CA1154736A

CA1154736A - Hydroprocessing catalyst having bimodal pore distribution

Info

Publication number: CA1154736A
Application number: CA000372384A
Authority: CA
Inventors: Hong C. Chen
Original assignee: Chevron Research and Technology Co
Current assignee: Chevron USA Inc
Priority date: 1980-06-09
Filing date: 1981-03-05
Publication date: 1983-10-04
Also published as: JPH0154096B2; JPS5712832A; US4435278A

Abstract

ABSTRACT

A process for hydroprocessing a hydrocarbo-naceous feedstock containing constituents boiling above 350°C comprises contacting said feedstock with hydroqen under hydroprocessing conditions witn a catalyst compo-sition comprising a rigidly interconnected pack containing inorganic matrix oxide and about 10-95% fluid catalytic cracking catalyst microspheroids, based upon the total weight of said matrix oxide and said microspheroids, said pack characterized by a pore volume of at least 0.15 cc.
per cc., at least about 30% of said pore volume present as pores having diameters within the range of 50-250 Angstroms and at least about 5% of said pore volume present as pores having diameters greater than 1,000 Angstroms.

Description

MAVING BIMODAL PORE DISTRIBUTION

BACKGROUND OF THE INVENTION
05 This invention relates to catalytic hydro-processing of hydrocarbonaceous feedstocks and parti-cularly hydroprocessing of heavy hydrocarhon feedstocks containing large amounts of metals, sulfur, nitrogen, and asphaltenes. The catalyst of this invention is prepared from fluid catalytic cracking catalyst microspheroids and is especially active for hydrodemetalation. The catalyst is particularly resistant to fouling and plugging when used in fixed beds.
PRIOR ART
The large ~uantities of spent catalyst generated in the hydrocarbon processinq industry have prompted a number of proposals for utilization of spent catalytic material. U.S. patent 3,893,911 teaches the use of spent vanadium-contaminated desulfurization catalyst for demetalation. U.S. patent 3,900,390 describes a two-stage hydrotreating process in which spent catalyst is regen-erated and cycled Setween zones. U.S. patent 3,985,643 suggests the use of aged desulfurization catalyst for demetaIation.
A number of workers have proposed the use of waste catalyst fines in catalyst manufacture. U.S.
patents 3,867,281 and 4,012,339 disclose catalyst preparations usinq fines produced in catalyst manufac-ture. Spent catalyst fines, i.e. used fines having partially degraded activity, mechanical strength, size, etc., have also been proposed for use in catalyst manufac-ture. U.S. patent 3,43fi,357 teaches the use of spent fluid catalytic cracking (FCC~ fines as additives to a Y-type zeolite in a non-hydrogenative crackinq cata7yst.
U.S. patent 4,107,087 discloses the prepa~ation of ~ r~.

~S~36 catalysts containing ground hydroprocessing catalyst materials from which metals have been extracted. United States patent 4,171,285 describes desulfurization using a catalyst prepared from spent FCC fines and sulfur reactive agents. United States patent 4,152~250 suggests adding ground used catalyst to sepiolite-based catalyst supports. Other catalyst preparations employing fines or other pretreated refractory particles are described in United States patents 3,850,849 (precalcined alumina), 3,900,427 (~imodal catalyst containing up to 10% fines) and 4,061,595 (calcined bauxite fines). None of the above-mentioned patents, however, described catalysts having the composition and properties of this invention and which are prepared from FCC
microspheroids.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a novel catalyst composition prepared from fluid catalytic cracking microspheroids and which as a particularly desirable bimodal pore volume distribution. Such a catalyst provides excelLent hydro-demetalation activity and fouling resistance. It is a further object to provide such a catalyst which also possesses good hydrocracking activity. A further object is to provide methods for preparing and using such catalysts.
In its composition aspects, this invention is a hydroprocessing catalyst comprising a rigidly interconnected pack containing inorganic matrix oxide and about 10-95% fluid catalytic cracking catalyst microspheroids, based on the total weight of the matrix oxide and the microspheroids. The pack is characterized by a pore volume of at least 0.15 cc. per g of the pack with at least about 30% oE the pore volume present as pores having diameters within the range of 50-250 Angstroms and at least about 5% of the pore vo]ume present asporeshaving diameters greater than 1,000 Angstroms. In another aspect, this ~ :1 invention is a process for preparing a composition comprising a rigidly interconnected pack containing inorganic matrix oxide and about 10-95% fluid catalytic cracking catalyst microspheroids, based upon the total weight of the matrix oxide and the micro-spheroids, said pack characterized by a pore volume of at least 0.15 cc. per g of the pack, at least about 30~ of said pore volume present as pore having diameters within the range of 50-250 Angstroms and at least about 5% of said pore volume present as pores having diameters greater than 1,000 Angstroms, said process comprising the steps of (a) forming a dispersion of fluid catalytic cracking catalyst microspheroids in an inorganic oxide sol, tb~ forming said dispersion into a shaped article and (c) drying and calcining the shaped article. In its processing aspects this invention comprises a process for hydroprocessing a hydrocarbonaceous feedstock containing constituents boiling above 350C comprising contacting said feedstock with hydrogen under hydroprocessing conditions with a catalyst composition comprising a rigidly interconnected pack containing inorganic matrix oxide and about 10-95% fluid catalytic cracking cata:Lyst microspheroids, based upon the total weight of said matrix oxide and said micro-spheroids, said pack characterized by a pore volume of at least 0.15 cc. per g of the pack, at least about 30% of said pore volume present as pores having diameters within the range of 50-250 An~stroms and at least about 5% of said pore volume present as pores having diameters greater than 1,000 Angstroms~
BRIEF DESCRIPTION OF THE DRA~INGS
Figure 1 is a pore volume distribution of an unimpreg-nated catalyst of this invention.
Figure 2 is a pore volume distribution for the catalyst of Figure 1, after impregnation 01 FIG. 3 is a pore volume distrihution of an unim-pregnated catalyst of this invention.
FIG. 4 is a pore volume distribution for the catalyst of FIG. 3 after impregnation.
05 FIG. 5 is a bar graph showing the metals removal capability of catalysts of this invention compared to other catalysts described herein.
FIG. 6 is a comparison of electron microprobe analyses of the iron content of the catalyst of this invention compared with a catalyst having a similar pore size distribution.
DETAILED DESCRIPTION
In normal fluid catalytic cracking operations, microspheroidal catalysts are contacted with hydrocarbon feedstock in a fluidized bed of microspheroidal catalyst particles. FCC catalysts typically consist of amorphous silica and alumina and a dispersed zeolitic molecular sieve component such as Y-type zeolite. Because FCC
catalysts operate in the absence of added hydrogen, no hydrogenation components are present. Fresh FCC catalysts are typically 50-70 microns in diameter~ Any of the commercially available FCC catalyst microspheroids are suitable for use in the catalyst of this invention.
~uring operation, FCC catalyst particles are continuously withdrawn from the FCC reactor and conducted to a fluidized bed regenerator where they are reacted with an oxidizing gas to remove deposited sulfur and carhon.
After one or more cycles, the used, or equilibrium, catalyst microspheroids become contaminated with metals, sulfur, carbon, etc. from the feedstock.
After a large number of cycles hetween the FCC
reactor and the reqenerator, the catalyst particles become so reduced in size throu~h attrition that they will be entrained from the fluidized bed. These smaller particles are normally removed from the system hy electrostatic '7~

01 precipitators or other means disposed in the regenerator exhaust gas stream. These microspheroidal fines are termed spent FCC fines, and are typically 10-50 microns in diameter, however, some suhmicron material may also be 05 present. The spent FCC fines also contain small amounts of contaminants from the feedstoc]c, including iron, nickel, vanadium, sulfur, carbon and minor amounts of other components. For purposes of this invention spent fluid catalytic cracking fines have the composition and properties listed in Table 1.

COMPOSITION AND CHARACTERIS~ICS OF
SPENT FCC FINES

15 Mean Particle Diameter, microns 5-50 Bulk Density, grams/cc 0.25-75 Surface Area~ meter2/gram 50-200 Pore Volume, cc/gram 0.1-0.6 Fe concentration, % by weight 0.25-1 20 C concentration, ~ by weight 0.1-2 Ni concentration, ppm 50-1000 V concentration, ppm 50 1000 Used FCC catalyst microspheroids are defined as microspheroids which have been through one or more FCC
regeneration cycles, and have a mean diameter of 50-70 microns.
It has been found according to this invention that a catalyst with excellent hydroproce!3sing activity, ~ 30 especially for hydrocracking and demetalation, can be prepared using large amounts of fresh, used, or spent FCC
catalyst microspheroids. In addition, the utilization of spent FCC fines in the catalyst of this invention provides at least a partial solution to a serious refinery waste disposal problem.

'73~i The composition of this invention comprises a rigidly interconnected pack containing fluid catalytic cracking catalyst microspheroids and inorganic matrix oxide. The inorganic matrix oxide functions to bind the FCC fines together and provides micropore volume to the catalyst. The macropores are believed to be present between the FCC microspheroids and the inorganic matrix oxide. The matrix oxide is substantially inactive for hydrogenation, in contrast to hydrogenation components such as Groups VI~ and VIII metals which can also be present, e.g., as oxides, in the catalyst. The matrix oxide can be for example alumina, silica, or mixtures thereof. The preferred matrix oxide is alumina, either amorphous alumina or the more active forms of alumina such as gamma alumina, beta alumina, etc. The pack has a pore volume of at least about 0.15 cubic centimeter per gram, preferably from 0.15 to 0.75 cubic centimeter per gram, and more preferably 0.25 to 0.50 cubic centimeter per gram. The pore volume is obtained by multiplying the pore volume per unit mass by the bulk density of the pack. The pore volume is present in a bimodal distribution in which one large portion of the pore volume is present in 50-250 Angstrom micropores and another significant portion of the pore volume is present in pores great-er than l,000 Angstroms. The macropores provide access channels to the more highly active micropores. Such a pore distribu~ion is particularly effective for hydrometalation of heavy hydro-carbonaceous fractions, i.e., those fractions containing com-ponents boiling above about 350C. The pore size distribution of the composition of this invention is determined by mercury in-trusion porosimetry. The pore size distribution of the specific material disclosed herein were determined using a Model MIC 901 instrument manufactured by Micromeritics Instrument Corporation, ~5~'~3~i 01 Norcross, Georgia. The volume of mercury penetrating into the pores of the samples and the correspond;ng pressure was recorded and the pore diameters corresponding to the applied pressures were obtained from the Washburn equation 05 using a 140 contact angle and 473 dyne/cm. surface tension for mercury. A mercury intrusion curve was obtained by plotting volume of mercury versus pore diameter. The samples had been heat treated at 1 mm. H~
pressure at 454C for ~5 minutes.
Table 2 sets forth the pore volume distribution of the composition of this invention.

Pore Volume Distribution (Mercury Porosimeter) AngstrGms Satisfactory Preferred Most Preferred 50-250 >30 >40 >45 250-1000 <65 <45 <2S
1000~ > 5 >10 >15 The proportion of FCC catalyst microspheroids in the composition should be at least about ln ~ei~ht percent of the total weight of matrix oxide and FCC catalyst microspheroids in the pack. While smaller amounts of FCC
microspheroids can be used to advanta~3e, at leas~ about 25% is preferred to provide a sufficient macropore volume for hi~h metals removal. More preferahly a~ least about 40 weight percent FCC catalyst microsl?heroids should he present in the pack. To provide acceptable catalyst strength, the spent FCC fines should preferably constitute - 30 no more than 95 percent by weight of the total FCC fines and matrix oxide in the pack.
Although not necessary for demetalation~hydrogen-ation components, in addition to those present in the spent fines due to prior FCC service, can be included in the catalyst. Such additional hydroyenatlon components ~ ,a r~A~

01 are selected from Groups VIII and VIB of the Periodic Table of the Elements; Handbook of Chemistry and Physics, 45th edition, Chemical ~ubber Company, 1964. The hydro-genation components can be present as metals, metal oxides 05 or metal sulfides, and function to retard fouling due to coking. The hydrogenation components also provide hydrocracking activity. Preferably the pack should contain at least about 0.5 weight percent calculated as metal of at least one metal t metal oxide or metal sulfide of Group VIB metals. It i5 also preferred that the pack contain at least 0.5 wei~ht percent of at least one metal, metal oxide, or metal sulfide of Group VIII metals, calculated as metals. More preferably the composition should contain about 0.5 to 20 weight percent calculated as metal of a Group VIB metal, metal oxide, or metal sulfide and about 0.5 to 10 weight percent calculated as metal of a Group VIII metal, metal oxide, or metal sulfide. Suitable combinations of Group VIB and Group VIII metals include Mo-Co, Mo-Ni, W-Ni, W-Co, Mo-Ni-Co, and W-Ni-Co. The more preferred composition is, calculated as metals, 0.5 to 5 weight percent Co and 0.5 to 15 weight percent Mo. The most preferre~ composition, calculated as metals, is 0.5-3 weight percent Co and 0.5-5 weight percent Mo.
The Group VIB or VIII hydrogenation components can be supplied by preparing a shaped composition con-taining FCC catalyst microspheroids and matrix oxide, and then impregnating the support with suitable solutions of hydrogenation metals by methods conventional in the art.
Alternately the hydrogenation metals, metal compounds, or precursors thereof, can be combined with the FCC catalyst microspheroids and matrix oxide by coprecipitation, co-gellation, or by comulling prior to shaping and cal-ciningO According to this invention catalyst compositions can be prepared which demonstrate a removals capacity for ~59~7~t~

01 total iron, nickel, and vanadium from a hydrocarbon feedstock of more than 0.1 grams metals per cubic centi-meter of catalyst pack. This level of metals removal can be obtained using conventional hydroprocessing conditions 05 such as the hydrogen pressures of 6 to 250 atmospheres, temperatures from 90 to 550C, space velocities of 0.01 to 20 hrs~l and hydrogen addition or recycle of 15 to 3500 cu. meter per cu. meter.
The catalyst composition of this invention can be prepared by forming a dispersion of FCC catalyst micro-spheroids in an inorganic oxide sol. The inorganic solcontains particles of the inorganic matrix oxide such as alumina, silica, etc. in an aqeuous medium. The pH of the sol should be maintained within the range of about 2 to 9. Generally, a lower pH will result in a smaller macro-pore volume and a higher pH will result in a larger macro-pore voume. Appropriate pH's are provided by including appropriate amounts of acid, such as formic acid, acetic acid, nitric acid, etc. The pH of the sol is dif~icult to measure directly because of the high solids concentra-tion. Consequently, the pH of the sol is defined for convenience as the pH of a solution containing 25 grams of the sol added to 100 cc of water. The relative amounts of water, FCC catalyst microspheroids, matrix oxide, hydroxide, or other precursor in the mix are selected to provide an easily formable mix, and can be routinely determined for any composition by those skilled in the art of catalyst manufacture.
The dispersion of the FCC catalyst microspheroids in the sol is formed into a shaped article by pelletizing, extrusion spherodizing, etc. using conventional e~uip-ment. The preferred forming technique is extrusion. The extrudate can be made into the form of cylinders, fluted cylinders, winged cylinders, or other irregular shapes to provide the proper interstitial voids. The preferred 01 shape is a right circular cylinder having a 0.40-15 mm.
diameter with a length/diameter ratio of 0.5-5. The extrudate is cut or broken into pieces havinq the desired lengths. The broken extrudate is dried and calcined to 05 provide a rigid article. Alternatively, the dispersion of the FCC microspheroids in the sol can be formed into spheres with 0.40-15 mm. diameter using a spherodizer or marumerizer. Calcining can be performed using conven-tional techniques such as heating in air, oxyyen or steam at 90 to 850C for 1 to 30 hours. During calcination any metals present are typically converted to an oxide form.
The dispersion of microspheroids in the inorganic oxide sol should contain at least about 10% FCC catalyst microspheroids on a dry weight basis J based upon the total weight of the microspheroids and the inorganic oxide.
Preferably the sol contains at least 25% and more pref-erably at least 40% FCC catalyst microspheroids on a dry weight basis based on the total of the microspheroids and the inorganic oxide. In order to provide acceptable catalyst strength, the upper limit of FCC catalyst micro-spheroids in the sol is about 95 weight percent on a dryweight basis.
Suitable hydrogenation components can be added directly to the sol as powders, slurries, or solutions as metals, oxides, sulfides, or precursors thereof such as the metal salts. The catalyst can also be prepared without hydrogenation metals and the metals later impregnated thereon, e.g.l by contact with the appropriate solutions of metal salts. Preferably the impregnated metals are converted to the oxide form, e.g., by cal-cination ln air, oxy~en or steam at temperatures of about90 to 850C for at least about 1 to 30 hours.
The pore volume distribution for the catalyst of this invention is governed by the process variables and the starting materials. Generally, the larger the amount ~5~73~

01 of FCC catalyst microspheroids added to the sol the greater the percent pore volume present as macropores larger than 1,000 Angstroms. As described above the micropore volume relative to the macropore volume can he 05 varied by adjustin~ the pH of the sol. The macropore volume will also be determined by the type of matrix oxide used. For example, if precalcined alumina constitutes a portion of the matrix oxide, the total pore volume will be larger and more of the ~ore volume will be concentrated in 1,000+ Angstrom macropores. The 10-250 Angstroms micropore volume will depend mainly upon the micropore structure of the matrix oxide powder used and also upon the FCC microspheroids pore structure. Based on the teachings herein, those skilled in the art of catalyst preparation can select starting materials and adjust the parameters to increase or decrease the micropore or macropore volume.
The co~position of this invention, with or without catalytic metals in addition to those already present in used or spent FCC fines, is particularly useful in processes where catalyst diffusion resistance is a significant factor. An example of such a process is the hydrodemetalation of heavy hydrocarbonaceous materials, wherein metals are often associated with large asphaltene moleculeæ. Heavy hydrocarbonaceous fractions suitable for hydroprocessing accordin~ to this invention include crude oil heavy petroleum fractions such as atmospheric or vacuum residua, vacuum gas oils, deasphalted petroleum residua and synthetic crudes or crude fractions derived from coal, oil shale, or tar sands. The catalyst of this invention is also particularly useful for hydroprocessin~
hydrocarbonaceous feedstock containin~ 40 ppmw or more total Fe, V, and Ni and/or 5 wt.% or ~ore n-heptane-insoluble asphaltenes.

.

~:~5~736 01 The composition of this invention can be used for widely varied heavy hydrocarbonaceous feedstocks at widely varying processing conditions. The quantity of metals and the composition and structure of metals-containing mole-05 cules may vary significantly depending upon the source of the heavy feedstock. Heavy feedstocks typically contain other heteroatoms such as sulfur, nitrogen, and oxygen.
Consequently, the reactivity of heteroatom-containin~
molecules over the catalyst of this invention can vary considerably. In the refining of petroleum stock, synthetic crudes or fractions derived from coal, shale, or - tar sands, the processing conditions may vary signifi-cantly depending upon the objective of the process. For example, in the manufacture of fuel oil sulfur removal is of prime importance, while in the pretreatment of feed-stock for downstream processing nitrogen and metal removal is usually of prime importance.
When metals are catalytically or thermally removed from heavy hydrocarbonaceous fractions, the metals deposit on the catalystr and may poison the active surface or physically block the catalyst pores, thus hindering diffusion of molecules into the catalyst. In the composition of this invention, the macropores p~ovide channels for rapid diffusion, thereby alleviating pore mouth blocking, and providing a larger pore volume to accommodate metals~ hence a larger metals capacity. The - micropore volume in the 50-250 Angstrom diameter range provides the high surface area needed to provide high catalytic activity.
3~ According to this invention, a hydrocarbonaceous feedstock, particularly heavy hydrocarbonaceous feedstocks as described above, is hydroprocessed by contacting the feedstock with hydrogen under hydroprocessing conditions, in contact with a catalyst composition of this inven-tion. Suitable hydroprocessing conditions include ~S~36 01 temperatures of 90 to 550C, preferably 150 to 480C and more preferably 20~ to ~50C; total press~res of 6 to 250, preferably 13 to 200 and more preferably 20 to 19~ atmo-spheres; hydrogen pressures of 3 to 23n, preferably lO to 05 l90 and more preferably 15 to 180; hydrogen addition or recycle rate of 15 to 3500, or more preferably gn to 1800 cubic meters gas per cubic meter of liquid; and a liquid hourly space velocity (LHSV) of 0.01 to 20 hours l, preferably 0.1 to 15 hours l,and more preferably 0.2 to lO
hours l. The catalyst composition is preferably deployed in a fixed bed downflow reactor; however, other reactor systems such as moving, ebullating, or fll~idized beds may be employed.
While not intending to be bound by any theory, it is believed that catalysts containing used or spent FCC
catalyst microspheroids are resistant to interstitial metals plugging because the catalysts have been rendered relatively inactive toward the me~als in ~he feed, as ; compared to càtalysts without used or spent FCC catalyst microspheroids. The relative inactivity of the spent or used FCC fines permits metals-containing orqanic molecules in the feedstock to penetrate further into the interior of the catalyst before reacting and depositing metals on the catalyst. In this way the deposited metals, particularly iron, do not plu~ the entrance to the pores of the cata-lyst, but rather are distributed more uniformly through the pore volume.
Even though the catalyst of this invention may be intrinsically less active than some prior art catalysts, the apparent activity can be higher for reactions such as hydrodemetalation which are adversely affected by pore mouth plugging.
The presence of the aluminosilicate zeolite component in the FCC catalytic microspheroids imparts a measure of hydrocrackin~ activity to the catalyst. It is believed that this hydrocracking activity is also enhanced by the resistance to pore mouth plugging, permitting a longer run life.
t is contemplated that the catalyst of this invention will be best used in a fixed bed reactor containing other hydroprocessing catalysts, for example upstream of active hydro-desulfurization, hydrocracking, or hydrodenitrogenation catalysts.
In this manner the hydrodemetalation ability of the novel catalyst can be used advantageously to reduce the metals content of the feed to the downstream catalysts. It is preferred that the catalyst of this invention be used in a fixed bed reactor above an active hydrodesulfurization catalyst, for example, one containing from 0.5 to 6 weight percent cobalt and 3 to 15 weight percent molybdenum, on a conventional alumina or silica-alumina support having a large pore volume in the range of 80-150 Angstroms with little pore volume greater than l,000 Angstroms. Examples of such catalysts are described in United States patent 4,066,574. The processes and catalysts of this invention will be further illustrated by the following nonlimit-~0 ing examples.
Example 1 1,000 grams of amorphous alumina powder ~Kaiser SAmedium powder) were calcined ~n air at 750F for 4 hours. The calcined powder was combined with an additional l,000 grams of identical alumina which was not calcined, and with 2,000 grams spent FCC fines by mixing the dry powders for 10 minutes in a Simpson muller. The spent FCC fines had the composition as shown in Table 3. A formic acid solution was prepared by adding 2850 cc distilled water to 120 grams 88% formic acid. The acid solution was added to the mixed powders in 50 cc aliquots every 10 seconds and mixed for 2 hours to provide an e~trudable dis-persion having 46.7~ volatiles. The r~

~L~5~36 volatiles content was determined by an Ohaus Moisture 01 Determination Balance, Model 6000, Ohaus Scale Corporation, Blokam Park, N.J. A 25 gram aliquot of the mix was added to 100 cc of water and a pH of 47 04 was measured using a Reckman Digital pH meter, Model 350n.
One-fourth of the remaining mixture was extruded with a 2 inch Bonnot extruder using a 1/8 inch diameter die. The extrusion was dried on a screen tray and placed in a precision Freas Mechanical Convection Cabinet, Model 845, at 120C for 2 hours with horizontal air flow. The temperature was then raised to 200C for an additional 2 hours.
The dried extrusion was calcined at 675C in the presence of steam for 2 hours with an additional 1 hour hold at 675C in dry air. The caIcined extrudate was allowed to cool in dry air. Pore size distribution of the calcined extrudate was measured using a Micromeritics MIC
901 mercury intrusion porosimeter. Mercury intrusion porosimetry is capable of measuring pores larger than about 50 Angstroms. The cumulative pore volume dis-tribution is shown in FIG. 1. A plot of the derivative of the pore volume with respect to the logarithm of the pore diameter shows sharp peaks in the range of 80 to 150 Angstroms and 4,000 through 6,000 Angstroms. 0.21 cc per gram pore volume (34%) is present in the range of 80 to 150 Angstoms and 0.04 cc per gram (7%) is present in the range of 4,000 to 6,000 Angstroms. This composition was designated as catalyst I.
The calcined extrudate was impregnated with a - 30 solution containing nickel and molybdenum salts. A stock phosphomolybdic acid (PMA) solution was prepared by dissolving 79.3 grams of 85% H3PO4 and 447 grams of MoO3 in 1500 ml. of distilled water. 175 ml. of the stock PM~
solution was heated to 43C and 31 grams o~ NiCO3 was 3 added with stirring. The solution was cooled to 27~C and ~:~LS~36 01 diluted to 245 ml. An additional small quantity of H3PO4 was a~ded to make the solution clear. The resulting solution was sprayed onto 300 grams of the calcined extrudate in a plastic bag. The extrudate was agitated 05 within the bag until excess liquid had ~een taken up hy the extrudate.
After spraying, the composition was allowed to stand for 1 hour before drying on a screen tray in a pre-heated Freas oven at 120C for 1 hour. After drying, the material was calcined in 0~57 meters3/hr. dry air for 6 hours at 93C, 4 hours at 232C, 4 hours at 400C, and 4 hours at 510C. The calcined, impregnated catalyst is designated as catalyst A. The pore diameter dlstribution was measured by mercury intrusion porosimetry as pre-lS viously described and the results depicted in FIG. 2.
After impregnation the total pore volume was 0.42 cc per gram. 0.24 cc per gram was present as 50 to 250 Angstroms diamater pores or 57%~ 0~06 cc per gram was present at 250 to 1,000 Angstoms pores, or 14% and 0.12 cc per gram or 29% was present at pores larger than 1,000 Angstroms.
The curve of differential pore volume with respect to the differentiaI logarithmic pore diameter indicated pore distribution peaks in the range of 80 to 150 Angstrom with 0.11 cc per gram or 26% pore volume and in the 2,000 to 4,000 Angstroms diameter range with 0.02 cc per gram or 5 pore volume.

COMPOSITIONS AND PROPERTIES OF
FCC PRECIPITATOR FINES
_ Particle D~nsity, g/cc n.~01 05 N2 Area, m /g 124 Skeletal Density, g/cc 2.92 Composition, Wt%
Al O3 60.4 Si~2 36.9 Fe 0.72 C 0.30 Ni 0.023 V 0.014 Example 2 200 gram of Kaiser SA medium amorphous alumina powder was calcined at 750F for 4 hours in air and com-bined with 200 grams of identical uncalcined alumina, and 400 grams of spent FCC fines having the composition of Table 3. The mixture was mixed for 5 minutes in a small Baker-Perkins mixer. A formic acid solution was prepared

2~0 by adding 24 grams 88~ formic acid to 570 ml. of distilled water. The acid solution was added to the mixed powders in 20 ml. aliquots and mixed slowly for 5 minutes. The p~
of a 25 gram aliquot of the resulting sol added to 100 cc of water was measured as 4.39. A volatiles content of 44.7~ was measured.
The resulting mixture was extruded in a 51 mm Bonnot extruder using a 1.95 mm die with cooling water in the ~arrel. The extrusion speed was very slow. The extrusions were dried on a screen tray and placed into a - 30 preheated Freas oven at 120C for 2 hours after which time the temperature was raised to 200C. The extrusions were steam calcined with steam at 675C by heating the furnace up in the presence of steam and holding for 1 hour at 675C. The atmosphere was switched to n. 57 m3/hr dry air

3 and the temperature was held an additional half hour at ~1 ~47~

01 675C. The resulting catalyst support was cooled down in dry air. The pore distribution of the support is sho~m in FIG. 3. The total pore volume was .64 cc per gram~ 0.38 cc per gram or 59~ of the pore volume is present as pores 05 in the 50 to 250 Angstrom range. 0.08 cc per gram or 12%
of the pore volume is present in pores in the 250 to 1,0~0 Angstrom, 0.18 cc per gram or 28~ of the pore volume is present in pores greater than 1,000 Angstrom. Differen-tial pore volume with respect to the di~ferential logarithmic pore diameter showed a peak in the range of 80 to 150 Angstroms, accounting for 0.22 cc per gram or 34 percent of the pore volume and a peak at 3,000 to 6,000 An~stroms accounting for 0.04 cc per gram or 6% of the pore volume.
The catalyst support was screened and only that portion larger than 20 mesh (U.S. sieve) was used. The cobalt phosphomolybdic acid solution was prepared by add-ing 330 ml. of crude PMA solution; 1.44 Sp. C.r., contain-ing 20% Mo to 150 grams Co (NO3)2 6 H2O and 120 ml-distilled water. The acid solution was added slowly to the screened support (350 grams) in an evacuated flask.
Sufficient acid solution was added to immerse the support. After 10 minutes the acid solution was drained and the support was blown for 10 minutes with cold air and for 10 minutes at 65C. The impregnated support was calcined in 0.57 m3/hr air for 6 hours at 80C, 4 hours at 200C, and 4 hours at 510C. providing impregnated catalyst B. The pore volume distribution of B was measured as above and is shown in FIG. 4. The differ-ential pore volume with respect to the differentiallogarithmic pore diameter showed peaks in the 80 to 250 Angstroms region accounting for 0.18 cc per ~ram or 40% of the pore volume and in the 3,000 to 10,000 Angstrom region accounting for 0.10 cc per gram or 22% of the pore volume. Catalyst C is a commercially available hydro-~LS4~36 01 demetalation catalyst containing cobalt and molybdenum.
Catalyst D is a commercially available silica-alumina catalyst containinq nickel, moly~denum, and phosphorus.
Comparative Example 05 500 ~rams Kaiser alumina and 500 grams Catapal SB
alumina (Conoco) were char~ed to a mixer. 30 grams of 90%
formic acid were added to 500 ml. distilled water. The resulting solution was added to the mixed powders while mixing in the mixer. An extrudable dispersion with 55%
volatiles was obtained. The mixture was extruded with a 51 mm Bonnot extruder using a 1.95 mm die. The extrusion was dried on a screen tray in a preheated Freas convection cabinet at 120C for 1/2 hour. The temperature was then raised to 200C for another 1/2 hour. The dried extrusion was calcined at 820C for one hour in 0.57 m3/hr dry air.
The catalyst support was desi~nated catalyst E. Table 4 depicts the properties of catalysts herein described.
Catalyst L is a catalyst prepared from spent FCC catalyst fines in the same manner as catalyst A, but with a higher Ni and Mo content. Catalyst M is a prior art desulfuri-zation catalyst.
The following examples depict the presentation of - catalyst using varies quantities of FCC microspheroids and alumina.
Example 3 400 grams spent FCC fines and 400 grams ~aiser alumina were charged to a ~aker-Perkins mixer. 24 grams~
88% formic acid was added to 430 ml. distilled water. The resulting solution was added to the powders while mixing ` 30 in the mixer. An extrudable dispersion with 41% volatiles was obtained. The mixture was extruded with a 51 mm.
Bonnott extruder using a 1.95 mm die and with coolin~ H2O
in barrel. The extrusions were dried on a screen tray and in a preheated Freas convection cabinet at 120C for 2 hours. The temperature was then raised to 200C for ~ "

~L5~36 01 another 2 hours. The extrusions were steam-calcined at 675C by heating the furnace up in the presence of steam and holding for 1 hour at 675C. The atmosphere was switched to 0.57 meters3/hr dry air and the temperature 05 was held an additional half hour at 675C. The resulting catalyst support was cooled down in dry air. The catalyst support was designated as catalyst F.
Example 4 450 grams spent FCC fines and 450 grams Kaiser alumina were charged to a Baker-Perkins mixer. 44 grams 70.6~ nitric acid was added to 500 cc distilled water.
The resulting solution was added to the powders while mixing in the mixer. An extrudable dispersion with 39.1 volatiles was obtained. The mixture was extruded with a Ram extruder using 1.95 mm die. The extrusions were dried in a screen tray and in a preheated Freas convection cabinet at 1~0C for 2 hours. The temperature`was then raised to 200C for another 2 hours. The extrusions were steam calcined at 675C by heating the furnace up in the presence of steam and holdin~ for one hour at 675C. The atmosphere was switched to 0.57 meters3/hr dry air and the temperature was held an additional half hour at 675C.
The resulting'catalyst was cooled down in dr~ air. It is designated as catalyst G.
Example 5 800 grams spent FCC fines were charged to a Baker-Perkins mixer. 400 ml. distilled water was added to the powder while mixing. An extrudable dispersion with 31% volatiles was o~tained. The mixture was extruded with 30 a 51 mm Bonnott extruder using 1.95 mm die and with cooling water in barrel. The extrusions were dried and steam-calcined in the same manner as Example 3 and Example

4. The resultin~ catalyst is designated catalyst ~.

~5~36 Example 6 01 300 grams of used (equilibrium) Davidson CBZ-l fluid catalytic cracking catalyst (W. R. Grace), wi~h particle diameters of about 50-70 microns, were charged with 406 grams Kaiser SA medium alumina to a Baker-Per~ins 05 mixer. 20 ml. of glacial acetic acid was added to 500 ml.
distilled water. The resulting solution was added to the powders while mixing in the mixer. An extrudable dispersion with 45~ volatiles was obtained. The mixture was extruded with a 51 mm Bonnot extruder with a 1.95 mm die. The extrusion was dried and calcined in the manner of Example 3~ and designated catalyst J.
- Example 7 -Solution A was prepared by dissolving 280 grams NitNO3)2 6 H2O and 30 ml. 88~ formic acid in 1000 ml.
distilled water. Solution B was prepared using 24 ml.
concentrated ammonia (58% NH40H), 700 ml. of a stock ammonium molybdate solution containing about 20~ Mo, and 500 ml. distilled water. 1000 grams Kaiser SA medium alumina and 1000 grams fresh Davidson GRZ-l FCC catalyst were charged to a Simpson Muller heated to about 45C with jacketed steam. Solution A was added first to the powder, followed by solution B, while mixing in the Muller. An extrudable dispersion with ~7% volatiles resulted. The dispersion was extruded with a 51 mm. Bonnot extruder with a 2.54 mm die. The extrusion was dried and steam calcined as in Examples 3 and 4, except that the calcination temperature was 510C rather than 675C. The resulting catalyst was designated catalyst K.
The properties of catalysts F through K, includ-ing catalyst I of Example I~ are shown in Table 5.

-Ca) ~ G O O G.
O U~
O
~1 C
c I~ o\O o\O O O~
O ~ ~ C~
~30 0 0 0 C
O

I~ ~ I` d~
z ~c . - - -O U~ I~ ~ ~ ~ O
~ ~1 ~1 E~ u~.
H L
C~
pO~
~ ,~ O p~ o'. d~ ~
N ~ O a~ a) O ~C) d' ~. ~ ~ ~--C,~ Ci o o O ~ _1o. ~P

~ O o~ o\O O~o a~
m0 . I . . ~ ~ ~1 ~ -cr~ o ~

o 0~O 0~O 00 I` ~ c~ ~ ~~r ~ ~ ~ o ~ 1 ~1 0 r~

c ~ c - c c ~ o,a o u~ ~ ~ o ~I v o ~ a~ ~ O-~ o 0-~ 0 '~ V C~ ~ ~ V ~ ~ SJ O O +
~ Z ~ U~ rl ~ V
E~ C a ~-- ~-- h-- ~-,1 1 0 0 ~: o ~ o ~ O ~ o Ln o o U~ o O O ~

~IL154L~36 o o cn v ~9 1 r In co cn ~r oo * u~

O ~ o O O ~ ~ r~ ri~ o ~ C~
o c~ r~. .
~ a~ e r-/ I~

0 ~ C.) ~`1 00 ~53 r~ er cn ~ d~ u~
`I ' o ~ ') o r` ~ C3 H E~ O ~D r~ . ~ o ~1 r~ r~
O r~ O
Ec~

o o o ~ n cn ~ r~ ~r - aJ ~ t`~l cr~N ~ ~ L~ r l I`
X r~
~ ~D r~
g r~ O

o ~ ~ oer r ~ c~
SJ ~ er rl ~3 0 .- ~ ~ O , ,~ ~
" ,~ o z L 1~ o ~ CG u ~ o ~ o ,~ c~ cn u~ I~ cn In r~ . ~ O C , r-l r I
O r1 0 ~ 0 ~ '0 0 C r ~ ~1 Q~ r~ ~ r a) ~ ~ c c~
~ ~ r~ C t~
Jl 0 0 C r 0 C ~ ~1 ~ S~ 0 ~ O ~ ~J
r~tl) U U~ - C~
U~rJ C ~ r~ U~
c ) 0 ~ o ~Q
rl .r1 1~ + ~1 3 1 ~ 0 U~ O ~
1-1 r1 ~ r1 ~ rl~ ~ O a) 1 U~ Q
t~ r~ 0 L~ a ~ c ~ e ~
IJ ~a) r-l .~ ~ ~ ~;5.1 E31~3 0 ~1 .a 11) ~1 ~
U~ rl lS i O Cl ~ t S ~11 .C 0 .r~ J aJ al al r-l 1--l0 0 1¢ /~ O ~ ~ 51 U~
U~ J0 C5~ ~U1 r ~ O a o u) _~ ~I r-1 E~ rl ~ 0 ~
r-~ r~ 0I O O rl ~ rl h ~ a) r-l 0 d~ dP d~5 dP dP ~5 ~ aJ IU ~U O Ln ~ ~ ~ 0 rl h h ~J h 111 C`l r~ ~ r-l 0 r-~
a~ ~J ~ .IJ ~ ~ 1 ~ ~0 0 _S O t~ r-l ~ * 1 O U'~ O
O O

~:~L5~36 01Example 8 Catalyst A, and commereial eatalysts C, and D
were tested in a fixe~ bed pilot plant reaetor under hydroprocessin~ eonditions. The temperature of the 05 reactor for each run was gradually raised from 368 to 427C according to Table 6.

Fixed Bed Reaetor ~eatup Rate Te~perature, C 368 379 390 402 413 427 Time at Temperature, hr. 150 125 100 125 150 350 The feedstock was a deasphalted oil having the properties set forth in Table 7 API 16.3 S, w~.% 1.89 N, wt.~ 0.31 Ni, ppm 7.9 V, ppm 5-3 Fe, ppm 2.9 Ramsbottom Carbon, wt.% 4.4 Distillation, ASTM D1160,C
LV~, ST/5 399/446 10/30 468j531 LV% recovered 56 Table 8 shows the activity for removal of metals, hydrodesulfurization and hydrocraeking relative to eatalyst ~. Catalyst A whieh had a signifieantly lower catalytic metals content than eatalyst ~ demonstrated com-parable aetivity for hydroeraeking, hydrodesulfurization, 3 and iron removal. Catalyst A demonstrated significantly 01 greater vanadium and nickel removal activity. Catalyst D, however, did have a greater denitrification activity.
Catalyst C showed inferior performance in all respects to catalysts of this invention. FIG. 5 shows the demetal-05 ation capability of catalysts A and F of this inventionrelative to other catalysts described herein.
The striking plugging resistance of catalyst A
of this invention was investigated by examining the cata-lyst near the entrance of each of the beds after the runs were completed. Three pellets of catalysts A and C and four pellets of catalyst D were examined. All three pellets of catalyst C had an iron containin~ crust formed on the outside. One out of four pellets of catalyst D had an iron-containing crust. Catalyst A had no such crust.
FIG. 6 depicts an electron microprobe examination of catalysts A and C, with similar macropore ~istributions.
The position where the alumina concentration drops to 0 represents the edge of the pellets. It is seen that catalyst C had almost no iron present except at the outward edge. Catalyst A, on the other hand, had sub-stantial quantities of iron as deep as 40 microns within the particle. It can be inferred that since catalyst C is intrinsically more active for iron removal than catalyst A, the iron plu~ging indicates that the iron-containing organic molecules reacted quickly near the outside surface of catalyst C, releasing iron which plugged the pores in a short time. The crust outside catalyst C may sh~t off the pores and prevent hydrocarbonaceous molecules from reaching the active surface within the catalyst. Catalyst A, on the other hand, has a lower intrinsic rate of Fe removal, permitting hydrocarbonaceous molecules to enter the pores of the catalyst and contact the active surface within the catalyst. Consequently, catalyst A has a higher overall rate of Fe removal than catalyst C, as shown in Table 8.

~S~36 COMPARISON OF CATALYST ACTIVITY
D C A
Fe Crust Outside1 in 4 Yes No 05 Catalyst Relative Rate Constant at 427C
kHCR 1 0.65 kHDS .1 0.69 kV 1 1 1.55 kNi 1 0.82 1.36 kFE 1 0.5~ 0.90 Relative Content in Product at 427C
Total N ` 1 1.46 1.27 Basic N 1 2,15 1.12 Ramsbottom Carbon 1 1.58 Example 9 Catalyst L of this invention and prior art desulfurization catalyst M were tested in a fixed bed pilot plant under the same hydroprocessing condition. The feedstock was an Arabian Heavy Vacuum residuum containing

5.1~ S, 37 ppm Ni, 116 ppm V, and 11% by weight hot heptane-insoluble asphaltenes. Table 9 d~picts the relative demetala~ion activity of L and M at 416C.

Catalyst L M
KNi 1.14 Kv 1.55 ~5~736 01 Those skilled in the art will be able to make various modifications in the compositions and methods disclosed herein without departinq from the spirit and scope of the invention, and such modifications are con-05 templated as equivalents to the invention herein claimed.

Claims

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

1. A hydroprocessing catalyst comprising a rigidly inter-connected pack containing inorganic matrix oxide and about 10-95% fluid catalytic cracking catalyst microspheroids, based on the total weight of said matrix oxide and said microspheroids, said pack characterized by a pore volume of at least 0.15 cc per g of the pack, at least about 30% of said pore volume pre-sent as pores having diameters within the range of 50-250 Ang-stroms and at least about 5% of said pore volume present as pores having diameters greater than 1,000 Angstroms.

2. The catalyst of claim 1 in which said matrix oxide consists essentially of silica, alumina, or mixtures thereof.

3. The catalyst of claim 2 in which said microspheroids comprise fresh or used fluid catalytic cracking catalyst having a mean diameter within the range of 50-70 microns.

4. The catalyst of claim 2 in which said mircrospheroids comprise spent fluid catalytic cracking catalyst fines having a mean diameter within the range of 10-50 microns.

5. The catalyst of claim 3 or 4 in which at least about 10% of said pore volume is present as pores having diameters greater than 1,000 Angstroms.

6. The catalyst of claim 3 or 4 in which at least about 15% of said pore volume is present as pores having diameter greater than 1,000 Angstroms.

7. The catalyst of claim 2 in which said microspheroids comprise at least about 25 weight percent of the total of said matrix oxide and said microspheroids in said pack.

8. The catalyst of claim 2 in which said pack contains 0.5-20 weight percent as metal of a Group VIB metal, metal oxide, or metal sulfide.

9. The catalyst of claim 2 in which said pack contains 0.5-20 weight percent as metal of a Group VIB metal, metal oxide or metal sulfide and 0.5-10 weight percent as metal of a Group VIII metal, metal oxide, or metal sulfide.

10. A process for preparing a hydropricessing catalyst comprising a rigidly interconnected pack containing inorganic matrix oxide and about 10-95% fluid catalytic cracking catalyst microspheroids, based upon the total weight of said matrix oxide and said microspheroids, said pack characterized by a pore volume of at least .15 cc per g of the pack, at least about 30%
of said pore volume present as pores having diameters within the range of 50-250 Angstroms and at least about 5% of said pore volume present as pores having diameters greater than 1,000 Angstroms, said method comprising the steps of (a) forming a dispersion of fluid catalytic cracking catalyst microspheroids in an inorganic oxide sol;
(b) forming said dispersion into a shaped article; and (e) drying and calcining the shaped article.

11. The process of claim 10 wherein said inorganic oxide consists essentially of silica, alumina, or mixtures thereof.

12. The process of Claim 10 wherein at least 10%
of the pore volume of said pack is present as pores having diameters greater than 1000 Angstroms.

13. The process of Claim 10 wherein at least 15%
of said pore volume is present as pores having diameters greater than 1000 Angstroms.

14. The process of Claim 10 wherein said dispersion contains at least 25% fluid catalytic cracking catalyst microspheroids on a dry weight basis, based upon the total weight of said microspheroids and said matrix oxide.

15. The process of Claim 10 wherein said dispersion contains at least 40% fluid catalytic cracking catalyst microspheroids on a dry weight basis, based upon the total weight of said microspheroids and said matrix oxide.

16. The process of Claim 10 in which said microspheroids comprise spent fluid catalytic cracking catalyst fines having a mean diameter within the range of 10-50 microns.

17. The process of Claim 10 further comprising including within said shaped article about 0.5 to 20 weight percent as metal of a Group VIB metal, metal oxide metal sulfide, or precursor thereof.

18. The process of Claim 10 further comprising including within said shaped article about 0.5 to 20 weight percent as metal of a Group VIB metal, metal oxide, metal sulfide, or precursor thereof and about 0.5 to 10 weight percent as metal of a Group VIII metal, metal oxide, or metal sulfide, or precursor thereof.

19. A process for hydroprocessing a hydrocarbonaceous feed-stock containing constituents boiling above 350°C comprising contacting said feedstock with hydrogen under hydroprocessing conditions with a catalyst composition comprising a rigidly interconnected pack containing inorganic matrix oxide and about 10-95% fluid catalytic cracking catalyst microspheroids, based upon the total weight of said matrix oxide and said microspher-oids, said pack characterized by a pore volume of at least 0.15 cc per g of the pack, at least about 30% of said pore volume present as pores having diameters within the range of 50-250 Angstroms and at least about 5% of said pore volume present as pores having diameters greater than 1,000 Angstroms.

20. The process of claim 19 in which said matrix oxide in said composition consists essentially of silica, alumina, or mixtures thereof.

21. The process of claim 20 in which said microspheroids comprise fresh or used fluid catalytic cracking catalyst having a mean diameter within the range of 50-70 microns.

22. The process of claim 20 in which said microspheroids comprise spent fluid catalytic cracking catalyst fines having a mean diameter within the range of 10-50 microns.

23. The process of claim 21 or 22 in which said hydrocarbon-aceous feedstock contains at least 10 ppm total Ni, V, and Fe and said hydroprocessing conditions are effective for hydrodemetalizing said feedstock in contact with said catalyst.

24. The process of Claim 19 in which said pack contains 0.5-20 weight percent as metal of a Group VIB
metal, metal oxide, or metal sulfide.

25. The process of Claim 19 in which said pack contains 0.5-20 weight percent as metals of a Group VIB
metal, metal oxide, or metal sulfide, and 0.5-10 weight percent as metal of a Group VIII metal, metal oxide, or metal sulfide.

26. The process of Claim 23 in which at least 10%
of said pore volume of said pack is present as pores having diameters greater than 1000 Angstroms.

27. The process of Claim 23 in which at least 15%
of said pore volume of said pack is present as pores having diameters greater than 1000 Angstroms.