.48 cm) ex.tl-udates and spray dried tablets was a part of a 35 inch long (0.89 m), 1 inch diameter (2.54 cm), 316 stainless steel pipe. The reactor used for the 1/2 inch (1.27 cln) diameter extrudates and spray dried tablets required a 1.5 inch (3.81 cm) diameter pipe. Otherwise the r.lini-reactors were the same. The pipes fo both of these mini-reactors were erected upright. Both reactors were fitted with a beaded wire heater and heater control means to control the temperature in their reactor zones and were well insulated. In every experiment, in either size reactor, the catalyst pellets were installed in the mini-reactors to form a catalyst bed 7 inches high (17.8 cm). Beneath the catalyst bed, but still in the pipe, 11 inches (27.9 cm) of spacers were installed to support the catalyst pellets. Above the catalyst bed, but still in the pipe, a 17-inch (43.2 cm) section of the pipe was used as a preheater and mixing zone. This zone contained porcelain saddles for column packing. The preheater section also had a beaded wire heater wrapped around it as did the heater for the reactor section of the pipe described above. Into this preheater there was fed 99 percent pure ethylbenzene (EB) and water. As the EB and water fed through the preheater stage they were heated to a temperature approaching reaction temperature. This temperature is above the vapor forming phase of the EB and the water. The porcelain saddles and boiling action of the EB and water caused the EB and water to become a well mixed vapcr mixture. In this vapor state t mixed ture entered the reactor zone of the pipe in which were located the catalyst pellets (extrudates or tablets). The liquid hourly space velocity (LHSV) (LHSV is defined as the volume flow of fluid per hour divided by the volume of catalyst present) of the ES-steam mixture was maintained at 1.0 vol/vol/hour. The weight ratio of the steam used to the EB used was maintained at 2.0:1. For each batch of pellets tested, the operating temperature for the reactor was kept constant for each of the runs of a particular formulation, i.e., all the F-1 formulation experiments were made at 575 C, the F-2 at 6100C and the F-3 at 600 C. Conversion data are given in Table II. TABLE II Examples and Comparative Runs Made at Constant Temperatures for Each Formulation Average Type Crush % Conv. of Pllet of Strength Operating EB Experiment No. FormulationÚ Diameter Pellet lb (kg) Temp. ( C) to Styrene Comparative Run 1 F-1 1/8" (0.32 cm) EXê 19 (8.6) 575 38.86 Example 1 F-1 1/8" (0.32 cm) SDT 37 (16.8) 575 48.82 Comparative Run 2 F-1 3/16" (0.48 cm) EX 13 (5.9) 575 40.30 Example 2 F-1 3/16" (0.48 cm) SDT 35 (15.9) 575 41.14 Comparative Run 3 F-1 1/2" (1.27 cm) EX 37 (16.8) 575 9.13 Example 3 F-1 1/2" (1.27 cm) SDT 37 (16.8) 575 17.24 Comparative Run 4 F-2 3/8" (0.32 cm) EX 20 (9.1) 610 57.49 Example 4 F-2 1/8" (0.32 cm) SDT 20 (9.1) 610 61.24 Comparative Run 5 F-2 3/16" (0.48 cm) EX 16 (7.25) 610 50.39 Example 5 F-2 3/16" (0.48 cm) SDT 30 (13.6) 610 57.49 Comparative Run 6 F-2 3/2" (1.27 cm) EX 36 (16.3) 610 29.32 Example 6 F-2 1/2" (1.27 cm) SDT 36 (16.3) 610 35.64 Comparative Run 7 F-3 1/8" (0.32 cm) EX 21 (9.52) 600 55.38 Example 7 F-3 1/8" (0.32 cm) SDT 21 (9.52) 600 58.40 Comparative Run 8 F-3 3/16" (0.48 cm) EX 6 (2.72) 600 50.89 Example 8 F-3 3/16" (0.48 cm) SDT 16 (7.25) 600 56.44 Comparative Run 9 F-3 1/2" (1.27 cm) EX 15 (6.80) 600 33.13 Example 9 F-3 1/2" (1.27 cm) SDT 15 (6.80) 600 38.24 ÚSee Table I for formulation data for F-1, F-2, and F-3 êPellets made by conventional catalyst extrusion methods. Spray dried tablet made by the method of this invention. From Table II it can be seen that the crush strength of the spray dried tablets prepared by the method of this :invention ras as good or better tan that of the conventionally made extrudates for a given formulation and a given diameter. Further, it is seen that in every case the tablet made by the method of this invention produced a higher conversion of ethylbenzene to sty rent. The extrudate pellets cf the three formula tiocs used were made by the conventional extrusion method. This method is as follows: First the soluble components used for making the extrudates for each particular batch were dissolved in water. The water-insoluble components were in powder form and were thoroughly mixed. The water-soluble constituents cf the formula tions in Table I are K2CO3#3/2H2O, K2Cr2O7, and V2O5. The small particles of water-insoluble constituents of the formulation being used were then added to the solution of water-soluble constituents of that formulation and thoroughly mixed to form a slurry having about 75 weight percent solid material. This solid material percentage is calculated by considering both the soluble and insoluble material as solid. Next the resulting mixed slurries were dried in an oven at 110 C until the free water content of each mixture was do to 10 to 12 weight percent so that a paste was formed. The paste for each formulation and each of the three diameters used was then extruded using a commerical type pellet mill. The extrudates formed by this pellet mill varied in length from 1/8 inch (0.32 cm) to 1/2 inch (1.27 cm) for each of the three diameter pellet extrudates produced, with The larger diameter pellets tending to have the longer lengths. These lengths were formed as the continuous extrusions of paste exiting from the pellet die was cut by a knife. The pellet extrudates were then calcined at a temperature cf about 7000C-9000C for 3 hours. The different batches of spray dried tablets made for the comparative runs of Table II were made by first forming the constituents of the particular formulation into a water slurry in the same way the mixture used to form the paste for the conventional extrudate pellets above was made. Thus, the water-soluble constituents were added to water and this solution was thoroughly mixed with the water-insoluble components obtained from The same source from which the insoluble constituents were obtained. The slurry contained about 35 weight percent solid material. The weight percent of the solid material of the slurry was calculated as including the water-soluble as well as the water-insoluble constituents. The slurry was fed to a laboratory disk type spray drier where it was led from a reservoir to the top of the atomizer wherein it was passed down a feed tube to an atomizer wheel. The slurry entered the interior of the wheel and because of the high rotational speed of the wheel (40,000 rpm), it is flung outward at a high rate of speed in droplet form. These droplets produced a very fine, uniform mist. This mist entered the drying chamber of the atomizer from the periphery of the atomizer wheel. The atomizer wheel had a diameter of 63 millimeters. The drying air at the drying chamber inlet was maintained at 2100C and the outlet temperature in the cyclone filter was maintained at 900C. The feed rate to the atomizer was maintained at about 1000 grams/hour. The spray dried microspheres produced for all the e > .peri- mental runs using spray dried tablets contained about 2 percent moisture. Their diameters ranged from about 10 microns to about 50 microns with most of the microspheres having a diameter close to 30 microns. Under an electron microscope some of these microspheres appeared to be of the hollow ruptured type. These microspheres were then fed to a manually operated pellet press having dies with the same inside diameter as that desired for the tablets1 i.e. 1/8 inch (0.32 cm), 3/16 inch (0.48 cm), and i/2 ine (1.27 cm). The dies used were filled with the spray dried microspheres. Sufficient amounts of microspheres were used in the dies so that the length and diameter of the tablets formea- were the size Ti3 tablets were cylindrical in shape with ends which were slightly convex. Following the tabletting of the spray dried microsphere the formed tablets were then calcined in the same way as were the conventionally made extrudates above, i.e., these spray dried tablets were heated at a temperature of about 700C to about 9000C for about 3 hours. The crush strength of these spray dried tablets used in Table II were measured following the calcining of the spray dried tablets.

Claims: WHAT IS CLAIMED IS: 1. A method for making an unsupported fixed- -bed catalyst tablet said method characterized by (a) spray drying a slurry of catalyst source constituents into microspheres; and (b) forming the catalyst tablet by subjecting a selected amount of the microspheres to a compres sive pressure. 2. The catalyst tablets made by the process of Claim 1. 3. The process of Claim 1 wherein the microspheres are subjected to a compressive pressure of at least 3000 psi (212 kg/cm2). 4. A process as in Claim 1 wherein following the compression of the microspheres into tablets, the tablets are calcined at a temperature of at least 5000C for a time of at least one hour. 5. The calcined tablets made by the process of Claim 4. 6. A method for making an improved unsupported fixed-bed catalyst tablet characterized by (a) forming microspheres from a slurry of catalyst source constituents of the oxides of iron, potassium, and chromium by spray drying a slurry containing these catalyst source constituents; (b) forming a catalyst tablet by subjecting a preselected amount of the mocrosphere to a compres sive pressure of at least 3000 psi (212 kg/cmê); and (c) calcining the tablet at a temperature greater than 5000C. 7. The catalyst tablet made by the process of Claim 6. 8. A method for making an unsupported fixed -bed catalyst tablet for use in the dehydrogenation of ethylbenzene to styrene characterized by (a) spray drying a slurry into microspheres, with said microspheres having an average diameter of from 20 microns to 200 microns and a moisture con tent no greater than eight percent, with said slurry being compound of water and catalyst source constituents of the oxides of iron, potassium, and chromium, and with said slurry having a water con tent of from 20 weight percent to 70 weight percent; ; (b) forming a substantially cylindrically shaped tablet from a preselected amount of said micro spheres by subjecting these microspheres to a compres sive pressure of at least about 22,000 psi (1550 kg/cm2), said tablet having a diameter of from 1/8 inch (0.32 cm) to 1/2 inch (1.27 cm); and (c) calcining the tablet at a temperature of at least 500qC.

Inventors: CASTOR, WILLIAM MACK, MENEGOS, PETE JAMES
Applicants: THE DOW CHEMICAL COMPANY
Application year: 1979
Main classification: B01J37
IPC codes: B01J37, B01J23, C07C5