United States Patent (19) 11 Patent Number: 4,595,672 Ho et al. (45) Date of Patent: Jun. 17, 1986 (54) METHOD OF MAKING SELF-PROMOTED 2,914,462 11/1959 Hemminger ...... 208/112 HYDROTREATING CATALYSTS 3,074,783 1/1963 Paull ...... 423/437 3,148,135 9/1964 Schlinger et al...... 208/107 X 75 Inventors: Teh C. Ho, Bridgewater; Larry E. 3,686,137 8/1972 Gatti ...... 252/439 X McCandlish, Highland Park, both of 3,893,947 7/1975 Young ...... 252/439 N.J. 3,965,041 6/1976 Klinken et al...... 252/439 X 4,243,553 /1981 Naumann et al. . ... 252/43 N 73) Assignee: Exxon Research and Engineering Co., 4,243,554 1/1981 Naumann et al...... 252/439 Florham Park, N.J. Primary Examiner-William G. Wright 21 Appl. No.: 680,379 Attorney, Agent, or Firm-Edward M. Corcoran 22 Filed: Dec. 11, 1984 57 ABSTRACT Self-promoted molybdenum and tungsten sulfide hy Related U.S. Application Data drotreating catalysts are prepared by heating one or 63 Continuation-in-part of Ser. No. 603,834, Apr. 25, more water soluble catalyst precursors in a non-oxidiz 1984, abandoned, which is a continuation of Ser. No. ing atmosphere in the presence of sulfur at a tempera 454,220, Dec. 29, 1982, abandoned. ture of at least about 200° C. The precursors will be one 51 Int. Cl...... B01J 27/047; B01J 31/00; or more compounds of the formula ML(MoW1-yO4) B01J 27/051; C10G 1/06 wherein M is one or more promoter metals selected 52 U.S. Cl...... 502/219; 502/162; from the group consisting essentially of Mn, Fe, Co, Ni, - 502/220; 208/421; 208/112; 208/143; 208/217; Cu, Zn and mixtures thereof, wherein Osys 1 and 208/216 R; 208/254 H; 518/713; 518/714; wherein L is a nitrogen containing, neutral multiden 518/715; 208/422 tate, chelating . In a preferred embodiment the 58 Field of Search ...... 502/162,219, 220 ligand L will comprise one or more chelating alkyl dior (56) References Cited triamines and the non-oxidizing atmosphere will com prise H2S. U.S. PATENT DOCUMENTS 2,715,603 8/ 1955 Lanning et al...... 208/96 7 Claims, No Drawings 4,595,672 1. 2 lower surface areas. Thus, those skilled in the art are METHOD OF MAKING SELF-PROMOTED constantly trying to achieve catalysts that have higher HYDROTREATING CATALYSTS surface areas. More recently, it has been disclosed in U.S. Pat. Nos. 4,243,553, and 4,243,554 that molybde CROSS REFERENCE TO RELATED 5 num sulfide catalysts of relatively high surface area may APPLICATIONS be obtained by thermally decomposing selected thi This application is a continuation-in-part of U.S. Ser. omolybdate salts at temperatures ranging from No. 603,834 filed on Apr. 25, 1984 now abandoned 300-800° C. in the presence of essentially inert, oxy which is a Rule 60 Continuation of U.S. Ser. No. gen-free atmospheres. Suitable atmospheres are dis 454,220 (abandoned) which was filed on Dec. 29, 1982. 10 closed as consisting of argon, a vacuum, nitrogen and hydrogen. In U.S. Pat. No. 4,243,554 an ammonium BACKGROUND OF THE INVENTION thiomolybdate salt is decomposed at a rate in excess of 1. Field of the Invention 15 C. per minute, whereas in U.S. Pat. No. 4,243,553, a This invention relates to self-promoted molybdenum substituted ammonium thiomolybdate salt is thermally and tungsten sulfide hydrotreating catalysts. More par 15 decomposed at a very slow heating rate of from about ticularly, this invention relates to self-promoted molyb denum and tungsten sulfide hydrotreating catalysts 0.5 to 2 C./min. The processes disclosed in these pa produced by heating one or more water soluble molyb tents are claimed to produce molybdenum disulfide date and/or tungstate catalyst precursors containing the catalysts having superior properties for water gas shift promoter metal as part of the precursor molecule in the 20 and methanation reactions and for catalyzed hydroge presence of sulfur at elevated temperature for a time nation or hydrotreating reactions. sufficient to form said self-promoted catalyst. SUMMARY OF THE INVENTION 2. Background of the Disclosure The petroleum industry is increasingly turning to Self-promoted molybdenum and tungsten sulfide hy coal, tar sands, heavy crudes and resids as sources for 25 droprocessing catalysts are obtained by heating one or future feedstocks. Feedstocks derived from these heavy more water soluble catalyst precursors of the formula materials contain more sulfur and nitrogen than feed ML(MoWO4) in a non-oxidizing atmosphere in the stocks derived from more conventional crude oils. Such presence of sulfur at a temperature of at least about 200 feedstocks are commonly referred to as being dirty C. for a time sufficient to form said catalyst, wherein M feeds. These feeds therefore require a considerable 30 comprises one or more divalent promoter metals se amount of upgrading in order to obtain usable products lected from the group consisting essentially of Mn, Fe, therefrom, such upgrading or refining generally being Co, Ni, Cu, Zn and mixtures thereof, wherein y is any accomplished by hydrotreating process which are well value ranging from 0 to 1, and wherein L is one or known in the industry. more, neutral, nitrogen-containing ligand at least one of These processes require the treating with hydrogen 35 which is a chelating polydentate ligand. In a preferred of various hydrocarbon fractions, or whole heavy feeds, embodiment M will be selected from the group consist or feedstocks, in the presence of hydrotreating catalysts ing of (a) Fe, Co, Ni and mixtures thereof and (b) mix to effect conversion of at least a portion of the feeds, or tures of (a) with Mn, Cu, Zn and mixtures thereof. In a feedstocks or lower molecular weight hydrocarbons, or particularly preferred embodiment ligand L will have a to effect the removal of unwanted components, or com of six and will be either three bidentate or two pounds, or their conversion to innocuous or less unde tridentate chelating, alkyl , M will be sirable compounds. Hydrotreating may be applied to a selected from the group consisting essentially of Ni, Fe, variety of feedstocks, e.g., solvents, light, middle, or Co and mixtures thereof and the non-oxidizing atmo heavy distillate feeds and residual feeds, or fuels. In sphere will contain hydrogen sulfide as the source of hydrotreating relatively light feeds, the feeds are 45 sulfur. treated with hydrogen, often to improve such com Hydroprocessing is meant to include any process that pounds in the presence of hydrogen, which processes is carried out in the presence of hydrogen, including, are collectively known as hydrotreating or hydrorefin but not limited to, hydrocracking, hydrodenitrogena ing processes, it being understood that hydrorefining tion, hydrodesulfurization, hydrogenation of aromatic also includes some hydrogenation of aromatic and un 50 saturated aliphatic hydrocarbons. Thus, U.S. Pat. No. and aliphatic unsaturated hydrocarbons, methanation, 2,914,462 discloses the use of molybdenum sulfide for water gas shift, etc. These reactions include hydrotreat hydrodesulfurizing gas oil and U.S. Pat. No. 3,148,135 ing and hydrorefining reactions, the difference gener discloses the use of molybdenum sulfide for hydrorefin ally being thought of as more of a difference in degree ing sulfur and nitrogen-containing hydrocarbon oils. 55 than in kind, with hydrotreating conditions being more U.S. Pat. No. 2,715,603, discloses the use of molybde severe than hydrorefining conditions. Some of the cata num sulfide as a catalyst for the hydrogenation of heavy lysts of this invention have hydrotreating or hydrorefin oils, while U.S. Pat. No. 3,074,783 discloses the use of ing activities substantially greater than that of conven molybdenum sulfides for producing sulfur-free hydro tional hydrotreating catalysts such as cobalt molybdate gen and carbon dioxide, wherein the molybdenum sul 60 on alumina. fide converts carbonyl sulfide to hydrogen sulfide. Mo The catalysts of this invention may be used in bulk lybdenum and tungsten sulfides have other uses as cata form or supported on a suitable inorganic refractory lysts, including hydrogenation, methanation, water gas oxide support such as alumina. A particularly signifi shift, etc. reactions. cant advantage of this invention is that the water solu In general, with molybdenum and other transition 65 bility of the catalyst precursor permits the precursor to metal sulfide catalysts as well as with other types of be impregnated onto a suitable support such as alumina, catalysts, higher catalyst surface areas generally result via conventional impregnation techniques such as incip in more active catalysts than similar catalysts with ient wetness and adsorption. 4,595,672 3 4. of ligands useful in the catalyst precursors of this inven DETAILED DESCRIPTION OF THE tion are set forth below. INVENTION Monodentate ligands will include NH3 as well as As hereinbefore stated, the catalyst precursor is a alkyl and aryl such as ethyl amine, dimethyl water soluble metallate having the formula 5 amine, pyridine, etc. Useful chelating bidentate amine ML(MoWO4) wherein M is one or more divalent ligands are illustrated by , 2,2'-bipyri promoter metals selected from the group consisting of dine, 1,10-phenylene bis(dimethyl-amine), o-phenylene Mn, Fe, Co, Ni, Cu, Zn and mixtures thereof. Prefera diamine, tetramethylethylenediamine and propane-1,3 bly M will be selected from the group consisting of (a) diamine. Similarly, useful chelating tridentate amine Ni, Co, Fe and mixtures thereof and (b) mixtures of (a) 10 ligands are represented by terpyridine and diethylene with Zn, Cu, Min and mixtures thereof. Still more pref triamine while triethylenetetramine is illustrative of a erably M will be selected from the group consisting of useful chelating quadradentate amine ligand. Useful Fe, Ni, Co and mixtures thereof. Thus, the promoter chelating pentadentate ligands include tetrae metal may be a single metal such as Ni in which case the thylenepentamine while sepulchrate (an octazacryp 15 tate) is illustrative of a suitable chelating hexadentate precursor will have the formula (NiL)(MoWO4). ligand. However, as a practical matter it will be pre Alternatively the promoter metal may be a mixture of ferred to use chelating, polydentate alkyl amines for L. two, three, four, five or even six promoter metals. For Illustrative, but not limiting examples of alkyl amines the case of two promoter metals, such as Niand Co, the that are useful in the catalyst precursor of this invention precursor will have the formula (NiaCola)L(MoW1 20 include ethylenediamine, , and tetra yO4) wherein 0

Space Hydrogen Pressure Velocity Gas Rate Feed Temp., C. psig V/V/Hr SCFAB . Naphtha Typical 100-370 150-800 0.5-0 100-2000 Diesel Typical 2004.00 250-1500 0.5-6 500-6000 Heavy Typical 260-430 250-2500 0.3-4 1000-6000 Lube Oil Typical 200-450 100-3000 0.2-5 100-10,000 Residuum Typical 340-450 1000-5000 0.1-2 2000-0,000 The invention will be further understood by refer ence to the following examples. SCF/hr for each 10 cc of catalyst in the reactor. The temperature in the reactor was then raised to 325-360 EXAMPLES C. and kept at this temperature for one to three hours to Catalyst Precursor Preparation form the catalyst after which the temperature in the A tris(ethylenediamine) nickel molybdate Ni(en)- 45 reactor was lowered to 100° C., the H2S/H2 gas flow 3MoO4 catalyst precursor was prepared by dissolving was stopped and the reactor was purged with nitrogen ammonium molybdate into ethylenediamine (en) and until room temperature was reached. the resulting solution cooled to 0°C. in an ice bath. An Reaction Conditions aqueous solution of nickel chloride was slowly added, in aliquots, to the above solution, with agitation after 50 At least about 20 cc of each catalyst was loaded into the addition of each aliquot. A precipitate was formed a stainless steel, fixed-bed reactor. The conditions in the and recovered by vacuum filtration. This precipitate reactor were as set forth below: was NiCen)3MoO4 and was washed with distilled water and acetone and then dried in a vacuum oven at 50 C. Temperature 325 C. for three hours. The resulting cake was screened, pellet 55 Pressure 3.15 MPa. ized, sized to 20/40 mesh (Tyler). More specifically, Hydrogen rate 3000 SCFMbb 20.5 gm of (NH4)6Mo7O24.4H2O (ammonium hep LHSV 2, 3 and 4 V/V/Hr. tamolybdate) was added to 500 ml of ethylene-diamine (en) in a 250 ml Erlenmeyer flask. This amount of en The liquid product was analyzed for sulfur by X-ray was in excess of that stoichiometrically required to form 60 fluorescence and for nitrogen by combustion analysis. the precursor and the excess aided in precipitating same The feedstock used was a light catalytic cycle oil from solution. From 40 to 50 cc of distilled H2O was (LCCO) that was about 20 wt.% paraffinic having used twice to wash off any solid or solution remaining properties sets forth in Table 1. on the sides of the flask. The resulting solution was In all of these experiments, the results obtained from cooled to 0°C. in an ice bath and kept in the bath for the 65 the catalysts of this invention were compared to results duration of the preparation. In a separate flask 27 gm of obtained for commercial HDS and HDN catalysts com NiCl2.6H2O were dissolved into 300 ml of distilled prising cobalt molybdate on y-Al2O3 and nickel molyb H2O. This Ni2+ solution was added slowly, in aliquots, date on y-Al2O3, respectively. The cobalt molybdate 4,595,672 7 8 comprised 12.5 percent molybdenum oxide and 3.5 The final catalyst was sulfided at 400 C. for one hour percent cobalt oxide supported on the gamma alumina with a 10% H2S in hydrogen mixture, following the and the nickel molybdate comprised 18 percent molyb procedure for Examples 1-3. denum oxide and 3.5 percent nickel oxide on gamma This catalyst gave a % HDS of 58.1 and % HDN of alumina. These commercial catalysts were sulfided en 31.3 when tested with the LCCO feed at 325 C., 3.15 ploying the same procedure used to form the catalysts MPa and 3,000 SCF of hydrogen per bbl of oil at an of this invention, except that the temperature was 360' LHSV of 3.0, C. for one hour. TABLE 1 EXAMPLE 1. 10 LCCO Feed Gravity (API) 18.6 In this experiment, the LCCO feed was hydrotreated Sulfur, wt.% 1.5 at an LHSV of 2 comparing two of the catalysts of this Nitrogen, ppm 370 invention to the commercial cobalt molydate on alu mina HDS catalyst. The results are set forth in Table 2. GC distillation 15 Wt. 2 Temp., C. EXAMPLE 2 5 231 10 251 This experiment was the same as in Example 1 except 50 293 that the LHSV was 3. The results are shown in Table 3. 70 321 90 352 EXAMPLE 3 20 95 364 In this experiment, the unsupported catalyst of this invention prepared from the Co(en)3MoO4 was com pared to the commercial HDN catalyst, the results of TABLE 2 which are shown in Table 4. These results show the % HDN % HDS remarkable HDN selectivity for the catalyst of this 25 Catalyst invention. The liquid hourly space velocity (LHSV) cobalt molybdate on y-Al2O3 25.5 87.4 used in this invention was 4. Catalyst Precursor Ni(en)3MoO4 83.0 86.8 EXAMPLE 4 Co(en)3MoO4 supported on y-Al2O3 40.3 90.9 In this experiment, the LCCO feed was hydrotreated 30 at i HSV ranging from 1 to 6 with a catalyst prepared TABLE 3 by impregnating a chromia on alumina support material with a Ni(en)3MoO4 salt. % HDN % HidS The Ni(en)3MoO4 salt was prepared by dissolving Catalyst 35 cobalt molybdate on y-Al2O3 19.0 83.6 40.6 g of ammonium paramolybdate in a mixture of 900 Catalyst Precursor ml ethylenediamine (en) and 100 ml water in a 2 liter Ni(en)3MoO4 69.6 80.2 round bottom, three-neck flask. Next, 56 g of nickel Co(en)3MoO4 supported on y-Al2O3 25.5 85.1 chloride was dissolved in 100 ml H2O and transferred to a dropping funnel. While vigorously stirring the molyb date solution with an air driver stirrer, the nickel chlo TABLE 4 ride solution was added to the flask via the dropping % HDN % HS

funnel. A violet powder precipitated. This precipitate Catalyst was filtered, washed with acetone and then vacuum cobalt molybdate on y-Al2O3 12.8 8 dried at 50 C. 94.6 gms of product was obtained (calcu 45 lated yield=94 g). Catalyst Precursor 50 g of 19% Cr2O3 on Al2O3 in the form of 'pellets Co(en)3MoO4 82.4 87.6 (Alfa Products Div. Morton Thiokol, Inc.) were cal cinated at 500 C. for 3 hrs and, after cooling, crushed to What is claimed is: a -20-40 mesh powder. This powder was then placed 50 1. A process for preparing a supported, self-promoted into a 500 ml ROTOVAC flask. 45.8g of the Ni(en)- catalyst, said process comprising: 3MoO4 were dissolved in 120 ml of water and added to (i) compositing a porous, inorganic refractory oxide the flask. The flask was evacuated and rotated in a 70 support with a water soluble catalyst precursor salt C. water bath until the water was completely removed. characterized by (ML) (MoWO4) wherein M The final impregnated solid weighed 104.6 gms. 55 comprises one or more divalent promoter metals This impregnate was then ground, pelletized and selected from the group consisting of Mn, Fe, Co, sulfided at 360° C. for one hour following the procedure Ni, Cu, Zn and mixtures thereof, wherein y is any for Examples 1-3. This catalyst gave a % HDS of 70.5 value ranging from 0 to 1, and wherein L is one or and % HDN of 56.6 when tested with the LCCO feed more neutral, nitrogen-containing ligands at least at 325 C., 3.15 MPa and 3,000 SCF of hydrogen per bbl 60 one of which is a chelating polydentate ligand; and of oil at an LHLSV of 3.0. (ii) heating said composite formed in (i) in a non-oxi dizing atmosphere in the presence of excess sulfur EXAMPLE 5 in the form of one or more sulfur bearing com 25 grams of MgO in 20-40 mesh size were impreg pounds and at a temperature of at least about 200 nated with 87.2 cc of solution containing 30.7 grams of 65 C. to form said self-promoted catalyst. Ni(en)3MoO4. The resulting impregnate was vacuum 2. The process of claim 1 wherein said promoter dried at 50 C. overnight. The final impregnated solids metal M comprises at least one metal selected from the weighed 61.6 grams. group consisting of (a) Fe, Co, Ni and mixtures thereof 4,595,672 10 and (b) mixtures of (a) with Zn, Cu, Mn and mixtures 5. The process of either of claims 3 or 4 wherein said thereof. support comprises alumina. 6. The process of either of claims 1 or 2 wherein said 3. The process of claim 2 wherein L has a total den support comprises chromium oxide. ticity of six and is one or more chelating, polydentate 5 7. The process of claim 6 wherein said chromium alkyl amines. oxide support is supported on a refractory, inorganic 4. The process of claim 3 wherein said sulfur bearing oxide support material. compound comprises H2S. a: s k

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