JPH0210694B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention provides a distillation tower with a more suitable grade of feed oil having low metal values and Conradson carbon values for use as feed oil in the Residual Conversion (RCC) process or current modern FCC processes. It relates to manufacturing from basic materials. The high boiling fraction of crude oil consisting of inferior grades of carbon-metallic oil components with high metal values and Conradson carbon values is
It is converted into a metal-poor feed oil suitable for the RCC process. More specifically, the present invention provides solid particulate sorbents with or without metal additives provided for specifically immobilizing vanadium compounds deposited on the sorbent particles during processing of metal-containing feed oils. It concerns the manufacture and use of substances. Metal additives for vanadium immobilization are added during absorbent manufacture, either by fresh absorbent impregnation or at any point in the absorbent-hydrocarbon contact and regeneration cycle for feed oil treatment. This application is a patent application (RI6124), serial number 277752
(registered March 9, 1981) and is concerned in particular with improvements in identified absorbent materials and their use in the demetalization and decarbonization of atmospheric distillation residue-containing materials. BACKGROUND OF THE INVENTION The main innovation in FCC catalysts and their use dates back to the 1960s.
The introduction of molecular sieves or zeolites in the early 1990s. These materials were incorporated into the matrix of amorphous and/or amorphous/kaolin materials that comprised the FCC catalysts of the era. These new zeolite catalysts contain crystalline aluminosilicate zeolites in amorphous or amorphous/kaolin matrices such as silica, arsina, silica-alumina, kaolin, clay, etc. Amorphous or amorphous matter/
It was at least 1000-10000 times more active in cracking hydrocarbons than kaolin-containing silica-alumina catalysts. This introduction of zeolite cracking catalysts revolutionized fluid catalytic cracking. New innovations have evolved to address advanced features such as riser cracking, reduced contact times, new regeneration methods, the development of new and improved zeolite catalysts, and so on. The development of this new catalyst is based on the development of various zeolites, such as synthetic types X and Y and naturally occurring phoriasite; thermal-steaming of zeolites by incorporating rare earth ions or ammonium ions by ion exchange techniques ( increased hydrothermal stability; and the development of more abrasion-resistant matrices for supporting zeolites. These zeolite catalyst developments provide the petroleum industry with the ability to greatly increase feedstock production with increased conversion and selectivity using the same equipment without expansion and without installing new equipment. Gave. After the introduction of zeolite-containing catalysts, the petroleum industry began to struggle with the lack of availability of crude oil in terms of quantity and quality due to the increased demand for higher octane gasoline. The world crude oil supply map dates back to the late 1960s and
This changed dramatically in the 1970s. The supply situation is
The era of surplus of light crude oil, which does not contain mercaptans, has turned into a shortage, and the amount of heavy crude oil, which contains more sulfur, continues to increase. These heavy, sulfur-rich crudes present processing problems to oil refiners in that these heavy crudes also invariably contain much higher metal and Conradson carbon values and are associated with significantly higher asphaltene contents. I have presented it. The effects of heavy metals and Conradson carbon on zeolite-containing FCC catalysts have been described in the literature with a highly detrimental effect on reducing catalyst activity and selectivity for gasoline production and an equally detrimental effect on catalyst life. Metal content and Conradson carbon are two extremely influential constraints on the operation of FCC equipment.
It imposes constraints on vacuum residue conversion (RCC) equipment with a view to obtaining maximum conversion, selectivity, and catalyst life. Relatively high levels of these impurities are extremely detrimental to the catalytic conversion process.
As metal and Conradson carbon levels are further increased by available crude oil,
The working capacity and efficiency of RCC devices, especially FCC devices, are adversely affected or even become uneconomical.
These deleterious effects may occur even if sufficient hydrogen is present in the feed oil to produce an ideal gasoline consisting of a mixture of only toluene and isomeric pentenes (unless a catalyst with such ideal selectivity is devised). (assuming) also occurs. The effect of the Conradson carbon increase is to increase the portion of the feed oil that is converted to coke that is deposited onto the catalyst. In a typical gas oil cracking operation using a crystalline zeolite-containing catalyst in an FCC unit,
On average, the amount of coke deposited on the catalyst is about 4% of the feed oil.
-5% by weight. This coke formation has been based on four different coking mechanisms. These include fouling coke from deleterious reactions caused by metal deposits, catalytic coke caused by acid spot cracking, associated hydrocarbons resulting from pore structure adsorption and/or poor stripping, and conversion. Conradson carbon, which results from the pyrolytic distillation of hydrocarbons in the zone. Two other sources of coke have also been postulated in the atmospheric distillation residue in addition to the four mentioned above. They include (1) adsorbed and adsorbed hydrocarbons that cannot be vaporized and removed by ordinary effective stripping, and (2) high molecular weight nitrogen-containing hydrocarbon compounds adsorbed onto the catalyst acid sites; It is. Both of these two types of coke formation phenomena greatly add to the complexity of residual oil processing. Therefore, high-boiling fractions of crude oil, such as atmospheric distillation residue, residual oil fraction, topping crude oil,
In such processes, coke formation based on the feed oil consists of the four types present in gas oil processing, coke from high-boiling non-volatile hydrocarbons, and high-boiling nitrogen-containing molecules adsorbed onto the catalyst. This is the total with related coke. When processing atmospheric distillation residues, coke formation on a clean catalyst is approximately 4% by weight of the feed oil and the Conradson carbon value of the heavy feedstock.
It may be evaluated as the sum of the % feed oil boiling above 1050〓 and an additional correction factor related to the % nitrogen in the feed oil. The coked catalyst is returned to equilibrium activity by burning off the deactivated coke in the presence of air in the regeneration zone, and the regenerated catalyst is recycled to the reaction zone. The heat generated during regeneration is partially removed by the catalyst and transferred to the reaction zone for feed oil vaporization and to absorb heat for the endothermic cracking reaction. The temperature in the regenerator is usually limited due to metallurgical constraints and hydrothermal stability of the catalyst. The hydrothermal stability of a crystalline zeolite-containing catalyst is determined by the temperature and steam partial pressure at which the crystalline zeolite does not rapidly lose its crystalline structure and begins to form a less active amorphous material. The presence of steam in high-temperature operating regimes is extremely important and has a significant hydrogen content (hydrogen to carbon atomic ratio generally greater than about 0.5) adsorption and absorption (occlusion).
It is generated by the combustion of carbonaceous materials. This carbonaceous material is primarily composed of 1500-1700 carbonaceous materials with moderate hydrogen content and high boiling high molecular weight nitrogen-containing hydrocarbons and related polyphyllins and asphaltenes.
It is a high-boiling storage hydrocarbon with a boiling point of High molecular weight nitrogen compounds are usually about 1025〓
It has a boiling point of , and may be either basic, acidic or neutral in nature. Basic nitrogen compounds neutralize acidic sites, while those that are more acidic are attracted to metal sites on the catalyst. Polyphyllines and asphaltenes also generally have boiling points above 1025– and can contain elements other than carbon and hydrogen. As used herein, the term "heavy hydrocarbon" refers to about
Includes all carbon- and hydrogen-containing compounds that do not boil below 1025〓. Heavy metals in the feed oil are generally present as porphyrins and/or asphaltenes. However, some of these metals, particularly iron and copper, may be present as free metals or inorganic compounds resulting either from corrosion of processing equipment or from contaminants from other refining steps. As the Conradson carbon value of the feedstock increases,
Coke production increases and this increased load increases the regeneration temperature and thus the equipment is constrained in terms of the amount of feed oil that can be processed due to the Conradson carbon content of the feed oil. A new development in atmospheric distillation residue processing, as described in the co-pending US patent application cited below, can operate at regenerator temperatures ranging from 1300 to 1600. However, even these high regeneration temperatures limit the Conradson carbon value of the feed oil to about 8, resulting in about 12-13 weight percent coke on the catalyst based on the weight of the feed oil. This level is the limit unless significant water is introduced to further control the temperature. The metal-containing fraction of the atmospheric distillation residue contains Ni-V-Fe-Cu in the form of porphyrins and asphaltenes. These metal-containing hydrocarbons are deposited on the catalyst during processing and are decomposed to some extent, depositing metals on the catalyst, or are carried away by the coke-adhering catalyst as metal-porphyrins or metal asphaltenes to form metal oxides during regeneration. is converted to by combustion. The detrimental efficiency of these metals, as taught in the literature, is to cause non-selective or degradative cracking and dehydrogenation to produce coke and light gases such as hydrogen, methane and ethane. These mechanisms negatively impact selectivity and result in poor yield and quality of gasoline and light cycle oil. Increased light gas production on the one hand impairs yield and selectivity, which also has an undesirable effect on gas compressor capacity.
In addition to its negative impact on the yield, increased coke formation also has a negative effect on the activity-selectivity of the catalyst, greatly increasing the regenerator air demand and compressor capacity, making it uncontrollable and/or Can result in dangerous regenerator temperatures. These problems of conventional methods have been greatly minimized with the development of new methods that can handle atmospheric residues or crude oils containing high metal values and Conradson carbon values that were previously unacceptable to direct FCC processing. Ta. Typically, less desirable crude oils require expensive vacuum distillation and other processing to isolate suitable metal-free feed oils and produce sulfur-containing vacuum kettle residues as by-products. However, some crude oils, such as Mexican Mayan or Venezuelan crude, contain unusually high metal and Conradson carbon values. Direct processing of these inferior grades of crude oil in a catalytic cracking process leads to uneconomical operations. This is due to the high combustion loads imposed on the regenerator to remove carbonaceous deposits due to metals and the high catalyst addition rates required to maintain catalyst activity and selectivity. Addition rates are on the order of 4-8 lb/bbl or more, which at current catalyst prices adds an additional catalyst cost on the order of $2-8/lb in processing costs. Thus, developing and validating economic means to process more of a lower quality crude oil such as Mexican Mayan is desirable due to its availability and relative cost compared to Middle Eastern crude oils. The literature has proposed many methods to reduce the metal content values and Conradson carbon values of atmospherically distilled crude oil and other contaminated oil fractions. One such method is described in U.S. Pat. No. 4,243,514, assigned to Engelhardt Minerals and Chemicals, and German Patent No.
No. 2,904,230, these patents are incorporated herein by reference. Essentially, these conventional methods contact atmospheric distillation resid fractions or other contaminated oils with an absorbent material at elevated temperatures in an absorption zone, such as a fluidized bed, to obtain metal values and Conradson carbon values. Including lowering. Patent No.
One of the absorbents described in 4243514 is an inert solid initially composed of kaolin, which
Spray-dried to yield microspherical particles with a surface area less than m ² /g and a catalytic microactivity (MAT) value less than 20, the material is then heated at elevated temperatures for better abrasion resistance. Fire. If the vanadia content on such an absorbent exceeds 500 ppm
As it increases within the 30000 ppm range, the absorbent begins to have fluidization problems and more importantly begins to cause coking blockages in the reactor riser.
This has traditionally been overcome by draining the bulk of the used absorbent inventory and adding new virgin material in its place. This blockage may require shutdown of the absorbent contacting equipment. DISCLOSURE OF THE INVENTION The present invention provides a method for converting higher grade feed oils with low metal values and Conradson carbon values for catalytic conversion, such as the atmospheric residue catalytic conversion (RCC) process, to extremely high metal values and Conradson carbon production values. The present invention relates to and provides methods for producing lower grades of crude oil or other carbon-metal-containing oil components. The present invention also provides improved methods for treating crude oil or crude oil fractions containing significant levels of metals and/or Conradson carbon-forming components suitable for RCC processing or for use in typical gas-oil fluid catalytic cracking (FCC) processes. It can be applied to providing supply oil. Residual fractions obtained from distillation of low quality crude oils contain substantial amounts of metals such as Ni, V, Fe, Cu, Na and have materials that produce high Conradson carbon values. These residual oils are a combination of solid absorbent particulate matter that has a catalytic cracking activity of less than about 20 MAT and has relatively low activity or no significant activity, including low-quality high-boiling oils, including residual oil fractions. Residual Residue Conversion (RCC), which involves preliminary contacting under conditions of time, pressure, and temperature sufficient to reduce metal values and Conradson carbon values to within more acceptable limits for a catalytic cracking process.
This makes it more suitable as a feed oil according to the present invention for processing by catalytic conversion such as. For example, when vanadium pentoxide and/or sodium vanadate accumulates on absorbent particles, the elevated temperatures encountered in the absorbent regeneration zone to remove carbonaceous deposits may cause significant levels of vanadium deposits to be absorbed by the absorbent particles. It has been found that the agent flows and forms a liquid film on the agent particles. Under this condition, interruption or reduction of particle flow results in agglomeration between liquid-coated absorbent particles. When agglomeration occurs, fluidization is interrupted and difficult to restart. This condition results, for example, in the cessation of particle flow in the cyclone immersion leg, inefficient operation of the cyclone, rapid increase in absorbent losses, and ultimately equipment shutdown. In certain aspects, the present invention relates to the co-pending application (R16124) modified as provided herein and herein referred to as Hydrothermal Visbreaking Process.
It is concerned with providing improved absorbent particulate materials for use in methods such as those described in Serial No. 277752. It has now been recognized that in this hydrovisbreaking operation, when using the absorbent particulate materials specifically identified herein, significant economies can be realized with respect to improved operations for metal removal and decarbonization of feed oils. be. The present invention thus relates to improved characterization of absorbent particulate materials, methods for their preparation, and methods for use in hydrothermal visbreaking operations without the addition of molecular hydrogen. The improved solid absorbent particulate material of the present invention has a vacancy of at least 0.4 cc/g, with or without the use of one or more metal additive molecules to immobilize the liquefied vanadia. It consists of a high pore volume clay-type material composition with a pore volume that provides greater absorption properties for heavy oil components and provides greater absorbent stability at temperature conditions used up to 1600 °C. .
In yet another aspect, the improved absorbent material has a pore size that readily absorbs high levels of metal deposits and residual high boiling components into the pores rather than surface deposits that cause particle agglomeration. It has a pore volume. Surface deposition of metals, particularly vanadia, causes a reduction in the absorption properties of the absorbent by blocking the pore openings and causing particle agglomeration as described herein. Thus, the improved high pore volume materials of the present invention allow more contaminating metal components, such as vanadia and asphaltenes, to be absorbed within the sorbent pores rather than being collected on the external particle surfaces. The use of high pore volume sorbent materials considerably reduces the tendency for particle agglomeration due to high metal binding as observed with low pore volume sorbents. Additionally, when there are relatively large amounts of heavy bottoms boiling above 1025㎓, low pore volume materials can cause particle coating with sticky asphaltic material that facilitates particle agglomeration, causing riser reactor and product Accompanied by blockage and coke buildup within the separation system. However, by using a larger pore volume while limiting the pore volume occupied by the heavy feed oil as supplied here, the loading of asphaltic material that causes particle agglomeration is reduced over time. It is considerably reduced. The crude oil processing capacity of the atmospheric distillation residue cracking method is limited by its Conradson carbon character, particularly by the concentration of metal impurities in the feed oil, and more specifically by the concentration of vanadia in the high boiling fraction of the crude oil being processed. Constrained by. Regarding this, R.C.C.
Prior to the present invention, it was generally accepted that upper limits for feed oil to equipment involve a total metal content significantly lower than about 8% Conradson carbon and about 50 ppm Ni+V. Therefore, Mexican
100ppmNi as found in Mayan crude oil
Crude oil with a metal level higher than +V and a Conradson carbon value of approximately 8% (with a Conradson carbon value of 17%)
An efficient and economical metal removal system - Conradson carbon reduction system is required upstream or prior to a catalytic cracking (FCC) or atmospheric crude cracking (RCC) operation to treat 400 ppm total metals). be done. In known conventional metal removal systems, a sorbent material with low catalytic activity is used to adsorb the Conradson carbon and a portion of the metal onto its surface. In this operation, the absorbent surface area is small, approximately 25 m ² /
g or less, and the corresponding pore volume is also small, about 0.2 cc/g or less.
Equilibrium absorbents with these properties are about 0.15 cc/g or less and about 0.10 cc/g or even lower 0.06
cc/g, with much smaller pore volumes. When using absorbent materials of these characteristics with solids to oil ratios in the range of 6-8, it is quite clear that the absorption capacity of the absorbent granules is less than the volume of feed oil being treated. . Therefore, the rapid deposition of hydrocarbonaceous substances, metal impurities, and sticky asphalt onto absorbent particles of limited properties of this type causes pore clogging of the absorbent particles and over-covering of the external surface; Promote particle agglomeration. Joint application of applicants (R16124), serial number 277752
In , vanadia deposited on the solid sorbent surface flows as a liquid under the high temperature conditions of the operation encountered in the regeneration zone to remove the deposited carbonaceous material, and such vanadia flow flows through the sorbent contactor. It has been observed that lower temperature regions and regions of more static flow cause particle sintering, pore collapse and particle agglomeration. When such particle agglomeration occurs, for example, in areas of standpipes, cyclone dip legs and associated somewhat stagnant particle streams, a reduction in the fluidization and flow properties of the solid absorbent granules occurs, which can lead to process stoppage. and rapidly cause interruptions. Furthermore, as mentioned above, when using low pore volume solid absorbent materials, the heavy high-boiling oil component consisting of asphalt is not absorbed and the particles are covered with non-volatile asphalt, which in turn acts as a sticky material. It acts to cause particles to stick to each other and to the riser reactor walls, resulting in blockage of the riser reactor and product separator. This problem is also observed in fluid coking operations, where coke globules, which cannot absorb feed oil, easily aggregate to form large clumps, effectively clogging the system. The present invention is therefore directed to providing improved solid absorbent granules that substantially reduce, if not eliminate, the undesirable operation of contaminant loading on the solid and its attendant defluidization. According to the present invention, the adverse conditions identified here with respect to pore clogging, particle sintering, and particle agglomeration are at least 0.4 cc/g pore volume and preferably 0.5 cc/g
This is substantially reduced through the use of high pore volume solid absorbent particulate materials, such as those with pore volumes ranging from 0.8 cc/g to 0.8 cc/g. According to another aspect, the present invention relates to a method of making a desirable high pore volume, thermally stable solid absorbent particulate material. The properties of this high pore volume material can be improved by the addition of one or more additive metals as defined below, which metals combine with it a stream of vanadia at regeneration temperature conditions. It is effective to immobilize and form a higher melting point material following deposition on the absorbent material. Particularly desirable high pore volume clay absorbent materials include carbon black, sugar, organic materials such as methylcellulose and starch, polymeric materials such as nylon, polyacrylonitrile, polybutene, polystyrene, high temperature decomposable inorganic salts such as nitrates, nitrites, carbonates, The desired pore size can be achieved during its manufacture by incorporating one or more components of sulfides of various molecular weights and structures to obtain the desired pore size after decomposition. The high pore volume solid sorbent materials provided and produced in accordance with the present invention should be used in similar equipment described in U.S. Patent Serial No. 277,752, but under the operating conditions specifically recited herein, in which , the solids of the invention are used for very long periods of operation, thereby making a significant contribution to the economy and efficiency of their operation. Other advantages attributed to the solid absorbent material of the present invention will become clearer from the description below. The absorbent particulate material of the present invention may in one particular case contain one or more of carbon black, polymeric substances that can be decomposed during high temperature drying or subsequent high temperature processing, sugar, etc., kaolin, etc. clay, montmorillonite, smectite, or other suitable material, which mixture, if subsequently spray dried, has a particle diameter in the range of about 20 to about 50 microns, preferably 40 to 50 microns. This produces microspherical absorbent granules with dimensions within the flowable particle size range of 80 microns or greater. Calcination of the spray-dried material can be accomplished in the regeneration stage of the process, or separately prior to use, by combustion to remove the carbon black or decompose the active material to yield the desired large pore absorbent. can be achieved at temperatures sufficient to The pore size of the absorbent is thus essentially determined by the size of the encapsulated material that is removed by calcination and/or combustion. The preferred pore volume of the finished microspherical absorbent is at least
0.4cc/g, preferably 0.5 to about 0.8cc/g
is within the range of Therefore, when using a 7/1 absorbent/oil ratio, the total pore volume of the absorbent is approximately
It is within the range of 2.8cc/cc supplied oil to approximately 5.6cc/cc supplied oil. In the case of sorbents with larger pore volumes than previously used, the pores are exposed to the deposited high-boiling carbonaceous material over an extended period of operation time during which the deposited hydrocarbonaceous material is removed by combustion. It is not overfilled with constituent materials, and the deposited vanadia, together with or alone with added metals, cannot flow out of the pores and accumulate on the external surfaces of the solid particles, causing pore blockage and agglomeration. In addition to the substantially increased pore volume provided by the sorbent materials of the present invention, which is an antidote to short run times, the increased pore volume in combination with the immobilizing metal additive is , aids the hydrothermal visbreaking operation of the present invention by allowing a much larger buildup of metal contaminants on the absorbent material before it must be discarded. The large pore sorbent materials of the present invention are modified as described above by the inclusion of one or more vanadia immobilized metal additives selected from oxides or salts of metal additive materials. or the organometallic compound of the additive material can be added to the absorbent material during or after the absorbent granule production or during the oil treatment cycle, for example during the removal of metals and/or Conradson carbon. For example, sodium vanadate and/or vanadium pentoxide deposited on the agent are immobilized. In the case of high pore volume absorbents, there is less need to provide additive metals as defined herein in the virgin absorbent material. Useful for addition after vanadia has accumulated considerably. The present invention thus provides an improved absorbent and an improved process for the treatment of high boiling feed oils containing significant levels of hydrocarbon materials boiling above 1025 and an amount of vanadium of at least 1.0 ppm. More specifically, sorbent particulate materials with improved high pore volume and high metal absorption capacity are also used for the reasons described herein and caused in part by particularly low melting point vanadium compound contaminants. It also reduces agglomeration and fluidity loss. The heavy high-boiling fraction of gas oils and all types of feed oils used in FCC operations and more particularly in atmospheric distillation residue cracking operations contain highly variable amounts of vanadium,
They consist of nickel, iron and copper, and vanadium is very often their main part. The invention described herein can thus be used in a process known as the Residual Crucking (RCC) process to treat hydrocarbon compositions with higher metal content than those processed in gas oil cracking (FCC) operations. Excessive carbon and
It is particularly useful for removing metal-containing oil components. Some crude oil fractions and some FCC loaded feedstocks obtained by crude oil distillation contain significant amounts (greater than 1.0 ppm) of heavy metals such as Ni, V, Fe,
Contains Cu and Na. Of these metals, vanadium, as discussed here, has been particularly recognized as a villain. Residual fractions from crude oil distillations have even higher amounts of heavy metals and hydrocarbons that produce high Conradsonian carbon. As used throughout this specification, "vanadia" refers collectively to oxides of vanadium. As vanadium oxide levels build up on the absorbent material, the elevated temperature encountered in the regeneration zone causes vanadium pentoxide (V ₂ O ₅ ) to flow as liquid vanadia. This flow of vanadium is particularly important due to its low surface area and below 0.4 cc/g.
At high vanadia levels in absorbents with low pore volumes below 0.2 cc/g, the outside of the absorbent microspheres is coated with liquid, thereby causing agglomeration between the absorbent particles in the colder region; This has a negative effect on the fluidization properties of the absorbent particles. The high pore volume adsorbent particles of the present invention can be of any size, depending on the size appropriate for the conversion operation in which the adsorbent is to be used. For example, although fluidizable dimensions are preferred in the riser contact zone, absorbent particles may also be used in larger sized particles such as those used in solid particle moving beds in contact with partially evaporated or unevaporated feed oil. It can be used as It is believed that many of the problems with conventional methods of atmospheric distillation residue cracking are caused by contaminants, including asphalt and vanadium, and these types of problems can be overcome with the high pore volume absorbent particles of the present invention alone. or to a substantial extent by use in combination with selected metal additives as defined herein for at least some improvement in absorbent life during the process. The present invention is suitable for use in distillation residues, residual oils, topping crude oils, and other high-boiling carbon materials consisting of relatively high vanadium-to-nickel ratios and high Conradson carbon values.
It is particularly effective in treating hydrocarbon feed oils containing metal substances. Hydrocarbon cuts or high boiling feed oils having high levels of metal impurities and Conradson carbon forming components are preferably first treated with a diluent material such as water, steam, or a combination thereof in a reaction zone such as a riser zone. Adjustment of temperature and reduction of hydrocarbon partial pressures are effected upon contact with the solid absorbent particulate materials of the present invention that provide the surface area and high pore volume as defined herein at temperatures of about 900°C or higher. Ru. The residence time of the charged feed oil varies over the boiling point range and is generally less than 5 seconds. Preferably, the residence time for high boiling residues and atmospheric distillation residues is in the range of 0.5-3 seconds.
Preferred high pore volume sorbent materials according to the invention of fluidizable particle size are generally spray dried in the form of microspherical particles within a particle size range of 20 to 150 microns, preferably between about 40 and about 80 microns. and may or may not be calcined before use. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic elevation view of an arrangement of equipment for carrying out the visbreaking demetallization process of the present invention. FIG. 2 is a graph showing the change in absorbent properties as the amount of vanadium on the absorbent increases and the effect of metal additives on the absorbent properties. FIG. 3 is a graph showing the time required to accumulate vanadium on the absorbent at various vanadium levels in the feed oil and absorbent addition rate of 3% of vessel loading. DESCRIPTION OF SPECIFIC EMBODIMENTS While it is not intended to specifically define the exact mechanism by which vanadia immobilization is obtained, the metal additives of the present invention may be compounds with vanadia that have a melting point above the temperature achieved in the regeneration operation; It can be said that they form a complex or an alloy. The atomic ratio of additive metal to vanadium used directly on the absorbent material is reduced by the addition of an oxide of the additive metal such as TiO ₂ or In ₂ O ₃
at least 0.5 depending on the number of additive metal atoms in
and preferably at least 0.1, forming a stable, high melting point binary oxide with vanadium pentoxide (V ₂ O ₅ ). Therefore, the melting point of this binary oxide material is generally significantly higher than the operating temperature encountered in the regenerator. Although the amount of metal additive initially depends on the method used for its addition and is significantly higher than the preferred minimum ratio, especially when it is incorporated into the solid absorbent prior to use,
The additive metal to vanadium ratio on the absorbent decreases as vanadium is deposited onto the solid absorbent. Alternatively, the metal additive can be added to the process in a preferred and selected minimum ratio of at least an equivalent to the vanadium metal content of the feed oil. This or any other suitable method may include forming a binary mixture with the low melting point vanadia deposited and/or formed to form a solid having a melting point of at least about 1600, preferably at least about 1700, or higher. Producing materials can be used to ensure proper metal additive concentrations.
This high melting point product ensures that high levels of vanadia flow and coat the absorbent pore structure and do not cause particle agglomeration and/or sintering as described herein. Additive Examples Additive metals of the present invention include elements from the Periodic Table of Elements shown in Table A. The melting points in Table A are based on a 1:1 molar ratio of metal additive oxide in a stable valence state under regenerator conditions to vanadium pentoxide.

TABLE Other elements that can be used with considerable success include silicon and aluminum. In particular, Si, Al, Ti, along with high pore volume kaolinite clays
Preferably, from 1 to 20% by weight of one or more of Zr, Ba, Mg and Ca is used. The present invention also recognizes that mixtures of these additive metals with vanadia form high melting point binary, ternary, quaternary and more multicomponent reaction mixtures. Examples of such additional ternary and quaternary components are shown in Table B. Table B Compound melting point, VO−TiO ₂ −ZrO ₂ ＜1800 Ra ₃ −V−Ti ₂ O ₉ ＜1800 BaO−K ₂ O−TiO ₂ −V ₂ O ₄ ＜1800 BaO−Na ₂ O−TiO ₂ − V ₂ O ₅ <1800 In the treatment of high-boiling carbonaceous and metal-containing feed oils containing sulfur and in the regeneration of absorbent materials consisting of metal-contaminated deposits, vanadium is
Compounds such as sulfates, and oxysulfides are also susceptible to the formation of binary, ternary, quaternary or more multicomponent reaction mixtures with metal additives as defined by the present disclosure. can be formed. Without wishing to be bound by any theory or mechanism, it has been observed that the reaction of metal additives with vanadia generally produces a two-component reaction product. For example, in the case of manganese acetate reacting with vanadium pentoxide, the compound formed was not certain, but it was recognized as Mn ₂ V ₂ O ₇ . When titania reacts with vanadium pentoxide, the true compound could not be identified because the reaction is believed to involve the replacement of Ti ⁺⁴ with V ⁺⁴ in the crystal structure. For example, the X-ray diagram of titania and the X-ray diagram of vanadium pentoxide
Disappearance of the diagram was observed, indicating vanadium substitution. The metal additive may be a compound of magnesium, calcium, barium, titanium, zirconium, manganese, indium, lanthanum, or a mixture of compounds of these metals. If the additive is introduced directly into the high pore volume adsorbent demetallization process, i.e. into the riser contacting zone or falling particle contacting zone, into the regenerator, or into any intermediate zone thereof. When introduced directly, the metal additive is preferably an organometallic compound that is soluble in the hydrocarbon feed oil or in a hydrocarbon that is miscible with the feed oil. Examples of preferred organometallic compounds are tetraisopropyl titanate, Ti(C ₃ H ₃ O) ₄ available as TYZOR from DuPont; methylcyclopentadienyl manganese tricarbonyl (MMT);
Mn(CO) ₃ C ₆ H ₇ ; Zirconium isopropoxide, Zr(C ₃ H ₇ O) ₄ ; Barium acetate, Ba
( _{C2H3O2 ) 2} ; Calcium oxalate, Ca( _{C2O4 )} ; Magnesium stearate, Mg( _{C18H35CO2 ) 2} ; Indium 2,4 _- pentanedionate, _In
(C ₅ H ₇ O ₂ ) ₃ ; tantalum ethoxide, Ta
( _{C2H5O ) 5} ; and zirconium-2,4-pentaionate, _Zr ( _{C5H7O2 )4 .} Other preferred process additives are titanium tetrachloride and manganese acetate, both of which are relatively inexpensive. These additives are just a few examples of the variety of materials available; others include alcoholates, esters, phenolates, naphthenates, carboxylates, dienylsandurthi compounds, and soluble in hydrocarbon solvents. Contains various inorganic compounds. Organometallic additives are introduced directly into the hydrocarbon processing zone or visbreaking zone, preferably near the bottom of the riser reaction zone, so that the metal additives are absorbed before or with the heavy metals in the feed oil. The agent can be deposited onto the agent particles. When the additive metal in the sorbent material of the present invention reaches the regenerator, its oxides may be removed either by direct decomposition of the additive to metal oxides or by the decomposition of the additive to free metal which in turn is transferred to the regenerator. It is formed either by being oxidized under conditions. This provides an intimate mixture of metal additives and undesirable heavy metal contaminants in the feed oil, and is one of the most effective ways to capture vanadium pentoxide as soon as it is formed in the regenerator. I believe that it is. The metal additive is introduced into the riser visbreaking zone with the feed oil in sufficient amount that the atomic ratio between the metal additive and vanadium in the feed oil is at least 0.25 and preferably in the range of 0.5 to 3.0. They can be introduced by mixing. It is preferable to delay the addition of metal additives until significant levels of metal deposits have accumulated to maintain process economics as long as possible. If the metal additives are added directly to the absorbent during absorbent manufacture or at some other time before introducing the absorbent into the riser reaction vessel, the metal additives are water-soluble inorganic salts of these metals. are preferred, such as acetates, halides, nitrates, sulfates, sulfides and/or carbonates. If the metal additive is not added to the absorbent before or during particle formation, it can be added by an impregnation method to dry absorbent particles, preferably spray-dried microspheres. The inorganic metal additive may be introduced into the process system of Figure 1 described below along with the water-containing stream, for example by directly cooling the solids in the regenerator;
Alternatively, the flow may be used to lift and fluidize the absorbent solid material for stripping. A particularly suitable absorbent material for demetallizing high boiling and atmospheric distillation resids is high pore volume dehydrated kaolin clay. According to analysis, kaolin clay contains approximately 51-53% (wt%) _SiO2 , 41-45
% Al ₂ O ₃ and 0 to 1% H ₂ O, with the remainder consisting of small amounts of naturally occurring impurities. These impurities may include titanium, which is bound in the clay and is not in a form that can trap significant amounts of vanadium. To facilitate spray drying, the powdered dehydrated kaolinite clay is dispersed in water under conditions that form a solid suspension or slurry that provides a random arrangement that contributes to high pore volume. In preferred preparation methods, binder materials consisting of silica, alumina, calcia, boria, magnesia or titania can be used to achieve abrasion resistance and higher pore volume and to avoid expensive calcinations. The spray dryer used can have countercurrent or cocurrent movement or mixed countercurrent/cocurrent movement of the suspension and hot air for the production of microspheres. The air can be heated electrically or by other indirect means. Combustion gases such as those obtained in air from the combustion of hydrocarbon heating oils can also be used. When using a cocurrent dryer, the air inlet temperature can be as high as 649℃ (1200〓), and the clay can be as high as about 121℃ to 316℃ (250〓 to 600〓).
should be loaded at a sufficient rate to ensure an air outlet temperature of . At these temperatures, the free water of the suspension is removed without removing the water of hydration (water of crystallization) from the crude clay components. Partial or total dehydration of the coarse clay during spray drying is expected. The product of the spray dryer can be fractionated to obtain microspheres of desired particle size. Calcination of the particles can, but need not, be completed after the addition of one or more metal components as defined herein, or the spray-dried particles can be subjected to a calcination operation prior to metal addition. It can be completed by introducing Approximately 1600〓 to 2100〓 to obtain maximum hardness particles
It may be advantageous if the microspheres are calcined at a temperature of 0, but it is also possible to dehydrate the microspheres by firing at a lower temperature. Temperatures of about 1000° to 1600° can be used to convert the clay into a substance known as ``metakaolin.'' After calcination, these microspheres should be cooled and, if necessary, fractionated to obtain the desired particle size range. Examples of titania-containing absorbents Mass (A) Tap water 11 (B) Na ₂ SiO ₃ - PQ “N” brand 8.35 (C) Concentrated sulfuric acid 1.15 (D) Alum 0.8Kg (E) Clay-Hydride AF 12Kg (F) Titania-Dupont's Anatase 5Kg (G) Sodium Pyrophosphate 150mg In one particular embodiment, components G, E, and F are added in this order to water of 8 at pH 2 and ambient conditions with mixing. A 70% solids slurry is obtained, which is retained for further processing. Tap water (A) is added to a homogenization mixer (Kday Mill) along with sulfuric acid (C) and mixed for 5 minutes. Sodium silicate (B) is then added continuously to the stirred acid solution over a period of 15 minutes to form a silica sol. The 70% solids slurry from the first stage is then added to the stirred Kadey mill and mixed for 15 minutes. PH of solution
is maintained at 2.0-2.5 by adding acid if necessary. Keep the temperature below 120℃ during addition, mixing, and acidification.
The viscosity of the solution is adjusted to 100 centipoise by adding water. The resulting mixture is immediately atomized, ie, sprayed into a heated gas atmosphere using a commercially available spray dryer with air and steam having an inlet temperature of 400°C and an outlet temperature of 130°C. The resulting microspherical particles were washed with hot water at 20 °C and heated at 350 °C.
Dry for an hour. This results in an absorbent containing 25% by weight of titanium as titanium dioxide on a volatile-free basis. In some instances of absorbent manufacture, mixing and subsequent spray drying is done quickly to prevent premature solidification of the gel. In this regard, the silica sol and solid slurry are added separately to the spray dryer nozzle and the two streams are instantaneously and homogeneously mixed. Such a mixing method is described in U.S. Patent No. 4126579,
This patent is incorporated herein by reference. The air atomizer delivers the two components into the nozzle at a pressure of about 30 to 90 psi and the air in the nozzle to about 50 to 60 psi, preferably about 51-53 psi.
should be kept at As an alternative to premixing with both components, the metal additive can also be separately fed to the nozzle via a separate system operating at a pressure of about 30 to 90 psi. Titania-impregnated absorbent 75 g of absorbent (uncalcined) are dried at 100° C. under vacuum for 2 hours. 2.4ml dupont tizer
Dissolve TPT (tetraisopropyl titanate) in 75 ml of cyclohexane. This titanium solution was added to the vacuum-dried absorbent and left in contact for 30 minutes with stirring. Excess solution is then driven off the impregnated absorbent to yield dry solid particles. The absorbent is then humidified. This absorbent is regenerated as a shallow bed (burning off the organic components) in a 900° furnace for 6 hours. This step yields an absorbent containing 0.53% by weight of Ti on the absorbent. Mixing the Additive with the Absorbent In another preferred embodiment of the invention, the metal additive can be incorporated directly into the absorbent material. The metal additive is mixed into the aqueous slurry of raw absorbent material in an amount to provide a concentration of about 1 to 25% by weight on the final absorbent. The metal additive can be added in the form of water-soluble compounds such as nitrates, halides, sulfates, carbonates, etc., or as oxides or hydrogels such as titania or zirconia gels. Other active gelatinous precipitates or other gel-like materials may also be used. This mixture was spray dried to deposit the active metal additive within the matrix and/or on the outer surface of the catalyst particles.
The finished absorbent results as microspherical particles of 200 microns. Since the vanadium concentration on the spent absorbent can be as high as 4% by weight of the particle weight, the concentration of additive metals is preferably in the range of 1 to 8% as elemental metal. More preferably, sufficient metal additive is present to maintain at least the preferred minimum atomic ratio of additive metal to vanadium at all times. Moving Bed Absorbent A hydrosol containing the absorbent material described in this invention is introduced as drops of the hydrosol into a water-immiscible liquid in which the hydrosol solidifies into spherical bead-like particles of hydrogel. Larger dimension balls typically range in diameter from about 1/64 to about 1/4 inch. The resulting spherical hydrogel beads
Dry at 300℃ for 6 hours and bake at 1300℃ for 3 hours. The use of these calcined spherical beads has particular advantages in moving bed processes. Typical feed oils anticipated for demetallization according to the present invention can include any oil fraction consisting of undesirable metal levels for catalytic cracking, such as whole crude oil, atmospheric gas oil, heavy vacuum gas oil, etc. Residual heavy fractions contained together with oil and topping residues, atmospheric distillation residues, vacuum fractionation bottoms, other distillates containing heavy residues, coal-derived oils, shale oils, waxes, untreated or deasphalted residual oils, and mixtures of such distillates with gas oils, and the like. Thus, a relatively small amount (5-25%) of demetalized atmospheric distillation residue or other hydrocarbon feed oil may be mixed with atmospheric or vacuum gas oil to provide a feed oil for catalytic conversion. Can be done. High vanadium feed oils for FCC processing are those having more than 0.1 ppm up to about 0.5 ppm vanadium. High vanadium feedstocks for RCC processing, on the other hand, contain more than 1.0 ppm vanadium, usually more than about 5.0 ppm. In one particular example, the carbon-metallic feed oil to be visbroken and demetallized in accordance with the present invention has a boiling point of 650㎓ or higher and has a nickel equivalent (formula: Ni equivalent) of at least 4 ppm. =Ni+
total metal ppm added to the nickel equivalent by V/4.8+Fe/7.1+Cu/1.23), a Conradson carbon residual value greater than about 1.0, and at least
It has a vanadium content of 1.0ppm. Feedstocks for which the process of the invention is particularly useful have a heavy metal content of at least about 5 ppm nickel equivalent and a vanadium content of at least 2.0. The higher the heavy metal content, the higher the proportion of vanadium in the heavy metal content, and the higher the Conradson carbon content of the material with a boiling point of 1025〓 or higher, the greater the increase in the present invention with or without metal additives as provided herein. High pore volume solid absorbent materials and their use are more advantageous. A particularly preferred hydrocarbon feed oil for demetalization and reforming treatment according to the process of the invention is 1025
〓650〓+ containing 20% or more of residual oil fraction with a boiling point above
Contains 70% or more of the above substances, and has a nickel equivalent of 5.5ppm or more, of which at least 5ppm
is vanadium and has a vanadium to nickel atomic ratio of at least 1.0, and a Conradson carbon residual value of greater than 4.0. The specified resid feed also has a hydrogen to carbon ratio of less than about 1.8 and an amount of coke precursors sufficient to produce about 4 to 14 percent or more coke by weight based on the fresh feed. You can also do that. Sodium vanadate has a low melting point and can also flow in the same manner as vanadium pentoxide, causing particle agglomeration. Although it is desirable to maintain low sodium levels in the feed oil to minimize agglomeration and at the same time avoid sodium vanadate on the absorbent, the metal additives of this invention may also be used in compounds, alloys, or complexes with sodium vanadate. It is also effective to prevent these compounds from melting and flowing by forming. Regarding heavy metal tolerance levels on the high pore volume sorbent itself, such metals range from approximately 3000 to 3000 in total metals.
70000ppm range, and more commonly from 10000
It can accumulate on the absorbent to high levels in the range of 30000ppm, the majority of which is vanadium. The demetalization decarburization and hydrothermal visbreaking process of the present invention produces large amounts of coke which is initially deposited as hydrocarbonaceous material in amounts up to 14% by weight based on the weight of fresh feed oil. This carbonaceous material deposit, often referred to as coke, can be deposited on the sorbent depending on the sorbent-to-oil ratio (absorbent weight to feed oil weight) used in the demetalization/decarbonization zone, such as the riser contact zone. It is deposited on the absorbent particulate material in an amount ranging from about 0.3 to 3% by weight. The severity of the thermal visbreaking operation carried out in the presence of steam and/or water should however be low enough that the thermal conversion of the feed oil to gasoline and light products is relatively low, preferably 20 vol. % or less. Even at these low levels of conversion, hydrothermal visbreaking processes, whether thermal and/or somewhat catalytic, can reduce the Conradson carbon value of the feed oil to at least 20
%, preferably 40 to 70%, and reduce the heavy metal content of the residual feed oil by at least 50%, preferably in the range of 75 to 90%. The high-boiling feed oil to be demetalized and decarbonized by the absorbent material of the present invention is in one embodiment introduced separately into the bottom of the riser reaction zone and provided in accordance with the present invention. The hot absorbent is introduced under conditions that form a suspension with the particulate material.
Steam, naphtha, water, flue gas and/or some other suitable diluent material such as nitrogen or carbon dioxide may be introduced into the riser separately or together with the high boiling point feed oil to combine the feed oil with the solid absorbent material. atomized and vaporized contact to form a fluidizable suspension. These diluents may come from fresh sources or, when purity permits, may be recycled from the process stream of the associated refinery operation. If circulating diluent streams are used, they may contain hydrogen sulfide and other sulfur compounds that may help passivate harmful catalytic activity due to heavy metals that accumulate on the absorbent material. It should be understood that water can be introduced either as a liquid or as steam. In terms of energy savings, water is preferably introduced as a liquid. The water primarily disperses the feed oil in intimate contact with the absorbent, reduces the oil partial pressure, and accelerates the formation of a suspension of the feed oil and absorbent to create the desired vapor in the riser contact zone. Added as a vapor source to achieve high velocity and hydrocarbon residence time. When the high boiling feed oil moves up the riser under the visbreaking conditions specified herein, it is used in the art as a feed oil to dry gas, wet gas, naphtha, and atmospheric distillation residue cracking operations. Four products, known as high boiling demetalized and decarbonized oil products, are formed that are suitable for loading into conventional FCC operations. At the upper or discharge end of the riser, the absorbent particles are preferably rapidly separated from the product vapor to minimize thermal and catalytic cracking to its existing extent. Solid sorbent particles containing carbonaceous deposits formed in the metal and riser contact zone are sent to a regenerator operation to burn off the carbonaceous deposits. The separated product vapors are normally sent to a fractionation column for fractionation to obtain the four basic products defined above. Preferred conditions for the contact of feed oil and absorbent in the riser are summarized in Table C, in which the abbreviations used have the following meanings: "Temp"
is temperature, “Dil” is diluent, “PP” is partial pressure, “Wgt”
is weight, “V” is steam, “Res” is retention, “S/O”
is absorbent to oil ratio, “sorb” is absorbent, “bbl”
is barrel, “MAT” is microactivity by MAT test using standard Davison-supplied oil, “Vel” is velocity, “cge” is loading, “d” is density, and “Reg” is regeneration.

In treating carbon-metallic feedstock according to the present invention, the regeneration gas can be any gas capable of providing oxygen to convert carbonaceous deposits to carbon oxides. The amount of oxygen in the regeneration gas required per pound of coke for combustion depends on the desired ratio of carbon dioxide to carbon monoxide in the effluent flue gas, and on other oxidizable substances present in the coke, e.g. It depends on the amount of hydrogen, sulfur, nitrogen, and other elements that can form gaseous oxides at the regeneration temperature conditions. Regeneration of solid absorbent granular material is approximately 1000– to 1600
〓, preferably from 1150〓 to about 1400〓 or 1500〓
operating at temperatures in the range of 100 to effect combustion of carbonaceous deposits while maintaining temperatures below temperatures that cause significant deterioration of the absorbent. Adjustment of the combustion rate can be controlled, at least in part, by the oxidizing gas used and the relative amounts of carbonaceous material introduced into the regeneration zone per unit time. The rate of introduction of carbonaceous material into the regenerator is controlled by regulating the flow rate of absorbent into the regenerator, the rate of withdrawal of regenerated absorbent is controlled,
The rate of oxidizing gas introduction is controlled. These factors are due to the fact that the ratio of carbon dioxide to carbon monoxide in the effluent gas is approximately
It can be controlled to be less than 4.0 and preferably about 1.5 or less so that the flue gas is CO rich. Additionally, water, either as liquid or steam, is added to the regenerator to help regulate the temperature therein and influence the production of CO rather than carbon dioxide. On the other hand, only a portion of the separated absorbent material is passed to the regenerator and the remaining portion is recycled directly to the riser reactor where it is subjected to high temperature stripping in admixture with the regenerated granular material sent to the riser. be able to. The regenerator carbonaceous material combustion reaction is conducted such that the amount of carbon remaining on the regenerated sorbent is less than about 0.50%, and preferably less than about 0.25%, on a substantially dry weight basis. When the metal additive is applied to the absorbent material, it can be applied as an aqueous or hydrocarbon solution.
Alternatively, it is introduced as a volatile compound during the processing cycle. It may be added at any point during the movement of the absorbent in the process system. This includes, but is not limited to, the bottom of the riser reactor along the riser reactor, the solids concentrate bed in the collection tank around the top of the riser, the stripper provided in the system, the regenerator air inlet, Includes addition to the regenerator solids bed, and regenerated absorbent standpipe. The high pore volume sorbents of the present invention are loaded for use in hydrothermal visbreaking operations as described herein, with or without metal additives, and without molecular hydrogenation. Referring now to FIG. 1 by way of example, absorbent circulation and operating factors are adjusted to process conditions by methods well known to those skilled in the art. 1150−
The regenerated high temperature absorbent material at a temperature in the range of 1400° is contacted at the bottom or upper portion of the riser reactor with a high boiling resid feed oil charged therein depending on the desired contact time. The fluidizing gas first suspends the absorbent solids and then contacts the charge feed oil. The feed oil is dispersed with diluent, steam, water, flue gas or a combination thereof injected at point 2. Water and/or naphtha is first injected as required at point 3 to suspend the solids, evaporating the feed oil, fluidizing the absorbent, and dissolving the solids and gas in the bottom initial portion of the riser. conditioning upon contact of a forming suspension of substances;
help. The absorbent and the gaseous material consisting of vaporized and non-vaporized high boiling hydrocarbons are separated from each other for 0.1-5 seconds;
It travels upward in the riser 4 for a contact time limited to preferably within the range of 0.5-3 seconds or as long as required, with substantially no thermal and/or metallurgical conversion of the charge oil. Achieve the desired demetalization and decoking without any hassle. Absorbents consisting of hydrocarbons and metal deposits are 900−1100
It is quickly separated from the vaporous hydrocarbons at the riser outlet 6, which is at a temperature in the range . The gaseous substances, consisting of vaporous hydrocarbons, steam, wet and dry gaseous substances, pass through one or more cyclones, such as a multi-stage cyclone represented by cyclone 7, in which an associated absorbent The particles are separated and recovered by the dip leg, and the gaseous material consisting of hydrocarbon vapors is sent via a transfer line 8 to a fractionating tube (not shown). Absorbent particulate material consisting of hydrocarbonaceous material decomposition products of the feed oil component and metal deposits with a boiling point above 1025〓 is introduced by 21 into the stripper 10 to further remove any entrained or formed hydrocarbon vapors. It is collected as a fluidized bed of solids flowing downwardly in countercurrent with the stripping gas for regeneration, and then all or part of it is sent to a regeneration reactor 11 to form a fluidized bed 12 of solids to be regenerated. Conditions under which an oxygen-containing gas, such as air with or without enriched oxygen content, or carbon dioxide mixed with an oxygen-containing gas, burns carbonaceous deposits and forms carbon dioxide and other combustion products as specified herein. into a dense fluidized bed of solids in regeneration reactor 11 maintained at . CO rich or
The resulting flue gas, which has not become CO-rich, is processed through a cyclone 22 and exits the regeneration reactor 11 via line 23. The regenerated solid sorbent particles containing up to 0.5% carbon are passed to stripper 15 and to line 1 to remove entrained combustion gases as required.
6 to the bottom of the riser before repeating the cycle. The regenerated solids can also be stripped in a withdrawal well in the upper part of the bed 12 by means not shown. In one embodiment of the invention, a portion of the recovered solid sorbent material, contaminated with hydrocarbonaceous material and metal deposits, is routed through conduit 42 to the riser reactor, bypassing the regeneration reactor; Subsequently, high-temperature stripping is performed in a mixed state with the newly regenerated thermal catalyst. This method of operation relies on lowering the regenerated catalyst temperature while simultaneously providing additional high temperature visbreaking of deposited hydrocarbonaceous material. It is also expected to remove some carbonaceous deposits by reacting with CO ₂ rich gas in such a zone between the regenerator and riser reactor. Bypassing the regeneration reactor as defined above reduces vanadium oxidation, increases thermal decomposition of liquid hydrocarbons, and at the same time lowers the regeneration temperature by reducing the amount of carbonaceous deposits loaded into the regenerator. It can be used for In one particular embodiment, the regeneration of the sorbent material includes combustion of the carbonaceous deposit sufficient to provide solid sorbent particles containing no more than 0.2%, preferably no more than 0.10% by weight carbon. desirable in When the metal level on the absorbent becomes unacceptably high, reducing the effectiveness of the absorbent to an undesirably low level or exceeding the desired equilibrium conditions, additional absorbent material is added to conduits 42 and 43. It can be replaced by a deactivated absorbent which is extracted by Points 18 and 19 can be used to add fresh absorbent with or without metal additives. In the case of virgin absorbents made without additives, the metal additives are added as aqueous solutions or organometallic compounds in aqueous or hydrocarbon solvents at points 18 and 19 and addition points 20 and 20' in riser 4. , and at addition points 2 and 3 on the supply oil line 1, and the addition point near the bottom of the vessel 5 can also be used for this purpose. Addition of metal additives is not limited to these points, but can be introduced at any point in the oil/absorbent treatment cycle. Inlet conduits 20 and 20' are also for the purpose of adding feed oil to be demetalized and decarbonized to obtain various contact times in the riser. Examples of Additive Additives The present patent application describes the use of high pore volume clay absorbent materials in combination with one or more selected additive metals as defined herein, as oxides or salts thereof, or in combination as described above. A new attempt is described to specifically overcome the harmful effects of vanadium pentoxide by using it without the use of vanadium pentoxide. These metal additives are particularly useful in immobilizing vanadia by creating complexes, compounds or alloys of vanadia with melting points higher than the temperatures encountered in the regeneration zone. Based on the metallic element content of the absorbent material, these metal additives may range from about 0.5 to 25% by weight of the original absorbent, more preferably from about 1 to 8%.
It can be used in concentrations in the range of %. When adding one or more immobilizing metals during a visbreaking operation, those metal elements can accumulate to much higher concentrations than the equilibrium absorbent material, and displace the absorbent. can be maintained at the desired level by Absorbent materials that can be used in accordance with the present invention include clay solids with little or no catalytic activity and provide a particle pore volume of at least 0.4 cc/g and are catalytically used. A cracking catalyst may be included. However, M.A.T.
Clays made in accordance with the present invention are preferred to some extent because they have a low catalytic activity of less than about 20 and are therefore considered relatively inert. Clays suitable for this purpose include bentonite, kaolin, montmorillonite, smectite, and other bilayer silicates, mullite, pumice, silica, laterite, and combinations of one or more of these similar materials. The surface area of these absorbents is such that their pore volume is at least 0.4 cc/g or 0.5 cc/g.
changed during the preparation according to the invention by substantially increasing by more than g, preferably the clay is
Measured by ASTM Test Method No. D3907-80
Have a microactivity of 20 or less. As one example of including additives, tetraisopropyl titanate (TPT) was mixed with heavy gas oil (HGO) to form a solution of 1 part TPT to 1 part HGO. This solution was added to the oil supply piping to the riser in an amount sufficient to yield 1 part titanium for every 1 part by weight vanadium in the feed oil.
The feed oil charged to the riser was atmospheric distillation residue processed at 600,000 lb/day and had a vanadium content of 20 ppm. Based on the vanadium content and the molecular weight of TPT, it was determined that 420 lb/day of TPT would be added to 600,000 lb/day of atmospheric distillation residue. Figure 2 shows the results of adding TPT to the absorbent. Absorbent samples of various vanadium levels were taken during two process periods without the additive of the present invention (dots and crosses), and the same samples were taken during addition of the additive (black squares). These samples were subjected to the clumping test described below to determine the flow properties of the vanadium-containing absorbent particles. The vanadium-containing absorbent samples were placed in separate ceramic crucibles, dried and fired in air at 1400 °C for 2 hours. The crucible was cooled to room temperature. Vanajia is
Although it is a liquid at the operating temperature (1400°), it flows over the absorbent surface and causes agglomeration of the absorbent particles when it cools below its solidification temperature. The degree of cohesion shown in Figure 2 is a macroscopic and mechanical evaluation of particle fusion, i.e. flow - no change in flow properties between virgin and used absorbent; soft - of used absorbent. Substantially all of the material is free-flowing and small amounts of agglomerates are easily broken down into free-flowing absorbents; intermediate-free-flowing absorbents contain both free-flowing particles and molten agglomerates in a 1:1 ratio. Hard - Substantially all of the absorbent particles are fused together as a hard mass with very few free-flowing particles. The absorbent of Figure 2 was used to treat atmospheric distillation residues that did not have low vanadium and Conradson carbon values. Two long-term operations of about 30 days (dot and x)
In , the absorbent particles began to show cohesiveness at a vanadium level of 10,000 ppm, and by 20,000 ppm they showed agglomeration into hard clumps (decreased flowability).
In the third period (black square), additives
TPT was added to the gas oil hydrocarbon solution as described above during the process cycle. With this addition
Operation at vanadium levels of 20,000 to 25,000 ppm was possible without any reduction in fluidization due to particle agglomeration. Another example of the metal additive specified above was the use of methylcyclopentadienyl manganese tricarbonyl (MMT). Two drams of this material were added over a two hour period to at least partially immobilize the vanadium on the absorbent. Each drum weighs 40 pounds and contains 25
Contained % MMT by weight. Based on a manganese concentration of 28.3% by weight in MMT and a circulating sorbent system loading of 42 tons, approximately 700 ppm Mn was deposited on the sorbent. The MMT additive also improved the circulation efficiency of the absorbent by reducing particle agglomeration. In the fluidized solid system shown in Figure 1, the rate of metal accumulation on the circulating sorbent depends on the metals in the feed oil, the amount of circulating sorbent, the rate of addition and withdrawal of the sorbent,
It is a function of the absorbent to oil ratio and the absorbent pore volume. Figures 3 and 4 show the rate of metal accumulation on the circulating absorbent when the metal content in the feed oil is varied, with constant retention, constant absorbent addition and withdrawal rate. These figures show that for a feed oil with a metal level of 20-70 ppm, the total metal level on the absorbent is approximately 90-
It is shown that equilibrium is reached after 150 days. By utilizing these diagrams, as well as similar diagrams that can be developed for higher levels of metals, larger pore volume addition rates, and scheduled circulation loadings, absorbent material The required concentration of metal additive to be provided can be determined to yield a preferred minimum atomic ratio of metal additive to vanadium content. For example, in Figure 3, this particular device is
It has an absorbent loading of 9000 lbs., an absorbent addition rate of 1.35 lbs./barrel of feed oil/day, and a feedstock feed rate of 200 lbs./day. Assuming that the metal content is entirely vanadium, curve 1 in Figure 3 shows that when vanadium in the feed oil is 70 ppm,
It is used to show that after 150 days of continuous operation, the vanadium level on the catalyst reaches equilibrium at about 17,000 ppm and thereafter remains constant over time. Thus, when preparing absorbent granules containing titania additives, the absorbent contains at least 8500 ppm titania and a titanium/vanadium atomic ratio of at least 0.5 is maintained during use to immobilize deposited vanadium. It is designed to ensure that the Similar calculations can be performed using other curves or combinations of these curves for lower or higher levels of vanadium (120 ppm on absorbent
Vanadium is approximately 30,000 ppm under the conditions shown in Figure 3.
equilibrium is reached). Hydrothermal visbreaking, herein referred to as thermal visbreaking or hydrovisbreaking, is a high pore volume absorbent in the high temperature processing of residual oil feedstocks with boiling points above 1025〓 and variable amounts of vanadium. The vanadium accumulation rate above, and the planned and selected level of the upper limit of metal contaminants allowed on the solid sorbent before replacement by an sorbent with lower metal content, depends on the feed oil metal content, especially the feed It is a function of the vanadium content of the oil. The predetermined upper limit for metal contaminants may be referred to as an equilibrium condition because the addition and withdrawal rates are maintained not to exceed the preselected upper metal level for the selected equilibrium condition. Table G shows a typical case for a 40,000 barrel/day unit, where the vanadium content in the feed oil is
It varies from 1ppm to 25ppm and then to 400ppm. To limit the preselected level of vanadium on the sorbent to an upper predetermined equilibrium state equal to the additive immobilizing metal and the sorbent capacity, the sorbent addition or displacement rate should be adjusted from 5,000 to 30,000 ppm at equilibrium. Vanadium values can be varied to yield. As explained elsewhere, vanadium, such as vanadium pentoxide and/or sodium vanadate, on the absorbent melts and flows over the absorbent surface at regenerator temperatures above 1200 °C, causing particle fusion and agglomeration. . Table H presents the economic advantages of introducing additives into the riser as aqueous or hydrocarbon solutions. Table H shows the economic difference ($/day saved) that can be realized by utilizing additives and operating at a level of 30,000 ppm vanadium on the absorbent versus a level of vanadium on the absorbent of 10,000 ppm. It shows. As shown in Table H, for FCC operation,
Processing a feedstock with 1 ppm vanadium represents a savings of at least $28/day with TPT as the additive and $168/day with titanium tetrachloride as the additive. As a comparison, for RCC operations, processing heavy hydrocarbon oils containing 25 to 100 ppm vanadium costs $500 to $2000/day with TPT as an additive and $4000/day with titanium tetrachloride as an additive.
Showing savings of $22,400/day. The regeneration reactor diagrammatically depicted in FIG. 1 is a simple one-zone concentrated solids fluidized bed in a single regeneration zone. The playback operation of the present invention is not necessarily limited to the single-stage playback operation shown, but may consist of two or multiple stages of separate playback bands, which may be in a stacked or side-by-side relationship. ,
Internal and/or external transfer piping may be provided between the zones. Several multi-stage regenerator arrangements known in the art may be used with advantage, or one or more arrangements described in more detail in other co-pending patent applications may have particular advantages. It can be used with. The determination that vanadia deposited on the absorbent flows at the regeneration temperature, causing agglomeration between the absorbent particles, and the selection of elements and their salts that interfere with this process were investigated in three ways. agglomeration or agglomeration techniques, vanadia diffusion from or compound formation with metal additives in alumina-ceramic crucibles, and spectroscopic studies and differential thermal analysis of vanadia-metal additive mixtures. , is. Agglomeration Test Clays that were spray dried to produce microspherical particles with a particle size of 20 to 150 microns were deposited with vanadia at various concentrations. Clay containing vanadia and clay containing vanadia at various concentrations were placed in separate ceramic crucibles and fired in air at 1400 °C for 2 hours. At the end of this time, the crucible was removed from the Matsufuru furnace and cooled to room temperature. The surface texture and flow characteristics of these samples were observed and the results are reported in Table D.

As shown in Table D, vanadia-free clays do not form any shells, lumps or fused particles at the temperatures encountered in the regeneration reactor portion of the process described in this invention. At vanadia concentrations of 1000-5000 ppm, agglomeration was observed, but the shells binding the particles were easily broken down to free-flowing crusted particles. At vanadia concentrations of 5000 ppm and above, the particularly low pore volume clays used begin to clump in an undesirable manner and do not flow even when gently tapped. The appearance of this phenomenon is
These agglomerated particles must be forcibly removed during cooling below the solidification temperature in the crucible or in the cooled operating equipment for entry into the equipment for cleaning of clogged dip legs and other repairs. This is illustrated by the observation that solid lumps of absorbent are often found. This phenomenon makes repairs of the operating equipment lengthy and complicated, since this material has to be scraped off. Crucible Diffusion Test An extension of this agglomeration test is to use a ceramic alumina crucible to determine whether vanadia will react with a given metal additive. If vanadia does not react with metal additives or forms only a few compounds,
Vanadia diffuses through or across the porous alumina wall and is deposited as a yellow to orange deposit on the outer wall of the crucible. On the other hand, when compound formation occurs, there is little or no vanadia deposit on the outside of the crucible wall. Two series of tests were conducted. In the first series, shown in Table E, a 1:1 mixture by weight of vanadium pentoxide and metal additives was placed in a crucible and heated to 1500 °C in air for 12 hours. Compound formation or vanadia diffusion was as recorded in Table E.

[Table] In the second series of tests, vanadia-containing substances were similarly tested. A 1:1 weight ratio of vanadium pentoxide and metal additives was heated to 1500 ml in air for 12 hours. The results are shown in Table F. The material reported in Table F as containing 24,000 ppm vanadia on clay without metal additives was calcined at 1,500 ml and then examined by scanning electron microscopy (SEM). The fused particles initially showed a pattern of fused particles. However, when this material was continuously irradiated with electrons, the fused particles separated due to the heat generated by the irradiated electrons. Melting and flow of vanadia could be observed when the initially single fused particle separated into two or more individual microspherical particles.

[Table]
24000 Manganese Oxide None Investigation of the ability of several elements to immobilize vanadium pentoxide was continued using DuPont differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM) instruments. The metal additives considered in DTA are titania, barium oxide, calcium oxide, the lanthanide series, magnesium oxide and indium oxide, all excellent additives for the formation of high melting point vanadates with melting points of 1800㎓ or higher. It was shown that Copper gave intermediate results with a compound that melts at about 1500㎓. Lead oxide, molybdena, tin oxide, chromia, zinc oxide,
Results are poor for materials such as cobalt oxide, cadmium oxide, and certain rare earths.
The concept of the invention described here is based on the FCC as described above.
It is useful in the treatment of feed oil for both RCC and RCC. The present invention provides a method for processing high-boiling carbon-metallic materials, including feedstocks with high metal content and high Conradson carbon-forming components, to produce a low-metallic material suitable for use as a feed oil for FCC and, in particular, RCC equipment. It is particularly useful in providing products with low Conradson carbon values. Examples of these high boiling point oils are atmospheric distillation residues,
Residuals or other oils, or crude oil fractions containing metals and/or residues as defined herein. Although the visbreaking process of the present invention is preferably carried out in a riser reactor because of the desired constrained temperature-contact time factors, other types of reactors may also be used with upward or downward solids flow. good. Thermal visbreaking operations thus involve the use of downwardly moving, cocurrently flowing liquid (non-volatile) or partially vaporized feedstocks under contact conditions of pressure, temperature and weight-time-space velocity as specified herein. It may be carried out with a moving bed type of flowing absorbent. Preparation of the Absorbent The absorbent material of the present invention, particularly the absorbent material consisting of finely divided flowable granules with a particle size in the range of 20 to 80 microns, comprises low catalytically active clays with a pore volume greater than 0.4 cc/g; They can be made by a number of different methods to provide thermal stability in the presence of steam at temperatures ranging from about 900° to about 1600°. As mentioned above, the selected clay materials were treated with carbon black, sugar,
such as an organic material, a polymeric material, or an inorganic material that decomposes during high temperature contact to provide a clay material with the desired porosity and thermal stability for use in the hydrothermal visbreaking described herein. or mixed with more than one ingredient. Absorbent Preparation Method 1 12 grams of tap water and 25 grams of sodium pyrophosphate hydrate were added into a homogenizing mixer called a KD mill. This phosphate is a surfactant and disperses 22 kg of fine kaolinite clay named Hydrite UF. The clay was added over 15 minutes with vigorous stirring. The following is a typical chemical analysis of hydrite/kaolinite. Aluminum oxide 38.38 Silicon dioxide 45.30 Loss on ignition at 950°C 13.97 Iron oxide 0.30 Calcium oxide 0.05 Magnesium oxide 0.25 Titanium oxide 1.44 Hydrite UF kaolinite is the finest kaolinite available and is further identified as follows:

[Table] (Solid content 50%. Sodium hexametaphosphate 0.5% by weight of kaolinite. Measured at 10 R.PM with a Burckfield viscometer) 2. Add 2.8 kg of Catapal alumina to this clay slurry and stir the mixture for 15 minutes. Stirred. Catapal alumina is identified as alpha monohydrate (boehmite) as follows: Al ₂ O ₃ 74.2% Na ₂ O 0.004% Loss on ignition 25.8% SiO ₂ 0.003% Carbon 0.36% Sulfur None Fe ₂ O ₃ 0.005% After firing for 3 hours in TiO ₂ 0.120% 900㎓, the crystal structure is gamma alumina. 3 into a stirred slurry of 150 ml of concentrated H ₂ SO ₄ over 3 minutes. 11 of H ₂ SO ₄ was added dropwise into the stirred slurry. 11 parts of _H2O was added with stirring for 15 minutes. The obtained slurry is 3
It has a viscosity of 1100 centipoise at a pH of 130㎓. 4. The clay slurry was spray dried at inlet and outlet air temperatures of 255〓 and 750〓, respectively. 5. The microspheroidal solid from the spray dryer was placed in an oven at room temperature and heated to 1850° for 3 hours. Heating was stopped and the material was slowly cooled to 300 ml over 16 hours. 6 This method resulted in a fluid clay adsorbent material with 13% by weight alumina binder. The surface area is 31 m ² /g and the pore volume is 0.51 cc/g with a median pore diameter. Preparation of clay adsorbent with silica binder B600-142-1C 1 Into the homogenization mixer (Kday Mill)
17 tap water and 160 g of sodium pyrophosphate hydrate. While stirring, 16Kg of Hydrite UF Kaolinite clay was added over 20 minutes. 2 To this stirred clay slurry was added 2 "N" brand sodium metasilicate for 5 minutes. 3. The resulting viscous clay slurry was diluted with tap water at 125°C while stirring at 16°C. 4. The slurry was spray dried with an inlet air temperature of 750° and an outlet temperature of 250°. 5. The microspheroidal solid was placed in an 80° oven and heated to 1900° for the next 3 hours. The heat was removed and the material was allowed to cool to 300 ml over 16 hours. 6 This fluid clay adsorbent contained 5% silica binder and 93% clay by weight. The pore volume of this material is 0.41cc/g, while the surface area is
It was 14m ² /g. Preparation of clay adsorbent using carbon black 1 Into the homogenization mixer (Kday Mill)
24 g of water and 350 g (0.35 Kg) of lignin ( _CBO3 - carbon black) as a dispersant were added. The mixture was stirred to completely mix the dispersant, and then 7 kg of carbon black (United N219L - particle diameter 280 Å) was added to the KD.
The carbon black was added to the mill mixture to disperse it in the water. The mixture was stirred for 15 minutes. next
32.4 Kg of Hydrite UF clay was added to the mixture in 4 parts over a mixing time of approximately 15 minutes. Following the clay addition, the mixture was further stirred for an additional 15 minutes to form a homogeneous slurry. 2. The homogeneous slurry is then heated to an inlet temperature of about 255〓 and 750℃.
Spray-dried at an outlet temperature of . The product of the spray-drying operation, consisting of microspheroidal solids, is heated, if necessary, gradually in an oven to a temperature of about 1850 °C.
It may be heated or baked by heating for a period of time. The calcined material should then be slowly cooled to about 300 ml over an extended period of up to 16 hours.
During calcination of the spray-dried material, the carbon black in the solids, which comprises about 20%, is burned off and at least 0.5
Provides high pore volume clay particles of cc/g. In another embodiment, the present invention provides for high pore volume particles of the present invention to pre-fill the pores with the feed oil between the solid absorbent particles and the metal-containing feed oil in the thermal visbreaking zone. It involves maintaining a certain relationship, such as when used with a volume of heavy oil that limits the selected solids to oil ratio to within the range of 1/4 to about 2/3. More specifically, the thermal visbreaking operation produces a newly created absorbent particle clay material with a pore volume of at least 0.4 cc/g and only about 1/4 to about 2 of the solid pore volume. The solids-to-oil ratio is filled with heavy feed oil consisting of sticky asphaltic material up to 1/3, starting with the minimum particle agglomeration and demetalization of the heavy feed oil as described above. and decarbonization. The relationships defined herein for pore volume, pore opening, zeolite content, catalyst-to-oil ratio limiting the degree of pore filling, temperature and contact time are not only particularly desirable, but are also useful for the thermal visbreaking operation of the present invention. It is an important relationship in operation that contributes significantly to efficiency and therefore economy. Table G shows the amount of catalyst replacement required in a typical metal removal unit processing 40,000 barrels of feed oil per day. For example, if the acceptable metal level in the sorbent at equilibrium is 10,000 ppm vanadium, and the feed oil contains 400 ppm vanadium, the metal fed to the unit per day would be 5,200 lbs. Supplied 250 tons (replacement amount) of new catalyst. Table G shows that the sorbent compositions of the present invention can be used to operate with higher levels of vanadium on the catalyst, greatly reducing the amount of catalyst displacement. Table H shows, for example, that when the metal in the feed oil is 100 ppm, the cost of titanium additive is 5 cents per barrel of feed oil, the new sorbent addition is $18,000 per day, and the daily cost savings are 22000
This indicates that it will be a dollar amount. Tables G and H specifically confirm the working efficiency and economy of on-board quantities. That is, Table G identifies several absorbent addition rates that have been identified as necessary to maintain vanadium metal contamination at a given level for feed oils of various levels of vanadium content. The advantage of using the high pore volume sorbent of the present invention, which allows operation at high metal content levels, is clearly seen with this data. In addition to Table G, Table H further describes the immobilization of vanadia with TPT in absorbents.
It shows the significant advantages that can be achieved by using one of the _TiCl4 .

【table】

【table】

[Table] Although various aspects of the invention have been described above and specific embodiments in support thereof have been discussed, undue restrictions may be imposed for reasons other than those defined by the claims. It should be understood that this should not be done.

[Brief explanation of drawings]

FIG. 1 is a schematic elevation view of an arrangement of equipment for carrying out the visbreaking demetalization method of the present invention. FIG. 2 is a graph showing the change in absorbent properties as the amount of vanadium on the absorbent increases and the effect of metal additives on the absorbent properties. FIG. 3 is a graph showing the time required to significantly accumulate vanadium on the absorbent at various vanadium levels in the feed oil and at an absorbent addition rate of 3% of the vessel inventory. FIG. 4 is a graph showing the time required to significantly accumulate vanadium on the absorbent at various vanadium levels in the feed oil and at an absorbent addition rate of 4% of the vessel inventory.

Claims (1)

[Claims] 1. For the demetalization and decarbonization of high-boiling residual oils containing vanadium and asphaltenes, with a pore volume in the range of 0.4 to 0.5 cc/g and a pore opening of at least 500 angstroms. A composition consisting of a clay sorbent. 2 (a) a clay sorbent with a pore volume in the range of 0.4 to 0.5 cc/g and a pore opening of at least 500 angstroms, and (b) silicon, aluminum, titanium, zirconium, barium, magnesium, calcium, 1 to 20% by weight of a metal compound selected from the group consisting of: and mixtures thereof. 3 slurrying the kaolinite clay with a thermally decomposable dispersant, spray drying the slurry to form a microspheroidal solid, heating the microsphere solid for up to 3 hours, and then 0.4 to 0.5 by slowly raising and cooling the spherical solid to about 300 °C (149 °C) over a period of up to about 16 hours.
Method of producing a clay sorbent for demetallizing and decarbonizing high-boiling residual oils containing vanadium and asphaltenes with a pore volume in the range of cc/g and a pore opening of at least 500 angstroms. . 4 Alpha alumina is a dispersant that can be decomposed by heat.
The method according to claim 3, which is a monohydrate. 5. The method according to claim 3, wherein the thermally decomposable dispersant is carbon black. 6. The method of claim 3, wherein the thermally decomposable dispersant is selected from the group consisting of sugar, carbon black and lignin. 7. The method according to claim 3, wherein the spray drying is carried out at a temperature in the range of 7250 to 750°C (121 to 399°C). 8. The method of claim 3, wherein the slurry has a pH of about 3.