CA1236818A - Immobilization of vanadia deposited on sorbent materials during visbreaking treatment of carbo- metallic oils - Google Patents

Abstract

ABSTRACT

A solid sorbent particulate, its method of preparation and use is disclosed for the treatmenbt of a residual hydrocarbon oil feed or a high boiling portion thereof boiling above 1050F° and having a significant content of asphaltenes, Conradson carbon metals such as Ni, V, Fe and Cu to provide a higher grade of oil products by contacting the feed comprising metal contaminants and high carbon forming constituents with a high pore volume sorbent material of at least 0.4 cc/g in a visbreaking zone in which operation the effectiveness of the high pore volume sorbent material is further improved by a metal additive to immobilize low melting point vanadium compounds. The sorbent material pore volume, sorbent to oil ratio and operating conditions are such that the volume of sorbent pores filled with oil feed is limited to the range of 1/4 to 2/3 and along with carbonaceous material metal contaminanls are encouraged to deposit within the pores rather than on the exterior surface of the solid sorbent in a hydrothermal visbreaking operation in the absence of added molecular hydrogen.

Description

1~36818 IMMOBILIZATION OF VEND DEPOSITED ON SORBENT MATERIALS
DURING VlSBREAKlNG TREATMENT OF CARBO-METAI LIT OILS

Technical Field This invention relates to producing a more suitable grade of oil 5 feed material from the bottom of the barrel having lowered metals and Conrad son carbon values for use as feed stock in a reduced crude conversion (RCC) process or a present day modern FCC
process. A high boiling portion of crude oil comprising a poor grade of carbo-metallic oil components having high metals and 10 Conrad son carbon values is converted according to this invention to a lower metals containing feed suitable for an RCC process.
More particularly, this invention is related to the preparation and use of a solid particulate sorbent material with and without metal additives provided to particularly immobilize vanadium compounds 15 deposited on the sorbent particulate during treatment of the metals containing oil feed. The metal additive for vanadium immobilization may be added during sorbent manufacture by impregnation of the virgin sorbent, or at any point in the sorbent hydrocarbon contact and regeneration cycle for treatment of the oil feed.

~() This application is particularly concerned with improvements on sorbent material described in Canadian Registration 1,175,000 issued September 25, 1984 and its use in demetallizing and decarbonizing reduced crude containing materials.

Background of the Invention A major breakthrough in FCC catalysts and method of use came in the early 1960's with the introduction of molecular sieves or zealots. These materials were incorporated into the matrix of amorphous and/or amorphous/kaolin materials constituting the FCC
catalysts of that time. These new zeolitic catalysts, containing a R i - I )90D
I
, ~236818 crystalline aluminosilicate zealot in an amorphous or amorphous/kaolin matrix of silica, alumina, silica-alumina, kaolin, clay or the like, were at least 1,000-10,000 times more active for cracking hydrocarbons than the earlier amorphous or 5 amorphous/kaolin containing silica-alumina catalysts. This introduction of zeolitic cracking catalysts revolutionized the fluid catalytic cracking process. New innovations were developed to handle these high activities, such as riser cracking, shortened contact times, new regeneration processes, new improved zeolitic 10 catalyst developments, and the like.

The new catalyst developments revolved around the development t of various zealots such as synthetic types X and Y
and naturally occurring faujasites; increased thermal-steam (hydrothermal) stability of zealots through the inclusion of rare 15 earth ions or ammonium ions via ion-exchange techniques; and the development of more attrition resistant matrices for supporting the zealots .

These zeolitic catalyst developments gave the petroleum industry the capability of greatly increasing throughput of I feed stock with increased conversion and selectivity while employing the same units without expansion and without requiring new unit construction .

After the introduction of zealot containing catalysts, the petroleum industry began to suffer from a lack of crude availability 25 as to quantity and quality accompanied by increasing demand for gasoline with increasing octane values. The world crude supply picture changed dramatically in the late 1960's and 1970's. From a surplus of light, sweet crudest the supply situation changed to a tighter supply with an ever increasing amount of heavier cruxes 30 with higher sulfur contents. These heavier and higher sulfur Al - 6090D

:~Z3~ 8 cruxes presented processing problems to the petroleum refiner in the t these heavier cruxes invariably also contained much higher metals and Conrad son carbon values, with accompanying significantly increased asphaltic content.

S The effects of heavy metal and Conrad son carbon on a zealot containing FCC catalyst have been described in the literature as to their highly unfavorable effect in lowering catalyst activity and selectivity for gasoline production and their equally harmful effect on catalyst life.

Metal content and Conrad son carton are two very effective restraints on the operation of a fCC unit and impose restraints on a Reduced Crude Conversion (RCC) unit from the standpoint of obtaining maximum conversion, selectivity and catalyst life.
Relatively high levels of these contaminants are highly detrimental 15 to a catalytic conversion process. As metals and Conrad son carbon levels are increased still further by available crude oils, the operating capacity and efficiency of a RCC unit and especially a ~'CC unit are adversely affected or even made uneconomical. These adverse effects occur even though there is enough hydrogen in the I feed to produce an ideal gasoline consisting of a mixture of only Tulane and isometric pontoons (assuming a catalyst with such ideal selectivity could be devised).

The effect of increased Conrad son carbon is to increase that portion of the feed stock converted to coke deposited on the 25 catalyst. In typical gas oil cracking operations employing a crystalline zealot containing catalyst in an FCC unit, the amount of coke deposited on the catalyst averages about I wit% of the feed.
This coke production has been attributed to four different coking mechanisms, namely, contaminant coke from adverse reactions 30 callused by metal deposits, catalytic coke caused by acid site ODE

~231~;8~8 cracking, entrained hydrocarbons resulting from pore structure adsorption and/or poor stripping, and Conrad son carbon resulting from pyrolytic distillation of hydrocarbons in the conversion zone.
wrier has also been postulated two other sources of coke present in 5 reduced cruxes in addition to the four above identified. They are:
(1) adsorbed and absorbed high boiling hydrocarbons which do not vaporize and cannot be removed by normally efficient stripping, and

(2) high molecular weight nitrogen containing hydrocarbon compounds adsorbed on the catalyst's acid sites. Boyle of these two 10 types of coke producing phenomena add greatly to the complexity of resin oil processing. Therefore in the processing of the higher boiling fractions or portions of crude oil, e . g ., reduced crudest residual fractions, topped crude, and the like, the coke production based on feed is the summation of the four types present in gas oil 15 processing, plus coke from the higher boiling unvaporizable hydrocarbons and coke associated with -the high boiling nitrogen containing molecules which are adsorbed on the catalyst. Coke production on clean catalyst, when processing reduced crudest may be estimated as approximately 4 wit% of the feed plus the Conrad son I carbon value of the heavy feed stock, plus an additional correction Factor related to % of feed boiling above luff and % nitrogen in the feed.

The coked catalyst is brought back to equilibrium activity by burning off the deactivating coke in a regeneration zone in the 25 presence of air, and the regenerated catalyst is recycled back to the reaction zone. The heat generated during regeneration is removed in part by the catalyst and carried to the reaction zone for vaporization of the feed and to provide heat for the endothermic cracking reaction. The temperature in the regenerator is normally 30 limited because of metallurgical limitations and the hydrothermal stability of the catalyst.

R~-~030D

3L;~36818 I

The hydrothermal stability of a crystalline zealot containing catalyst is determined by the temperature and steam partial pressure at which the crystalline zealot begins to rapidly lose its crystalline structure and to yield a lower activity amorphous material. The presence of steam in high -temperature operating modes is highly critical and is generated by the burning of adsorbed and absorbed (sorbed) carbonaceous material which has a significant hydrogen content (hydrogen to carbon atomic ratios generally greater than about 0 . 5). This carbonaceous material is 10 principally the high boiling sorbed hydrocarbons with boiling pullets as high as 1500-1700F or above that have a modest hydrogen content and the high boiling high molecular weight nitrogen containing hydrocarbons, as well as related porphyrins and asphaltenes. The high molecular weight nitrogen compounds usually lo boil above 102SF and may be either basic, acidic or neutral in nature. The basic nitrogen compounds may neutralize acid sites while those that are more acidic may be attracted -to metal sites on the catalyst. The porphyrins and asphaltenes also generally boil above luff and may contain elements other than carbon and 20 hydrogen. As used in this specification, the term "heavy hydrocarbons" includes all carbon and hydrogen containing compounds that do not boil below about 1025F, regardless of whether other elements are also present in the compound.

'Lye heavy metals in the feed are generally present as 25 porphyrins and/or asphaltenes. However, certain of these metals, particularly iron and copper, may be present as the free metal or as inorganic compounds resulting from either corrosion of process equipment or contaminants from other refining processes.

As the Conrad son carbon value of the eedstock increases, 30 coke production increases and this increased load will raise the regeneration temperature; thus the unit may be limited as to the ~2~6818 amount of feed that can be processed because of its Conrad son carbon content. A new development in reduced crude processing can operate at regenerator temperatures in the range of 1350 up to - 5 1600F . But even these higher regenerator temperatures place a limit on the Conrad son carbon value of the feed at approximately 8, which yields about 12-13 wit% coke on the catalyst based on the weight of the feed. This level is controlling unless considerable water is introduced to further control temperature.

The metal containing fractions of reduced cruxes contain Ni-V-Fe-Cu in the form of porphyrins and asphaltenes. These metal containing hydrocarbons are deposited on the catalyst during processing and are cracked to some extent to deposit the metal on the catalyst or are carried over by the coked catalyst as the 15 metallo-porphyrin or asphaltene and converted by burning to the metal oxide during regeneration. The adverse effects of these metals as taught in the literature are to cause non-selective or degradative cracking and dehydrogenation to produce increased amounts of coke and light gases such as hydrogen, methane and 20 ethanes These mechanisms adversely affect selectivity, resulting in poor yields and quality of gasoline and light cycle oil. The increased production of light gases, while impairing the yield and selectivity also have an undesirable effect on the gas compressor capacity. The increase in coke production, in addition to its 25 negative impact on yield, also adversely affects catalyst activity-selectivity, greatly increases regenerator air demand and compressor capacity, and may result in uncontrollable and/or dangerous regenerator temperatures.

These problems of the prior art have been greatly minimized I by the development of a new process which can handle reduced crewless or crude oils containing high metals and Conrad son carbon fitj9oD

Jo , ~2368~8 values previously not acceptable for direct FCC processing.
Normally, the less desirable cruxes require expensive vacuum distillation and other treatments to isolate suitable metals free feed stocks and produce as a by-product, sulfur containing vacuum 5 still bottoms. However, certain crude oils such as Mexican Mayan or Venezuelan crude oils contain abnormally high metals and Conrad son carbon values. If these poor grades of crude are processed directly in a catalytic cracking process, they will lead to an uneconomical operation because of the high burning load imposed 10 on the regenerator to remove carbonaceous deposits catalyst deactivation by metals and a high catalyst addition rate required to maintain catalyst activity and selectivity. The addition rate can be as high as q-8 lobs. blue . or more which at today's catalyst prices, can add as much as blue. of additional catalyst cost to the 5 processing economics . It is thus desirable to develop and identify and economical means or processing more of the poor grade cruxes oils, such as a Mexican Mayan, because of their availability and relative cost as compared to Middle East crudest The literature suggests many processes for the reduction of 20 the metals content and Conrad son carbon values of reduced cruxes and other contaminated oil fractions. One such process is that described in U . S . Patent 4, 243, 514 and German Intent No . 29 04 230 assigned to Engelhard Minerals and Chemicals, Inc.
Basically, these 25 prior art processes involve contacting a reduced crude fraction or other contaminated oil with sorbent material at elevated temperatures in a sorbing zone, such as a fluid bed, to produce a product of reduced metal and reduced Conrad son carbon value. One of the sorbents described in Patent No. 9,243,514 is an inert solid initially 30 composed of kaolin, which has been spray dried to yield rnicrospherical particles having a surface area below 100 m go and a catalytic cracking micro-activity (MAT) value of less than 20 which 1' 1-60~0D

~23~ 8 Muriel is subsequently calcined at high temperature so as to achieve better attrition resistance. As the vend content on such sorbents increases above 5000 ppm and into the range of 10,000-30,000 ppm, the sorbent begins to have fluidization problems 5 and more importantly, coking plugging of the reactor riser which have been overcome previously by removal of most of the spent sorbent inventory and addition of fresh virgin material in place thereof. This plugging may require shutting down the sorbent contacting facility.

to Disclosure of the Invention The present invention is concerned with and provides a method of producing a higher grade of feed stock for catalytic conversion such as in a reduced crude catalytic conversion (RCC) process having lowered metals and Conrad son carbon values from a poor 15 grade of crude oil or other carbo-metallic containing oil component is having extremely high metals and Conrad son carbon producing values .

The invention is also applicable to processing crude oils or crawled oil fractions comprising significant levels of metals and/or I Conrad son carbon producing components to provide an improved fecdslock suitable for RCC processing, or or use in a typical yes oil fluid catalytic (FCC) cracking process.

Residual fractions obtained from the distillation of poor quality crude oils contain substantial amounts of metals such as Nix V, Fe, 25 Cut No and have high Conrad son carbon production materials.
There residual oils are made more suitable as feed stocks according to this invention for processing by catalytic conversions as in a reduced crude conversion (RCC) affecting a preliminary contacting of the poor quality high boiling oil containing residual oil fraction RI- igloo ~Z368~8 g with a solid sorbent particle material exhibiting relatively low or no significant catalytic cracking activity less than about 20 MATS
under conditions of time, pressure and temperatures sufficient to reduce the metals and Conrad son carbon values of the feed within 5 more acceptable limits for catalytic cracking processing.

-It has been found for example, that as vanadium pent oxide and/or sodium vendettas build up on a sorbent particulate, the elevated temperatures encountered in the sorbent regeneration zones to remove carbonaceous deposits cause significant levels of vend 10 deposits to flow and form a liquid coating on the sorbent particles.
Under this condition an interruption or decrease in particle flow result in coalescence between the liquid coated sorbent particles.
Once coalescence occurs, fluidization is interrupted and becomes difficult to reinitiate. This condition results for example in 15 stoppage of particle flow in cyclone duplex, ineffective operation of cyclones, rapid increases in the loss of the sorbent, and will finally result with unit shutdown.

In a particular aspect, the present invention is concerned with providing an improved sorbent particle material for use in a process 20 such as described in Canadian Registration 1,175,000 modified as herein provided and referred herein to as a hydrothermal visbrcaking process. In this hydrovisbreaking operation, it has been recognized that significant economics can be realized in conjunction with improving the 25 operation for metals removal and decarbonization of the feed when employing sorbent particulate material particularly identified herein.
The present invention is thus concerned with an improved sorbent particulate material characterization, its method of preparation and method of use in a hydrothermal visbreaking operation in the 30 absence of added molecular hydrogen.

ED

~23~8~8 The improved solid sorbent particulate material of this invention, particularly comprises a high pore volume clay type material composition of at least 0.4 cc per gram (cc/g) pore volume used with or without one or more metal additive molecules for 5 immobilizing liquidized vend, said composition providing greater absorbency characteristics for heavy oil components and greater sorbed t stability at the temperature conditions employed up to 1600F. In yet another aspect, the improved sorbent material is of a pore size and volume which readily absorbs high levels of metal 10 deposits and high boiling components of the residual oil feed within its pores in preference to surface deposition contributing to particle agglomeration. Surface deposition of metals, particularly vend, contributes to reducing the absorption characteristics of the sorbed t by blocking pore openings and causing coalescence of particles as 15 herein described. Thus the improved high pore volume material of this invention, allows more contaminating metal components such as vanadium and asphaltenes to be absorbed within the sorbent pores rather than collect on the particle outer surface. The use of the high pore volume sorbent material considerably reduces the 20 tendency for particle coalescence due to high metals bonding as observed with low pore volume sorbent material. Furthermore, relatively large volumes of the heavy bottoms boiling above 1025F
result in particle coating of low pore volume material with a tacky asphaltic material which also facilitates coalescence of particles, 25 resulting in plugging and coking within a riser reactor and product separator lines. However, by employing the larger pore volume material in conjunction with restricting the volume of the pores occupied by the heavy oil feed as herein provided, the loading for asphaltic material to cause particle coalescence is considerably 30 reduced over and extended operating period.

The ability of a reduced crude cracking process to handle crude oil is limited by its Conrad son carbon characteristics and ~2368~8 particularly by the concentration of metal contaminants in the feed and more particularly by the concentration of vend in the high boiling portion of the crude oil being processes. In this regard, it is generally recognized prior to this invention that an upper limit S for the oil feed to an RCC unit is associated with- a Conrad son carbon of about 8% and a total metals content considerably below about 50 ppm No V. Thus in order to process crude oils comprising high metals level, greater than 100 ppm No + V and a Conrad son carbon value about 8% such as found in Mexican Mayan lo crude oil (17% Conrad son carbon and total metals of 400 ppm), an efficient as well as an economic metals removal system - Conrad son carbon reduction system is required upstream or in front of a catalytic cracking (FCC) or a reduced crude cracking (RCC) operation .

In a known prior art metals removal system, a sorbent material of low catalytic activity is used to absorb a portion of the Conrad son carbon and metals on its surface. In this operation, the sorbent surface area is low, about 25 mug or less and its corresponding pore volume is also low, approximately about 0.2 cc/g 20 or less. An equilibrium sorbent of these characteristics has an even much lower pore volume of about 0.15 cc/g and less, down to about 0.10 cc/g or even lower 0. 06 cc/g . When using a sorbent material of these characteristics to provide solids to oil ratio in the range of 6-8, it is quite apparent that the absorption power of the 25 sorbent particulate is less than the volume of feed being processed.
Thus the rapid deposition of hydrocarbonaceous material, metal contaminants and tacky asphaltic material on a sorbent particle of such limited characteristics can rapidly cause pore plugging and excessive coverage of the exterior surface of the sorbent particle 30 promoting particle coalescence or agglomeration. It has been noted and identified in Canadian registration 1,175,000 that vend deposited on the surface of the solid GOOD

I

~23~8 sorbent will flow as a liquid under high temperature conditions of operation encountered in a regeneration zone to remove deposited carbonaceous neutral and such vend flow causes particle sistering, pore collapse and particle coalescence in cooler areas of 5 the sorbent contacting unit and more static flow area. When such particles coalescence is permitted to occur such as in stand pipes, cyclone duplex and related somewhat stagnant particle flow areas, there is a 105s in fluidization and flow characteristics of -the solid sorbent particulate which rapidly contributes to stoppage and 10 shutdown of the process.

furthermore as recited above when using a low pore volume solids sorbent material, the heavy high boiling oil components comprising asphalt is not absorbed but coats the particle with unvolatilized asphalt which then serves as a sticky mass to cause 15 particles to stick together and to the riser reactor wall eventually resulting in plugging of the riser reactor and product separator.
Russ problem is also observed in fluid coking operations where coke micro spheres unable to absorb the oil feed readily coalesce to form large lumps and eventual plugging of the system.

'the present invention is therefore concerned with providing an impure Ted solids sorbent particulate material which will materially reduce if not eliminate such as undesirable operation of solids loading of contaminants and resultant defluidization thereof.

on accordance with the present invention, the adverse conditions herein identified with respect to pore plugging, particle sistering and particle coalescence is substantially reduced through the lose of a large pore volume solid sorbent particulate material such as one containing a pore volume of at least O . 4 cc/g and preferably in the range of Owe cc/g up to about Owe cc/g pore volume. In yet another aspect the present invention is concerned Rowley) ~;~36S18 with methods of preparation of the desired large pore volume and thermally stable solid sorbent particulate material. The sorbent characteristics of the large pore material may be improved by adding one or more additive metals defined below which will be 5 effective in immobilizing the flow of vend at regeneration temperature conditions by combining therewith to form higher molting point materials following deposition on the sorbent material.

A particularly desired high pore volume clay sorbent material may be attained during preparation thereof by the incorporation of 10 one or more of the components of carbon black, sugar, organic materials such as methylcel]usolve, starch; polymer materials such as nylon, polyacrylonitriles, polybutenes, polystyrene; high temperature decomposition of inorganic salts such as nitrates, nitrites, carbonates, sulfites of various molecular weights and I structure to get a desired pore size following decomposition.

The large pore solid sorbent particulate materials provided and prepared according to this invention are to be employed in apparatus similar to that disclosed in Canadian Registration 1,175,000 but under operating conditions specifically recited herein, in which 20 operation, the solids of this invention are employed for a greatly extended on stream operating time thereby contributing measurably to the economics and efficiency of the operation. Other advantages contributed by the solid sorbent materials of this invention will become more apparent from the following discussion.

The sorbent particulate material of this invention may be prepared in a specific case by mixing one or more of carbon black, a polymeric material decomposable during high temperature drying or subsequent high temperature treatment, sugar, etc. in a slurry of clay such as kaolin, montmoril]onite smectite or other suitable JO material, which mixture if thereafter spray dried to yield a Bud ~23~8~8 I

micro spherical sorbent particulate of a size in the range of about 20 to about 150 microns and preferably within the fluidizable particle range of 40 to 80 or more microns. Calcination of the spray dried material may be accomplished in the regeneration step of the 5 process or separately effected before use at a temperature sufficient -to remove carbon black by burning or decompose organic material whichever to yield the desired large pore sorbent material]. Thus the pore size of the sorbent material is determined Essex tidally by the size of the occluded material removed by calcination and/or 10 burning. A preferred pore volume of the finished micro spherical sorben-t is at least 0.4 cc/g and preferably is within the range of 0 . 5 -to about 0. 8 cc/g . Thus when one employs a sorb entoil ratio of 7/l, the total pore volume of the sorbent will be within the range of about 2.8 cc/cc of feed up to about 5.6 cc/cc of feed.
15 With this larger sorbent pore volume than employed heretofore, -the pores will not be over filled with deposited high boiling carbon producing component materials and metal contaminants for a much longer period of operating time deposited hydrocarbonaceous material is removed by burning, and deposited vend will be I discouraged from flowing from the pores with or without additive metals to accumulate on the outer surface of the solids particle and cause pore plugging and coalescence.

In addition to the substantially increased pore volume provided by the sorbent material of this invention being a deterrent to short 25 term operation, the increased pore volume in combination with immobilizing metal additives further enhances the hydrothermal visbreaking operation of this invention by permitting an even much larger accumulation of metal contaminants on the sorbent material before discard thereof is required.

The large pore sorbent material of this invention may be modified as suggested above by the inclusion of one or mow e lZ36818 vend immobilizing metal additives selected from the oxide or salt thereof or an organo-metallic compound of the additive material may be added to the sorbent material during or after manufacture of the sorbent particulate or during the oil processing cycle so as to 5 immobilize for example sodium vendettas, and/or vanadium pent oxide deposited on the sorbent during processing of the oil for metals and/or Conrad son carbon removal. With the large pore volume sorbent material -there is less need for providing an additive metal hereirl identified in the virgin sorbent material. Addition after 10 considerable accumulation of vend will be helpful.

The described invention thus provides an improved sorbent and an improved method for treatment t of high boiling oil feeds containing significant levels of hydrocarbon materials boiling above 1025F and an amount of vanadium of at least 1.0 ppm. More Lo particularly, the sorbent particulate material of improved high pore volume and metals adsorption capacity reduces also the phenomenon of particle coalescence and loss of fluidization for the reasons herein described and caused in part particularly by vanadium compound contaminants of low melting point. Gas oil and heavier 20 high boiling portions of oil feeds of all types utilized in FCC
operation and more particularly in reduced crude cracking operation comprise vanadium, nickel, iron and copper in considerably varying amounts with vanadium quite of ten being a major portion thereof .
The invention described herein is thus particularly use us in the 25 removal of excessive carbo-metallic containing oil components from feeds to be utilized in a process known as a reduced crude cracking (RCC) process processing hydrocarbon composition of higher metals content than processed in gas oil cracking (FCC) operations .

Some crude oil fractions and some FCC charge stocks obtained ho the distillation of crude oils contain significant amounts (greater ~Z368~8 than 1. 0 ppm) of heavy metals such as Nix V, Fe, Cut No . Of these metals, vanadium has been identified as a particularly bad actor as herein described. Residual fractions from crude oil distillation have even greater amounts of heavy metals and also have 5 high Conrad son carbon producing hydrocarbons. As use throughout the specifications, "vend" refers collectively to the oxides of vanadium. It has been found that as the vanadium oxide level builds up on the sorbent material the elevated temperatures encountered in the regeneration zone cause vanadium pent oxide 10 (VOW) to flow as liquid vend. This flowing of vend, particularly at high vend levels in sorbent materials with low surface area and low pore volume below . 4 cc/g and particularly below 0. 2 cc/g can also coat the outside of the sorbent micro spheres with liquid and thereby cause coalescence in cooler 15 areas between sorbent particles which adversely affect its fluidiza1:ion properties. it is to be understood that the large pore volume sorben-t particles of this invention can be of any size, depending on the size appropriate to the conversion process in which the sorbent is to be employed. Thus, while a fluidizable size 20 is preferred in a riser contact zone, the sorbent particles may be employed as larger size particles, such as those used in solid particle moving beds systems in contact with partially vaporized or unvaporized feeds.

Many of the problems of the prior art related to reduced crude 25 cracking are believed to be caused by asphaltic and vanadium containing contaminants and such problems are overcome in substantial measure by employing the large pore sorbent particle material of this invention either alone or in combination wit to a select metal additive herein identified for at least part of the 30 sorbent life in the process.

Rugged 123~L8 This invention is especially effective for the -treatment of reduced crudest residual oils, topped cruxes and other high boiling carbo-metallic containing hydrocarbon feed comprising relatively high vanadium to rlickel ratios and high Conrad son carbon values.
The hydrocarbon fractions or high boiling oil -feeds having a high level of metal contaminants and Conrad son carbon producing components values are preferably initially contacted in a reaction zone such as riser reactor zone with a delineate material such as water, steam or a combination thereof to provide temperature control and hydrocarbon partial pressure reduction upon contact with the solid sorbent particulate material of this invention providing surface area and high pore volume herein defined at temperatures above about 900~F. Residence time of -the oil feed charged will vary with boiling range and generally is below 5 ITS seconds. Preferably the residence time for high boiling residual oils and reduced crude will be in the range of 0.5-3 seconds. The preferred high pore volume sorbent material according to this invention of fluidizable particle size is a spray dried composition in the form of micro spherical particles generally in the size range of 20 to 150 microns and preferably between about 40 and about 80 microns, which may or may not be calcined prior to use.

or of Description o the Dr_win(ls Figure 1 is a schematic diagram in elevation of an arrangement of an apparatus for carrying out the visbreaking-demetallizing process of the invention.

Figure 2 is a graph showing changes in sorbent properties with increasing amounts of vanadium on the sorbent and the effect of a metal additive on sorbent properties.

Al foggily ~Z36818 Figure 3 is a graph showing the time required to build up vanadium on a sorbent at varying vanadium levels in a feed and a sorbent addition rate of 4% of inventory.

Discussion of the Specific Embodiment s it is no-t proposed to specifically define the exact mechanism for obtaining the immobilization of vend except to say that metal additives of this invention will form compounds, complexes or alloys with vend which have higher melting points than the temperatures permitted to be achieved in the regenera lion operation. the atomic ratio of additive metals to vanadium desirably employed on the sorbent material is at least 0. 5 and preferably at least 1.0 depending on the number of additive metal atoms in -the oxide of the additive metal, e . g . Shea or Inn, form a stable, high melting binary oxide material with vanadium pent oxide (VOW).
S Thus, the melting point of the binary oxide material is generally well above the operating temperatures to be encountered in the regenerator. Although, the amount of metal additive may be initially considerably above the preferred minimum ratio depending upon procedure employed for addition thereof and particularly if it is incorporated in the solid sorbent prior to use, the ratio of additive metal to vanadium on the sorbent will decrease as vanadium is deposited on the solid sorbent. Alternatively, the metal additive may be added to the process at a preferred and selected minimum rate at least equivalent to the vanadium metal content of the feed.
This or any other suitable approach may be employed to identify and confirm suitable metal additive concentrations which can form binary mixtures with deposited and/or formed low melting point vend so as to yield a solid material that has a melting point of at least about 1600F and preferably at least about 1700F or higher.
'30 This high melting point product ensures that high levels of vend ~Z3~8~8 -lo will not flow, so as to cover the sorbent pore structure to cause particle coalescence and/or sistering as herein descried.

Examples of Additives The additive metals of this invention include those elements 5 from the Periodic chart of elements shown in Table A. The melting points of Table A are based on a 1:1 mole ratio of the metal additive oxide in its stable valence slate under regenerator conditions to vanadium pent oxide.

TABLE A

lo MOP. of :1/1 M xture - OF

JEEP [IA My, Cay So, Be <l790 Group IIIB So, Y, Lowe Group IVY 'I'm, Or, lo 1700-2000 Group VB Nub, '['aye Lowe Group VIIB My, To, Roy Group VIII Nix Rut Rho Pod, Ox, If, Pi <160() Group If lo In, Ill <1800 Grout) VA Bit As, Sub ~1600 Lanthanide Series All <1800 Astound Series All <1800 Other elements which may be employed with considerable success include silicon and aluminum. In particular it is desirable to employ with the large pore volume coolant clay from 1 to 20 wit%
of one or more of Six Al, Tip Or, Be, My and Cay This invention also recognizes that mixture of these additive me tats with vend may occur to form high melting ternary y, I [ - 6090D

~Z36818 qua ternary, or higher component reaction mixtures. Examples of such additional ternary and qua ternary compounds are shown in Table B.

TOE LYE B

Cosnpound M . P I

VOW Shea ZrO2 <1800 Ba3-V-Ti2O9 <1800 BaO-K2O-TiO2-V2O4 <1800 ~3aO-Na2O-Tio2-v2o5 <1800 l 0 It is also recognized that in treating a sulfur con twining high boiling carbo-metallic containing oil feed and regeneration of the sorbent material comprising metal contaminant deposits in the presence of an oxygen containing gas, vanadium will also likely form compounds, such as vanadium sulfides, sulfates, and Lrj oxysulfides, which may also form binary, ternary, quanternary or hither component reaction mixtures with the metal additives identified by this invention disclosure.

Chile not wishing to be bound by any one theory or mechanism, it has been observed that a reaction of the metal 20 additive with vend generally yields a binary reaction product.
In the case of manganese acetate for example, reacting with vanadium pent oxide, the compound formed was tentatively identified as Mn2 V2 07- When titanic was reacted with vanadium pent oxide, no true compound could be identified because the reaction is 25 believed to involve the substitution of To 4 in the crystalline structure by V 4. Thus, the disappearance of the titanic x-ray pattern and the vanadium pent oxide x-ray pattern was observed, indicating vanadium substitution.

Al- 6090D

~23~

The metal additives may be compounds of magnesium, calcium, barium, titanium, zirconium, manganese, indium, lanthanum, or a mixture of the compounds of these metals. Where the additive is introduced directly into the high pore volume sorbent demetallizing 5 process, that is into a riser contact zone or a falling particle contact zone, into the regenerator or into any intermediate section thereof, the metal additives are preferably organo-metallic compounds soluble in the hydrocarbon feed or in a hydrocarbon solvent miscible with the feed. Examples of preferred ] 0 organo-metallic compounds are tetraisopropyltitanate, To (C3H30) 4, available as TWEEZER* from the Dupont Company;
methylcyclopentadienyl manganese tricarbonyl MET), lo (CO) 3 C6H7; zirconium isopropoxide, Or (C3H70) 4; barium acetate, Be (C2H302) 2; calcium oxa]ate, Cay (C204); magnesium Stewart, My (Kiwi) 2; Indium I pentanedionate - In (C5H702)3; Tantalum ethoxide -To (C2H50)5; and zirconium 2,4 - penitent - Or (C5H702)4.
Other preferred process additives include titanium tetrachloride and manganese acetate, both of which are relatively inexpensive. These additives are only a partial example of the various materiel available I and others would include alcoholates, esters, fanlights, naphthenates, carboxy]ates, Donnelly sandwich compounds, and various inorganic compounds soluble in hydrocarbon solvents.

The organo-metallic additives may be introduced directly into the hydrocarbon treatment or visbreaking zone, preferably near the 25 bottom of a riser reaction zone so that the metal additive will be deposited on the sorbent particulate before or along with the heavy metals in the oil feed. When the additive metal in the sorbent material of the invention reaches the regenerator, its oxide is formed, either by decomposition of the additive directly to the metal 30 oxide or by decomposition of the additive to the free metal which is then oxidized under the regenerator conditions. This provides an intimate mixture of metal additive and undesired heavy metal *Trade Mark Owned ~23~ 8 I

contaminants in the feed and is believed to be a most effective method for tying up vanadium pent oxide as soon as it is formed in the regenerator. The metal additive may be introduced into the riser visbreaker zone by mixing it with the feed in an amount 5 sufficient to give an atomic ratio between the metal additive and the vanadium in the feed of at least 0 . 25, preferably in the range of 0 . 5 to 3 . 0. The addition of metal additive is preferably delayed until significant levels of metal deposits are accumulated so that the economics of the process will be preserved as long as possible.

If the metal additive is added directly to the sorbent during sorbent manufacture or at some other time before the sorbent is introduced into the riser reactor, the metal additives are preferably water soluble inorganic salts of these metals, such as the acetate, halide, nitrate, sulfate, sulfite and/or carbonate. If -the metal 15 additive is not added to the sorbent before or during particle formation, then it can be added by impregnation techniclues to the dried sorbent particles which are preferably spray dry ted micros phones .

inorganic metal additives may be introduced into -the process 20 system of Figure 1 discussed below along with water containing streams, such as can be used to directly cool the solids in like regenerator or to lift, fluid to strip sorbent solid material.

A sorbed t material particularly suitable for demetallizing high boiling residual oils and reduced cruxes is a dehydrated kaolin clay 25 of large pore volume. According to analysis, a kaolin clay contains about 51 to 53% (wit%) Sue, 41 to 45% Allah and 0 to 1% HO, the remainder consisting of small amounts of originally present impurities. Although these impurities may include titanium, this titanium is bound up in the clay and is not in a form capable of 30 typing up significant amounts of vanadium. In order to facilitate Tao spray drying, a powdered dehydrated coolant clay is dispersed in water under conditions to form a suspension or a slurry of solids which will provide random orientation contributing to large pore volume. In preferred preparation cases in order to achieve 5 attrition resistance and a greater pore volume and avoid expensive calcination, a binder material consisting of silica, alumina, calcium, bone, magnesia or titanic may be employed.

'rho spray driers used can have countercurrent or concurrent or a mixed countercurrent/cocurrent movement of the suspension 10 and the hot air for the production of micro spheres. The air can be heated electrically or by other indirect means. Combustion gases, such as those obtained in the air from the combustion of hydrocar bun heating oils, can also be used .

If a concurrent dryer is used, the air inlet temperature can be 15 as high as 649C (1200F) and the clay should be charged at a rate sufficient -to guarantee an air outlet temper azure of about 121 to 316C (250 to 600F). At these temperatures the free moisture of the suspension is driven away without removing the we ton of hydration (water of crystallinization) from the crude clay 20 component. A dehydration of part of all of the crude clay during the spray drying may be envisioned. The product of the spray dryer can be separated in order to obtain micro spheres of the desired particle size. Calcination of the particles although not necessarily required, can be completed after the addition of one or 25 more metal components herein identified or by in traducing the spray-dried particles before metal addition directly into a calcining operation .

Although it is advantageous in some cases to calcite the micro spheres at temperatures of about 1600 to Lowe' in order to 30 obtain porticoes of maximum hardness, it is also possible to Xl-~O~)OI:~

lZ3~8~8 dehydrate the micro spheres by calcining at lower temperatures.
Temperatures of about 1000 to 1600F can be used, to transform the clay into a material known as "metakaolin". After ca]cination, the micro spheres should be cooled down and, if necessary, fractionated 5 to obtain the desired particle size range.

Example of Titanic Containing Sorbent MATERIALS AMOUNT
, A) Tap Water 11 liters B) Nash - PI Corp. 'N' Brand 8.35 liters C) Concern, H2SO4 1.15 liters D) Alum 0.8 kg.
E) Clay - Hydrate A 12 kg.
F) Titanic - Dupont Aunts 5 kg.
Go Sodium Pyrophosphate 150 gym.

In one specific example, ingredients G, E, and F in this order are added while mixing to 8 liters of water at a pi of 2 and ambient conditions to obtain a 70 wit% solids slurry which is held for further processing.

Tap water (A) is added to a homogenizing mixer (Kay Mill) 20 with sulfuric acid (C) and mixed for five minutes. Sodium silicate B is then added continuously over a fifteen minute period (600 ml/min) to the stirred acid solution to provide a silica sol.

The 70 wit% solids slurry from the first step is then added to a stirred Kay Mill* and mixed for fifteen minutes. The pi of the 25 solution is maintained at 2.0-2.5 by addition of acid if needed. The temperature during addition, mixing, acidification is maintained below 120F and viscosity of the solution adjusted to 1000 CUPS by the addition of water.
*Trade Mark owe) lZ368~8 The resulting mixture is immediately atomized, i . e. sprayed, into a heated gaseous atmosphere, such as air and/or steam having an inlet temperature of 400C, and an outlet temperature of 130C, using a commercially available spray drier. The resulting S micro spherical particles are washed with 20 liters of hot water an dried at 350F for 3 hours. This yields a sorbent containing 25 White titanium as titanium dioxide on a volatile free basis.

In some examples of sorbent preparation, mixing and subsequent spray drying take place rapidly to prevent premature 10 setting of a gel. In this connection, the silica sol and the solids slurry may be added separately to a spray drier nozzle and the two streams mixed instantaneously and homogeneously. Such a mixing process is described in U . S . Patent No . 4 ,126, 579 The air atomizer should feed the 15 two components into the nozzle at pressures of about 30 to 90 psi and maintain the air in the nozzle at about 50 to 60 psi, preferably about 51-53 psi. As an alternative to premixing with either component, the metal additive may also be fed separately to the nozzle via a separate line operated at pressures of about 30 to 90 JO psi.

Titanic Impregnated Sorbent Seventy-five grams of sorbent (not calcined) is dried at 100C
under vacuum for two hours . 2. ml of Dupont Tweezer TOT (twitter isopropyl titantae~ is dissolved in 75 ml. of cyclohexane. The 25 titanium solution is added to the vacuum dried sorbent and allowed to contact with agitation for 30 minutes. Excess solution is then stripped from the impregnated sorbent to yield dried solid particles.
The sorbent is then humidified. The sorbent is then regenerated (organic moieties burned off) as a shallow bed in a furnace at 900F

I - ODE

1~36~
~26-for 6 hours . This procedure yields a sorbent containing 0 . 53 wit%
To on sorbent.

Additive Mixed with Sorben-t As another prey erred embodiment of the invention, -the metal 5 additive may be incorporated directly into the sorbent material. To an aqueous slurry of the raw sorbent material is mixed the metal additive in an amount to yield approximately 1 to 25 wit%
concentration on the finished sorbent. The metal additive can be added in the form of a water soluble compound such as the nitrate, 10 halide, sulfate, carbonate, or the like, and/or as an oxide or hydrous gel, such as titanic or zircon gel.

Other active gelatinous precipitates or other gel like materials may also be used. This mixture may be spray dried to yield the finished sorbent as a micro spherical particle of 10 to 200 microns in lo size with the active metal additive deposited within the matrix and/or on the outer surface of the catalyst particle. Since the concentration of vanadium on spent sorbent can be as high as 4 wit%
of particle weight, the concentration of additive metal is preferably in the range of 1 to 8% as the metal element. More preferably, 20 there is sufficient metal additive to maintain at least -the preferred minimum atomic ratio of additive metal to vanadium at all times.

Moving Bed Sorbent A hydrosol containing the sorbent materials described in this invention is introduced as drops of hydrosol into a water immiscible 25 liquid wherein the hydrosol sets to spheroidal bead-like particles of hydrogen. The larger size spheres are ordinarily within the range of about 1/64 to about 1/4 inch in diameter. The resulting spherical hydrogen beads are dried at 300F for 6 hours and Al - 6D90D

1236~318 calcined for 3 hours at 1300F. The use of these calcined spherical beads is of particular advantage in a moving bed process.

Representative feed stock contemplated for demetallizing treatment according -to this invention include any oil fraction 5 comprising undesired metal levels for catalytic cracking thereof such as whole crude oils; atmospheric gas oils, heavy vacuum gas oils and heavy fractions of crude oils included with topped crude, reduced crude, vacuum fractionator bottoms, other fractions containing heavy residue, coal-derived oils, shale oils, waxes, 10 untreated or disaffiliated residue and blends of such fractions with gas oils and the like. Thus, a relatively small amount (S-25%) of a dernetallized reduced crude or other heavy hydrocarbon feed stock may be mixed with atmospheric or vacuum yes oils to provide a feed stock for catalytic conversion. A high vanadium containing oil l 5 feed for FCC processing is one having more than 0 . I ppm vanadium up to about 5 . 0 ppm . A high vanadium feed for RCC processing on the other hand is one having more than 1. 0 ppm vanadium and usually more than about 5 . 0 ppm.

A carbo-metallic feed to be visbrokcn and demetallizecl 20 according to this invention is one in a specific example boiling above 650F having a heavy metal content of at least about I ppm nickel equivalents, (ppm total metals being converted to nickel equivalents by the formula: No En . = No + V/4 . 8 Fe/7 .1 +
Queue. 23), a Conrad son carbon residue value treater than about 25 1. 0, and a vanadium content of at least l . 0 ppm The feed stocks for which the method of this invention is particularly useful will have a heavy metal content of at least about 5 ppm of nickel equivalents, a vanadium content of at least 2 . 0 . The greater the heavy metal content, the greater the proportion of vanadium in that 30 heavy metal content, and the higher the Conrad son carbon content old the material boiling above 1025F, the more advantageous is the Al -60901) ~LZ3G~18 increased high pore volume solid sorbent material of this invention with and without metal additives and use thereof as herein provided .

A particularly preferred hydrocarbon feed stock for 5 dernetallization and upgrading treatment by the method of the invention includes a fraction of crude oil comprising 70% or more of a 650F+ material having a resin fraction greater than 20% boiling above 1025f' at atmospheric pressure, a metals content t of greater than 5 . 5 ppm nickel equivalents of which at least 5 ppm is 10 vanadium, a vanadium to nickel atomic ratio of at least 1. 0, and a Conrad son carbon residue greater than 4Ø This identified residual oil feed may also have a hydrogen to carbon ratio of less than about 1.8 and coke precursors in an amount sufficient to yield about 4 to 14% or greater coke by weight based on -fresh feed.

I Sodium vendettas have low melting points and Moe also flow and cause particle coalescence in a similar manner to vanadium pent oxide. Although it is desirable to maintain low sodium levels in the weed in order to minimize coalescence, as well as to avoid sodium vendettas on -the sorbent, the metal additives of the present invention are also effective in forming compounds, alloys, or complexes with sodium vendettas so as to prevent these compounds from melting and flowing.

With respect to the tolerance levels of heavy metals on the high pore volume sorbent itself, such metals may accumulate on the sorbent to levels in the range of from about 3,000 to 70,000 ppm of total metals, and more usually to high levels in the range of 10,000 to 30, 000 ppm, of which a large proportion thereof is vanadium .

The demetallizing decarbonizing and hydrothermal visbreaking process of the invention will produce large amounts of coke initially ~Z3~318 deposited as hydrocarbonaceous material in amounts up to 14 percent by weight based on the weight of fresh feed. This carbonaceous material deposit often referred to as coke is laid down on the sorbent particle material in amounts in the range of about 5 0.3 Jo 3 percent by weight of serenity, depending upon the sorbent to oil ratio (weight of sorbent to weight of feed stock) employed in the demetallizing and decarbonizing zone such as a riser contact zone. The severity of the thermal visbreaking operation affected in the presence of steam and/or water should be sufficiently low 10 however, so that thermal conversion of the feed to gasoline and lighter products is kept relatively low and preferably below 20 volume percent. Even at these low levels of conversion severity, whether thermal and/or some catalytic, the hydrothermal visbreaking process is effective for reducing the Conrad son carbon Lo value of the feed at least 20 percent, preferably in the range of 40 to 70 percent, and reduce the heavy metals content of the residual owl teed by at least 50 percent and preferably in the range of 75 to 90 percent.

The high boiling feed to be demetallized and decarbonized by 20 the sorbent material of this invention is introduced in Gone embodiment into a bottom portion of a riser reaction zone under conditions -to form a suspension with hot sorbent particulate material separately introduced and provided in accordance with this invention. Steam, naphtha, water, flue gas and/or some other 25 suitable delineate material suet- as nitrogen or carbon dioxide is introduced separately to the riser or along with the high boiling feed to aid atomized and vaporized contact of the feed with the solids sorbent particulate material and form a fluidizable suspension therewith. These delineates may be from a fresh source or may be 30 recycled as purity permits from a process stream of a refinery operation in association therewith.

En L -ODE

~Z368~8 ~30-Where recycle delineate streams are used, they may contain hydrogen sulfide and other sulfur compounds which may help passivity adverse catalytic activity by heavy metals accumulating on the sorbent material. It is to be understood that water may be 5 introduced either as a liquid or as steam. In the interest of energy conservation, the water is preferably introduced as a liquid.

Water is added primarily as a source of vapor for dispersing the feed in intimate contact with sorbent particles, for reducing the oil partial pressure and for accelerating the feed and sorbent 10 formed suspension to achieve the vapor velocity and hydrocarbon residence time desired in a riser contact zone.

As the high boiling feed if avers up the riser under visbreaking conditions herein specified, it forms four products known in the industry as dry gas, wet gas, naphtha and a high lo boiling demetallized and decarbonized oil product suitable as for use as feed to a reduced crude or cracking operation or in some cases the Lied may be suitable charged to a conventional FCC operation.
A t the upper end or discharge end of the riser, the sorbent particles are preferably quickly separated from product vapors to 20 minimize thermal cracking and catalytic to the extent present. The solid sorbent particles which contain metals and carbonaceous deposits wormed in the riser contact zone are sent to a regenerator operation to burn off the carbonaceous deposits . I he separated product vapors are normally sent to a fractionator for separation to 25 provide the four basic products above identified.

The preferred conditions for contacting feed and sorbent in the riser are summarized in Table C, in which the abbreviations used have the following meanings: "Temp." for temperature, "Dip."
for delineate, "pup" for partial pressure, "wit" for weight, "V" for 30 vapor, "Ryes. " for residence, "S/O" for sorbent to oil ratios, Rl-6090V

Libya "sorb. " for sorbent, "blue" for barrel, "MAT" for micro activity by the MAT test using a standard Davison feed stock, "Vet. " for velocity, "age" for charge, "d" for density and "Reg. " for regenera ted .

T BYE C - Sorbed t Riser C n itchiness Broad Operating Preferred Prompter Range Range Feed rump. - 400-800F 400-650F
l 0 Steam Tempt . - EYE 300-400F
Reg. Sorbent Temp. - 900-1500F 1150-1400F
Riser Exit Temp. - 800-1400F 900-1100F
Pressure - 0-l00 Asia 10-50 Asia Water Feed by Wit . 0 . 01-0 . 30 0 . 04-0 . lo lo Dip . pp/Feed pup - 0 . 25-3 . 0 1. 0-2 . 5 Dip . wgt/Feed wit - I . 4 0 .1-0 . 3 V. Toes . Time - 0.1-5 0. 5-3 sea .
S/O, WCJt - 3-18 5-1 2 Ibis . Sorb . blue Feed 0 I . 0 0 . 2-2 . 0 Inlet Sorb. MAT - <25 void OWE <20 Outlet Sorb. MAT - <20 vol. % lo V. Vet. - 25-90 ft/sec 30-60 V. Vel./Sorb. Vet. >1.0 1.2-2.0 Dill Cue. Vet. - 5-90 ft/sec 10-50 Oil Cue. Vet. - 1-50 ft/sec 5-50 Inlet Sorb. d - 1-9 Ibs/ft3 2-6 Outlet Sorb. d - 1-6 Ibs/ft3 1-3 In treating carbo-metallic containing oil feed stocks in accordance with the prison invention, the regenerating gas may be I -i?OgOI) ~L23~1~18 any yes which can provide oxygen to convert carbonaceous deposits to carbon oxides. The amount of oxygen in the regeneration gas retIuired per pound of coke for combustion depends upon the carton dioxide to carbon monoxide ratio desired in the effluent flue 5 gases and upon the amount of other oxidizable materials present in the coke, such as hydrogen, sulfur, nitrogen and other elements capable of forming gaseous oxides at regenerator temperature conditions .

Roy regenerator for the solid sorbent particulate material is 10 operated at temperatures in the range of about 1000 up to 1600F, preferably 1150 to about 1400F or 1500F to achieve combustion of carbonaceous deposits while keeping sorbent temperatures below that at which significant sorbent degradation can occur. In order to control the rate of burning which, in turn, l 5 can be controlled at least in part by relative amounts of oxidizing gas employed and carbonaceous material introduced into the regeneration zone per unit of time. The rate of introducing carbonaceous material into the regenerator is controlled by regulating the rate of flow or sorbent thereto; the rate of removal 20 of regenerated sorbent is controlled and the rate of introducing oxidizing gas is controlled. These parameters may be regulated such that the ratio of carbon dioxide to carbon monoxide in the effluent vases is less than about 4.0 and preferably less than about 1.5 or less so that the flue gas is CO rich. In addition, water, 25 either as liquid or steam, may be added to -the regenerator to help control temperatures therein and to influence CO production in preference to carbon dioxide. On the other hand, only a portion of the separated sorbent material may be passed to the regenerator with the remaining portion thereof recycled dire try to the riser 30 reactor following high temperature stripping in admixture with regenerated particulate material passed to the riser.

Rl-s~09OD

~23G~8 The regenerator carbonaceous material combustion reaction is carried out so that the amount of carbon remaining on regenerated sorbent is less than about 0.50 and preferably less than about 0.25 percent on a substantially moisture-free weight basis.

When a metal additive is provided with -the solid sorbent material it is introduced as an aqueous or hydrocarbon solution or as a volatile compound during the processing cycle. It may be added at any point of sorbent travel in the processing system.
This would include, but not be limited to the addition of the metal additive to a bottom portion of the riser reactor along the riser reactor length to a dense bed of solids in a collector vessel about the upper end of the riser, to the strippers provided in the system, to the regenerator air inlet, separately to the regenerator bed of solids, and to the regenerated sorbent stand pipe.

'Lowe high pore volume sorben-t material of this invention with or without the metal additive is charged for use in a hydrothermal visbreaking operation as herein described in the absence of added molecular hydrogen.

Referring now to Figure 1 by way of example, sorbent particle circulation and operating parameters are brought up to process conditions by methods well-known to those skilled in the art. The high temperature sorbent material of regeneration at a temperature in -the range of 1150-1400~F contacts the high boiling residual oil feed charged in a bottom or upper portion of the riser reactor depending on contact time desired therein. A f]uidizing gas may initially suspend the sorbent solids before contact with charged oil feed. The oil feed is dispersed with a delineate, steam, water, flue gas or a combination thereof injected at point 2. Water and/or naphtha may be initially injected as required at point 3 to suspend 3û solids and aid in feed vaporization, sorbent fluidization and RI - ODE

~23S8~8 controlling contact time of a formed suspension of solids and gasifor~m material in a bottom initial portion of riser 4. The sorbent and gasiform material comprising vaporous and unvaporized high boiling hydrocarbons travel up through riser 4 for a con tact time restricted to within the range of 0 .1-5 seconds, preferably 0 . 5-3 seconds or whatever is required to achieve desired demetallization and decoying in the absence of substantial thermal and/or metals conversion of charged oil. The sorbent comprising hydrocarbonaceous and metal deposits is rapidly separated from vaporous hydrocarbons at the riser outlet 6 at a temperature in the range of 900-1100~F. A gasiform material comprising vaporous hydrocarbons, steam, wet and dry gaseous materials pass through one or more cyclones such as a multi-stage cyclone represented by cyclone 7 wherein entrained sorbent particles are separated and recovered by duplex provided with the gasiform material comprising hydrocarbon vapors being sent to a fractionator (not shown) via transfer line 8. The sorbent particle material comprising hydrocarbonaceous material decomposition products of -the feed components boiling above 1025F and metal deposits are collected as 2û a downwardly flowing fluid bed of solids countercurrent to stripping gas introduced by 21 to stripper 10 for further removal of any entrained or formed hydrocarbon vapors before all or a portion thereon is passed to a regenerator vessel 11 -to form a dells fluidized bed of solid 12 to be regenerated. An oxygen containing gas such as air with or without oxygen enrichment or carbon dioxide mixed with an oxygen containing gas is admitted to the dense fluid bed of solids 12 in regeneration vessel I maintained under conditions to burn carbonaceous deposits and form carbon oxides and other combustion products as herein identified. The resulting flue gas which may or may not be CO rich, depending on the operation selected is processed through cyclones 22 and exits from regenerator vessel 11 via line 23. The regenerated solid sorbent particulate containing less -than 0 . 5 weight per cent carbon . .

Lowe is transferred to stripper 15 for removal as required of any entrained combustible gases and before transfer to a bottom portion of the riser via line 16 to repeat the cycle. The regenerated solids may also be stripped in the withdrawal well in the upper portion of 5 bed 12 by means not shown.

n one embodiment of -this invention, a portion of the recovered solid sorbent ma tonal contaminated with hydrocarbonaceous material and metal deposits may bypass the regenerator vessel through conduit 42 for recycle -to the riser 10 reactor following high temperature stripping thereof in admixture with hot freshly regenerated catalyst. This method of operation may be relied upon to reduce the regenerated catalyst t temperature as well as effect further high temperature visbreaking of deposited hydrocarbonaceous materials. It is even contemplated removing lo some carbonaceous deposits by reacting with a C02 rich gas in such a zone between the regenerator and riser reactor.

The bypass of the regenerator as above identified may be used to reduce vanadium oxidation, to increase thermal decomposition of liquid hydrocarbons as well as reduce regeneration temperatures by 20 reducing the amount of carbonaceous deposits charged -to the regenerator. Other advantages will be apparent to those skilled in the art.

[n a particular embodiment it is desirable in regeneration of the sorbent material to effect combustion of carbonaceous deposits 25 sufficient to provide a solid sorbent particle containing less than O . 2 weight percent carbon and preferably less than O .10 weight percent carbon.

t such time that the metal level on the sorbent becomes inLolerabl~ high such that sorbent effectiveness drops to an Al -guy) ~23~ 8 undesired low level or a desired equilibrium conditions is exceeded, additional sorbent material can be added to replace deactivated sorbent withdrawn by conduits 42 and 43. Points 18 and 19 can be utilized to add virgin sorbents with or without metal additives. In 5 the case of a virgin sorbent prepared without additive, the metal additive as an aqueous solution or as an organo-metallic compound in aqueous or hydrocarbon solvents can be added at points 18 and 19, as well as at addition points 2 and 3 on feed line 1, addition points 20 and 202 in riser 4 and addition point near the bottom of 10 vessel 5 may also be employed for this purpose. The addition of -the metal additive is not limited to these locations, but can be introduced at any point in the oil/sorbent processing cycle. Inlet conduits 20 and 201 are also for the purpose of adding feed to be demetallized and decarbonized to obtain different contact times in lo the riser.

Examples of Additive Addit_n '['his application describes a new and novel approach to offsetting the adverse effects particularly of vanadium pent oxide by the use of large pore volume clay sorbent material with or without 20 one or more select added metals herein identified, as -their oxides or their salts as discussed above. These metal additives serve particularly to immobilize vend by creating complexes, compounds or alloys of vend having melting porn is which are higher than the temperatures encountered in the regeneration zone. These 25 metal additives based on the metal element content of the sorben-t may be used in concentrations in the range of from about 0.5 to 25 percent, more preferably about 1 to 8 percent by weight of virgin sorbed t . When adding the one or more immobilizing metals during the visbreaking operation, the metal elements may be built up to a 30 much higher concentration as equilibrium sorbent material and be maintained at a desired level by sorbent replacement.

Rl-6090D

~23~ 8 The sorbent material which may be employed according to this invention include clay solids of little or no catalytic activity providing a particle pore volume of at least 0 . 4 cc/g and may include some catalytically spent cracking catalysts. However, clays 5 prepared in accordance with this invention which are considered relatively inert because of low activity catalytically below about 20 MATS are employed with some degree of preference Clays suitable for this purpose include bentonite, kaolin, montmorillonite, smectites, and other 2-layered lamellar silicates, Malta, pumice, 10 silica, literate, and combinations of one or more of these of like materials. The surface area of these sorbents are altered during preparation according to this invention by substantially increasing the pore volume thereof to at least 0 . 4 cc/g or greater than 0 . 5 cc/g and preferably the clays have a micro-activity value as 15 measured by the ASTM Test Method No. r~3907-80 of below 20.

As one example of additive involvement, tetraisopropylt;tanate (TOT) was mixed with a heavy gas oil (HO) to form a solution of 1 part TOT to 1 part HO. This solution was added to the oil feed line to the riser in an amount sufficient to yield 1 part titanium by 20 weight to 1 part vanadium in the feed. The oil feed charged to the riser was a reduced crude processed at 600, 000 Its . per day with a vanadium content of 20 ppm. Based on the vanadium content and the molecular weight of the Tear, this equated to adding 420 Its. of TOT per day Lo 600,000 Its. of reduced crude feed per day.

The results of adding TOT to the sorbent are shown in Figure 2. Sorbent samples at varying vanadium levels were taken during two process periods (dots and X's) when the additive of the invention was not utilized, and similar samples were taken during additive addition (boxes). These samples were then subjected to 30 the clumping test described below to determine the flow chclracteristics owe vend containing sorbent particles. The vend 61)90D

~Z368~8 containing sorbent samples were placed in individual ceramic crucibles, dried and calcined at 1400F in air for two hours. The crucibles were cooled to room temperature. Vend, while liquid at operating temperature (1400F), will flow across the sorbent surface 5 and cause sorbent particle coalescence when cooled down below the solidification point. The degree of coalescence shown in Figure 2 is a visual and mechanical estimation of particle fusion, namely, flowing --- no change in flow characteristics between virgin sorbent and used sorbent; soft --- substantially all of used sorbent free 10 flowing with a small amount of clumps easily crushed to obtain free flowing sorbent; intermediate --- free flowing sorbent containing both free flowing particles and fused masses in approximately a 1:1 ratio; and hard --- substantially all of the sorbent particles fused into a hard mass with very few free flowing particles.

The sorbent of Figure 2 was used in the treatment of a reduced crude no lower vanadium and Conrad son carbon values. In two extended runs of approximately 30 days (dots and X's), the sorbent particles began to show coalescence properties at vanadium levels of 10, 000 ppm, and by 20,000 ppm had showed coalescence into a hard mass (loss of fluidization proper-ties) in -the third period (boxes), the additive TOT was added during the processing cycle to a hydrocarbon solution of gas oil as discussed above. This additive permitted operation in the 20,000 to 25,000 ppm level of vanadium without any loss in fluidization through particle 25 coalescence.

Another example of a metal additive identified above was the use of methylcyclopentadienyl manganese Tricarbonyl (MET). Two drums of this material were added over a two hour period to at least partially immobilize the vanadium on the sorbed t . Each drum 30 wised ~10 lobs. and contained 25 wit% MUTT in a hydrocarbon solvent . Based on a manganese concern traction of 2~3 . 3 wit% My in R~-6090D

MET and a circulating sorbent inventory of I tons, approximately 700 ppm My was deposited on the sorbent. The MET additions also improved the circulating efficiency of the sorbent by reducing particle coalescence.

In a fluidized solids system represented by Figure 1, the rate of metals build up on the circulating sorbent is a function of metals in the feed, the sorbent circulating inventory, the sorbent addition and withdrawal rates, the sorbent to oil ratio and the sorbent pore volume. Figures 3 and 4 give the rate of metal buildup on a ] 0 circulating sorbent at constant inventory, constant sorbent addition and withdrawal rate and varying metals con-tent in the feed. These figures show that for feed metals Icvels of 20-70 ppm, total metal levels on the sorbent equilibrate after about 90-150 days.
Thereafter, the metals level on sorbent remains constant with time.
By utilizing theses figures, or similar figures that can be developed for hither metals levels and higher porosity material (pore volume) addition rates and preselected circulating inventories, the required concern tractions of the metal add lives provided with the sorbed t material can be determined so as to yield a preferred minimum atomic ratio of metal additive Lo vanadium content.

Thor example, in Figure 3, this particular unit has 9,00~ Its.
of sorbent inventory, a sorben-t addition rate of 1.35 Ib./bbl. of feed per day, and a feed rate is 200 Ibid. Assuming the metals content is all vanadium, Curve 1 in Figure 3 would be utilized to SUE that after 150 days of continuous operation with 70 ppm vanadium in the feed, the vanadium level on the catalyst would equilibrate at about 17,000 ppm and then remain constant with time.
Thus, in preparing a sorbent particulate containing a titanic additive, the sorbent is prepared such that it will contain at least 8, 500 ppm titanium to ensure that at least 0 . 5 atomic ratio of titanium to vanadium is maintained during use to immobilize ~23t~ 8 deposited vanadium. Similar calculations can be performed for lower and higher equilibrium vanadium values using other curves or multiples of these curves (120 ppm vanadium on sorbent would equilibrate at about 30,000 ppm under the conditions of Figure 3).

In the high temperature treatment of residual oil feeds c comprising components boiling above 1025F and of varying vanadium content herein referred to as hydrothermal visbreaking, thermal visbreaking or hydrovisbreaking the rate of vanadium buildup on a high pore volume sorbent and the uppermost predetermined and selected level of metal contaminants permitted on the solid sorbent before replacement with sorbent of less metals is a function of metals content of the feed and particularly the vanadium content of the feed. A predetermined upper limit of metal contaminants may be referred to as equilibrium state for addition and withdrawal rates maintained so as not to exceed the preselected upper metals level for the selected state of equilibrium. Table G
presents a typical case for a 40,000 blued unit in which the vanadium content of the feed is varied from 1 ppm up to 25 and then to 400 ppm. In order to restrict preselected levels of vanadium on the sorbent at an upper predetermined equilibrium state equated to additive immobilizing metal and capacity of sorbent material, the sorbent addition or replacement rate can be varied to yield the equilibrated vanadium values of from 5,000 to 30,000 ppm.
As explained elsewhere, vanadium as vanadium pent oxide and/or sodium vendetta on the sorbent, undergoes melting at regenerator temperatures above 1200F and flows across the sorbent surface, causing particle fusion and coalescence.

Table H presents an economic advantage for introducing an additive into the riser as an aqueous or hydrocarbon solution.
Table H demonstrates the economic differential (savings in $/day) that can be realized by utilizing the additives and opportune at the ~Z36~3~8 3G, 000 ppm level versus the 10, 000 ppm level of vanadium on sorbent .

As shown in Table H, treatment of a feed stock having 1 ppm vanadium for FCC operations would show a savings of at least 5 $28/day with TOT as the additive and $168/day with titanium tetrachloride as the additive. In comparison, treatment of a heavy hydrocarbon oil containing 25 to 100 ppm vanadium for an RCC
operations would show savings of $500 to $2, Ode with TOT as the additive and $4,000 to $22,400/day with titanium tetrachloride as 10 the additive.

Roy regenerator vessel as diagrammatically illustrated in Figure 1 is a simple one zone-dense fluid bed of solids in a single regeneration zone. The regeneration operation of -this invention is not necessarily limited to the single stage regeneration operation lo Sheehan but can comprise two or more separate regeneration zones in stacked or side by side relationship, with internal and/or external circulation transfer lines from zone to zone. Some multistage regenerator arrangements known in the prior art may be used with advantage or one or more arrangements described in more detail in I other cop ending applications may be used with particular advantage 'rho determination that vend deposited on a sorbent would flow and cause coalescence between sorbent particulate at regenerator temperatures, and the selection of those elements and their salts which would prevent this process were studied by three 25 methods, namely: the clumping or lump formation technique, vend diffusion from or compounds formation with a metal additive in an alumina-ceramic crucible, and through spectroscopic studies and differential thermal analyses of vend metal additive mixtures.

Rudy sty Clumping Test A clay, spray dried to yield micro spherical particles in the 20 to 150 micron size, had vend deposited upon it in varying concentrations. Clay free of vend and clay containing varying 5 vend concentrations were placed in individual ceramic crucibles and calcined at 1400F in air for two hours. At the end of this time period, the crucibles were withdrawn from the muffle furnace and cooled to room temperature. The surface texture and flow characteristics of these samples were noted and the results are 10 reported in Table D.

TABLE D

V25 Surface Flow ( concentration_- Texture Chat ~acteristics O Free Free flowing lo 1,000-'"000 Surface clumped Broke crust for free flowing 5,000-20,000 Surface clumped Total clumpinc3 no flow As shown in Table D, the clay free of vend does not form I any crust or clumps or fused particles at temperatures encountered in the regenerator section of the process described in this invention . At vend concentrations of 1, 000 - 5, 000 ppm, clumping was observed but the crusts binding particles could be readily broken into free flowing, crusty particles. At vend 25 concentrations above 5,000 ppm, the particular low pore volume clay employed begins to clump and bind badly and does not flow at all even with moderate impact. While liquid at operating temperature manifestation of this phenomenon is demonstrated by the finding that when these coalesced particles are cooled down below their 30 solidification point in a crucible, Ott in an operating unit cooled ~Z3~8 down in order to facilitate entrance to the unit for cleaning out plugged duplex and other repairs, a solid mass of sorbent is often found which must be forcibly removed. This phenomena makes process turnaround lengthy and complex for an operating unit as 5 this material must be chipped out.

Crucible Diffusion Test An extension of tech lumping test is the use of a ceramic-alumina crucible to determine whether vend reacts with a given metal additive. If vend does not react with the metal 10 additive or only a small amount of compound formation occurs, then the vend diffuses through and over the porous alumina walls and deposits as a yellowish to orange deposit on the outside wall of the crucible. On the other hand, when compound formation occurs, err are little or no vend deposits formed on -the outside of the 15 crucible wall. Two series of tests were performed. To the first series shown in Table E, a 1:1 mixture by weight of Ye nadir pent oxide and the metal additive was placed in the crucible and heated to 1500F in air for 12 hours. Compound formation or vend diffusion was as noted in Table E.

TALL'. E
1 Part VOW t 1 Part Metal Additive 1500F - Air - 12 Hours Diffusion of Compound Metal Additive Vanadium oration Titanic No Yes Manganese Acetate No Yes l,anthan Oxide No Yes RUDY

~.2368~

Alumina Yes No Barium Acetate No Yes Copper Oxide Yes Partial In the second series of tests, a vend containing material 5 was tested in a similar manner . A one to one ratio by weigh t of vanadium pent oxide and the metal additive were heated to 1500F in air for lo hours. The results are shown in Table F. The material reported in Table F as containing 24,000 ppm vend on clay with no metal additive was fired at 1500F and then studied in a 10 scanning electron microscope (SUM). The fused particles initially gave a picture of fused particles. However, as the material was continllously bombarded, the fused particles separated due to -the heat generated by the bombarding electrons. One was able -to observe the melting and flowing of vend as the initial single 15 fused particles separated into two or more distinct micro spherical particles .

TABLE _ 1 Part VOW - Catalyst + 1 Part Metal Additive 1500F - Air - 12 Hours Vend Metal Particle CoJlcenl r anion L Em Add live Formation 24,000 None Yes 24,000 Calcium Oxide No 24,000 Magnesium Oxide No 24,000 Manganese Oxide No The study of the capability of certain elements -to immobilize vanadium pent oxide was extended by use of Dupont differential thermal analysis (DATA), x-ray diffraction (XRD) and scanning RUDY

~Z3~8~8 lo -electron microscope (SUM) instruments. The metal additives studied on the DATA showed that titanic, barium oxide, calcium oxide, the lanthanide series, magnesium oxide and indium oxide all were excellent additives for the formation of high melting vendettas, with 5 melting points of 1800F or higher. Copper gave intermediate results with compound melting at approximately 1500F. Poor results were obtained with materials such as lead oxide, molybdena, tin oxide, Crimea, zinc oxide, cobalt oxide, cadmium oxide and some of the rare earths. The concepts of the invention described 10 herein are useful in the treatment of both FCC and RCC feeds as described above. The present invention is particularly useful in the treatment of high boiling carbo-metallic material containing feed stock of high metals content and Conrad son carbon producing components to provide products of lowered metals-Conradson carbon 15 values suitable for use as feed stocks for FCC and particularly for RCC units. Examples of these high boiling oils are reduced crudest residual oils and other oils or crude oil fractions containing metals and/or residue as herein defined.

Although the visbreaking process of this invention is 20 preferably conducted in a riser reactor because of desired restricted temperature - contact time parameters, other types of reactors may be employed with either upward or downward solid flow. Thus the thermal visbreaking operation may be conducted with a type of down flowing moving bed of sorbent which moves in I concurrent relation to liquid (unvaporized) or partially vaporized feed stock under contact conditions of pressure, temperature and weight hourly space velocity as particularly defined herein.

Sorbent Preparation Lowe sorben-t material of the present invention and particularly 30 comprising finely divided fluidizable particulate of a size in the RUDY

~.~368~8 range of 20 to 80 microns may be prepared by any number of difference ways to provide a low catalytic activity clay of a pore volume in excess of 0.4 cc/g and one which will be thermally stable in the presence of steam at temperatures in the range of about . 900F up to about 160CF. As provided above, the selected clay material is mixed during preparation thereof with one or more components such as carbon black, sugar, an organic material, a polymer material or an inorganic salt which will decompose during high temperature contact to provide a clay substance of the desired 10 porosity and thermal stability for use in the hydrothermal is breaking operation herein discussed.

Sorbent Preparation Techniques Into a homogenizing mixer called a Kay Mill Nazi added 12 L of tap water and 25 gyms. of sodium pyrophosphate hydrate. The phosphate is a surface active agent to disperse 22 kg. of a fine coolant clay named HYDRATE US. The clay was added over a I minute period with vigorous agitation.

The following is a typical chemical analysis of a Hydrate coolant:

Aluminum Oxide 38.38 Calcium Oxide 0 05 Silicon Dioxide 45.30 Magnesium Oxide 0.25 Ignition Loss at Titanium Oxide 1. 44 950C 13.97 Iron Oxide 0 . 30 25 HYDRATE US Coolant, the finest coolant available, is further identified as follows:

Sue Median 325 Mesh Particle Size Brightness Residue Oil omicrons) (GEE.% of Moo) OH Max. (%) Adsorption %
, _ _ _ _ _ _ 0.20 82.0-85.0 ~.2-5.2 0.20 47 5 Aqueous Viscosity Centipoise ~00 (58% solids, 0. 5% sodium herametaphosphate on weight of Colette .
Measured at 10 RUM on Brook field Viscometer. ) lo 2. To the clay slurry was added 2.8 kg. of Catapult Alumina and the mixture was stirred for 15 minutes.

Catapal Alumina is identified as Alpha MindWrite (Boehmite) as comprising:
Allah 74 . 2% NATO 0.00~%
Ignition Loss 25.8% Sue 0.003%
Glrbon 0 . 36% Sulfur Nil Foe 0 ()05'~ Shea 0.120%

After calcination or 3 Halsey at 900F crystal structure is gamma alumina.

3. Over a three minutes period, 150 ml. of concentrated H2SO~
was dripped into the stirred slurry. Eleven liters of H2SO~
was dripped into the stirred slurry. Eleven liters of HO was added during a 15 minute period with stirring. The resultant slurry had a pi of 3 and a viscosity of 1l00 CUPS at 130F.

R I - 60')0D

~2368~8 a The clay slurry was spray dried at an inlet and outlet air temperature of 255F and 750F respectively.

5. The micro spherical solid from the spray drier was placed in a furnace at room temperature and heated to 1850F in 3 hours.
Heating was stopped and the material was slowly cooled to 30()F over a 16 hour period.

6. Issue procedure yielded a fluidizable clay adsorbent material wit to 13 wit% alumina binder . The surface area was 31 mug and the pore volume was 0.51 cc/g with medium pore radius of lo AYE.

Preparation of Clay Adsorbent with Silica Binder Blake _ _ . _ _ 1. Unto a homogenizing mixer (Kay Mill) was placed lo I. of tap HO and 160 ye. of sodium pyrophosphate hydrate. With stirring, 16 kg. of HYDRATE US Coolant Clay was added over It a 20 minute period.

2. To this stirred clay slurry was added 2 L of "N" Brand sodium metasilicate during 5 minute period.

3. The resultant thick clay slurry was diluted with 16 1. of tap HO while mixing at EYE.

20 I. The slurry was spray dried at 750F inlet air temperature and 250F outlet temperature.

5. The micro spherical solid was then placed in a furnace at 80F
and heated to 1900F during the next 3 hours. Heating was stopped and the material cooled to 300F over a 16 hour US period.

6. The fluidizable clay adsorbent contained 5 wit% silica binder and 93 wit% clay . The pore volume of the material was 0 . I
cc/g while the surface area was 14m2/g.

Preparation of Clay Adsorbent with Carbon Black I, 1. Into a homogenizing mixer (Kay Mill) was added 24 liters of water and 350 gym. (0. 35 kg. ) of lignin (CBO3-Carbon Black) as a dispersant. This mixture was agitated to thoroughly mix dispersant before adding 7 kg. of carbon black (United N219L
- Particle diameter AYE) to the Kay Mill mixture to get the carbon black dispersed in the water. The mixture was agitated for 15 minutes. Then 32.4 kg. of HYDRATE US Clay was added to the mixture in 4 portions over a mixture period of about 15 minutes. Following the clay addition, the mixture was further agitated for another 15 minutes to form a homogeneous slurry.

2. The homogeneous slurry was then spray dried a an inlet temperature of about 255F and an outlet temperature of about 750F.

The product of the spray drying operation comprising 20 micro spherical solids may be heated or calcined, if desired, by heating in a furnace gradually -to an elevated temperature up to 1850F in about 3 hours. The calcined material should then be slowly cooled to about 300F over an extended period up to a 16 hour period. During calcination of the spray dried material, the 25 carbon black in the solids comprising about 20% carbon black is burned out to provide a high pore volume clay particle of at least 0.5 cc/gm.

Al - 60901~

~23~8~8 In yet another embodiment, the present invention is concerned with maintaining a relationship in the thermal visbreaking zone between solid sorbent particulate and metals containing oil feed such that the high pore volume particulate of this invention will be used 5 with a volume of heavy oil feed which limits filling the pores with oil feed to within the range of 1/4 up to about 2/3 at a preselected solids to oil ratio. In a more particular aspect, the thermal visbreaking operation is initiated with -freshly prepared sorbent particle clay material of at least ova. cc/g pore volume and a solids 10 to oil ratio so that only about 1/4 up to about 2/3 of the solids pore volume will be initially filled with heavy oil feed comprising tacky asphaltic material to minimize coalescence of particles as discussed above and to effect demetallization and decarbonization of the heavy oil feed.

The relationships herein identified with respect to pore volume, pore openings, zealot content, catalyst to oil ratio to restrict pore filling, temperature and contact time are not only particularly desirable but a critical relationship in operating significantly contributing to the efficiency and thus economics of 20 the thermal visbreaking operation of this invention.

The following tables G and I particularly identify with the operating efficiency and economics of the inventory. That is, Table G, identified some sorben-t addition rates identified as required to maintain vanadium metal contaminant at a given level for feeds with I different levels of vanadium content. The advantage of using the large pore volume sorbent of this invention which permits operating at high metals content level is clearly identified with this data.
Table H in addition to Table G is identifying further significant advantages that one can achieve by employing one of TOT and Tokyo 30 in the sorbent for immobilizing vend.

I -60901>
. . .

~Z368:18 TABLE G
40, 000 BLUE . DAY UNIT
Total ~,'anadium#Metal Level on Equilibrium Material 5 PPM DAY 500010,000 20,000 30,000 0.5%1.0% 2.0% 3.0%
Daily Tonnage Replacement ~00 5200 500 = 82 lo 10G 1300 125 63 32 21 So 650 63 32 16 10 RUDY

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Having thus generally described various aspects of the present invention and discussed specific embodiments in support thereof, it is to be understood that no undue restrictions are -to be imposed by reasons thereof except as defined by the following claims.

What is claimed is:

GUY

Claims (8)

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

1. A composition of matter comprising a clay of at least 0.4 cc/g pore volume prepared by slurring kaolinite clay with a high pore volume producing dispersant material which will thermally decompose, spray drying the slurry of clay and dispersant to form microspherical solids, heating said microspherical solids to an elevated temperature over a time period up to about 3 hours and thereafter slowly cooling the heated solids to about 300°F. over a time period up to about 16 hours.

2. The composition of claim 1 wherein the thermally decomposable dispersant material is a material selected from the group of materials comprising, sugar, carbon black, a thermally decomposable organic material, a thermally decomposable inorganic material such as salts of a molecular weight and structure providing desired pore size upon decomposition.

3. The composition of claim 1 wherein the thermally decomposable dispersant material comprises carbon black.

4. A method for preparing a solid sorbent clay particles of at least 0.4 cc/g pore volume which comprises, forming a slurried mixture of kaolinite and sodium pyrophosphate in water, adding alpha monhydrate alumina to said slurry during agitated mixing of the slurry, adding sulphuric acid and water slowly to the stirred slurry to provide the slurry with a pH of about 3, spray drying the pH adjusted slurry at a temperature up to about 750°F.
to form microspherical solids, heating the microspherical solids to an elevated temperature, and recovering a cooler clay sorbent particle material comprising an alumina binder and a pore volume of at least 0.5 cc/gm.

5. A method for preparing a solid clay sorbent particle material of at least 0.4 cc/gm pore volume which comprises, forming a slurry of water, lignin and carbon black, adding kaolinite clay to said slurry with stirred agitation, spray drying the slurried clay at a temperature up to about 750°F., heating the spray dried material up to a temperature of about 1850° F., slowly cooling the heated and calcined spray dried material, and recovering a clay particle material depleted of carbon black and comprising a pore volume of at least 0.4 cc/gm.

6. A method according to claim 4 to which one or more metals for immobilizing vanadium is added during preparation of the solids.

7. A method of preparing solid sorbent particulate material comprising a pore volume of at least 0.4 cc/g which comprises, forming a homogenized slurry mix of water, sodium pyrophosphate and very small particle kaolinite clay, adding sodium metasilicate to the clay slurry with stirring to produce a thick clay slurry, dilute the thick clay slurry with water while mixing at a temperature of 125° F., spray drying the diluted clay slurry at a temperature within the range of 250°F. to about 750°F. to produce microspherical solid products, heating the microspherical particles to an elevated temperature for an extended period of time, cooling the heated material, and recovering fluidizable clay adsorbent particles containing 5 weight percent of silica binder and 93 wt % of clay providing a pore volume of at least 0.41 cc/g and a surface area of at least 14 m2/g.

8. A composition of matter for demetallizing and decarbonizing high boiling residual oils comprising vanadium and asphaltenes which comprises a clay sorbent material provided with a pore volume in the range of 0.4 cc/g to 0.5 cc/g and a pore opening of at least 500 Angstroms, and said clay sorbent provided with from 1 to 20 wt %
of a metal or compounds of metals selected from the group consisting of silica, alumina, titanium, zirconium, barium, magnesium, calcium and mixtures thereof.