CA2122110A1 - Hydroprocessing catalyst material and process for production thereof - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A hydroprocessing catalyst comprising: (i) a transition metal compound; and (ii) a support comprising from about 5 to 100 percent by weight of a delaminatedinterlayered clay selected from naturally occurring, synthetic clay and mixturesthereof, and from 0 to about 95 percent by weight of at least one other support material. The hydroprocessing catalyst may be produced by a process comprising the steps of (i)reacting a naturally occurring, a synthetic clay or a mixture thereof, the clay having an average particle size of less than about 5µm, with a pillaring agent to produce a flocculated clay; (ii) drying the flocculated clay to produce a delaminated interlayered clay, with the proviso that the flocculated clay is not air-dried; (iii) mixing and kneading the delaminated interlayered clay, an aqueous liquid and an inorganic oxide to form a wet mixture; (iv) extruding the wet mixture to form extrudates of substantially uniform structure; (v) calcining the extrudates; and (vi) impregnating the extrudates with a transition metal compound to produce the hydroprocessing catalyst.

Description

--` 2122110 HYDROPROCESSING CATALYST MATERIAL
AND PROCESS FOR PRODUCIION THEREOF

The present invention relates to a hydroprocessing catalyst material and 5 a process for production thereof. More particularly, the present invention relates to a hydroprocessing catalyst material made using naturally occurring and/or synthetic delaminated clays, and to the process for production thereof.
It is known to upgrade coal 1iquids to distillate products suitable for commercial refining to transportation fuels. These coal liquids contain high l0 concentrations of large aromatic molecules as well as significant amounts of heteroatoms such as oxygen, nitrogen and sulfur. Upgrading of coal liquids involves catalytic hydroprocessing to reduce the molecular weight and remove the heteroatoms.
A substantial amount of the aromatic components are also hydrogenated. This is achieved by passing the coal liquid over a porous catalyst contained in a fixed-bed l5 reactor under hydrogen pressure.
Currently, the catalysts which are being utilized in upgrading of coal liquids are conventional hydrotreating catalysts which are used in commercial petroleum refining. Generally, these catalysts consist of combinations of transition metals such as molybdenum, tungsten, cobalt and nickel supported on a porous high 20 surface area material such as an oxide (e.g. ~-alumina). Combinations of transition metals may be used, such as Co-Mo, Ni-Mo and Ni-W. Transition metals Co and Ni are generally used as promoters and, in order to generate the active form of the catalyst, it is necessary to carry out sulfiding with H2S to convert the metals to the corresponding sulflde form.
Some coal liquefaction processes (e.g. the NEDOL coal liquefaction process) utilize a hydrogen donor solvent in the treatment of coal during the primary liquefaction stage. In order to be economically efficient, the process requires successful, continuous rehydrogenation and recycle of the spent hydrogen donor solvent rnaterial. Typically, in the rehydrogenation process, the heavy coal liquid 30 distillate from the liquefaction process is hydrogenated over a fixed catalyst bed. In operation, the feedstock comprising the spent hydrogen donor solvent contacts the sulfided catalyst metals on the support structure in the presence of hydrogen, and thus " ~ ,.3~

212211~
rehydrogenation of the solvent occurs. In addition to solvent hydrogenation, theheavier fraction (boiling point > 350C) of the combined feedstock is hydrocracked to increase the light portion of the total product. These lighter oil products may then be distilled off prior to recycling.
An alternative procedure for conversion of coal to liquid fuels is to carry out the primary liquefaction step by coprocessing coal with bitumen. The coprocessed liquid material so produced has similar characteristics to a liquid produced entirely from coal in that it contains large amounts of aromatic hydrocarbons and heteroatoms which must be removed by hydrogenation. After the primary liquefaction process, the coprocessed liquid is first distilled off and then upgraded by hydroprocessing in a fixed bed reactor. Typically, in hydroprocessing, the heavy coprocessed 1iquid distillate from the primary liquefaction step is hydrogenated over a fixed catalyst bed. In operation, the feedstock comprising the coprocessed liquid contacts the catalyst metals which are in a sulfided state on the support structure, and thus hydrogenation of the liquid occurs.
A number of problems have been encountered in the development of hydroprocessing technology for secondary upgrading of liquid products from coal.One of the major problems concerns deactivation of the hydroprocessing catalyst due to the adsorption thereon of certain components of the feedstock and subsequent formation of carbonaceous deposits on the catalyst surface. Stohl et al. (American Chemical Society, Division of Fuel Chemistry, Preprints 30(4), 148 (1985)), the contents of which are hereby incorporated by reference, have shown that the loss of activity and occurrence of carbon deposition appears to correlate with the base strength of the nitrogen compounds in the coa1 liquid feedstock with some contribution from phenolic compounds. These heteroatomic components of the feedstock are thought to foul and deactivate the catalyst through irreversible adsorption at acidic sites on the ~-alumina oxide catalyst support. Similarly, polynuclear aromatic compounds contained in the feedstock may also adsorb on andfoul t~e catalyst surface where they form coke.
One approach to improving catalyst performance has been to develop a ~-alurnina catalyst support with an optimum bimodal pore structure to offset the effects of pore plugging through the accumulation of carbonaceous deposits - see, for example, Nishijima et al. (Proceedings of 4th International Symposium on Catalyst Deactivation, Antwerp, Belgium (1987)), the contents of which are hereby incorporated by reference.
Another approach to overcoming the problem of formation of carbonaceous deposits during upgrading of coal liquids is to utilize a carbon support.
Carbon supports have been found to confer much higher resistance than alumina tocoke deposition by prob1ematic feedstock components - see, for example, Scaroni et al. (Applied Catalysis, 14, 173 (1985)). Further, British patent application 2,056,478A (published March 18, 1981) teaches that sulfided Mo/C catalyst was more active for upgrading coal liquids than a sulfided Co-Mo/~-alumina catalyst.Unfortunately, a prob1em encountered with the use of carbon as a catalyst support in fixed bed reactors is its low crush strength.
Another strategy in the development of cata1yst supports relates to the use of c1ay materia1s. Indeed, United States patents 4,761,391 and 4,844,790 (both lS to Occelli and hereinafter co11ectively referred to as Occelli), the contents of which are hereby incorporated by reference, disc1Ose the use of particular delaminated clays as a constituent of hydrocarbon conversion catalysts. The preamble of Occelli refers to the stacking arrangement in smectite clays, a well known class of naturally occurring and synthetic layered clays which swell or expand when exposed to moisture, Examples of such clays include montmorillonite, hectorite, beidellite,nontronite, saponite and Laponite, a synthetic hectorite. The stacking arrangement of smectite clays is il1ustrated schematica11y in Figure l. In Figure 1, each silicon-different element-si1icon sandwich is referred to as a layer, A multi-layered structure is referred to as a platelet.
The preamble of Occelli also discloses production of pillared clays by intercalating thermally stable, robust, three dimensional pillars between adjacent layers of the clay. The intercalation is achieved through an ion-exchange process using large cations called pillaring agents. The intercalated pillars confer an acidity to the clay and provide an enlarged spacing between adjacent layers of from approximately 6 to 10 A and an array of rectangular openings (8 by 16 A) therebyallowing the laminated pillared clay to act as a two-dimensional molecular sieve. The pillars are formed by calcination of the clay after the cation exchange process is complete.

The preamble of Occelli further discloses that synthetic smectite clays such as synthetic hectorite (e.g. Laponite) may be delaminated when freeze-drying or gas-drying is the final step of the clay flocculation process. A so-produced delaminated clay has a disordered, random platelet orientation when compared to the S ordered stacking arrangement in laminated pillared clays. The disordered platelet orientation has been referred to as a house-of-cards type structure. In this case, the process of adding the pillaring agent brings about flocculation which involves separation of the clay sheets. On freeæ-drying or gas-drying, the delaminated structure is formed A comparison of platelet orientation in a pillared interlayered clay (PIL.C; the laminated clay) versus that in a delaminated interlayered clay (DILC; the delaminated clay) is shown in Figure 2 As illustrated, the laminated clay has a relatively well ordered structure made up exclusively of platelets arranged stackwise in a face-to-face manner. In contrast, the de1aminated clay, in addition to including 15 some platelets arranged in a face-to-face manner, further includes many platelets arranged in an edge-to-edge and face-to-edge manner thereby generating the house-of-cards type structure The house-of-cards structure comprises mesopores (20 to 500A in diameter) by virtue of the arrangement of groups of p1atelets and micropores (less than 20 A in diameter) by virtue of the spacing between the clay layers This 20 combined mesoporosity and microporosity in delaminated clays leads to desirable catalytic properties which are not found in laminated clays, Occelli also teaches the use of pillared clay materials as hydrocracking catalysts - see Occelli and Rennard, Catal~sis Today, 2 (1988) 309-319 In this case, the catalyst forming procedure involves initially producing a pillared montmorillonite 25 which is then used either as the cracking component of the catalyst or as thehydrogenation component When the pil1ared clay is used as the cracking component, the hydrogenation metals Ni and Mo are loaded onto a separate and different material, namely an alumina hydrate powder previously calcined at 400C. The metals are loaded using a one-step co-impregnation procedure and then the oven-dried 30 impregnated alumina is mix-mulled with the pillaIed clay, peptized with 1% nitric acid and extruded The extrudates are oven dried and thereafter calcined at 450Cfor 18 hours When the clay material is used to support the hydrogenation metals, ~ r ~ "

the pillared montmorillonite powder of < 100 mesh siæ is calcined at 400C and then loaded with the metals using the same one-step co-impregnation described above.
The oven-dried metals-loaded pillared clay is then mix-mulled with ammonium Y-æolite (cracking component), peptized with 1% nitric acid and extruded. The 5 extrudates are then heat treated as above.
Thus, in this case, the catalyst is fabricated by producing the cracking or hydrogenation component separately, and thereafter mixing the components prior to catalyst extrusion. Unfortunate1y, one can expect to experience a considerable loss of catalyst definition in this process since impregnation of powders with metal 10 solutions is difficult. Thus, utilizing Occelli's procedure, the metals may not be effectively dispersed within the catalyst structure. Further, Occelli makes no mention of the importance, if any, of the physical properties of the clay (e.g. specific particle size, aspect ratio, etc.) being result effective on the pore size of the final catalyst.
United States patent 5,114,895 (Holmgren et al.), the contents of which 15 are hereby incorporated by reference, disclose the use of alumina clay compositions which consist essential}y of a layered clay homogeneously dispersed in an inorganic oxide matrix. The process of preparing the compositions comprises adding a clay material to a hydrosol of a precursor of the inorganic oxide (e.g. an aluminum hydrosol) and mixing in a ball mill. Spherical particles are formed from the clay 20 containing hydrosol by adding hexamethylene tetrammine to the mixture to gel the material into spheres when dropped through a tower of oil maintained at 95C. After the spheres are removed from the hot oil they are pressure aged at 140C for 2 hours, washed with 10 liters of dilute ammonium hydroxide solution and dried at 110C. As will be apparent to those of skill in the art, Holmgren et al. do not relate 25 to incorporation of a delaminated clay into the hydrosol. The principal reason for this is that there is no teaching in Holmgren et al. of the special drying step (e.g. freeze-drying or spray-drying) which must be conducted in order to preserve the delaminated structure.
It is an object of the present invention to provide a novel 30 hydroprocessing catalyst comprising a delaminated naturally occurring or synthetic clay.

It is another object of the present invention to provide a process for producing a hydroprocessing catalyst comprising a delaminated naturally occurring or synthetic clay.
Accordingly, in one of its aspects, the present invention provides a 5 hydroprocessing catalyst comprising: (i) a transition metal compound; and (ii) a support comprising from about 5 to 100 percent by weight of a delaminated interlayered clay selected from a naturally occurring clay, a synthetic clay andmixtures thereof, and from 0 to about 95 percent by weight of at least one othersupport material.
In another of its aspects, the present invention provides a process for producing a hydroprocessing cata1yst comprising the steps of:
(i) reacting a clay selected from a naturally occurring clay, a synthetic clay and mixtures thereof, the clay having an average particle size of less than about 5~m, with a pillaring agent to produce a flocculated clay; and (ii) drying the flocculated clay to produce a delaminated interlayered clay, with the proviso that the flocculated clay is not air-dried;
(iii) mixing and kneading the delaminated interlayered c1ay, an aqueous liquid and an inorganic oxide to forrn a wet mixture;
(iv) extruding the wet mixture to form extrudates of substantially 20 uniform structure;
(v) calcining the extrudates; and (vi) impregnating the extrudates with a transition metal compound to produce the hydroprocessing catalyst.
Thus, according to the present process, extrusion and calcining are 25 carried out initially to generate the catalyst support pore structure and facilitate metals dispersion thereafter.
Embodiments of the present invention will be described with reference to the accompanying drawings, in which: -Figure 1 is a schematic illustration of the stacking arrangement in a 30 montmoril10nite clay;
Figure 2 is a schematic illustration of platelet orientation in a laminated pillared interlayered clay versus that in a delaminated interlayered clay;

2~22110 Figure 3 is a graphical illustration of the relationship between pore volume distribution and average pore diameter, as determined by BET ni~rogen adsorption data, for three clay materials;
Figure 4 is a graphical illustration of the XRD spectra for a clay S material (Laponite RD) before and after flocculation/delamination thereof;
Figure S is a graphical illustration of the XRD spectra for another clay materia1 (Polargel NF) before pillaring/delamination, air-dried pillared and freeze-dried delaminated;
Figure 6 is a graphical illustration of the surface area-normalized Lewis acidity for sulfided Ni-Mo catalysts supported y-alumina and delaminated clay composite materials;
Figure 7 is a schematic of an automated microreactor system used for catalyst screening during hydroprocessing of coal derived liquids;
Figure 8 is a graphical illustration of catalyst deactivation time profiles for a number of hydroprocessing catalysts;
Figure 9 is a schematic of a gradientless, continuous stirred tank reactor suitab1e for screening the present hydroprocessing catalyst material; and Figure 10 is a graphical illustration of the effect of catalyst composition on the conversion of nitrogen in coprocessed gas oil Accordingly, it has been discovered that useful hydroprocessing catalyst materials may be made from naturally occurring clays, synthetic clays and mixtures thereof provided the starting clay has an average particle size of less than about 5~4m The use of hydroprocessing catalysts in the petroleum industry is known and is well documented. Generally, hydroprocessing catalysts encompass both hydrotreating and hydrocracking catalysts. Typically, hydrotreating catalysts are utilized to facilitate removal of organosulfur and organonitrogen compounds fromrefinery feedstocks as a treatment step prior to quality assessment of the final fuel product. Similarly, hydrocracking catalysts may be used in processes for converting gas oils to transportation fuels and for refining lubricating oils. The cost associated with llydroprocessing catalysts (i.e. the cost of obtaining/purchasing and of using the catalysts) represents a major cost associated with the conversion of primary hydrocarbons to refined fuel products. Accordingly, a catalyst material which is more resistant to fouling and poisoning is a distinct advantage in the overall efficiency of the process.
Hydroprocessing cata1ysts generally comprise molybdate and/or tungstate catalysts promoted by nickel and/or cobalt and supported on an inert S material, usually y-alumina (~-Al203). Typically, cornmercial hydroprocessing catalysts are prepared by supporting the active metal oxides (eg. MoO3, W03) on y-a1umina. This supporting process may involve successive impregnation/calcinationsteps followed by promotion with CoO or NiO. After loading into a reactor, the catalysts are activated for hydroprocessing operations by a sulfidation step which 10 serves to convert the supported metal oxide-based catalyst to the more stable metal sulfide-based (eg. MoS2, WS2) catalyst. During hydroprocessing, the catalyst activity is usually sustained by the presence of organosulfur compounds in the feedstocks.
These compounds supply sulfur to the catalyst through hydrogen sulfide (H2S) formation.
15Accordingly, as used throughout this specification, the term "hydroprocessing catalyst" is meant to encompass, inter alia, catalyst materials which are used in hydrotreating and hydrocracking processes. Non-limiting examples of such catalysts are those used for hydrotreating (hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation and hydrogenation of olefins and 20 aromatics), hydrocracking and hydrofinishing. Hydroprocessing catalysts may also be used to treat (typically upgrade) the following non-limiting feedstocks: tar sands bitumen, heavy oils, shale oils, heavy gas oils, cycle oils, coker distillates, middle distillates, kerosenes, pyrolysis gasolines and naphthas.
The naturally occurring or synthetic clays suitable for use in the present 25 invention are smectite clays. Such clays are well known and are described in Chemistry ~f Clays and Cla~ Materials, Edited by A.C.D. Newman, John Wiley & - :
Sons, New York (Mineralogical Society, 1987), the contents of which are hereby incorporated by reference. Non-limiting examples of suitable naturally occurringclays include montmorillonite, beidellite, nontronite, saponite, hectorite and the like.
30 The most preferred naturally occurring clay useful in the present invention is montmorillonite. Non-limiting examples of synthetic clays suitable for use in the present invention include hectorites (e.g. Laponite) and saponites.

It has been discovered that useful catalyst materials can be made from delaminated naturally occurring or synthetic clays provided that the original clay, prior to delamination, has an average particle siæ of less than about 5,um.
Preferably, the clay has an average particle size in the range of from about 0.01 to S about 5~m, more preferably from about O.Ol to about 4,um, most preferably fromabout 0.025 to about 3,um. A naturally occurring clay having an average particle size in this range is commercially available from American Colloid Company under the tradename Polargel NF. A synthetic clay having an average particle siæ of 0.025,um is commercialiy available from Laporte Inc. under the tradename Laponite RD.
Initially, the naturally occurring or synthetic clay (or mixture thereof) is reacted with a pillaring agent to produce a flocculated clay comprising a randomly oriented house-of-cards arrangement of clay platelets which, on drying (e.g. freeæ-drying or spray-drying), form face-to-edge and edge-to-edge structures having both microporosity and mesoporosity. The choice of pillaring agent is not particularly 15 restricted. Preferably, the pillaring agent is provided in an aqueous medium and, when used in this manner, results in the production of a flocculated reaction product.
Examples of suitable pil1aring agents include polyoxy metal cations, mixtures ofpolyoxy metal cations, colloidal particles comprising silica, alumina, titania, tin oxide, chromia, antimony oxide or mixtures thereof and cationic metal clusters 20 comprising molybdenum, tungsten, nickel or cobalt. The more preferred pillaring agents are aqueous solutions of polyoxy metal cations selected from the group comprising polyoxyaluminum cations, polyoxyzirconium cations, polyoxychromium cations, polyoxygallium cations and rnixtures of such cations. The most preferred pillaring agents are cations having the empirical formulae ~AII3O4(OH)24(H2O)lJ7+, 25 lAI8(OH)20ZrO]6+ and mixtures thereof. Such cations may be found in solutions of aluminum chlorhydroxide (Chlorohydrol) or aluminum zirconium tetrachlorohydrex-glycine (Rezal 36G), both commercially availab1e from Reheis Chemicat Company.
The amount of pillaring agent required is primarily dependent on the cation exchange capacity (c.e.c.) of the naturally occurring clay or synthetic clay.
30 The amount of pillaring agent typically found to be effective for flocculation and delamination of the smectite clay is in the range of from about 10 to about 100 fold excess over the cation exchange capaciql To minimize washing and optimize the ',',''t.' ", ""'`'""'~ '""'',."",'''''''""' "`"'' .~

-` 2122110 economics of the process it is preferred that the amount of pillaring agent used be in the range of from about 10 to about 15 fold excess over the cation exchange capacity.
Drying of the delaminated clay while it is still flocculated in the aqueous suspension may be accomplished using conventional freeze-drying or spray-5 drying techniques or the gaseous medium drying technique disclosed in Occelli. Thepreferred drying technique is spray-drying which may be readily adap~ed for commercial operations. As is known in the art, air-drying should be avoided since it leads to the production of a pillared interlayered clay (i.e. PILC) and not to the desired delaminated interlayered clay (i.e. DII,C).
The delaminated natuMlly occurring or synthetic clay is then used to fabricate a hydroprocessing catalyst support material. When used in a hydroprocessing catalyst support, the delaminated clay, alone or in the form of a composite with another support material, described herein acts as a support for a transition metal catalyst as described hereinabove. The delaminated clay may be used 15 exclusively as the support or it may be mixed with conventional support materials such as ~-alumina. It is preferred that the hydroprocessing catalyst comprise a support containing from about 5% to 100%, more preferably from about 5% to about75 %, by weight of delaminated clay with the balance being made up of at least one other support material, Non-limiting examples of other support materials include ~-20 alumina, silica, silica-alumina, zirconia, titania, chromia and zeolite. The most preferred other support material is ~-alumina.
The delaminated naturally occurring or synthetic clay is then mixed (e.g. mix-mulled) and kneaded with an inorganic oxide to form a wet mixture. Themanner by which the delaminated clay and inorganic oxide is mixed and kneaded is25 not particularly restricted and is within the purview of a person skilled in the art. For example, mixing, also knovn in this context as mix-mulling, may be carried out using a mechanical mixer, t~e rate of which may be controlled. The mixing period should be suff~cient to ensure formation of a substantially completely homogeneous mix Water is added to the mix to form a paste-like composition. Kneading may be carried 30 out using a suitable mechanical device or, alternatively, by using a hand spatula, and involves applying pressure to resis~ant paste-like materials to facilitate homogenizing of the mix thereby forming a wet mixture.

--` 2122110 Extrusion of the wet mixture is carried out with the purpose of shaping the wet mixture to the required geometrical form for catalysts supports. The extrusion step is typically conducted by passing the wet mixture under pressure - through a small orifice to form extrudates of a substantially uniform structure.
S Extrusion may be carried out using a conventional extruder. Preferably, the wet mixture is extruded in the presence of a peptizing agent. Such agents are known in the art and include, for example, nitric acid.
Calcining of the catalyst support extrudates prior to metals impregnation is carried out primarily to remove water from the extrudates. Calcining 10 also serves the purpose of generating a high surface area and forming the required pore structure within the bulk of the catalyst support material. Calcining may be carried out using conventional techniques within the purview of a person skilled in the art. Thus, as is known by those of skill in the art, calcination or calcining involves strong thermal treatment with the purpose of conversion of metals or metal 15 salts to their corresponding oxides through heating and oxidation in air. The thermal treatment also involves formation of oxides from the corresponding hydroxide forms.
Thermal treatment of hydroxides leads to crystalline phase transitions and loss of hydroxide groups and protons which are liberated as water. In addition to phase transitions, the calcining treatment given to a precursor material (e.g. various forms 20 of alumina) affects other properties that influence its behaviour as a catalyst material.
Among the more important of these are changes in crystallite size, surface area, pore size distribution and pore volume. A general discussion of calcining may be found in Applied Industrial Catalysis, Vol. 3, (Bruce E. Leach, Editor), Chapter 4 Aluminas for Catalysts - Their Preparation and Properties, by Richard K. Oberlander 25 (Academic Press, 1984), the contents of which are hereby incorporated by reference.
The manner by which the transition metal catalyst is loaded onto the support material is not particularly restricted and is within the purview of a person skilled in the art. The preferred loading technique for impregnation of the catalyst support with the metal ingredients is the pore filling method. In the pore filling 30 method the pore volume of the catalyst support is initially determined usually by fi11ing the pores with water. The volume required to fill the pores is then used to make an aqueous solution containing a calculated amount of the metal salt. This :

aqueous solution is then added dropwise to the support material which is contained in a glass vessel or similar container. Preferably, addition of the aqueous solution is done while agitating the g1ass vessel or similar container under a partial vacuum.
The aqueous solution is added until the pores are observed to be filled. The S impregnated support is then dried slowly in air (to prevent loss of solution from the pores) and is then calcined in air to convert the metal salt to the corresponding oxide as described hereinabove The choice of transition metal compound for loading on to the support material is not restricted. Preferably, the transition metal compound comprises a 10 transition metal selected from Group VI or Group VIII of the Periodic Table. More preferably the transition metal is selected from the group comprising Mo, W, Co, Ni, Pt, Pd, Ru and mixtures thereof. The most preferred transition meta1 compound comprises Mo.
Embodiments of the present invention will be described with reference 15 to the following Examples which are not intended to limit the scope of the invention.

EXAMPLE 1 - Preparation Of A H~/droprocessing Catalyst Comprising A
DILC Produced From Laponite RD ~ `
As is known to those skilled in the art Laponite RD is a synthetic 20 hectorite comrnercially available from Laporte Inc. and has an average particle size of 0.025 ~m. A sample of Laponite RD was made into an aqueous suspension in a dass reactor vessel by dispersing a 40 g quantity of the material in 1800 mL of deionized water (approximately 2.0 wt% suspension). The temperature was raised to 50C with rapid agitation. A solution of pillaring agent ZrACH, comprising 3625 wt% alurninum zirconium tetrachlorohydrex-glycine (Rezal 36G) from Reheis, Inc., which had been previously aged by refluxing for 48 h, was added dropwise to the Laponite RD suspension. Based on a Laponite RD cation exchange capacity of 70 meq/lOOg the calculated amount of pillaring agent used to flocculate the Laponite RD
suspension was a 15 fold excess. The floccu1ated suspension was agitated 30 continuously for 12 h and was then centrifuged and washed continuously to remove excess pillaring agent. The wet material was recovered and freeze-dried in a Labconco Freeze Dryer-3 under vacuum of 7 x 10-2 millibar to produce a delaminated synthetic hectorite.
The delaminated interlayered clay (DILC) was ground using a jar mill, sieved to < 200 mesh Si7R and then mixed in a mortar with the correct proportion5 of y-a1umina to give a mixture containing 15 wt% DILC in ^y-alumina. A calculated amount of solution containing S wt% nitric acid as peptizing agent was mixed with the dry solid and the resulting paste was mix-mulled and kneaded mechanically for a period of 40 minutes. The paste was then passed through an extruder to form l/32"
extrudates. The extrudates containing 15 wt% Laponite RD DILC were air-dried and10 then calcined in air. The initial calcination involved heating the extrudate support materia1 at a ramped temperature of 2C/min to a temperature of 300C which was maintained for a period of 3 h. Thereafter, the support material was further heated at a ramped temperature of 2C/min to a temperature of 500C which was maintained for a period of 5 h.
Final catalyst materials were prepared from the extrudates by loading with l6% MoO3, 4% NiO. MolyWenum was impregnated first, using the pore filling method, as herein described, and then nickel. In the case of molybdenum, two sequential impregnations were required. The pore filling impregnations were carried out in an evacuated glass vessel fitted with a calibrated glass burette. After loading 20 the catalyst extrudates into the vessel, the flask and catalyst pores were evacuated and the pores then filled with an aqueous solution containing a calculated amount of metal salt. The aqueous solution was added dropwise onto the catalyst support materialwhilst agitating the glass vessel and contents. The aqueous solution was added until the pores were observed to be filled. After first determining the pore volume of the 25 calcined support using the above technique, the composition was first impregnated with an aqueous solution containing the calculated amount of ammonium paramolybdate (NH4)6Mo,O24~H2O. After the first impregnation, the material was oven dried carefully overnight by slowly ramping the temperature at 2C/min to amaximum of l00~C. The material was impregnated again in a similar manner with 30 approximately the same quantity of an aqueous solution of ammonium paramolybdate and thereafter dried in the same manner. The support was then calcined as described above and then impregnated with a solution containing the calculated amount of Ni(NO3)2~H~O to produce the approximate theoretical Mo/Ni ratio. The sample was again carefully o-ven dried by temperature ramping overnight to 100C maximum.
After impregnation with Mo and Ni was complete the catalyst extrudates were calcined under air atmosphere as described above. After drying and calcining, the 5 final extrudates were prepared for catalyst screening by reducing the particle size to between 20 and 40 mesh.

EXAMPLE 2 - Preparation Of A Hydroprocessing Catalyst Comprising A
DILC Produced From Polar~el NF
As is known to those skilled in the art Polargel NF is a naturally occurring montmorillonite (white bentonite) commercially available from AmericanColloid Company and has an average particle size of approximately 3 ,um. A
dispersion of clay sample was prepared by suspending a 20 g quantity of the material in 1500 mL of deionized water giving a concentration of approximately 1.3 wt%.
15 The pH was adjusted to 4.00 with buffer solution and the temperature of the suspension was adjusted to 50C, pillaring agent was added and the mixture agitated overnight for a period of 16 hours. In this case, the pillaring agent was a 50 wt%
solution of Chlorohydrol commercially available from Reheis Chemical Company.
The cation exchange capacity of Polargel NF was estimated to be approximately 8020 meq/lOOg and based on tbis estimate a 10 fold excess of pillaring agent was added.
After flocculation, the suspension was centrifuged and the material was continuously washed until free from chloride ion i.e. excess pillaring agent. The material was then freeze-dried a~ above to produce a delaminated interlayered clay and ground to < 200 mesh. The delaminated Polargel NF was used to prepare a catalyst support material 25 by combining 30 wt% with ~-alumina and extruding as described above. The extrudates were similarly dried and calcined and impregnated with approximately 16 wt% MoO3 and 4 wt% NiO followed by drying and calcining to produce the finished catalyst.

30 E~AMPLE 3 - Preparation Of A PILC From Accofloc 350 Accofloc 350 is a naturally occurring montmorillonite clay containing a wide range of particle size and is commercially available from American Colloid Company. Initially the clay material was sieved to < 200 mesh. The clay was thenfully converted to a sodium form by ion-exchange. This was achieved by making a suspension of 120 g of clay material in 2000 mL of 0.50 M NaCl solution. The resulting suspension was stirred for approximately 20 h at 70 C. After each sodium 5 ion-exchange the clay material was separated by centrifuging. Three ion-exchanges were made, after which the ion-exchanged clay material was washed continuously with deionized water until it was free of chloride ion. The ion-exchanged material was then dried at approximately 120 C for 18 h and ground and sieved to ~ 200 mesh.
The dried, ion-exchanged Accofloc 350 was then pillared with pillaring agent comprising a 50 wt% aqueous Chlorohydrol solution. This was done by dispersing the ion-exchanged clay material in deionized water and adjusting the pH
to 4,00 as described in Example 2. In this case an approximately 100 fold excess of pillaring agent over the cation exchange capacity of the clay material was added and 15 the suspension was then stirred continuously for 17 h at 50 C. The pillared clay material was then washed continuously until free of chloride. The prod~ct was dried in air for 24 h at 115 C and then under vacuum for approximately 24 h at 100 C.
The dried PILC was then analyzed by XRD and BET N2 adsorption to confirm the laminated interlayered structure by measurement of basal spacing and pore size 20 distribution, EXAMPLE 4 - Preparation Of A Hvdroprocessin~ Catalyst Comprising A
PILC Produced FromVolclav HPM-20 Volclay HPM-20 is a naturally occurring montmorillonite clay 25 containing a wide range of particle size and is commercially available from American Colloid Company. Initially the cla,v material was sieved to < 200 mesh. The claywas then fully converted to the sodium form by ion-exchange as described in Example 3. The ion-exchanged material was then dried at approximately 120 C for 18 h and ground and sieved to <200 mesh. The material was then pillared as described in 30 Example 3 and the pillared c1ay material was used to fabricate a Ni-Mo catalyst as described in Example 1.

EXAMPLE 5 - Determination of Pore Volume Distributions of Delaminated and Pillared Clays from BET Nitrogen Adsorption Data Samples of freeæ-dried delaminated Laponite RD (starting material supplied by Laporte Inc.), freeæ-dried delaminated Polargel NF and air-dried pillared Accofloc 350 (starting materials supplied by American Colloid Company) were analyæd for BET surface area and pore size distribution. BET N2 adsorption and desorption isotherms were obtained using a Quantachrome Autosorb unit. Samples < 200 mesh were thoroughly outgassed at 280 C for 24 h prior to N2 adsorption/desorption measurements. The incremental pore volume distributions were determined from the N2 adsorption isotherms for the three samples. Values of Dv(d) cm31Alg were calculated, normalized and then compared as line charts. Figure 3 presents line charts of the pore size distributions for the three samples.
The pore size distributions shown in Figure 3 reveal two different pore types in the delaminated clay samples. These may be classified as micropores - <20 A (2 nm) diameter, and mesopores - between 20 - 500 A (2-50 nm) diameter.
The pore sizes generated have important implications in the hydroprocessing of petroleum and coal derived feedstocks due to the corresponding differences in distribution of molecular sizes in these materials which are dependent upon the primary upgrading process and the material boiling ranges.
In Pigun 3 it is observed that the pore volume distributions, as a function of the a.rea under each graph, are markedly different for each of the clay samples. Delaminated Polargel NF has approximately 75 % of pore diameters greater than 20 A, delaminated Laponite RD has approximately 50% of pore diameters greater than 20 A and pillared (laminated) Accofloc 350 has approximate1y 25% ofpore diameters greater than 20 A. Therefore delaminated Polargel NF has the lowest amount of microporosity and contains a large range of mesopore diameters between20-200 A. It is apparent that these pores are formed through delamination of thenatural montmorillonite during the flocculation process and through formation ofedge-to-edge and edge-to-face structures which are retained during freeze-drying.
Figure 3 conf~ns that delamination has occurred for Laponite RD and that in thiscase, the mesopore diameter range is narrower and lies between 20-70 A. In the case 212211 o of the pillared Accofloc 350 which is largely a laminated material, very little mesopore is present which restricts this materia1 to micropore applications.
The importance of these results is realized when considering the fabrication of hydroprocessing catalysts. Thus microporosity is of little value in 5 processing large gas oil molecules which are unable to penetrate into the pores.
Table 1 summarizes the BET N2 adsorption resu1ts for the delaminated and pillared clay samples, It is observed that for both delaminated clays the ratio of micropore to mesopore area is approximately 1:1 whereas in pillared Accofloc 350 the ratio is approximately 3:1. Examination of the average pore diameters for the three samples 10 shows that delaminated Polargel NF has an average value of approximately 87 Awhich is significantly larger than for delaminated Laponite RD which has an average value of approxirnately 27 A. Pillared Accofloc 350 has an average pore diameterof approxirnately 38 A. The total surface area of delaminated Laponite RD is thelargest which is a consequence of the 1arge amount of micropores in the material.
:
EXAMPLE 6 - Structural Characterization Of PILC And DILC Clay Materials Bv XRD
X-ray diffraction (XRD) analysis was carried out on pillared and delaminated naturally occurring and synthetic clays and was used to confirm the 20 formation of delaminated structures and to rewal the particle size effects and structural changes. Powdered pillared and delaminated interlayered clay samples were mounted in custom-made aluminum holders using the side-loading technique.
XRD spectra were collected on a SIEMENS D500TT automated diffractometer. X-ra,v diffraction data were collected over the angular range 2-70 (2~) using Cu K~
25 radiation, Layered clay rninera1s such as montmorillonites and synthetic hectorites are laminated structures and the distance between the lamellae is called the basal spacing. Intercalation with a pillaring agent alters the basal spacing distance. X-ray diffraction is a reflection-interference phenomenon that is used in the powder 30 diffraction (XRD) method to measure the basal spacing distance from diffracted intensity data using the Bragg equation [)~ = 2d x sin~. To measure the change in the basal spacing distance, it is necessary to monitor the diffraction of the first order ........ .. ..... ... .. ....

-` 2122110 or (001) reflection from the basal spacing planes. A perfectly delaminated interlayered clay (DILC) structure does not display first order or (001) diffraction.
Therefore, by monitoring this phenomenon, the extent of delamination in DILC's may be assessed.
S
TABLE 1 - BET N~ Adsorption Data for DILC Laponite RD, DILC
Polar~el NF, and PILC Accofloc 350 ¦ Laponite RD Polargel NF ¦ Accofloc 350 l Freeze-dried Freeze-dried Air-dried ¦ Delaminated Delaminated Pillared l Multi-Point BET Surface 377 144 156 ¦
Area (m2/g) Mesopore Area (m2/g) 203 68 46 Micropore Area t-method 174 76 110 Total Pore Volume (cm3/g) ¦ 0.26 0.31 0.15 Average Pore Diameter A ¦ 27 87 38 Pigure 4 shows the X-ray diffractograms obtained for two samples:
(1) Laponite RD, before flocculation and delamination, and (2) freeze-dried 20 delaminated Laponite RD. The spectral region of interest which is located in the low angle region 3-13 (2~) compares the diffraction of the two different samples. In spectrum 1, the position of the (001) reflection peak was used to calculate the basal spacing of the synthetic clay Laponite RD, i.e. the degree of separation between the stacked aluminosilicate layers which make up the structure of smectite clays. From 25 spectrum 1, the calculated basal spacing of Laponite RD, before flocculation and delamination, was 14.0 A. Figure 4 also shows the XRD diffractogram of freeze-dried delaminated Laponite (spectrum 2). The absence of an easily observable basal spacing peak in the (001) plane as in spectrum 1, indicates that delamination had occ;urred and there is a loss of crystallinity due to separation of the layers. This 30 indicates a reduction in the extent of stacking, i.e. the number of Laponite RD
aluminosilicate layers.

Figure 5 shows the X-ray diff~ctograms obt~ined for three samples:
(1) Polargel NF, before pillaring or delamination, (2) delaminated and freeæ-dried Polargel NF, and (3) air-dried pillared Polargel NF. The spectral region of interest which is located in the low angle region 3-13 (2~) compares the basal spacing peaks for the three different samples. Spectrum 1 illustrates that Polargel NF, beforepillaring, had a basal spacing of 9.92 A. Spectrum 3 in Figure 5 was measured from a Polargel NF sample that was pillared and air-dried. It was found that the basal spacing peak was shifted towards the low end of the angular scale (2~). The lower angular value in the air-dried pillared Polargel NF translates into a basal spacing of ~ ~6 A. Pigure 5 a~so shows t~e XRD d1~ractogram oî ~reeze-dried del~minated Polargel NF (spectrum 2) The location of the basal spacing peak in spectrum 2, similar to tbat in spectrum 3, corresponds to a basal spacing of 1S.S A. However, the basal spacing peak in spectrum 2 is considerably less intense than in spectrum 3.
This indicates that there is a loss of crystallinity due to the delamination and freeze-drying process when compared to air-drying which allows layer stacking to occur.The weak diffraction signal in spectrum 2 is again explained by a reduction in the extent of stacking, i.e. of the number of Polargel NF aluminosilicate layers. The experimental results presented show dramatic differences between the forms of naturally occurring and synthetic clay aggregates after freeze-drying compared to air-drying. These products give markedly different structures which strongly influence their pore size and surface area distribution.

EXAMPLE 7 - Determination Of Surface Acidity Of Ni-Mo Catalyst Supported On ~y-Alumina And Composites Containin~ ~ILC Or DILC
Materials By Fourier Transform Infrared (FTIR) Spectroscop~
Catalyst surface characterization was undertaken to evaluate the propensity for materials to adsorb basic nitrogen components from petro1eum feedstocks since they are known to foul catalyst supports and act as coke precursors.
Measurements were carried out using the FTIR/pyridine adsorption technique.
Pyridine was used as a model compound to simulate feedstock basic nitrogen components. The results showed that the catalyst materials studied may be grouped according to their Lewis acidity. It was shown that Ni-Mo on 100% delaminated æA ~

::- 2~22~0 Polargel NF material has the lowest propensity to adsorb basic nitrogen components.
Ni-Mo catalysts on composite supports containing delaminated smectite clays wereprepared as described in the previous Examples above. The catalysts were calcined in air at 400 C prior to carrying out the adsorption/desorption measurements.
5 Preparation of sample pellets was followed by a degassing step. Infrared spectra of adsorbed pyridine were measured on a Nicolet 60SX FTIR spectrometer at 2 cm-' resolution. The FTIR spectrometer was fltted with a temperature- and pressure-control1ed optical cell used in the transmittance mode. For each measurement, ~ lS
mg of catalyst sample was pressed into a self-supporting wafer ~ 13 mm in diameter.
10 The wafer was then mounted in the optical cell, evacuated at ~105 torr, and degassed by heating for 16 h at 400C.
To probe the catalyst surface acidity, the sample temperature was maintained at 100 C and ~25 Torr of pyridine vapor was introduced into the system and allowed to adsorb at the surface of the pellet for one hour. This temperature was 15 selected to minimize the physical adsorption phenomenon. The wafer was then evacuated at 100C and at progressively higher temperatures (200, 300 and 400 C) at a rate of 10C/min to desorb the chemically bound pyridine. The pressure readings were ~lo-5 torr throughout the desorption experiment. Spectra were recorded at each temperature after pumping for 30 and 60 min respectively. In each 20 case, the 30 and 60 min-spectra were ratioed against the baseline degassed Ni-Mo supported catalyst spectrum previously stored.
Table 2 lists the infrared frequency ranges for various chemically adsorbed pyridine species on solid acid surfaces. The Table reveals that the vibration bands at ~ 1540 and ~ 1640 cm-l can be used to identify Br~nsted acid sites. The25 vibration band at ~ 1450 cm~l is typical of pyridine bound to Lewis acid sites.
Designations 8a, 8b, 19a and l9b refer to pyridine molecular vibrations combining cyclic C-C and C-N bond stretching modes are assigned based on normal coordinateanalysis of pyridine and variously monosubstituted pyridines.
The FTIR spectra of the following catalyst samples:

Catalyst No. Description CM-l Ni-Mo/100% y-alumina CM-2 Ni-Mo/15% Laponite RD DILC: 85% y-alumina CM-3 Ni-Mo/30% Polargel NF DILC: 70% ~-alumina CM-4 Ni-Mo/100% Polargel NF DILC

disp1ay mainly Lewis acidity. A bar chart showing the surface area-normalized absorbance values for FTIR pyridine adsorption at 100C of the Lewis-sensitive band 10 at ~ 1450 cm ~ of the sulfided Ni-Mo catalysts is presented in Figure 6. The Figure also displays the surface area-normalized absorbance values at the top of each bar.
It is observed that, at 100C, the ~-alumina-supported Ni-Mo catalyst shows a stronger pyridine adsorption than the Ni-Mo catalyst supported partially or fully on delaminated Polargel NF materials. Similarly, Ni-Mo supported on 15% delaminated :
15 Laponite RD composite gave a weaker absorbance.

TABLE 2 - Infrared Vibration Bands of Pyridine Adsorbed on Acid Solids in the 1400-1700 cm-l Regioni 20Hydrogen-bondedCoordinately-bonded Pyridinium Ion Pyridine Pyridine (Br~nsted Type) (Lewis Type) ;
1440-1447 (vs;19b)1447-1460 (vs;19b) 1485-1490 (w;19a) 1488-1503 (v;19a) 1485-1500 (vs;19b) 1540 (S;19a) 251580-1600 (s;8a;8b)1580 (v;8b) 1600-1633 (s;8a) 1620 (s;8b) 1640 (s;8a) , . . . .
vs: very strong; s: strong; w: wealc; v: varla~le 212211~
This in~rared characterization study using pyridine adsorption as a means of probing the surface acidity of the above materials showed that delaminated naturally occurring and synthetic clays typically exhibit both Br~nsted and Lewis acidity under ambient conditions. The general trend observed in Figure 6 shows that 5 the adsorption of basic nitrogen compounds on composites containing delaminated montmorillonite and delaminated synthetic hectorite is considerably reduced compared to 100% y-alumina.

EXAMPLE 8 - Hydroprocessin~ Of NEDOL Process Spent Donor Solvent In this Example a feedstock comprising NEDOL process spent donor solvent was upgraded (in this case, hydrogenated). The feedstock was filtered and characterized by elemental analysis, ASTM D-1160 distillation, aromaticity using 13C
NMR and insolubles. Since the spent donor solvent was very low in sulfur content, for the purpose of maintaining the Ni-Mo catalyst activity during screening, sulfur 15 was added by spiking the feedstock with 3 wt% buthanethiol following the procedure of Inoue et al. (Proc, Int. Conf. on Coal Science, 193 (1985)). The characteristics of the feedstock, both unspiked and spiked, are presented in Table 3.
The Ni-Mo supported catalysts used in this Example were prepared as described in previous Examples above. The catalyst materials (CM) were as follows:
20Catalyst No. CatalystMetals Support Composition CM-l Ni-Mo 100% ~-alumina CM-2 Ni-Mo 15% Laponite RD DILC/85% ~-alumina CM-5 Ni-Mo 30% Polargel NF PILC/70% y-alumina CM-6 Ni-Mo 30% Volday HPM-20 PILC/70% y-alumina Figure 7 presents a schematic representation of the automated microreactor system used to screen the CM series of Ni-Mo catalysts in hydrogenation of the NEDOL
process spent donor solvent. Catalyst particles of 14-20 mesh were loaded into af~ed-bed stainless steel tubular reactor 0.305 m in length, and 0.635 cm ID, which 30 was operated in the continuous upflow mode. The catalyst bed was 0.14m in length ', ' . , i ' -; ' . . .. ' -' -,: .,. ,. ' and had a volume of 4.50 cm3. Pre-heating and post-heating zones were filled with quartz particles of 20-48 mesh. The catalyst was presulfided in-situ using a mixture TABLE 3 - Characteristics Of NEDOL Process Spent Donor Solvent Unspiked Spiked Density at 15C (g/cm3) 1.027 Elemental Analysis (wt%) l Carbon 88.90 87.90 ¦
Hydrogen 8.60 9.34 l Nitrogen 0.65 0.56 I .
Sulfur 0.069 1.21 Oxygen 1.60 1.60 D-1160 Distillation (wt%) IBP = 102C
IBP - 200C 0.90 200 - 350C 60.40 350- 525C 36.20 + 525C 2.20 ¦ Loss 0.30 Hexane Insolubles (wt%) ¦ 4.15 Toluene Insolubles (wt%) 0.86 Ash (wt%) r l I ~
Aromatic Carbon (13C NMR)% 58.00 ,~
25 of 10% H2S/H2. The temperature of the catalyst bed was slowly Mised at a rate of 2C/min up to a maximum of 350C with 5h stops at 250C, 300C, and 350C.
The reactor was then cooled to room temperature and the liquid feedstock was , ` 2122110 introduced. The standard operating conditions for hydroprocessing the NEDOL
process spent donor solvent were:

Temperature: 380C
S Hydrogen pressure: 10.3 MPa (1500 psig) LHSV: 1.00 Hydrogen flowrate: 1000 L H2/L liquid feed (5500 scf/bbl) The time-on-steam experiments were carried out for between 150 - 200 h.
For the purpose of monitoring the catalyst activity, samples of hydrogenated product were taken at regular intervals throughout the course of the experimental run and were analyzed for nitrogen and sulfur content and aromaticity.
The atomic hydrogen/carbon ratio was determined using elemental analysis. The oxygen content of the products was significantly low such that it was not measurable 15 by standard analytical methods.
The major reactions occurring during hydrotreatment of the heavy coal liquid are heteroatom removal, hydrodenitrogenation (HDN), hydrodeoxygenation (HDO), and hydrodesulfurization (HDS) and aromatic ring saturation. Significant fouling of the catalyst surface is demonstrated by those catalysts showing a steady 20 decline in nitrogen conversion. Since tbe nitrogen in coal liquids is contained in aromatic type structures, nitrogen removal ~lrst involves hydrogenation of the aromatic ring as a f1rst step in networks that are limited by thermodynamic equilibrium. The second step involves C-N bond cleavage.
Figure 8 presents results of nitrogen conversion in NEDOL process 25 spent donor solvent with time-on-stream for the catalysts CM-l, CM-2, CM-5 and CM-6. Differences in performance for the four catalysts are readily apparent from Figure 8. Specifically, CM-l (containing 100% ~-alumina3 is seen to deactivate rapidly over a period of time-on-stream of approximately 140 h, the nitrogen conversion falling from approximately 80% to less than 60% during this time period.
30 This rapid deactivation is attributed to the acidic nature of ~-alumina which strongly adsorbs basic nitrogen from the feedstock. The two catalysts containing pillared interlayered clays (PILCs) in the supports of CM-5 and CM-6 (containing 30%

-` 212211~
Polargel NF PILC and 30% Volclay HPM-20 PILC respectively) demonstrate an improved overall performance with some initial deactivation occurring over the first 50-100 h after which the activity stabilizes. It is obsened that the conversions of the two catalysts converge with the support containing Polargel NF PILC giving 5 marginal1y better performance. Overall for the t~vo pillared montmorillonites, the catalyst fabricated from Volclay HPM-20 shows a poorer performance than that from Polargel NF and this is believed to be due to the lower purity of the former.
Figure 8 revea1s that the catalyst material giving the best overall performance is that containing the delaminated interlayered clay (DILC) in the 10 material CM-2 (containing 15% Laponite RD DILC). Thus it is shown from the experimental data that over a period of time-on-stream of approximately 160 h, the catalyst shows virtually no loss in activity and maintains a constant nitrogen conversion which never fal1s below 70%. Thus although the catalyst containing 100% ~-alumina has the highest initial activity, it falls below that of the delaminated clay after approximately 40 h. After approximately 140 h time-on-stream, the ~ -catalyst containing the Laponite RD DILC has a nitrogen conversion which is approximately 6% higher than the catalyst containing Polargel NF PILC. The conclusions from these results are that the improved pore structure and surface area of the delaminated clay material facilitates an improved catalyst performance.
EXAMPLE 9 - HvdroprocessinR Of Coprocessed Heavy Gas Oil In this Example, a feedstock comprising a coprocessed liquid was upgraded by hydroprocessing over Ni-Mo catalyst supported on composites containing delaminated or pillared interlayered clay. The coprocessed liquid feedstock was 25 derived from coprocessing 70% Cold Lake Bitumen with 30% Forestburg Coal. Thefeedstock was filtered and characterized through elemental analysis, ASTM D-1160distillation, aromaticity using 13C NMR and insolubles. The characteristics of the feedstock are provided in Table 4. ~ `
The Ni-Mo supported catalysts used in this Example were prepared as 30 described in the previous Examples above. The catalyst materials (CM) used were as follows:

2122~10 Catalyst No. Catalyst Metals Support Composition CM-2 Ni-Mo 15% Laponite RD DILC/85% ~-alumina CM4 Ni-Mo 100% Polargel NF MLC
CM-6 Ni-Mo 30% Volclay HPM-20 PILC/70% y-alumina TABLE 4 - Characteristics of Coprocessed Heavy Gas Oil ¦ Density at 15C (g/cm3) ¦0.9729 ¦
.
¦ Elemental Analysis (wt%) Carbon 85.60 Hydrogen 10.80 Nitrogen 0.70 Sulfur 2.29 Oxygen 0.80 D-1160 Distillation (wt%) IBP = 171C
IBP - 205C 0.0 205 - 375C 32.1 375 - 525C 66.3 + 525C 1.4 ¦ Loss 0.30 0.2 rexane Insolubles (wt%) ¦ 1.68 I ~ ~:
'~
Toluene Insolubles (wt%) 0.11 ¦ Aromatic Carbon (13C NMR)% 58.00 ~

Catalysts CM-2, CM~ and CM-6 were tested in hydroprocessing the coprocessed gas ~ ~ ;
oil. The hydroprocessing experiments were carried out using the automated microreactor system shown in Figure 7 equipped with a Robinson-Mahoney ~ 212211~
gradientless stirred tank reactor shown schematically in Figure 9. The reactor was a continuous flow unit equipped with an annular catalyst basket and internal recycle impeller with a hollow shaft to allow sparging with hydrogen gas. Accordingly, the reactor provided complete mixing of the liquid contents and hence, was substantially 5 free from both temperature and concentration gradients.
In the hydroprocessing experiments, catalyst particles of 14-20 mesh were loaded into the annular basket of the reactor and the weight of the catalyst material was recorded. The catalyst was initially presulfided using a liquid mixture of 3 wt% butanethiol in diesel fuel which was passed over the catalyst bed while10 rotating the internal recycle impeller at 2000 rpm. As in Example 8, while maintaining the reactor at 10.3 MPa (1500 psig) hydrogen pressure, the temperature of the catalyst bed was raised at 2C/minute up to 350C with 5 h stops at 250,300 and 350C. A hydrogen flowrate of 80 mL H2/mL liquid feed was used. The catalyst was then de-edged for 72 h using the diesel fuel feedstock. The de-edging lS conditions were: temperature 380C, hydrogen pressure 10.3 MPa, weight hourlyspace velocity (WHSV) 0.75 and hydrogen flowrate lO00 mL HJmL liquid feed.
At the end of the de-edging period, the coprocessed gas oil was introduced into the reactor at WHSV 0.75 and the internal recycle impeller rate was increased to 2500 rpm to compensate for the heavier feed. The initial starting 20 temperature was 380C with hydrogen pressure and flowrate the same as during de-edging conditions. Por each of the catalysts, the operating temperatures chosen for determinations of nitrogen corlversion in the coprocessed gas oil were 300, 340, 360 and 380C at WHSV 0.75. Reactor performance was monitored by taking 1iquid samples at 6 h interva1s and measuring product density. This provided a 25 reliable indication of when the reactor operation had reached steady-state conditions.
When steady-state conditions were established, at least four samples were taken at 6 h intervals and submitted for analysis for nitrogen, sulfur and aromatics content.
Figure lO presents plots of percent conversion of coprocessed gas oil nitrogen versus reaction temperature for the three catalysts tested. It is shown that 30 the most active Ni-Mo catalyst giving the highest conversions of nitrogen was CM-2, i.e. the material containing a support consisting of 15% Laponite RD DILC combined with 85% )~-alumina. Figure lO also shows that the Ni-Mo catalyst with the lowest nitrogen conversions was CM-4, i.e. the catalyst containing a support consisting of 100% Polargel NF DILC. These results show that the optimum catalyst activity is obtained by forn~ing a composite support material consisting of the delaminated smectite clay material contained in the oxide matrix which, it this case was ~r-5 alumina.

- . ,, ,.,,,. ~,,,, ~ ." f,j"r~,, $, ,.. ... ,,.,,. ~.. ~, ,. , ,:: .~ ~. , . f".i,, ,j,~ .,,

Claims (31)

What is claimed is:

1. A hydroprocessing catalyst comprising: (i) a transition metal compound; and (ii) a support comprising from about 5 to 100 percent by weight ofa delaminated interlayered clay selected from a naturally occurring clay, a synthetic clay and mixtures thereof, and from 0 to about 95 percent by weight of at least one other support material.

2. The catalyst defined in claim 1, wherein the support comprises from about 5 to 75 percent by weight of a delaminated interlayered clay selected fromnaturally occurring, synthetic clay and mixtures thereof, and from about 25 to about 95 percent by weight of at least one other support material.

3. The catalyst defined in claim 2, wherein the clay is a naturally occurring smectite clay.

4. The catalyst defined in claim 3, wherein the naturally occurring smectite clay is selected from the group comprising montmorillonite, beidellite,nontronite, saponite and hectorite.

5. The catalyst defined in claim 3, wherein the naturally occurring smectite clay is montmorillonite.

6. The catalyst defined in claim 2, wherein me clay is a synthetic smectite clay.

7. The catalyst defined in claim 6, wherein the synthetic smectite clay is selected from hectorite, saponite and mixtures thereof.

8. The catalyst defined in claim 6, wherein the synthetic smectite clay is hectorite.

9. The catalyst defined in claim 2, wherein the other support material isselected from the group comprising .gamma.-alumina, silica, silica-alumina, zirconia, titania, chromia and zeolite.

10. The catalyst defined in claim 5, wherein the other support material is .gamma.-alumina.

11. The catalyst defined in claim 8, wherein the other support material is .gamma.-alumina.

12. The catalyst defined in claim 2, wherein the transition metal compound comprises a transition metal selected from Group VI or Group VIII of the Periodic Table.

13. The catalyst defined in claim 5, wherein the transition metal is selected from the group comprising Mo, W, Co, Ni, Pt, Pd, Ru and mixtures thereof.

14. The catalyst defined in claim 8, wherein the transition metal is selected from the group comprising Mo, W, Co, Ni, Pt, Pd, Ru and mixtures thereof.

15. A process for producing a hydroprocessing catalyst comprising the steps of:
(i) reacting a clay selected from a naturally occurring clay, a synthetic clay and mixtures thereof, the clay having an average particle size of less than about 5µm, with a pillaring agent to produce a flocculated clay; and (ii) drying the flocculated clay to produce a delaminated interlayered clay, with the proviso that the flocculated clay is not air-dried;
(iii) mixing and kneading the delaminated interlayered clay, an aqueous liquid and an inorganic oxide to form a wet mixture;
(iv) extruding the wet mixture to form extrudates of substantially uniform structure;
(v) calcining the extrudates; and (vi) impregnating the extrudates with a transition metal compound to produce the hydroprocessing catalyst.

16. The process defined in claim 15, wherein the clay is a naturally occurring smectite clay.

17. The process defined in claim 16, wherein the naturally occurring smectite clay is selected from the group comprising montmorillonite, beidellite,nontronite, saponite and hectorite.

18. The process defined in claim 16, wherein the naturally occurring smectite clay is montmorillonite.

19. The process defined in claim 15, wherein the clay is a synthetic smectite clay.

20. The process defined in claim 19, wherein the synthetic smectite clay is selected from hectorite, saponite and mixtures thereof.

21. The process defined in claim 19, wherein the synthetic smectite clay is hectorite.

22. The process defined in claim 15, wherein the pillaring agent is selected from the group comprising polyoxy metal cations, mixtures of polyoxy metal cations, colloidal particles comprising silica, alumina, titania, tin oxide, chromia, antimony oxide and mixtures thereof, and cationic metal clusters comprising molybdenum, tungsten, nickel, cobalt and mixtures thereof.

23. The process defined in claim 15, wherein the pillaring agent is an aqueous solution of polyoxy metal cations selected from the group comprising polyoxyaluminum cations, polyoxyzirconium cations, polyoxychromium cations, polyoxygallium cations and mixtures of such cations.

24. The process defined in claim 15, wherein the pillaring agent is an aqueous solution of cations having the empirical formulae [Al13O4(OH)24(H2O)12]7+, [Al8(OH)20ZrO]6+ and mixtures thereof.

25. The process defined in claim 15, wherein drying in step (ii) is accomplished by freeze-drying.

26. The process defined in claim 15, wherein drying in step (ii) is accomplished by spray-drying.

27. The process defined in claim 15, wherein drying in step (ii) is accomplished by non-air, gaseous medium-drying.

28. Use of the catalyst defined in claim 2 in a hydroprocessing process.

29. The use defined in claim 28, wherein the hydroprocessing process is a process selected from the group comprising hydrotreating, hydrocracking and hydrofinishing.

30. The use defined in claim 29, wherein hydrotreating comprises one of hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation and hydrogenationof at least one olefins and aromatics.

31. The use defined in claim 29, wherein hydroprocessing comprises treatment of a feedstock selected from the group consisting of tar sands bitumen, heavy oils, shale oils, heavy gas oils, cycle oils, coker distillates, middle distillates, kerosenes, pyrolysis gasolines and naphthas.