HIGH SURFACE AREA CATALYSTS, THEIR PREPARATION, AND HYDROCARBON PROCESSES USING THEM

Abstract: A high surface area catalyst is prepared by adding a thermally decomposable compound of at least one catalytic metal to a hydrocarbon oil chargestock (10) in amounts such that the resulting mixture has a ratio of Conradson carbon atoms to catalytic metal atoms of less than 750 to 1. The mixture is heated (12) in the presence of H₂ and/or H₂S-­ containing gas (14) to produce a solid, high surface area catal­ yst which is separated from the remaining chargestock, e.g. by filtering, centrifuging or settling (18). The thus recovered catalyst may be combined with other catalytic materials, and is useful in the catalytic processing of hydrocarbonaceous oils (e.g. in catalytic cracking, hydrocracking, reforming, hyd­ rodesulfurization).

Description: HIGH SURFACE AREA CATALYSTS, THEIR PREPARATION, END HYDROCARBON PROCESSES USING THEI This invention relates to the preparation of high surface area catalysts and catalyst supports and their use in hydrocarbon treating processes and chemical processes. Hydrorefining processes utilizing dispersed catalysts in adnixture with a hydrocarbonaceous oil are well known. The term "hydrorefining" is intended herein to designate a catalytic treatment, in the presence of hydrogen, of a hydrocarbonaceous oil to upgrade the oil by eliminating or reducing the concentration of contaminants in the oil such as sulfur compounds, nitrogenous compounds, metal contaminants and/or to convert at least a portion of the heavy constituents of the oil such as asphaltenes or coke precursors to lower boiling hydrocarbon products, and to reduce the Conradson carbon residue of the oil. U.S. Patent 3,161,585 discloses a hydrorefining process in which a petroleum oil chargestock containing a colloidally dispersed catalyst selected from the group consisting of a metal of Groups VS and VIB, an oxide of said metal and a sulfide of said metal is reacted with hydrogen at hydrorefining conditions. This patent teaches that a concentration of the dispersed catalyst, calculated as the elemental metal, in the oil chargestock is from about 0.1 weight percent to about 10 weight percent of the initial chargestoc. U.S. Patent 3,331,769 discloses a hydrorefining process in which a metal component (Group VB, Group VIB, iron group metal) colloidally dispersed in a hydrocarbon aceous oil is reacted in contact with a fixed bed of a conventional supported hydrodesulfurization catalyst in the hydrorefining zone. The concentration of the dispersed metal component which is used in the hydrorefining stage in combination with the supported catalyst ranges from 250 to 2500 weight parts per million (wppm). U.S. Patent 3,657,111 disclosed a process for hydrorefixing an asphaltene-containing hydrocarbon chargestock which comprises dissolving in the chargestock a hydrocarbon-soluble oxovanadate salt and forming a colloidally dispresed catalytic vanadium sulfide in situ within the chargestock bv reacting the resulting solution, at hydrorefining conditions, with hydrogen end hydrogen sulfide. U.S. Patent 3,131,142 discloses a slurry hydro- cracking process in which an oil soluble dispersible com pound of Groups IV to VIII is added to c heavy oil feed. The catalyst is used in amounts ranging from 0.1 to 1 weight percent, calculated as the metal, based on the oil feed. U.S. Patent 1,876,270 discloses the use of oil soluble organometallic compounds in thermal crackling or in destructive hydrogenation (hydrocracking) of hydrocarbons to lower boiling products. U.S. Patent 2,091,831 discloses cracking or destructive hydrogenation carried out in the presence of oil soluble salts cf acid organic compounds selected fro::i the group consisting of carboxylic acids and phenols with a metal of Group VI and Group VIII of the Periodic Table. The oil soluble salt is used in amounts between 4 and 20 weight percent based on the feed. It has now been found that high surface area catalysts can be prepared by adding a thermally decomposable metal compound catalyst precursor to a hydrocarbon oil having a Conradson carbon content up to about 50 weight percenr, converting the catalyst precursor to a catalyst within the oil feed and recovering tie resulting high surface area catalyst. IT accordance with the invention, there is provided a method of preparing a high surface urrea catalyst comprising the steps of: (a) adding to a hydrocarbon oil chargestock having a Conradson carbon content of up to 50 weight percent, at least one thermally decomposable metal compound in an amount sufficient to provide a ratio of atoms of oil chargestock Conradson carbon to atoms of metal constituent of said thermally decomposable metal compound of less than 750 to 1, said metal constituent being selected from the metals of Group II, Group III, Group Th7, Group V, Group VIB, Croup VIII and Group VIII of the hereinafter specified Periodic Table of Elements and mixtures of such metals; (b) beating said thermally decomposable metal compound within said chargestock at an elevated temperature in Lhe presence of a gas selected from a hydrogen-containing gas, a hydrogen silfide-containing gas, and a gas comprising hydrogen and hydrogen sulfide to produce a solid, high surface area catalyst with said chargestock, and (c) recovering said high surface arca catalyst. By the expression "ratio of atoms of Conrad son carbon of the oil chargestock to atoms of metal constituent" is intended herein the following relation: weight of Conradson carbon residue 12 weight of the metal constituent of the thermally decomposable compound atomic weight of the metal The high surface area catalysts of the present invention are preferably made by utilizing a hydrocarbonaceous oil chargestock boiling at atmospheric pressure above about 2210C, preferably above about 280 C, more preferably above about 3430C. These hydrocarbon oils may be derived from any source such as petroleum, oil shale, tar sands and oils derived from coal liquefaction processes. The Conradson carbon residue of these oils will generally range up to about SO weight percent, preferably bclow about 30 weight percent (as to Conradson carbon residue, see ASTM test D-189-65). By way of example, suitable hyd-;ocarbon oil chargestocks for the process of the present invention include virgin gas cti, vacuum gas oil, coker gas oil, visbreaker gas oil, petroleum dlstillates, white oils, hydrocarbon oils derived rrem coal liquefaction processes, coal liquefaction bottolus, synthetic polymer oils such as ethylene oligomers, synthetic and natural waxes, etc. Preferably, the oil is a mixture of hydrocarbons boiling at atmospheric pressure, in the ranee of about 343 to 5650C. More preferably, the hydrocarbon chargestock comprises at least 50 percent of the Conradson carbon in the form of a hydrocarbon stream comprising more than 1 weight percent Conradson carbon residue, such as iesidua, whole crudes, etc. To the hydrocarbon oil chargestock is added a thernally decomposable metal compound, wherein the metal constituent is selected from the group consisting of Groups II, III, IV, V, VIB, VIIB, VIII and mixtures thereof of the Periodic Table of Elements. A sufficient amount of a single thermally decomposable metal compound or of a mixture of metal compounds is added to the oil to provide a ratio of atoms of Conradson carbon of the oil chargestock to atom of metal constituent of the thermally decomposable compound or compounds of less than about 750 to 1, preferably less than abon. 500 to 1, more preferably loss than 100 to 1. Suitable ranges of ratio of atoms of Conradson carbon of thc oil to atom of metal con stituont of the thermally decomposable metal compound include an atomic ratio ranging from about 2 to 1 to about 600 to 1, preferably from about 2 to 1 to about 300 to 1, more preferably from about 4 to 1 to about 100 to 1. Tils, the amount t of thermally decomposable metal compound added will vary depending on the Conradson carbon of the oil feed actually used so as to provide the ratio required to obtain high surface area catalytic solids. Suitable thermally decomposable metal compound con vertlble (under preparation conditions) to solid, non colloidal catalyst include (1) inorganic metal compounds such as carbonyls, halides, oxyhalides, poly acids such as isopoly acids and heteropolyacids (e.g., phosphomolybdic acid, and molybdosilicic acid); (2) metal salts of organic acids such as acylic and alicyclic aliphatic carboxylic acids and thiocarboxylic acids containing to or more carbon atoms (e.g., naphthenic acids); aromatic carboxylic acids (toluic acid); sulfonic acids (e.g., toluenesulfonic acid); sulfinic acid; mercaptens; xanthic acids; phenols, di- and polyhydroxy aromatIc compounds; (3) organometallic compounds such as metal chelates, e.g., with 1,3-diketones, ethylenediamine, ethylenediaminetetraacetic acid, phthalocyanines, etc.; (4) metal salts of organic gamines such as aliphatic amines, aromatic amines and quaternary ammonium compounds. The metal constituent of the thermally decomposable metal compound, that is convertible to a solid, non-colloidal catalyst, is selected from the group consisting of Groups II, III, IV, V, VIB, VIIB and VIII and mixtures thereof of the Periodic Table of Elements, in accordance with the table published by E. H. Sargent and Co., copyright 1962, Dyna Slide Co., that is, zlnc, antimony, bismuth, titanium, cerium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel and the noble metals including platinum, iridium, palladium, osmium, ruthenium and rhodium. te preferred metal constituent of the thermally decomposable compound is selected from the group consistiong of molybdenum, tungsten, vanadium, chromium, cobalt, titanium, iron, nickel and mlxtures thereof. Preferred compounds of the given metals include the salts of cyclic (straight or branched chain) aliphatic carboxylic acids, salts of alicyclic aliphatic carboxylic acids, heteropolyacids, carbonyls, phenolates and organoamine salts. When th thermally decomposable metal compound is added to the hycrocarbonaceous chargestock, it first dcsolves or disperses in the oil and subsequently, under catalyst pre- paration conditions herein described, is converted to a solid high surface area catalyst. Tne oil chargestock comprising the thermally decom- posable metal compound is heated at a temperature ranging from about 199 C to about 571 C, preferably ;-. a temperature rang- ing from about 260 C to about 482 C, more preferably at a temperature ranging from about 316 C to about 449 C, at a pressure of either from atmospheric or superatmospheric, prefereby at superatmospheric pressure In the presence of 2 gas selected from the group consisting of a hydrogen-ccntain- ing gas, a hydrogen sulfide-containing gas, and a gas comprising hydrogen and hydrogen sulfide, preferably at least 50 psig of such gas More preferably, the gas comprises hydrogen and hydrogen sulfide. The hydrogen sulfide may comprise from about 1 to 90 mole percent, more preferably from about 2 to 50 mole percent of the hydrogen-containing gas. Suitable total pressures in the catalyst preparation zone when the heating step is being conducted include a pressure ranging up to about 5000 psig, 'preferably a pressure ranging from about 100 to about 3000 psig. Suitable reaction times include from about 5 minutes to about 4 hours, preferably from about 10 minutes to 2 hours. Contact of the solution under catalyst prepar.9tion conditions in the reaction zone within the hydrogen sulfide containing gas converts the metal compound to the corresponding metal catalyst. The oil containlng the solids is removed from the catalyst preparation zone. The solids may be separated from the oil b conven- tional means, for example, by settling or centrifuging or filtration of the scurry. The recovered solids are the high surface area catalysts of the present invention. The surface area of these catalysts will be at least about 50 m2/g and range from about 60 to about 600 m2/g, usually from about 00 to about 500 m2/g. Generally, the high surface area catalyst of the present invention comprise at least 10 eight percent, preferably above abort 20 weight percent, c.ore preferably above about 40 weight percent of the metal constituent, calculated as elemental metal, corresponding to the metal constituent of the added the-mally decomposable metal compound, said weight being based on the total high surface rea catalyst. The catalyst of the present invention may be prepared either in a batch process or In a contintlous type operation. The solids that are recovered from the reaction produce of the catalyst preparation zone are suitable as catalysts, catalyst components or catalyst supports for use in a number of chemical processes and hydrocarbon treating processes such as catalytic cracking, hydrogenation, hydrogen refining, hydrodesulfurization, hydrocracking, reforming, etc., expecially for hydroprocesses. The term "hydroprocess" is intended herein to mean a process conducted in the presence of hydrogen il. which the hydrocarbonaceous oil feed is either upgraded (refined) without substantial change in the boiling range of the oil or a process in which the hydrocarbonaceous oil is converted to lower boiling hydrocarbon products The operating conditions to be employed in the hydrocarbon treating processes are well known and will vary with the particular reaction desired. The following table surnnarizes typical reaction conditions in which the catalysts of the present invention can be utilized. Principal Hydrogen Rate Reaction Desired Temperature, F. Pressure, psig SCF/bbl Hydrorefining 500-800 50-2000 500-10,000 Hydrodesulfurization 600-850 500-3500 300-20,000 Hydrocracking 450-950 200-3000 300-10,000 Catalytic Cracking 700-1300 0-50 0 Catalytic Reforming 850-1000 50-1000 500-10,000 The feedstocks suitable for the treating process in accordance with the inventIon include any of he well known feeds conventionally employed in the desired treating processes Suitable feedstocks for the hydrocarbon creating processes of the present invention include hydrocarbonaceous oils derived from any source such as petroleum, shale, tar sand, coal liquefaction processes. Typically, such feeds Include naphthas, gas oils, atmospheric residue, vacuum residua, whole petroleum crude oils, including heavy crude oils, bitumen, etc. The motel constituent or metal constituents of the solids of the present invention can be varied by urging ore or more initial thermally decomposable me compounds which are subsequently thermally decomposed. Alternatively, the recovered solids may be used as support terlals for on kno7n catalytic metal components. Thus, a recovered solid may be composited in a conventional manner with metal constituents that are known to catalyze a given process. The compositing of the solids with the additional catalytic agents may be performed by impregnating the recovered solids comprising one or more metal constituents with catalytic components or precursors in any conventional way, such as contact or the solids with a dissolved salt of the desired metal or metals or by a method such as disclosed in U.S. Patent 3,959,179 The compositing of the recovered solids may be performed by depositing a desired catalytic metal component or precursor of a catalytic metal component on the surface of the solids, including contacting of the solids it vapor phase materials. Furthermore, physical mixtures of two or more different recovered solids may be used in certain processes, for example, a catalytic recovered solid having one or more metal constituents which is different from another recovered catalytic solid herein differert initial thermally decomposable metal compounds were used. The catalyst of the present invention may be used in a moving bed, fixed bed, fluidized bed, ebullating bed, suspension (transferline) or in slurry processes. The invention is now further described by usy of non-limitative examples thereof, a.d with refcrence to the accompanying drawings in which: Figure 1 is a schematic flow plan of one embodiment of the invention. Figure 2 is a graph slowing the surface areas of a molybdenum-. containing catalyst relative to the atomic ratio of Conracison carbon to metal constituent of the catalyst precursors. Figure 3 is a graph showing the effect of preparation variables on the formation of tungsten containing catalysts. Referring to figure 1, a mixture of a gas oil fted having an atmospheric pressure boiling point of from about 3430C to 5650C and Cold Take Crude containing an added thermally decomposable metal compound is introduced by line 10 into a catalyst preparation reactor 12 and maintained therein for 10 minutes to 2 hours. The ratio of atoms of Conradson carbon of the oil to atoms or metal constituent of the added thermally decomposable metal compound is between 5 to 1 and 100 to 1. A gaseous mixture comprising hydrogen and from about 2 to 50 mole percent hydrogen sulfide is introduced into reactor 12 by line 14. The catalyst preparation zone in reactor 12 is maintained at a temperature from about 316 to about 449 C and at a pressure ranging from about 100 to 3000 psig. The reactor effluent is removed by line 16. The effluent comprises an oil, gases and a solid. The solid is the high surface area catalyst of the present invention. The surface area of the recovered catalyst ranges from about 100 to about 400 m2/g. The effluent is introduced into a gas-liqui separator 18 where hydrogen and light hydrocarbons are removed overhead through line 20. The liquid stream containing dispersed catalyst solids is removed from separator vessel 18 via line 22. The catalytic solids are removed from the liquid stream 22 by conventional means such as centrifuging, settling, etc. The following examples are presented to illustrate the invention. EXAMPLE 1 A high surfacc area catalyst of the present invLr:t ion was pi- pared as follows: a mixture of 17.3 grams of molybdenum naphthenate (6% molybdenum content) from Shepherd Chemical Company and 371.3 g.a.:s of light Arabian vacuum gas oil (0.46 wt.% Conradson carbon content) was charged to a 1 litre autoclave under 2000 psig of hydrogen pressure at room temperature. The autoclave was heated to 4490C over a period of 95.8 minutes and held at this temperature for 28 minutes and cooled rapidly. The autoclave was vented and tile liquid contents containing a solid precipitaLe was discharged. The solids were isolated by filtration, washed sequentially with toluene and hexane and dried under inert atmosphare. The solids weighed 1.88 grams and gave the analyse listed in Table I. The isolated solids comprise an embodiment of the high surface art catalysts of the present invention. TABLE I Composition Atomic Analysis*, element wt.7 Ratio No 47.12 1.03 8 34.98 2.22 C 11.82 2.00 H 1.12 2.26 Characteristics Pore Volume, cc/g 2.1 Surface Area, m2/g 335 C Pore Diameter, A 240 * X-ray pattern shows NoS2 EXAMPLE 2 (Run 345) A mixture of 90.5 g. of Light Arab vacuum gas oil (Conradson carbon content 0.46 wt.%) and 25.95 g. of molybdenum naphthenate (6.0% molybdenum content, obtained from the Shepherd Chemical Co.) was charged to a 300 cc stirred autoclave. The ratio of atoms of Conradson carbon to atoms of molybdenum in this mixture is 2.14. The air was flushed with hydrogen and the autoclave then prEssured with 100 psia of H2S and 2000 psia of hydrogen at room temperature. The autoclave was heated at 724 0F for 30 minutes, cooled to room temperature, vented and the autoclave contents filtered to isolate a solid The solid was washed on the filter paper with 0.8 l of hot toluene and then with 0.5 l of warm hexane to remove all adsorbed heavy hydrocarbons. The washed solid was then dried in an oil pump vacuum oven at 160 C. for 1 hr. The dried solids weighed 2.S4 g. and contained 54.8% molybdenum, 7.36% C and 0.82% H. The surface area of this solid was 361 mê/g. EXAMPLE 3 (Forms 329, 340, 344 and 354) Experiments similar co Example 2 were carried out in which various portions of the gas oil were replaced by Cold Lake crude (Conradson carbon 12.8 wt.%) so as to adjust the ratio of atoms of Conradson carbon to molybdenum to 6.5, 34.8, 300 and 616. The surface areas of these solids products ware respectively 356 m2/g 281 m2/g, 153 m2/g, and 64 m2/g. The carbon contents of these solids were 14.03%, 21.50%, 39.00%, and 49.10%, respectively. The tolybdenum contents were 48.2%, 42.9%, 31.6% and 22.4%, respectively. EXAMPLES 4 (Experiments 327 and 321 Experiments similar to Example 3 were done in which no H2S was added to the autoclave. The Conradson carbon to molybdenum atom ratios were 6.5 and 8.9, and the surface are obtained were 242 m2/g and 227 m2/g, respectively. The carbon contents of these solids were 16.60% and 16.35%, respectively. The molybdenum contents were 46.6% and 47.0%, respectively. EXAmPLE 5 The results of Examples 2, 3 and 4 were plotted in Figure 2 and show that solids with surface areas greater than 2 50 m Ig are obtained when the Conradson carbon to metal atomic ratio in the feed mixture is less than about 750. It is also shown that the presence of H2S enhances the surface area obta ined. EXAMPLE 6 (Run 445) A mixture of 88.4 g. of Light Arab vacuum gas oil (Conradson carbon contenc 0.46 wt.%), 3.1 g. of Cold Lake crude (Conradson carbon content 12.8 wt.%) and 25.95 g. of tungsten resinate (22.2 wt.% tungsten obtained from Engelhand Industries) was charged to a 300 cc stirred autoclave and the air flushed out with hydrogen. n this mixture the Cold Lake crude provided 50% of the Conradson carbon in the system, and the Conradson carbon to tungsten atomic ratio was 2.17. The autoclave was pressured to 100 psig with H2S and 2000 psia with H2, heated at 725 F. for 30 minutes followed by 840 F. for 30 minutes. After cooling to room temperature, the reactor contents were washed out with toluene and filtered. The solids were washed with 0.8 l hot toluene and with 0.5 l warm hexane and oil pump vacuum oven dried at 160 C. for 1 hr. The dried solids weighted 9.6 g. and had a surface area a cf 144 m2/g, a carbon conte':t of 9.48%, a hydrogen content of 0.69% and a molybdenum content of 59.74. EXAMPLE 7 (Runs 343, 355, 339, 337, 320, 416 are 417) Experiments similar to Example 6 were done except that the atomic ratio of Conradson carbon to tungsten was progressively increased by reducing the amount of tungsten resinate charged and increasing the amount of Cold Lake crude charged. Results are tabulated beio in Table II. TABLE II Charge % of Con. Car- Con. C to Solids Properties Run Gas Cold Lake Tungsten ben from Cold Tungsten S.A. No. oil, g. Crude, g. Resinate, g. Lake Crude Atomic Ratio mê/g C, % H, % W, % 343 81.45 9.05 25.95 76 4.2 169 9.47 0.80 57.8 355 100.2 11.2 11.2 76 11.9 203 12.10 0.70 66.4 339 100.2 11.1 7.0 76 19 200 11.87 0.82 68.5 337 100.2 11.1 2.80 76 47.6 197 13.07 0.82 62.8 320 100.2 11.1 1.40 76 95.2 165 18.04 1.43 54.5 416 67.6 43.7 1.40 95 300 102 37.05 2.15 42.6 417 None 111.3 1.40 100 725 21 57.3 3.07 23.7 EXAMPLE 8 (Run 318) A run was made similar to Example 6 except no Cold i2ke crude was addled, The charge was 111.3 g. gas oil ond 1.4G g. of cungsten resinate. The Conradson carbon to tungsten atomic ratio was 25.2. The gas charged was 100 psia H2S and 2000 psia H2. The recovered solids weighed 0.45 g. and had a surface area of 66 mê/g with a carbon content of 10.50% and hydrogen content of 1.28%. The tungsten content was 69.1%. EXAMPLE 9 (Run 317) A run was made similar to Example 8 except no H2S was S added co the feed gas. The recovered solid weighed 0.46 g. and had a surface area less than 1 mê/g. The carbon content was 10.15% and hydrogen content was 1.65%. The tungsten content was 67.6%. Z 7 10 The results of Examples 6,7,8 and 9 are plotted in Figure 3 and show the following: (1) higher surface area is obtained when more than 50% of the Conradson carbon is supplied by addition of a hydrocarbon component with greater than 1 Conradson carbon such as z resid or heavy crude, and (2) to obtain a tungsten containing solid with surface area greater than 50 mê/g, the Conradson carbon to tungsten atom ratio should be less than about 600/1. EXAMPLE 11 (Runs 375A, 344, 329, 336) Experiments were done at several temperatures (with sufficient holding at each temperature to insure completion of che reaction) to determine the preferred temperature for preparing the high surface area molybdenum-carbon compcsition. In each case the charge was 25.95g. of molybdenum naphthenate, 83.8g. of Lighc Arabian vacuum gas oil and 6.70 g. of Cold Lake crude. The Conradson carbon to molybdenum atom ratio fo this mixture is 6.5. The gas charged was 100 psia H2S and 2000 psia H2 at room temperature. Results are tabulated in Table III and show chat 725 F. is about the optimum temperature. TABLE III EFFECT OF TEMPERATURE Run No. 375A 342 329 336 Temperature, F. 390 600 725 840 Time, Sin. 180 60 30 30 Solid Product Yield, g. 2.90 3.66 5.23 3.39 S.A., mê/g 50 296 356 330 C,% 31.98 22.60 14.03 19.50 H,% 4.22 2.30 1.90 1.29 Mg, % 53.7 42.5 48.2 45.9 Example 12 (Runs 323, 353, 332, 329, 404) Experiments ware done at 725 F. for 30 minutes using the charge mixture described in Example 11 to determine the importance of the gas composition and pressure. Results are tabulated in Table IV. These results show that a pressure of H2S or hydrogen is required to make t¸e high surface area metal-carbon composition, and that it is preferably to have both H2 and H2S pressure. TABLE IV EFFECT OF GAS COMPOSITION AND PRESSURE Run No. 333 333 447 332 329 404 H2 Pressure Charged at 0 2000 0 0 2000 500 Room Temp., psia H2S Pressure Charged at 0 0 50 100 100 100 Room Temp., psia Solid Product (filterable) Yiled, g. 0.00 3.00 4.23 4.00 3.23 3.61 S.A., mê/g -- 193 315 233 356 356 C, % -- 16.41 31.93 29.66 14.03 22.81 H, % -- 2.14 2.52 2.22 1.90 1.33 Mo, % -- 51.9 36.8 38.9 48.2 43.1 EXAMPLE 13 Experiments in gas oil medium only at 6.5 Conradson carbon to metal atomic ratio and at 7254F. for 30 nin. with 2000 psia H2 and no H2S charged at roon temperature were performed with a variety of metals and metal combinations. Results are tabulated in Table V. 1 TABLE V 2 METAL SCREENING 3 2000 psia H2 and 0 psia H2S 4 Conradson Carbon Derived From Gas Oil 5 Metal Solid Properties 6 Run S.A., 7 No. Name Added As m2/g C,% H,% Metal,% 8 371 Ti Resinate 142 7.41 1.52 74.6 9 369 V Naphthenate 88 6.07 1.11 -10 368 Cr Naphthenate 431 28.63 4.54 33.0 11 370 Fe Naphthenate No filterable solid -12 372 Co Naphthenate 2 2.16 0.54 -13 316 Ni Naphthenate 4 2.90 0.46 70.8 14 402 Mo Carboayl 117 13.08 1.29 82.4 15 396 Fe/Mo* Naphthenates 232 9.51 1.50 54.7 16 398 Co/Mo* Naphthenates 283 9.75 1.46 56.6 17 397 Ni/Mo* Naphthenates 249 8.71 1.12 55.3 18 *35/65 atom ratio MPLE 14 Experiment were performed under the conditions of Example 13 except that 100 psia of H2S was added at room temperature. Results are tabulated in Table VI. 1 TABLE V 2 METAL SCREENING 3 2000 psia H2 and 0 psia H2S 4 Conradson Carbon Derived From Gas Oil 5 Metal Solid Properties 6 Run S.A., 7 No. Name Added As m2/g C,% H,% Metal,% 8 376 Ti Resinate 187 6.22 1.52 62.6 9 374 V Naphthenate 69 5.98 1.19 -10 373 Cr Naphthenate 187 18.20 3.00 42.6 11 375 Fe Naphthenate 11 4.28 1.17 93.7 12 377 Co Naphthenate 49 8.33 0.68 59.4 13 378 Ni Naphthenate 11 1.18 0.10 57.3 14 386 Co/Mo* Naphthenates 173 43.59 2.57 25.3 15 *35/65 atom ratio EXEMPLE 15 Experiments were performed under the conditions of Example 14 except that Cold Lake crude was added to supply 69% of the Conradson carbon in the system, the ocher 31% being supplied by the gas oil. The Conradson carbon to metal atomic ratio was 6.4. Results are tabulated in Table VII. TABLE VII METAL SCREENING 2000 psia H2 and 100 psia H2S 31% of Conradson Carbon Derived From Gas Oil, 69% Derived From Cold Lake Crude Metal Solid Properties Run S. A., No. Name Added as mê/g C, % H, % Metal, % 383 Ti Resinate 137 7.16 1.03 58.1 381 V Naphthenate 75 3.90 0.85 -380 Cr Naphthenate No filterable solid -382 Fe Naphthenate 5 3.40 0.43 84.6 347 Co Naphthenate 70 4.17 0.93 59.0 379 Ni Naphthenate 10 3.73 0.54 61.8 446 Fe/Mo* Naphthenates 274 10.92 1.22 51.8 387 Co/Mo* Naphthenates 320 14.94 1.64 48.1 405 Ni/Mo* Naphthenates 200 10.92 1.25 49.2 * 35/65 atom ratio. EXAMPLE 16 (Run 340) A mixture of 33.5 of molybdene naphthenate (6 wt.% molybdenum content) and 66.5 g. of Cold Lake crude oil (13.22 wt.% Conradson carbon) was charged to a 300 cc stirred autoclave. this mixture had a Conradson carbon to molybdenum atomic ratio of 35 to 1. The autoclave was Flushed with hydrogen and pressured to 100 psia with H2S then to 2950 psia with H,. The autoclave as heated with stirring at 725 F. for 30 min. and 8400r. for 30 min. The average total pressure on reaction conditions was about 3000 psig. The reactor was coled, discharged and the contents filtered. The solid were washed with hot toluene followed by hexane to remove absorbed hydrocarbons, and then vacum oven dried. The recovered solids weighed 4.69 g. The solids had a surface area of 281 mê/g, a carbon content of 21.51 wt.%, a hydrogen content of 1.29 wt.% and a molybdenum content of 42.9 wt.%. EXAMPLE 17 In this example the precursor used to form the high surface area molybdenum catalyst was phosphomolybdic acid (20 MoO2#2H3PO4#48H2O, suplied by J. T. Baker Chemical Company). The preparation was carried out as follows. To a 30 ml stirred autoclave, there was charged 91.64 g. of Light Arabian vacuu, gas oil (0.46% Conradson carbon) and â solution comprised of 0.565 g. of phosphomolybdic acid in 1.695 g. of anhydrous isopropyl alcohol. The ratio of atoms of Conradson carbon to atoms of molybdenum in this mixture is 125/1. The autoclave was flushed with hydrogen and then pressured with 105 psia of H2S and 20C0 psia of hydrogen ac room temperature. The aucoclave was heated at 725 F. for 30 minutes followed by a 3G minute period at 840 F. Upon cooling to room temperature, the autoclave was depressured and the liquid concents were discharged and filitered to isolate the solid product. Adhering oil was removed from the solids by washing sequentially with toluene and hexane. The wasned solids were then dried aC 80 C. in an oil pump vacuum oven. There was recovered 0.49 g. of dry solids which had a surface area of 123 m2/g and contained 56 weight percent molybdenum. EXAMPLE 18 This example illustrates the use of a high surface area molybdenum catalyst and a cobalt irttpregnated high surface area molybdenum caralyst for the slurry thydrocracking of a Light Arabian vacuum gas oil. (A) Presaration of Molybdenum Catalyst The high surface area molybdenum cacalyst was prepared as follows. A mixture of 86.5 g of molybdenum naphthenate (6% molybdenum), 241.6 g. of Light Arabian vacuum gas oil (0.46% Conradson carbon content) and 60.7 g. of Cold Lake crude (12.8% Conradson carbon content) was charged to a one liter stirred autoclave and pressured with 2000 psia hydrogen at room temperature, The autoclave gas heated over a perIod of 95 minutes to a run temperature of 8400F. and was held at this temperature for 28 minutes and then cooled rapidly to room temperature. The resultant solids, isolated by filtration, were washed with toluene and then with hexane prior to dying under vacuum. There was recovered 11.17 g. of molybdenum catalyst which exhibited a surface area of 244 mê/g and contained 49 wt.% molybdenum. This catalyst is designated hereinafter as Catalyst A. (B) Preparation of Cobalt Impregnated Molybdenum Catalyst (Run 21-R-40) A sample of 0.41 g. of catalyst A, high surface area molybdenum catalyst powder, was mixed with 1.17 g. of cobalt naphthenate (6% cobalt) in a 300 ml autoclave at room temperature. The reactor was flushed with hydrogen and then charged, at room temperature, with 200 psia hydrogen sulfide and 1300 psia hydrogen. Reactor temperature was raised to 662 F. over the course of 95 minutes and was held at 602 F.- 678 F. for 30 minutes followed by rapid cooling to room temperature. The reactor was vented and flushed with nitrogen. Upon opening, it was observed that water and light hydro carbons, resulting from the decomposition or cobalt naphthenate, had condensed on the upper surfaces of the reactor. These deposits were removed. The cobalt impregnated molybdenum catalyst, which was observed as z black powder on the buttom of the reactor, was not removed, but left in the reactor or a vacuum gas o-.1 hydrocracking test. The atomic ratio of cobalt to molybdenum in the finished catalyst was 0.57. This catalyst is designated hereinafter as catalyst B. (C) Vacuum Gas Oil Hydrocracking Runs For the hydrocracking runs a 300 ml stirred auto- dave was charged w with catalyst and approximately 90 g. of a Light Arabian vacuum gas oil. See table for quantities charged. The autoclave was then flushed with hydrogen, charged with 2000 psia hydrogen at room temperature and heated over the course of 30 minutes to the run temperate, of 840 F. After a reaction time of 300 minutes at 840 F. the reactor was cooled rapidly to room temperature and the contents were analyzed. Hydrocracking results obtained with the high surface area catalysts are shown in Table VIII relative to the results obtained in a non-catalytic thermal hydrocracking run. As is apparent from the data, thc high surface area catalysts gave hydrocracking results much superior to those obtained in the purely thermal conversion run. In particular, product desulfuriuzation was much higher, product unsaturation was much lower (lower bromine numbers) and the 655 F. conversion product distillate to naphtha ratios were, desIrably, higher. TABLE VIII VACUUM GAS OIL HYDROCRACKING RUNS Run No. 21-R-25 08-R-57 21-R-40 Gas Oil Charged, g. 94.95 92.20 a2.43 Catalyst A None B Charge, g. 0.41 0.41 g of Catalyst A + Cobalt Conversion of 650 F. + 44.8 59.7 54.3 to 650 F, Products,% Sulfur Removed Fro 61.0 5.4 86.0 Gas Oil, % Bromine Number of Total 3.9 16.6 1.6 Liquid Product Weight Ratio of Distil - 3.3 3.12 3.6 late (355-650 F.) to Naphtha (i-355 F.) H2 Consumation, SCF/B 501 553 651 of Feed EXAMPLE 19 Ths example shows the preparation of a cobalt pro moted molybdenum catalyst (coprecipitated catalyst) from a blend of oil soluble cobalt and molybdenum compounds according to the practice of this invention. The procedure used was similar to that of Example 2. The ratio of atoms of Conradson carbon to the sum of the atoms of molybdenum and cobalt in this preparation was 6.5/1. From a reactor charge consisting of 102.8 g. of Light Arabian vacuur gas oil, 8.22 g of Cold Lake crude, 6.92 g. of cobalt napthenate (6% cobalt by weight) and 20.74 g of molybdenum naphthenate (6% Mo by weight) there was recovered 3.11 g. of dry cobalt-molybdenum catalyst which exhibited a surface area of 253 mê/g. This catalyst is designated hereinafter as cstalyst C. The catalysts desulfurization activity was determined using the following procedure. To a 300 ml autoclave there was added the calcined presulfided catalyst powder, typically about 0,6g., and 92 g. of light Arabian vacuum gas oil which contained 2.42 wt.% sulfur. The reactor was flushed with hydrogen and then charged at room tetrpera':ure with 40 psia hydrogen sulfide and 2000 psia hydrogen. The reactor was heated as rapidly as possible (#25 minutes) to a temperature of 725 F, held there with stirring for 30 minutes and then the temperature was increased to 8000F for a final 25 minute contact prior to cooling to room temperature. Reactor products ere discharged and analyzed for sulfur content. As shown in Table IX the coprecipitated cobalt molydbdenum catalyst (Run 60-R-15) had desulfurization activity superior to that of the non-promoted molybdenum catalyst of this invention (Run 21-R-57). TABLE IX COPRECIPITATED COBAIT-MOLYBDENUM CATALYST Run No. 60-R-15 21-R-57 Cobalt Incor- Coprecip- No porated by: itation cobalt C Co/Mo Atomic---- No Ratio Relative Desulf. 2.32 Act. EXAMPLE 20 A sample of high surface area molybdenum-containing solid powder was prepared according to this invention and had the following properties; surface area 330 m2/g; C, 12.53 wt.%; H, 1.41 wt%; Mo, 47.8 wt.%, This powder was impregnated with cobalt as follows. To a charge of 6.06 grams of vacuum oven dried molybdenum catalyst powder contained in a 5" diameter evaporating dish there was added dropwise, with stirring, 24.11 grams of a solution comprised of 7.4 wt.% cobaltous acetate tetrahy- drate, 7.0 wt.% isopropyl alcohol and 85.6 wt.% deionized water. The amount of impregnation solution added was just sufficient to impart a glistening wet appearance to the powder. After a 15 minuce drying period in a vacuum oven at 80 C., the solids were treated with the impregnation diluent (8 wt.% isopropyl alcohol + 92 wt. % water) to again reach the glistening wet surface appearance arc chen were dried a final tine for 90 minutes at 80 C. in a vacuum oven. There was recovered 7.G2 g. of cobaltous acetate impregnated molydbenum catalyst powder. This cobalt impregnated powder was then plled using bentonire as che binder in the proportion or. 74 wt.% to 26 wt.% bentonice. The pills were cackled and screened to 12-48 mesh. The surface area of the finished catalyst 2 was 180 m /g. This catalyst is designated hereinafter as catalyst D. Catalyst D was tested for desulfurization of vacu' gas oil in 2 continuous unit at 685 F., 1 V/V/Hr., 1500 psi H2 pressure in direct comparison with a commonly used scanderd commercially available desufurization catalyst (12-48 mesh). The catalyst of this invention was found to have an activity, on a catalyst volume equivalent basis, 68% greater than the given commercially available desulfurization caralyst, which itsclf is a high activity desulfurizatic: catalyst. EXAMPLE 21 A catalyst of che present invention, prepared with molybdenum naphthalate precursor, containing 47.6 weight percent molybdenum and having a surface area of 330 m2/g was blended with betonite as a binder in a 71/29 weight ratio. The blend was pilled, cracked and screended to 12-48 esh screen size. The resulting finished catalyst, herein- fater designated catalyst E, was tested for desulfurization of light Arab vacuum gas oil containing 2.34 weight percent sulfur at 1500 psig and 0.97 volumes of liquid feed per vol- ume of catalyst per hour in a continuous unit. The results are summarized in Table X. TABLE X Catalyst Age, Kr. and Oil 209 425 Temperature F. 661 684 H2 Fed, SCF/Bbl. 1683 2061 Desulfurization. % 69.9 83.7 In this specification, the mesh size referred to is of the Tyler mesh series. The following ap;ro;;imate conversions of units apply: Lengths given in inches (") are converted to centimeters by multiplying by 2.54. Temperatures given in F are converted to C by subtracting 32 and then dividing by 1.8. Pressures given in pound per square unch (psi) are onverted to kg/cmê by multuplying by 0.070307 Volumes given in Standard Cubic Feet (SCF) arc converted to litres by multiplying by 28.32. Volumes given in barrels (bbl) are converted to litres by multiplying by 159.0.

Claims: CLAIMS 1. A method of preparing a high surface area catalyst, characterized by comprising the steps of: (a) adding to a hydrocarbon oil chargestock having a Conradson carbon content of up to 50 weight percent, at least one thermally deconiposable metal compound in an amount sufficient to provide a ratio of atoms of oil chargestock Conradson Carbon to atoms of metal constituent of said thermally decom?Gsable metal compound of less than 750 to 1, said metal constituent being selected from the metals of Group II, Group III, Group IV, Group V, Group VIB, Group VIIB, and Group VIII of the Pcricdic Table of Elements and mixtures of such metals; ; (b) heating said thermally decomposable metal corrjound within said chargestock 2t an elevated temperature in the presence of a gas selected from hyrogen-containing gas, a hydrogen sulfide-containing gas, and a gas comprising hydrogen and hydrogen sulfide to produce 2 solid, high surface area catalyst within said chargestock and, (c) recovering, a high surface area catalyst. 2. The method of claim 1 characterized in that said thermally decomposable metal compound is selected from inorganic metal compound±, salts of organic acids, organometallic compounds and salts of organic gamines. The method of claim 1 or claim 2 characterized in that said thermally decomposable metal compound is selected from salts of acyclic aliphatic carboxylic acids and salts of alicyclic aliphatic carboxylic acids. 4. The method of any one of claims 1 to 3 characterized in that said thermally decomposable metal compound is a salt of a naphthenic acid. 5. The method of any one of claims 1 to 4 characterized in that the metal constituent of said thermally decomposable metal. compound is selected from molybdenum, tungsten, chromium, vanadium, cobalt, titanium, iron, nickel and mixtures thereof. 6. The method of any one of claims 1 to 5 characterized in that at leapt one additional catalyst component is composited with the high surface area catalyst recovered in step (c). 7, The method of apv one of claims 1 to 6 characterized in that the catalyst recovered in step (c) has a surface area of at least 50 m2/g. 8. The method of any one of claims 1 to 6 characterized in that the amount of thermally decomposalle metal compound(s) added in step (a) is/are such as to provide in the catalyst recovered in step (c) at least 10 wt % of the metal component(s) thereof (calculated as elemental etal) based on the total weight of catalyst recovery d in step (c). 9. A high surface area catalyst characterized in that it has been prepared by a method according to any one of claims 1 to 8. 10. h catalytic hydrocarbon treating process comprising contactir.g a hydrocarbonaceous oil feed-at treating conditions in the presence of a catalyst, characterized in that the catalyst is a high surface area catalyst according co claim 9. 11. The process of claim 10 characterized in that said process is a hydropropcess and herein said oil and said catalyst are contacted. in the presence of added hydrogen. 12. The process of claim 10 characterized in that said hydrocarbon treating process is a catalytic cracking process conducted in the absence of added hydrogen. 13. The process of claim 11 characterized in that said hydroprocess is a hydrocracking process or a hydrodesulfurization process, or a reforming process 14. The process of any one of claims 10 to 13 characterized in that said liydrocarbonaceous oil feed of said hydrocarbon treating process is selected from petroleum derived oils, tar sand oil, shale oil, liquid products derived fro coal liquefaction processes, cqal liquefaction bottoms, and mixtures thereof.

Inventors: ALDRIDGE, CLYDE LEE, BEARDEN JR., ROBY
Applicants: EXXON RESEARCH AND ENGINEERING COMPANY
Application year: 1979
Main classification: C10G49
IPC codes: B01J37, C10G49, B01J23, C10G11, C10G35